CA1219590A - Modified poly (oxazolidone/urethane) compositions - Google Patents
Modified poly (oxazolidone/urethane) compositionsInfo
- Publication number
- CA1219590A CA1219590A CA000449482A CA449482A CA1219590A CA 1219590 A CA1219590 A CA 1219590A CA 000449482 A CA000449482 A CA 000449482A CA 449482 A CA449482 A CA 449482A CA 1219590 A CA1219590 A CA 1219590A
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- Prior art keywords
- prepolymer
- monomer
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction 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
- C08G18/58—Epoxy resins
-
- 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
- C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
Abstract
MODIFIED POLY(OXAZOLIDONE/
URETHANE) COMPOSITIONS
Abstract of the Disclosure Isocyanate-reactive prepolymers containing at least one terminal epoxide group with an associated secondary hydroxy group and grafted thereto a polymeric moiety derived from polymerizing an ethylenically un-saturated monomer are disclosed. When reacted with isocyanate, these prepolymers form thermoset composi-tions which comprise oxazolidone groups in the backbone that are separated by ester linkages, urethane linkages in side chains attached to the backbone, and polymeric moieties derived from one or more ethylenically unsatur-ated monomer grafted to the polymer backbone.
* * * * * *
URETHANE) COMPOSITIONS
Abstract of the Disclosure Isocyanate-reactive prepolymers containing at least one terminal epoxide group with an associated secondary hydroxy group and grafted thereto a polymeric moiety derived from polymerizing an ethylenically un-saturated monomer are disclosed. When reacted with isocyanate, these prepolymers form thermoset composi-tions which comprise oxazolidone groups in the backbone that are separated by ester linkages, urethane linkages in side chains attached to the backbone, and polymeric moieties derived from one or more ethylenically unsatur-ated monomer grafted to the polymer backbone.
* * * * * *
Description
l~L~S~10 MODIFIED POL~(OXAZOLIDON~/
URETHANE) COMPOSITIONS
.
Backqround of the Invention . . , Field of the Invention The present invention relates to modified poly-(oxazolidone/urethane) compositions.
Déscription of the Prior Art The prior art illustrates the sequential reactionof polyol, acid anhydride and polyepoxy compound to form a prepolymer which is then cured. For instance, 10 in U.S. Patent No. 3,576,903 to G. L. Groff the first step of the reaction to form the prepolymer involves reaction of acid anhydride and polyhydroxy compound to ~ield an acid-terminated polymer. This acid-terminated polymer is then reacted with an epoxy compound such that at least two epoxide equivalent weights are present for each carboxyl equivalent weight of acid-terminated poly-mer. Groff then teaches curing of this prepolymer by use of an active hydrogen compound known to react with epoxy resins (e.g., polybasic acids, cyclic anhydrides, cyclic dianhydrides, and aromatic or aliphatic diamines) rather than with any compound containing an isocyanate group.
The formation of polymers containing oxazolidone and urethane linkages by reaction o a polyisocyanate with a prepolymer formed by a two step reaction involv-ing (1) reaction of a dicarboxylic acid or anhydride(e.g., phthalic anhydride) and saturated dihydric alcohol ~ollowed by (2) reaction with a diepoxide is described in U.S. Patent No. 3,847,~74 to Y. Murakami et al. The reaction conditions described in this C-6446/6912 ~r~
: . ~
9~
patent yield a prepolymer which contains a hydroxy group at one end and a terminal epoxide group with adjacent secondary, non-terminal hydroxy group at the other end.
A diisocyanate will react with such a prepolymer to form a recurring polymer unit containing urethane and oxazolidone linkages in the backbone and urethane side chains.
Related Application Poly(oxazolidone/urethane) compositions contain-ing oxazolidone linkages in its polymer backbone which are separated by ester linkages and which also contains urethane linkages in a side chain are described in applicants' U.S. Patent 4,386,191.
Such compositions are formed by reaction ; of an epoxy and hydroxy group-containing prepolymer with a polyisocyanate, e.g., a diisocyante. The pre-polymer is formed by reaction of polyol, acid anhydride and diepoxide, preferably in a single step reaction.
The polymer ultimately formed can be used to form ther-~- moset compositions for making molded articles, e.g., by reaction injection molding (RIM~.
Summary of the Present Invention The present invention relates to an improvement of the invention described in the aforementioned related application. It involves the incorporation of a poly-meric segment from an ethylenically unsaturated monomer to modify and improve the physical properties 5~) of the resulting cured polymer, e.g., in a preferred embodiment to increase the crystallinity of the thermo-set making it more resilient and giving it a better heat sag resistance. This latter feature can be important when the product containing ~he thermoset is one which is coated and goes through repetitive heat cycles. Heat sa~ results in loss of shape for the part thereby causing cracking and/or separation of the coating.
The incorporation of the polymeric segment into the modified prepolymer compositions of the present invention can be accomplished in various ways. One way is to first form a copolymer of a major amount of the desired unsaturated monomer and an unsaturated dicar-boxylic acid anhydride and then mix that anhydride-containing copolymer product with polyol, acid anhydrideand polyepoxy compound followed by heating to form the modified prepolymer. Alternatively, the relatively small amount of unsaturated dicarboxylic acid anhydride can be combined with polyol, acid anhydride, polyepoxy compound and heated so that an unsaturated prepolymer is formed which can be mixed with the relatively larger amount of unsaturated monomer, intended as the modifier, andan initiator. Freeradical polymerizationbonds the polymeric segment to the moiety from the unsaturated anhydride. Finally, unsaturated anhydride,and monomer, with initiator~ can both be added to polyol, acid anhydride, and polyepoxy compound and heated The ; molecular weight of the polymeric segment can be adjusted by various known techniques including changes in the ratio of monomer to initiator, the use of a chain transfer agent or modification of the temperature of the free radical polymerization.
C-6~46/6912 ' ' ~ i ~%~L~3~i~0 Reaction of any of the abo~e-described epoxy-con-taining polyols with a polyisocyanate, e.g., diisocyan-ate, yields thermoset compositions. The physical property change~ of such modified compositions, due to the presence of polymer segments derived from the un-saturated monomer component, can be varied due to the type o~ unsaturated monomer chosen. Use of monomers tending to produce relatively rigid polymeric segments (e.g., styrene, methyl methacrylate and/or acryloni-triie) will tend to produce harder, more rigid and tough thermoset compositions. Use of monomers tendingto produce relatively rubbery polymers (e.g., the alkyl acrylates or higher alkyl methacrylates) will produce more impact resistant compositions.
Description of the Preferred Embodiments The modified poly(oxazolidone/urethane)composi-tions of the present invention are formed by reacting a polyisocyanate, e.g., diisocyanate, with a modified prepolymer composition containing a prepolymer having terminal epoxy groups and non-terminal, secondary hydroxy groups~
The modified prepolymer is formed by the incorpor-ation of polymer segments from an unsaturated monomer.
Grafting of the polymeric segments from unsaturated monomer onto the basic prepolymer (which is the subject of U.S. Patent 4,386,191 is accomplished by using a relatively smaller amount of an unsaturated acid anhydride. Generally speaking, the mole ratios of unsaturated monomer to unsaturated anhydride will range from about 700:1 to about 3:1. The amount of unsatur-ated monomer to all the other reactants used to form C-6~46/6912 ! ,.;
5~(~
the basic prepolymer from polyol, anhydride and poly~
epoxy compound will generally be from about 1% to about ~0~ .
As described in U, S. Patent 4,386,191 the basic prepolymer is formed by reaction of polyol, anhydride and diepoxide. Gener-ally speaking, the amounts of these three reactants will be 2 moles of hydroxy as polyol with 2 moles or less of anhydride and 2 moles or more of diepoxide.
Such a prepolymer, as will be described in greater detail below, is modified by the presence of polymeric segments from an ethylenically unsaturated monomer with the segments being bonded thereto by means of a moiety from an unsaturated dicarboxylic acid anhydride.
If desired all reactants ~polyol, anhydride, poly-epoxide, unsaturated anhydride and unsaturated monomer) can be combined with initiator and heated. Alterna-tively, a copolymer of unsaturated anhydride and mono-mer can first be formed followed by its combination with polyol, anhydride,polyepoxy compound, and catalyst, with heating. Finally, polyol, anhydride, unsaturated anhydridel and polyepoxide can be reacted, forming an unsaturated prepolymer which can be combined with un-saturated monomer and initiator and heated.
Representative acid anhydrides which can bechosen to form the basic prepolymer encompass both the aromatic and aliphatic anhydrides including: adipic, glutaric, sebacic, succinic, phthalic, tetrachlorophthalic, and te*rabromophthalic .
Representative polyols include: polyethylene gly-col, polypropylene ylycol, polypropylene triol, 2,4-butanediol, pentaerythritol, 2,3-butanediol, ethylene , .
-- 6 ~
glycol, propylene glycol, and mixtures thereof, tri-methylene glycol, 1,12-dihydroxyoctadecane, 1,4-dihydroxycyclohexane, 2,2-dimethyl-1,3-propanediol,
URETHANE) COMPOSITIONS
.
Backqround of the Invention . . , Field of the Invention The present invention relates to modified poly-(oxazolidone/urethane) compositions.
Déscription of the Prior Art The prior art illustrates the sequential reactionof polyol, acid anhydride and polyepoxy compound to form a prepolymer which is then cured. For instance, 10 in U.S. Patent No. 3,576,903 to G. L. Groff the first step of the reaction to form the prepolymer involves reaction of acid anhydride and polyhydroxy compound to ~ield an acid-terminated polymer. This acid-terminated polymer is then reacted with an epoxy compound such that at least two epoxide equivalent weights are present for each carboxyl equivalent weight of acid-terminated poly-mer. Groff then teaches curing of this prepolymer by use of an active hydrogen compound known to react with epoxy resins (e.g., polybasic acids, cyclic anhydrides, cyclic dianhydrides, and aromatic or aliphatic diamines) rather than with any compound containing an isocyanate group.
The formation of polymers containing oxazolidone and urethane linkages by reaction o a polyisocyanate with a prepolymer formed by a two step reaction involv-ing (1) reaction of a dicarboxylic acid or anhydride(e.g., phthalic anhydride) and saturated dihydric alcohol ~ollowed by (2) reaction with a diepoxide is described in U.S. Patent No. 3,847,~74 to Y. Murakami et al. The reaction conditions described in this C-6446/6912 ~r~
: . ~
9~
patent yield a prepolymer which contains a hydroxy group at one end and a terminal epoxide group with adjacent secondary, non-terminal hydroxy group at the other end.
A diisocyanate will react with such a prepolymer to form a recurring polymer unit containing urethane and oxazolidone linkages in the backbone and urethane side chains.
Related Application Poly(oxazolidone/urethane) compositions contain-ing oxazolidone linkages in its polymer backbone which are separated by ester linkages and which also contains urethane linkages in a side chain are described in applicants' U.S. Patent 4,386,191.
Such compositions are formed by reaction ; of an epoxy and hydroxy group-containing prepolymer with a polyisocyanate, e.g., a diisocyante. The pre-polymer is formed by reaction of polyol, acid anhydride and diepoxide, preferably in a single step reaction.
The polymer ultimately formed can be used to form ther-~- moset compositions for making molded articles, e.g., by reaction injection molding (RIM~.
Summary of the Present Invention The present invention relates to an improvement of the invention described in the aforementioned related application. It involves the incorporation of a poly-meric segment from an ethylenically unsaturated monomer to modify and improve the physical properties 5~) of the resulting cured polymer, e.g., in a preferred embodiment to increase the crystallinity of the thermo-set making it more resilient and giving it a better heat sag resistance. This latter feature can be important when the product containing ~he thermoset is one which is coated and goes through repetitive heat cycles. Heat sa~ results in loss of shape for the part thereby causing cracking and/or separation of the coating.
The incorporation of the polymeric segment into the modified prepolymer compositions of the present invention can be accomplished in various ways. One way is to first form a copolymer of a major amount of the desired unsaturated monomer and an unsaturated dicar-boxylic acid anhydride and then mix that anhydride-containing copolymer product with polyol, acid anhydrideand polyepoxy compound followed by heating to form the modified prepolymer. Alternatively, the relatively small amount of unsaturated dicarboxylic acid anhydride can be combined with polyol, acid anhydride, polyepoxy compound and heated so that an unsaturated prepolymer is formed which can be mixed with the relatively larger amount of unsaturated monomer, intended as the modifier, andan initiator. Freeradical polymerizationbonds the polymeric segment to the moiety from the unsaturated anhydride. Finally, unsaturated anhydride,and monomer, with initiator~ can both be added to polyol, acid anhydride, and polyepoxy compound and heated The ; molecular weight of the polymeric segment can be adjusted by various known techniques including changes in the ratio of monomer to initiator, the use of a chain transfer agent or modification of the temperature of the free radical polymerization.
