US3856883A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Graded rubber particles having hydroxy functionality and a polymeric crosslinking agent
Assignee: Ford Motor Co
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Filing: 1974-03-15
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Granted: 1974-12-24
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Expires: 1994-03-15
Abstract
Abstract Improvements in impact strength and fatigue properties of thermosets are made by incorporating therein particulate gradedrubber having functionality for reaction with constituents of the thermosets. The graded-rubber particles are characterized by having a rubbery core, a glass-like polymeric outer shell and hydroxy, surface functionality. In most thermoset systems, the thermosetable constituents, exclusive of particulate material, include a reactive prepolymer and, where applicable, a crosslinking agent. The thermosetable prepolymers illustrated for use with these hydroxy-functional, graded-rubber particles are carboxy-functional resins, epoxy-functional resins, hydroxyfunctional resins, melamine-formaldehyde resins and novalac (phenol-formaldehyde) resins.
Inventors
- 👤 R Dickie
- 👤 S Newman
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-23 18:32
CPC Classifications
C; C08; C08L; C08L57/00; C08L57/06; C08L57/10; C08J; C08J3/00; C08J3/12; C08J3/128; C08J3/24; C08J3/246; C08L63/00; C08J2333/00; C08J2333/04; C08J2333/06; C08J2333/10; C08J2333/12; Y; Y10; Y10S; Y10S525/00; Y10S525/902
Claims Analysis
Total Claims: 30
Claim 1
Independent Claim
122 words
IN A METHOD FOR FORMING A THERMOSET MATERIAL WHICH WHEREIN A CROSSLINKABLE RESIN AND A CROSSLINKING AMOUNT OF A CROSSLINKING AGENT REACTIVE THEREWITH ARE INTIMATELY MIXED AND REACTED WITH EACH OTHER, THE IMPROVEMENT WHEREIN: A. SAID CROSSLINKING AGENT IS A GRADED-RUBBER PARTICLE CONSISTING ESSENTIALLY OF I. ABOUT 10 TO ABOUT 90 WEIGHT PERCENT OF A CORE OF CROSSLINKED ACRYLIC POLYMER CONSISTING ESSENTIALLY OF A. A MINOR AND CROSSLINKING AMOUNT OF A DI- OR TRIFUNCTIONAL MONOMER CONTAINING 2 OR MORE NONCONJUGATED TERMINAL ETHYLENIC GROUPS, SAID MINOR AND CROSSLINKING AMOUNT NOT EXCEEDING ABOUT 20 MOLE PERCENT OF THE CORE REACTANTS, AND B. A REMAINDER CONSISTING ESSENTIALLY OF A MONOFUNCTIONAL MONOACRYLATE, SAID REMAINDER CONSTITUTING AT A MINIMUM ABOUT 80 MOLE PERCENT OF THE CORE REACTANTS
Claim 2
Dependent Claim
122 words
