US4507444A
Expired / Lapsed
US
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High-impact polymer alloys
Assignee: Bayer AG
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Filing: 1981-08-21
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Granted: 1985-03-26
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Expires: 2001-08-21
Abstract
Abstract A process of making radically polymerizable compositions suitable for the production of impact resistant optically clear glass like plastic and forming the glass from such compositions is disclosed. Also taught are the polymerizable compositions and the final glass produced. An isocyanate terminated prepolymer based upon a polyol selected from polyesters, polyester amides, polycarbonates and polyacetals and diisocyanates selected from branched aliphatic isocyanates, cycloaliphatic isocyanates and aliphatic or cycloaliphatic isocyanates graft polymerized with vinyl monomers is chain extended with aliphatic or cyloaliphatic diamines while in solution in vinyl monomers consisting mainly of methacrylic acid esters. The chain extension is carried out with a deficit of amine and preferably to a viscosity at 20% solids in the vinyl monomers of between 200 and 30,000 cP at 20° C. The composition is then radically polymerized to form the high impact glass like plastic alloy.
Inventors
- 👤 Wilhelm Slawyk
- 👤 Gerhard Balle
- 👤 Manfred Munzer
- 👤 Adolf Wohnhas, deceased
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 13:44
CPC Classifications
C; C08; C08G; C08G18/00; C08G18/06; C08G18/28; C08G18/67; C08G18/671; C08G18/672; C08F; C08F283/00; C08F283/006; C08F283/008; C08F290/00; C08F290/02; C08F290/06; C08F290/067; C08G18/40; C08G18/63; C08G18/637; C08G2270/00
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
373 words
A process for the production of optically clear high-impact polymer alloys by the radically initiated polymerization of homogeneous mixtures of: (A) from about 40 to 92%, by weight, of one or more monomeric esters of methacrylic acid and, optionally, small quantities of one or more copolymerizable vinyl monomers wherein from about 80-100 mol %, based on the total quantities of polymerizable monomers, of one or more monomeric esters of methacrylic acid and from about 0-20 mol %, based on the total quantity of polymerizable monmers, of one or more copolymerizable vinyl monomers are employed; and (B) from about 8 to 60 parts of a substantially linear polyurethane urea elastomer; wherein the polyurethane urea elastomer is initially synthesized by polyaddition from: (1) one or more substantially linear polyester, polyester amide, polyacetal or polycarbonate Polyols having a molecular weight of from about 500 to 6000 and, optionally, from about 0 to 20 mol %, based on the total polyol component, of diols having a molecular weight of from about 62 to 500; (2) a polyisocyanate selected from the group consisting of isophorone diisocyanate, 4, 4'-dicyclohexyl methane diisocyanate and graft polymerization products of an aliphatic or cycloaliphatic diisocyanate and 10 to 100 parts by weight of a vinyl monomer per 100 parts of diisocyanate; (3) one or more aliphatic or cycloaliphatic diamines; and, optionally, (4) a saturated or olefinically unsaturated compound having monofunctional reactivity towards isocyanates; by preparing a prepolymer containing from about 1 to 5%, by weight, of NCO groups from component (1) and (2) in a first stage, reacting the prepolymer dissolved in the polymerizable monomeric ester of methacrylic acid in a second stage with component (3) in an isocyanate:amino-equivalent ratio of between about 1.01:1 and 1.5:1, optionally in the presence of more copolymerizable vinyl monomers, until an about 20% solution of polyurethane urea in the monomer would have a viscosity of from about 200 to 30,000 cP at 20° C., optionally reacting any free NCO groups still present in a third reaction stage by adding component (4), adjusting the solids content of the solution to from about 8 to 60%, by weight, optionally by adding more vinyl monmers, and finally subjecting the mixture to radically initiated polymerization in known manner, optionally in molds.