C-6~46/6912 ' ' ~ i ~%~L~3~i~0 Reaction of any of the abo~e-described epoxy-con-taining polyols with a polyisocyanate, e.g., diisocyan-ate, yields thermoset compositions. The physical property change~ of such modified compositions, due to the presence of polymer segments derived from the un-saturated monomer component, can be varied due to the type o~ unsaturated monomer chosen. Use of monomers tending to produce relatively rigid polymeric segments (e.g., styrene, methyl methacrylate and/or acryloni-triie) will tend to produce harder, more rigid and tough thermoset compositions. Use of monomers tendingto produce relatively rubbery polymers (e.g., the alkyl acrylates or higher alkyl methacrylates) will produce more impact resistant compositions.
Description of the Preferred Embodiments The modified poly(oxazolidone/urethane)composi-tions of the present invention are formed by reacting a polyisocyanate, e.g., diisocyanate, with a modified prepolymer composition containing a prepolymer having terminal epoxy groups and non-terminal, secondary hydroxy groups~
The modified prepolymer is formed by the incorpor-ation of polymer segments from an unsaturated monomer.
Grafting of the polymeric segments from unsaturated monomer onto the basic prepolymer (which is the subject of U.S. Patent 4,386,191 is accomplished by using a relatively smaller amount of an unsaturated acid anhydride. Generally speaking, the mole ratios of unsaturated monomer to unsaturated anhydride will range from about 700:1 to about 3:1. The amount of unsatur-ated monomer to all the other reactants used to form C-6~46/6912 ! ,.;
5~(~
the basic prepolymer from polyol, anhydride and poly~
epoxy compound will generally be from about 1% to about ~0~ .
As described in U, S. Patent 4,386,191 the basic prepolymer is formed by reaction of polyol, anhydride and diepoxide. Gener-ally speaking, the amounts of these three reactants will be 2 moles of hydroxy as polyol with 2 moles or less of anhydride and 2 moles or more of diepoxide.
Such a prepolymer, as will be described in greater detail below, is modified by the presence of polymeric segments from an ethylenically unsaturated monomer with the segments being bonded thereto by means of a moiety from an unsaturated dicarboxylic acid anhydride.
If desired all reactants ~polyol, anhydride, poly-epoxide, unsaturated anhydride and unsaturated monomer) can be combined with initiator and heated. Alterna-tively, a copolymer of unsaturated anhydride and mono-mer can first be formed followed by its combination with polyol, anhydride,polyepoxy compound, and catalyst, with heating. Finally, polyol, anhydride, unsaturated anhydridel and polyepoxide can be reacted, forming an unsaturated prepolymer which can be combined with un-saturated monomer and initiator and heated.
Representative acid anhydrides which can bechosen to form the basic prepolymer encompass both the aromatic and aliphatic anhydrides including: adipic, glutaric, sebacic, succinic, phthalic, tetrachlorophthalic, and te*rabromophthalic .
Representative polyols include: polyethylene gly-col, polypropylene ylycol, polypropylene triol, 2,4-butanediol, pentaerythritol, 2,3-butanediol, ethylene , .
-- 6 ~
glycol, propylene glycol, and mixtures thereof, tri-methylene glycol, 1,12-dihydroxyoctadecane, 1,4-dihydroxycyclohexane, 2,2-dimethyl-1,3-propanediol,
2-ethyl-2-butylpropanediol, glycerol, erythritol, sorbitol, mannitol, inositol,trimethylol propane, dipentaerythritol, polybutadiene diol, polytetramethyl-ene diol, polycaprolactone diol and phosphorus con-taining diols and polyols.
The type of diepoxides shown in U.S. Patent No.
4,066,628 to K. Ashida et al., can be employed for use in con-nection with the present invention. Such diepoxides include the diglycidyl ethers of dihydric mononuclear and fused ring phenols, the diglycidyl ethers of non-fused polynuclear phenols having an alkylene, sulfone, carboxy, oxygen or sulfur bridging group between the phenol rings, the diglycidyl ethers of novolac resins, dicyclopentadiene dioxide, vinyl cyclohexene dioxide, the dicyclohexyl oxide carboxylates, and the diglycidyl derivatives of aromatic primary amines. Some repre-; sentative diepoxides include the diglycidyl ethers of bisphenol A, hydroquinone, resorcinol, catechol, methyl-hydroquinone, 1,6-hexanediol, 1,12-dodecanediol, alicyclic diepoxides, such as vinylcyclohexene dioxide, and dicyclopentadiene dioxide.
The combination of unsaturated anhydride and un-sa~urated monomer is responsible for forming the novel polymer-grafted prepolymer compositions of the present ; invention.
Representative ethylenically unsaturated anhydrides which can be chosen can be selected from the group con-sisting of maleic anhydride, itaconic anhydride, pro-penyl succinic anhydride, citraconic anhydride, , ~, ~z~s~c) mesaconic anhydride, cyclohexene dicarboxylic anhydride, and endomethylene cyclohexene dicarboxylic anhydride.
These compounds contain unsaturation so as to be capable o~ polymerizing ~ith ethylenically unsaturated monomer chosen as modifier and also contain a functional group reactive with the hydroxyl groups of the polyol employed in forming the modi~ied prepolymer.
Various types of ethylenically unsaturated monomers can be chosen including acrylonitrile, styrene, buta-diene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, styrene,~ -methylstyrene, methylstyrene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butyl-styrene, phenylstyrene, cyclohexylstyrene, benzylsty-rene, and the like; substituted styrenes such as chloro-styrene, 2,5-dichlorostyrene, bromostyrene, fluoro-styrene, trifluoromethylstyrene, iodostyrene, cyano-styrene, nitrostyrene, N,N-dimethylaminostyrene, ace-toxylstyrene 7 methyl 4-vinylbenzoate, phenoxystyrene, p-vinyl diphenyl sulfide, p-vinylphenyl phenyl oxide, and the like; the acrylic and substituted acrylic mon-omers such as acrylic acid, methacrylic acid, methyl-acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl meth-acrylate, methyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, isopropyl methacrylate, octyl meth-acrylate, methacrylonitrile, methyl d~chloroacrylate~
ethyl ~-ethoxyacrylate,~ ethoxyacrylate, methyl ~- ace-taminoacrylate, butyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate,c~- chloroacrylo-nitrile, N,N-dimethylacrylamide, N,N-dibenzylacrylamide, N-butylacrylamide, methacrylyl ~ormamide, and the like;
the vinyl esters, vinyl ethers, vinyl ketones, etc. such as vinyl acetate-, vinyl chloroacetate, vinyl alcohol, 5'3V
vinyl butyrat~, isopropenyl acetate, vinyl formate, vinyl acrylate, vinyl methacrylate, vinyl methoxy acetate, vinyl benzoate, vinyl iodide, vinyl toluene, vinyl naphthalene, vinyl bromide, vinyl fluoride, vinylidene bromide, l-chloro-l-fluoro-ethylene, vinyl-idene fluoride, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ethers, vinyl butyl ethers, vinyl 2-eth-ylhexyl ether, vinyl phenyl ether, vinyl 2-methoxy-ethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro - 1,2-pyran, 2-butoxy-2'vinyloxy diethyl ether, vinyl 2-ethylmercaptoethyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl phosphonates such as bis ~-chloroethyl vinyl phosphonate),vinyl phenyl ketone, vinyl ethyl sulfide, vinyl ethyl sul-~one, N-methyl-N-vinyl acetamide, N-vinyl-pyrrolidone, vinyl imidazole, divinyl sulfide, divinyl sulfoxide, divinyl sulfone~ sodium vinyl sulfonate, methyl vinyl sulfonate, N-vinyl pyrrole, and the like; dimethyl fumarate, dimethyl maleate, maleic acid, crotonic acid, fumaric acid, itaconic acid, monomethyl itaconate, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, glycidyl acrylate, allyl alcohol, glycol monoesters of itaconic acid, dichlorobutadiene, vinyl pyridine, and the like~ Any of the known polymeri2able monomers can be used and the compounds listed above are ; illustrative and not restrictive of the monomers suit-; able for use in this invention.
Chain transfer agents, such as halogen-containing compounds, sulfur-containing compounds and dipentene can be effectively used, if desired, to control the molecular weight of the polymeric segment. The amount of chain transfer agent that is utilized can vary from .
~,2~
about 0.1% to about 10%, by weight, of the ethyleni-cally unsaturated monomers that are employed.
The initiator~ which can be used to bring about graft polymerization between the unsaturated anhydride moiety and monomer can be one of those conventionally employed in conventional amount. For example, the con-centration o~ the initiatorcan vary from about 0.001 to about 5 percent, preferably from about 0.2 to about 1.5 percent; however, any e~ective catalytic amount is satisfactory. Illustrative initiatorsare the well-known free radical type of vinyl polymerization init-iators for example, the peroxides, persul~ates, perbo-rates, percarbonates, azo compounds, etc., including hydrogen peroxide, dibenzoyl peroxide, acetyl perox-ide, benzoyl hydroperoxide, t-butyl hydroperoxide, di t-butyl peroxide, lauroyl peroxide, butylryl per-oxide, diisopropylbenzene hydroperoxide, cumene hydro-peroxide, diace-tyl peroxide, di-alpha-cumyl peroxide, dipropyl peroxide, diisopropyl peroxide, isopropyl t-butyl peroxid~, butyl t-butyl peroxide, dilauroyl peroxide, di~uroyl peroxide, ditriphenylmethyl perox-ide, bis(p-methoxy-benzoyl) peroxide, rubrene peroxide, ascaridol, t-butyl peroxybenzoate, t-butyl peroctoate, diethyl peroxyterephthalate, propyl hydroperoxide, iso-propyl hydroperoxide, n-butyl hydroperoxide, t-butyl hydroperoxide, cyclohexyl hydroperoxide, transdecalin hydroperoxide, alpha-methylbenzyl hydroperoxide, tetra-lin hydroperoxide, triphenylmethyl hydroperoxide, di-phenylmethyl hydroperoxide, 2,2'-azo-bis(2-methyl butyronitrile), 2,2'-azo-bis~2-methylheptonitrile), l,l'-azo-bis(l-cyclohexane carbonitrile), dimethyl alpha, alpha'-azo-isobutyrate, 4,4'-azo-bis(4-cyano-pentanoic acid), azo-bisisobutyrcnitrile, persuccinic acid, diisopropyl peroxy dicarbonate, and -the like.
A mixture of catalysts may also be used.
The temperature and catalysts are chosen such that the catalyst has a satisEactory half-life at the temperature employed; preferably, the half life should be about 25 percent or less of the residence time in the reactor at the given temperature.
Depending upon the amounts of polyol, anhydride and diepoxide reacted in forming the basic prepolymer various structures are possible. Reaction of 2 moles of hydroxy as polyol with 2 moles or less of anhydride and 2 mo~es or more of diepoxide will produce the fol-lowing prepolymer as the major prepolymer component in the composition, with R1-R5 independently being any group to which carbon atoms (or oxygen atoms) can be covalently bound to form a backbone chain, either unsubstituted (e.g.~ alkylene, arylene, alkylene/aryl-ene chains optionally interrupted by hetero atoms or groups, such as carbonyl, ester~ ether, sulfonyl, phos-phonyl, etc.) or substituted (as aboYe, with halogen,alkyl, aryl~ alkoxy, phenoxy, cyano, etc. substitution) and R is derived from R1-R5 to form a monovalent sub-s~ituent or is hydrogen:
R R R R R O O O ~ R R R R~ R
~I \ I .1 1 ll ll l 1 / \/
W R4-C--C-OC-R5-CO-R1-OC-R2-CO-C- C-R3~
O OH R R OH O
(I) s~
The presence of unsaturated anhydride and modi-fier will change either or both R2 and R5 in the above formula since these moieties would be due to the pres-ence of the unsaturated anhydride and would have the structure with the -CR-CR- comprising a portion of the backbone segments R2 and R5:
R7 ~ CR C ~
R8 R6 n Rg R10 m where R6-R13 are the same as R, above, in covering any atom or group of atoms to which carbon can be covalent-ly bound (including hydrogen). It can be, for example, any group derived from the initiator employed in this invention (e.g., benæoyloxy, acetyloxy, aryl, alkyl, cyano-isopropyl, 2-cyano-4-methyl-2-pentyl, t-butoxy, hydroxy, cumyl, cumyloxy, alkylcarboxy, etc.). R in the above formula is derived from the acid anhydride reactant and can also be hydrogen with m and n being O or any positive integer.
C-6446~6912 ~21~S~
- llA -Formation of this type of prepolymer is favored when the molar amount of anhydride is no more than 2 and the amount of diepoxide is not less than that of acid anhydride, based upon a molar amount of hydroxy groups in the polyol set at 2.
