CA1331062C - Segmented polyether polyurethane - Google Patents
Segmented polyether polyurethaneInfo
- Publication number
- CA1331062C CA1331062C CA000603098A CA603098A CA1331062C CA 1331062 C CA1331062 C CA 1331062C CA 000603098 A CA000603098 A CA 000603098A CA 603098 A CA603098 A CA 603098A CA 1331062 C CA1331062 C CA 1331062C
- Authority
- CA
- Canada
- Prior art keywords
- urea
- glycol
- polyether polyurethane
- polyurethane
- molecular weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
- C08G18/4808—Mixtures of two or more polyetherdiols
Abstract
Abstract A hydrophilic, segmented polyether polyurethane-urea that exhibits an increase in tensile strength and elongation when wet with water and is capable of forming visually clear films permeable to water vapor is disclosed.
Description
1331~2 :
., --1-- ..
SEGMENTED POLYETHER POLYURETHANE
':
DesceiPtion Technical Field This invention relates to a segmented polyether polyurethane-urea resin having certain controlled physical properties, and in particular to -a segmented polyether polyurethane-urea resin that --exhibits an increase in tensile strength and -~ ~ -elongation when wet with water and that can be formed into a visually clear film that is permeable to water - - ~
vapor and is hydrophilic. -~- -Background of the Invention Segmented polyurethanes are prepared from hydroxyl terminated low molecular weight polyethers or polyesters or mixtures thereof by reacting these -materials with a stoichiometric excess of a diisocyanate to produce an isocyanate terminated prepolymer. This reactive prepolymer is then chain extended with a difunctional compound containing an ~` active hydrogen such as water, glycols, aminoalcohols ~` or diamines.
Diamine-extended polyurethanes have a ;~
relatively high urea linkage content due to their diamine extension. This high urea linkage content results in relatively high levels of hydrogen bonding which, in turn,~produces strong elastic materials with good flex life properties. However, this high level of hydrogen bonding renders the polyurethane non-thermoplastic. This non-thermoplastic nature severely restricts the processes which may be utilized to fabricate these polyurethanes into useful devlces. Technigues such as extrusion, injection molding and heat sealing cannot be utilized due to 35 the polyurethanes' inability to melt and flow prior ~ ~5, to decomposition.
, '~
: :
~ 3 ~ 2 ~- ~
Segmented polyurethanes have also been synthesized utilizing relatively low molecular weight diols as chain extension agents. The use of diols produces a segmented polyurethane having reduced levels of hydrogen bonding. As a result of this reduction in hydrogen bonding, these particular polyurethanes have reduced physical properties such as elongation, ultimate tensile strength and flex life as compared to their equivalent diamine extended counterparts. However, this relatively lower level of hydrogen bonding renders the polyurethane thermoplastic ancl allows i~t to be extruded, injection molded, heat sealed, etc.
It is known that the mechanical properties and predominately the elastic properties of linear segmented polyurethane block copolymers arise from a ~: ~
two phase microstructure. This two phase structure ;~--is derived from the individual chain structure of the polyurethane.
Segmented polyurethane polymer chains may be considered as a series of alternating "soft" and "hard" blocks. Typically, the ~soft" blocks are diisocyanate-coupled relatively low melting point polyester or polyether polymers of relatively low molecular weight. The "hard" blocks include single diurethane linkages resulting when a diisocyanate molecule couples two polyester or polyether molecules. More particularly, they are the - :
relatively higher melting urethane or urea chain segments formed by the reaction of diisocyanate with a glycol and/or a diamine chain extender.
The polar nature of the recurring rigid -~hard~ urethane/urea chain segments results in their strong mutual attraction. This attraction ~both inter- and intra-molecular) leads to aggregation and '~
ordering into crystalline and paracrystalline domains (also called pseudo crystalline domains) in a mobile polymer matrix. The high level of urethane and urea hydrogen atoms together with carbonyl and ether oxygen groups permits extensive hydrogen bonding in these systems. The level of this hydrogen bonding restricts the mobility of chain segments to organize extensively into crystalline lattices. The result is a polymer system in which there are at least three levels of association.
Portions of "hard" blocks form discernible crystalline domains while portions of the "soft"
blocks form the basis for an amorphous polymer ~ ;
matrix. There is, however, at least a third "phase"
which is formed from the complex interaction of paracrystallinity and hydrogen bonding. This leads to the formation of what has been described as "pseudo crosslinksn. That is, primary polyurethane chains are crosslinked in effect, but not in fact.
20 The overall consequence is the formation of a labile i ~ -~
network of polymer chains which display many of the mechanical, chemical and physical properties of truly crosslinked networks. This type of ~pseudo ;-crosslinking" may be partially reversed or enhanced "
by heat and solvation.
Extrudable, water-extended j ~-polytetramethylene ether polyurethane-urea resins are described in U.S. Patent No. 4,062,834 to Gilding et -~
al. The described resins have been rendered ;- ` --~
extrudable by a reduction and rearrangement of the hydrogen bonds in the polymer chain. This is : , , -accomplished by reacting the isocyanate terminated prepolymer with water to form an unstable carbamate ~.
which in turn decomposes to form an amine and carbon - -~
35 dioxide. The so formed amine terminated prepolymer -:: . ..
': ~- ,-:
;~ ~
g 3 ~ 2 is then reacted with another molecule of isocyanate terminated prepolymer. The polyurethanes thus produced prove to be thermoplastic; however, the physical properties such as elongation, ultimate tensile strength and flex life are inferior.
U.S. Patent No. 3,635,907 to Schulze, et al. -discloses a polyurethane wherein a mixture of chain extenders such as diamines, hydrazine, or hydrazine derivatives, and aminoalcohols is utilized for chain extension, followed by further addition of a diisocyanate and a diol. The ultimate tensile strength of the polyurethane is varied by varying the quantity of diisocyanate added (column 4, lines 8-11). The reaction between the chain extenders and the NCO-groups of the prepolymer is terminated by the addition of aliphatic alcohols (column 1, lines 70-72). Films produced from polyurethanes derived :
from linear polyesters admixed with relatively low molecular weight aliphatic diols are said to be non-porous and impermeable to water vapor (column 2, lines 27-28).
The present invention provides segmented -polyether polyurethane-urea resins which have superior physical properties such as an increase in strength when wet with water, elongation, ultimate tensile strength, and flex life. Some of the present resins may be readily extruded, injection molded and heat sealed, and can be made into visually clear films that are hydrophilic and are permeable to water vapor. Such films are eminently well suited for the fabrication of wound dressings.
Summary of the Invention The present invention contemplates a hydrophilic, segmented polyether polyurethane-urea that exhibits an increase in tensile strength and :
:~:` - ,, -~ ~ .
~ 3 ~ ; ;?
elongation when wet with water, and that is capableof forming a visually clear film. In addition, films embodying this invention exhibit a moisture vapor transport rate several orders of magnitude higher than that of silicone-derived films. This polyurethane-urea is a reaction product of a diisocyanate-polyalkylene ether glycol mixture -prepolymer chain extended with a difunctional amine chain extender such as an aliphatic diamine and/or an 10 alkanolamine. -More particularly, segmented ~ ~
polyurethane-urea resins of the present invention are ~ i derived from a prepolymer formed from a diisocyanate reacted with a certain mixture of polyalkylene ether glycols to form an isocyanate-terminated prepolymer.
The polyalkylene ether glycols selected for the; ~ ~ -mixture have repeating alkyleneoxy segments of ;. - i ` -~
unequal lengths. That is, a polyalkylene ether glycol having relatively lonqer alkyleneoxy segments is mixed with at least one other polyalkylene ether glycol having relatively shorter alkyleneoxy segments. This prepolymer is then chain extended to a desired, relatively hiyher, number average molecular weight, usually in the range of about 20,000 to about 260,000, by reaction with an admixture of at least one difunctional chain .. ;-~. --- -extender, such as an aliphatic diamine, and preferably admixed with at least one chain control agent such as a monofunctional amine. Optionally, a -polymeric wetting agent such as polyvinylpyrrolidone or the like is also present.
Control of the hydrophilicity of the present ; ~
polyurethane-urea resins can be done intrinsically by ~ -selecting a desired mixture of polyalkylene ether 35 glycols and by adjusting the ratio of these ;
.`: -. ~.... -polyalkylene ether glycols as the prepolymer of the eesin is made. Hydrophilicity of the resin can also be controlled extrinsically by incorporation into the prepared resin of a hydrophilic polymer that is soluble in the segmented polyurethane resin, e.g., polyvinylpyrrolidone. As the degree of hydrophilicity is varied, the rate of moisture transport and vapor permeability through the present polyurethanes are also varied.
The present polyurethane-urea resins can be processed into porous films or membranes, if desired, in accordance wi1:h practices taught in U.S. Patent No. 4,704,130 to Gilding et al. Such porous films have utility as membranes for various separation ~ -- ;
processes, for wound dressings, and the like.
Numerous other advantages and features of the present invention will become readily apparent from the following detailed description of invention, the accompanying examples and the appended claims. - -~
Brief Description of Drawinqs In the drawings, ~
FIGURES 1 through 15 are graphical - -representations showing constant dry tensile strength - wet tensile strength differential contours (expressed in kilograms per square millimeter) derived from a multiple regression model of experimental data.
In FIGURES 1, 3, 5, 7, 9, 11, 13 and 15 all variables except the coordinate variables were held at their mean experimental values, and in FIGURES 2, 4, 6, 8, 10, 12 and 14 all variables except the coordinate variables were held at about their optimum values.
The mean experimental values were as follows: ~
mole percent polyethylene glycol (PEG) 49.026 ~ ' ,. ' h molecular weight of PEG 1426 molecular weight of polytetramethylene --glycol (PTMEG) 1268.2 extension 23.776 mole fraction ethylene diamine (EDA) 0.49026 ~
The optimum values were as follows: - ;
mole percent PEG 25 - J
molecular weight of PEG 2000 10 molecular weight of PTMEG 2000 -extension 40 --~
mole fraction of EDA 0.5 Detailed DescriPtion of the Preferred Embodiments ; ~ -While this invention is susceptible to embodiment in many different forms, preferred embodiments of the invention are shown. It should be understood, however, that the present disclosure is -` .:
to be considered as an exemplification of the ~-principles of this invention and is not intended to limit the invention to the embodiments illustrated.