Claim 2
Dependent Claim
373 words
A process for the production of optically clear high-impact polymer alloys by the radically initiated polymerization of homogeneous mixtures of: (A) from about 40 to 92%, by weight, of one or more monomeric esters of methacrylic acid and, optionally, small quantities of one or more copolymerizable vinyl monomers wherein from about 80-100 mol %, based on the total quantities of polymerizable monomers, of one or more monomeric esters of methacrylic acid and from about 0-20 mol %, based on the total quantity of polymerizable monmers, of one or more copolymerizable vinyl monomers are employed; and (B) from about 8 to 60 parts of a substantially linear polyurethane urea elastomer; wherein the polyurethane urea elastomer is initially synthesized by polyaddition from: (1) one or more substantially linear polyester, polyester amide, polyacetal or polycarbonate Polyols having a molecular weight of from about 500 to 6000 and, optionally, from about 0 to 20 mol %, based on the total polyol component, of diols having a molecular weight of from about 62 to 500; (2) a polyisocyanate selected from the group consisting of isophorone diisocyanate, 4, 4'-dicyclohexyl methane diisocyanate and graft polymerization products of an aliphatic or cycloaliphatic diisocyanate and 10 to 100 parts by weight of a vinyl monomer per 100 parts of diisocyanate; (3) one or more aliphatic or cycloaliphatic diamines; and, optionally, (4) a saturated or olefinically unsaturated compound having monofunctional reactivity towards isocyanates; by preparing a prepolymer containing from about 1 to 5%, by weight, of NCO groups from component (1) and (2) in a first stage, reacting the prepolymer dissolved in the polymerizable monomeric ester of methacrylic acid in a second stage with component (3) in an isocyanate:amino-equivalent ratio of between about 1.01:1 and 1.5:1, optionally in the presence of more copolymerizable vinyl monomers, until an about 20% solution of polyurethane urea in the monomer would have a viscosity of from about 200 to 30,000 cP at 20° C., optionally reacting any free NCO groups still present in a third reaction stage by adding component (4), adjusting the solids content of the solution to from about 8 to 60%, by weight, optionally by adding more vinyl monmers, and finally subjecting the mixture to radically initiated polymerization in known manner, optionally in molds.
Claim 3
Dependent Claim
52 words
A process as claimed in claim 1, wherein a polyester of adipic acid and one or more aliphatic diols, optionally in combination with up to about 30 mol % of a polyester of phthalic acid, isophthalic acid or terephthalic acid, or a mixed polyester of corresponding composition is used as component (1).
Claim 4
Dependent Claim
47 words
A process as claimed in claim 2, wherein the polyester component used additionally contains a polyester diol containing polymerizable double bonds based on maleic acid, fumaric acid or itaconic acid or consists of a mixed polyester or a combination of mixed polyesters having a corresponding gross composition.
Claim 5
Dependent Claim
56 words
A process as claimed in claims 1, 2 or 3, wherein a hexamethylene diisocyanate, 2,2,4- and/or 2,4,4-trimethyl hexamethylene diisocyanate, cyclohexane diisocyanate, methyl cyclohexane diisocyanate, bicyclohexyl methane diisocyanate or isophorone diisocyanate modified by graft copolymerization with from about 10 to 100%, by weight, based on diisocyanate, of one or more vinyl monomers is used as the diisocyanate.
Claim 6
Dependent Claim
17 words
A process as claimed in claims 1, 2 or 3, wherein isophorone diamine is used as chain-extender.
Claim 7
Dependent Claim
29 words
A process as claimed in claims 1, 2 or 3, wherein a compound free from olefinically unsaturated groups and having monofunctional reactivity towards isocyanates is used as the chain-terminator.
Claim 8
Dependent Claim
20 words
A process as claimed in claim 6, wherein an alcohol or a primary or secondary alkylamine is used as chain-terminator.
Claim 9
Dependent Claim
31 words
A process as claimed in claims 1, 2 or 3, wherein a compound containing an olefinic double bond in the molecule and having monofunctional reactivity towards isocyanates is used as chain-terminator.
Claim 10
Dependent Claim
40 words
A process as claimed in claim 8, wherein the chain terminator is selected from the group consisting of an olefinically unsaturated alcohol, an olefinically unsaturated primary or secondary aliphatic amine and a hydroxyl ester of an α, β-unsaturated carboxylic acid.
Claim 11
Dependent Claim
8 words
The product of the process of claim 6.