Depending upon the precise amounts of reactants employed, however, it is also possible to yield a pre-polymer in which one end contains a terminal epoxy group with associated non~terminal, hydroxy group, and the other end terminates in a hydroxy group. This pre-polymer has the formula given below with R, R1 and R3 having the same meaning as R-R5, above, and R2 having the same meaning as either R2 or R5:
O O R R R R R
" " ' ' ~ \/' HO-R1-OC-R2-CO-C--C-R3~7 R OH O
(II) ~21~5C3~
This type of prepolymer is produced in the process shown in U.S. Patent No. 3r 847~ 874 to Y. Murakami and is favored in the reaction when khe molar amount of acid anhydride is present in amounts which approximate one half the molar amount of the hydroxy groups in the polyol that is present, In Formula II R2 has the same for the modified prepolymer of the present invention given for R2 in regard to Formula I, above.
The present invention includes prepolymer composi-tions which contain mixtures of both the aforementioned modified prepolymers as well as either one alone.
The modified prepolymer composition can be formed by mixing the polyol, anhydride and diepoxide with suitable modifying monomer and unsaturated anhydride (or copolymer thereof) pxeferably in the presence of an effective amount (0.02 to 2%, by weight of all the reaction ingredients) of a catalyst designed to promote the reaction as well as the thQrmoset formulation.
Representative catalysts tending to favor oxazolidone formation include the quaternary ammonium salts (e.g,, tetramethyl ammonium chloride); the metal alkoxides (e.g., lithium n-butoxide); the metal halides (e.g., lithium chloride) and their complexes (e.g., lithium chloride/hexamethylphosphoramide complex); and the organometallic compounds (e.g., trialkyl aluminum).
Catalysts which favor urethane formation include the organotin compounds, diamines, and polyamines.
Once the modified prepolymer composition has been formed it is combined with a desired polyisocyanate, e.g,, diisocyante, to form a reaction mixture from which the modified poly(oxazolidone/urethane) thermoset compositions of the present invention can be formed.
1Z1~5J90 If desired, the reaction medium can contain up to about 60%, by weight, of other materials which do not inter-fere with the reaction of the prepolymer and polyiso-cyanate. Representative ingredients include additional diepoxide or polyepoxide (functions as a solvent, if liquid), diol o~ polyol, and acrylate or methacrylate ester polymer to impart flexibility to the final prod-uct. If desired the reaction medium can also contain up to about 10%, by weight, of one or more of the fol-lowing additives: blowing agents, ~lame retardants, coupling agents, dyes, stabilizers and mold releasing agents.
The amount of polyisocyanate chosen for reaction with the modi~ied prepolymer should be substantially equivalent in regard to its isocyanate functionality (on an equivalent bases) to the total equivalents of epoxide and hydroxy groups in the prepolymer composi-tion and any added ingredients which would react with the isocvanate. A slight excess o~ isocyanate (up to ahout 5% on a weight basis) can be toleratad but greater amounts whould be avoided since the formation of isocyanurate linkages would be favored. In general, the respective molar amount of oxazolidone and urethane linkages to one another in the thermoset will depend upon the type or types of prepolymers present and the presence o~ other isocyanate reactive groups added to the reaction mixture. If only the prepolymer composi-tion and polyisocyanate are used and the diepoxy/di-hydroxy prepolymer is present, a near 50:50 (oxazoli-done:urethane) molar ratio polymer is produced. If the prepolymer composition contains the dual hydroxy, epoxy prepolymer to a greater degree, a greater number C-64~6/6912 ~L~5~3~
of urethane linkages will be formed as compared to oxa-zolidone linkages, unless additional epoxy moieties are added. Addition of additional hydroxy group compounds, e.g., diol or polyol, will yield a larger molar amount S of urethane, whereas addition of epoxide materials, e.g., diepoxides, will incr~ase the oxazolidone content of the product. The molar amount of oxazolidone to urethane can range from 90:10 to 1:99. When the molar amount of hydroxy groups in the polyol is 2, the amount of anhy-dride should not exceed about 2 and the amount of die-poxide should not be less than that of anhydride.
Any polyisocyanate capable of reaction with theepoxy and hydroxy groups contained in the prepolymer to form the desired oxazolidone and urethane linkages is contemplated for use by the present invention. Repre-sentative examples of suitable conventional polyiso-cyanates, which are used to form urethane polymers, for example, include such aromatic and aliphatic types as:
the tolylene diisocyanates,the methylene bis(phenyl isocyanates), such as methylene bis~4-phenyl isocyanate), dianisidine diisocyanate, toluidine diisocyantes, m-xylene diisocyanate, 1,5-naphthylene diisocyanate, P-phenylene diisocyanate, and hexamethylene diisocyanate, carbodiimide modified diisocyanate (e.g., ~SONATE 143L
from Upjohn Co.) and other di~ and higher polyisocyan-ates. Mixtures of such isocyanates can be used, ifdesired as well as polymeric polyisocyanates.
The resulting thermoset composition formed from the above-described reac~ion mixture is one which con-tains oxazolidone and urethane linkages in the recur-ring unit or units and which is essentially free ofsubstantial amounts of isocyanurate linkages. The ultimate type of recurring unit and its amount will * Trademark , 12:~S~
be dictated by the type of prepolymer or prepolymers mainly presen-t in the prepolymer composition. Modified prepolymer (I) described above will produce a recurring unit of the following formula with R-R5 having the same meaning as R1-R5 and R6-R19 are independently the same as R1-R5 and also include hydrogen:
r ~ R
1 0 ~ ' ~ al9 C=O ~,3 --R ~ -N--C Rs R~o O O O O E~10 0 R14--C--N JEI--¦ ~C ~C~- R4-C-C--O-C-a~ C-O-R1-O-C-R2-C-O-C---C - R3-~ C~ I
O R~ O R11 R,7 R12 R1s O ` ¦
I C=O
N~ I
~III) where either or both R2 and R5 in the above formula may have the structure \
CR~ CR
R(CH2CHR6) / \ (CH2CHR7)mR
with R6 and R7 having the same meaning given hereto-fore~
Presence of modified prepolymer (II) will yield the following recurring unit with R-R3 having the same meaning as R1-R3 and R4-R11 are the same and also include hydrogen:
12~5~
~ ` R
r . I C=O R, 1 EI O O O R~ O R, o~C ~ R--n O~R,-O-C--R~-C OC , ~C~ o/ ~0 _ _ _ _ _ _ _ _ _ _ _ _ __ __ _ _ _ , (IV) Prepolymer compositions containing both prepolymers (I) and (II) would have a certain defined amount of both recurring units ~III) and(IV) dependiny on the amounts of prepolymer~ (I) and (II) in the composition reacted with the polyisocyanate.
Recurring unit III has oxazolidone linkages in its backbone by virtue of reaction of the polyisocyanate with the terminal epoxy groups of prepolymer I. It has urethane groups in pendant side chains, rather than in the same chain as the oxazolidone, due to reaction of the pendant, non-terminal secondary hydroxy group in the prepolymer. The oxazolidone linkages in the recurring unit III are separated from one another by the addition-al presence in the backbone of ester linkages which are derived from the anhydride reactant~
Recurring unit IV has a urethane linkage adjacent one end of the backbone of the recurring unit and an oxazolidone linkage at the other end. A urethane link-age exists in a side chain of the unit intermediate the urethane and oxazolidone linkages. Ester linkages lie in the backbone intermediate the oxazolidone linkages in the backbone and the urethane linkages in the side chain.
~21~S~
Poly(oxazolidone/urethane) thermoset compositions which ~orm a part of the present invention include those which contain recurring unit III, either alone, or in combination with no more than about 90% of IV.
The thermoset compositions of the present inven-tion are useful in the fabrication of molded articles of manu~acture, for example, by reaction injection molding techniques. If desired, the thermoset composi-tions can be combined with suitable relnforcing agents including gla*ss fibers or flakes, graphite, wollastonite, mica, KELVAR aromatic polyamide fiber, nylon fiber, either alone or in combination with one or more coupling agents.
The present invention is illustrated by the Examples which follow.
* Trademark 5~3~
A mixture containing 420 grams (0.428 equivalent weight of hydroxy groups~ of polypropylene glycol (NIAX
polyol PPG 2025 from Union Carbide Co.), 58 grams (0.392 equivalent weight) of phthalic anhydride, 1.0 gram (0.010 equivalent we;ght) of maleic anhydride, 154 grams (0.806 epoxy equivalent weight) of the di-glycidyl ether of bisphenol A (EP~N 828 brand,~rom ShelI Chemical Co.), and 3.5 grams of lithium chloride/
dimethylformamide complex (1/1.5) was heated at 125C.-135C. After 2-1/2 hours of heating, the resulting product was found to be free of acidic material.
The above unsaturated product was cooled to 35C.
and added to 70 grams (1.32 equi~alent weights) of acrylonitrile and 1.0 gram of a free radical azobisiso-butyronitrileinitiator (VAZO 64 brand from Du Pont).
The mixture was purged with nitrogen for 30 minutes and then heated to 70C. to initiate polymerization.
The mixture was subjected to cooling to maintain the temperature between 70C. and 90C. until the free radi-cal polymerization subsided. This took about one hour.
The product was stripped at high vacuum to eliminate residual monomers. The grafted prepolymer product, a free flowing liquid, had a viscosity o~ 500 poise (by Brookfield Viscometer Model L~T) at 22C.
A mixture of 80 grams (0.044 mole epoxy) of the above acrylonitrile-grafted prepolymer, 25.3 grams (0.816 hydroxy equivalent weight) o~ e~hylene glycol, 40 mg. of stannous octoate, and 8 mg. of dibutyltin dilaurate (T-12 brand from M and T Chemical Co.) was stirred under vacuum with 130 grams (0.909 isocyanate * Trademark ~Z~l~5.C3~
equivalent weight) of a carbodlimide modifi~d 4,~'-diphenyl methane diisocyanate (ISONATE 143L brand from Upjohn Chemical Co.). The final mixture, after becoming homogeneous, was poured into a preheated mold ~70C.). The resin cured in less than 30 seconds and was demolded and post-cured at 125C. for 1 hour. The thermoset plaque (3.1~ mm. thick) gave 415 kg/cm~ of tensile strength (ASTM D412), 11.6 x 103 kg/cm of flexural modulus (ASTM D 474), and 1.92 J/cm of notched IZOD impact resistance (ASTM D 256).
A specimen (2.54 cm x 15~24 cm) was cut from the thermoset plaque for the heat sag test which is a measurement of the ability of a plastic sample to resist distortion at an elevated temperature. The specimen was clamped onto a fixture at one end which left a 10.2 cm unsupported length. The fixture with the specimen was placed in an oven at 132C. for 60 minutes. ~he difference between the vertical dis-tances from the unsupported end of the specimen to the base of the test fixture measured before and after the heating was the heat sag. The specimen showed a heatsag of 1.1 cm.
~23l~
A mixture contalning 420 grams (0.428 hydroxy equivalent weight) of polypropylene glycol (NIAXpolyol PPG 2025 from Union Carbide Co.), 58 grams (0.392 equivalent weight) of phthalic anhydride, 0.20 grams ~0.002 equivalent weight) of maleic anhydride, 154 grams (0.806 epoxy equivalent weight) of the diglycidyl ether of bisphenol A (EPON 828 brand from Shell Chem-ical Co.), 3.5 grams of lithium chloride/dimethyl formamide (1/1.5 complex), 70 grams (1.32 equivalent weight) of acrylonitrile, 0.80 grams of benzoyl perox-ide, and 0.40 grams of t-butyl hydroperoxide was purged with nitrogen for 30 minutes. The mixture was stirred and heated at 125C. - 5C. until the resulting product was free of acidic material and the free radical poly-merization completed as indicated by slow condensation of acrylonitrile monomers inside the condenser. The residual monomers were stripped by high vacuum. The resulting prepolymer product was a yellow viscous liquid (6,000 poise at 24~C.) and had an epoxide equi-valent of 1847.
A thermoset plaque was made from the above prepoly-mer using the same compositions and procedures as they were described in the third paragraph of Example 1.
The thermoset plaque gave 462 kg/cm2 of tensile strength (ASTM D 412), 12.7 x 103 kg/cm2 of flexural modulus (ASTM D 474), 1.27 ~/cm of notched IZOD (ASTM D 256), and 0.8 cm of heat sag.
