WO1984002705A1 - Dense star polymers and a process for producing dense star polymers - Google Patents
Dense star polymers and a process for producing dense star polymers Download PDFInfo
- Publication number
- WO1984002705A1 WO1984002705A1 PCT/US1983/002052 US8302052W WO8402705A1 WO 1984002705 A1 WO1984002705 A1 WO 1984002705A1 US 8302052 W US8302052 W US 8302052W WO 8402705 A1 WO8402705 A1 WO 8402705A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- core
- polymer
- branches
- moiety
- moieties
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/64—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings
- C07C233/77—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups
- C07C233/78—Carboxylic acid amides having carbon atoms of carboxamide groups bound to carbon atoms of six-membered aromatic rings having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by amino groups with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/51—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent
- A61K47/56—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule
- A61K47/59—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyureas or polyurethanes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/51—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent
- A61K47/56—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule
- A61K47/59—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyureas or polyurethanes
- A61K47/593—Polyesters, e.g. PLGA or polylactide-co-glycolide
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/50—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates
- A61K47/51—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent
- A61K47/56—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule
- A61K47/59—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient the non-active ingredient being chemically bound to the active ingredient, e.g. polymer-drug conjugates the non-active ingredient being a modifying agent the modifying agent being an organic macromolecular compound, e.g. an oligomeric, polymeric or dendrimeric molecule obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyureas or polyurethanes
- A61K47/595—Polyamides, e.g. nylon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/04—Breaking emulsions
- B01D17/047—Breaking emulsions with separation aids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C237/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups
- C07C237/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton
- C07C237/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
- C07C237/10—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by amino groups having the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by nitrogen atoms not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/48—Polymers modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/028—Polyamidoamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/005—Dendritic macromolecules
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/005—Dendritic macromolecules
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S424/00—Drug, bio-affecting and body treating compositions
- Y10S424/16—Dendrimers and dendritic polymers
Definitions
- This invention relates to a novel class of branched polymers containing dendritic branches having functional groups uniformly distributed on the periphery of such branches. This invention also relates to pro Waits for preparing such polymers as well as applications therefore.
- Organic polymers are generally classified in a structural sense as either linear or branched.
- the repeating units (often called mers) are divalent and are connected one to another in a linear sequence.
- branched polymers at least some of the mers possess a valency greater than 2 such that the mers are connected in a nonlinear sequence.
- the term "branching" usually implies that the individual molecular units of the branches are discrete from the polymer backbone, yet have the same chemical constitution as the polymer backbone.
- regularly repeating side groups which are inherent in the monomer structure and/or are of different chemical constitution than the polymer backbone are not considered as branches, e.g., dependent methyl groups of linear polypropylene.
- branched polymer To produce a branched polymer, it is necessary to employ an initiator, a monomer, or both that possess at least three moieties that function in the polymerization reaction. Such monomer or initiators are often called polyfunctional.
- the simplest branched polymers are the chain branched polymers wherein a linear backbone bears one or more essentially linear pendant groups. This simple form of branching, often called comb branching, may be regular wherein the branches are uniformly and regularly distributed on the polymer backbone or irregular wherein the branches are distributed in nonuniform or random fashion on the polymer backbone. See T. A. Orofino, Polymer, 2, 295-314 (1961).
- regular comb branching is a comb branched polystyrene as described by T. Altores et al. in J. Polymer Sci., Part A, Vol. 3, 4131-4151 (1965) and an example of irregular comb branching is illustrated by graft copolymers as described by Sorenson et al. in "Preparative Methods of Polymer Chemistry” , 2nd Ed. , Interscience Publishers, 213-214 (1968).
- branching is exemplified by cross-linked or network polymers wherein the polymer chains are connected via tetravalent compounds, e.g., polystyrene molecules bridged or cross-linked with divinylbenzene.
- tetravalent compounds e.g., polystyrene molecules bridged or cross-linked with divinylbenzene.
- many of the individual branches are not linear in that each branch may itself contain groups pendant from a linear chain.
- each polymer macromolecule backbone
- the chemical constitution of the cross-linkages may vary from that of the polymer macromolecules.
- the various branches or cross-linkages may be structurally similar (called regular cross-linked) or they may be structurally dissimilar (called irregularly cross-linked).
- regular cross-linked polymers is a ladder- type poly(phenylsilsesquinone) as described by Sorenson et al., supra, at page 390. The foregoing and other types of branched polymers are described by H. G. Elias in Macromolecules, Vol. I, Plenum Press, New York (1977).
- star branched polymers having so-called star structured branching wherein the individual branches radiate out from a nucleus and there are at least 3 branches per nucleus.
- Such star branched polymers are illustrated by the polyquaternary compositions described in USP Nos. 4,036,808 and 4,102,827.
- Star branched polymers prepared from olefins and unsaturated acids are described in USP 4,141,847.
- the star branched polymers offer several advantages over polymers having other types of branching. For example, it is found that the star branched polymers may exhibit higher concentrations of functional, groups thus making them more active for their intended purpose.
- star branched polymers are often less sensitive to degradation by shearing which is a very useful property in formulations such as paints, in enhanced oil recovery and other viscosity applications. Additionally, the star branched polymers have relatively low intrinsic viscosities even at high molecular weight.
- star branched polymers offer many of the aforementioned advantages over polymers having more conventional branching, it is highly desirable to provide polymers which exhibit even greater concentrations of functional groups per unit volume of the polymer macro molecule as well as a more uniform distribution of such functional groups in the exterior regions of the macromolecule. In addition, it is often desirable to provide polymers having macromolecular configurations that are more spheroidal and compact than are the star branched polymers.
- this invention is a dense star polymer having at least one branch (hereinafter called a core branch) emanating from a core, each core branch having at least one terminal group provided that (1) the ratio of terminal groups to the core branches is greater than 1:1, preferably 2:1 or more, (2) the density of terminal groups per unit volume in the polymer is at least 1.5 times that of a conventional star polymer having similar core and monomeric moieties and a comparable molecular weight and number of core branches, each of such branches of the conventional star polymer bearing only one terminal group, and (3) a molecular volume that is no more than 60 percent of the molecular volume of said conventional star polymer as determined by dimensional studies using scaled Corey-Pauling molecular models.
- a core branch emanating from a core, each core branch having at least one terminal group provided that (1) the ratio of terminal groups to the core branches is greater than 1:1, preferably 2:1 or more, (2) the density of terminal groups per unit volume in the polymer is at least 1.5 times that of a conventional star polymer having similar core and monomeric moieties
- the term "dense” as it modifies "star polymer” means that it has a smaller molecular volume than a conventional star polymer having the same molecular weight.
- the conventional star polymer which is used as the base for comparison with the dense star polymer is one that has the same molecular same core and monomeric components and same number of core branches as the dense star polymer.
- the number of terminal groups is greater for the dense star polymer molecule than in the conventional star polymer molecule, the chemical structure of the terminal groups is the same.
- this invention is. a polymer having a novel ordered star branched structure (herein called starburst structure).
- dendrimer is a polymer having a polyvalent core that is covalently bonded to at least two ordered dendritic (tree-like) branches which extend through at least two generations.
- ordered second generation dendritic branch is depicted by the following configuration:
- a primary characteristic of the ordered dendritic branch which distinguishes it from conventional branches of conventional polymers is the uniform or essentially symmetrical character of the branches as is shown in the foregoing illustrations.
- the number of terminal groups on the dendritic branch is an exact multiple of the number of terminal groups in the previous generation.
- Another aspect of this invention is a process for producing the dense star polymer comprising the steps of
- a first organic coreactant having (a) one moiety (hereinafter called a core reactive moiety) which is reactive with the N/E moieties of the core compound and (b) an N/E moiety which does not react with the N/E moiety of the core under conditions sufficient to form a core adduct wherein each N/E moiety of the core compound has reacted with the core reactive moiety of a different molecule of the first coreactant;
- a second organic coreactant having (a) one moiety (hereinafter called an adduct reactive moiety) which will react with the N/E moieties of the core adduct and (b) an N/E moiety which does not react with the N/E moiety of the core adduct under conditions sufficient to form a first generation adduct having a number of N/E moieties that are at least twice the number of N/E moieties in the core adduct; and (C) contacting the first generation adduct with an excess of a third organic coreactant having one moiety that is reactive with the N/E moieties of the first generation adduct and an N/E moiety that does not react with the N/E moieties of the first generation adduct under conditions sufficient to form a second generation dendrimer.
- the first coreactant differs from the second coreactant, and the second coreactant differs from the third coreactant, but the first and third coreactants may be the same or different compounds.
- the third and higher generation dendrimers are formed by repeating steps (B) and (C) of the aforementioned process.
- aspects of this invention are methods for using the dense star polymer in such applications as demulsifiers for oil/water emulsions, wet strength agents in the manufacture of paper, agents for modifying viscosity in aqueous formulations such as paints and the like.
- demulsifiers for oil/water emulsions wet strength agents in the manufacture of paper
- agents for modifying viscosity in aqueous formulations such as paints and the like.
- demulsification method an emulsion of oil and water is contacted with a demulsifying amount of the dense star polymer under conditions sufficient to cause phase separation.
- the dense star polymers of the presen € invention exhibit the following properties which are unique or are superior to similar properties of conventional star branched polymers and other branched polymers having similar molecular weight and terminal groups: (a) greater branch density;
- the core is covalently bonded to at least one core branch, preferably at least two, most preferably at least three, core branches with each core branch having a calculated length of at least 3 Angstrom units
- polymers preferably have an average of at least 2, more preferably at least 3 and most preferably at least 4 terminal groups per polymer molecule.
- the core branches have a dendritic character, most preferably an ordered dendritic character as defined hereinafter.
- the terminal groups are functional groups that are sufficiently reactive to undergo addition or substitution reactions.
- the dense star polymers differ from conventional star or star-branched polymers in that the dense star polymers have a greater concentration of terminal groups per unit of molecular volume than do conventional star polymers having an equivalent number of core branches and an equivalent core branch length.
- the density of terminal groups per unit volume in the dense star polymer is at least 1.5 times the density of terminal groups in the conventional star polymer, preferably at least 5 times, more preferably at least 10 times, most preferably from 15 to 50 times.
- the ratio of terminal groups per core branch in the dense polymer is preferably at least 2, more preferably at least 3, most preferably from 4 to 1024.
- the molecular volume of the dense star polymer is no more than 50 volume percent, more preferably from 16 to 50, most preferably from 7 to 40 volume percent of the molecular volume of the conventional star polymer.
- the density of terminal (primary) amine moieties in the polymer is readily expressed as the molar ratio of primary amine moieties to the total of secondary and tertiary amine moieties.
- this 1° amine: (2°amino + 3° amine.) is preferably from 0.37:1 to 1.33:1, more preferably from 0.69:1 to 1.2:1, most preferably from 1.1:1 to 1.2:1.
- the preferred dendrimers of the present invention are characterized as having a polyvalent core that is covalently bonded to at least two ordered dendritic branches which extend through at least two generations.
- ordered branching can be illustrated by the following sequence wherein G indicates the number of generations:
- G is the number of generations and N is the repeating unit multiplicity which is at least 2 as in the case of amines.
- the total number of terminal groups in the dendrimer is determined by the following:
- the dendrimers of the present invention can be represented in its component parts as follows: wherein the Core, Terminal Moiety, G and N c are as defined before and the Repeat Unit has a valency or functionality of N r + 1 wherein N r is as defined before.
- I is a trivalent core atom or molecule having a covalent bond with each of the three. dendritic branches, Z is a terminal moiety and "a" and "b" are as defined hereinbefore.
- An example of such a ternary dendrimer is polyamidoamme represented by the following structural formula:
- Y represents a divalent amide moiety such as
- the core atom or molecule may be any monovalent or monofunctional moiety or any polyvalent or polyfunctional moiety, preferably a polyvalent or polyfunctional moiety having from 2 to 2300 valence bonds or functional sites available for bonding with the dendritic branches, most preferably from 2 to 200 valence bonds or functional sites.
- the dense star has only one core branch and must be compared with a linear polymer in order to determine appropriate terminal group density and molecular volume.
- this dense star must have at least 2 generations in order to exhibit the desired density of terminal groups.
- Y may be any other divalent organic moiety such as, for example, alkylene, alkylene oxide, alkyleneamine, with the depicted amide moiety being the most preferred.
- the terminal groups of the dendrimer may be any functionally active moiety that can be used to propagate the dendritic branch to the next generation. Examples of such other moieties include carboxy, aziridinyl, oxazolinyl, haloalkyl, oxiranyl, hydroxy and isocyanato, with amine or carboxylic ester moieties being preferred. While the dendrimers preferably have dendritic branches having 2 to 6 generations, dendrimers having dendritic branches up to 12 generations are suitably made and employed in the practice of this invention.
- amidoamine dendimers of this invention are represented by the formula:
- A is a n-valent core derived from a nucleophilic compound
- R is hydrogen or lower alkyl
- B is a divalent moiety capable of linking amine groups
- n is an integer of 3 or more corresponding to the number of the core branches
- Z is hydrogen or wherein R 1 is hydrogen or
- R is hydrogen or methyl
- B is the divalent residue of a polyamine, most preferably an alkylene polyamine such as ethylene diamine or a polyalkyiene polyamine such as triethylene tetramine
- n is an integer from 3 to 2000, more preferably from 3 to 1000, most preferably from 3 to 125, and Z is most preferably
- the dense star polymers of this invention are readily prepared by reacting a compound capable of generating a polyvalent core with a compound or compounds which causes propagation of dendritic branches from the core.
- a compound capable of generating a polyvalent core with a compound or compounds which causes propagation of dendritic branches from the core.
- the successive excess reactant method it is essential to maintain an excess of coreactant to reactive moieties in the terminal groups in the core, core adduct or subsequent adducts and dendrimers in order to prevent cross-linking and to maintain the ordered character of the dendritic branches.
- this excess of coreactant to reactive moieties in the terminal groups is from 2:1 to 120:1, preferably from 3:1 to 20:1 on a molar basis.
- the compound capable of/generating a polyvalent core, W(X) n wherein W is the polyvalent core atom and is covalently bonded to nX reactive terminal groups (n>2), is reacted with a partially pro tected multifunctional reagent, wherein U represents a multivalent .moiety covalently bonded to protected moieties (m>2), and to one T, a moiety capable of reacting with X to form wherein X' and T' represent the residue of reaction between X and X.
- This first generation compound is then subjected to activation conditions whereby the moieties are made reactive (deprotected) and reacted with the partially protected multifunctional reagent, to form the second generation protected dendrimer,
- This protected dendrimer can be activated and reacted again in a similar manner to provide the third generation protected dendrimer. Both the successive excess reactant and the partially protected reactant method are specifically illustrated hereinafter.
- the successive excess reactant method of preparing the dendrimers is illustrated by the preparation of the aforementioned ternary dendritic polyamidoamine.
- ammonia a nucleophilic core compound
- methyl acrylate is first reacted with methyl acrylate under conditions sufficient to cause the Michael addition of one molecule of the ammonia to three molecules of the methyl acrylate to form the following core adduct:
- this compound is then reacted with excess ethylenediamine under conditions such that one amine group of the ethyl enediamine molecule reacts with the methyl carboxylate groups of the core adduct to form a first generation adduct having three amidoamine moieties represented by the formula:
- the molar excess of ethylene diamine to methyl acrylate moieties is preferably from 4:1 to 50:1. Following removal of unreacted ethylenediamine, this first generation adduct is then reacted with excess methyl acrylate under Michael's addition conditions to form a second generation adduct having terminal methyl ester moieties:
- the molar excess of coreactant to reactive moieties in each case is preferably from 1.1:1 to 40:1, most preferably from 3:1 to 10:1.