In the present polyurethane-ureaæ the level of ~pseudo crosslinking" and general phase separation present can be adjusted in a controllable, predictable fashion. This enables the physical and mechanical properties to be tailored to specific requirements. The modification of these materials has been accomplished by controlling the following --parameters. -The ~soft" block of the resins of the 30 present invention is ideally a relatively low melting - ~ -point polyether of low molecular weight. The "hard" ~ -block is ideally formed from the diurethane linkages resulting from the reaction of two polyether molecules and the urethane/urea segments formed from the reaction of diisocyanate and/or an alkanolamine and a diamine.
~ J ~ ~
The stoichiometry of the polyurethane-ureas -of the present invention is such that the "soft"
blocks are of relatively greater block length than the corresponding ~hard" blocks. In fact, the "hard"
blocks can be better characterized as ~hard" units as they are present in limited numbers and are of relatively short block length. This situation ensures that little true crystallization of the ~hard~ block can take place. Crystallization of the ;
"soft~ block is possible, but produces less rigid crystallites than those potentially formed from the ~hard" blocks. The stoichiometry of the diamines and alkanolamines used in the chain extension of these polyurethane-ureas allows adjustment of the degree and distribution of hydrogen bonding in the produced polymers.
The polyurethane-ureas of the present -invention, while encompassing traditional theories, depart, however, from the currently held views -20 regarding phase separation, hydrogen bonding, etc. - -This departure can be seen clearly in the current - -polyurethane-urea's mechanical properties after eguilibration in a series of organic and agueous ~
solutions as will be described in greater detail ~ -hereinbelow.
As previously described, conventional polyurethanes obtain their mechanical properties from ~pseudo crosslinks~. These crosslinks are considered to be a function of the level of hydrogen bonding between the various polar groups present in the polymer's structure. The placement of these polar ; - ~
groups and, therefore, hydrogen bonds is accepted as `~ ~"!, ~ ~' being predominately in the ~hard~ blocks of the polymer (i.e., associated wth the urethane and urea ;~
linkages).
~ - : -... .,: , , . ~ ~. .
,, . ~.
, . ,, :;
Contributions to the strength of the material from the "soft" block portions are considered negligible by conventional theories. It ' would be expected, therefore, that an equilibration --5with a liquid which disrupts hydrogen bonds (e.g., ~ -water) would reduce the polymer's mechanical strength and elongation. However, such a reduction in mechanical strength and elongation for polyurethane-ureas of the present invention is not observed when these polyurethane-ureas are equilibrated with water. In fact, the contrary is found to be the case. The polyurethane-ureas of the ;-present invention increase in tensile strength and elongation when wet with water.
While not wishing to be bound by a -particular theory, it is believed that the polymers ~ -of the present invention behave as follows. Water, being a small, highly polar molecule, is known to participate in "bridging~ reactions with various ~ -20 chemical groupings through its hydrogen atom. In the -~
case of the polyurethanes of the present invention, the hydrogen atoms in the water molecules participate in a ~bridging" reaction between oxygen atoms in the ;~
polyether ~soft~ block segments. The "soft" blocks are considered to be coiled and the hydrogen ~bridging~ takes place both between oxygen contained ~ ~
in adjacent loops of the mixed polyether coil and -; -between oxygen present in other surrounding coils (either in the same polymer chain or a second --~
30 chain). The ~bridging" increases the strength of the -respective chain which is observed as an increase in mechanical strength of the polymer.
The observed increase in elongation is ~ - -believed to be due to the changing balance of the inter- to intra-molecular ~bridging" that is present -, ,.
.~ .
~, ~
~ 3 ~ 2 as the materials are placed under tensile stress.
The stress also induces chain slippage which allows alignment and optimization of "bridging~ and hydrogen bonding. When equilibrated with a liquid which is not capable of "bridging" (e.g., methanol) the - polyurethane-ureas of the present invention do not show an increase in mechanical properties. As a matter of fact, decrease in tensile strength and elongation is observed as compared with dry samples of the same materials. The observed decrease is considered to be due to methanol's effect on the balance of ~pseuclo crosslinking" and "pseudo crystallinityn.
The present segmented polyurethane-urea lS resins are the reaction products of certain :~
isocyanate-terminated prepolymers with certain amounts of chain extenders or chain extender mixtures. The aforementioned prepolymers, in turn, are the products of the reaction of a stoichiometric 20 excess of a diisocyanate with an admixture of ~ i polyalkylene ether glycols having repeating alkyleneoxy groups of different size, i.e., the length of repeating alkylene units is different in i-each of the glycols. The preferred mol ratio of ~ -diisocyanate-to-polyalkylene ether glycol mixture is about 3:2. The prepolymer contains no residual hydroxyl groups.
Any of a wide variety of organic diisocyanates may be utilized for present purposes, including aromatic, aliphatic and cycloaliphatic diisocyanates and combinations thereof.
Aepresentative diisocyanates include toluene diisocyanate (TDI), diphenylmethylene diisocyanate ~MDI), hexamethylene diisocyanate, cyclohexylene ; -~
35 diisocyanate, methylene dicyclohexane diisocyanate, i~
., --1-- ..
SEGMENTED POLYETHER POLYURETHANE
':
DesceiPtion Technical Field This invention relates to a segmented polyether polyurethane-urea resin having certain controlled physical properties, and in particular to -a segmented polyether polyurethane-urea resin that --exhibits an increase in tensile strength and -~ ~ -elongation when wet with water and that can be formed into a visually clear film that is permeable to water - - ~
vapor and is hydrophilic. -~- -Background of the Invention Segmented polyurethanes are prepared from hydroxyl terminated low molecular weight polyethers or polyesters or mixtures thereof by reacting these -materials with a stoichiometric excess of a diisocyanate to produce an isocyanate terminated prepolymer. This reactive prepolymer is then chain extended with a difunctional compound containing an ~` active hydrogen such as water, glycols, aminoalcohols ~` or diamines.
Diamine-extended polyurethanes have a ;~
relatively high urea linkage content due to their diamine extension. This high urea linkage content results in relatively high levels of hydrogen bonding which, in turn,~produces strong elastic materials with good flex life properties. However, this high level of hydrogen bonding renders the polyurethane non-thermoplastic. This non-thermoplastic nature severely restricts the processes which may be utilized to fabricate these polyurethanes into useful devlces. Technigues such as extrusion, injection molding and heat sealing cannot be utilized due to 35 the polyurethanes' inability to melt and flow prior ~ ~5, to decomposition.
, '~
: :
~ 3 ~ 2 ~- ~
Segmented polyurethanes have also been synthesized utilizing relatively low molecular weight diols as chain extension agents. The use of diols produces a segmented polyurethane having reduced levels of hydrogen bonding. As a result of this reduction in hydrogen bonding, these particular polyurethanes have reduced physical properties such as elongation, ultimate tensile strength and flex life as compared to their equivalent diamine extended counterparts. However, this relatively lower level of hydrogen bonding renders the polyurethane thermoplastic ancl allows i~t to be extruded, injection molded, heat sealed, etc.
It is known that the mechanical properties and predominately the elastic properties of linear segmented polyurethane block copolymers arise from a ~: ~
two phase microstructure. This two phase structure ;~--is derived from the individual chain structure of the polyurethane.
Segmented polyurethane polymer chains may be considered as a series of alternating "soft" and "hard" blocks. Typically, the ~soft" blocks are diisocyanate-coupled relatively low melting point polyester or polyether polymers of relatively low molecular weight. The "hard" blocks include single diurethane linkages resulting when a diisocyanate molecule couples two polyester or polyether molecules. More particularly, they are the - :
relatively higher melting urethane or urea chain segments formed by the reaction of diisocyanate with a glycol and/or a diamine chain extender.
The polar nature of the recurring rigid -~hard~ urethane/urea chain segments results in their strong mutual attraction. This attraction ~both inter- and intra-molecular) leads to aggregation and '~
ordering into crystalline and paracrystalline domains (also called pseudo crystalline domains) in a mobile polymer matrix. The high level of urethane and urea hydrogen atoms together with carbonyl and ether oxygen groups permits extensive hydrogen bonding in these systems. The level of this hydrogen bonding restricts the mobility of chain segments to organize extensively into crystalline lattices. The result is a polymer system in which there are at least three levels of association.
Portions of "hard" blocks form discernible crystalline domains while portions of the "soft"
blocks form the basis for an amorphous polymer ~ ;
matrix. There is, however, at least a third "phase"
which is formed from the complex interaction of paracrystallinity and hydrogen bonding. This leads to the formation of what has been described as "pseudo crosslinksn. That is, primary polyurethane chains are crosslinked in effect, but not in fact.
20 The overall consequence is the formation of a labile i ~ -~
network of polymer chains which display many of the mechanical, chemical and physical properties of truly crosslinked networks. This type of ~pseudo ;-crosslinking" may be partially reversed or enhanced "
by heat and solvation.
Extrudable, water-extended j ~-polytetramethylene ether polyurethane-urea resins are described in U.S. Patent No. 4,062,834 to Gilding et -~
al. The described resins have been rendered ;- ` --~
extrudable by a reduction and rearrangement of the hydrogen bonds in the polymer chain. This is : , , -accomplished by reacting the isocyanate terminated prepolymer with water to form an unstable carbamate ~.
which in turn decomposes to form an amine and carbon - -~
35 dioxide. The so formed amine terminated prepolymer -:: . ..
': ~- ,-:
;~ ~
g 3 ~ 2 is then reacted with another molecule of isocyanate terminated prepolymer. The polyurethanes thus produced prove to be thermoplastic; however, the physical properties such as elongation, ultimate tensile strength and flex life are inferior.
U.S. Patent No. 3,635,907 to Schulze, et al. -discloses a polyurethane wherein a mixture of chain extenders such as diamines, hydrazine, or hydrazine derivatives, and aminoalcohols is utilized for chain extension, followed by further addition of a diisocyanate and a diol. The ultimate tensile strength of the polyurethane is varied by varying the quantity of diisocyanate added (column 4, lines 8-11). The reaction between the chain extenders and the NCO-groups of the prepolymer is terminated by the addition of aliphatic alcohols (column 1, lines 70-72). Films produced from polyurethanes derived :
from linear polyesters admixed with relatively low molecular weight aliphatic diols are said to be non-porous and impermeable to water vapor (column 2, lines 27-28).
The present invention provides segmented -polyether polyurethane-urea resins which have superior physical properties such as an increase in strength when wet with water, elongation, ultimate tensile strength, and flex life. Some of the present resins may be readily extruded, injection molded and heat sealed, and can be made into visually clear films that are hydrophilic and are permeable to water vapor. Such films are eminently well suited for the fabrication of wound dressings.