, lZ3L~S~C3() - 21. -~XAMPLES 3-5 Thé procedures set forth in Example 2 were applied in the following Examples. The various ingredients for the Examples are listed in Table I:
TAB~E I
__.
EXAMPLE NUMBER
Ingredients (~ram) 3 4 5 NIAX PPG 2025 Polyol 420 420 420 Phthalic Anhydride 58 58 58 Maleic Anhydride 0.50 2.0 1.0 EPON 828 Diepoxide 154154 154 LiCl DMF Complex (1/1.5) 3.5 3.5 0 ADOGEN 464 Catalyst 0 0 2.8 Acrylonitrile 70 70 70 Benzoyl Peroxide 0.80 0.80 0.80 ~-Butyl Hydroperoxide 0.40 0.40 0.40 Grafted prepolymer products obtained from these examples were employed to make thermoset plaques using the same compositions and procedures described in the third paragraph of Example 1. The physical property characteristics for the thermoset plaques are listed in Table II:
*.Trademark ~2:1~S~() EXAMPLES 3-5 (con;t'd.) TABLE II
EXAMPLE ~MBER
Physical Properties 3 4 5 Tensile Strength (kg/cm2) 423450 406 Flexural Modulus 10(kg/cm2) at Room Temperature: 16,900 14,500 12,000 at 70C.: 10,200 7,700 7,000 Notched IZOD Impact (J/cm~: 0.45 0.65 0.86 Heat Sag (cm): 1.0 1.0 0.5 ~2 1~3$C3~
Into a reaction flask equipped with a condenser, a nitrogen inlet, a thermometer, and a mechanical stir-rer was charged 150 gm. of polyethylene glycol (NIAXpolyol PPG 600 from Union Carbide Corp.), 72.5 gm. of phthalic anhydride, 1~0 gm. of maleic anhydride, and 190 gm. of the diglycidyl ether of bisphenol A. ~he mixture was heated at 120C. for about 35 minutes until the resulting product was not acidic.
The foregoing product was added to 230 gm. of acetone, 96 gm. of acrylonitrile, and 1.5 gm. of 2,2'-azobis-2,4-dimethylvaleronitrile initiator. After being ~lushed with nitrogen for 30 minutes the mixture was heated at 55-62C. for one hour. The resulting prepolymer product was stripped by high vacuum and had an epoxide equivalent of 1109.
A mixture containing 66.4 gm. of the foregoing pre-polymert 4.6 gm. of polyethylene glycol tCARBOWAX
PEG 20Q) and 20 mg~ of dibutyltin dilaurate was mixed with 65 ym. of a modi~ied diphenylmethane diisocyanate tISONATE 191 diisocyanate from Upjohn). After being made homogeneous, the mixture was poured into a pre-heated mold held at 80C. and cured for two minutes.
* Trademark . . , lZ~5~3() EXAMPLE_ ?
Into a reaction flask equipped with a condenser, a nitrogen inlet, a thermometer, and a mechanical stir-rer was charged 420 gm. of polypropylene glycol (NIAXpolyol PPG 2025), 58 gm. of phthalic anhydride, 1.0 gm.
of maleic anhydride, 70 gm. of acrylonitrile, 154 gm.
of the diglycidyl ether of bisphenol A, 3.5 gm. of lithium chloride/dimethyl formamide complex, 0.50 gm.
Of benzoylperoxide, and 0.45 gm.of t-butyl hydroperoxide The mixture, after being flushed with nitrogen at room temperature, was heated by an oil bath at 130C. In about three hours the resulting product was free of acidic material. The product was stripped by vacuum.
~ mixture containing 80 gm. of the above product, 25.3 gm. of ethylene glycol, 8 mg. of dibutyltin di-laurate, and 40 mg. of tin octoate was mixed with 130 gm. of a modified diphenylmethane diisocyanate (ISONATE
143L brand). The mixture, after being made homogeneous, was poured into a preheated (70C.) mold and cured in 10 seconds. The cured, molded part was then remo~ed from the mold and post cured at 125C. for one hour.
12~L~i.C~V
A mixture containing 420 grams (0.430 hydroxy equi~alent weight) of polypropylene glycol (~I~ Polyol PPG 2025 brand ~rom Union Carbide Co.), 58.0 grams (0.392 equivalent weight) of phthalic anhydride, 1.0 grams (Q.010 equivalent weight) of maleic anhydride, 33.5 grams (0.632 equi~alent weight) of acrylonitrile and 1.1 grams of azobisisobutyronitrileinitiator (VAZO
64 brand from DuPont) was purged with nitrogen for 30 minutes and heated at 70-80C. for about 45 minutes till the free radical polymerization subsided. The mixture was added with 154 grams (0.806 epoxy equiva-lent weight) of diglycidyl ether of bisphenol A (EPON
828 brand from Shell Chemical Co~) and 3.5 grams of lithium chloride/dimethyl formamide (1/1.5 complex).
The mixture was then heated at 125-135C. for about one hour till the resulting product was free of acidic material. A polyacrylonitrile grafted prepolymer was obtained.
A mixture of 80 grams of the above polyacryloni-trile grafted prepolymer, 25.3 grams (0.816 hydroxy equivalent weight) of ethylene glycol, 160 milligrams of stannous octoate, and 8 milligrams of dibutyltin dilaurate (T-12 brand from M and T Chemical Co.) was stirred under vacuum with 130 grams (0.909 isocyanate equivalent weight) of a modified 4,4l-diphenyl methane diisocyanate (ISONATE 143L brand from Upjohn Chemical Co.). The final mixture, after being homogeneous, was poured into a preheated mold (70C.). The resin cured in less than 30 seconds and was demolded and post cured at 125C. for 1 hour. The thermoset plaque (3.18 mm C-6~46/6912 ~Z1~3S9~) EXAMPLE 8 (co:nt'd.) thick) gave 384 kg/cm2 of tensile strength (ASTM ~412), 9.91 x 103 kg/c~ of flexural modulus (ASTM D474), and 1.33 J/cm of notched IZOD impact reslstance (ASTM D256).
The heat sag resistance of the sample was measured to be 2.7 cm by the same way as described in Example 1.
~2 195'30 A mixture containing 420 grams (0.430 hydroxy equivalent weight) of polypropylene glycol (NIAX polyol PPG 2025 brand from Union Carbide Co.), 58.0 grams (0.392 equivalent weight) of phthalic anhydride, 1.0 grams (0.010 equivalent weight) o-f maleic anhydride, 70.3 grams (1.33 equivalent weights) o~ acrylonitrile and 1.1 grams of azobisisobutyronitrileinitiator (VAZO
64 brand from Du Pont) was purged with nitrogen for 30 minutes and heated at 70-80C. for about 45 minutes till the free radical polymerization subsided. The mixture was added with 154 grams (0.806 epoxy equiva-lent weight) of diglycidyl ether of bisphenol A (EPON
828 brand ~rom Shell Chemical Co.) and 3.5 grams of lithium chloride/dimethyl formamide (1/1.5 complex).The mixture was then heated at 125-135C. for about one hour till the resulting product was free of acidic material. A polyacrylonitrile-grafted prepolymer was obtained.
A mixture of 80 grams o~ the abo~e polyacrylonitrile grafted prepolymer, 25.3 grams (0.816 hydroxy equiva-lent weight) of ethylene glycol, 160 milligrams of stannous octoate, and 8 milligrams of dibutyltin di-laurate (T-12 brand from M and T Chemical Co.) was stirred under vacuum with 130 grams (0.909 isocyanate equivalent weight) of a modified 4,4'-diphenyl methane diisocyanate (ISONATE 143L brand from Upjohn Chemical Co.). The final mixture, a~ter being homogeneous, was poured into a preheated mold (70C.). The resin cured in less than 30 seconds and was demolded and post cured EXAMPI.E 9 (cont'd~) at 125C. for 1 hour. The thermoset plaque (3.18 mm thick) gave 382 kg/cm2 of tensile strength (ASTM
D412), 11.8 x 103 kg/cm2 o~ flexural modulus (ASTM D474), and 1.07 J/cm of notched IZOD impact resistance (ASTM
D256). The heat sag resistance of the sample was measured to be 0.3 cm by the same way as described in Example 1.
~21~S~
A mixture containing 420 grams (0,~30 hydroxy equivalent ~eight) of polypropylene glycol (NIAX Polyol PPG 2025 brand from Union Carbide Co.), 58.0 grams (0.392 equivalent weight) of phthalic anhydride, 1.0 grams (0.010 equivalent weight) of maleic anhydride, 112 grams (2.11 equivalent weight) of acrylonitrile and 1.1 grams of azobisisobutyronitrileinitiator (VAZO 64 brand from Du Pont) was purged with nitrogen for 30 minutes and heated at 70-80C. for about 45 minutes till the free radical polymerization subsided. The mixture was added with 1~4 grams (0.806 epoxy equivalent weight) of diglycidyl ether of bisphenol A (EPON 828 brand from Shell Chemical Co.) and 3.5 grams of lithium chloride/
dimethyl formamide (1/1.5 complex). The mixture was then heated at 125-135C. for about one hour till the resulting product ~as free of acidic material. The polyacrylonitrile grafted prepolymer was obtained.
A mixture of 80 grams of the above polyacrylonitrile grafted prepolymer, 25.3 grams (0.816 hydroxy equivalent weight) of ethylene glycol, 160 milligrams of stannous octoate, and 8 milligrams of dibutyltin dilaurate (T-12 brand from M and T Chemical Co.) was stirred under 25 vacuum with 13Q grams (0.909 isocyanate equivalent weight) of a modified 4,4'-diphenyl methane diisocyanate (ISONATE 143L brand from Upjohn Chemical Co.~. The final mixture, after being homogeneous, was poured into a preheated mold (70C.). The resin cured in less than 30 30 seconds and was demolded and post cured at 125C. for 1 hour. The -thermoset plaque (3.18 mm thick) gave 384 kg/cm2 of tensile strength (ASTM ~412), 10.1 x 103 ~lZ~95,C3() EXAMPLE l a (cont'd.) kg/cm2 of flexural modulus (ASTM D474), and 1.87 J/cm of notched IZOD impact resistance (ASTM D256). The heat sag resistance of the sample was measured to be 1.1 cm by the same way as described in Example l.
19~9~
~ 31 -A mixture containing 420 grams (0.430 hydroxy equi-valent weight) of polypropylene glycol (NIAX Polyol PPG
2025 brand from Union Carbide Co.), 59 grams (0.602 equivalent weight) of phthalic anhydride, 154 grams (0.806 epoxy equivalent weight) of the diglycidyl ether of bisphenol A (EPON 828 brand from Shell Chemical Co ), and 2.5 grams of lithium chloride/dimethylformamide (1/1.5 complex) was heated at 125_135C. for about 75 minutes till the resulting product was free of acidic material. The product, a free flowing liquid, had a viscosity of 1,080 poise at 24C.
A mixture of 80 grams of the above product, 25.3 grams of ethylene glycol, 80 milligrams of stannous ocatoate, and 16 milligrams of dibutyltin dilaurate (T-12 brand from M and T Chemical Co.) was stirred under vacuum with 132 grams of a modified 4,4'-diphenyl meth-ane diisocyanate (ISONATE 143L brand from Upjohn Co.).
The final mixture, after being homogeneous, was poured into a preheated mold (70C.). The resin cured in less than 30 seconds and was demolded and post cured at 125C.
for 1 hour. The thermoset plaque (3.18 mm thick) gave 422 kg/cm2 of tensile strength (ASTM D412), 11.3 x 103 25 kg/cm2 of flexural modulus (ASTM D474), 1.06 J/cm of notched IZOD and 0.3 cm of heat sag.
12~553V
A mixture containing 420 grams (0.430 hydrox,v equi-valent ~eight) of polypropylene glycol (NIAX polyol PPG
2025 from Union Carbide Co.), 58 grams (0.392 equivalent weight) of phthalic anhydride, 2.0 grams (0.020 equiva-lent weight~ of maleic anhydride, 154 grams (0.806 epoxy equivalent weight) of the diglycidyl ether of bisphenol A (EPON 828 brand from Shell Chemical Co.), 2.22 grams of lithium chloride in methanol (30~ LiCl), 33.4 grams (0.321 equivalent weight) of styrene, 0.80 grams of benzoylperoxide, and 0.40 gramsof t-butyl hydro-peroxide was purged with nitrogen for 30 minutes. The mixture was stirred and heated at 125C.~5C. until the resulting product was free of acidic material and the free radical polymerization subsided. The residual monomers were stripped by high vacuum. The resulting prepolymer product was a cloudy viscous liquid (2240 poise at 24C.).
A thermoset plaque was made from the above prepoly-mer using the same compositions and procedures as they were described in the third paragraph of Example 1.
The thermoset plaque gave 485 kg/cm2 of tensile strength (ASTM D 412), 9.35 x 103 kg/cm2 of flexural modulus (ASTM D 474), 2.30 ~/cm of notched IZOD (ASTM D 256), and 1.8 cm of heat sag.
S~3V
A mixture containing 840 grams (0.860 hydroxy equi-valent weight) of polypropylene glycol (NIAX polyol PPG
2025 from Union Carbide Co.) and 4.22 grams of a 30%
lithium chloride solution in methanol was sparged with nitrogen at a rate of 5 liter/minute for one hour. To the the mixturewas thenadded 116 grams (0.784 equivalent weight) of phthalic anhydride, 2.0 grams (0.~20equivalent weight) of maleic anhydride, and 308 grams (1.61 epoxy equiva-lent weight) of the diylycidyl ether of bisphenol A
(EPON 828 brand from Shell Chemical Co.). The result-ing mixture was then stirred and heated at 120-4C.
until the resulting product had an acid number of less than 1.
