US4524162A
Expired / Lapsed
US
⏱️ 0.0 years remaining
Low shrinking curable molding compositions containing a poly(acrylate)
Assignee: Union Carbide Corp
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Filing: 1983-05-26
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Granted: 1985-06-18
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Expires: 2003-05-26
Abstract
Abstract This invention is directed to curable molding compositions containing a mixture of a poly(acrylate); a polymerizable ethylenically unsaturated monomer which serves to crosslink the poly(acrylate) to a thermoset product; a crosslinkable vinyl monomer having a reactivity ratio (r 1 ) with styrene of greater than one and at least one of the following: (i) a second crosslinkable vinyl monomer having a reactivity ratio (r 1 ) with styrene of greater than one, (ii) an epoxy compound having at least one 1,2-epoxy group per molecule, and (iii) an unsaturated fatty acid ester; and a thermoplastic polymer low profile additive. The curable molding compositions exhibit improved shrink control during the curing reaction. This invention is also directed to fiber reinforced thermoset resin articles which exhibit generally improved surface appearance quality and can be produced by a rapid injection molding process from the curable molding compositions.
Inventors
- 👤 Linda A. Domeier
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 15:41
CPC Classifications
C; C08; C08F; C08F263/00; C08F263/02; C08F263/04; C08F222/00; C08F222/10; C08F222/1006; C08F222/102; C08F222/1025; C08F291/00
Claims Analysis
Total Claims: 32
Claim 1
Independent Claim
179 words
A curable molding composition suitable for the preparation of fiber reinforced molded articles by a rapid cure, injection molding process, comprising a mixture of: (a) a poly(acrylate) characterized by the following empirical formula: ##STR27## wherein R is the hydroxy-free residue of an organic polyhydric alcohol which contains alcoholic hydroxyl groups bonded to different carbon atoms, R 1 and R 2 are independently hydrogen or methyl, and n is 1 to 3; (b) an ethylenically unsaturated monomer which is soluble in and copolymerizable with (a); (c) a crosslinkable vinyl monomer having a reactivity ratio (r 1 ) with styrene of greater than one and at least one of the following: (i) a second crosslinkable vinyl monomer having a reactivity ratio (r 1 ) with styrene of greater than one; (ii) an epoxy compound having at least one 1,2-epoxy group per molecule; and (iii) an unsaturated fatty acid ester; and (d) a thermoplastic polymer low profile additive which is soluble in the mixture of (a), (b) and (c), said composition having a viscosity of from about 10 to about 1000 centipoise.
Claim 2
Dependent Claim
179 words
A curable molding composition suitable for the preparation of fiber reinforced molded articles by a rapid cure, injection molding process, comprising a mixture of: (a) a poly(acrylate) characterized by the following empirical formula: ##STR27## wherein R is the hydroxy-free residue of an organic polyhydric alcohol which contains alcoholic hydroxyl groups bonded to different carbon atoms, R 1 and R 2 are independently hydrogen or methyl, and n is 1 to 3; (b) an ethylenically unsaturated monomer which is soluble in and copolymerizable with (a); (c) a crosslinkable vinyl monomer having a reactivity ratio (r 1 ) with styrene of greater than one and at least one of the following: (i) a second crosslinkable vinyl monomer having a reactivity ratio (r 1 ) with styrene of greater than one; (ii) an epoxy compound having at least one 1,2-epoxy group per molecule; and (iii) an unsaturated fatty acid ester; and (d) a thermoplastic polymer low profile additive which is soluble in the mixture of (a), (b) and (c), said composition having a viscosity of from about 10 to about 1000 centipoise.
Claim 3
Dependent Claim
57 words
A curable molding composition as defined in claim 1 wherein the poly(acrylate) is selected from one or more of the following: ethoxylated bisphenol A dimethacrylate, ethoxylated bisphenol A diacrylate, propoxylated bisphenol A dimethacrylate, propoxylated bisphenol A diacrylate, tetraethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, diethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate.
Claim 4
Dependent Claim
30 words
A curable molding composition as defined in claim 1 wherein the poly(acrylate) is blended with at least one other thermosettable organic material containing two or more polymerizable carbon-carbon double bonds.
Claim 5
Dependent Claim
26 words
A curable molding composition as defined in claim 1 wherein the poly(acrylate) is present in an amount of from about 10 to about 75 weight percent.
Claim 6
Dependent Claim
16 words
A curable molding composition as defined in claim 1 wherein the ethylenically unsaturated monomer comprises styrene.
Claim 7
Dependent Claim
22 words
A curable molding composition as defined in claim 1 wherein the ethylenically unsaturated monomer comprises a mixture of styrene and 2-hydroxyethyl methacrylate.
Claim 8
Dependent Claim
28 words
A curable molding composition as defined in claim 1 wherein the ethylenically unsaturated monomer is present in an amount of from about 10 to about 75 weight percent.
Claim 9
Dependent Claim
30 words
A curable molding composition as defined in claim 1 wherein the crosslinkable vinyl monomer having a reactivity ratio (r 1 ) with styrene of greater than one comprises vinyl acetate.
Claim 10
Dependent Claim
41 words
A curable molding composition as defined in claim 1 wherein the crosslinkable vinyl monomer having a reactivity ratio (r 1 ) with styrene of greater than one is present in an amount of from about 1 to about 30 weight percent.
Claim 11
Dependent Claim
58 words
A curable molding composition as defined in claim 1 wherein the second crosslinkable vinyl monomer having a reactivity ratio (r 1 ) with styrene of greater than one is selected from vinyl stearate, vinyl norbornene, dicyclopentadiene, butyl vinyl ether, diallyl phthalate, dodecene, 1-octene, 1-nonene, 1-decene, alpha olefin mixtures, a compound of the following formula: ##STR28## and mixtures thereof.