- Similar dendrimers containing amidoamine moieties can be made by using organic amines as the. core compound, e.g., ethylenediamine which produces a tetra-brancheddendrimer or diethylenetriamine which produces a pentabranched dendrimer.
- dendrimers made by the successive excess reactant method are polysulfides made by (1) reacting a polythiol, C(CH 2 SH) 4 , under basic conditions with epichlorosulfide to form the first generation polyepisulfide.
- Polyaminosulfide dendrimers can be prepared by reacting ammonia or an amine having a plurality of primary amine groups with an excess of ethylene sulfide to form a. polysulfide and then with excess aziridine to form a first gene'ration polyaminosulfide which can be reacted with excess ethylene sulfide and then with excess aziridine to form further generations using general reaction conditions described in USP 2, 105, 845 and Nathan et al. , J. Am. Chem. Soc, 63, 2361 (1941). The polyether.
- dendrimers can also be prepared by the excess reactant method by reacting hexahalobenzene with phenol of thiophenol to form a first generation polyarylether or polyarylsulfide and then with excess halogen to form the first generation polyhaloarylpolysulfide and then with further phenol or thiophenol to form further generations according to the procedures and conditions as described by D. D. MacNicol et al., Tetrahedron Letters, 23, 4131-4 (1982).
- a polyol such as pentaerythritol, C(CH 2 OH) 4
- alkali metal salt form e.g., sodium or lithium
- a partially protected compound such as tosylate ester of 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo[2,2,2]octane to form a protected first generation polyether
- polyether dendrimers are particularly desirable for use in highly alkaline or highly acidic media wherein hydrolysis of a polyaraidoamine dendrimer would be unacceptable.
- polyamine dendrimers may be prepared by reacting ammonia or an amine having a plurality of primary amine groups with N-substituted aziridine such as N-tosyl aziridine,
- water or hydrogen sulfide may be employed as nucleophilic cores for the production of binary dendrimers.
- nucleophilic core compounds include phosphine, polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and both linear and branched polyethylenimine; primary amines such as methylamine, hydroxyethylamine, octadecylamine and polymethylenediamines such as hexamethylenediamine; polyaminoalkylarenes such as 1,3,5-tris(amindmethyl)benzene; tris(aminoalkyl)amines such as tris(aminoethyl)amine; heterocyclic amines such as imidazolines and piperidines; and various other amines such as hydroxyethylaminoethylamine, mercaptoethylamine, morpholine,
- nucleophilic cores include polyols such as the aforementioned pentaerythritol, ethylene glycol and polyalkylene polyols such as polyethylene glycol and polypropylene glycol; 1,2-dimercaptoethane and polyalkylene polymercaptans; thiophenols, and phenols.
- ammonia and the polyalkylene polyamines are preferred for the preparation of polyamidoamine dendrimers by the successive excess reactant method and the polyols are preferred for the preparation of polyether dendrimers by the partially protected reactant method.
- coreactant materials used to react with the nucleophilic core compounds include ⁇ , ⁇ -ethylenically unsaturated carboxylic esters and amides as well as esters, acids and nitriles containing an acrylyl moiety such as, for example, methyl acrylate, ethyl acrylate, acrylonitrile, methyl itaconate, dimethyl fumarates, maleic anhydride, acrylamide, with methyl acrylate being the preferred coreactant material.
- acrylyl moiety such as, for example, methyl acrylate, ethyl acrylate, acrylonitrile, methyl itaconate, dimethyl fumarates, maleic anhydride, acrylamide, with methyl acrylate being the preferred coreactant material.
- other preferred unsaturated reactants are volatile or otherwise readily removed from the core/coreactant reaction products without deleteriously. affecting the reaction product.
- Examples of the second coreactant materials used to react with the adduct of the nucleophilic core and the first coreactant include various polyamines such as alkylene polyamines and polyalkylene polyamines such as ethylenediamine and diethylenetriamine; benzylic polyamines such as tris(1,3,5-aminomethy1)benzene; alkanolamines such as ethanolamine; and aziridine arid derivatives thereof such as N-aminoethyl aziridine.
- the volatile polyamines such as ethylenediamine and diethylenetriamine are preferred, with ethylenediamine being especially preferred.
- the dendrimers can be prepared by reacting an electrophilic core such as a polyester with a coreactant such as a polyamine to form a core adduct which is then reacted with a suitable second coreactant such as an unsaturated ester to form the first generation polyamidoamine. Thereafter, this first generation product is react d with a suitable third coreactant such as polyamine a then with the second coreactant such as unsaturated ester to form the desired second generation dendrimer.
- an electrophilic core such as a polyester
- a coreactant such as a polyamine
- a suitable second coreactant such as an unsaturated ester
- Suitable electrophilic cores include the C 1 -C 4 alkyl esters of various polycarboxylic acids such as benzene tricarboxylic acid, oxalic acid, terphthalic acid and various other carboxylic acids represented by the formula:
- Y is hydrocarbyl or a hydrocarbon polyl wherein the hydrocarbon. radical is alkyl, aryl, cycloalkyl, alkylene, arylene, cycloalkylene, and corresponding trivalent, tetravalent, pentavalent and hexavalent radicals of such hydrocarbons; and Z is a whole number from 1 to 6.
- Preferred electrophilic cores include poly(methyl acrylates), poly(acryloyl chloride), poly(methacryloyl chloride), alkyl acrylate/alkyl methacrylate copolymers, polymers of alkyl fumarates, and polymers of alkyl itaconates. Of the electrophilic cores, alkyl acrylate/alkyljmethacrylate copolymers and alkyl acrylate/alkyl itaponate copolymers are most preferred.
- Suitable first coreactants for reaction with the electrophilic core include polyalkylene polyamines such as ethylenediamine, diethylenetfiamine, triethylenetetramine and other polyamines represented by the formula:
- R 1 and R 2 independently represent hydrogen or an alkyl, preferably C 1 -C 4 alkyl, hydroxyalkyl, cyanoalkyl, or amido; n is at. least 2 and preferably 2 to 6 and m is 2 to 100, preferably 2 to 5.
- suitable second coreactants to be used in preparing dendrimers from electrophilic cores include alkyl esters of ethylenically unsaturated carboxylic acids such as methyl acrylate, methyl methacrylate, ethyl acrylate and the like.
- Exampies of suitable third coreactants are those illustrated for the first coreactant.
- the dendrimers can be reacted with a wide variety of compounds, to. produce the polyfunctional compounds having the unique characteristics that are attributable to the structure of the dendrimer.
- a dendrimer having terminal amine moieties, as in the polyamidoamine dendrimer may be reacted with an unsaturated nitrile to yield a polynitrile (nitrile-terminated) dendrimer.
- the polyamidoamine dendrimer may be reacted with (1) an ⁇ , ⁇ -ethylenically unsaturated amide to form a polyamide (amide-terminated) dendrimer, (2) an or, ⁇ -ethylenically unsaturated fester to form a polyester (ester-terminated) dendrimer, (3) an oxirane to yield a polyol (hydroxy-terminated) dendrimer, or (4) an ethylenically unsaturated sulfide to yield a polymercapto (thiol-terminated) dendrimer.
- the dendrimer may be reacted with an appropriate difunctional or trifunctional compound such as an alkyl dihalide or an aromatic diisocyanate to form a poly(dendrimer) having a plurality of dendrimers linked together through the residues of the polyhalide or polyisocyanate.
- an appropriate difunctional or trifunctional compound such as an alkyl dihalide or an aromatic diisocyanate
- such derivatives of the dendrimers are prepared using procedures and conditions conventional for carrying out reactions of organic compounds bearing the particular functional group with the particular organic reactant.
- a third generation polyamine dendrimer is prepared. Upon analysis, it is determined that this dendrimer has four core branches with 4 terminal primary amine moieties per core branch, thereby providing 16 terminal primary amine moieties per molecule of dendrimer. This dendrimer has a molecular volume between 60,000 and 120,000 cubic ⁇ (60 and 120 nm 3 ) and a terminal amine density of 2 to 6(x
- the triester (4.57 g, 6.3 x 10 -3 mole) produced in part B was mixed with 1.96 g (1.89 x 10 -2 mole) of aminoethylethanolamine and heated at 90°C for 48 hours to form 5.8 g of a light yellow, highly viscous syrup.
- Example 2 To 100 ml of an oil-in-water emulsion containing about 5 percent of crude oil having a specific gravity of ⁇ 0.98 g/ml was added one part per million based on the emulsion of the dendrimer (ethylene diamine core) of Example 2. The emulsion was then shaken for 3 minutes to effectively disperse the dendrimer into the emulsion. The emulsion was allowed to stand for 10 minutes and visually evaluated. After 10 minutes, the emulsion appeared to be completely resolved into two phases having a distinct interface wherein the aqueous phase was essentially transparent.
- the dendrimer ethylene diamine core
- the emulsion was similarly resolved using 0.5 ppm and 1 ppm of the quatemized form.
- This quatemized form was prepared by reacting the 32.42 g (0.01 mole) of the dendrimer in 100 ml of methanol with 24.32 g (0.16 mole) of 2-hydroxy-3-chloropropyl trimethyl ammonium chloride in 30 ml of water at 50°C for 12 hours.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polymers & Plastics (AREA)
- Animal Behavior & Ethology (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Thermal Sciences (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Physics & Mathematics (AREA)
- Polyamides (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polyethers (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Polyesters Or Polycarbonates (AREA)
- Multicomponent Fibers (AREA)
- Paper (AREA)
Abstract
The star polymers of this invention have at least one core branch eminating from a core, each core branch having at least one terminal group provided that (1) the ratio of terminal groups to the core branches is greater than 1:1, (2) the density of terminal groups per unit volume in the polymer is at least 1.5 times that of a conventional star polymer having similar core and monomeric moieties and a comparable molecular weight and number of core branches, each of such branches of the conventional star polymer bearing only one terminal group and (3) a molecular volume that is no more than 60 percent of the molecular volume of said conventional star polymer. Such star polymers are useful as demulsifiers for oil/water emulsions, wet strength agents in the manufacture of paper and agents for modifying viscosity in aqueous formulations such as paints.
Description
DENSE STAR POLYMERS AND A PROCESS FOR PRODUCING DENSE STAR POLYMERS
This invention relates to a novel class of branched polymers containing dendritic branches having functional groups uniformly distributed on the periphery of such branches. This invention also relates to pro cesses for preparing such polymers as well as applications therefore.
Organic polymers are generally classified in a structural sense as either linear or branched. In the case of linear polymers, the repeating units (often called mers) are divalent and are connected one to another in a linear sequence. In the case of branched polymers, at least some of the mers possess a valency greater than 2 such that the mers are connected in a nonlinear sequence. The term "branching" usually implies that the individual molecular units of the branches are discrete from the polymer backbone, yet have the same chemical constitution as the polymer backbone. Thus, regularly repeating side groups which are inherent in the monomer structure and/or are of different chemical constitution than the polymer backbone are not considered as branches, e.g., dependent
methyl groups of linear polypropylene. To produce a branched polymer, it is necessary to employ an initiator, a monomer, or both that possess at least three moieties that function in the polymerization reaction. Such monomer or initiators are often called polyfunctional. The simplest branched polymers are the chain branched polymers wherein a linear backbone bears one or more essentially linear pendant groups. This simple form of branching, often called comb branching, may be regular wherein the branches are uniformly and regularly distributed on the polymer backbone or irregular wherein the branches are distributed in nonuniform or random fashion on the polymer backbone. See T. A. Orofino, Polymer, 2, 295-314 (1961). An example of regular comb branching is a comb branched polystyrene as described by T. Altores et al. in J. Polymer Sci., Part A, Vol. 3, 4131-4151 (1965) and an example of irregular comb branching is illustrated by graft copolymers as described by Sorenson et al. in "Preparative Methods of Polymer Chemistry" , 2nd Ed. , Interscience Publishers, 213-214 (1968).
Another type of branching is exemplified by cross-linked or network polymers wherein the polymer chains are connected via tetravalent compounds, e.g., polystyrene molecules bridged or cross-linked with divinylbenzene. .In this type of branching, many of the individual branches are not linear in that each branch may itself contain groups pendant from a linear chain. More importantly in network branching, each polymer macromolecule (backbone) is cross-linked at two or more sites to two other polymer macromolecules. Also the chemical constitution of the cross-linkages may vary from that of the polymer macromolecules. In this so-called cross-linked or network branched polymer, the
various branches or cross-linkages may be structurally similar (called regular cross-linked) or they may be structurally dissimilar (called irregularly cross-linked). An example of regular cross-linked polymers is a ladder- type poly(phenylsilsesquinone) as described by Sorenson et al., supra, at page 390. The foregoing and other types of branched polymers are described by H. G. Elias in Macromolecules, Vol. I, Plenum Press, New York (1977).
More recently, there have been developed polymers having so-called star structured branching wherein the individual branches radiate out from a nucleus and there are at least 3 branches per nucleus. Such star branched polymers are illustrated by the polyquaternary compositions described in USP Nos. 4,036,808 and 4,102,827. Star branched polymers prepared from olefins and unsaturated acids are described in USP 4,141,847. The star branched polymers offer several advantages over polymers having other types of branching. For example, it is found that the star branched polymers may exhibit higher concentrations of functional, groups thus making them more active for their intended purpose. In addition, such star branched polymers are often less sensitive to degradation by shearing which is a very useful property in formulations such as paints, in enhanced oil recovery and other viscosity applications. Additionally, the star branched polymers have relatively low intrinsic viscosities even at high molecular weight.
While the star branched polymers offer many of the aforementioned advantages over polymers having more conventional branching, it is highly desirable to provide polymers which exhibit even greater concentrations of functional groups per unit volume of the polymer macro
molecule as well as a more uniform distribution of such functional groups in the exterior regions of the macromolecule. In addition, it is often desirable to provide polymers having macromolecular configurations that are more spheroidal and compact than are the star branched polymers.
In its broadest aspect, this invention is a dense star polymer having at least one branch (hereinafter called a core branch) emanating from a core, each core branch having at least one terminal group provided that (1) the ratio of terminal groups to the core branches is greater than 1:1, preferably 2:1 or more, (2) the density of terminal groups per unit volume in the polymer is at least 1.5 times that of a conventional star polymer having similar core and monomeric moieties and a comparable molecular weight and number of core branches, each of such branches of the conventional star polymer bearing only one terminal group, and (3) a molecular volume that is no more than 60 percent of the molecular volume of said conventional star polymer as determined by dimensional studies using scaled Corey-Pauling molecular models. For purposes of this invention, the term "dense" as it modifies "star polymer" means that it has a smaller molecular volume than a conventional star polymer having the same molecular weight. The conventional star polymer which is used as the base for comparison with the dense star polymer is one that has the same molecular same core and monomeric components and same number of core branches as the dense star polymer. In addition while the number of terminal groups is greater for the dense star polymer molecule than in the conventional star polymer molecule, the chemical structure of the terminal groups is the same.
In a somewhat more limited and preferred aspect, this invention is. a polymer having a novel ordered star branched structure (herein called starburst structure). Hereinafter this polymer having a starburst structure is called a dendrimer. Thus, a "dendrimer" is a polymer having a polyvalent core that is covalently bonded to at least two ordered dendritic (tree-like) branches which extend through at least two generations. As an illustration, an ordered second generation dendritic branch is depicted by the following configuration:
wherein "a" represents the first generation and "b" represents the second generation. An ordered, third generation dendritic branch is depicted by the following configuration:
wherein "a" and "b" represent the first and second generation, respectively, and "c" represents the third generation. A primary characteristic of the ordered dendritic branch which distinguishes it from conventional branches of conventional polymers is the uniform or
essentially symmetrical character of the branches as is shown in the foregoing illustrations. In addition, with each new generation, the number of terminal groups on the dendritic branch is an exact multiple of the number of terminal groups in the previous generation.