To 540 grams of the above product was added 62 grams (0.60 equivalent weight) of styrene, 0.90 gram of an azo initiator (VAZO 52 brand from Du Pont), and 2.4 grams of bromotrichloromethane. The mixture was sparged with nitrogen for 30 minutes and then was heated with stirring at 50-56C. for about 16 hours.
The resulting product was a viscous liquid (620 poise at 24C.) and had an epoxide equivalent of 1883.
A thermoset plaque was made from the above pre-polymer as described in Example 1. It had a tensile stren~th (ASTM D 412) of 460 kg/cmZ~ a flexural modulus ~ASTM D 474) of 13.1 x 103 kg/cm2, a notched IZOD (ASTMD 256) of 1.55 J/cm., and a heat sag of 0.6 cm.
12~L5aS90 A mixture containing 300 grams ~1.0 hydroxy equiva-lent weight) of polye-thylene glycol (CARBOWAX 600 from Union Carbide) and 2.77 grams of a 30~ lithium chloride solution in methanol was stripped by applying 5 mm Hg vacuum for 10 minutes. To the mixture was then added 145 grams (0.98 equivalent weight) of phthalic anhydride,
The type of diepoxides shown in U.S. Patent No.
4,066,628 to K. Ashida et al., can be employed for use in con-nection with the present invention. Such diepoxides include the diglycidyl ethers of dihydric mononuclear and fused ring phenols, the diglycidyl ethers of non-fused polynuclear phenols having an alkylene, sulfone, carboxy, oxygen or sulfur bridging group between the phenol rings, the diglycidyl ethers of novolac resins, dicyclopentadiene dioxide, vinyl cyclohexene dioxide, the dicyclohexyl oxide carboxylates, and the diglycidyl derivatives of aromatic primary amines. Some repre-; sentative diepoxides include the diglycidyl ethers of bisphenol A, hydroquinone, resorcinol, catechol, methyl-hydroquinone, 1,6-hexanediol, 1,12-dodecanediol, alicyclic diepoxides, such as vinylcyclohexene dioxide, and dicyclopentadiene dioxide.
The combination of unsaturated anhydride and un-sa~urated monomer is responsible for forming the novel polymer-grafted prepolymer compositions of the present ; invention.
Representative ethylenically unsaturated anhydrides which can be chosen can be selected from the group con-sisting of maleic anhydride, itaconic anhydride, pro-penyl succinic anhydride, citraconic anhydride, , ~, ~z~s~c) mesaconic anhydride, cyclohexene dicarboxylic anhydride, and endomethylene cyclohexene dicarboxylic anhydride.
These compounds contain unsaturation so as to be capable o~ polymerizing ~ith ethylenically unsaturated monomer chosen as modifier and also contain a functional group reactive with the hydroxyl groups of the polyol employed in forming the modi~ied prepolymer.
Various types of ethylenically unsaturated monomers can be chosen including acrylonitrile, styrene, buta-diene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene, styrene,~ -methylstyrene, methylstyrene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butyl-styrene, phenylstyrene, cyclohexylstyrene, benzylsty-rene, and the like; substituted styrenes such as chloro-styrene, 2,5-dichlorostyrene, bromostyrene, fluoro-styrene, trifluoromethylstyrene, iodostyrene, cyano-styrene, nitrostyrene, N,N-dimethylaminostyrene, ace-toxylstyrene 7 methyl 4-vinylbenzoate, phenoxystyrene, p-vinyl diphenyl sulfide, p-vinylphenyl phenyl oxide, and the like; the acrylic and substituted acrylic mon-omers such as acrylic acid, methacrylic acid, methyl-acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl meth-acrylate, methyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, isopropyl methacrylate, octyl meth-acrylate, methacrylonitrile, methyl d~chloroacrylate~
ethyl ~-ethoxyacrylate,~ ethoxyacrylate, methyl ~- ace-taminoacrylate, butyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate,c~- chloroacrylo-nitrile, N,N-dimethylacrylamide, N,N-dibenzylacrylamide, N-butylacrylamide, methacrylyl ~ormamide, and the like;
the vinyl esters, vinyl ethers, vinyl ketones, etc. such as vinyl acetate-, vinyl chloroacetate, vinyl alcohol, 5'3V
vinyl butyrat~, isopropenyl acetate, vinyl formate, vinyl acrylate, vinyl methacrylate, vinyl methoxy acetate, vinyl benzoate, vinyl iodide, vinyl toluene, vinyl naphthalene, vinyl bromide, vinyl fluoride, vinylidene bromide, l-chloro-l-fluoro-ethylene, vinyl-idene fluoride, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ethers, vinyl butyl ethers, vinyl 2-eth-ylhexyl ether, vinyl phenyl ether, vinyl 2-methoxy-ethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro - 1,2-pyran, 2-butoxy-2'vinyloxy diethyl ether, vinyl 2-ethylmercaptoethyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl phosphonates such as bis ~-chloroethyl vinyl phosphonate),vinyl phenyl ketone, vinyl ethyl sulfide, vinyl ethyl sul-~one, N-methyl-N-vinyl acetamide, N-vinyl-pyrrolidone, vinyl imidazole, divinyl sulfide, divinyl sulfoxide, divinyl sulfone~ sodium vinyl sulfonate, methyl vinyl sulfonate, N-vinyl pyrrole, and the like; dimethyl fumarate, dimethyl maleate, maleic acid, crotonic acid, fumaric acid, itaconic acid, monomethyl itaconate, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, glycidyl acrylate, allyl alcohol, glycol monoesters of itaconic acid, dichlorobutadiene, vinyl pyridine, and the like~ Any of the known polymeri2able monomers can be used and the compounds listed above are ; illustrative and not restrictive of the monomers suit-; able for use in this invention.
Chain transfer agents, such as halogen-containing compounds, sulfur-containing compounds and dipentene can be effectively used, if desired, to control the molecular weight of the polymeric segment. The amount of chain transfer agent that is utilized can vary from .
~,2~
about 0.1% to about 10%, by weight, of the ethyleni-cally unsaturated monomers that are employed.
The initiator~ which can be used to bring about graft polymerization between the unsaturated anhydride moiety and monomer can be one of those conventionally employed in conventional amount. For example, the con-centration o~ the initiatorcan vary from about 0.001 to about 5 percent, preferably from about 0.2 to about 1.5 percent; however, any e~ective catalytic amount is satisfactory. Illustrative initiatorsare the well-known free radical type of vinyl polymerization init-iators for example, the peroxides, persul~ates, perbo-rates, percarbonates, azo compounds, etc., including hydrogen peroxide, dibenzoyl peroxide, acetyl perox-ide, benzoyl hydroperoxide, t-butyl hydroperoxide, di t-butyl peroxide, lauroyl peroxide, butylryl per-oxide, diisopropylbenzene hydroperoxide, cumene hydro-peroxide, diace-tyl peroxide, di-alpha-cumyl peroxide, dipropyl peroxide, diisopropyl peroxide, isopropyl t-butyl peroxid~, butyl t-butyl peroxide, dilauroyl peroxide, di~uroyl peroxide, ditriphenylmethyl perox-ide, bis(p-methoxy-benzoyl) peroxide, rubrene peroxide, ascaridol, t-butyl peroxybenzoate, t-butyl peroctoate, diethyl peroxyterephthalate, propyl hydroperoxide, iso-propyl hydroperoxide, n-butyl hydroperoxide, t-butyl hydroperoxide, cyclohexyl hydroperoxide, transdecalin hydroperoxide, alpha-methylbenzyl hydroperoxide, tetra-lin hydroperoxide, triphenylmethyl hydroperoxide, di-phenylmethyl hydroperoxide, 2,2'-azo-bis(2-methyl butyronitrile), 2,2'-azo-bis~2-methylheptonitrile), l,l'-azo-bis(l-cyclohexane carbonitrile), dimethyl alpha, alpha'-azo-isobutyrate, 4,4'-azo-bis(4-cyano-pentanoic acid), azo-bisisobutyrcnitrile, persuccinic acid, diisopropyl peroxy dicarbonate, and -the like.
A mixture of catalysts may also be used.
The temperature and catalysts are chosen such that the catalyst has a satisEactory half-life at the temperature employed; preferably, the half life should be about 25 percent or less of the residence time in the reactor at the given temperature.
Depending upon the amounts of polyol, anhydride and diepoxide reacted in forming the basic prepolymer various structures are possible. Reaction of 2 moles of hydroxy as polyol with 2 moles or less of anhydride and 2 mo~es or more of diepoxide will produce the fol-lowing prepolymer as the major prepolymer component in the composition, with R1-R5 independently being any group to which carbon atoms (or oxygen atoms) can be covalently bound to form a backbone chain, either unsubstituted (e.g.~ alkylene, arylene, alkylene/aryl-ene chains optionally interrupted by hetero atoms or groups, such as carbonyl, ester~ ether, sulfonyl, phos-phonyl, etc.) or substituted (as aboYe, with halogen,alkyl, aryl~ alkoxy, phenoxy, cyano, etc. substitution) and R is derived from R1-R5 to form a monovalent sub-s~ituent or is hydrogen:
R R R R R O O O ~ R R R R~ R
~I \ I .1 1 ll ll l 1 / \/
W R4-C--C-OC-R5-CO-R1-OC-R2-CO-C- C-R3~
O OH R R OH O
(I) s~
The presence of unsaturated anhydride and modi-fier will change either or both R2 and R5 in the above formula since these moieties would be due to the pres-ence of the unsaturated anhydride and would have the structure with the -CR-CR- comprising a portion of the backbone segments R2 and R5:
R7 ~ CR C ~
R8 R6 n Rg R10 m where R6-R13 are the same as R, above, in covering any atom or group of atoms to which carbon can be covalent-ly bound (including hydrogen). It can be, for example, any group derived from the initiator employed in this invention (e.g., benæoyloxy, acetyloxy, aryl, alkyl, cyano-isopropyl, 2-cyano-4-methyl-2-pentyl, t-butoxy, hydroxy, cumyl, cumyloxy, alkylcarboxy, etc.). R in the above formula is derived from the acid anhydride reactant and can also be hydrogen with m and n being O or any positive integer.
C-6446~6912 ~21~S~
- llA -Formation of this type of prepolymer is favored when the molar amount of anhydride is no more than 2 and the amount of diepoxide is not less than that of acid anhydride, based upon a molar amount of hydroxy groups in the polyol set at 2.
Depending upon the precise amounts of reactants employed, however, it is also possible to yield a pre-polymer in which one end contains a terminal epoxy group with associated non~terminal, hydroxy group, and the other end terminates in a hydroxy group. This pre-polymer has the formula given below with R, R1 and R3 having the same meaning as R-R5, above, and R2 having the same meaning as either R2 or R5:
O O R R R R R
" " ' ' ~ \/' HO-R1-OC-R2-CO-C--C-R3~7 R OH O
(II) ~21~5C3~
This type of prepolymer is produced in the process shown in U.S. Patent No. 3r 847~ 874 to Y. Murakami and is favored in the reaction when khe molar amount of acid anhydride is present in amounts which approximate one half the molar amount of the hydroxy groups in the polyol that is present, In Formula II R2 has the same for the modified prepolymer of the present invention given for R2 in regard to Formula I, above.
The present invention includes prepolymer composi-tions which contain mixtures of both the aforementioned modified prepolymers as well as either one alone.
The modified prepolymer composition can be formed by mixing the polyol, anhydride and diepoxide with suitable modifying monomer and unsaturated anhydride (or copolymer thereof) pxeferably in the presence of an effective amount (0.02 to 2%, by weight of all the reaction ingredients) of a catalyst designed to promote the reaction as well as the thQrmoset formulation.
Representative catalysts tending to favor oxazolidone formation include the quaternary ammonium salts (e.g,, tetramethyl ammonium chloride); the metal alkoxides (e.g., lithium n-butoxide); the metal halides (e.g., lithium chloride) and their complexes (e.g., lithium chloride/hexamethylphosphoramide complex); and the organometallic compounds (e.g., trialkyl aluminum).
Catalysts which favor urethane formation include the organotin compounds, diamines, and polyamines.
Once the modified prepolymer composition has been formed it is combined with a desired polyisocyanate, e.g,, diisocyante, to form a reaction mixture from which the modified poly(oxazolidone/urethane) thermoset compositions of the present invention can be formed.
1Z1~5J90 If desired, the reaction medium can contain up to about 60%, by weight, of other materials which do not inter-fere with the reaction of the prepolymer and polyiso-cyanate. Representative ingredients include additional diepoxide or polyepoxide (functions as a solvent, if liquid), diol o~ polyol, and acrylate or methacrylate ester polymer to impart flexibility to the final prod-uct. If desired the reaction medium can also contain up to about 10%, by weight, of one or more of the fol-lowing additives: blowing agents, ~lame retardants, coupling agents, dyes, stabilizers and mold releasing agents.