Summary of the Invention The present invention contemplates a hydrophilic, segmented polyether polyurethane-urea that exhibits an increase in tensile strength and :
:~:` - ,, -~ ~ .
~ 3 ~ ; ;?
elongation when wet with water, and that is capableof forming a visually clear film. In addition, films embodying this invention exhibit a moisture vapor transport rate several orders of magnitude higher than that of silicone-derived films. This polyurethane-urea is a reaction product of a diisocyanate-polyalkylene ether glycol mixture -prepolymer chain extended with a difunctional amine chain extender such as an aliphatic diamine and/or an 10 alkanolamine. -More particularly, segmented ~ ~
polyurethane-urea resins of the present invention are ~ i derived from a prepolymer formed from a diisocyanate reacted with a certain mixture of polyalkylene ether glycols to form an isocyanate-terminated prepolymer.
The polyalkylene ether glycols selected for the; ~ ~ -mixture have repeating alkyleneoxy segments of ;. - i ` -~
unequal lengths. That is, a polyalkylene ether glycol having relatively lonqer alkyleneoxy segments is mixed with at least one other polyalkylene ether glycol having relatively shorter alkyleneoxy segments. This prepolymer is then chain extended to a desired, relatively hiyher, number average molecular weight, usually in the range of about 20,000 to about 260,000, by reaction with an admixture of at least one difunctional chain .. ;-~. --- -extender, such as an aliphatic diamine, and preferably admixed with at least one chain control agent such as a monofunctional amine. Optionally, a -polymeric wetting agent such as polyvinylpyrrolidone or the like is also present.
Control of the hydrophilicity of the present ; ~
polyurethane-urea resins can be done intrinsically by ~ -selecting a desired mixture of polyalkylene ether 35 glycols and by adjusting the ratio of these ;
.`: -. ~.... -polyalkylene ether glycols as the prepolymer of the eesin is made. Hydrophilicity of the resin can also be controlled extrinsically by incorporation into the prepared resin of a hydrophilic polymer that is soluble in the segmented polyurethane resin, e.g., polyvinylpyrrolidone. As the degree of hydrophilicity is varied, the rate of moisture transport and vapor permeability through the present polyurethanes are also varied.
The present polyurethane-urea resins can be processed into porous films or membranes, if desired, in accordance wi1:h practices taught in U.S. Patent No. 4,704,130 to Gilding et al. Such porous films have utility as membranes for various separation ~ -- ;
processes, for wound dressings, and the like.
Numerous other advantages and features of the present invention will become readily apparent from the following detailed description of invention, the accompanying examples and the appended claims. - -~
Brief Description of Drawinqs In the drawings, ~
FIGURES 1 through 15 are graphical - -representations showing constant dry tensile strength - wet tensile strength differential contours (expressed in kilograms per square millimeter) derived from a multiple regression model of experimental data.
In FIGURES 1, 3, 5, 7, 9, 11, 13 and 15 all variables except the coordinate variables were held at their mean experimental values, and in FIGURES 2, 4, 6, 8, 10, 12 and 14 all variables except the coordinate variables were held at about their optimum values.
The mean experimental values were as follows: ~
mole percent polyethylene glycol (PEG) 49.026 ~ ' ,. ' h molecular weight of PEG 1426 molecular weight of polytetramethylene --glycol (PTMEG) 1268.2 extension 23.776 mole fraction ethylene diamine (EDA) 0.49026 ~
The optimum values were as follows: - ;
mole percent PEG 25 - J
molecular weight of PEG 2000 10 molecular weight of PTMEG 2000 -extension 40 --~
mole fraction of EDA 0.5 Detailed DescriPtion of the Preferred Embodiments ; ~ -While this invention is susceptible to embodiment in many different forms, preferred embodiments of the invention are shown. It should be understood, however, that the present disclosure is -` .:
to be considered as an exemplification of the ~-principles of this invention and is not intended to limit the invention to the embodiments illustrated.
In the present polyurethane-ureaæ the level of ~pseudo crosslinking" and general phase separation present can be adjusted in a controllable, predictable fashion. This enables the physical and mechanical properties to be tailored to specific requirements. The modification of these materials has been accomplished by controlling the following --parameters. -The ~soft" block of the resins of the 30 present invention is ideally a relatively low melting - ~ -point polyether of low molecular weight. The "hard" ~ -block is ideally formed from the diurethane linkages resulting from the reaction of two polyether molecules and the urethane/urea segments formed from the reaction of diisocyanate and/or an alkanolamine and a diamine.
~ J ~ ~
The stoichiometry of the polyurethane-ureas -of the present invention is such that the "soft"
blocks are of relatively greater block length than the corresponding ~hard" blocks. In fact, the "hard"
blocks can be better characterized as ~hard" units as they are present in limited numbers and are of relatively short block length. This situation ensures that little true crystallization of the ~hard~ block can take place. Crystallization of the ;
"soft~ block is possible, but produces less rigid crystallites than those potentially formed from the ~hard" blocks. The stoichiometry of the diamines and alkanolamines used in the chain extension of these polyurethane-ureas allows adjustment of the degree and distribution of hydrogen bonding in the produced polymers.
The polyurethane-ureas of the present -invention, while encompassing traditional theories, depart, however, from the currently held views -20 regarding phase separation, hydrogen bonding, etc. - -This departure can be seen clearly in the current - -polyurethane-urea's mechanical properties after eguilibration in a series of organic and agueous ~
solutions as will be described in greater detail ~ -hereinbelow.
As previously described, conventional polyurethanes obtain their mechanical properties from ~pseudo crosslinks~. These crosslinks are considered to be a function of the level of hydrogen bonding between the various polar groups present in the polymer's structure. The placement of these polar ; - ~
groups and, therefore, hydrogen bonds is accepted as `~ ~"!, ~ ~' being predominately in the ~hard~ blocks of the polymer (i.e., associated wth the urethane and urea ;~
linkages).
~ - : -... .,: , , . ~ ~. .
,, . ~.
, . ,, :;
Contributions to the strength of the material from the "soft" block portions are considered negligible by conventional theories. It ' would be expected, therefore, that an equilibration --5with a liquid which disrupts hydrogen bonds (e.g., ~ -water) would reduce the polymer's mechanical strength and elongation. However, such a reduction in mechanical strength and elongation for polyurethane-ureas of the present invention is not observed when these polyurethane-ureas are equilibrated with water. In fact, the contrary is found to be the case. The polyurethane-ureas of the ;-present invention increase in tensile strength and elongation when wet with water.
While not wishing to be bound by a -particular theory, it is believed that the polymers ~ -of the present invention behave as follows. Water, being a small, highly polar molecule, is known to participate in "bridging~ reactions with various ~ -20 chemical groupings through its hydrogen atom. In the -~
case of the polyurethanes of the present invention, the hydrogen atoms in the water molecules participate in a ~bridging" reaction between oxygen atoms in the ;~
polyether ~soft~ block segments. The "soft" blocks are considered to be coiled and the hydrogen ~bridging~ takes place both between oxygen contained ~ ~
in adjacent loops of the mixed polyether coil and -; -between oxygen present in other surrounding coils (either in the same polymer chain or a second --~
30 chain). The ~bridging" increases the strength of the -respective chain which is observed as an increase in mechanical strength of the polymer.
The observed increase in elongation is ~ - -believed to be due to the changing balance of the inter- to intra-molecular ~bridging" that is present -, ,.
.~ .
~, ~
~ 3 ~ 2 as the materials are placed under tensile stress.
The stress also induces chain slippage which allows alignment and optimization of "bridging~ and hydrogen bonding. When equilibrated with a liquid which is not capable of "bridging" (e.g., methanol) the - polyurethane-ureas of the present invention do not show an increase in mechanical properties. As a matter of fact, decrease in tensile strength and elongation is observed as compared with dry samples of the same materials. The observed decrease is considered to be due to methanol's effect on the balance of ~pseuclo crosslinking" and "pseudo crystallinityn.
The present segmented polyurethane-urea lS resins are the reaction products of certain :~
isocyanate-terminated prepolymers with certain amounts of chain extenders or chain extender mixtures. The aforementioned prepolymers, in turn, are the products of the reaction of a stoichiometric 20 excess of a diisocyanate with an admixture of ~ i polyalkylene ether glycols having repeating alkyleneoxy groups of different size, i.e., the length of repeating alkylene units is different in i-each of the glycols. The preferred mol ratio of ~ -diisocyanate-to-polyalkylene ether glycol mixture is about 3:2. The prepolymer contains no residual hydroxyl groups.
Any of a wide variety of organic diisocyanates may be utilized for present purposes, including aromatic, aliphatic and cycloaliphatic diisocyanates and combinations thereof.
Aepresentative diisocyanates include toluene diisocyanate (TDI), diphenylmethylene diisocyanate ~MDI), hexamethylene diisocyanate, cyclohexylene ; -~
35 diisocyanate, methylene dicyclohexane diisocyanate, i~
2,2,4-trimethyl hexamethylene diisocyanate, .. . :. i . ~. ~
.; . - :
' ~ ~. .,~..,': ' J ~ 2 isophorone diisocyanate, m-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,5-naphthylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, l,10-decamethylene diisocyanate and - 1,4-cyclohexylene diisocyanate. The preferred -diisocyanates are aromatic in nature, e.g., TDI, MDI, and the like.
The polyalkylene ether glycols that constitute an admixture suitable for the present purposes are chosen so that the repeating alkyleneoxy segments in each of the glycols is of a different -size. The polyalkylene ether glycol having the relatively shorter alkyleneoxy segments preferably ~-has a number average molecular weight in the range of about 1,000 to about 3,000. The polyalkylene ether glycol having the relatively longer alkyleneoxy segments has a number average molecular weight of at least about 800, and the molecular weight can be as high as about 4,000. Preferably the polyalkylene ether glycols that constitute the admixture have substantially the same number average molecular -weight, more preferably a number average molecular weight of about 2,000.
It is also preferable that the polyalkylene ;-ether glycol having the relatively shorter alkyleneoxy segments constitutes at least about 10 --mole percent of the admixture, and the polyalkylene ether glycol having the relatively longer alkyleneoxy segments constitutes a major portion of the admixture, i.e., more than about 50 mole percent of ;
the glycol admixture. Particularly preferred are polyalkylene ether glycol admixtures containing about 25 mole percent of the glycol having the relatively shorter alkyleneoxy segments and about 75 mole percent of the glycol having the relatively longer alkyleneoxy segments.
