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US 4,769,419 AGranted
Modified structural adhesives
OwnerTerrance H. Dawdyinventor
Life of this patent
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Abstract
Novel structural adhesive compositions for metal-bonding applications. The adhesives comprise olefinic-terminated liquid rubbers which are reacted with monoisocyanate compounds. The compositions according to the present invention are especially useful in formulating ambient temperature curable structural adhesive compositions.
Claims20
Urethane modified olefinic-terminated liquid elastomer having the formula ##STR11## wherein R.sup.1 is hydrogen, an alkyl group of 1 to 4 carbon atoms, --CH.dbd.CH.sub.2, or --R.sup.4 --CH.dbd.CH.sub.2 wherein R.sup.4 is an alkylene group of 1 to 4 carbon atoms;
- R.sup.2 is ##STR12## wherein R.sup.5 is an alkylene group having from 1 to 6 carbon atoms and R.sup.6 is phenyl, naphthyl, an alkylene group having from 1 to 24 carbon atoms or m-isopropenyl-.alpha.-.alpha.-dimethylbenzyl;
- and
- R.sup.3 is ##STR13## wherein R.sup.1 and R.sup.2 are as previously defined, R.sup.7 is --CH.dbd.CH.sub.2 or ##STR14## R8 is hydrogen or methyl;
- and v from about 5 to about 98 weight;
- w is zero to about 95 percent by weight;
- x is from zero to about 40 percent by weight;
- y is from zero to about 40 percent by weight;
- and z is from zero to about 5 percent by weight;
- said percent by weight being based on the total weight of R.sup.3.
6 more elements
An ambient temperature-curable structural adhesive composition comprising
- (A) from about 10 to about 80 percent by weight of a urethane olefinic-terminated liquid rubber having the formula;
- ##STR15## wherein R.sup.1 is hydrogen, an alkyl group of 1 to 4 carbon atoms, --C.dbd.CH.sub.2, or --R.sup.4 --CH.dbd.CH.sub.2 wherein R.sup.4 is an allylene group of 1 to 4 carbons atoms;
- R.sup.2 is ##STR16## wherein R.sup.5 is an alkylene group having from 1 to 6 carbon atoms and R.sup.6 is phenyl, naphthyl or an alkylene group having from 1 to 24 carbon atoms or m-isoprenyl-.alpha.,.alpha.-dimethylbenzyl;
- and
- R.sup.3 is ##STR17## wherein R.sup.1 and R.sup.2 are as previously defined, R.sup.7 is --CH.dbd.CH.sub.2 or ##STR18## R.sup.8 is hydrogen or methyl and v is in the range from about 5 to about 98 percent by weight;
- w is from zero to about 95 percent by weight;
- x is from zero to about 40 percent by weight;
- y is from zero to about 40 percent by weight;
- and z is from zero to about 5 percent by weight;
- said percent by weight being based on the total weight of R.sup.3
- (B) from about 10 to about 90 percent by weight of an olefinic monomer selected from the group consisting of methyl methacrylate, butyl methacrylate, methyl acrylate, butyl acrylate, cyclohexyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, ethyl acrylate, diethylene glycol dimethacrylate, dicyclopentadienyloxyethyl methacrylate, 2-ethylhexylmethacrylate, hexyl methacrylate, cyclohexylmethacrylate, lauryl methacrylate, tetrahydrofurfuryl methacrylate, metharylic acid, acrylic acid, acrylonitrile, methacrylonitrile, styrene, vinyl styrene, vinyl acetate, chlorostyrene, glycidyl methacrylate, itaconic acid, acrylamide, methacrylamide, vinylidene chloride, 2,3-dichloro-1,3-butadiene, 2-chloro-1,3-butadiene, methylstyrene and n-butyl styrene;
- (C) from 0 to about 40 percent by weight of an olefinic urethane reaction product of an isocyanate-functional prepolymer and a hydroxy-functional monomer having an unit of polymerizable olefinic unsaturation, such reaction product being characterized by the presence of at least two units of olefinic unsaturation and the substantial absence of free isocyanate groups wherein said hydroxy-functional monomer has an average molecular weight from about 50 to about 3,000;
- and said isocyanate-functional prepolymer is an adduct of polyisocyanate compound having at least two free isocyanate groups and a polyol having an molecular weight from about 50 and about 3000;
- (D) from 0 to about 20 percent by weight of phosphorous-containing compound having one or more olefinic group and no less than one P--OH groups, said phosphorous-containing compound having the formula ##STR19## wherein R.sup.8 is selected from the group consisting of hydrogen, an alkyl group having from 1 to 8 carbon atoms, and CH.sub.2 --CH--;
- R.sup.9 is selected from the group consisting of hydrogen, an alkyl group having from 1 to 8 carbon atoms;
- A is selected from the group consisting of R.sup.10 O and (R.sup.11 O).sub.n, wherein R.sub.10 is an aliphatic or cycloaliphatic alkylene group containing from 1 to 9 carbon atoms;
- R.sup.11 is an alkylene group having from 1 to 7 carbon atoms;
- n is an interger from 2 to 10, and m is one or two;
- and,
- (E) an ambient temperature-active free radical source which is capable of initiating and propagating the cure of said adhesive compositon
- the weight percents of each of (A) through and including (E) being based on the total weight of (A) through and including (E);
- (F) from about 0.05 to about 10 percent by weight, based on the total weight of (A) through and including (E) of at least one oxidizing agent which is interactive with a peroxygen compound to produce free radicals which are capable of initiating and propagating free radical polymerization reactions wherein the oxidizing agent is added to effectively cure components (A)-(E) of the ambient temperature curable structural adhesive composition.