Another aspect of this invention is a process for producing the dense star polymer comprising the steps of
(A) contacting (1) a core compound having at least one nucleophilic or one electrophilic moiety (hereinafter referred to in the alternative as N/E moieties) with
(2) an excess of a first organic coreactant having (a) one moiety (hereinafter called a core reactive moiety) which is reactive with the N/E moieties of the core compound and (b) an N/E moiety which does not react with the N/E moiety of the core under conditions sufficient to form a core adduct wherein each N/E moiety of the core compound has reacted with the core reactive moiety of a different molecule of the first coreactant;
(B) contacting (1) the core adduct having at least twice the number of N/E moieties as the core compound with
(2) an excess of a second organic coreactant having (a) one moiety (hereinafter called an adduct reactive moiety) which will react with the N/E moieties of the core adduct and (b) an N/E moiety which does not react with the N/E moiety of
the core adduct under conditions sufficient to form a first generation adduct having a number of N/E moieties that are at least twice the number of N/E moieties in the core adduct; and (C) contacting the first generation adduct with an excess of a third organic coreactant having one moiety that is reactive with the N/E moieties of the first generation adduct and an N/E moiety that does not react with the N/E moieties of the first generation adduct under conditions sufficient to form a second generation dendrimer. In the foregoing process, the first coreactant differs from the second coreactant, and the second coreactant differs from the third coreactant, but the first and third coreactants may be the same or different compounds. The third and higher generation dendrimers are formed by repeating steps (B) and (C) of the aforementioned process.
Other aspects of this invention are methods for using the dense star polymer in such applications as demulsifiers for oil/water emulsions, wet strength agents in the manufacture of paper, agents for modifying viscosity in aqueous formulations such as paints and the like. For example, in a demulsification method, an emulsion of oil and water is contacted with a demulsifying amount of the dense star polymer under conditions sufficient to cause phase separation.
The dense star polymers of the presen€ invention exhibit the following properties which are unique or are superior to similar properties of conventional star branched polymers and other branched polymers having similar molecular weight and terminal groups:
(a) greater branch density;
(b) greater terminal group density;
(c) greater accessibility of terminal groups to chemically reactive species; and (d) lower viscosity.
In the dense star polymers of the present invention, the core is covalently bonded to at least one core branch, preferably at least two, most preferably at least three, core branches with each core branch having a calculated length of at least 3 Angstrom units
(A) (0.3 nm), preferably at least 4 A (0.4 nm), most preferably at least 6 A (0.6 nm). These polymers preferably have an average of at least 2, more preferably at least 3 and most preferably at least 4 terminal groups per polymer molecule. Preferably, the core branches have a dendritic character, most preferably an ordered dendritic character as defined hereinafter. In preferred dense star polymers, the terminal groups are functional groups that are sufficiently reactive to undergo addition or substitution reactions. Examples of such functional groups include amino, hydroxy, raercapto, carboxy, alkenyl, allyl, vinyl, amido, halo, urea, oxiranyl, aziridinyl, oxazolinyl, imidazolinyl,. sulfonato, phosphonato, isocyanato and isothiocyanato. The dense star polymers differ from conventional star or star-branched polymers in that the dense star polymers have a greater concentration of terminal groups per unit of molecular volume than do conventional star polymers having an equivalent number of core branches and an equivalent core branch length. Thus, the density of terminal groups per unit volume in the dense star polymer is at least 1.5 times the density of terminal groups in the conventional star polymer,
preferably at least 5 times, more preferably at least 10 times, most preferably from 15 to 50 times. The ratio of terminal groups per core branch in the dense polymer is preferably at least 2, more preferably at least 3, most preferably from 4 to 1024. Preferably, for a given polymer molecular weight, the molecular volume of the dense star polymer is no more than 50 volume percent, more preferably from 16 to 50, most preferably from 7 to 40 volume percent of the molecular volume of the conventional star polymer.
In the preferred polyamidoamine dense star polymers, the density of terminal (primary) amine moieties in the polymer is readily expressed as the molar ratio of primary amine moieties to the total of secondary and tertiary amine moieties. In such polymers this 1° amine: (2°amino + 3° amine.) is preferably from 0.37:1 to 1.33:1, more preferably from 0.69:1 to 1.2:1, most preferably from 1.1:1 to 1.2:1.
The preferred dendrimers of the present invention are characterized as having a polyvalent core that is covalently bonded to at least two ordered dendritic branches which extend through at least two generations. Such ordered branching can be illustrated by the following sequence wherein G indicates the number of generations:
Mathematically, the relationship between the number of terminal groups on a dendritic branch and the number of generations of the branch can be represented as follows:
wherein G is the number of generations and N is the repeating unit multiplicity which is at least 2 as in the case of amines. The total number of terminal groups in the dendrimer is determined by the following:
wherein G and Nr are as defined before and Nc represents the valency (often called core funtionality) of the core compound. Accordingly, the dendrimers of the present invention can be represented in its component parts as follows:
wherein the Core, Terminal Moiety, G and Nc are as defined before and the Repeat Unit has a valency or functionality of Nr + 1 wherein Nr is as defined before.
An illustration of a functionally active dendrimer of a ternary or trivalent core which has three ordered, second generation dendritic branches is depicted by the following configuration:
wherein I is a trivalent core atom or molecule having a covalent bond with each of the three. dendritic branches, Z is a terminal moiety and "a" and "b" are as defined hereinbefore. An example of such a ternary dendrimer is polyamidoamme represented by the following structural formula:
wherein Y represents a divalent amide moiety such as
and "a" and "b" indicate first and second generations, respectively. In these two illustrations, Nc is 3 and Nr is 2. In the latter of the two illustrations, the Repeat Unit is YN. While the foregoing configuration and formula illustrate a trivalent core, the core atom or molecule may be any monovalent or monofunctional moiety or any polyvalent or polyfunctional moiety, preferably a polyvalent or polyfunctional moiety having from 2 to 2300 valence bonds or functional sites available for bonding with the dendritic branches, most preferably from 2 to 200 valence bonds or functional sites. In cases wherein the core is a monovalent or monofunctional moiety, the
dense star has only one core branch and must be compared with a linear polymer in order to determine appropriate terminal group density and molecular volume. Accordingly, this dense star must have at least 2 generations in order to exhibit the desired density of terminal groups. Also, Y may be any other divalent organic moiety such as, for example, alkylene, alkylene oxide, alkyleneamine, with the depicted amide moiety being the most preferred. In addition to amine, the terminal groups of the dendrimer may be any functionally active moiety that can be used to propagate the dendritic branch to the next generation. Examples of such other moieties include carboxy, aziridinyl, oxazolinyl, haloalkyl, oxiranyl, hydroxy and isocyanato, with amine or carboxylic ester moieties being preferred. While the dendrimers preferably have dendritic branches having 2 to 6 generations, dendrimers having dendritic branches up to 12 generations are suitably made and employed in the practice of this invention.
More preferably, the amidoamine dendimers of this invention are represented by the formula:
wherein A is a n-valent core derived from a nucleophilic compound, R is hydrogen or lower alkyl, B is a divalent moiety capable of linking amine groups, n is an integer of 3 or more corresponding to the number of the core branches and Z is hydrogen or
wherein R1 is hydrogen or
wherein each generation is represented by
R is hydrogen or methyl; B is the divalent residue of a polyamine, most preferably an alkylene polyamine such as ethylene diamine or a polyalkyiene polyamine such as triethylene tetramine; n is an integer from 3 to 2000, more preferably from 3 to 1000, most preferably from 3 to 125, and Z is most preferably
The dense star polymers of this invention are readily prepared by reacting a compound capable of generating a polyvalent core with a compound or compounds which causes propagation of dendritic branches from the core. In one method of preparing these dendrimers (herein called the successive excess reactant method), it is essential to maintain an excess of coreactant to reactive moieties in the terminal groups in the core, core adduct or subsequent adducts and dendrimers in order to prevent cross-linking and to maintain the ordered character of the dendritic branches. In general, this excess of coreactant to reactive moieties in the terminal groups is from 2:1 to 120:1, preferably from 3:1 to 20:1 on a molar basis.
Alternatively, the compound capable of/generating a polyvalent core, W(X)n, wherein W is the polyvalent core atom and is covalently bonded to nX reactive terminal groups (n>2), is reacted with a partially pro
tected multifunctional reagent,
wherein U represents a multivalent .moiety covalently bonded to
protected moieties (m>2), and to one T, a moiety capable of reacting with X to form wherein X' and T'
represent the residue of reaction between X and X. This first generation compound is then subjected to activation conditions whereby the
moieties are made reactive (deprotected) and reacted with the partially protected multifunctional reagent, to form the second generation protected dendrimer, This protected
dendrimer can be activated and reacted again in a similar manner to provide the third generation protected dendrimer. Both the successive excess reactant and the partially protected reactant method are specifically illustrated hereinafter.
The successive excess reactant method of preparing the dendrimers is illustrated by the preparation of the aforementioned ternary dendritic polyamidoamine. In this method, ammonia, a nucleophilic core compound, is first reacted with methyl acrylate under conditions sufficient to cause the Michael addition of one molecule of the ammonia to three molecules of the methyl acrylate to form the following core adduct:
Following removal of unreacted methyl acrylate, this compound is then reacted with excess ethylenediamine under conditions such that one amine group of the ethyl
enediamine molecule reacts with the methyl carboxylate groups of the core adduct to form a first generation adduct having three amidoamine moieties represented by the formula:
The molar excess of ethylene diamine to methyl acrylate moieties is preferably from 4:1 to 50:1. Following removal of unreacted ethylenediamine, this first generation adduct is then reacted with excess methyl acrylate under Michael's addition conditions to form a second generation adduct having terminal methyl ester moieties:
which is then reacted with excess ethylenediamine under amide forming conditions to produce the desired polyamidoamine dendrimer having ordered, second generation dendritic branches with terminal amine moieties. The molar excess of coreactant to reactive moieties in each case is preferably from 1.1:1 to 40:1, most preferably from 3:1 to 10:1. Similar dendrimers containing amidoamine moieties can be made by using organic amines as the. core compound, e.g., ethylenediamine which produces a tetra-brancheddendrimer or diethylenetriamine which produces a pentabranched dendrimer.
Other dendrimers made by the successive excess reactant method are polysulfides made by (1) reacting a
polythiol, C(CH2SH)4, under basic conditions with epichlorosulfide to form the first generation polyepisulfide.
and (2) then reacting this polyepisulfide with hydrogen sulfide to form the first generation polysulfide which can- be further reacted with epichlorosulfide and hydrogen sulfide to form subsequent generations. The conditions and procedures which may be suitably employed for polysulfide formation are generally described in Weissberger, Heterocyclic Compounds with Three- and Four-Membered Rings, Interscience Publishers, N.Y., 605 (1964) and Meade et ai., J. Chem. Soc 1894 (1948). Polyaminosulfide dendrimers can be prepared by reacting ammonia or an amine having a plurality of primary amine groups with an excess of ethylene sulfide to form a. polysulfide and then with excess aziridine to form a first gene'ration polyaminosulfide which can be reacted with excess ethylene sulfide and then with excess aziridine to form further generations using general reaction conditions described in USP 2, 105, 845 and Nathan et al. , J. Am. Chem. Soc, 63, 2361 (1941). The polyether. or polysulfide dendrimers can also be prepared by the excess reactant method by reacting hexahalobenzene with phenol of thiophenol to form a first generation polyarylether or polyarylsulfide and then with excess halogen to form the first generation polyhaloarylpolysulfide and then with further phenol or thiophenol to form further generations according to the procedures and conditions as described by D. D. MacNicol et al., Tetrahedron Letters, 23, 4131-4 (1982).
Illustrative of the partially protected reactant method, a polyol such as pentaerythritol, C(CH2OH)4, is employed as the polyvalent core generating compound and is converted to alkali metal salt form, e.g., sodium or lithium, by reaction with alkali metal hydroxide or zero valence alkali metal and then reacted with a molar excess of a partially protected compound such as tosylate ester of 1-ethyl-4-hydroxymethyl-2,6,7-trioxabicyclo[2,2,2]octane to form a protected first generation polyether,
which is then activated by reacting with acid such as hydrochloric acid to form the unprotected first generation polyether, C(CH2O-CH2C[CH2OH]3)4. This polyether is converted to alkali metal salt form by reaction with alkali metal hydroxide or zero valence alkali metal and then reacted with a molar excess of.the partially protected tosylate ether tb form the protected second generation polyether. The foregoing sequence is repeated as desired for additional generation development according to conditions and procedures described in Endo et al., J. Polym. Sci., Polym. Lett. Ed., 18, 457 (1980), Yokoyama et al., Macromolecules, 15, 11-17 (1982), and Pedlas et al., Macromolecules, 15, 217-223 (1982). These polyether dendrimers are particularly desirable for use in highly alkaline or highly acidic media wherein hydrolysis of a polyaraidoamine dendrimer would be unacceptable. As an example of other dendrimers that are suitably prepared by the partially protected reactant method, polyamine dendrimers may be prepared by reacting ammonia or an amine having a plurality of primary amine groups with N-substituted aziridine such as N-tosyl aziridine,
to form a protected first generation polysulfonamide and then activated with acid such as hydrochloric acid to form the first generation polyamine salt and reacted with further N-tosyl aziridine to form the protected second generation polysulfonamide which sequence can be repeated to produce higher generation polyamines using the general reaction conditions described in Humrichause, C. P., PhD Thesis from University of Pennsylvania, "N-Substituted Aziridines as Alkylating Agents", Ref. No. 66-10, 624 (1966).
In either of the foregoing methods of dendrimer preparation, water or hydrogen sulfide may be employed as nucleophilic cores for the production of binary dendrimers. Examples of other nucleophilic core compounds include phosphine, polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine and both linear and branched polyethylenimine; primary amines such as methylamine, hydroxyethylamine, octadecylamine and polymethylenediamines such as hexamethylenediamine; polyaminoalkylarenes such as 1,3,5-tris(amindmethyl)benzene; tris(aminoalkyl)amines such as tris(aminoethyl)amine; heterocyclic amines such as imidazolines and piperidines; and various other amines such as hydroxyethylaminoethylamine, mercaptoethylamine, morpholine, piperazine, amino derivatives of polyvinylbenzyl chloride and other benzylic polyamines such as tris(1,3,5-aminomethyl)benzene. Other suitable nucleophilic cores
include polyols such as the aforementioned pentaerythritol, ethylene glycol and polyalkylene polyols such as polyethylene glycol and polypropylene glycol; 1,2-dimercaptoethane and polyalkylene polymercaptans; thiophenols, and phenols. Of the core compounds, ammonia and the polyalkylene polyamines are preferred for the preparation of polyamidoamine dendrimers by the successive excess reactant method and the polyols are preferred for the preparation of polyether dendrimers by the partially protected reactant method.
Examples of coreactant materials used to react with the nucleophilic core compounds include α,β-ethylenically unsaturated carboxylic esters and amides as well as esters, acids and nitriles containing an acrylyl moiety such as, for example, methyl acrylate, ethyl acrylate, acrylonitrile, methyl itaconate, dimethyl fumarates, maleic anhydride, acrylamide, with methyl acrylate being the preferred coreactant material. In general other preferred unsaturated reactants are volatile or otherwise readily removed from the core/coreactant reaction products without deleteriously. affecting the reaction product.