~ ` ~ 3 3 ~
Illusteative of the polyalkylene ether glycol admixtures useful in the formation of the -prepolymer are polyethylene glycol with polytetramethylene glycol, polypropylene glycol with ~- -S 1,2-polydimethylethylene glycol, polydecamethylene -glycol with polyethylene glycol, and the like. A
preferred polyalkylene ether glycol admixture is that of polytetramethylene glycol and polyethylene -glycol. For films suitable for use in wound dressings, a preferred combination is polytetramethylene glycol (PTMEG) having a number ~ ~-average molecular weight of about 2,000 and polyethylene glycol (PEG) having a number average molecular weight of about 2,000 in a mole ratio of-about 1:1 to about 3:1, respectively, for an optimum degree of hydrophilicity in combination with a desired degree of hydrogen bonding in the produced film.
The formation of the isocyanate terminated 20 prepolymer occurs in a liguid state and at a ~` -temperature of about 50 to about 100C., preferably at about 80 to about 85C. The reaction time is ! ;'',~" ~'.~,' ," ' about 1 to about 1-1/2 hours. Although it is preferred that this reaction take place in a melt, it 25 may equally well be carried out in solution using a suitable solvent sucb as dimethylacetamide (~ AC), ~,.,!,,.,' ,, ~',Y,'~
; dimethylformamide ~ F), tetrahydrofuran (THF), or ; `
the like. The preferred solvent is ~ C. If the reaction takes place in the melt, the prepolymer is 30 then dissolved in the aforementioned solvent.
When dissolution is complete, the prepolymer : i8 ch~in extended to the desired number average ` ~
-~ ~ molecular weight, usually in the range of about ~ ; -i~; , 20,000 to about 260,000, using a difunctional chain 35 extender, preferably an admixture of such chain ;; i~
extenders. In the chain extender admixture at least 3 ~
-13- ;
one chain extender is an aliphatic diamine and at least one other chain extender is an alkanolamine.
Suitable aliphatic diamine chain extenders include ethylene diamine, m-xylylene diamine, propylene diamine, and the like. Suitable alkanolamine chain extenders include ethanolamine, ~ -and the like. Other chain extenders such as diols can also be present. A preferred combination of ~
chain extenders is ethylene diamine with -ethanolamine. The mol ratio of ethylene diamine to ethanolamine can be about 0.25:0.~5 to about 0.75:0.25. ;~ ~ -A preferred monofunctional amine chain control agent includes at least one member of the group consisting of 3,3-dimethylbutylamine, dimethylcyclohexylamine, 1,5-dimethylhexylamine, and ; -~ ~-dimethylethylene diamine. The amount of the chain control agent is dependent on the amount of NCO-groups present in the prepolymer and the desired 20 chain extension. In any particular case, sufficient ,~
chain control agent is added to react with the ;~
remaining NCO-groups present after the desired degree -of chain extension has been achieved.
The chain extender and chain control agent 25 are dissolved in a suitable solvent such as DMAC, ~?-`
DMF, THF, etc. as mentioned hereinabove.
The prepolymer is then reacted with the ch`ain extender and chain control agent solution to obtain the desired chain extension of the prepolymer. This reaction is usually carried out at a temperature of about 80 to about 85C. over a time period of about 2 to about 3-1/2 hours. A ` ~
polyurethane-urea resin solution is thus produced. ~ -Optionally, the hydrophilicity of the polyurethane resin may be enhanced by the use of an .` ~.: ~;
:
~.~3~ ~2 extrinsic wetting agent such as polyvinylpyrrolidone or the like, which is added to the polymerized resin prior to film forming. The amount of polyvinylpyrrolidone utilized for this purpose is ~ ~
about 1 to about S0 percent by weight of the ~ ~ -composition.
The following examples illustrate typical ~ ~ ~
preparations of polyurethane-ureas embodying the - ~ -present invention. In these examples, the -~
polyurethane-urea prepolymer was prepared in a suitable reactor vessel equipped with an agitator, a --temperature sensor, a temperature control and a nitrogen source and bleed. The chain extenders and - - . --chain control agents were admixed in a separate - ;~
mixing vessel and the resulting admixture was then added to the reactor vessel.
Polytetramethylene glycol (M.W. 1000; 257.14 grams) and polyethylene glycol (M.W. 1000; 28.57 grams) were combined and melted at a temperature of approximately 40 to 45C. in the reactor under a nitrogen blanket. 4,4'-Diphenylmethane diisocyanate ; ` ~
(117.86 grams) was added to the reactor under ~` `~ ` ^
agitation. The resulting mixture was stirred, heated to a temperature of about 60 to 65C. and maintained within this temperature range for a time period of about 1 to about 1-1/2 hours to produce a molten prepolymer. Dry dimethylacetamide (DMAC; 857.59 grams) was then added to the molten prepolymer and the admixture was stirred until dissolution of the prepolymer was complete. This occurred in about 15 to about 30 minutes. ` `~
Dry DMAC (850.0 grams), ethanolamine (4.68 grams), ethylene diamine (4.60 grams) and dimethylethylene diamine (0.88 grams) were combined ~. ~3 oJ~ 2 in a separate vessel, mixed at room temperature, and ~hen added rapidly to the prepolymer solution with vigorous agitation. Thereafter, the prepolymer solution containing these additives was maintained at a temperature of approximately 80 to 85 ~C. for a time period of about 2 to about 3-1/2 hours.
The resultant polyurethane resin solution was colorless and viscous, and was cast into a visually clear film. ~ -Polytetramethylene glycol (M.W. 1000; 214.29 grams) and polyethylene glycol (M.W. 1000; 71.43 grams) were combined and melted at a temperature of approximately 40 to 45C. in the reactor under a nitrogen blanket. 4,4'-Diphenylmethane diisocyanate (117.86 grams) was added to the reactor under agitation. The resulting mixture was stirred, heated to a temperature of about 60 to 65C. and maintained within this temperature range for a time period of about 1 to about 1-1/2 hours. Dry dimethylacetamide (DMAC; 857.59 grams) was then added to the molten prepolymer and the admixture was stirred until dissolution of the prepolymer was complete. This occurred in about 15 to about 30 minutes.
Dry DMAC (350.0 grams), ethanolamine (4.86 -grams), ethylene diamine (4.77 grams) and dimethylethylene diamine (0.92 grams) were combined together in a separate vessel, mixed at room - --temperature, and then added rapidly to the prepolymer solution with vigorous agitation. Thereafter, the prepolymer solution containing the additives was maintained at a temperature of approximately 80 to 85C. for a time period of about 2 to about 3-1/2 hours.
i 2 :
The resultant polyurethane resin solution was colorless and viscous, and was cast into a visually clear film.
EXAMPLE 3 ~ ;
Polytetramethylene glycol (M.W. 1000; 142.86 grams) and polyethylene glycol (M.W. 1000; 142.86 ~-grams) were combined and melted at a temperature of approximately 40 to 45C. in the reactor under a nitrogen blanket. 4,4'-Diphenylmethane diisocyanate (117.86 grams) was added to the reactor under agitation. The resulting mixture was stirred, heated ~ ~;
to a temperature of about 60 to 65C. and maintained within this temperature range for a time period of -~
about 1 to about 1-1/2 hours to produce a molten -~
prepolymer. Dry dimethylacetamide (DMAC; 857.59 grams) was then added to the molten prepolymer and the admixture was stirred until dissolution of the -prepolymer was complete. This occurred in about 15 ~ -to about 30 minutes.
Dry DMAC (350.0 grams), ethanolamine (4.47 grams), ethylene diamine (4.49 grams) and dimethylethylene diamine (0.84 grams) were combined -together in a separate vessel, mixed at room temperature, and then added rapidly to the prepolymer 25 solution with vigorous agitation. Thereafter, the - --~
prepolymer solution containing these additives was - `
maintained at a temperature of approximately 80 to 85C. for a time period of about 2 to about 3-1/2 hours.
The resultant polyurethane resin solution was colorless and viscous, and was cast into a visually clear film.
Polytetramethylene glycol (M.W. 1000; 71.43 grams) and polyethylene glycol (M.W. 1000; 214.29 ... : . :~ ; .:
': .~ ., :. .::
~- ~ 3 ~ 1~ P-~ 2 grams) were combined and melted at approximately 40 to 45C. in the reactor under a nitrogen blanket.
.; . - :
' ~ ~. .,~..,': ' J ~ 2 isophorone diisocyanate, m-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 1,5-naphthylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, l,10-decamethylene diisocyanate and - 1,4-cyclohexylene diisocyanate. The preferred -diisocyanates are aromatic in nature, e.g., TDI, MDI, and the like.
The polyalkylene ether glycols that constitute an admixture suitable for the present purposes are chosen so that the repeating alkyleneoxy segments in each of the glycols is of a different -size. The polyalkylene ether glycol having the relatively shorter alkyleneoxy segments preferably ~-has a number average molecular weight in the range of about 1,000 to about 3,000. The polyalkylene ether glycol having the relatively longer alkyleneoxy segments has a number average molecular weight of at least about 800, and the molecular weight can be as high as about 4,000. Preferably the polyalkylene ether glycols that constitute the admixture have substantially the same number average molecular -weight, more preferably a number average molecular weight of about 2,000.
It is also preferable that the polyalkylene ;-ether glycol having the relatively shorter alkyleneoxy segments constitutes at least about 10 --mole percent of the admixture, and the polyalkylene ether glycol having the relatively longer alkyleneoxy segments constitutes a major portion of the admixture, i.e., more than about 50 mole percent of ;
the glycol admixture. Particularly preferred are polyalkylene ether glycol admixtures containing about 25 mole percent of the glycol having the relatively shorter alkyleneoxy segments and about 75 mole percent of the glycol having the relatively longer alkyleneoxy segments.
~ ` ~ 3 3 ~
Illusteative of the polyalkylene ether glycol admixtures useful in the formation of the -prepolymer are polyethylene glycol with polytetramethylene glycol, polypropylene glycol with ~- -S 1,2-polydimethylethylene glycol, polydecamethylene -glycol with polyethylene glycol, and the like. A
preferred polyalkylene ether glycol admixture is that of polytetramethylene glycol and polyethylene -glycol. For films suitable for use in wound dressings, a preferred combination is polytetramethylene glycol (PTMEG) having a number ~ ~-average molecular weight of about 2,000 and polyethylene glycol (PEG) having a number average molecular weight of about 2,000 in a mole ratio of-about 1:1 to about 3:1, respectively, for an optimum degree of hydrophilicity in combination with a desired degree of hydrogen bonding in the produced film.