The amount of polyisocyanate chosen for reaction with the modi~ied prepolymer should be substantially equivalent in regard to its isocyanate functionality (on an equivalent bases) to the total equivalents of epoxide and hydroxy groups in the prepolymer composi-tion and any added ingredients which would react with the isocvanate. A slight excess o~ isocyanate (up to ahout 5% on a weight basis) can be toleratad but greater amounts whould be avoided since the formation of isocyanurate linkages would be favored. In general, the respective molar amount of oxazolidone and urethane linkages to one another in the thermoset will depend upon the type or types of prepolymers present and the presence o~ other isocyanate reactive groups added to the reaction mixture. If only the prepolymer composi-tion and polyisocyanate are used and the diepoxy/di-hydroxy prepolymer is present, a near 50:50 (oxazoli-done:urethane) molar ratio polymer is produced. If the prepolymer composition contains the dual hydroxy, epoxy prepolymer to a greater degree, a greater number C-64~6/6912 ~L~5~3~
of urethane linkages will be formed as compared to oxa-zolidone linkages, unless additional epoxy moieties are added. Addition of additional hydroxy group compounds, e.g., diol or polyol, will yield a larger molar amount S of urethane, whereas addition of epoxide materials, e.g., diepoxides, will incr~ase the oxazolidone content of the product. The molar amount of oxazolidone to urethane can range from 90:10 to 1:99. When the molar amount of hydroxy groups in the polyol is 2, the amount of anhy-dride should not exceed about 2 and the amount of die-poxide should not be less than that of anhydride.
Any polyisocyanate capable of reaction with theepoxy and hydroxy groups contained in the prepolymer to form the desired oxazolidone and urethane linkages is contemplated for use by the present invention. Repre-sentative examples of suitable conventional polyiso-cyanates, which are used to form urethane polymers, for example, include such aromatic and aliphatic types as:
the tolylene diisocyanates,the methylene bis(phenyl isocyanates), such as methylene bis~4-phenyl isocyanate), dianisidine diisocyanate, toluidine diisocyantes, m-xylene diisocyanate, 1,5-naphthylene diisocyanate, P-phenylene diisocyanate, and hexamethylene diisocyanate, carbodiimide modified diisocyanate (e.g., ~SONATE 143L
from Upjohn Co.) and other di~ and higher polyisocyan-ates. Mixtures of such isocyanates can be used, ifdesired as well as polymeric polyisocyanates.
The resulting thermoset composition formed from the above-described reac~ion mixture is one which con-tains oxazolidone and urethane linkages in the recur-ring unit or units and which is essentially free ofsubstantial amounts of isocyanurate linkages. The ultimate type of recurring unit and its amount will * Trademark , 12:~S~
be dictated by the type of prepolymer or prepolymers mainly presen-t in the prepolymer composition. Modified prepolymer (I) described above will produce a recurring unit of the following formula with R-R5 having the same meaning as R1-R5 and R6-R19 are independently the same as R1-R5 and also include hydrogen:
r ~ R
1 0 ~ ' ~ al9 C=O ~,3 --R ~ -N--C Rs R~o O O O O E~10 0 R14--C--N JEI--¦ ~C ~C~- R4-C-C--O-C-a~ C-O-R1-O-C-R2-C-O-C---C - R3-~ C~ I
O R~ O R11 R,7 R12 R1s O ` ¦
I C=O
N~ I
~III) where either or both R2 and R5 in the above formula may have the structure \
CR~ CR
R(CH2CHR6) / \ (CH2CHR7)mR
with R6 and R7 having the same meaning given hereto-fore~
Presence of modified prepolymer (II) will yield the following recurring unit with R-R3 having the same meaning as R1-R3 and R4-R11 are the same and also include hydrogen:
12~5~
~ ` R
r . I C=O R, 1 EI O O O R~ O R, o~C ~ R--n O~R,-O-C--R~-C OC , ~C~ o/ ~0 _ _ _ _ _ _ _ _ _ _ _ _ __ __ _ _ _ , (IV) Prepolymer compositions containing both prepolymers (I) and (II) would have a certain defined amount of both recurring units ~III) and(IV) dependiny on the amounts of prepolymer~ (I) and (II) in the composition reacted with the polyisocyanate.
Recurring unit III has oxazolidone linkages in its backbone by virtue of reaction of the polyisocyanate with the terminal epoxy groups of prepolymer I. It has urethane groups in pendant side chains, rather than in the same chain as the oxazolidone, due to reaction of the pendant, non-terminal secondary hydroxy group in the prepolymer. The oxazolidone linkages in the recurring unit III are separated from one another by the addition-al presence in the backbone of ester linkages which are derived from the anhydride reactant~
Recurring unit IV has a urethane linkage adjacent one end of the backbone of the recurring unit and an oxazolidone linkage at the other end. A urethane link-age exists in a side chain of the unit intermediate the urethane and oxazolidone linkages. Ester linkages lie in the backbone intermediate the oxazolidone linkages in the backbone and the urethane linkages in the side chain.
~21~S~
Poly(oxazolidone/urethane) thermoset compositions which ~orm a part of the present invention include those which contain recurring unit III, either alone, or in combination with no more than about 90% of IV.
The thermoset compositions of the present inven-tion are useful in the fabrication of molded articles of manu~acture, for example, by reaction injection molding techniques. If desired, the thermoset composi-tions can be combined with suitable relnforcing agents including gla*ss fibers or flakes, graphite, wollastonite, mica, KELVAR aromatic polyamide fiber, nylon fiber, either alone or in combination with one or more coupling agents.
The present invention is illustrated by the Examples which follow.
* Trademark 5~3~
A mixture containing 420 grams (0.428 equivalent weight of hydroxy groups~ of polypropylene glycol (NIAX
polyol PPG 2025 from Union Carbide Co.), 58 grams (0.392 equivalent weight) of phthalic anhydride, 1.0 gram (0.010 equivalent we;ght) of maleic anhydride, 154 grams (0.806 epoxy equivalent weight) of the di-glycidyl ether of bisphenol A (EP~N 828 brand,~rom ShelI Chemical Co.), and 3.5 grams of lithium chloride/
dimethylformamide complex (1/1.5) was heated at 125C.-135C. After 2-1/2 hours of heating, the resulting product was found to be free of acidic material.
The above unsaturated product was cooled to 35C.
and added to 70 grams (1.32 equi~alent weights) of acrylonitrile and 1.0 gram of a free radical azobisiso-butyronitrileinitiator (VAZO 64 brand from Du Pont).
The mixture was purged with nitrogen for 30 minutes and then heated to 70C. to initiate polymerization.
The mixture was subjected to cooling to maintain the temperature between 70C. and 90C. until the free radi-cal polymerization subsided. This took about one hour.
The product was stripped at high vacuum to eliminate residual monomers. The grafted prepolymer product, a free flowing liquid, had a viscosity o~ 500 poise (by Brookfield Viscometer Model L~T) at 22C.
A mixture of 80 grams (0.044 mole epoxy) of the above acrylonitrile-grafted prepolymer, 25.3 grams (0.816 hydroxy equivalent weight) o~ e~hylene glycol, 40 mg. of stannous octoate, and 8 mg. of dibutyltin dilaurate (T-12 brand from M and T Chemical Co.) was stirred under vacuum with 130 grams (0.909 isocyanate * Trademark ~Z~l~5.C3~
equivalent weight) of a carbodlimide modifi~d 4,~'-diphenyl methane diisocyanate (ISONATE 143L brand from Upjohn Chemical Co.). The final mixture, after becoming homogeneous, was poured into a preheated mold ~70C.). The resin cured in less than 30 seconds and was demolded and post-cured at 125C. for 1 hour. The thermoset plaque (3.1~ mm. thick) gave 415 kg/cm~ of tensile strength (ASTM D412), 11.6 x 103 kg/cm of flexural modulus (ASTM D 474), and 1.92 J/cm of notched IZOD impact resistance (ASTM D 256).
A specimen (2.54 cm x 15~24 cm) was cut from the thermoset plaque for the heat sag test which is a measurement of the ability of a plastic sample to resist distortion at an elevated temperature. The specimen was clamped onto a fixture at one end which left a 10.2 cm unsupported length. The fixture with the specimen was placed in an oven at 132C. for 60 minutes. ~he difference between the vertical dis-tances from the unsupported end of the specimen to the base of the test fixture measured before and after the heating was the heat sag. The specimen showed a heatsag of 1.1 cm.
~23l~
A mixture contalning 420 grams (0.428 hydroxy equivalent weight) of polypropylene glycol (NIAXpolyol PPG 2025 from Union Carbide Co.), 58 grams (0.392 equivalent weight) of phthalic anhydride, 0.20 grams ~0.002 equivalent weight) of maleic anhydride, 154 grams (0.806 epoxy equivalent weight) of the diglycidyl ether of bisphenol A (EPON 828 brand from Shell Chem-ical Co.), 3.5 grams of lithium chloride/dimethyl formamide (1/1.5 complex), 70 grams (1.32 equivalent weight) of acrylonitrile, 0.80 grams of benzoyl perox-ide, and 0.40 grams of t-butyl hydroperoxide was purged with nitrogen for 30 minutes. The mixture was stirred and heated at 125C. - 5C. until the resulting product was free of acidic material and the free radical poly-merization completed as indicated by slow condensation of acrylonitrile monomers inside the condenser. The residual monomers were stripped by high vacuum. The resulting prepolymer product was a yellow viscous liquid (6,000 poise at 24~C.) and had an epoxide equi-valent of 1847.
A thermoset plaque was made from the above prepoly-mer using the same compositions and procedures as they were described in the third paragraph of Example 1.
The thermoset plaque gave 462 kg/cm2 of tensile strength (ASTM D 412), 12.7 x 103 kg/cm2 of flexural modulus (ASTM D 474), 1.27 ~/cm of notched IZOD (ASTM D 256), and 0.8 cm of heat sag.
, lZ3L~S~C3() - 21. -~XAMPLES 3-5 Thé procedures set forth in Example 2 were applied in the following Examples. The various ingredients for the Examples are listed in Table I:
TAB~E I
__.
EXAMPLE NUMBER
Ingredients (~ram) 3 4 5 NIAX PPG 2025 Polyol 420 420 420 Phthalic Anhydride 58 58 58 Maleic Anhydride 0.50 2.0 1.0 EPON 828 Diepoxide 154154 154 LiCl DMF Complex (1/1.5) 3.5 3.5 0 ADOGEN 464 Catalyst 0 0 2.8 Acrylonitrile 70 70 70 Benzoyl Peroxide 0.80 0.80 0.80 ~-Butyl Hydroperoxide 0.40 0.40 0.40 Grafted prepolymer products obtained from these examples were employed to make thermoset plaques using the same compositions and procedures described in the third paragraph of Example 1. The physical property characteristics for the thermoset plaques are listed in Table II:
*.Trademark ~2:1~S~() EXAMPLES 3-5 (con;t'd.) TABLE II
EXAMPLE ~MBER
Physical Properties 3 4 5 Tensile Strength (kg/cm2) 423450 406 Flexural Modulus 10(kg/cm2) at Room Temperature: 16,900 14,500 12,000 at 70C.: 10,200 7,700 7,000 Notched IZOD Impact (J/cm~: 0.45 0.65 0.86 Heat Sag (cm): 1.0 1.0 0.5 ~2 1~3$C3~
Into a reaction flask equipped with a condenser, a nitrogen inlet, a thermometer, and a mechanical stir-rer was charged 150 gm. of polyethylene glycol (NIAXpolyol PPG 600 from Union Carbide Corp.), 72.5 gm. of phthalic anhydride, 1~0 gm. of maleic anhydride, and 190 gm. of the diglycidyl ether of bisphenol A. ~he mixture was heated at 120C. for about 35 minutes until the resulting product was not acidic.
The foregoing product was added to 230 gm. of acetone, 96 gm. of acrylonitrile, and 1.5 gm. of 2,2'-azobis-2,4-dimethylvaleronitrile initiator. After being ~lushed with nitrogen for 30 minutes the mixture was heated at 55-62C. for one hour. The resulting prepolymer product was stripped by high vacuum and had an epoxide equivalent of 1109.
A mixture containing 66.4 gm. of the foregoing pre-polymert 4.6 gm. of polyethylene glycol tCARBOWAX
PEG 20Q) and 20 mg~ of dibutyltin dilaurate was mixed with 65 ym. of a modi~ied diphenylmethane diisocyanate tISONATE 191 diisocyanate from Upjohn). After being made homogeneous, the mixture was poured into a pre-heated mold held at 80C. and cured for two minutes.
* Trademark . . , lZ~5~3() EXAMPLE_ ?