Examples of the second coreactant materials used to react with the adduct of the nucleophilic core and the first coreactant include various polyamines such as alkylene polyamines and polyalkylene polyamines such as ethylenediamine and diethylenetriamine; benzylic polyamines such as tris(1,3,5-aminomethy1)benzene; alkanolamines such as ethanolamine; and aziridine arid derivatives thereof such as N-aminoethyl aziridine. Of these second coreactant materials, the volatile polyamines such as ethylenediamine and diethylenetriamine are preferred, with ethylenediamine being especially preferred.
Alternatively, the dendrimers can be prepared by reacting an electrophilic core such as a polyester with a coreactant such as a polyamine to form a core adduct which is then reacted with a suitable second coreactant such as an unsaturated ester to form the first generation polyamidoamine. Thereafter, this first generation product is react d with a suitable third coreactant such as polyamine a then with the second coreactant such as unsaturated ester to form the desired second generation dendrimer. Examples of suitable electrophilic cores include the C1-C4 alkyl esters of various polycarboxylic acids such as benzene tricarboxylic acid, oxalic acid, terphthalic acid and various other carboxylic acids represented by the formula:
wherein Y is hydrocarbyl or a hydrocarbon polyl wherein the hydrocarbon. radical is alkyl, aryl, cycloalkyl, alkylene, arylene, cycloalkylene, and corresponding trivalent, tetravalent, pentavalent and hexavalent radicals of such hydrocarbons; and Z is a whole number from 1 to 6. Preferred electrophilic cores include poly(methyl acrylates), poly(acryloyl chloride), poly(methacryloyl chloride), alkyl acrylate/alkyl methacrylate copolymers, polymers of alkyl fumarates, and polymers of alkyl itaconates. Of the electrophilic cores, alkyl acrylate/alkyljmethacrylate copolymers and alkyl acrylate/alkyl itaponate copolymers are most preferred.
Suitable first coreactants for reaction with the electrophilic core include polyalkylene polyamines
such as ethylenediamine, diethylenetfiamine, triethylenetetramine and other polyamines represented by the formula:
wherein R 1 and R2 independently represent hydrogen or an alkyl, preferably C1-C4 alkyl, hydroxyalkyl, cyanoalkyl, or amido; n is at. least 2 and preferably 2 to 6 and m is 2 to 100, preferably 2 to 5. Examples of suitable second coreactants to be used in preparing dendrimers from electrophilic cores include alkyl esters of ethylenically unsaturated carboxylic acids such as methyl acrylate, methyl methacrylate, ethyl acrylate and the like. Exampies of suitable third coreactants are those illustrated for the first coreactant.
Thus prepared, the dendrimers can be reacted with a wide variety of compounds, to. produce the polyfunctional compounds having the unique characteristics that are attributable to the structure of the dendrimer. For example, a dendrimer having terminal amine moieties, as in the polyamidoamine dendrimer, may be reacted with an unsaturated nitrile to yield a polynitrile (nitrile-terminated) dendrimer. Alternatively, the polyamidoamine dendrimer may be reacted with (1) an α,β-ethylenically unsaturated amide to form a polyamide (amide-terminated) dendrimer, (2) an or,β-ethylenically unsaturated fester to form a polyester (ester-terminated) dendrimer, (3) an oxirane to yield a polyol (hydroxy-terminated) dendrimer, or
(4) an ethylenically unsaturated sulfide to yield a polymercapto (thiol-terminated) dendrimer. In addition, the dendrimer may be reacted with an appropriate difunctional or trifunctional compound such as an alkyl dihalide or an aromatic diisocyanate to form a poly(dendrimer) having a plurality of dendrimers linked together through the residues of the polyhalide or polyisocyanate. In all instances, such derivatives of the dendrimers are prepared using procedures and conditions conventional for carrying out reactions of organic compounds bearing the particular functional group with the particular organic reactant.
Such reactions are further exemplified by the following working examples. In such working examples, all parts and percentages are by weight unless otherwise indicated.
Example 1
A. Preparation of Core Adduct
To a one-liter, 3-neck flask equipped with stirrer, condenser and thermowell, and containing methyl acrylate (296.5 g, 3.45 moles) was added at room temperature with stirring over a 6-hour period ammonia (8.7 g, 0.58 mole) dissolved in 102.2 g of methanol. The mixture was allowed to stand at room temperature for 48 hours at which point excess methyl acrylate was removed by vacuum distillation (1 ram Hg (130 Pa) at 22°C) yielding 156 g of residue. This residue is analyzed by size exclusion chromatography, C13 NMR and liquid chromatography. This analysis indicated the coreactant adduct to be the Michael's addition product of 1 mole of ammonia and 3 moles of methyl acrylate at a 97.8 percent yield.
B. Preparation of First Generation Adduct
To ethylenediamine (505.8 g, 8.43 moles) dissolved in 215.4 g of methanol in a 3-liter reaction flask equipped with stirrer, condenser and thermowell, was added the aforementioned ammonia/methyl acrylate adduct (28.1 g, 0.1022 mole), and the reaction mixture was allowed to stand at room temperature for 55 hours. The resulting mixture (747.6 g) was subjected to vacuum distillation to remove excess ethylenediamine and methanol at 2 mm Hg (270 Pa) and 72ºC. The residue (35.4 g) was analyzed by size exclusion chromatography and other suitable analytical techniques. The analyses indicated that essentially all of the ester moieties of the ammonia/methyl acrylate adduct had been converted to amides in the form of a compound represented by the following structural formula:
thus indicating a yield of 98.6 percent.
C. Preparation of Second Generation Polyester Dendrimer
To methyl acrylate (93.2 g, 1.084 moles) in a one-liter flask equipped with condenser, stirrer and thermowell, and heated to 32°C was added the aforementioned first generation adduct (18 g, 0.0501 mole) dissolved in 58.1 g of methanol over 1.5 hours. The resulting mixture was maintained at 32°C for an additional 5 hours and allowed to stand, an additional 18 hours at room temperature. The reaction mixture (165.7 g) was stripped of methanol and excess methyl acrylate by vacuum distillation (2 mm Hg (270 Pa) and 50°C) to produce 43.1 g of residue. Analysis by suitable techniques indicated the product to be a second generation polyester dendrimer represented by the following formula:
To ethylenediamine (328.8 g, 5.48 moles) dissolved in 210.2 g of methanol at room temperature in the aforementioned flask was added with stirring the second generation polyester dendrimer (34.9 g, 0.0398 mole) dissolved in 45.3 g of methanol. The resulting mixture was allowed to stand for 66 hours at room temperature at which time excess ethylenediamine and methanol was stripped from the product by vacuum distillation (2 mm Hg (270 Pa) at 72ºC) to yield 41.1 g (99.0 percent yield) of product. This product was determined by size exclusion chromatography to be the second generation polyamine of the aforementioned polyester dendrimer.
E. Preparation of Third Generation Polyester Dendrimer To methyl acrylate (65.1 g, 0.757 mole) was added the aforementioned second generation polyamine dendrimer (28.4 g, 0.0272 mole) dissolved in 84.6 g of methanol over a period of 1 hour and 15 minutes. The resulting mixture was allowed to stand for 18 hours at 25°C after which time excess methyl acrylate and methanol were removed by vacuum distillation (2 mm Hg (270 Pa) at 50°C) to yield 56.3 g (100.0 percent yield) of product residue. Analysis of this residue by suitable analytical techniques indicated that it was a third generation polyester dendrimer having 3 core branches with 4 terminal ester moieties per core branch thereby providing 12 terminal ester moieties per dendrimer molecule.
F. Preparation of Third Generation Polyamine Dendrimer
To ethylenediamine (437.6 g, 7.29 moles) dissolved in 192 g of methanol was added the aforementioned third generation polyester dendrimer (44.9 g, 0.0216 mole) dissolved in 69.7 g of methanol. The addition occured over a period of 48 hours at 25°C with stirring. The resulting reaction mixture was then allowed to stand for 19 hours at 25°C after which time excess methanol and ethylenediamine were removed by vacuum distillation (2 mm Hg (270 Pa) at 72°C) to yield 51.2 g of residual product. Analysis of this residue indicated a yield of 85.3 percent of a third generation polyamine dendrimer having 3 core branches with 4 terminal primary amine moieties per core branch, thereby providing 12 terminal primary amine moieties per molecule of dendrimer. This dendrimer was calculated to have a molecular volume between 50,000 and
97,000 cubic Å (50 and 97 nm3 and a density of a terminal amine moiety between 1 to 3 (x 10 -4) moieties/cubic Å (0.1 and 0.3 moieties/nm3).
Example 2
Following the procedure of Example 1, except that a molar equivalent amount of ethylenediamine was substituted for ammonia as the core compound, a third generation polyamine dendrimer is prepared. Upon analysis, it is determined that this dendrimer has four core branches with 4 terminal primary amine moieties per core branch, thereby providing 16 terminal primary amine moieties per molecule of dendrimer. This dendrimer has a molecular volume between 60,000 and 120,000 cubic Å (60 and 120 nm3) and a terminal amine density of 2 to 6(x
10-4) amines/cubic Å (0.2 and 0.6 amines/nm3).
Similar dendrimers were obtained when equimolar amounts of 1,2-diaminopropane, 1,3-diaminopropane and 1,6-diaminohexane (hexamethylenediamine) were substituted for the ethylenediamine as the core compound in the foregoing procedure. When an equimolar amount of dodecylamine or benzylamine was substituted for the ethylenediamine as the core compound, the resulting dense star polymers had 2 core branches per molecule with 4 terminal primary amine groups per branch, thereby providing a total of 8 primary amine groups per polymer molecule.
Substitution of triaminoethylamine for ethylenediamine as the core compound yielded a dendrimer having 6 core branches with 4 terminal primary amine moieties per core branch, thereby providing 24 terminal primary amine moieties per molecule of dendrimer.
Example 3
A. First Amidation
Following the procedure of Example 1, 5 g (0.0198 mole) of trimethyl-1,3,5-benzenetricarboxylate was mixed with 6.3 g (0.0368 mole) of aminoethylethanolamine (NH2CH2CH2NHCH2CH2OH) to form a white paste. This mixture was heated at 120°C for 3 hours to form 9.48 g of a light yellow syrup which infrared and nuclear magnetic resonance spectral analysis indicate was an amidoamine represented by the structural formula:
A 9.48 g. (0.0202 mole) of this amidoamine was combined with a stoichiometric excess (11.0 g, 0.127 mole) of methyl acrylate and heated for 24 hours at 80°C which, after devolatilization, was a light yellow syrup weighing 14.66 g. Nuclear magnetic resonance (H1) and infrared spectral analysis of the syrup indicated that it was a triester represented by the structural formula:
C. Second Amidation
Following the procedure of part A of this example, the triester (4.57 g, 6.3 x 10-3 mole) produced in part B was mixed with 1.96 g (1.89 x 10-2 mole) of aminoethylethanolamine and heated at 90°C for 48 hours to form 5.8 g of a light yellow, highly viscous syrup. Analysis of this product by nuclear magnetic resonance (H1) (DMSO-d6) and infrared spectroscopy indicated that it was triamidoamine represented by the structural formula:
Example 4
A. First Amidation
A 27.3-g portion (0.1 mole) of a triester represented by the formula:
was mixed with 30 g (0.405 mole) of N-methyl ethylenediamine (MEDA) and 16.6 g of methanol and then heated at 63ºC for 11 hours. The product was then stripped of unreacted MEDA and methanol to yield 36.1 g of a triamide represented by the formula:
B. First Alkylation
To the aforementioned triamide (36.1 gp 0.09 mole) was added 38.5 g of methanol to yield a clear solution to which was added 50.5 g (0.59 mole) of methyl acrylate dropwise over a period of 2 hours at 38°C. The temperature of the resulting mixture was increased to
53°C for 5 additional hours after which unreacted methyl acrylate and methanol were removed under vacuum to yield 61 g of a light yellow syrup. Analysis of this product by nuclear m etic resonance (H1) spectroscopy indicated that it is r esented by the formula:
C. Second Amidation
To 60.8 g of the aforementioned first alkylation product were added with stirring 42.7 g of methanol. and 26.6 g (0.359 mole) αf MEDA followed by heating the resulting mixture at 65ºC for 6 hours. Vacuum stripping of the mixture yielded 72.7 g of a light yellow syrup. Analysis of this product (syrup) indicated that it was a mixture of isomers having the following structures:
Alkylation of the aforementioned second amidation product with methyl acrylate and then amidation of the resulting alkylated product with MEDA in accordance with aforementioned procedures yielded a mixture of isomers having core branches with dendritic characteristics.
Example 5 - Demulsification Method
To 100 ml of an oil-in-water emulsion containing about 5 percent of crude oil having a specific gravity of ~0.98 g/ml was added one part per million based on the emulsion of the dendrimer (ethylene diamine core) of Example 2. The emulsion was then shaken for 3 minutes to effectively disperse the dendrimer into the emulsion. The emulsion was allowed to stand for 10 minutes and visually evaluated. After 10 minutes, the emulsion appeared to be completely resolved into two phases having a distinct interface wherein the aqueous phase was essentially transparent.
Following the foregoing procedure except substituting a quatemized form of the foregoing dendrimer for the dendrimer, the emulsion was similarly resolved using 0.5 ppm and 1 ppm of the quatemized form. This quatemized form was prepared by reacting the 32.42 g (0.01 mole) of the dendrimer in 100 ml of methanol with 24.32 g (0.16 mole) of 2-hydroxy-3-chloropropyl trimethyl ammonium chloride in 30 ml of water at 50°C for 12 hours.
Claims
1. A star polymer having at least one core branch emanating from a core, each core branch having at least one terminal group provided that (1) the ratio of terminal groups to the core branches is greater than 1:1, (2) the density of terminal groups per unit volume in the polymer is at least 1.5 times that of a conventional star polymer having similar core and monomeric moieties and a comparable molecular weight and number of core branches, each of such branches of the conventional star polymer bearing only one terminal group, and (3) a molecular volume that is no more than 60 percent of. the molecular volume of said conventional star polymer.
2. The star polymer of Claim 1 having (1) at least 2 core branches per core, (2) a terminal group density at least 5 times that of the corresponding conventional star polymer, (3) a molecular volume that is no more than 50 percent of the volume of the conventional star polymer, and (4) a ratio of terminal groups to core branches is 2:1 or more.
3. The polymer of Claim 1 which is a dendrimer having a polyvalent core that is covalently bonded to at least 1 ordered dendritic branch which extends to two generations such that each dendritic branch has at least four terminal groups and a symmetrical structure.
4. The polymer of Claim 1 wherein the dendritic branches contain amidoamine linkages.
5. The polymer of Claim 1 wherein the core is derived from a nucleophilic compound and the branches are polyamidoamines wherein the terminal groups are primary amine groups.
6. The polymer of- Claim 1 wherein the nucleophilic core is derived from a core compound having a plurality of active hydrogens capable of undergoing a Michael's addition reaction with an ethylenically unsaturated group.
7. The polymer of Claim 5 wherein the nucleophilic compound is an amine having a plurality of amine hydrogens.
8. The polymer of Claim 5 wherein the branches are polyamidoamine which is derived from the reaction of an alkyl ester of an or ,β-ethylenically unsaturated carboxylic acid or an α,β-ethylenically unsaturated amide and an alkylene polyamine or a polyalkylene polyamine.
9. The polymer of Claim 8 wherein the nucleophilic compound is ammonia, the ester is methyl acrylate and the polyamine is ethylenediamine.