The formation of the isocyanate terminated 20 prepolymer occurs in a liguid state and at a ~` -temperature of about 50 to about 100C., preferably at about 80 to about 85C. The reaction time is ! ;'',~" ~'.~,' ," ' about 1 to about 1-1/2 hours. Although it is preferred that this reaction take place in a melt, it 25 may equally well be carried out in solution using a suitable solvent sucb as dimethylacetamide (~ AC), ~,.,!,,.,' ,, ~',Y,'~
; dimethylformamide ~ F), tetrahydrofuran (THF), or ; `
the like. The preferred solvent is ~ C. If the reaction takes place in the melt, the prepolymer is 30 then dissolved in the aforementioned solvent.
When dissolution is complete, the prepolymer : i8 ch~in extended to the desired number average ` ~
-~ ~ molecular weight, usually in the range of about ~ ; -i~; , 20,000 to about 260,000, using a difunctional chain 35 extender, preferably an admixture of such chain ;; i~
extenders. In the chain extender admixture at least 3 ~
-13- ;
one chain extender is an aliphatic diamine and at least one other chain extender is an alkanolamine.
Suitable aliphatic diamine chain extenders include ethylene diamine, m-xylylene diamine, propylene diamine, and the like. Suitable alkanolamine chain extenders include ethanolamine, ~ -and the like. Other chain extenders such as diols can also be present. A preferred combination of ~
chain extenders is ethylene diamine with -ethanolamine. The mol ratio of ethylene diamine to ethanolamine can be about 0.25:0.~5 to about 0.75:0.25. ;~ ~ -A preferred monofunctional amine chain control agent includes at least one member of the group consisting of 3,3-dimethylbutylamine, dimethylcyclohexylamine, 1,5-dimethylhexylamine, and ; -~ ~-dimethylethylene diamine. The amount of the chain control agent is dependent on the amount of NCO-groups present in the prepolymer and the desired 20 chain extension. In any particular case, sufficient ,~
chain control agent is added to react with the ;~
remaining NCO-groups present after the desired degree -of chain extension has been achieved.
The chain extender and chain control agent 25 are dissolved in a suitable solvent such as DMAC, ~?-`
DMF, THF, etc. as mentioned hereinabove.
The prepolymer is then reacted with the ch`ain extender and chain control agent solution to obtain the desired chain extension of the prepolymer. This reaction is usually carried out at a temperature of about 80 to about 85C. over a time period of about 2 to about 3-1/2 hours. A ` ~
polyurethane-urea resin solution is thus produced. ~ -Optionally, the hydrophilicity of the polyurethane resin may be enhanced by the use of an .` ~.: ~;
:
~.~3~ ~2 extrinsic wetting agent such as polyvinylpyrrolidone or the like, which is added to the polymerized resin prior to film forming. The amount of polyvinylpyrrolidone utilized for this purpose is ~ ~
about 1 to about S0 percent by weight of the ~ ~ -composition.
The following examples illustrate typical ~ ~ ~
preparations of polyurethane-ureas embodying the - ~ -present invention. In these examples, the -~
polyurethane-urea prepolymer was prepared in a suitable reactor vessel equipped with an agitator, a --temperature sensor, a temperature control and a nitrogen source and bleed. The chain extenders and - - . --chain control agents were admixed in a separate - ;~
mixing vessel and the resulting admixture was then added to the reactor vessel.
Polytetramethylene glycol (M.W. 1000; 257.14 grams) and polyethylene glycol (M.W. 1000; 28.57 grams) were combined and melted at a temperature of approximately 40 to 45C. in the reactor under a nitrogen blanket. 4,4'-Diphenylmethane diisocyanate ; ` ~
(117.86 grams) was added to the reactor under ~` `~ ` ^
agitation. The resulting mixture was stirred, heated to a temperature of about 60 to 65C. and maintained within this temperature range for a time period of about 1 to about 1-1/2 hours to produce a molten prepolymer. Dry dimethylacetamide (DMAC; 857.59 grams) was then added to the molten prepolymer and the admixture was stirred until dissolution of the prepolymer was complete. This occurred in about 15 to about 30 minutes. ` `~
Dry DMAC (850.0 grams), ethanolamine (4.68 grams), ethylene diamine (4.60 grams) and dimethylethylene diamine (0.88 grams) were combined ~. ~3 oJ~ 2 in a separate vessel, mixed at room temperature, and ~hen added rapidly to the prepolymer solution with vigorous agitation. Thereafter, the prepolymer solution containing these additives was maintained at a temperature of approximately 80 to 85 ~C. for a time period of about 2 to about 3-1/2 hours.
The resultant polyurethane resin solution was colorless and viscous, and was cast into a visually clear film. ~ -Polytetramethylene glycol (M.W. 1000; 214.29 grams) and polyethylene glycol (M.W. 1000; 71.43 grams) were combined and melted at a temperature of approximately 40 to 45C. in the reactor under a nitrogen blanket. 4,4'-Diphenylmethane diisocyanate (117.86 grams) was added to the reactor under agitation. The resulting mixture was stirred, heated to a temperature of about 60 to 65C. and maintained within this temperature range for a time period of about 1 to about 1-1/2 hours. Dry dimethylacetamide (DMAC; 857.59 grams) was then added to the molten prepolymer and the admixture was stirred until dissolution of the prepolymer was complete. This occurred in about 15 to about 30 minutes.
Dry DMAC (350.0 grams), ethanolamine (4.86 -grams), ethylene diamine (4.77 grams) and dimethylethylene diamine (0.92 grams) were combined together in a separate vessel, mixed at room - --temperature, and then added rapidly to the prepolymer solution with vigorous agitation. Thereafter, the prepolymer solution containing the additives was maintained at a temperature of approximately 80 to 85C. for a time period of about 2 to about 3-1/2 hours.
i 2 :
The resultant polyurethane resin solution was colorless and viscous, and was cast into a visually clear film.
EXAMPLE 3 ~ ;
Polytetramethylene glycol (M.W. 1000; 142.86 grams) and polyethylene glycol (M.W. 1000; 142.86 ~-grams) were combined and melted at a temperature of approximately 40 to 45C. in the reactor under a nitrogen blanket. 4,4'-Diphenylmethane diisocyanate (117.86 grams) was added to the reactor under agitation. The resulting mixture was stirred, heated ~ ~;
to a temperature of about 60 to 65C. and maintained within this temperature range for a time period of -~
about 1 to about 1-1/2 hours to produce a molten -~
prepolymer. Dry dimethylacetamide (DMAC; 857.59 grams) was then added to the molten prepolymer and the admixture was stirred until dissolution of the -prepolymer was complete. This occurred in about 15 ~ -to about 30 minutes.
Dry DMAC (350.0 grams), ethanolamine (4.47 grams), ethylene diamine (4.49 grams) and dimethylethylene diamine (0.84 grams) were combined -together in a separate vessel, mixed at room temperature, and then added rapidly to the prepolymer 25 solution with vigorous agitation. Thereafter, the - --~
prepolymer solution containing these additives was - `
maintained at a temperature of approximately 80 to 85C. for a time period of about 2 to about 3-1/2 hours.
The resultant polyurethane resin solution was colorless and viscous, and was cast into a visually clear film.
Polytetramethylene glycol (M.W. 1000; 71.43 grams) and polyethylene glycol (M.W. 1000; 214.29 ... : . :~ ; .:
': .~ ., :. .::
~- ~ 3 ~ 1~ P-~ 2 grams) were combined and melted at approximately 40 to 45C. in the reactor under a nitrogen blanket.
4,4'-Diphenylmethane diisocyanate (117.86 grams) was added to the reactor under agitation. The resulting mixture was stirred, heated to a temperature of about 60 to 65C. and maintained within this temperature range for a time period of about 1 to about 1-1/2 hours to produce a molten prepolymer. Dry dimethylacetamide (DMAC; 857.61 grams) was then added to the molten prepolymer and the admixture was stirred until dissolution of the prepolymer was complete. This occurred in about 15 to about 30 minutes.
Dry DMAC (350.0 grams), ethanolamine (4.34 grams), ethylene diamine (4.27 grams) and dimethylethylene diamine (0.82 grams) were combined - ~ -in a separate vessel, mixed at room temperature, and then added rapidly to the prepolymer solution with vigorous agitation. Thereafter, the prepolymer solution containing these additives was maintained at a temperature of approximately 80 to 85C. for a time period of about 2 to about 3-1/2 hours.
The resultant polyurethane resin solution was colorless and viscous, and was cast into a visually clear film.
In a manner similar to that of the foregoing examples, additional polyurethane-ureas embodying this invention were prepared and the physical ~ .
properties thereof noted. The amounts of reactants used and the properties noted are set forth in the Tables hereinbelow.
. . - .
~' ; ".'.
..
~ 3 ~
TABLE I
CCMPO6ITION AND P9YSICAL ClPUU4CrERISTICS OF THE PREPOLYMER
~)IE
MWT MWT CHAIN ~ISC0SITY FRACTION
5AMPLE % ~ PSG2 PIMEG3 EXI~NSION %NKD5 (CPS) EDA
001 75 1000 1000 40 1.090 3400 0.25 002 50 1000 1000 10 1.050 390 0.25 003 25 1000 1000 20 1.070 2460 0.25 004 75 1000 1000 10 1.020 900 0.75 10 005 25 1000 1000 40 1.070 14480 0.75 006 50 1000 1000 20 1.040 5010 0.75 007 75 1000 1000 20 0.980 3060 0.50 008 50 1000 1000 40 1.040 13680 0.50 009 25 1000 1000 10 1.050 2160 0.50 15 010 25 1000 650 20 1.300 2810 0.50 011 50 1000 650 10 1.190 890 0.50 012 75 1000 650 40 1.080 16840 0.50 013 75 1000 650 10 1.090 630 0.25 014 25 1000 650 40 1.280 11320 0.75 20 015 50 1000 650 20 1.190 2610 0.25 016 50 1000 650 40 1.220 3970 0.50 017 25 1000 650 40 1.340 5100 0.25 018 25 1000 650 10 1.340 1590 0.75 019 50 1000 650 40 1.190 9640 0.75 25 020 75 1000 650 20 1.120 1240 0.75 021 50 1000 2000 20 0.820 1450 0.50 022 25 1000 2000 40 0.780 8220 0.50 023 75 1000 2000 10 0.910 790 0.50 024 75 1000 2000 40 0.930 1600 0.75 30 025 50 1000 2000 10 0.860 6300 0.75 026 25 1000 2000 10 0.740 1880 0.25 027 50 1000 1000 20 1.060 3560 0.50 028 25 1000 2000 20 0.920 1320 0.75 029 50 1000 1000 20 1.060 1530 0.50 35 030 75 1000 2000 20 0.790 4350 0.25 ", .. .