IN A METHOD FOR FORMING A THERMOSET MATERIAL WHICH WHEREIN A CROSSLINKABLE RESIN AND A CROSSLINKING AMOUNT OF A CROSSLINKING AGENT REACTIVE THEREWITH ARE INTIMATELY MIXED AND REACTED WITH EACH OTHER, THE IMPROVEMENT WHEREIN: A. SAID CROSSLINKING AGENT IS A GRADED-RUBBER PARTICLE CONSISTING ESSENTIALLY OF I. ABOUT 10 TO ABOUT 90 WEIGHT PERCENT OF A CORE OF CROSSLINKED ACRYLIC POLYMER CONSISTING ESSENTIALLY OF A. A MINOR AND CROSSLINKING AMOUNT OF A DI- OR TRIFUNCTIONAL MONOMER CONTAINING 2 OR MORE NONCONJUGATED TERMINAL ETHYLENIC GROUPS, SAID MINOR AND CROSSLINKING AMOUNT NOT EXCEEDING ABOUT 20 MOLE PERCENT OF THE CORE REACTANTS, AND B. A REMAINDER CONSISTING ESSENTIALLY OF A MONOFUNCTIONAL MONOACRYLATE, SAID REMAINDER CONSTITUTING AT A MINIMUM ABOUT 80 MOLE PERCENT OF THE CORE REACTANTS
Claim 3
Dependent Claim
139 words
ABOUT 90 TO ABOUT 10 WEIGHT PERCENT OF AN OUTER SHELL HAVING GLASS TRANSITION TEMPERATURE ABOVE THAT OF SAID CORE AND CONSISTING ESSENTIALLY OF THE POLYMERIZATION PRODUCT OF A MIXTURE OF ABOUT 30 TO ABOUT 98 MOLE PERCENT METHYL METHACRYLATE 0 TO ABOUT 68 MOLE PERCENT OF UNSATURATED MONOMERS SELECTED FROM MONOFUNCTIONAL MONOACYLTES, DICRYLATES, MONOVINYL HYDROCARBONS AND ABOUT 2 TO ABOUT 35 MOLE PERCENT OF A MONOMER HAVING AN OLEFINIC GROUP REACTABLE WITH SAID METHYL METHACRYLATE AND HYDROXYFUNCTIONAL GROUP WHICH A. REMAINS UNREACTED IN SAID POLYMERIZATION AND B, PROVIDES THAT SHELL WITH HYDROXY SURFACEFUNCTIONALITY THAT IS REACTIVE WITH SAID CROSSLINKABLE RESIN, AND B. SAID CROSSLINKABLE RESIN IS SELECTED FROM MELAMINEFORMALDEHYDE RESINS, COPOLYMERS OF UNSATURATED MONOMERS HAVING REPEATING FUNCTIONAL GROUPS SELECTED FROM CARBOXY FUNCTIONALITY EPOXY FUNCTIONALITY, AND HYDROXY FUNCTIONALITY, AND A POLYEPOXIDE HAVING AT LEAST TWO EPOXIDE GROUPS PER MOLECULE.
Claim 4
Dependent Claim
139 words
ABOUT 90 TO ABOUT 10 WEIGHT PERCENT OF AN OUTER SHELL HAVING GLASS TRANSITION TEMPERATURE ABOVE THAT OF SAID CORE AND CONSISTING ESSENTIALLY OF THE POLYMERIZATION PRODUCT OF A MIXTURE OF ABOUT 30 TO ABOUT 98 MOLE PERCENT METHYL METHACRYLATE 0 TO ABOUT 68 MOLE PERCENT OF UNSATURATED MONOMERS SELECTED FROM MONOFUNCTIONAL MONOACYLTES, DICRYLATES, MONOVINYL HYDROCARBONS AND ABOUT 2 TO ABOUT 35 MOLE PERCENT OF A MONOMER HAVING AN OLEFINIC GROUP REACTABLE WITH SAID METHYL METHACRYLATE AND HYDROXYFUNCTIONAL GROUP WHICH A. REMAINS UNREACTED IN SAID POLYMERIZATION AND B, PROVIDES THAT SHELL WITH HYDROXY SURFACEFUNCTIONALITY THAT IS REACTIVE WITH SAID CROSSLINKABLE RESIN, AND B. SAID CROSSLINKABLE RESIN IS SELECTED FROM MELAMINEFORMALDEHYDE RESINS, COPOLYMERS OF UNSATURATED MONOMERS HAVING REPEATING FUNCTIONAL GROUPS SELECTED FROM CARBOXY FUNCTIONALITY EPOXY FUNCTIONALITY, AND HYDROXY FUNCTIONALITY, AND A POLYEPOXIDE HAVING AT LEAST TWO EPOXIDE GROUPS PER MOLECULE.