10. A process for producing the dense star polymer of Claim 1 comprising the steps of:
(A) contacting
(1) a core compound having at least one nucleophilic or one electrophilic moiety (N/E moieties) with
(2) an excess of a first organic coreactant having (a) one core reactive moiety which is reactive with the N/E moieties of the core compound, and (b)an N/E moiety which does not react with the N/E moiety of the core under conditions sufficient.to form a core adduct wherein each N/E moiety of the core compound has reacted with the core reactive moiety of a different molecule of the first coreactant;
(B) contacting
(1) the core adduct having at least twice the number of N/E moieties as the core compound with (2) an excess of a second organic coreactant having (a) one adduct reactive moiety which will react with the N/E moieties of the core adduct and (b) a N/E moiety which does not react with the N/E moiety of the core adduct under conditions sufficient to form a first generation adduct having a number of N/E moieties that are at least twice the number of N/E moieties in the core adduct; and (C) contacting the first generation adduct with an excess of a third organic coreactant having one moiety that is reactive with the N/E moieties of the first generation adduct and an N/E moiety that does not react with the N/E moieties of the first generation adduct under conditions sufficient to form a second generation dendrimer, wherein the first coreactant differs from the second coreactant, and the second coreactant differs from the third coreactant, but the first and third coreactants may be the same or different compounds.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR8307680A BR8307680A (en) | 1983-01-07 | 1983-12-29 | STAR-SHAPED DENSY POLYMERS AND A PROCESS FOR THE PRODUCTION OF STAR-SHAPED DENSY POLYMERS |
JP59500653A JPH0670132B2 (en) | 1983-01-07 | 1983-12-29 | Dendritic polymer |
JP5144319A JPH0742352B2 (en) | 1983-01-07 | 1993-05-24 | Method for producing dendritic polymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US06/456,226 US4507466A (en) | 1983-01-07 | 1983-01-07 | Dense star polymers having core, core branches, terminal groups |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1984002705A1 true WO1984002705A1 (en) | 1984-07-19 |
Family
ID=23811962
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1983/002052 WO1984002705A1 (en) | 1983-01-07 | 1983-12-29 | Dense star polymers and a process for producing dense star polymers |
Country Status (12)
Country | Link |
---|---|
US (1) | US4507466A (en) |
EP (3) | EP0608908B1 (en) |
JP (2) | JPH0670132B2 (en) |
AT (3) | ATE179731T1 (en) |
AU (1) | AU560604B2 (en) |
BR (1) | BR8307680A (en) |
CA (1) | CA1244586A (en) |
DE (5) | DE3486372T2 (en) |
MX (1) | MX163770B (en) |
NZ (1) | NZ206742A (en) |
WO (1) | WO1984002705A1 (en) |
ZA (1) | ZA84128B (en) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4857630A (en) * | 1987-12-07 | 1989-08-15 | E. I. Du Pont De Nemours And Company | Hyperbranched polyarylene |
US5070183A (en) * | 1987-12-07 | 1991-12-03 | E. I. Du Pont De Nemours And Company | Hyperbranched polyarylene |
US5136014A (en) * | 1990-06-22 | 1992-08-04 | E. I. Du Pont De Nemours And Company | Hyperbranched polyesters |
US5183862A (en) * | 1990-06-22 | 1993-02-02 | E. I. Du Pont De Nemours And Company | Hyperbranched polyesters |
US5270402A (en) * | 1990-06-22 | 1993-12-14 | E. I. Du Pont De Nemours And Company | Hyperbranched polyesters |
US5338532A (en) * | 1986-08-18 | 1994-08-16 | The Dow Chemical Company | Starburst conjugates |
US5527524A (en) * | 1986-08-18 | 1996-06-18 | The Dow Chemical Company | Dense star polymer conjugates |
US5560929A (en) * | 1986-08-18 | 1996-10-01 | The Dow Chemical Company | Structured copolymers and their use as absorbents, gels and carriers of metal ions |
WO1996035456A2 (en) * | 1995-05-11 | 1996-11-14 | Schering Aktiengesellschaft | Use of polymeric contrast agents of medium molecular weight for differentiating between benign and malignant tumours using modern imaging techniques |
US5714166A (en) * | 1986-08-18 | 1998-02-03 | The Dow Chemical Company | Bioactive and/or targeted dendrimer conjugates |
US6177414B1 (en) | 1986-08-18 | 2001-01-23 | The Dow Chemical Company | Starburst conjugates |
US6193950B1 (en) | 1989-11-21 | 2001-02-27 | Schering Ag | Cascade polymer bound complexing compounds, their complexes and conjugates, processes for their production, and pharmaceutical agents containing them |
US6933126B2 (en) | 2001-09-19 | 2005-08-23 | Applera Corporation | Membrane transportable fluorescent substrates |
US7064174B2 (en) | 2000-02-07 | 2006-06-20 | Biocompatibles Uk Limited | Silicon containing compounds |
US7192744B2 (en) | 2000-04-05 | 2007-03-20 | Qiagen Gmbh | Targeted transfection of cells using a biotinylated dendrimer |
CN104744709A (en) * | 2015-04-10 | 2015-07-01 | 上海汇锐化工科技有限公司 | Dendritic polyamide type ester quaternary ammonium salt and synthetic process thereof |
US9737611B2 (en) | 2012-05-21 | 2017-08-22 | University Of Miami | Dendrimer conjugates for coating cells |
US10640611B2 (en) | 2013-11-29 | 2020-05-05 | Byk-Chemie, Gmbh | Polyamine addition compounds |
Families Citing this family (287)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5693741A (en) | 1988-03-15 | 1997-12-02 | The Boeing Company | Liquid molding compounds |
US5516876A (en) | 1983-09-27 | 1996-05-14 | The Boeing Company | Polyimide oligomers and blends |
US5969079A (en) | 1985-09-05 | 1999-10-19 | The Boeing Company | Oligomers with multiple chemically functional end caps |
US5512676A (en) | 1987-09-03 | 1996-04-30 | The Boeing Company | Extended amideimide hub for multidimensional oligomers |
US5714566A (en) | 1981-11-13 | 1998-02-03 | The Boeing Company | Method for making multiple chemically functional oligomers |
US5210213A (en) | 1983-06-17 | 1993-05-11 | The Boeing Company | Dimensional, crosslinkable oligomers |
US5705598A (en) | 1985-04-23 | 1998-01-06 | The Boeing Company | Polyester sulfone oligomers and blends |
US4568737A (en) * | 1983-01-07 | 1986-02-04 | The Dow Chemical Company | Dense star polymers and dendrimers |
US4631337A (en) * | 1983-01-07 | 1986-12-23 | The Dow Chemical Company | Hydrolytically-stable dense star polyamine |
US4587329A (en) * | 1984-08-17 | 1986-05-06 | The Dow Chemical Company | Dense star polymers having two dimensional molecular diameter |
US4599400A (en) * | 1984-12-18 | 1986-07-08 | The Dow Chemical Company | Star/comb-branched polyamide |
US5618907A (en) | 1985-04-23 | 1997-04-08 | The Boeing Company | Thallium catalyzed multidimensional ester oligomers |
US4871779A (en) * | 1985-12-23 | 1989-10-03 | The Dow Chemical Company | Ion exchange/chelation resins containing dense star polymers having ion exchange or chelate capabilities |
US5482830A (en) * | 1986-02-25 | 1996-01-09 | Biostar, Inc. | Devices and methods for detection of an analyte based upon light interference |
US4694064A (en) * | 1986-02-28 | 1987-09-15 | The Dow Chemical Company | Rod-shaped dendrimer |
US4713975A (en) * | 1986-05-30 | 1987-12-22 | The Dow Chemical Company | Dense star polymers for calibrating/characterizing sub-micron apertures |
GB8613652D0 (en) * | 1986-06-05 | 1986-07-09 | Grace W R Ab | Compositions for sizing paper |
EP0271180B2 (en) * | 1986-08-18 | 1997-06-18 | The Dow Chemical Company | Starburst conjugates |
GB2198738B (en) * | 1986-10-07 | 1990-12-12 | Allied Corp | Process for producing multiple monolayers of polymeric linkages and devices comprising multiple monolayers |
US5145930A (en) * | 1987-12-07 | 1992-09-08 | E. I. Du Pont De Nemours And Company | Preparation of hyperbranched polyarylenes |
US5817744A (en) | 1988-03-14 | 1998-10-06 | The Boeing Company | Phenylethynyl capped imides |
US5229020A (en) * | 1989-05-30 | 1993-07-20 | Exxon Chemical Patents Inc. | Branched amido-amine dispersant additives |
US5041516A (en) * | 1989-06-21 | 1991-08-20 | Cornell Research Foundation, Inc. | Dendritic molecules and method of production |
US5136096A (en) * | 1989-08-31 | 1992-08-04 | University Of South Florida | Multifunctional synthons as used in the preparation of cascade polymers or unimolecular micelles |
US5541057A (en) * | 1989-09-18 | 1996-07-30 | Biostar, Inc. | Methods for detection of an analyte |
US5639671A (en) * | 1989-09-18 | 1997-06-17 | Biostar, Inc. | Methods for optimizing of an optical assay device |
US4938885A (en) * | 1989-09-28 | 1990-07-03 | Texaco Inc. | Antioxidant dispersant polymer dendrimer |
CA2035605A1 (en) * | 1990-02-14 | 1991-08-15 | Eric K. Eisenhart | Emulsion thickeners |
US5631329A (en) * | 1990-08-27 | 1997-05-20 | Dendritech, Inc. | Process for producing hyper-comb-branched polymers |
US5773527A (en) * | 1990-08-27 | 1998-06-30 | Dendritech, Inc. | Non-crosslinked, polybranched polymers |
ATE152147T1 (en) * | 1990-11-19 | 1997-05-15 | Cornell Res Foundation Inc | HYPERBRANCHED POLYESTERS |
US5098475A (en) * | 1991-01-28 | 1992-03-24 | Xerox Corporation | Inks with dendrimer colorants |
US5955377A (en) * | 1991-02-11 | 1999-09-21 | Biostar, Inc. | Methods and kits for the amplification of thin film based assays |
US5550063A (en) * | 1991-02-11 | 1996-08-27 | Biostar, Inc. | Methods for production of an optical assay device |
US5418136A (en) * | 1991-10-01 | 1995-05-23 | Biostar, Inc. | Devices for detection of an analyte based upon light interference |
US5264543A (en) * | 1991-10-30 | 1993-11-23 | E. I. Du Pont De Nemours And Company | Hyperbranched aramid |
US5196502A (en) * | 1991-11-05 | 1993-03-23 | Eastman Kodak Company | Method for the preparation of multiply-branched aromatic polyesters |
US5871713A (en) * | 1991-12-04 | 1999-02-16 | Guerbet S.A. | Macromolecular polyamine iodine-containing compound, process for its preparation and its use as a contrast agent |
US5530092A (en) * | 1992-01-13 | 1996-06-25 | Dsm N.V. | Dendritic macromolecule and the preparation thereof |
KR100240799B1 (en) † | 1992-01-13 | 2000-01-15 | 윌리암 로엘프 드 보에르 | Dendritic macromolecule and the preparation thereof |
US5610268A (en) * | 1992-01-13 | 1997-03-11 | Dsm N.V. | Dendritic macromolecule and the preparation thereof |
US5493000A (en) * | 1992-02-21 | 1996-02-20 | Alliedsignal Inc. | Fractal polymers and graft copolymers formed from same |
ATE156158T1 (en) | 1992-04-14 | 1997-08-15 | Cornell Res Foundation Inc | MACROMOLECULES BASED ON DENDRITIC POLYMERS AND METHOD FOR THE PRODUCTION |
US5494829A (en) * | 1992-07-31 | 1996-02-27 | Biostar, Inc. | Devices and methods for detection of an analyte based upon light interference |
US5276110A (en) * | 1992-08-12 | 1994-01-04 | National Research Council Of Canada | Highly regular multi-arm star polymers |
DE4243704A1 (en) * | 1992-12-23 | 1994-06-30 | Henkel Kgaa | Granular detergents and / or cleaning agents |
US5387617A (en) * | 1993-01-22 | 1995-02-07 | The Dow Chemical Company | Small cell foams and blends and a process for their preparation |
CA2133967A1 (en) * | 1993-02-24 | 1994-09-01 | Spencer H. Lin | Immobilization of specific binding assay reagents |
US6121056A (en) * | 1993-02-24 | 2000-09-19 | Dade Behring Inc. | Random detection of antigens with antibodies immobilized on soluble submicron particles |
US5898005A (en) * | 1993-02-24 | 1999-04-27 | Dade Behring Inc. | Rapid detection of analytes with receptors immobilized on soluble submicron particles |
FR2703055B1 (en) * | 1993-03-22 | 1995-07-07 | Guerbet Sa | New polyiodinated compounds, their preparation and their use as contrast agents for radiology. |
US6001364A (en) | 1993-05-05 | 1999-12-14 | Gryphon Sciences | Hetero-polyoxime compounds and their preparation by parallel assembly |
ATE191148T1 (en) | 1993-05-05 | 2000-04-15 | Keith Rose | POLYOXIME COMPOUNDS AND THEIR PRODUCTION |
US6174530B1 (en) | 1993-05-05 | 2001-01-16 | Gryphon Sciences | Homogeneous polyoxime compositions and their preparation by parallel assembly |
US5552272A (en) * | 1993-06-10 | 1996-09-03 | Biostar, Inc. | Detection of an analyte by fluorescence using a thin film optical device |
US5422379A (en) * | 1993-09-07 | 1995-06-06 | University Of South Florida | Metallospheres and superclusters |
US5376690A (en) * | 1993-09-07 | 1994-12-27 | University Of South Florida | Metallospheres and superclusters |
US5837865A (en) * | 1993-10-15 | 1998-11-17 | Trustees Of The University Of Pennsylvania | Phosphorescent dendritic macromolecular compounds for imaging tissue oxygen |
JPH09507852A (en) * | 1994-01-05 | 1997-08-12 | アーキュール,インコーポレーテッド | Method for producing polymer having specific properties |
US20030220233A1 (en) | 1994-01-24 | 2003-11-27 | Neorx Corporation | Radiolabeled annexins |
US5968477A (en) * | 1994-01-24 | 1999-10-19 | Neorx Corporation | Radiolabeled annexin conjugates with hexose and a chelator |
JPH09508170A (en) * | 1994-01-28 | 1997-08-19 | デーエスエム ナムローゼ フェンノートシャップ | Dendritic polymeric substance and method for producing the same |
EP0682057A1 (en) * | 1994-05-09 | 1995-11-15 | Dsm N.V. | Process for improvement of the processing characteristics of a polymer composition and polymer compositions obtained therefrom |
AUPM623994A0 (en) * | 1994-06-15 | 1994-07-07 | Biomolecular Research Institute Limited | Antiviral dendrimers |
US5650101A (en) | 1994-07-25 | 1997-07-22 | University Of South Florida | Lock and key micelles |
US5863919A (en) | 1994-07-25 | 1999-01-26 | University Of South Florida | Lock and key micelles and monomer building blocks therefor |