. , ~ , :`~ ' ` . :"-.,, -' '~-",- ': :'`: ~.'- ':-` ,:
, :` :, - " ,,:, - ' ':
, , .
031 50 1000 1000 20 0.900 1410 0.50 03~ 50 1000 2000 40 0.800 10060 0.25 033 50 1000 1000 20 1.070 2860 0.50 034 25 600 650 10 1.420 690 0.25 035 50 600 1000 10 1.110 7000 0.50 036 75 600 2000 10 0.900 1780 0.75 -~
037 50 600 650 40 1.260 2770 0.25 038 25 600 1000 20 1.150 4590 0.50 039 75 600 1000 40 1.110 7440 0.50 040 50 600 2000 20 0.850 7540 0.75 041 25 600 2000 40 0.760 23700 0.75 042 25 600 1000 40 1.190 11440 0.25 043 75 600 650 20 1.310 1180 0.25 044 50 600 2000 40 0.820 6300 0.50 045 50 600 1000 40 1.170 4940 0.75 046 50 600 1000 20 1.130 3900 0.25 047 75 600 1000 10 1.120 2990 0.25 048 75 600 1000 20 1.540 5610 0.75 049 25 600 1000 10 1.130 2130 0.75 050 50 600 2000 10 0.880 1640 0.25 -051 75 600 2000 40 1.010 5090 0.25 052 25 600 2000 20 0.720 5790 0.25 053 25 600 2000 10 0.750 4050 0.50 054 75 600 2000 20 0.950 2780 0.50 055 75 600 650 40 1.070 7510 0.75 056 25 600 650 10 1.370 1690 0.75 057 50 600 650 10 1.270 1480 0.~5 058 ' 50 600 650 20 1.310 2300 0.50 059 75 600 650 10 1.220 620 0.50 1 Mole percent of polyethylene glycol present based on the polyalkylene glycols present in the composition.
2 Number average molecular weight of the polyethylene glycol. -3 Nhrdber average molecular weight of the polytetramethylene glycol.
4 Number of folds by which the prepolymer was chain extended.
Dry DMAC (350.0 grams), ethanolamine (4.34 grams), ethylene diamine (4.27 grams) and dimethylethylene diamine (0.82 grams) were combined - ~ -in a separate vessel, mixed at room temperature, and then added rapidly to the prepolymer solution with vigorous agitation. Thereafter, the prepolymer solution containing these additives was maintained at a temperature of approximately 80 to 85C. for a time period of about 2 to about 3-1/2 hours.
The resultant polyurethane resin solution was colorless and viscous, and was cast into a visually clear film.
In a manner similar to that of the foregoing examples, additional polyurethane-ureas embodying this invention were prepared and the physical ~ .
properties thereof noted. The amounts of reactants used and the properties noted are set forth in the Tables hereinbelow.
. . - .
~' ; ".'.
..
~ 3 ~
TABLE I
CCMPO6ITION AND P9YSICAL ClPUU4CrERISTICS OF THE PREPOLYMER
~)IE
MWT MWT CHAIN ~ISC0SITY FRACTION
5AMPLE % ~ PSG2 PIMEG3 EXI~NSION %NKD5 (CPS) EDA
001 75 1000 1000 40 1.090 3400 0.25 002 50 1000 1000 10 1.050 390 0.25 003 25 1000 1000 20 1.070 2460 0.25 004 75 1000 1000 10 1.020 900 0.75 10 005 25 1000 1000 40 1.070 14480 0.75 006 50 1000 1000 20 1.040 5010 0.75 007 75 1000 1000 20 0.980 3060 0.50 008 50 1000 1000 40 1.040 13680 0.50 009 25 1000 1000 10 1.050 2160 0.50 15 010 25 1000 650 20 1.300 2810 0.50 011 50 1000 650 10 1.190 890 0.50 012 75 1000 650 40 1.080 16840 0.50 013 75 1000 650 10 1.090 630 0.25 014 25 1000 650 40 1.280 11320 0.75 20 015 50 1000 650 20 1.190 2610 0.25 016 50 1000 650 40 1.220 3970 0.50 017 25 1000 650 40 1.340 5100 0.25 018 25 1000 650 10 1.340 1590 0.75 019 50 1000 650 40 1.190 9640 0.75 25 020 75 1000 650 20 1.120 1240 0.75 021 50 1000 2000 20 0.820 1450 0.50 022 25 1000 2000 40 0.780 8220 0.50 023 75 1000 2000 10 0.910 790 0.50 024 75 1000 2000 40 0.930 1600 0.75 30 025 50 1000 2000 10 0.860 6300 0.75 026 25 1000 2000 10 0.740 1880 0.25 027 50 1000 1000 20 1.060 3560 0.50 028 25 1000 2000 20 0.920 1320 0.75 029 50 1000 1000 20 1.060 1530 0.50 35 030 75 1000 2000 20 0.790 4350 0.25 ", .. .
. , ~ , :`~ ' ` . :"-.,, -' '~-",- ': :'`: ~.'- ':-` ,:
, :` :, - " ,,:, - ' ':
, , .
031 50 1000 1000 20 0.900 1410 0.50 03~ 50 1000 2000 40 0.800 10060 0.25 033 50 1000 1000 20 1.070 2860 0.50 034 25 600 650 10 1.420 690 0.25 035 50 600 1000 10 1.110 7000 0.50 036 75 600 2000 10 0.900 1780 0.75 -~
037 50 600 650 40 1.260 2770 0.25 038 25 600 1000 20 1.150 4590 0.50 039 75 600 1000 40 1.110 7440 0.50 040 50 600 2000 20 0.850 7540 0.75 041 25 600 2000 40 0.760 23700 0.75 042 25 600 1000 40 1.190 11440 0.25 043 75 600 650 20 1.310 1180 0.25 044 50 600 2000 40 0.820 6300 0.50 045 50 600 1000 40 1.170 4940 0.75 046 50 600 1000 20 1.130 3900 0.25 047 75 600 1000 10 1.120 2990 0.25 048 75 600 1000 20 1.540 5610 0.75 049 25 600 1000 10 1.130 2130 0.75 050 50 600 2000 10 0.880 1640 0.25 -051 75 600 2000 40 1.010 5090 0.25 052 25 600 2000 20 0.720 5790 0.25 053 25 600 2000 10 0.750 4050 0.50 054 75 600 2000 20 0.950 2780 0.50 055 75 600 650 40 1.070 7510 0.75 056 25 600 650 10 1.370 1690 0.75 057 50 600 650 10 1.270 1480 0.~5 058 ' 50 600 650 20 1.310 2300 0.50 059 75 600 650 10 1.220 620 0.50 1 Mole percent of polyethylene glycol present based on the polyalkylene glycols present in the composition.
2 Number average molecular weight of the polyethylene glycol. -3 Nhrdber average molecular weight of the polytetramethylene glycol.
4 Number of folds by which the prepolymer was chain extended.
5 Percent NK0-groups in the prepolymer.
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TABLE III
TENSILE STRENGTH AT BREAK (kg/mm ) SAMPLE DRY WET DIFFERENCEl PERCENT CHANGE
001 0.43 0.45-0.02 -4.65 002 0.28 0.260.02 7.14 003 1.67 1.650.02 1.20 004 0.69 0.360.33 47.83 005 5.30 4.810.49 9.25 006 3.10 1.921.18 38.06 007 0.55 0.57-0.02 -3.64 008 5.28 6.70-1.42 -26.89 009 2.38 3.40-1.02 -42.86 010 2.02 1.090.93 46.04 011 0.51 0.69-0.18 -35.29 012 1.75 1.510.24 13.71 013 0.11 0.080.03 27.27 014 6.10 3.432.67 43.77 015 0.70 0.520.18 25.71 016 1.78 ~.321.46 82.02 017 3.95 1.772.18 55.19 018 1.75 1.660.09 5.14 019 3.92 3.97-0.05 -1.28 020 0.77 0.93-0.16 -20.78 021 0.93 1.52-0.59 -63.44 022 3.33 3.67-0.34 -10.21 023 0.35 0.62-0.27 -77.14 024 1.52 1.74-0.22 -14.47 025 2.19 1.990.20 9.13 026 1.80 2.11-0.31 -17.22 027 1.35 1.61-0.26 -19.26 028 2.25 2.110.14 6.22 029 0.78 0.81-0.03 -3.85 030 0.80 2.54-1.74 -217.50 031 1.49 1.470.02 1.34 032 3.93 3.670.26 6.62 033 1.28 1.32-0.04 -3.13 ~:
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034 2.54 0.56 1.98 77.95 035 1.32 0.76 0.56 42.42 -036 2.57 2.28 0.29 11.28 037 7.40 2.60 4.80 64.86 038 4.35 3.61 0.74 17.01 -039 6.94 1.33 5.61 80.84 040 5.20 4.43 0.77 14.81 041 5.44 4.50 0.94 17.28 042 5.61 4.74 0.87 15.51 043 1.56 0.44 1.12 71.79 044 3.73 4.27 0.54 14.48 045 4.00 2.58 1.42 35.50 046 3.60 2.25 1.35 37.50 -~-047 1.83 1.00 0.83 45.36 --048 6.49 3.47 3.02 46.53 049 2.69 3.43 -0.74 -27.51 050 2.40 1.30 1.10 45.83 051 2.51 1.64 0.87 34.66 052 2.58 3.53 -0.95 -36.82 ~
053 2.49 2.91 -0.42 -16.87 ~ - -054 2.87 2.13 0.74 25.78 -055 6.45 2.29 4.16 64.50 056 4.38 2.96 1.42 32.42 057 4.04 1.51 2.53 62.62 OS8 4.13 1.74 2.39 ' 57.87 059 0.00 0.46 -0.46 0.00 1 Difference - Dry - Wet 30100 x Difference ~ u 2 Percent Change =
Dry ; p~sitive numbers indicate a decrease in tensile strength after wetting with watert negative numbers indicate an increase in tensile strength after wetting with water.
- .