Into a reaction flask equipped with a condenser, a nitrogen inlet, a thermometer, and a mechanical stir-rer was charged 420 gm. of polypropylene glycol (NIAXpolyol PPG 2025), 58 gm. of phthalic anhydride, 1.0 gm.
of maleic anhydride, 70 gm. of acrylonitrile, 154 gm.
of the diglycidyl ether of bisphenol A, 3.5 gm. of lithium chloride/dimethyl formamide complex, 0.50 gm.
Of benzoylperoxide, and 0.45 gm.of t-butyl hydroperoxide The mixture, after being flushed with nitrogen at room temperature, was heated by an oil bath at 130C. In about three hours the resulting product was free of acidic material. The product was stripped by vacuum.
~ mixture containing 80 gm. of the above product, 25.3 gm. of ethylene glycol, 8 mg. of dibutyltin di-laurate, and 40 mg. of tin octoate was mixed with 130 gm. of a modified diphenylmethane diisocyanate (ISONATE
143L brand). The mixture, after being made homogeneous, was poured into a preheated (70C.) mold and cured in 10 seconds. The cured, molded part was then remo~ed from the mold and post cured at 125C. for one hour.
12~L~i.C~V
A mixture containing 420 grams (0.430 hydroxy equi~alent weight) of polypropylene glycol (~I~ Polyol PPG 2025 brand ~rom Union Carbide Co.), 58.0 grams (0.392 equivalent weight) of phthalic anhydride, 1.0 grams (Q.010 equivalent weight) of maleic anhydride, 33.5 grams (0.632 equi~alent weight) of acrylonitrile and 1.1 grams of azobisisobutyronitrileinitiator (VAZO
64 brand from DuPont) was purged with nitrogen for 30 minutes and heated at 70-80C. for about 45 minutes till the free radical polymerization subsided. The mixture was added with 154 grams (0.806 epoxy equiva-lent weight) of diglycidyl ether of bisphenol A (EPON
828 brand from Shell Chemical Co~) and 3.5 grams of lithium chloride/dimethyl formamide (1/1.5 complex).
The mixture was then heated at 125-135C. for about one hour till the resulting product was free of acidic material. A polyacrylonitrile grafted prepolymer was obtained.
A mixture of 80 grams of the above polyacryloni-trile grafted prepolymer, 25.3 grams (0.816 hydroxy equivalent weight) of ethylene glycol, 160 milligrams of stannous octoate, and 8 milligrams of dibutyltin dilaurate (T-12 brand from M and T Chemical Co.) was stirred under vacuum with 130 grams (0.909 isocyanate equivalent weight) of a modified 4,4l-diphenyl methane diisocyanate (ISONATE 143L brand from Upjohn Chemical Co.). The final mixture, after being homogeneous, was poured into a preheated mold (70C.). The resin cured in less than 30 seconds and was demolded and post cured at 125C. for 1 hour. The thermoset plaque (3.18 mm C-6~46/6912 ~Z1~3S9~) EXAMPLE 8 (co:nt'd.) thick) gave 384 kg/cm2 of tensile strength (ASTM ~412), 9.91 x 103 kg/c~ of flexural modulus (ASTM D474), and 1.33 J/cm of notched IZOD impact reslstance (ASTM D256).
The heat sag resistance of the sample was measured to be 2.7 cm by the same way as described in Example 1.
~2 195'30 A mixture containing 420 grams (0.430 hydroxy equivalent weight) of polypropylene glycol (NIAX polyol PPG 2025 brand from Union Carbide Co.), 58.0 grams (0.392 equivalent weight) of phthalic anhydride, 1.0 grams (0.010 equivalent weight) o-f maleic anhydride, 70.3 grams (1.33 equivalent weights) o~ acrylonitrile and 1.1 grams of azobisisobutyronitrileinitiator (VAZO
64 brand from Du Pont) was purged with nitrogen for 30 minutes and heated at 70-80C. for about 45 minutes till the free radical polymerization subsided. The mixture was added with 154 grams (0.806 epoxy equiva-lent weight) of diglycidyl ether of bisphenol A (EPON
828 brand ~rom Shell Chemical Co.) and 3.5 grams of lithium chloride/dimethyl formamide (1/1.5 complex).The mixture was then heated at 125-135C. for about one hour till the resulting product was free of acidic material. A polyacrylonitrile-grafted prepolymer was obtained.
A mixture of 80 grams o~ the abo~e polyacrylonitrile grafted prepolymer, 25.3 grams (0.816 hydroxy equiva-lent weight) of ethylene glycol, 160 milligrams of stannous octoate, and 8 milligrams of dibutyltin di-laurate (T-12 brand from M and T Chemical Co.) was stirred under vacuum with 130 grams (0.909 isocyanate equivalent weight) of a modified 4,4'-diphenyl methane diisocyanate (ISONATE 143L brand from Upjohn Chemical Co.). The final mixture, a~ter being homogeneous, was poured into a preheated mold (70C.). The resin cured in less than 30 seconds and was demolded and post cured EXAMPI.E 9 (cont'd~) at 125C. for 1 hour. The thermoset plaque (3.18 mm thick) gave 382 kg/cm2 of tensile strength (ASTM
D412), 11.8 x 103 kg/cm2 o~ flexural modulus (ASTM D474), and 1.07 J/cm of notched IZOD impact resistance (ASTM
D256). The heat sag resistance of the sample was measured to be 0.3 cm by the same way as described in Example 1.
~21~S~
A mixture containing 420 grams (0,~30 hydroxy equivalent ~eight) of polypropylene glycol (NIAX Polyol PPG 2025 brand from Union Carbide Co.), 58.0 grams (0.392 equivalent weight) of phthalic anhydride, 1.0 grams (0.010 equivalent weight) of maleic anhydride, 112 grams (2.11 equivalent weight) of acrylonitrile and 1.1 grams of azobisisobutyronitrileinitiator (VAZO 64 brand from Du Pont) was purged with nitrogen for 30 minutes and heated at 70-80C. for about 45 minutes till the free radical polymerization subsided. The mixture was added with 1~4 grams (0.806 epoxy equivalent weight) of diglycidyl ether of bisphenol A (EPON 828 brand from Shell Chemical Co.) and 3.5 grams of lithium chloride/
dimethyl formamide (1/1.5 complex). The mixture was then heated at 125-135C. for about one hour till the resulting product ~as free of acidic material. The polyacrylonitrile grafted prepolymer was obtained.
A mixture of 80 grams of the above polyacrylonitrile grafted prepolymer, 25.3 grams (0.816 hydroxy equivalent weight) of ethylene glycol, 160 milligrams of stannous octoate, and 8 milligrams of dibutyltin dilaurate (T-12 brand from M and T Chemical Co.) was stirred under 25 vacuum with 13Q grams (0.909 isocyanate equivalent weight) of a modified 4,4'-diphenyl methane diisocyanate (ISONATE 143L brand from Upjohn Chemical Co.~. The final mixture, after being homogeneous, was poured into a preheated mold (70C.). The resin cured in less than 30 30 seconds and was demolded and post cured at 125C. for 1 hour. The -thermoset plaque (3.18 mm thick) gave 384 kg/cm2 of tensile strength (ASTM ~412), 10.1 x 103 ~lZ~95,C3() EXAMPLE l a (cont'd.) kg/cm2 of flexural modulus (ASTM D474), and 1.87 J/cm of notched IZOD impact resistance (ASTM D256). The heat sag resistance of the sample was measured to be 1.1 cm by the same way as described in Example l.
19~9~
~ 31 -A mixture containing 420 grams (0.430 hydroxy equi-valent weight) of polypropylene glycol (NIAX Polyol PPG
2025 brand from Union Carbide Co.), 59 grams (0.602 equivalent weight) of phthalic anhydride, 154 grams (0.806 epoxy equivalent weight) of the diglycidyl ether of bisphenol A (EPON 828 brand from Shell Chemical Co ), and 2.5 grams of lithium chloride/dimethylformamide (1/1.5 complex) was heated at 125_135C. for about 75 minutes till the resulting product was free of acidic material. The product, a free flowing liquid, had a viscosity of 1,080 poise at 24C.
A mixture of 80 grams of the above product, 25.3 grams of ethylene glycol, 80 milligrams of stannous ocatoate, and 16 milligrams of dibutyltin dilaurate (T-12 brand from M and T Chemical Co.) was stirred under vacuum with 132 grams of a modified 4,4'-diphenyl meth-ane diisocyanate (ISONATE 143L brand from Upjohn Co.).
The final mixture, after being homogeneous, was poured into a preheated mold (70C.). The resin cured in less than 30 seconds and was demolded and post cured at 125C.
for 1 hour. The thermoset plaque (3.18 mm thick) gave 422 kg/cm2 of tensile strength (ASTM D412), 11.3 x 103 25 kg/cm2 of flexural modulus (ASTM D474), 1.06 J/cm of notched IZOD and 0.3 cm of heat sag.
12~553V
A mixture containing 420 grams (0.430 hydrox,v equi-valent ~eight) of polypropylene glycol (NIAX polyol PPG
2025 from Union Carbide Co.), 58 grams (0.392 equivalent weight) of phthalic anhydride, 2.0 grams (0.020 equiva-lent weight~ of maleic anhydride, 154 grams (0.806 epoxy equivalent weight) of the diglycidyl ether of bisphenol A (EPON 828 brand from Shell Chemical Co.), 2.22 grams of lithium chloride in methanol (30~ LiCl), 33.4 grams (0.321 equivalent weight) of styrene, 0.80 grams of benzoylperoxide, and 0.40 gramsof t-butyl hydro-peroxide was purged with nitrogen for 30 minutes. The mixture was stirred and heated at 125C.~5C. until the resulting product was free of acidic material and the free radical polymerization subsided. The residual monomers were stripped by high vacuum. The resulting prepolymer product was a cloudy viscous liquid (2240 poise at 24C.).
A thermoset plaque was made from the above prepoly-mer using the same compositions and procedures as they were described in the third paragraph of Example 1.
The thermoset plaque gave 485 kg/cm2 of tensile strength (ASTM D 412), 9.35 x 103 kg/cm2 of flexural modulus (ASTM D 474), 2.30 ~/cm of notched IZOD (ASTM D 256), and 1.8 cm of heat sag.
S~3V
A mixture containing 840 grams (0.860 hydroxy equi-valent weight) of polypropylene glycol (NIAX polyol PPG
2025 from Union Carbide Co.) and 4.22 grams of a 30%
lithium chloride solution in methanol was sparged with nitrogen at a rate of 5 liter/minute for one hour. To the the mixturewas thenadded 116 grams (0.784 equivalent weight) of phthalic anhydride, 2.0 grams (0.~20equivalent weight) of maleic anhydride, and 308 grams (1.61 epoxy equiva-lent weight) of the diylycidyl ether of bisphenol A
(EPON 828 brand from Shell Chemical Co.). The result-ing mixture was then stirred and heated at 120-4C.
until the resulting product had an acid number of less than 1.
To 540 grams of the above product was added 62 grams (0.60 equivalent weight) of styrene, 0.90 gram of an azo initiator (VAZO 52 brand from Du Pont), and 2.4 grams of bromotrichloromethane. The mixture was sparged with nitrogen for 30 minutes and then was heated with stirring at 50-56C. for about 16 hours.
The resulting product was a viscous liquid (620 poise at 24C.) and had an epoxide equivalent of 1883.
A thermoset plaque was made from the above pre-polymer as described in Example 1. It had a tensile stren~th (ASTM D 412) of 460 kg/cmZ~ a flexural modulus ~ASTM D 474) of 13.1 x 103 kg/cm2, a notched IZOD (ASTMD 256) of 1.55 J/cm., and a heat sag of 0.6 cm.
12~L5aS90 A mixture containing 300 grams ~1.0 hydroxy equiva-lent weight) of polye-thylene glycol (CARBOWAX 600 from Union Carbide) and 2.77 grams of a 30~ lithium chloride solution in methanol was stripped by applying 5 mm Hg vacuum for 10 minutes. To the mixture was then added 145 grams (0.98 equivalent weight) of phthalic anhydride,
3.0 grams ~0.031 equivalent weight)~,of maleic anhydride and 382 grams (2.0 epoxy equivalents) of EPON 828 diepox-ide. The mixture was stirred and heated at 125-10C.
until the resulting product had an acid number of less than 1.
To the above product at 60C. was then added, with lS stirring, 152 grams of ethylene glycol. To the result-ing mixturewas thenadded 555 grams (4.34 equivalentweights) of n-butyl acrylate, 10.6 grams of hydroxy-ethyl methacrylate, 17 grams of bromotrichloromethane chain transfer agent and 5.54 grams of azobiscyano-pentanoic acid. The resulting mixture was sparged with nitrogen for 30 minutes and then was heated with stir-ring at 75-85C. External cooling was applied while the free radical polymerization increased the tempera-ture above 85C. After about 2 hours, a sample of the resulting product was found to have 0.7~ of unpolymer-ized monomer. The product was then cooled and trans-ferred to a jar. The product had an epoxide equivalent of 1889 and a viscosity of 7,350 poise at 24C.