US5449519C1 (en) | 1994-08-09 | 2001-05-01 | Revlon Consumer Prod Corp | Cosmetic compositions having keratolytic and anti-acne activity |
US6908903B1 (en) | 1994-12-07 | 2005-06-21 | Aletheon Pharmaceuticals, Inc. | Cluster clearing agents |
US6172045B1 (en) | 1994-12-07 | 2001-01-09 | Neorx Corporation | Cluster clearing agents |
US5886143A (en) * | 1994-12-07 | 1999-03-23 | Neorx Corporation | Hepatic-directed compounds and reagents for preparation thereof |
JP3099672B2 (en) * | 1995-03-31 | 2000-10-16 | 東洋インキ製造株式会社 | Method for producing star-shaped or comb-shaped branched aliphatic polyamino compound and curable resin composition |
WO1996035739A1 (en) * | 1995-05-03 | 1996-11-14 | Dsm N.V. | Star-shaped branched polyamide |
BE1009554A3 (en) * | 1995-05-03 | 1997-05-06 | Dsm Nv | Star shaped branched polyamide |
US6051429A (en) | 1995-06-07 | 2000-04-18 | Life Technologies, Inc. | Peptide-enhanced cationic lipid transfections |
DE19524045A1 (en) * | 1995-07-01 | 1997-01-02 | Basf Ag | Highly functionalized polyurethanes |
US5596027A (en) * | 1995-07-13 | 1997-01-21 | Videojet Systems International, Inc. | Condensation and water resistant jet ink |
US6083708A (en) * | 1995-08-11 | 2000-07-04 | Dade Behring Inc. | Polypeptide: dendrimer complexes |
IT1277596B1 (en) * | 1995-09-15 | 1997-11-11 | Bracco Spa | MACROMOLECULAR COMPOUNDS OF THE DENDRIMERIC TYPE |
GB2308363A (en) * | 1995-12-22 | 1997-06-25 | Courtaulds Coatings | Dendritic Polymers |
US20050025740A1 (en) * | 1996-01-05 | 2005-02-03 | Keith Rose | Polyoxime compounds and their preparation |
US6312809B1 (en) * | 1996-04-24 | 2001-11-06 | Sandia Corporation | Dendrimer monolayer films |
AUPO104496A0 (en) | 1996-07-17 | 1996-08-08 | Biomolecular Research Institute Limited | Angiogenic inhibitory compounds |
US6777530B1 (en) | 1996-10-18 | 2004-08-17 | Basf Aktiengesellschaft | Use of crosslinked nitrogenous compounds which are soluble or dispersible in water in detergents and cleaners |
WO1998030604A1 (en) * | 1997-01-13 | 1998-07-16 | Dendritech, Inc. | Nanocomposites of dendritic polymers |
US6025462A (en) * | 1997-03-06 | 2000-02-15 | Eic Laboratories, Inc. | Reflective and conductive star polymers |
FR2761691B1 (en) | 1997-04-03 | 1999-05-14 | Oreal | THIOL TERMINAL FUNCTION POLYMERS |
FR2761601A1 (en) | 1997-04-04 | 1998-10-09 | Oreal | SELF-TANNING COSMETIC COMPOSITIONS |
US5739218A (en) * | 1997-06-02 | 1998-04-14 | Dow Corning Corporation | Radially layered copoly (amidoamine-organosilicon) dendrimers |
JP2002501582A (en) * | 1997-06-04 | 2002-01-15 | パルプ アンド ペーパー リサーチ インスチチュート オブ カナダ | Dendrimer polymers for the manufacture of paper and paperboard |
US6673192B1 (en) | 1997-09-25 | 2004-01-06 | Loctite Corporation | Multi-amine compound primers for bonding of polyolefins with cyanoacrylate adhesives |
US6255424B1 (en) | 1997-11-25 | 2001-07-03 | Colorado School Of Mines | Dendritic polymers and convergent method of synthesis |
WO1999043760A1 (en) | 1998-02-27 | 1999-09-02 | Marconi Data Systems, Inc. | Fast drying jet ink composition |
US6399717B1 (en) * | 1998-03-26 | 2002-06-04 | The University Of South Florida | Dendritic materials for enhanced performance of energy storage devices |
US6288197B1 (en) | 1998-04-27 | 2001-09-11 | The University Of Akron | Supramolecular structures and process for making the same |
WO2000002656A2 (en) | 1998-07-10 | 2000-01-20 | Manzer Leo E | Supported dendrimer catalyst and its use in hydroformylation or carbon-carbon bond formation |
US6252025B1 (en) | 1998-08-11 | 2001-06-26 | Eastman Kodak Company | Vinyl hyperbranched polymer with photographically useful end groups |
US6818018B1 (en) | 1998-08-14 | 2004-11-16 | Incept Llc | In situ polymerizable hydrogels |
US6632457B1 (en) * | 1998-08-14 | 2003-10-14 | Incept Llc | Composite hydrogel drug delivery systems |
US6258896B1 (en) | 1998-12-18 | 2001-07-10 | 3M Innovative Properties Company | Dendritic polymer dispersants for hydrophobic particles in water-based systems |
US6395804B1 (en) | 1998-12-18 | 2002-05-28 | 3M Innovative Properties Company | Polyelectrolyte dispersants for hydrophobic particles in water-based systems |
US6262207B1 (en) | 1998-12-18 | 2001-07-17 | 3M Innovative Properties Company | ABN dispersants for hydrophobic particles in water-based systems |
US6224935B1 (en) | 1999-01-28 | 2001-05-01 | Cornell Research Foundation, Inc. | Ordered arrays via metal-initiated self-assembly of ligand containing dendrimers and bridging ligands |
US6485718B1 (en) | 1999-04-13 | 2002-11-26 | Pharmacia Corporation | Site specific ligation of proteins to synthetic particles |
US6448337B1 (en) | 1999-10-07 | 2002-09-10 | 3M Innovative Properties Company | Pressure sensitive adhesives possessing high load bearing capability |
US20020122782A1 (en) * | 1999-10-15 | 2002-09-05 | Gwen-Nelson Bichard | Hair treatment system |
US6733780B1 (en) | 1999-10-19 | 2004-05-11 | Genzyme Corporation | Direct compression polymer tablet core |
US7067111B1 (en) * | 1999-10-25 | 2006-06-27 | Board Of Regents, University Of Texas System | Ethylenedicysteine (EC)-drug conjugates, compositions and methods for tissue specific disease imaging |
ATE266668T1 (en) | 2000-02-07 | 2004-05-15 | Biocompatibles Uk Ltd | SILICON CONTAINING COMPOUNDS PRODUCED BY MICHAEL ADDITION AS MONOMERS AND MACROMERS |
US20040006036A1 (en) * | 2000-04-12 | 2004-01-08 | Gmr, A Delaware Corporation | Silencing transcription by methylation |
US6414084B1 (en) | 2000-04-13 | 2002-07-02 | General Electric Company | High flow polyphenylene ether formulations with dendritic polymers |
US6471968B1 (en) | 2000-05-12 | 2002-10-29 | Regents Of The University Of Michigan | Multifunctional nanodevice platform |
CA2410906C (en) * | 2000-06-02 | 2012-10-02 | Board Of Regents, The University Of Texas System | Ethylenedicysteine (ec)-drug conjugates |
US6448301B1 (en) | 2000-09-08 | 2002-09-10 | 3M Innovative Properties Company | Crosslinkable polymeric compositions and use thereof |
US20030082103A1 (en) * | 2000-10-11 | 2003-05-01 | Targesome, Inc. | Targeted therapeutic lipid constructs having cell surface targets |
US20030129223A1 (en) * | 2000-10-11 | 2003-07-10 | Targesome, Inc. | Targeted multivalent macromolecules |
US20030133972A1 (en) * | 2000-10-11 | 2003-07-17 | Targesome, Inc. | Targeted multivalent macromolecules |
US7045283B2 (en) | 2000-10-18 | 2006-05-16 | The Regents Of The University Of California | Methods of high-throughput screening for internalizing antibodies |
AUPR412801A0 (en) * | 2001-03-30 | 2001-05-03 | Starpharma Limited | Agent for the prevention and treatment of sexually transmitted disease s - I |
US20030003048A1 (en) * | 2001-04-26 | 2003-01-02 | Chun Li | Diagnostic imaging compositions, their methods of synthesis and use |
US7338805B2 (en) | 2001-05-04 | 2008-03-04 | Bio Merieux | Labeling reagents, methods for synthesizing such reagents and methods for detecting biological molecules |
US6635690B2 (en) | 2001-06-19 | 2003-10-21 | 3M Innovative Properties Company | Reactive oligomers |
CN100415198C (en) * | 2001-08-15 | 2008-09-03 | 3M创新有限公司 | Hardenable self-supporting structures and methods |
US9671396B2 (en) * | 2001-09-05 | 2017-06-06 | Joon Won Park | Solid substrate comprising array of dendrons and methods for using the same |
US7261875B2 (en) * | 2001-12-21 | 2007-08-28 | Board Of Regents, The University Of Texas System | Dendritic poly (amino acid) carriers and methods of use |
JP3984541B2 (en) * | 2001-12-26 | 2007-10-03 | 財団法人川村理化学研究所 | Particles comprising star-shaped polyoxazoline and method for producing the same |
US6984734B2 (en) | 2002-02-26 | 2006-01-10 | Board Of Regents, The University Of Texas System | Cyclo[n]pyrroles and methods thereto |
US7494655B2 (en) | 2002-03-05 | 2009-02-24 | Ramot At Tel-Aviv University Ltd. | Immunizing composition and method for inducing an immune response against the β-secretase cleavage site of amyloid precursor protein |
US6794450B2 (en) | 2002-03-06 | 2004-09-21 | General Electric Company | High flow compositions of compatibilized poly(arylene ether) polyamide blends |
US7166657B2 (en) * | 2002-03-15 | 2007-01-23 | Eastman Kodak Company | Article utilizing highly branched polymers to splay layered materials |
US20030180250A1 (en) * | 2002-03-22 | 2003-09-25 | Council Of Scientific And Industrial Research | Compositions and complexes containing a macromolecular compound as potential anti-inflammatory agents |
US6673870B2 (en) | 2002-05-13 | 2004-01-06 | The Procter & Gamble Company | Compositions of polyolefins and hyperbranched polymers with improved tensile properties |
GB0217298D0 (en) * | 2002-07-26 | 2002-09-04 | Univ Sheffield | Polymer |
US20040048099A1 (en) * | 2002-08-29 | 2004-03-11 | Chen Jian Ping | Organic light-emitting device using iptycene derivatives |
DE50309671D1 (en) | 2002-09-13 | 2008-06-05 | Starck H C Gmbh | Organic compounds with core-shell structure |
EP1551292B1 (en) | 2002-09-24 | 2016-04-27 | GOVERNMENT OF THE UNITED STATES OF AMERICA, as represented by THE SECRETARY, DEPARTMENT OF HEALTH AND HUMAN SERVICES | Imaging method for convection enhanced delivery of therapeutic agents |
CN101985443A (en) * | 2002-11-07 | 2011-03-16 | 得克萨斯大学体系董事会 | Ethylenedicysteine (EC)-drug conjugates, compositions and methods for tissue specific disease imaging |
US7129277B2 (en) | 2002-12-31 | 2006-10-31 | 3M Innovative Properties Company | Emulsions including surface-modified inorganic nanoparticles |
US7001580B2 (en) | 2002-12-31 | 2006-02-21 | 3M Innovative Properties Company | Emulsions including surface-modified organic molecules |
US7141612B2 (en) | 2002-12-31 | 2006-11-28 | 3M Innovative Properties Company | Stabilized foams including surface-modified organic molecules |
WO2004069878A2 (en) * | 2003-02-03 | 2004-08-19 | Dendritic Nanotechnologies Limited | Heterocycle functionalized dendritic polymers |
AU2004201833B2 (en) * | 2003-05-02 | 2010-04-22 | Almar Packaging International Inc. | Intermediate bulk container |
DE10331770A1 (en) * | 2003-07-11 | 2005-02-03 | Basf Ag | Process for the preparation of hyperbranched polymers |
US20050040551A1 (en) * | 2003-08-19 | 2005-02-24 | Biegler Robert M. | Hardenable dental article and method of manufacturing the same |
US20050042577A1 (en) * | 2003-08-19 | 2005-02-24 | Kvitrud James R. | Dental crown forms and methods |
US20050042576A1 (en) * | 2003-08-19 | 2005-02-24 | Oxman Joel D. | Dental article forms and methods |
AU2004276760B2 (en) * | 2003-09-22 | 2010-03-04 | Becton, Dickinson And Company | Quantification of analytes using internal standards |
EP1525890A1 (en) * | 2003-10-02 | 2005-04-27 | Complex Biosystems GmbH | Protein-Proteophore complexes |
US7608674B2 (en) * | 2003-11-03 | 2009-10-27 | Ilypsa, Inc. | Pharmaceutical compositions comprising cross-linked small molecule amine polymers |
US7335795B2 (en) * | 2004-03-22 | 2008-02-26 | Ilypsa, Inc. | Crosslinked amine polymers |
US7449605B2 (en) * | 2003-11-03 | 2008-11-11 | Ilypsa, Inc. | Crosslinked amine polymers |
US7459502B2 (en) * | 2003-11-03 | 2008-12-02 | Ilypsa, Inc. | Pharmaceutical compositions comprising crosslinked polyamine polymers |
US7385012B2 (en) * | 2003-11-03 | 2008-06-10 | Ilypsa, Inc. | Polyamine polymers |
US7767768B2 (en) * | 2003-11-03 | 2010-08-03 | Ilypsa, Inc. | Crosslinked amine polymers |
CA2545653C (en) * | 2003-11-21 | 2014-07-08 | Anp Technologies, Inc. | Asymmetrically branched polymer conjugates and microarray assays |
US9050378B2 (en) * | 2003-12-10 | 2015-06-09 | Board Of Regents, The University Of Texas System | N2S2 chelate-targeting ligand conjugates |
US20050171298A1 (en) * | 2004-01-29 | 2005-08-04 | Tomalia Donald A. | Pyrrolidone, piperidone and azetidinone terminated and functionalizes dendritic polymers |
FR2868071B1 (en) * | 2004-03-26 | 2006-06-09 | Biomerieux Sa | MARKING REAGENTS, METHODS FOR SYNTHESIZING SUCH REAGENTS AND METHODS FOR DETECTING BIOLOGICAL MOLECULES |
ATE432723T1 (en) * | 2004-03-29 | 2009-06-15 | Procter & Gamble | ABSORBENT ELEMENT FOR ABSORBENT ARTICLES CONTAINING HIGH PERMEABILITY HYDROGEL-FORMING, SWELLABLE POLYMERS |
DE102004015686A1 (en) * | 2004-03-29 | 2005-10-27 | Basf Ag | Swellable hydrogel-forming polymers with high permeability |
KR100843362B1 (en) | 2004-04-20 | 2008-07-02 | 덴드리틱 나노테크놀로지즈, 인크. | Dendritic polymers with enhanced amplification and interior functionality |
CA2565166C (en) | 2004-05-12 | 2017-12-12 | Nanosphere, Inc. | Bio-barcode based detection of target analytes |
FR2873388B1 (en) * | 2004-07-23 | 2012-04-06 | Biomerieux Sa | PROCESS FOR MARKING AND PURIFYING NUCLEIC ACIDS OF INTEREST PRESENT IN A BIOLOGICAL SAMPLE TO BE PROCESSED IN A SINGLE REACTION RECIPIENT |
CA2578205A1 (en) * | 2004-08-25 | 2006-03-30 | The Regents Of The University Of Michigan | Partially acetylated dendrimers and related methods of use |
US7985418B2 (en) | 2004-11-01 | 2011-07-26 | Genzyme Corporation | Aliphatic amine polymer salts for tableting |
US7606184B2 (en) * | 2005-01-04 | 2009-10-20 | Tdk Corporation | Multiplexers employing bandpass-filter architectures |
DE102005006030A1 (en) * | 2005-02-09 | 2006-08-10 | Basf Ag | Hyperbranched polymers as demulsifiers for cracking crude oil emulsions |
EP2308460A1 (en) | 2005-02-21 | 2011-04-13 | Basf Se | Composition comprising active agents and at least one nitrogen-containing hyper-branched polymer |
WO2006102484A2 (en) * | 2005-03-21 | 2006-09-28 | Anp Technologies, Inc. | Symmetrically branched polymer conjugates and microarray assays |