TABLE IV
PERCENT ELONGATION AT BREAR
SAMPLE DRYWET DIFFERENCEl PERCENT CHANGE2 ~ -0011035.0764.0271.0 26.2 002200.0152.0 48.0 24.0 0031000.0902.0 98.0 9.8 004475.0210.0 265.0 55.8 005875.0855.0 20.0 2.3 0061090.0750.0340.0 31.2 007890.0726.0 164.0 18.4 008775.0793.0 -18.0 -2.3 009745.0782.0 -37.0 -5.0 010650.0400.0 250.0 38.5 011480.0634.0 -154.0 -32.1 0121300.0948.0352.0 27.1 013180.091.0 89.0 49.4 014775.0693.0 82.0 10.6 0151040.0574.0466.0 44.8 016995.0826.0 169.0 17.0 017830.0694.0 136.0 16.4 018620.0673.0 -53.0 -8.5 019900.0850.0 50.0 5.6 020625.0632.0 -7.0 021860.0850.0 10.0 1.2 0221015.0941.0 74.0 7.3 023575.0681.0 -106.0 -18.4 024950.0853.0 97.0 10.2 0251005.0838.0167.0 16.6 0261250.01109.0141.0 11.3 0271075.0883.0192.0 17.9 028785.0687.0 98.0 12.5 029895.0742.0 153.0 17.1 0302370.01390.0980.0 41.4 0311162~01021.0141.0 12.1 0321100.01057.043.0 3,9 033sas.o~75.0 110.0 11.2 ~, -' ' ; ' ~ 3 3 ~
034 630.0 266.0 364.0 57.8 035 830.0 559.0 271.0 32.7 036 874.0 771.0 103.0 11.8 037 690.0 711.0 -21.0 -3.0 038 795.0 690.0 105.0 13.2 - 039 875.0 562.0 313.0 35.8 040 910.0 818.0 92.0 10.1 041 885.0 801.0 84.0 9.5 042 835.0 828.0 7.0 0.8 043 710.0 234.0 476.0 67.0 044 910.0 945.0 -35.0 -3.8 045 720.0 697.0 23.0 3.2 046 925.0 832.0 93.0 10.1 047 1175.0 868.0 307.0 26.1 048 670.0 591.0 79.0 11.8 049 815.0 786.0 29.0 3.6 050 1034.0 831.0 203.0 19.6 051 1260.0 881.0 379.0 30.1 052 1215.0 1124.0 91.0 7.5 053 1045.0 930.0 107.0 10.2 054 945.0 821.0 124.0 13.1 055 725.0 683.0 42.0 5.8 056 605.0 673.0 -68.0 -11.2 057 670.0 588.0 82.0 12.2 058 655.0 652.0 3.0 0.5 059 0.0 236.0 -236.0 O.o - .. .. ..
r, 1~ Difference = Dry - Wet 100 x Difference 2 Percent Change = -~ -Dry ; .. ... -~
positive numbers indicate a decrease in percent elongation after wetting with water; negative numbers `~
indicate an increase in percent elongation after wetting with water.
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~. '~ . ," ~ .' -26- ~ -The polyurethane resins of the present invention are particularly well suited for the -manufacture of components for wound dressings and closures inasmuch as the high level of hydrophilicity, and therefore the absorption capacity, inherent in these polymers are important properties in this regard. Environmental wound dressings rely upon being able to absorb wound exudate while maintaining a moist microenvironment at - -the wound site to obtain optimum healing.
Wounds or injuries to the skin generate ~ -varying amounts of discharge fluid known as exudate.
Modern wound care management techniques seek to maintain the moisture level at the wound site at a relatively high level. But, excessive build up of exudate is unacceptable. The present polyurethane -resins can be tailored to have properties, when cast ~ -into films, so as to absorb excess exudate while - -maintaining a high level of moisture at the wound -~
site.
In addition, the chemical, physical and - ;
mechanical properties of the present polyurethanes allow their use in a wide variety of other applications. The material's wet strength properties and selective permeability towards water vapor and other gases are particularly significant in this regard.
The present polymers may be coated onto textile substrates to provide breathability while retaining resistance to liquids, particularly water.
In a similar fashion, selectively permeable films may -be fabricated for use as containers for desiccants ;
and other absorbent agents (e.g., crystalline ~ -aluminosilicates, silica gel, etc.). The use of these films in this application has the advantage of .' .:' . ' '''~`:~' -' preventing particulate contamination of the article into which the desiccant package will be placed and reduction of efficiency due to nonspecific absorption. Films of these materials are also suitable for packaging. Their selective gaseous and moisture vapor transmission properties allow their application in the area of environmental packaging.
These polymers are biocompatible and noncytotoxic which makes them ideal for medical and biological applications. These properties enable the present polymers to be used as substrates for the support, growth and attachment of biological materials. They are of particular utility in the area of cell growth substrates for mammalian cell culture. The attachment and growth of cells to structures manufactured from these polymers makes - ~ -them ideal for use in bioreactor systems for large scale production of cell lines, etc. Immobilization of proteins, enzymes and other biologically active materials, while maintaining biological activity, allows the use of these polymers as active structures in biosensors and diagnostic test kits. Similarly, nonbiologically active catalysts may be incorporated in these polymers, thereby facilitating their use in -~
numerous chemical and physical processes.
Selective transport of chemical agents -..~
through polymer films fabricated from these polymers can be used in the areas of filtration, separation and purification of liquids and gases. These properties are also of use in the area of drug delivery over an extended time period where ~b therapeutic agents are delivered from a reservoir across a polymer membrane into the physiological environment.
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It is also envisaged that these polymers may be used as specialty coatings to inhibit corrosion of -metallic surfaces while facilitating selective ~ -gaseous transport.
The present segmented polyether polyurethane resins are also useful for the fabrication of vascular grafts, ureters and other biocompatible - -elements.
This invention has been described in terms ~
10 of specific embodiments set forth in detail, but it ~-should be understood that these are by way of illustration only and that the invention is not necessarily limited thereto. Modifications and ~ -variations will be apparent from this disclosure and may be resorted to without departing from the spirit of this invention, as those skilled in the art will ^
readily understand. Accordingly, such variations and modifications of the disclosed products are considered to be within the purview and scope of this : -20 invention and the following claims. ~
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TABLE III
TENSILE STRENGTH AT BREAK (kg/mm ) SAMPLE DRY WET DIFFERENCEl PERCENT CHANGE
001 0.43 0.45-0.02 -4.65 002 0.28 0.260.02 7.14 003 1.67 1.650.02 1.20 004 0.69 0.360.33 47.83 005 5.30 4.810.49 9.25 006 3.10 1.921.18 38.06 007 0.55 0.57-0.02 -3.64 008 5.28 6.70-1.42 -26.89 009 2.38 3.40-1.02 -42.86 010 2.02 1.090.93 46.04 011 0.51 0.69-0.18 -35.29 012 1.75 1.510.24 13.71 013 0.11 0.080.03 27.27 014 6.10 3.432.67 43.77 015 0.70 0.520.18 25.71 016 1.78 ~.321.46 82.02 017 3.95 1.772.18 55.19 018 1.75 1.660.09 5.14 019 3.92 3.97-0.05 -1.28 020 0.77 0.93-0.16 -20.78 021 0.93 1.52-0.59 -63.44 022 3.33 3.67-0.34 -10.21 023 0.35 0.62-0.27 -77.14 024 1.52 1.74-0.22 -14.47 025 2.19 1.990.20 9.13 026 1.80 2.11-0.31 -17.22 027 1.35 1.61-0.26 -19.26 028 2.25 2.110.14 6.22 029 0.78 0.81-0.03 -3.85 030 0.80 2.54-1.74 -217.50 031 1.49 1.470.02 1.34 032 3.93 3.670.26 6.62 033 1.28 1.32-0.04 -3.13 ~:
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034 2.54 0.56 1.98 77.95 035 1.32 0.76 0.56 42.42 -036 2.57 2.28 0.29 11.28 037 7.40 2.60 4.80 64.86 038 4.35 3.61 0.74 17.01 -039 6.94 1.33 5.61 80.84 040 5.20 4.43 0.77 14.81 041 5.44 4.50 0.94 17.28 042 5.61 4.74 0.87 15.51 043 1.56 0.44 1.12 71.79 044 3.73 4.27 0.54 14.48 045 4.00 2.58 1.42 35.50 046 3.60 2.25 1.35 37.50 -~-047 1.83 1.00 0.83 45.36 --048 6.49 3.47 3.02 46.53 049 2.69 3.43 -0.74 -27.51 050 2.40 1.30 1.10 45.83 051 2.51 1.64 0.87 34.66 052 2.58 3.53 -0.95 -36.82 ~
053 2.49 2.91 -0.42 -16.87 ~ - -054 2.87 2.13 0.74 25.78 -055 6.45 2.29 4.16 64.50 056 4.38 2.96 1.42 32.42 057 4.04 1.51 2.53 62.62 OS8 4.13 1.74 2.39 ' 57.87 059 0.00 0.46 -0.46 0.00 1 Difference - Dry - Wet 30100 x Difference ~ u 2 Percent Change =
Dry ; p~sitive numbers indicate a decrease in tensile strength after wetting with watert negative numbers indicate an increase in tensile strength after wetting with water.
- .