19 more elements
A multipack adhesive comprising a first and second package adhesive system, said packages being mixed at the time of use to provide a free radical curable adhesive;
- said first package comprising
- (A) from about 10 to about 80 percent by weight of a urethane olefinic-terminated liquid rubber having the formula:
- ##STR20## wherein R.sup.1 is hydrogen, an alkyl group of 1 to 4 carbon atoms, --C.dbd.CH.sub.2, or --R.sup.4 --CH.dbd.CH.sub.2 wherein R.sup.4 is an allylene group of 1 to 4 carbon atoms;
- R.sup.2 is ##STR21## wherein R.sup.5 is an alkylene group having from 1 to 6 carbon atoms and R.sup.6 is phenyl, naphthyl or an alkylene group having from 1 to 24 carbon atoms or m-isopropenyl-.alpha., .alpha.-dimethylbenzyl;
- and
- R.sup.3 is ##STR22## wherein R.sup.1 and R.sup.2 are as previously defined, R.sup.7 is --CH.dbd.CH.sub.2 or ##STR23## R.sup.8 is hydrogen or methyl and v is in the range from about 5 to about 98 percent by weight;
- w is from zero to about 95 percent by weight;
- x is from zero to about 40 percent by weight;
- y is from zero to about 40 percent by weight;
- and z is from zero to about 5 percent by weight;
- said percent by weight being based on the total weight of R.sup.3 ;
- (B) from about 10 to about 90 percent by weight of at least one olefinic monomer selected from the group consisting of methyl methacrylate, methyl acrylate, butyl acrylate, cyclohexyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, dicyclopentadienyloxyethyl methacrylate, 2-ethylhexyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, tetrahydrofurfuryl methacrylate, butyl methacrylate, ethyl acrylate, diethylene glycol dimethacrylate, metharylic acid, acrylic acid, acrylonitrile, methacrylonitrile, styrene, vinyl styrene, vinyl acetate, chlorostyrene, glycidyl methacrylate, itaconic acid, acrylamide, methacrylamide, vinylidene chloride, 2,3-dichloro-1,3-butadiene, 2-chloro-1,3-butadiene, methylstyrene and n-butyl styrene;
- (C) from 0 to about 40 percent by weight of an olefinic urethane reaction product of an isocyanate-functional prepolymer and a hydroxy-functional monomer having an unit of polymerizable olefinic unsaturation, such reaction product being characterized by the presence of at least two units of olefinic unsaturation and the substantial absence of free isocyanate groups wherein said hydroxy-functional monomer has an average molecular weight from about 50 to about 3,000;
- and said isocyanate functional prepolymer is an adduct of polyisocyanate compound having at least two free isocyanate groups and a polyol having an molecular weight from about 50 and about 3000;
- (D) from 0.1 to about 20 percent by weight of a phosphorus-containing compound having one or more olefinic group and no less than one P--OH groups, said phosphorous-containing compound having the formula ##STR24## wherein R.sup.8 is selected from the group consisting of hydrogen, an alkyl group having from 1 to 8 carbon atoms, and CH.sub.2 --C--;
- R.sup.9 is selected from the group consisting of hydrogen, an alkyl group having from 1 to 8 carbon atoms;
- A is selected from the group consisting of R.sup.10 O and (R.sup.11 O).sub.n, wherein R.sup.10 is an aliphatic or cycloaliphatic alkylene group containing from 1 to 9 carbon atoms;
- R.sup.11 is an alkylene group having from 1 to 7 carbon atoms;
- n is an interger from 2 to 10, and m is one or two;
- and,
- (E) an ambient temperature-active free radical source which is capable of initiating and propagating the cure of said adhesive compositon
- the weight percents of each of (A) through and including (E) being based on the total weight of (A) through and including (E);
- (F) from about 0.05 to about 10 percent by weight, based on the total weight of (A) through and including (E) of at least one oxidizing agent which is interactive with a peroxygen compound to produce free radicals which are capable of initiating and propagating free radical polymerization reactions;
- and
- said second package comprising
- a bonding accelerator containing at least one oxidizing agent of a room temperature-active redox couple catalyst system, said oxidizing agent being reactive at room temperature with said agent (E), when said first and second packages are mixed, to produce free radicals which are capable of initiating and propagating free radical polymerization reactions, the amount of said oxidizing agent being sufficient to interact with the total amount of agent (E).
23 more elements
Dependencies are inferred from the claim text.