Claim 12
Dependent Claim
343 words
A radically polymerizable optically clear composition comprising homogeneous mixtures of: (A) from about 40 to 92%, by weight, of one or more monomeric esters of methacrylic acid and, optionally, small quantities of one or more copolymerizable vinyl monomers wherein from about 80-100 mol %, based on the total quantities of polymerizable monomers, of one or more monomeric esters of methacrylic acid and from about 0-20 mol %, based on the total quantity of polymerizable monomers, of one or more copolymerizable vinyl monomers are employed; and (B) from about 8 to 60 parts of a substantially linear polyurethane urea elastomer; wherein the polyurethane elastomer is initially synthesized by polyaddition from: (1) one or more substantially linear polyester, polyester amide, polyacetal or polycarbonate polyols having a molecular weight of from about 500 to 6000 and, optionally, from about 0 to 20 mol %, based on the total polyol component, of diols having a molecular weight of from about 62 to 500; (2) a polyisocyanate selected from the group consisting of isophorone diisocyanate, 4,4'-dicyclohexyl methane diisocyanate and graft polymerization products of an aliphatic or cycloaliphatic diisocyanate and 10 to 100 parts by weight of a vinyl monomer per 100 parts of diisocyanate; (3) one or more aliphatic or cycloaliphatic diamines; and, optionally, (4) a saturated compound having monofunctional reactivity towards isocyanates; by preparing a prepolymer containing from about 1 to 5%, by weight, of NCO-groups from component (1) and (2) in a first stage, reacting the prepolymer dissolved in the polymerizable monomeric ester of methacrylic acid in a second stage with component (3) in an isocyanate:amine equivalent ratio of between about 1.01:1 and 1.5:1, optionally in the presence of more copolymerizable vinyl monomers, until an about 20% solution of polyurethane area in the monomer would have a viscosity of from about 200 to 30,000 cP at 20° C., optionally reacting any free NCO-groups still present in a third reaction stage by adding component (4), and adjusting the solids content of the solution to from about 8 to 60%, by weight, optionally by adding more vinyl monmers.
Claim 13
Dependent Claim
343 words
A radically polymerizable optically clear composition comprising homogeneous mixtures of: (A) from about 40 to 92%, by weight, of one or more monomeric esters of methacrylic acid and, optionally, small quantities of one or more copolymerizable vinyl monomers wherein from about 80-100 mol %, based on the total quantities of polymerizable monomers, of one or more monomeric esters of methacrylic acid and from about 0-20 mol %, based on the total quantity of polymerizable monomers, of one or more copolymerizable vinyl monomers are employed; and (B) from about 8 to 60 parts of a substantially linear polyurethane urea elastomer; wherein the polyurethane elastomer is initially synthesized by polyaddition from: (1) one or more substantially linear polyester, polyester amide, polyacetal or polycarbonate polyols having a molecular weight of from about 500 to 6000 and, optionally, from about 0 to 20 mol %, based on the total polyol component, of diols having a molecular weight of from about 62 to 500; (2) a polyisocyanate selected from the group consisting of isophorone diisocyanate, 4,4'-dicyclohexyl methane diisocyanate and graft polymerization products of an aliphatic or cycloaliphatic diisocyanate and 10 to 100 parts by weight of a vinyl monomer per 100 parts of diisocyanate; (3) one or more aliphatic or cycloaliphatic diamines; and, optionally, (4) a saturated compound having monofunctional reactivity towards isocyanates; by preparing a prepolymer containing from about 1 to 5%, by weight, of NCO-groups from component (1) and (2) in a first stage, reacting the prepolymer dissolved in the polymerizable monomeric ester of methacrylic acid in a second stage with component (3) in an isocyanate:amine equivalent ratio of between about 1.01:1 and 1.5:1, optionally in the presence of more copolymerizable vinyl monomers, until an about 20% solution of polyurethane area in the monomer would have a viscosity of from about 200 to 30,000 cP at 20° C., optionally reacting any free NCO-groups still present in a third reaction stage by adding component (4), and adjusting the solids content of the solution to from about 8 to 60%, by weight, optionally by adding more vinyl monmers.
