US4401793A
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Polymeric adducts with pendant polymerizable double bonds, their preparation and use as reactive thickeners in improved anaerobic compositions
Assignee: Ingredion Inc
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Filing: 1981-09-04
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Granted: 1983-08-30
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Expires: 2001-09-04
Abstract
Abstract Novel stable anaerobic compositions are prepared which contain, as a novel reactive thickener, a polymerizable polymeric adduct having pendant double bonds which is dissolved in a polymerizable monomeric diluent. The anaerobic compositions show improved performance properties. The thickener is prepared by reacting an anhydride-containing polymer with an excess of a C 2 -C 5 hydroxyalkyl acrylate or methacrylate (e.g. hydroxyethyl and hydroxypropyl methacrylate), optionally in the presence of (meth)acrylate monomers which are not reactive with the anhydride groups of the polymer and which act as an additional diluent. The polymer may be prepared by conventional free radical polymerization techniques using maleic, citraconic, and/or itaconic anhydride and an ethylenically unsaturated monomer (e.g. C 1 -C 10 alkyl acrylates or methacrylates or styrene).
Inventors
- 👤 Wen B. Chiao
- 👤 Dilip K. Ray-Chaudhuri
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 02:06
CPC Classifications
C; C08; C08F; C08F290/00; C08F290/02; C08F290/04; C08F290/046; C09; C09J; C09J4/00
Claims Analysis
Total Claims: 15
Claim 1
Independent Claim
170 words
An anaerobic composition, comprising: (A) about 5-95% by weight of a polymerizable, anaerobically curable C 2 -C 5 hydroxyalkyl acrylate or methacrylate monomer; (B) about 5-95% by weight of a polymerizable polymeric adduct having pendant double bonds as a reactive thickener; the adduct being the additive reaction product of the C 2 -C 5 hydroxyalkyl acrylate or methacrylate monomer of (A) and an anhydride-containing polymer derived from about 0.5-50 mole % maleic, citraconic, or itaconic anhydride and about 50-99.5 mole % of a monomer having the formula CH 2 ═C(R 1 )X, wherein R 1 is H, CH 3 or CN, X is a phenyl or COOR group, and R is a halogen substituted or unsubstituted C 1 -C 10 alkyl group or a halogen, alkoxy, or ester substituted or unsubstituted C 7 -C 20 aralkyl group, the adduct being free of unreacted anhydride groups; (C) 0-15% by weight of a carboxyl-containing monomer; and (D) a free radical inhibitor in sufficient concentration to initiate cure upon the exclusion of oxygen.
Claim 2
Dependent Claim
170 words
An anaerobic composition, comprising: (A) about 5-95% by weight of a polymerizable, anaerobically curable C 2 -C 5 hydroxyalkyl acrylate or methacrylate monomer; (B) about 5-95% by weight of a polymerizable polymeric adduct having pendant double bonds as a reactive thickener; the adduct being the additive reaction product of the C 2 -C 5 hydroxyalkyl acrylate or methacrylate monomer of (A) and an anhydride-containing polymer derived from about 0.5-50 mole % maleic, citraconic, or itaconic anhydride and about 50-99.5 mole % of a monomer having the formula CH 2 ═C(R 1 )X, wherein R 1 is H, CH 3 or CN, X is a phenyl or COOR group, and R is a halogen substituted or unsubstituted C 1 -C 10 alkyl group or a halogen, alkoxy, or ester substituted or unsubstituted C 7 -C 20 aralkyl group, the adduct being free of unreacted anhydride groups; (C) 0-15% by weight of a carboxyl-containing monomer; and (D) a free radical inhibitor in sufficient concentration to initiate cure upon the exclusion of oxygen.
Claim 3
Dependent Claim
28 words
The composition of claim 1, further comprising an additive for free radical polymerization selected from the group consisting of a stabilizer, an accelerator, a chelator, and mixtures thereof.
Claim 4
Dependent Claim
51 words
The composition of claim 1, wherein (A) is about 25-50% of hydroxyethyl methacrylate and (B) is about 50-75% of the reaction product of hydroxyethyl methacrylate and the polymer derived from about 75-98.5% of a C 1 -C 8 alkyl acrylate or methacrylate or styrene and about 1.5-25% maleic or citraconic anhydride.
Claim 5
Dependent Claim
48 words
The composition of claim 3, wherein (B) is the reaction product of hydroxyethyl methacrylate and the polymer of ethyl acrylate/maleic anhydride (95-98.5/1.5-5%), ethyl acrylate/citraconic anhydride (98.5/1.5%), ethyl methacrylate/maleic anhydride (96.5/3.5%), ethyl acrylate/methyl methacrylate/maleic anhydride (86.5-91.5/5-10/3.5%), ethyl acrylate/butyl acrylate/maleic anhydride (56.5-86.5/10-40/3.5%), butyl acrylate/styrene/maleic anhydride (82/15/3%), or styrene/maleic anhydride (75/25%).
Claim 6
Dependent Claim
18 words
The composition of claim 4, wherein (C) is acrylic or methacrylic acid present in an amount of 0.5-10%.