Claim 12
Dependent Claim
42 words
A curable molding composition as defined in claim 1 wherein the second crosslinkable vinyl monomer having a reactivity ratio (r 1 ) with styrene of greater than one is present in an amount of from about 1 to about 30 weight percent.
Claim 13
Dependent Claim
117 words
A curable molding composition as defined in claim 1 wherein the epoxy compound having at least one 1,2-epoxy group per molecule is selected from ##STR29## wherein n is an integer representing the number of repeating units and has a value of from 0 to about 10 and Z is an arylene radical having from 6 to about 20 carbon atoms; 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate having the formula; ##STR30## bis(2,3-epoxycyclopentyl)ether having the formula: ##STR31## vinyl cyclohexene dioxide having the formula: ##STR32## 2-(3,4-epoxycyclohexyl-5,5-spiro)-(3,4 epoxy)cyclohexane-m-dioxane having the formula: ##STR33## cyclohexylmethyl epoxycyclohexane carboxylate having the formula: ##STR34## 3-(3,4-epoxycyclohexane)-8,9-epoxy-2,4-dioxaspiro[5,5]-undecane having the formula: ##STR35## bis(3,4-epoxy-cyclohexylmethyl)adipate having the formula: ##STR36## epoxidized pentaerythritol tetratallate; epoxidized soy bean oil; octyl epoxytallate; epoxidized linseed oil; and mixtures thereof.
Claim 14
Dependent Claim
27 words
A curable molding composition as defined in claim 1 wherein the epoxy compound is present in an amount of from about 1 to about 30 weight percent.
Claim 15
Dependent Claim
35 words
A curable molding composition as defined in claim 1 wherein the unsaturated fatty acid ester is selected from tall oil, soybean oil, linseed oil, 2-ethylhexyl tallate, glycerol tallate, pentaerythritol tallate, glycerol oleate and mixtures thereof.
Claim 16
Dependent Claim
29 words
A curable molding composition as defined in claim 1 wherein the unsaturated fatty acid ester is present in an amount of from about 1 to about 30 weight percent.
Claim 17
Dependent Claim
36 words
A curable molding composition as defined in claim 1 wherein the thermoplastic polymer low profile additive is selected from thermoplastic polymers of vinyl acetate, saturated polyesters, polyalkyl acrylates or methacrylates, polystyrene or mixtures or copolymers thereof.
Claim 18
Dependent Claim
24 words
A curable molding composition as defined in claim 1 wherein the thermoplastic polymer low profile additive comprises a carboxylated vinyl acetate polymer or polystyrene.
Claim 19
Dependent Claim
40 words
A curable molding composition as defined in claim 17 wherein the carboxylated vinyl acetate polymer is a copolymer of vinyl acetate and an ethylenically unsaturated carboxylic acid selected from acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid.
Claim 20
Dependent Claim
24 words
A curable molding composition as defined in claim 17 wherein the carboxylated vinyl acetate polymer is a copolymer of vinyl acetate and acrylic acid.
Claim 21
Dependent Claim
30 words
A curable molding composition as defined in claim 1 wherein the thermoplastic polymer low profile additive is present in an amount of from about 5 to about 25 weight percent.
Claim 22
Dependent Claim
20 words
A curable molding composition as defined in claim 1 further comprising a free radical initiator or a mixture of initiators.
Claim 23
Dependent Claim
17 words
A curable molding composition as defined in claim 1 further comprising unsubstituted or substituted meta- and/or para-divinylbenzene.
Claim 24
Dependent Claim
30 words
A curable molding composition as defined in claim 22 wherein the unsubstituted or substituted meta- and/or para-divinylbenzene comprises unsubstituted meta-divinylbenzene, unsubstituted para-divinylbenzene or mixtures thereof or mixtures thereof containing ethylvinylbenzene.
Claim 25
Dependent Claim
31 words
A curable molding composition as defined in claim 1 wherein the unsubstituted or substituted meta, and/or para-divinylbenzene is present in an amount of from about 2 to about 75 weight percent.
Claim 26
Dependent Claim
24 words
A curable molding composition as defined in claim 1 further comprising a filler selected from calcium carbonate, clay, hydrated alumina, silica and mixtures thereof.
Claim 27
Dependent Claim
10 words
A molded article prepared from the composition of claim 1.
Claim 28
Dependent Claim
36 words
A molded article as defined in claim 26 which contains from about 10 to about 75 weight percent of one or more fibers having a melting point or a glass transition temperature above about 130° C.
Claim 29
Dependent Claim
23 words
A molded article as defined in claim 27 wherein the fiber is selected from fiberglass, carbon fibers, aromatic polyamide fibers, and mixtures thereof.
Claim 30
Dependent Claim
10 words
A molded article prepared from the composition of claim 25.
Claim 31
Dependent Claim
36 words
A molded article as defined in claim 29 which contains from about 10 to about 75 weight percent of one or more fibers having a melting point or a glass transition temperature above about 130° C.
Claim 32
Dependent Claim
23 words
A molded article as defined in claim 30 wherein the fiber is selected from fiberglass, carbon fibers, aromatic polyamide fibers, and mixtures thereof.
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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) | 1988-06-17 | 1988-12-17 | 1989-06-18 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-06-17 | 1992-12-17 | 1993-06-18 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-06-17 | 1996-12-17 | 1997-06-18 | $7700.00 | Window Closed / Lapsed |