Claim 5
Dependent Claim
140 words
about 90 to about 10 weight percent of an outer shell having glass transition temperature above that of said core and consisting essentially of the polymerization product of a mixture of about 30 to about 98 mole percent methyl methacrylate, 0 to about 68 mole percent of unsaturated monomers selected from monofunctional monoacylates, diacrylates, monovinyl hydrocarbons, and about 2 to about 35 mole percent of a monomer having an olefinic group reactable with said methyl methacrylate and a hydroxyfunctional group which a. remains unreacted in said polymerization and b. provides said shell with hydroxy surface-functionality that is reactive with said crosslinkable resin, and B. said crosslinkable resin is selected from melamine-formaldehyde resins, copolymers of unsaturated monomers having repeating functional groups selected from carboxy functionality, epoxy functionality, and hydroxy functionality, and a polyepoxide having at least two epoxide groups per molecule.
Claim 6
Dependent Claim
140 words
about 90 to about 10 weight percent of an outer shell having glass transition temperature above that of said core and consisting essentially of the polymerization product of a mixture of about 30 to about 98 mole percent methyl methacrylate, 0 to about 68 mole percent of unsaturated monomers selected from monofunctional monoacylates, diacrylates, monovinyl hydrocarbons, and about 2 to about 35 mole percent of a monomer having an olefinic group reactable with said methyl methacrylate and a hydroxyfunctional group which a. remains unreacted in said polymerization and b. provides said shell with hydroxy surface-functionality that is reactive with said crosslinkable resin, and B. said crosslinkable resin is selected from melamine-formaldehyde resins, copolymers of unsaturated monomers having repeating functional groups selected from carboxy functionality, epoxy functionality, and hydroxy functionality, and a polyepoxide having at least two epoxide groups per molecule.
Claim 7
Dependent Claim
73 words
A method in accordance with claim 1 wherein said core is formed from about 80 to about 98 mole percent of an ester of acrylic acid and a C2 - C8 monohydric alcohol and about 2 to about 20 mole percent of a divinyl benzene, a diester of acrylic or methacrylic acid and a C2 - C8 dihydric alcohol or a triester of acrylic or methacrylic acid and a C2 -C8 trihydric alcohol.
Claim 8
Dependent Claim
102 words
about 90 to about 10 weight percent of an outer shell having glass transition temperature above that of said core and consisting essentially of the polymerization product of a mixture of about 30 to about 98 mole percent methyl methacrylate, 0 to about 68 mole percent of unsaturated monomers selected from monofunctional monoacrylates, diacrylates, monovinyl hydrocarbons, and about 2 to about 35 mole percent of a monomer having an olefinic group reactable with said methyl methacrylate and a hydroxy-functional group which a. remains unreacted in said polymerization and b. provides said shell with hydroxy surfacefunctionality that is reactive with said crosslinkable resin.
Claim 9
Dependent Claim
102 words
about 90 to about 10 weight percent of an outer shell having glass transition temperature above that of said core and consisting essentially of the polymerization product of a mixture of about 30 to about 98 mole percent methyl methacrylate, 0 to about 68 mole percent of unsaturated monomers selected from monofunctional monoacrylates, diacrylates, monovinyl hydrocarbons, and about 2 to about 35 mole percent of a monomer having an olefinic group reactable with said methyl methacrylate and a hydroxy-functional group which a. remains unreacted in said polymerization and b. provides said shell with hydroxy surfacefunctionality that is reactive with said crosslinkable resin.
Claim 10
Dependent Claim
143 words
about 90 to about 10 weight percent of an outer shell having glass transition temperature above that of said core and consisting essentially of the polymerization product of a mixture of about 30 to about 98 mole percent methyl methacrylate, 0 to about 68 mole percent of unsaturated monomers selected from monofunctional monoacrylates, diacrylates, monovinyl hydrocarbons, and about 2 to about 35 mole percent of a monomer having an olefinic group reactable with said methyl methacrylate and a hydroxy-functional group which a. remains unreacted in said polymerization and b. provides said shell with hydroxy surfacefunctionality that is reactive with said crosslinkable resin, and B. said crosslinkable resin is selected from melamine-formaldehyde resins, novalac (phenol-formaldehyde) resins, copolymers of unsaturated monomers having repeating functional groups selected from carboxy functionality, eposy functioNality, and hydroxy functionality, and a polyepoxide having at least two epoxide groups per molecule.