JP4967378B2 (en) * | 2005-03-29 | 2012-07-04 | セイコーエプソン株式会社 | Ink composition |
US7482389B2 (en) | 2005-04-20 | 2009-01-27 | International Business Machines Corporation | Nanoporous media with lamellar structures |
US7960442B2 (en) * | 2005-04-20 | 2011-06-14 | International Business Machines Corporation | Nanoporous media templated from unsymmetrical amphiphilic porogens |
EP2325236A1 (en) | 2005-04-20 | 2011-05-25 | Dendritic Nanotechnologies Inc. | Dendritic polymers with enhanced amplification and interior functionality |
WO2006119160A2 (en) | 2005-05-02 | 2006-11-09 | Anp Technologies, Inc. | Polymer conjugate enhanced bioassays |
JP5274248B2 (en) | 2005-05-27 | 2013-08-28 | ザ ユニバーシティ オブ ノース カロライナ アット チャペル ヒル | Nitric oxide releasing particles for nitric oxide therapy and biomedical applications |
FR2886735B1 (en) * | 2005-06-01 | 2015-09-11 | Biomerieux Sa | PROCESS FOR MARKING OR PROCESSING A BIOLOGICAL SAMPLE CONTAINING BIOLOGICAL MOLECULES OF INTEREST, IN PARTICULAR NUCLEIC ACIDS |
DE102005028500A1 (en) * | 2005-06-17 | 2006-12-28 | Basf Ag | Aminocarboxylic acid esters with EO / PO / BuO block polymers and their use as emulsion breakers |
US7431845B2 (en) * | 2005-06-23 | 2008-10-07 | Nalco Company | Method of clarifying oily waste water |
US20070041934A1 (en) * | 2005-08-12 | 2007-02-22 | Regents Of The University Of Michigan | Dendrimer based compositions and methods of using the same |
EP1951266A2 (en) * | 2005-09-02 | 2008-08-06 | Genzyme Corporation | Method for removing phosphate and polymer used therefore |
BRPI0616078B8 (en) | 2005-09-15 | 2021-05-25 | Genzyme Corp | powder of an amine polymer pharmaceutical formulation, use of such powder and sachet formulation for amine polymers |
US20080066714A1 (en) * | 2005-09-20 | 2008-03-20 | George Robert Lee | Fuel compositions and its use |
EP3058972A1 (en) | 2005-11-17 | 2016-08-24 | Zogenix, Inc. | Delivery of viscous formulations by needle-free injection |
CA2634066A1 (en) * | 2005-12-13 | 2007-06-21 | Great Basin Scientific | Improved thin film biosensor and method and device for detection of analytes |
US8460879B2 (en) | 2006-02-21 | 2013-06-11 | The Trustees Of Tufts College | Methods and arrays for target analyte detection and determination of target analyte concentration in solution |
US8758723B2 (en) | 2006-04-19 | 2014-06-24 | The Board Of Regents Of The University Of Texas System | Compositions and methods for cellular imaging and therapy |
US8747870B2 (en) | 2006-04-20 | 2014-06-10 | University Of Utah Research Foundation | Polymeric compositions and methods of making and using thereof |
AU2007240613B2 (en) * | 2006-04-20 | 2013-11-28 | University Of Utah Research Foundation | Polymeric compositions and methods of making and using thereof |
EP2016114A2 (en) * | 2006-05-05 | 2009-01-21 | Genzyme Corporation | Amine condensation polymers as phosphate sequestrants |
JP2009538338A (en) * | 2006-05-22 | 2009-11-05 | イーラン ファーマスーティカルズ、インコーポレイテッド | Preparation of polymer complexes of therapeutic, agricultural and food additive compounds |
EP2049014A2 (en) * | 2006-07-18 | 2009-04-22 | Genzyme Corporation | Amine dendrimers |
EP2377507B1 (en) | 2006-09-13 | 2013-04-24 | 3M Innovative Properties Company | Dental compositions including organogelators, products, and methods |
DE102006043039A1 (en) * | 2006-09-14 | 2008-03-27 | H.C. Starck Gmbh | Semiconductor layers forming mixtures of organic compounds |
JP2010504975A (en) | 2006-09-29 | 2010-02-18 | ゲンズイメ コーポレーション | Amide dendrimer composition |
US10925977B2 (en) | 2006-10-05 | 2021-02-23 | Ceil>Point, LLC | Efficient synthesis of chelators for nuclear imaging and radiotherapy: compositions and applications |
EP1914279A3 (en) * | 2006-10-19 | 2008-05-07 | Seiko Epson Corporation | Photo curable ink composition set, and recording method and recordings employing ink compositon set |
US8268347B1 (en) | 2006-10-24 | 2012-09-18 | Aradigm Corporation | Dual action, inhaled formulations providing both an immediate and sustained release profile |
US20080132599A1 (en) | 2006-11-30 | 2008-06-05 | Seiko Epson Corporation. | Ink composition, two-pack curing ink composition set, and recording method and recorded matter using these |
US8163799B2 (en) | 2006-12-14 | 2012-04-24 | Genzyme Corporation | Amido-amine polymer compositions |
JP5472670B2 (en) | 2007-01-29 | 2014-04-16 | セイコーエプソン株式会社 | Ink set, ink jet recording method and recorded matter |
US7655745B2 (en) | 2007-02-15 | 2010-02-02 | Seiko Epson Corporation | Polysilane compound and synthesis method, ultraviolet-ray curable ink composition, inkjet recording method and apparatus, and ink container |
US20080207822A1 (en) * | 2007-02-22 | 2008-08-28 | General Electric Company | Composition and associated method |
WO2008103368A1 (en) * | 2007-02-23 | 2008-08-28 | Genzyme Corporation | Amine polymer compositions |
US8894197B2 (en) | 2007-03-01 | 2014-11-25 | Seiko Epson Corporation | Ink set, ink-jet recording method, and recorded material |
WO2008109095A1 (en) * | 2007-03-08 | 2008-09-12 | Genzyme Corporation | Sulfone polymer compositions |
US7914588B2 (en) * | 2007-04-10 | 2011-03-29 | Los Alamos National Security, Llc | Synthesis of fluorescent metal nanoclusters |
US20090088376A1 (en) * | 2007-04-19 | 2009-04-02 | The Regents Of The University Of Michigan | Dendrimer based compositions and methods of using the same |
WO2008133954A1 (en) * | 2007-04-27 | 2008-11-06 | Genzyme Corporation | Amido-amine dendrimer compositions |
FR2917090B1 (en) * | 2007-06-11 | 2012-06-15 | Biomerieux Sa | MARKING REAGENTS HAVING DIAZO AND NITRO FUNCTIONS, METHODS FOR SYNTHESIZING SUCH REAGENTS AND METHODS FOR DETECTING BIOLOGICAL MOLECULES |
US8658148B2 (en) * | 2007-06-22 | 2014-02-25 | Genzyme Corporation | Chemically modified dendrimers |
DE102007031865A1 (en) | 2007-07-05 | 2009-01-08 | Sitech Sitztechnik Gmbh | Seat i.e. vehicle seat, wear testing and/or soiling behavior testing method for use during seating of human on seat, involves assigning different seat-specific characteristics to seat for standardizable wear and/or soiling testing of seat |
JP2009040880A (en) * | 2007-08-08 | 2009-02-26 | Seiko Epson Corp | Photocurable type ink composition set, inkjet recording method and recorded material |
JP5267854B2 (en) * | 2007-08-08 | 2013-08-21 | セイコーエプソン株式会社 | Photocurable ink composition, ink jet recording method and recorded matter |
EP2028241A1 (en) * | 2007-08-09 | 2009-02-25 | Seiko Epson Corporation | Photocurable ink composition, ink cartridge, inkjet recording method and recorded matter |
JP4816976B2 (en) * | 2007-08-09 | 2011-11-16 | セイコーエプソン株式会社 | Photocurable ink composition |
EP2201024A1 (en) | 2007-08-28 | 2010-06-30 | Ramot At Tel Aviv University | Peptides inducing a cd4i conformation in hiv gp120 while retaining vacant cd4 binding site |
JP4766281B2 (en) * | 2007-09-18 | 2011-09-07 | セイコーエプソン株式会社 | Non-aqueous ink composition for ink jet recording, ink jet recording method and recorded matter |
EP2214646B1 (en) | 2007-10-05 | 2021-06-23 | Wayne State University | Dendrimers for sustained release of compounds |
MX2010003074A (en) | 2007-10-08 | 2010-07-06 | Basf Se | Use of hyperbranched polyesters and/or polyester amides for separating oil-in-water emulsions. |
US20100316589A1 (en) * | 2007-12-14 | 2010-12-16 | Hitesh Bhagat | Coated Pharmaceutical Compositions |
JP2009269397A (en) * | 2008-02-29 | 2009-11-19 | Seiko Epson Corp | Method of forming opaque layer, recording method, ink set, ink cartridge, and recording apparatus |
US8252834B2 (en) | 2008-03-12 | 2012-08-28 | The Regents Of The University Of Michigan | Dendrimer conjugates |
DE102008014158A1 (en) * | 2008-03-14 | 2009-09-17 | H.C. Starck Gmbh | Novel macromolecular compounds having a core-shell structure for use as semiconductors |
WO2009120875A2 (en) * | 2008-03-26 | 2009-10-01 | Shrieve Chemical Products, Inc. | Shale hydration inhibition agent(s) and method of use |
EP2829265B1 (en) | 2008-04-28 | 2016-08-24 | Zogenix, Inc. | Novel formulations for treatment of migraine |
WO2009154747A1 (en) * | 2008-06-20 | 2009-12-23 | Genzyme Corporation | Pharmaceutical compositions |
US8216549B2 (en) * | 2008-07-25 | 2012-07-10 | National Health Research Institutes | Method for making a ligand-quantum dot conjugate |
FR2934595B1 (en) * | 2008-07-29 | 2013-04-05 | Biomerieux Sa | MARKING REAGENTS HAVING A PYRIDINE CORE HAVING DIAZOMETHYL FUNCTION, METHODS FOR SYNTHESIZING SUCH REAGENTS AND METHODS FOR DETECTING BIOLOGICAL MOLECULES |
WO2010039861A2 (en) | 2008-09-30 | 2010-04-08 | The Regents Of The University Of Michigan | Dendrimer conjugates |
US8450529B2 (en) * | 2008-10-02 | 2013-05-28 | Covidien Lp | Branched polyamines and formulations thereof for use in medical devices |
WO2010044875A2 (en) * | 2008-10-16 | 2010-04-22 | Novan, Inc. | Nitric oxide releasing particles for oral care applications |
WO2010053993A1 (en) | 2008-11-04 | 2010-05-14 | The Trustees Of Columbia University In The City Of New York | Heterobifunctional polymers and methods for layer-by-layer construction of multilayer films |
WO2010054321A2 (en) | 2008-11-07 | 2010-05-14 | The Regents Of The University Of Michigan | Methods of treating autoimmune disorders and/or inflammatory disorders |
EP2186559A3 (en) | 2008-11-12 | 2010-08-18 | Basf Se | Tower packing for heat or mass transfer |
US8618180B2 (en) | 2008-12-29 | 2013-12-31 | Basf Se | Hyperbranched polyesters and polycarbonates as demulsifiers for cracking crude oil emulsions |
EP2396070A4 (en) * | 2009-02-12 | 2012-09-19 | Incept Llc | Drug delivery through hydrogel plugs |
EP2236541A1 (en) | 2009-03-25 | 2010-10-06 | DSM IP Assets B.V. | Polyesteramide macromolecule and composition comprising such a macromolecule. |
EP2467127B1 (en) | 2009-08-21 | 2023-08-02 | Novan, Inc. | Topical gels |
BR112012003804B1 (en) | 2009-08-21 | 2019-02-19 | Novan, Inc. | Wound Dressing, Method to Form an Injury Dressing, and Wound Dressing Kit |
WO2011036560A2 (en) | 2009-09-23 | 2011-03-31 | Novartis Ag | Glycoconjugate compositions and methods for treatment of hiv |
CA2777682C (en) | 2009-10-13 | 2015-02-24 | The Regents Of The University Of Michigan | Dendrimer compositions and methods of synthesis |
EP2488591A1 (en) * | 2009-10-13 | 2012-08-22 | Novan, Inc. | Nitric oxide-releasing coatings |
WO2011059586A2 (en) | 2009-10-30 | 2011-05-19 | The Regents Of The University Of Michigan | Multifunctional small molecules |
JP5692490B2 (en) * | 2010-01-28 | 2015-04-01 | セイコーエプソン株式会社 | Aqueous ink composition, ink jet recording method and recorded matter |
JP2011152747A (en) * | 2010-01-28 | 2011-08-11 | Seiko Epson Corp | Aqueous ink composition, inkjet recording method, and recorded matter |
WO2011141266A1 (en) | 2010-04-15 | 2011-11-17 | Basf Se | Process for producing flame-proofed polyurethane foams |
EP2588490B1 (en) | 2010-07-02 | 2017-02-22 | Angiochem Inc. | Short and d-amino acid-containing polypeptides for therapeutic conjugates and uses thereof |
WO2012043426A1 (en) | 2010-09-30 | 2012-04-05 | 株式会社カネカ | Composition containing branched polymer for vibration-damping material |
JP5790234B2 (en) | 2010-12-13 | 2015-10-07 | セイコーエプソン株式会社 | UV-curable ink composition for inkjet, inkjet recording apparatus using the same, inkjet recording method using the same, and ink set |
US8591876B2 (en) | 2010-12-15 | 2013-11-26 | Novan, Inc. | Methods of decreasing sebum production in the skin |
WO2012094620A2 (en) | 2011-01-09 | 2012-07-12 | Anp Technologies, Inc. | Hydrophobic molecule-induced branched polymer aggregates and their use |
EP2673357A2 (en) | 2011-02-07 | 2013-12-18 | Life Technologies Corporation | Compositions and methods for stabilizing susceptible compounds |
WO2012118819A2 (en) | 2011-02-28 | 2012-09-07 | Novan, Inc. | Nitric oxide-releasing s-nitrosothiol-modified silica particles and methods of making the same |
EP2495271B1 (en) | 2011-03-04 | 2014-04-23 | 3M Innovative Properties Co. | Polyether hybrid epoxy curatives |
US9006345B2 (en) | 2011-03-25 | 2015-04-14 | The Trustees Of Columbia University In The City Of New York | Heterotrifunctional molecules and methods for the synthesis of dendrimeric materials |
CN102757693B (en) | 2011-04-28 | 2015-11-18 | 精工爱普生株式会社 | Light curable type ink composition, recording method and device, light-cured type composition for ink jet recording and ink jet recording method |
WO2012162789A1 (en) * | 2011-06-01 | 2012-12-06 | University Of British Columbia | Polymers for reversing heparin-based anticoagulation |
EP3255110B1 (en) | 2011-07-08 | 2022-08-17 | Seiko Epson Corporation | Photocurable ink composition for ink jet recording and ink jet recording method |
JP2014521797A (en) | 2011-08-05 | 2014-08-28 | ビーエイエスエフ・ソシエタス・エウロパエア | Associative thickeners based on hyperbranched polymers |
JP5807776B2 (en) | 2011-09-12 | 2015-11-10 | セイコーエプソン株式会社 | Photocurable ink composition for inkjet recording |
US10226417B2 (en) | 2011-09-16 | 2019-03-12 | Peter Jarrett | Drug delivery systems and applications |
US9402911B2 (en) | 2011-12-08 | 2016-08-02 | The Regents Of The University Of Michigan | Multifunctional small molecules |
JP6024150B2 (en) | 2012-03-28 | 2016-11-09 | セイコーエプソン株式会社 | Ultraviolet curable clear ink composition and recording method |
EP2873410B1 (en) | 2012-07-10 | 2022-05-04 | Tokuyama Dental Corporation | Dental adhesive composition |
EP2953648B1 (en) | 2013-02-05 | 2021-04-21 | ANP Technologies, Inc. | Nanoparticles containing a taxane and their use |