TABLE IV
PERCENT ELONGATION AT BREAR
SAMPLE DRYWET DIFFERENCEl PERCENT CHANGE2 ~ -0011035.0764.0271.0 26.2 002200.0152.0 48.0 24.0 0031000.0902.0 98.0 9.8 004475.0210.0 265.0 55.8 005875.0855.0 20.0 2.3 0061090.0750.0340.0 31.2 007890.0726.0 164.0 18.4 008775.0793.0 -18.0 -2.3 009745.0782.0 -37.0 -5.0 010650.0400.0 250.0 38.5 011480.0634.0 -154.0 -32.1 0121300.0948.0352.0 27.1 013180.091.0 89.0 49.4 014775.0693.0 82.0 10.6 0151040.0574.0466.0 44.8 016995.0826.0 169.0 17.0 017830.0694.0 136.0 16.4 018620.0673.0 -53.0 -8.5 019900.0850.0 50.0 5.6 020625.0632.0 -7.0 021860.0850.0 10.0 1.2 0221015.0941.0 74.0 7.3 023575.0681.0 -106.0 -18.4 024950.0853.0 97.0 10.2 0251005.0838.0167.0 16.6 0261250.01109.0141.0 11.3 0271075.0883.0192.0 17.9 028785.0687.0 98.0 12.5 029895.0742.0 153.0 17.1 0302370.01390.0980.0 41.4 0311162~01021.0141.0 12.1 0321100.01057.043.0 3,9 033sas.o~75.0 110.0 11.2 ~, -' ' ; ' ~ 3 3 ~
034 630.0 266.0 364.0 57.8 035 830.0 559.0 271.0 32.7 036 874.0 771.0 103.0 11.8 037 690.0 711.0 -21.0 -3.0 038 795.0 690.0 105.0 13.2 - 039 875.0 562.0 313.0 35.8 040 910.0 818.0 92.0 10.1 041 885.0 801.0 84.0 9.5 042 835.0 828.0 7.0 0.8 043 710.0 234.0 476.0 67.0 044 910.0 945.0 -35.0 -3.8 045 720.0 697.0 23.0 3.2 046 925.0 832.0 93.0 10.1 047 1175.0 868.0 307.0 26.1 048 670.0 591.0 79.0 11.8 049 815.0 786.0 29.0 3.6 050 1034.0 831.0 203.0 19.6 051 1260.0 881.0 379.0 30.1 052 1215.0 1124.0 91.0 7.5 053 1045.0 930.0 107.0 10.2 054 945.0 821.0 124.0 13.1 055 725.0 683.0 42.0 5.8 056 605.0 673.0 -68.0 -11.2 057 670.0 588.0 82.0 12.2 058 655.0 652.0 3.0 0.5 059 0.0 236.0 -236.0 O.o - .. .. ..
r, 1~ Difference = Dry - Wet 100 x Difference 2 Percent Change = -~ -Dry ; .. ... -~
positive numbers indicate a decrease in percent elongation after wetting with water; negative numbers `~
indicate an increase in percent elongation after wetting with water.
'," ' ~
`" Y' ,' ."'. '' ;'~`' ~,~' / ~
r ~
~. '~ . ," ~ .' -26- ~ -The polyurethane resins of the present invention are particularly well suited for the -manufacture of components for wound dressings and closures inasmuch as the high level of hydrophilicity, and therefore the absorption capacity, inherent in these polymers are important properties in this regard. Environmental wound dressings rely upon being able to absorb wound exudate while maintaining a moist microenvironment at - -the wound site to obtain optimum healing.
Wounds or injuries to the skin generate ~ -varying amounts of discharge fluid known as exudate.
Modern wound care management techniques seek to maintain the moisture level at the wound site at a relatively high level. But, excessive build up of exudate is unacceptable. The present polyurethane -resins can be tailored to have properties, when cast ~ -into films, so as to absorb excess exudate while - -maintaining a high level of moisture at the wound -~
site.
In addition, the chemical, physical and - ;
mechanical properties of the present polyurethanes allow their use in a wide variety of other applications. The material's wet strength properties and selective permeability towards water vapor and other gases are particularly significant in this regard.
The present polymers may be coated onto textile substrates to provide breathability while retaining resistance to liquids, particularly water.
In a similar fashion, selectively permeable films may -be fabricated for use as containers for desiccants ;
and other absorbent agents (e.g., crystalline ~ -aluminosilicates, silica gel, etc.). The use of these films in this application has the advantage of .' .:' . ' '''~`:~' -' preventing particulate contamination of the article into which the desiccant package will be placed and reduction of efficiency due to nonspecific absorption. Films of these materials are also suitable for packaging. Their selective gaseous and moisture vapor transmission properties allow their application in the area of environmental packaging.
These polymers are biocompatible and noncytotoxic which makes them ideal for medical and biological applications. These properties enable the present polymers to be used as substrates for the support, growth and attachment of biological materials. They are of particular utility in the area of cell growth substrates for mammalian cell culture. The attachment and growth of cells to structures manufactured from these polymers makes - ~ -them ideal for use in bioreactor systems for large scale production of cell lines, etc. Immobilization of proteins, enzymes and other biologically active materials, while maintaining biological activity, allows the use of these polymers as active structures in biosensors and diagnostic test kits. Similarly, nonbiologically active catalysts may be incorporated in these polymers, thereby facilitating their use in -~
numerous chemical and physical processes.
Selective transport of chemical agents -..~
through polymer films fabricated from these polymers can be used in the areas of filtration, separation and purification of liquids and gases. These properties are also of use in the area of drug delivery over an extended time period where ~b therapeutic agents are delivered from a reservoir across a polymer membrane into the physiological environment.
. . ~
~ -: . -~-: , -, .: ~
: ,-, : :- : ::
.~: . ~ '' ' ' , ............................................... ! .
~ 3 ~ ~ ~ $ 2 - ~ ~
It is also envisaged that these polymers may be used as specialty coatings to inhibit corrosion of -metallic surfaces while facilitating selective ~ -gaseous transport.
The present segmented polyether polyurethane resins are also useful for the fabrication of vascular grafts, ureters and other biocompatible - -elements.
This invention has been described in terms ~
10 of specific embodiments set forth in detail, but it ~-should be understood that these are by way of illustration only and that the invention is not necessarily limited thereto. Modifications and ~ -variations will be apparent from this disclosure and may be resorted to without departing from the spirit of this invention, as those skilled in the art will ^
readily understand. Accordingly, such variations and modifications of the disclosed products are considered to be within the purview and scope of this : -20 invention and the following claims. ~
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Claims (10)
1. A hydrophilic but water-insoluble, segmented polyether polyurethane-urea having a wet strength greater than dry strength and capable of forming a visually clear film; said polyurethane-urea being the reaction product of a prepolymer derived from a stoichiometric excess of a diisocyanate reacted with an admixture of polyalkylene ether glycols each having different-length alkyleneoxy segments, and extended with a difunctional amine chain extender.
2. The segmented polyether polyurethane-urea of claim 1 wherein said admixture of polyalkylene ether glycols is constituted by polytetramethylene glycol and polyethylene glycol.
3. The segmented polyether polyurethane-urea of claim 2 wherein polytetramethylene glycol and polyethylene glycol are present in the admixture in a mole ratio of about 3:1.
4. The segmented polyether polyurethane-urea of claim 1 wherein said admixture of polyalkylene ether glycols comprises a relatively shorter segment glycol having a molecular weight in the range of about 1000 to about 3,000 and a relatively longer segment glycol having molecular weight of at least about 800.
5. The segmented polyether polyurethane-urea of claim 1 wherein said glycols have a number average molecular weight of about 2000.
6. The segmented polyether polyurethane-urea of claim 1 wherein said glycols have substantially the same number average molecular weight.
7. The segmented polyether polyurethane-urea of claim 6 wherein the polyalkylene ether glycol having relatively shorter alkyleneoxy segments constitutes at least about 10 mole percent of the admixture and the polyalkylene ether glycol having the relatively longer alkyleneoxy segments constitutes more than about 50 mole percent of the admixture.
8. The segmented polyether polyurethane-urea of claim 1 wherein the polyalkylene ether glycol having relatively longer alkyleneoxy segments and the polyalkylene ether glycol having relatively shorter alkyleneoxy segments are present in a mole ratio of about 3:1, respectively.
9. The segmented polyether polyurethane-urea of claim 8 wherein both of said glycols have substantially the same number average molecular weight.
10. The segmented polyether polyurethane-urea of claim 9 wherein said glycols have a number average molecular weight of about 2,000.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/208,153 US4849458A (en) | 1988-06-17 | 1988-06-17 | Segmented polyether polyurethane |
| US208,153 | 1994-03-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1331062C true CA1331062C (en) | 1994-07-26 |
Family
ID=22773398
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000603098A Expired - Fee Related CA1331062C (en) | 1988-06-17 | 1989-06-16 | Segmented polyether polyurethane |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4849458A (en) |
| EP (1) | EP0348105B1 (en) |
| JP (1) | JP3065629B2 (en) |
| AT (1) | ATE94178T1 (en) |
| AU (1) | AU616288B2 (en) |
| CA (1) | CA1331062C (en) |
| DE (1) | DE68908968T2 (en) |
| ES (1) | ES2058528T3 (en) |
| FI (1) | FI900800A0 (en) |
| IL (1) | IL90609A0 (en) |
| NZ (1) | NZ229578A (en) |
| WO (1) | WO1989012653A1 (en) |
| ZA (1) | ZA894494B (en) |
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-
1988
- 1988-06-17 US US07/208,153 patent/US4849458A/en not_active Expired - Lifetime
-
1989
- 1989-06-13 ZA ZA894494A patent/ZA894494B/en unknown
- 1989-06-14 IL IL90609A patent/IL90609A0/en unknown
- 1989-06-15 ES ES89306083T patent/ES2058528T3/en not_active Expired - Lifetime
- 1989-06-15 WO PCT/US1989/002618 patent/WO1989012653A1/en active Application Filing
- 1989-06-15 NZ NZ229578A patent/NZ229578A/en unknown
- 1989-06-15 AT AT89306083T patent/ATE94178T1/en not_active IP Right Cessation
- 1989-06-15 AU AU38452/89A patent/AU616288B2/en not_active Ceased
- 1989-06-15 EP EP89306083A patent/EP0348105B1/en not_active Expired - Lifetime
- 1989-06-15 JP JP1507147A patent/JP3065629B2/en not_active Expired - Fee Related
- 1989-06-15 DE DE89306083T patent/DE68908968T2/en not_active Expired - Fee Related
- 1989-06-16 CA CA000603098A patent/CA1331062C/en not_active Expired - Fee Related
-
1990
- 1990-02-16 FI FI900800A patent/FI900800A0/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0348105A2 (en) | 1989-12-27 |
| JP3065629B2 (en) | 2000-07-17 |
| AU616288B2 (en) | 1991-10-24 |
| ES2058528T3 (en) | 1994-11-01 |
| WO1989012653A1 (en) | 1989-12-28 |
| DE68908968D1 (en) | 1993-10-14 |
| AU3845289A (en) | 1990-01-12 |
| JPH02504650A (en) | 1990-12-27 |
| DE68908968T2 (en) | 1994-01-05 |
| EP0348105B1 (en) | 1993-09-08 |
| ATE94178T1 (en) | 1993-09-15 |
| EP0348105A3 (en) | 1990-07-04 |
| US4849458A (en) | 1989-07-18 |
| NZ229578A (en) | 1990-12-21 |
| ZA894494B (en) | 1990-03-28 |
| IL90609A0 (en) | 1990-01-18 |
| FI900800A0 (en) | 1990-02-16 |
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| MKLA | Lapsed |