Claim 7
Dependent Claim
51 words
The composition of claim 1, wherein (A) is about 25-50% of hydroxypropyl methacrylate and (B) is about 50-75% of the reaction product of hydroxypropyl methacrylate and the polymer derived from about 75-98.5% of a C 1 -C 8 alkyl acrylate or methacrylate or styrene and about 1.5-25% maleic or citraconic anhydride.
Claim 8
Dependent Claim
23 words
The composition of claim 5, wherein (B) is the reaction product of hydroxypropyl methacrylate and the polymer of methyl methacrylate/octyl acrylate/maleic anhydride (37/60/3%).
Claim 9
Dependent Claim
19 words
The composition of claim 7, wherein (C) is acrylic acid or methacrylic acid present in an amount of 0.5-10%.
Claim 10
Dependent Claim
124 words
The composition of claim 1, wherein the anaerobically curable monomer of (A) further comprises a monomer selected from the group consisting of (a) monofunctional acrylate and methacrylate esters or derivatives of the esters being selected from the group consisting of amide, cyano, chloro, and silane and (b) polyfunctional acrylate and methacrylate esters having the formula ##STR8## wherein R 5 is H, CH 3 , C 2 H 5 , or CH 2 OC(═O)C(R 6 )═CH 2 ; R 6 is H, Cl, CH 3 , or C 2 H 5 ; R 7 is H, OH, or O═C(═O)C(R 6 )═CH 2 ; m is an integer from 1 to 8; n is an integer from 1 to 20; and p is 0 or 1.
Claim 11
Dependent Claim
20 words
The composition of claim 9, wherein the monofunctional ester is isobornyl methacrylate and the polyfunctional ester is tetraethylene glycol dimethacrylate.
Claim 12
Dependent Claim
60 words
The composition of claim 1, wherein (A) is a mixture of about 27% hydroxyethyl methacrylate and 10% isobornyl methacrylate and (B) is the reaction product of ethyl acrylate/maleic anhydride polymer (98.5/1.5%) and wherein (A) is a mixture of 20% hydroxyethyl methacrylate and 17% tetraethylene glycol dimethacrylate and (B) is the reaction product of hydroxyethyl methacrylate and styrene/maleic anhydride polymer (75/25%).
Claim 13
Dependent Claim
124 words
The anaerobic composition of claim 1, prepared by: (a) polymerizing, in the presence of a solvent and a free radical initiator, the anhydride and the monomer having the formula CH 2 ═(C(R 1 )X; (b) stripping off any unreacted monomer and solvent from the anhydride-containing polymer; (c) reacting the stripped polymer with the C 2 -C 5 -hydroxyalkyl acrylate or methacrylate monomer to form the adduct, the hydroxyalkyl (meth)acrylate monomer being used in an excess of the number of moles required to react by addition with the anhydride groups of the polymer, the excess dissolving the adduct and serving as the anaerobically curable monomer of (A); and (d) adding a free radical initiator in sufficient concentration to initiate cure upon the exclusion of oxygen.
Claim 14
Dependent Claim
157 words
A process for improving an anaerobic composition based on a polymerizable anaerobically curable C 2 -C 5 hydroxyalkyl acrylate or methacrylate monomer, and a free radical initiator, which comprises the step of adding thereto from about 5-95% by weight of a reactive thickener, based on the total composition weight; the reactive thickener comprising at least one polymerizable polymeric adduct having pendant double bonds; the adduct being the addition reaction product of a C 2 -C 5 hydroxyalkyl acrylate or methacrylate monomer and an anhydride-containing polymer derived from about 0.5-50 mole % maleic, citraconic, or itaconic anhydride and about 50-99.5 mole % of a monomer having the formula CH 2 ═C(R 1 )X, wherein R 1 is H, CH 2 or CN, X is a phenyl or COOR group, and R is a halogen substituted or unsubstituted C 1 -C 10 alkyl group or a halogen, alkoxy, or ester substituted or unsubstituted C 7 -C 20 aralkyl group.
Claim 15
Dependent Claim
157 words
A process for improving an anaerobic composition based on a polymerizable anaerobically curable C 2 -C 5 hydroxyalkyl acrylate or methacrylate monomer, and a free radical initiator, which comprises the step of adding thereto from about 5-95% by weight of a reactive thickener, based on the total composition weight; the reactive thickener comprising at least one polymerizable polymeric adduct having pendant double bonds; the adduct being the addition reaction product of a C 2 -C 5 hydroxyalkyl acrylate or methacrylate monomer and an anhydride-containing polymer derived from about 0.5-50 mole % maleic, citraconic, or itaconic anhydride and about 50-99.5 mole % of a monomer having the formula CH 2 ═C(R 1 )X, wherein R 1 is H, CH 2 or CN, X is a phenyl or COOR group, and R is a halogen substituted or unsubstituted C 1 -C 10 alkyl group or a halogen, alkoxy, or ester substituted or unsubstituted C 7 -C 20 aralkyl group.
References Cited (Backward Citations)
US4104241A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-08-29 | 1987-02-28 | 1987-08-30 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-08-29 | 1991-02-28 | 1991-08-30 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-08-29 | 1995-02-28 | 1995-08-30 | $7700.00 | Window Closed / Lapsed |