DE102013013213B4 (en) * | 2013-08-09 | 2016-07-07 | Kautex Textron Gmbh & Co. Kg | Operating fluid container with integrated deaerating and / or venting valve |
EP2906613B1 (en) | 2014-01-13 | 2016-03-16 | Yang, Guanghua | Dendrimer compositions, methods of synthesis, and uses thereof |
AU2015253100B2 (en) | 2014-04-30 | 2018-01-18 | The Johns Hopkins University | Dendrimer compositions and their use in treatment of diseases of the eye |
CN106573070A (en) | 2014-08-13 | 2017-04-19 | 约翰霍普金斯大学 | Selective dendrimer delivery to brain tumors |
US10899932B2 (en) | 2014-10-24 | 2021-01-26 | Basf Se | Non-amphoteric, quaternisable and water-soluble polymers for modifying the surface charge of solid particles |
EP3230393B1 (en) * | 2014-12-12 | 2019-04-24 | Marcella Chiari | New clickable polymers and gels for microarray and other applications |
CN107108388B (en) | 2014-12-23 | 2021-02-26 | 巴斯夫欧洲公司 | Composition comprising (thio) phosphoric triamide and other compounds such as amines and colorants with improved urease-inhibiting effect |
WO2016144766A1 (en) | 2015-03-06 | 2016-09-15 | The University Of North Carolina At Chapel Hill | Polymeric metformin and its use as a therapeutic agent and as a delivery vehicle |
EP3939571A1 (en) * | 2015-05-21 | 2022-01-19 | Ohio State Innovation Foundation | Benzene-1,3,5-tricarboxamide derivatives and uses thereof |
WO2017053769A1 (en) | 2015-09-25 | 2017-03-30 | The United States Of America, As Represented By The Secretary, Department Of Health And Human Services | Triazole derivatives as p2y14 receptor antagonists |
US10335406B2 (en) | 2015-10-01 | 2019-07-02 | Elysium Therapeutics, Inc. | Opioid compositions resistant to overdose and abuse |
CA2998708C (en) | 2015-10-01 | 2019-09-03 | Elysium Therapeutics, Inc. | Polysubunit opioid prodrugs resistant to overdose and abuse |
CN105385137A (en) * | 2015-12-02 | 2016-03-09 | 威海晨源分子新材料有限公司 | Application of hyperbranched poly(amide amine)s in plastic processing |
JP2017148724A (en) * | 2016-02-24 | 2017-08-31 | 国立大学法人神戸大学 | Draw solute used in forward osmosis membrane separation and method for producing the same |
CA3045402A1 (en) | 2016-12-23 | 2018-06-28 | Basf Se | Stabilization of particles coated with non-amphoteric, quaternizable and water-soluble polymers using a dispersing component |
EP3595663A4 (en) | 2017-03-17 | 2021-01-13 | Elysium Therapeutics, Inc. | Polysubunit opioid prodrugs resistant to overdose and abuse |
US10597527B2 (en) * | 2017-12-21 | 2020-03-24 | Hongbin Zhu | Heavy oil demulsifier |
PL239642B1 (en) | 2018-08-16 | 2021-12-20 | Pomorski Univ Medyczny W Szczecinie | Composition for intravitreal administration of therapeutic protein |
WO2020047188A1 (en) * | 2018-08-29 | 2020-03-05 | Ecolab Usa Inc. | Multiple charged ionic compounds derived from polyamines and compositions thereof and use thereof as reverse emulsion breakers in oil and gas operations |
EP3725756A2 (en) | 2019-04-18 | 2020-10-21 | Basf Se | Compositions with improved urease-inhibiting effect comprising amines, or colorants, and an adduct of the three compounds n-(n-butyl) thiophosphoric acid triamide (nbpt), urea, and formaldehyde |
JPWO2020241338A1 (en) * | 2019-05-29 | 2020-12-03 | ||
US11452950B2 (en) * | 2019-07-24 | 2022-09-27 | Baker Hughes Holdings Llc | Demulsifying additive for separation of oil and water |
CA3163892A1 (en) | 2019-12-04 | 2021-06-10 | Ashvattha Therapeutics, Inc. | Dendrimer compositions and methods for drug delivery to the eye |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3578643A (en) * | 1969-06-06 | 1971-05-11 | Grace W R & Co | New polymers from nitrilotriacetonitrile and iminodiacetonitrile |
US3580891A (en) * | 1968-04-16 | 1971-05-25 | Seekay Chemical Co | Water-insoluble,cross-linked polymeric reaction product of ethylene diamine and nitrilotriacetic acid or derivative |
US4289872A (en) * | 1979-04-06 | 1981-09-15 | Allied Corporation | Macromolecular highly branched homogeneous compound based on lysine units |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3528928A (en) * | 1969-01-13 | 1970-09-15 | Petrolite Corp | Process of breaking oil-in-water emulsions |
BE756896A (en) * | 1969-10-01 | 1971-03-30 | Montedison Spa | BASIC POLYAMIDES, THEIR METHODS OF PREPARATION AND THEIR APPLICATIONS |
US4102827A (en) * | 1973-12-26 | 1978-07-25 | California Institute Of Technology | Novel polyelectrolytes |
US3985830B1 (en) * | 1974-07-15 | 1998-03-03 | Univ Akron | Star polymers and process for the preparation thereof |
CA1108792A (en) * | 1977-05-11 | 1981-09-08 | Thomas E. Kiovsky | Star-shaped dispersant viscosity index improver |
US4248984A (en) * | 1979-05-11 | 1981-02-03 | Arco Polymers, Inc. | Clear impact resistant thermoplastic star-block copolymers |
EP0066366B1 (en) * | 1981-04-27 | 1986-11-20 | The Dow Chemical Company | Branched polyamidoamines, method for their preparation and method of improving the wet strength of paper using them |
US4435548A (en) * | 1981-04-27 | 1984-03-06 | The Dow Chemical Company | Branched polyamidoamines |
US4409368A (en) * | 1981-07-13 | 1983-10-11 | The General Tire & Rubber Company | Preparation of star polymers |
-
1983
- 1983-01-07 US US06/456,226 patent/US4507466A/en not_active Expired - Lifetime
- 1983-12-29 BR BR8307680A patent/BR8307680A/en not_active IP Right Cessation
- 1983-12-29 WO PCT/US1983/002052 patent/WO1984002705A1/en unknown
- 1983-12-29 JP JP59500653A patent/JPH0670132B2/en not_active Expired - Fee Related
- 1983-12-29 AU AU24354/84A patent/AU560604B2/en not_active Expired
-
1984
- 1984-01-05 AT AT95105140T patent/ATE179731T1/en not_active IP Right Cessation
- 1984-01-05 NZ NZ206742A patent/NZ206742A/en unknown
- 1984-01-05 DE DE3486372T patent/DE3486372T2/en not_active Expired - Lifetime
- 1984-01-05 DE DE3486490T patent/DE3486490T2/en not_active Expired - Lifetime
- 1984-01-05 DE DE3486473T patent/DE3486473T2/en not_active Expired - Lifetime
- 1984-01-05 AT AT84100080T patent/ATE119177T1/en not_active IP Right Cessation
- 1984-01-05 DE DE0608908T patent/DE608908T1/en active Pending
- 1984-01-05 EP EP94102257A patent/EP0608908B1/en not_active Revoked
- 1984-01-05 DE DE0671429T patent/DE671429T1/en active Pending
- 1984-01-05 EP EP84100080A patent/EP0115771B1/en not_active Expired - Lifetime
- 1984-01-05 AT AT94102257T patent/ATE203039T1/en not_active IP Right Cessation
- 1984-01-05 EP EP95105140A patent/EP0671429B1/en not_active Expired - Lifetime
- 1984-01-06 ZA ZA84128A patent/ZA84128B/en unknown
- 1984-01-06 MX MX199974A patent/MX163770B/en unknown
- 1984-01-06 CA CA000444868A patent/CA1244586A/en not_active Expired
-
1993
- 1993-05-24 JP JP5144319A patent/JPH0742352B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3580891A (en) * | 1968-04-16 | 1971-05-25 | Seekay Chemical Co | Water-insoluble,cross-linked polymeric reaction product of ethylene diamine and nitrilotriacetic acid or derivative |
US3578643A (en) * | 1969-06-06 | 1971-05-11 | Grace W R & Co | New polymers from nitrilotriacetonitrile and iminodiacetonitrile |
US4289872A (en) * | 1979-04-06 | 1981-09-15 | Allied Corporation | Macromolecular highly branched homogeneous compound based on lysine units |
Cited By (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5714166A (en) * | 1986-08-18 | 1998-02-03 | The Dow Chemical Company | Bioactive and/or targeted dendrimer conjugates |
US6312679B1 (en) | 1986-08-18 | 2001-11-06 | The Dow Chemical Company | Dense star polymer conjugates as dyes |
US6177414B1 (en) | 1986-08-18 | 2001-01-23 | The Dow Chemical Company | Starburst conjugates |
US5338532A (en) * | 1986-08-18 | 1994-08-16 | The Dow Chemical Company | Starburst conjugates |
US5527524A (en) * | 1986-08-18 | 1996-06-18 | The Dow Chemical Company | Dense star polymer conjugates |
US5560929A (en) * | 1986-08-18 | 1996-10-01 | The Dow Chemical Company | Structured copolymers and their use as absorbents, gels and carriers of metal ions |
US5070183A (en) * | 1987-12-07 | 1991-12-03 | E. I. Du Pont De Nemours And Company | Hyperbranched polyarylene |
US4857630A (en) * | 1987-12-07 | 1989-08-15 | E. I. Du Pont De Nemours And Company | Hyperbranched polyarylene |
US6193950B1 (en) | 1989-11-21 | 2001-02-27 | Schering Ag | Cascade polymer bound complexing compounds, their complexes and conjugates, processes for their production, and pharmaceutical agents containing them |
US6576222B2 (en) | 1989-11-21 | 2003-06-10 | Schering Aktiengesellschaft | Cascade polymer bound complexing compounds, their complexes and conjugates, process for their production and pharmaceutical agents containing them |
US6855309B2 (en) | 1989-11-21 | 2005-02-15 | Schering, Ag | Cascade polymer bound complexing compounds, their complexes and conjugates, processes for their production, and pharmaceutical agents containing them |
US7208139B2 (en) | 1989-11-21 | 2007-04-24 | Schering Ag | Cascade polymer bound complexing compounds, their complexes and conjugates, processes for their production, and pharmaceutical agents containing them |
US5270402A (en) * | 1990-06-22 | 1993-12-14 | E. I. Du Pont De Nemours And Company | Hyperbranched polyesters |
US5183862A (en) * | 1990-06-22 | 1993-02-02 | E. I. Du Pont De Nemours And Company | Hyperbranched polyesters |
US5136014A (en) * | 1990-06-22 | 1992-08-04 | E. I. Du Pont De Nemours And Company | Hyperbranched polyesters |
WO1996035456A3 (en) * | 1995-05-11 | 1997-01-16 | Schering Ag | Use of polymeric contrast agents of medium molecular weight for differentiating between benign and malignant tumours using modern imaging techniques |
WO1996035456A2 (en) * | 1995-05-11 | 1996-11-14 | Schering Aktiengesellschaft | Use of polymeric contrast agents of medium molecular weight for differentiating between benign and malignant tumours using modern imaging techniques |
US7064174B2 (en) | 2000-02-07 | 2006-06-20 | Biocompatibles Uk Limited | Silicon containing compounds |
US7192744B2 (en) | 2000-04-05 | 2007-03-20 | Qiagen Gmbh | Targeted transfection of cells using a biotinylated dendrimer |
US6933126B2 (en) | 2001-09-19 | 2005-08-23 | Applera Corporation | Membrane transportable fluorescent substrates |
US9737611B2 (en) | 2012-05-21 | 2017-08-22 | University Of Miami | Dendrimer conjugates for coating cells |
US10493163B2 (en) | 2012-05-21 | 2019-12-03 | University Of Miami | Dendrimer conjugates for coating cells |
US11253602B2 (en) | 2012-05-21 | 2022-02-22 | University Of Miami | Dendrimer conjugates for coating cells |
US10640611B2 (en) | 2013-11-29 | 2020-05-05 | Byk-Chemie, Gmbh | Polyamine addition compounds |
CN104744709A (en) * | 2015-04-10 | 2015-07-01 | 上海汇锐化工科技有限公司 | Dendritic polyamide type ester quaternary ammonium salt and synthetic process thereof |
CN104744709B (en) * | 2015-04-10 | 2021-08-20 | 上海汇锐化工科技有限公司 | Dendritic polyamide type ester quaternary ammonium salt and synthesis process thereof |
Also Published As
Publication number | Publication date |
---|---|
DE3486372T2 (en) | 1995-06-29 |
DE671429T1 (en) | 1996-02-15 |
AU2435484A (en) | 1984-08-02 |
AU560604B2 (en) | 1987-04-09 |
CA1244586A (en) | 1988-11-08 |
EP0608908A3 (en) | 1995-03-29 |
JPH0693097A (en) | 1994-04-05 |
EP0115771A3 (en) | 1987-03-11 |
MX163770B (en) | 1992-06-19 |
DE3486490T2 (en) | 2001-10-31 |
ATE203039T1 (en) | 2001-07-15 |
BR8307680A (en) | 1984-12-11 |
DE3486473D1 (en) | 1999-06-10 |
JPH0670132B2 (en) | 1994-09-07 |
EP0608908B1 (en) | 2001-07-11 |
ZA84128B (en) | 1985-08-28 |
EP0671429B1 (en) | 1999-05-06 |
JPS60500295A (en) | 1985-03-07 |
EP0608908A2 (en) | 1994-08-03 |
ATE179731T1 (en) | 1999-05-15 |
EP0671429A1 (en) | 1995-09-13 |
JPH0742352B2 (en) | 1995-05-10 |
DE608908T1 (en) | 1995-06-14 |
DE3486490D1 (en) | 2001-08-16 |
DE3486372D1 (en) | 1995-04-06 |
EP0115771A2 (en) | 1984-08-15 |
DE3486473T2 (en) | 1999-09-02 |
ATE119177T1 (en) | 1995-03-15 |
EP0115771B1 (en) | 1995-03-01 |
US4507466A (en) | 1985-03-26 |
NZ206742A (en) | 1987-04-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU560604B2 (en) | Dense star polymers and a process for producing dense star polymers | |
US4558120A (en) | Dense star polymer | |
US4568737A (en) | Dense star polymers and dendrimers | |
US4587329A (en) | Dense star polymers having two dimensional molecular diameter | |
US4694064A (en) | Rod-shaped dendrimer | |
US4631337A (en) | Hydrolytically-stable dense star polyamine | |
US4737550A (en) | Bridged dense star polymers | |
US4857599A (en) | Modified dense star polymers | |
US4435548A (en) | Branched polyamidoamines | |
EP0195126B1 (en) | star-branched polyamides and star-branched polyamine derivates thereof | |
US5773527A (en) | Non-crosslinked, polybranched polymers | |
US4448708A (en) | Use of quaternized polyamidoamines as demulsifiers | |
JPH05239479A (en) | Oil-demulsifier | |
KR20010086434A (en) | Highly branched oligomers, process for their preparation and applications thereof | |
US3715335A (en) | Linear polyester backbone quaternary ammonium polyelectrolytes | |
EP0473088A2 (en) | Non-crosslinked, polybranched polymers | |
WO2003053536A1 (en) | Novel demulsifiers,their preparation and use in oil bearing formations | |
US4457860A (en) | Use of heterocyclic ammonium polyamidoamines as demulsifiers | |
US20050203193A1 (en) | Demulsifiers | |
FI83226B (en) | Polyamidoaminopolyamines | |
AU3879601A (en) | Highly branched oligomers, process for their preparation and applications thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Designated state(s): AU BR JP |