Claim 11
Dependent Claim
143 words
about 90 to about 10 weight percent of an outer shell having glass transition temperature above that of said core and consisting essentially of the polymerization product of a mixture of about 30 to about 98 mole percent methyl methacrylate, 0 to about 68 mole percent of unsaturated monomers selected from monofunctional monoacrylates, diacrylates, monovinyl hydrocarbons, and about 2 to about 35 mole percent of a monomer having an olefinic group reactable with said methyl methacrylate and a hydroxy-functional group which a. remains unreacted in said polymerization and b. provides said shell with hydroxy surfacefunctionality that is reactive with said crosslinkable resin, and B. said crosslinkable resin is selected from melamine-formaldehyde resins, novalac (phenol-formaldehyde) resins, copolymers of unsaturated monomers having repeating functional groups selected from carboxy functionality, eposy functioNality, and hydroxy functionality, and a polyepoxide having at least two epoxide groups per molecule.
Claim 12
Dependent Claim
102 words
about 90 to about 10 weight percent of an outer shell having glass transition temperature above that of said core and consisting essentially of the polymerization product of a mixture of about 30 to about 98 mole percent methyl methacrylate, 0 to about 68 mole percent of unsaturated monomers selected from monofunctional monoacrylates, diacrylates, monovinyl hydrocarbons, and about 2 to about 35 mole percent of a monomer having an olefinic group reactable with said methyl methacrylate and a hydroxy-functional group which a. remains unreacted in said polymerization and b. provides said shell with hydroxy surface-functionality that is reactive with said crosslinkable resin.
Claim 13
Dependent Claim
102 words
about 90 to about 10 weight percent of an outer shell having glass transition temperature above that of said core and consisting essentially of the polymerization product of a mixture of about 30 to about 98 mole percent methyl methacrylate, 0 to about 68 mole percent of unsaturated monomers selected from monofunctional monoacrylates, diacrylates, monovinyl hydrocarbons, and about 2 to about 35 mole percent of a monomer having an olefinic group reactable with said methyl methacrylate and a hydroxy-functional group which a. remains unreacted in said polymerization and b. provides said shell with hydroxy surface-functionality that is reactive with said crosslinkable resin.
Claim 14
Dependent Claim
18 words
A method in accordance with claim 1 wherein said crosslinkable resin is an epoxy-functional copolymer of unsaturated monomers.
Claim 15
Dependent Claim
18 words
A method in accordance with claim 1 wherein said crosslinkable resin is a hydroxy-functional copolymer of unsaturated monomers.
Claim 16
Dependent Claim
22 words
A method in accordance with claim 1 wherein said crosslinkable resin is a polyepoxide having at least two epoxide groups per molecule.
Claim 17
Dependent Claim
84 words
In a method for forming a thermoset material wherein a crosslinkable resin which is a copolymer of unsaturated monomers and has repeating functional groups selected from carboxy-functionality, epoxy-functionality and hydroxy-functionality is intimately mixed with crosslinking amounts of a polyepoxide having at least 2 epoxide groups per molecule and said crosslinkable resin and said polyepoxide are subsequently reacted with each other, the improvement wherein said polyepoxide and said crosslinkable resin are intimately mixed prior to reaction with graded-rubber particles, said graded-rubber particles consisting essentially of
Claim 18
Dependent Claim
84 words
In a method for forming a thermoset material wherein a crosslinkable resin which is a copolymer of unsaturated monomers and has repeating functional groups selected from carboxy-functionality, epoxy-functionality and hydroxy-functionality is intimately mixed with crosslinking amounts of a polyepoxide having at least 2 epoxide groups per molecule and said crosslinkable resin and said polyepoxide are subsequently reacted with each other, the improvement wherein said polyepoxide and said crosslinkable resin are intimately mixed prior to reaction with graded-rubber particles, said graded-rubber particles consisting essentially of
Claim 19
Dependent Claim
74 words
A method in accordance with claim 6 wherein said core is formed from about 80 to about 98 mole percent of an ester or acrylic acid and a C2 - C8 monohydric alcohol and about 2 to about 20 mole percent of a divinyl benzene, a diester of acrylic or methacrylic acid and a C2 - C8 dihydric alcohol or a triester of acrylic or methacrylic acid and a C2 - C8 trihydric alcohol.