Claim 14
Dependent Claim
173 words
A process for the production of radically polymerizable optically clear compositions comprising chain-extending in isocyanate terminated polyurethane prepolymer dissolved in about 40 to 92 wt. % of vinyl monomers being substantially monomeric esters of methacrylic acid wherein (A) the prepolymer has a free NCO content of between about 1 and 5 wt. % and is synthesized from (1) one or more substantially linear polyester, polyester amide, polyacetal or polycarbonate polyols having a molecular weight of from about 500 to 6000 and, optionally, from about 0 to 20 mol %, based on the total polyol component, of diols having a molecular weight of from about 62 to 500; and (2) a polyisocyanate selected from the group consisting of isophorone diisocyanate, 4,4'-dicyclohexyl methane diisocyanate and graft polymerization products of an aliphatic or cycloaliphatic diisocyanate and 10 to 100 parts by weight of a vinyl monomer per 100 parts of diisocyanate; and (b) The chain extension is effected with aliphatic or cycloaliphatic diamines at an isocyanate to amino equivalent ratio of between about 1.01:1 and 1.5:1.
Claim 15
Dependent Claim
173 words
A process for the production of radically polymerizable optically clear compositions comprising chain-extending in isocyanate terminated polyurethane prepolymer dissolved in about 40 to 92 wt. % of vinyl monomers being substantially monomeric esters of methacrylic acid wherein (A) the prepolymer has a free NCO content of between about 1 and 5 wt. % and is synthesized from (1) one or more substantially linear polyester, polyester amide, polyacetal or polycarbonate polyols having a molecular weight of from about 500 to 6000 and, optionally, from about 0 to 20 mol %, based on the total polyol component, of diols having a molecular weight of from about 62 to 500; and (2) a polyisocyanate selected from the group consisting of isophorone diisocyanate, 4,4'-dicyclohexyl methane diisocyanate and graft polymerization products of an aliphatic or cycloaliphatic diisocyanate and 10 to 100 parts by weight of a vinyl monomer per 100 parts of diisocyanate; and (b) The chain extension is effected with aliphatic or cycloaliphatic diamines at an isocyanate to amino equivalent ratio of between about 1.01:1 and 1.5:1.
Claim 16
Dependent Claim
72 words
The composition of claim 11 wherein the polyol is a polyester diol based on: (A) 50 to 100 mol %, of optionally olefinically unsaturated aliphatic dicarboxylic acids; and (B) from 0 to 50 mol %, of cycloaliphatic and/or aromatic dicarboxylic acids, with reference to the acid component of the polyester, having a molecular weight of from about 600 to 4000 and having a glass transition temperature of at most about -20° C.
Claim 17
Dependent Claim
40 words
The composition of claim 13 wherein the acid component of the polyester is derived from: (A) between about 65 and 95 mol % aliphatic dicarboxylic acid, and (B) between about 5 and 35 mol % cycloaliphatic and aromatic dicarboxylic acid.
Claim 18
Dependent Claim
359 words
A process for the production of optically clear high-impact polymer alloys by the radically initiated polymerization of homogeneous mixtures of: (A) from about 40 to 92%, by weight, of one or more monomeric esters of methacrylic acid and, optionally, small quantities of one or more copolymerizable vinyl monomers wherein from about 80-100 mol %, based on the total quantities of polymerizable monomers, of one or more monomeric esters of methacrylic acid and from about 0-20 mol %, based on the total quantity of polymerizable monomers, of one or more copolymerizable vinyl monomers are employed; and (B) from about 8 to 60 parts of a substantially linear polyurethane urea elastomer; wherein the polyurethane urea elastomer is initially synthesized by polyaddition from: (1) one or more substantially linear polyester, polyester amide, polyacetal or polycarbonate polyols having a molecular weight of from about 500 to 6000 and, optionally, from about 0 to 20 mol %, based on the total polyol component, of diols having a molecular weight of from about 62 to 500; (2) a polyisocyanate comprising graft polymerization products of an aliphatic or cycloaliphatic diisocyanate and 10 to 100 parts by weight of a vinyl monomer per 100 parts of diisocyanate; (3) one or more aliphatic or cycloaliphatic diamines; and, optionally, (4) a saturated or olefinically unsaturated compound having monofunctional reactivity towards isocyanates; by preparing a prepolymer containing from about 1 to 5%, by weight, of NCO-groups from components (1) and (2) in a first stage, reacting the prepolymer dissolved in the polymerizable monomeric ester of methacrylic acid in a second stage with component (3) in an isocyanate:amino-equivalent ratio of between about 1.01:1 and 1.5:1, optionally in the presence of more copolymerizable vinyl monomers, until an about 20% solution of polyurethane urea in the monomer would have a viscosity of from about 200 to 30,000 cP at 20° C., optionally reacting any free NCO-groups still present in a third reaction stage by adding component (4), adjusting the solids content of the solution to from about 8 to 60%, by weight, optionally by adding more vinyl monomers, and finally subjecting the mixture to radically initiated polymerization in known manner, optionally in molds.
