ADHESIVES PREPARED FROM DIPHENYLETHYLENE CONTAINING BLOCK COPOLYMERS
The present invention relates to adhesives and sealants prepared from novel anionic block copolymers of mono alkenyl arenes, diphenylethylenes and conjugated dienes. The block copolymers are unhydrogenated or selectively hydrogenated and have mono alkenyl arene/diphenylethylene end blocks and conjugated diene mid blocks. The block copolymer may be combined with tackifying resins, oils and other components to form the adhesives and sealants of the present invention.
1 . An adhesive composition comprising 100 parts by weight of at least one hydrogenated block copolymer, about 25 to about 300 parts by weight of a tackifying resin and about zero to about 200 parts by weight of an extending oil, wherein said hydrogenated block copolymer comprises an A-B-A, an (A-B)n or an (A-B)n-X polymer wherein:
i. A comprises a polymer block of a monoalkenyl arene and one or more 1,1-diphenylethylenes or its derivatives of the formula I:
wherein R 1 is hydrogen or an alkyl of 1 to 22 carbon atoms, a is 0, 1, 2, 3, 4, or 5 and bis 0, 1, 2, 3, 4, or 5.;
ii. B represents a polymer block of a hydrogenated conjugated diene;
iii. n is an integer from 2 to 30; and
iv. X represents the residue of coupling agent.
2 . The adhesive composition according to claim 1 wherein the weight ratio of monoalkenyl arene to 1,1-diphenylethylene is from 97:3 to 30:70.
3 . The adhesive composition according to claim 2 wherein said mono alkenyl arene is styrene, said 1,1-diphenylethylene is unsubstituted and said conjugated diene is selected from the group consisting of isoprene and butadiene.
4 . The adhesive composition according to claim 3 wherein said conjugated diene is butadiene, and wherein prior to hydrogenation about 10 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration.
5 . The adhesive composition according to claim 3 wherein said coupling agent is an alkoxy silane coupling agent selected from the group consisting of tetraethoxy silane, tetramethoxy silane, tetrabutoxy silane, methyl trimethoxy silane, methyl triethoxy silane, phenyl trimethoxy silane and isobutyl trimethoxy silane.
6 . The adhesive composition according to claim 3 wherein said A blocks have a number average molecular weight of between about 5,000 and about 60,000, and wherein said B blocks have a number average molecular weight of between about 10,000 and about 200,000.
7 . The adhesive composition according to claim 6 wherein the weight ratio of polymer block A to polymer block B is from 5/95 to 50/50.
8 . The adhesive composition according to claim 7 also comprising 0 to about 50 parts by weight of an end block resin.
9 . The adhesive composition according to claim 1 wherein said tackifying resin is selected from the group consisting of C 5 hydrocarbon resins, hydrogenated C 5 hydrocarbon resins, styrenated C 5 resins, C 5 /C 9 resins, styrenated terpene resins, fully hydrogenated or partially hydrogenated C 9 hydrocarbon resins, rosins esters, rosin derivatives and mixtures thereof.
10 . The adhesive composition according to claim 1 wherein said tackifying resin is selected from the group consisting of coumarone-indene resin, polyindene resin, poly(methyl indene) resin, polystyrene resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether and mixtures thereof.
11 . The adhesive composition according to claim 1 wherein said extending oil is a petroleum-based white oil having an aromatics content less than about 50 weight percent.
12 . The adhesive composition according to claim 1 also comprising additional components selected from the groups consisting of antioxidants, stabilizers, fillers, and additional auxiliaries.
13 . An adhesive composition comprising 100 parts by weight of at least one unhydrogenated block copolymer, about 25 to about 300 parts by weight of a tackifying resin and about zero to about 200 parts by weight of an extending oil, wherein said unhydrogenated block copolymer comprises an A-B-A, (A-B)n or (A-B)n-X polymer wherein:
i. A comprises a polymer block of a monoalkenyl arene and one or more 1,1-diphenylethylenes or its derivatives of the formula I:
wherein R 1 is hydrogen or an alkyl of 1 to 22 carbon atoms, a is 0, 1, 2, 3, 4, or 5 and b is 0, 1, 2, 3, 4, or 5.;
ii. B represents a polymer block of a conjugated diene;
iii. n is an integer from 2 to 30; and
iv. X represents the residue of coupling agent.
14 . The adhesive composition according to claim 13 wherein the weight ratio of monoalkenyl arene to 1,1-diphenylethylene is from 97:3 to 30:70.
15 . The adhesive composition according to claim 14 wherein said mono alkenyl arene is styrene, said 1,1-diphenylethylene is unsubstituted and said conjugated diene is selected from the group consisting of isoprene and butadiene.
16 . The adhesive composition according to claim 15 wherein said conjugated diene is butadiene, and wherein about 10 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration.
17 . The adhesive composition according to claim 15 wherein said coupling agent is an alkoxy silane coupling agent selected from the group consisting of tetraethoxy silane, tetramethoxy silane, tetrabutoxy silane, methyl trimethoxy silane, methyl triethoxy silane, phenyl trimethoxy silane and isobutyl trimethoxy silane.
18 . The adhesive composition according to claim 15 wherein said A blocks have a number average molecular weight of between about 5,000 and about 60,000, and wherein said B blocks have a number average molecular weight of between about 10,000 and about 200,000.
19 . The adhesive composition according to claim 18 wherein the weight ratio of polymer block A to polymer block B is from 5/95 to 50/50.
20 . The adhesive composition according to claim 19 also comprising 0 to about 50 parts by weight of an end block resin.
21 . The adhesive composition according to claim 13 wherein said tackifying resin is selected from the group consisting of C 5 hydrocarbon resins, hydrogenated C 5 hydrocarbon resins, styrenated C 5 resins, C 5 /C 9 resins, styrenated terpene resins, fully hydrogenated or partially hydrogenated C 9 hydrocarbon resins, rosins esters, rosin derivatives and mixtures thereof.
22 . The adhesive composition according to claim 13 wherein said tackifying resin is selected from the group consisting of coumarone-indene resin, polyindene resin, poly(methyl indene) resin, polystyrene resin, vinyltoluene-alphamethylstyrene resin, alphamethylstyrene resin, polyphenylene ether and mixtures thereof.
23 . The adhesive composition according to claim 13 wherein said extending oil is a petroleum-based white oil having an aromatics content less than about 50 weight percent.
24 . The adhesive composition according to claim 13 also comprising additional components selected from the groups consisting of antioxidants, stabilizers, fillers, and additional auxiliaries.