Claim 20
Dependent Claim
15 words
A method in accordance with claim 6 wherein the functionality of said copolymer is epoxy-functionality.
Claim 21
Dependent Claim
15 words
A method in accordance with claim 6 wherein the functionality of said copolymer is hydroxy-functionality.
Claim 22
Dependent Claim
15 words
A method in accordance with claim 6 wherein the functionality of said copolymer is carboxy-functionality.
Claim 23
Dependent Claim
40 words
In a thermoset material wherein a crosslinkable resin and a crosslinking amount of a crosslinking agent reactive therewith are intimately mixed and reacted with each other, the improvement wherein A. said crosslinking agent is a graded-rubber particle consisting essentially of
Claim 24
Dependent Claim
40 words
In a thermoset material wherein a crosslinkable resin and a crosslinking amount of a crosslinking agent reactive therewith are intimately mixed and reacted with each other, the improvement wherein A. said crosslinking agent is a graded-rubber particle consisting essentially of
Claim 25
Dependent Claim
73 words
A method in accordance with claim 11 wherein said core is formed from about 80 to about 98 mole percent of an ester of acrylic acid and a C2 - C8 monohydric alcohol and about 2 to about 20 mole percent if divinyl benzene, a diester of acrylic or methacrylic acid and a C2 - C8 dihydric alcohol or a triester of acrylic or methacrylic acid and a C2 - C8 trihydric alcohol.
Claim 26
Dependent Claim
19 words
A thermoset material in accordance with claim 12 wherein said crosslinkable resin is an epoxy-functional copolymer of unsaturated monomers.
Claim 27
Dependent Claim
19 words
A thermoset material in accordance with claim 12 wherein said crosslinkable resin is a hydroxy-functional copolymer of unsaturated monomers.
Claim 28
Dependent Claim
19 words
A thermoset material in accordance with claim 12 wherein said crosslinkable resin is a hydroxy-functional copolymer of unsaturated monomers.
Claim 29
Dependent Claim
71 words
In a thermoset material wherein a crosslinkable resin which is a copolymer of unsaturated monomers and has repeating functional groups selected from carboxy-functionality, epoxy-functionality and hydroxy-functionality and crosslinking amounts of a polyepoxide having at least 2 epoxide groups per molecule are intimately mixed and reacted with each other, the improvement wherein said polyepoxide and said crosslinkable resin are intimately mixed and reacted with graded-rubber particles, said graded-rubber particles consisting essentially of
Claim 30
Dependent Claim
71 words
In a thermoset material wherein a crosslinkable resin which is a copolymer of unsaturated monomers and has repeating functional groups selected from carboxy-functionality, epoxy-functionality and hydroxy-functionality and crosslinking amounts of a polyepoxide having at least 2 epoxide groups per molecule are intimately mixed and reacted with each other, the improvement wherein said polyepoxide and said crosslinkable resin are intimately mixed and reacted with graded-rubber particles, said graded-rubber particles consisting essentially of
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1977-12-23 | 1978-06-24 | 1978-12-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1981-12-23 | 1982-06-24 | 1982-12-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1985-12-23 | 1986-06-24 | 1986-12-24 | $7700.00 | Window Closed / Lapsed |