Claim 19
Dependent Claim
359 words
A process for the production of optically clear high-impact polymer alloys by the radically initiated polymerization of homogeneous mixtures of: (A) from about 40 to 92%, by weight, of one or more monomeric esters of methacrylic acid and, optionally, small quantities of one or more copolymerizable vinyl monomers wherein from about 80-100 mol %, based on the total quantities of polymerizable monomers, of one or more monomeric esters of methacrylic acid and from about 0-20 mol %, based on the total quantity of polymerizable monomers, of one or more copolymerizable vinyl monomers are employed; and (B) from about 8 to 60 parts of a substantially linear polyurethane urea elastomer; wherein the polyurethane urea elastomer is initially synthesized by polyaddition from: (1) one or more substantially linear polyester, polyester amide, polyacetal or polycarbonate polyols having a molecular weight of from about 500 to 6000 and, optionally, from about 0 to 20 mol %, based on the total polyol component, of diols having a molecular weight of from about 62 to 500; (2) a polyisocyanate comprising graft polymerization products of an aliphatic or cycloaliphatic diisocyanate and 10 to 100 parts by weight of a vinyl monomer per 100 parts of diisocyanate; (3) one or more aliphatic or cycloaliphatic diamines; and, optionally, (4) a saturated or olefinically unsaturated compound having monofunctional reactivity towards isocyanates; by preparing a prepolymer containing from about 1 to 5%, by weight, of NCO-groups from components (1) and (2) in a first stage, reacting the prepolymer dissolved in the polymerizable monomeric ester of methacrylic acid in a second stage with component (3) in an isocyanate:amino-equivalent ratio of between about 1.01:1 and 1.5:1, optionally in the presence of more copolymerizable vinyl monomers, until an about 20% solution of polyurethane urea in the monomer would have a viscosity of from about 200 to 30,000 cP at 20° C., optionally reacting any free NCO-groups still present in a third reaction stage by adding component (4), adjusting the solids content of the solution to from about 8 to 60%, by weight, optionally by adding more vinyl monomers, and finally subjecting the mixture to radically initiated polymerization in known manner, optionally in molds.
Claim 20
Dependent Claim
34 words
The process of claim 15 wherein said diisocyanate used for preparing the graft polymerization products is hexamethylene diisocyanate, 2,2,4- and/or 2,4,4-trimethyl hexamethylene diisocyanate, cyclohexane diisocyanate, methyl cyclohexane diisocyanate, bicyclohexyl methane diisocyanate or isophorone diisocyanate.
Claim 21
Dependent Claim
10 words
The product of the process of claim 15 or 16.
Claim 22
Dependent Claim
17 words
The composition of claim 11 wherein the component (4) is a monoalcohol or primary or secondary alkylamine.
Claim 23
Dependent Claim
8 words
The product of the process of claim 7.
References Cited (Backward Citations)
US4097439A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1988-03-25 | 1988-09-24 | 1989-03-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-03-25 | 1992-09-24 | 1993-03-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-03-25 | 1996-09-24 | 1997-03-26 | $7700.00 | Window Closed / Lapsed |