Thermoset plaques were made by using the procedures described in Example 1 with the following composition:
80 grams of the above prepolymer, 23.1 grams of ethylene glycol, 80 mg of stannous octoate, 64 mg of dibutyltin dilaurate and 157 grams of ISONATE 143L lsocyanate.
lZ195~3~) -- 35 ~
A mixture containing 315 grams (0.321 hydroxy equi-valent weight) of polypropylene glycol (NIAX Polyol PPG
2025 from Union Carbide) and 1.58 grams of a 30% lithium chloride solution in methanol was sparged by nitrogen at 5 liter/minu-te. After one hour sparging, it was mixed with 4.4 grams (0.045 equivalent weight) of maleic anhydride, 37>6 grams (0.254 equivalent weight) of phthalic anhydride, and 116 grams (0.607 epoxy equiva-lent weight) of the diglycidyl ether of bisphenol A
(EPON 828 brand from Shell Company). The mixture was heated with stirring at 120_5C. for about 25 hours until the product had an acid number of less than 1.
The above product, after cooling, was mixed with 65.7 grams of ethylene glycol, 114 grams (1.09 equiva-lent weights) of styrene, 4.0 grams of 2-hydroxyethyl methacrylate~ 4.7 grams of dipentene and 1.77 grams of an azobisisobutyronitrile initiator (VAZO 64 brand from Du Pont). The mixture was purged with nitrogen for 30 minutes and was heated with stirring to a tempera-ture above 60C. The external heating was controlled so that the polymerization temperature increased gradu-ally rom 60C. to 90C. in 2.5 hours. The product had 25 an epoxide equivalent of 2290 and a viscosity of 3800 poise at 25C.
A thermoset plaque was made from the above pre-polymer as in the method described in Example 1.
C-6446/6~12 5~3~
The Examples which are contained herein illustrate certain embodiments of the invention but should not be construed in a limiting sense. The scope o~ protection sought is set forth in the claims which follow.
until the resulting product had an acid number of less than 1.
To the above product at 60C. was then added, with lS stirring, 152 grams of ethylene glycol. To the result-ing mixturewas thenadded 555 grams (4.34 equivalentweights) of n-butyl acrylate, 10.6 grams of hydroxy-ethyl methacrylate, 17 grams of bromotrichloromethane chain transfer agent and 5.54 grams of azobiscyano-pentanoic acid. The resulting mixture was sparged with nitrogen for 30 minutes and then was heated with stir-ring at 75-85C. External cooling was applied while the free radical polymerization increased the tempera-ture above 85C. After about 2 hours, a sample of the resulting product was found to have 0.7~ of unpolymer-ized monomer. The product was then cooled and trans-ferred to a jar. The product had an epoxide equivalent of 1889 and a viscosity of 7,350 poise at 24C.
Thermoset plaques were made by using the procedures described in Example 1 with the following composition:
80 grams of the above prepolymer, 23.1 grams of ethylene glycol, 80 mg of stannous octoate, 64 mg of dibutyltin dilaurate and 157 grams of ISONATE 143L lsocyanate.
lZ195~3~) -- 35 ~
A mixture containing 315 grams (0.321 hydroxy equi-valent weight) of polypropylene glycol (NIAX Polyol PPG
2025 from Union Carbide) and 1.58 grams of a 30% lithium chloride solution in methanol was sparged by nitrogen at 5 liter/minu-te. After one hour sparging, it was mixed with 4.4 grams (0.045 equivalent weight) of maleic anhydride, 37>6 grams (0.254 equivalent weight) of phthalic anhydride, and 116 grams (0.607 epoxy equiva-lent weight) of the diglycidyl ether of bisphenol A
(EPON 828 brand from Shell Company). The mixture was heated with stirring at 120_5C. for about 25 hours until the product had an acid number of less than 1.
The above product, after cooling, was mixed with 65.7 grams of ethylene glycol, 114 grams (1.09 equiva-lent weights) of styrene, 4.0 grams of 2-hydroxyethyl methacrylate~ 4.7 grams of dipentene and 1.77 grams of an azobisisobutyronitrile initiator (VAZO 64 brand from Du Pont). The mixture was purged with nitrogen for 30 minutes and was heated with stirring to a tempera-ture above 60C. The external heating was controlled so that the polymerization temperature increased gradu-ally rom 60C. to 90C. in 2.5 hours. The product had 25 an epoxide equivalent of 2290 and a viscosity of 3800 poise at 25C.
A thermoset plaque was made from the above pre-polymer as in the method described in Example 1.
C-6446/6~12 5~3~
The Examples which are contained herein illustrate certain embodiments of the invention but should not be construed in a limiting sense. The scope o~ protection sought is set forth in the claims which follow.
Claims (20)
1. An isocyanate-reactive prepolymer containing at least one terminal epoxide group with an associated secondary hydroxy group, said prepolymer being modified by having grafted thereto a polymeric moiety derived from polymerizing an ethylenically unsaturated monomer.
2. A prepolymer as claimed in Claim 1 which has the formula with R1-R5 independently a group to which carbon atoms or oxygen atoms can be covalently bound to form a back-bone chain and R being derived from R1-R5 to form a monovalent substituent or hydrogen, with R1 and R5 being where R6-R13 are the same as R and m and n are 0 or any positive integer
3. A prepolymer as claimed in Claim 1 which has the formula with R1-R3 being independently a group to which carbon atoms or oxygen atoms can be covalently bound to form a backbone chain and R is derived from R1-R3 to form a monovalent substituent or is hydrogen, with R2 being where R6-R13 are the same as R and m and n are 0 or any positive integer.
4. A prepolymer as claimed in Claim 1 in which the polymeric moiety is derived from polymerizing a monomer which yields a relatively rigid polymeric material.
5. A prepolymer as claimed in Claim 2 wherein the polymeric moiety is derived from polymerizing a monomer which yields a relatively rigid polymeric material.
6. A prepolymer as claimed in Claim 3 in which the polymeric moiety is derived from polymerizing a monomer which yields a relatively rigid polymeric mater-ial.
7. A prepolymer as claimed in Claim 1 in which the ethylenically unsaturated monomer is selected from the group consisting of acrylonitrile, styrene, and methyl methacrylate.
8. A prepolymer as claimed in Claim 2 in which the ethylenically unsaturated monomer is selected from the group consisting of acrylonitrile, styrene, and methyl methacrylate.
9. A prepolymer as claimed in Claim 3 in which the ethylenically unsaturated monomer is selected from the group consisting of acrylonitrile, styrene, and methyl methacrylate.
10. A prepolymer as claimed in Claim 1 wherein the polymeric moiety is derived from polymerizing a monomer which yields a relatively rubbery polymeric material.
11. A prepolymer as claimed in Claim 2 wherein the polymeric moiety is derived from polymerizing a monomer which yields a relatively rubbery polymeric material.
12. A prepolymer as claimed in Claim 3 wherein the polymeric moiety is derived from polymerizing a monomer which yields a relatively rubbery polymeric material.
13. A prepolymer as claimed in Claim 1 in which the ethylenically unsaturated monomer is selected from the group consisting of the alkyl acrylates and higher alkyl methacrylates.
14. A prepolymer as claimed in Claim 2 wherein the ethylenically unsaturated monomer is selected from the group consisting of the alkyl acrylates and higher alkyl methacrylates.
15. A prepolymer as claimed in Claim 3 wherein the ethylenically unsaturated monomer is selected from the group consisting of the alkyl acrylates and higher alkyl methacrylates.
16. A thermoset composition containing oxazolidone and urethane linkages in its recurring unit which is essentially free of isocyanurate linkages, said oxazo-lidone linkages being present in the polymer backbone and separated from one another by ester linkages, said urethane linkages being present in side chains attached to the polymer backbone, the composition being modified by having grafted to the polymer backbone a polymeric moiety derived from polymerizing an ethylenically unsat-urated monomer.
17. A composition as claimed in Claim 16 in which the polymeric moiety is derived from polymerizing a monomer which yields a relatively rigid polymeric mater-ial.
18. A composition as claimed in Claim 16 wherein the ethylenically unsaturated monomer is selected from the group consisting of acrylonitrile, styrene, and methyl methacrylate.
19. A composition as claimed in Claim 16 wherein the polymeric moiety is derived from polymerizing a monomer which yields a relatively rubbery polymeric material.
20. A composition as claimed in Claim 16 wherein the ethylenically unsaturated monomer is selected from the group consisting of the alkyl acrylates and higher alkyl methacrylates.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/499,956 US4504633A (en) | 1983-06-01 | 1983-06-01 | Modified poly(oxazolidone/urethane) compositions |
| US499,956 | 1983-06-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1219590A true CA1219590A (en) | 1987-03-24 |
Family
ID=23987458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000449482A Expired CA1219590A (en) | 1983-06-01 | 1984-03-13 | Modified poly (oxazolidone/urethane) compositions |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4504633A (en) |
| EP (1) | EP0127976A3 (en) |
| JP (1) | JPS59227912A (en) |
| KR (1) | KR850002575A (en) |
| BR (1) | BR8402573A (en) |
| CA (1) | CA1219590A (en) |
| DD (1) | DD227712A5 (en) |
| ES (1) | ES533021A0 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2549277B1 (en) * | 1983-07-13 | 1985-10-25 | Alsthom Atlantique | METHOD OF INSULATION BY IMPREGNATION OF AN ELECTRICAL WINDING, AND VARNISH WITHOUT STABILIZED SOLVENT FOR USE IN THIS PROCESS |
| DE4019030A1 (en) * | 1990-06-14 | 1991-12-19 | Herberts Gmbh | EPOXY RESIN-BASED WATER-DISCOVERABLE BINDERS, METHOD FOR THE PRODUCTION AND USE THEREOF FOR AQUEOUS COATING AGENTS AND AQUEOUS COATING AGENTS |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US29118A (en) * | 1860-07-10 | Improved signal-lantern | ||
| US28715A (en) * | 1860-06-12 | Improvement in soldering handles of cutlery | ||
| USRE29118E (en) | 1963-02-06 | 1977-01-18 | Method of preparing polyurethanes from liquid, stable, reactive, film-forming polymer/polyol mixtures formed by polymerizing an ethylenically unsaturated monomer in a polyol | |
| USRE28715E (en) | 1964-08-12 | 1976-02-17 | Polyurethanes, reactive solutions and methods and their production | |
| DE1770619A1 (en) * | 1968-06-12 | 1971-11-11 | Bayer Ag | Graft polymers containing epoxy groups |
| BE759006A (en) * | 1969-11-20 | 1971-05-17 | Marles Kuhlmann Wyandotte | COPOLYMERS GRAFTS AND PREPARATION OF POLYURETHANES |
| US3823201A (en) * | 1972-12-04 | 1974-07-09 | Basf Wyandotte Corp | Highly-stable graft copolymer dispersions in polyols containing unsaturation and polyurethanes prepared therefrom |
| US4198488A (en) * | 1978-06-26 | 1980-04-15 | Union Carbide Corporation | Polymer-polyols and polyurethanes based thereon |
| US4261877A (en) * | 1979-03-06 | 1981-04-14 | Basf Wyandotte Corporation | Preparation of polyurethane from a blend of polyether polyols and a graft polyol which is the product of polymerization of an ethylenically unsaturated monomer with a polyol which contains unsaturation and oxyalkylene moieties |
| US4424316A (en) * | 1981-10-08 | 1984-01-03 | Stauffer Chemical Company | Compositions for forming poly(oxazolidone/urethane) thermosets and products therefrom |
| US4386191A (en) * | 1981-10-08 | 1983-05-31 | Stauffer Chemical Company | Compositions for forming poly(oxazolidone/urethane) thermosets and products therefrom |
-
1983
- 1983-06-01 US US06/499,956 patent/US4504633A/en not_active Expired - Fee Related
-
1984
- 1984-03-13 CA CA000449482A patent/CA1219590A/en not_active Expired
- 1984-04-07 KR KR1019840001826A patent/KR850002575A/en not_active IP Right Cessation
- 1984-05-14 JP JP59094763A patent/JPS59227912A/en active Pending
- 1984-05-18 EP EP84303401A patent/EP0127976A3/en not_active Withdrawn
- 1984-05-25 DD DD84263393A patent/DD227712A5/en not_active IP Right Cessation
- 1984-05-29 BR BR8402573A patent/BR8402573A/en unknown
- 1984-05-31 ES ES533021A patent/ES533021A0/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DD227712A5 (en) | 1985-09-25 |
| US4504633A (en) | 1985-03-12 |
| KR850002575A (en) | 1985-05-15 |
| EP0127976A2 (en) | 1984-12-12 |
| ES8602861A1 (en) | 1985-12-01 |
| ES533021A0 (en) | 1985-12-01 |
| EP0127976A3 (en) | 1986-05-07 |
| JPS59227912A (en) | 1984-12-21 |
| BR8402573A (en) | 1985-04-23 |
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