Adhesives and sealants from controlled distribution block copolymers
View Patent ↗The present invention relates to adhesives and sealants prepared from novel anionic block copolymers of mono alkenyl arenes and conjugated dienes, and to blends of such block copolymers with other polymers. The block copolymers are selectively hydrogenated and have mono alkenyl arene end blocks and controlled distribution blocks of mono alkenyl arenes and conjugated dienes. The block copolymer may be combined with tackifying resins, oils and other components to form the adhesives and sealants of the present invention.
1. A pressure sensitive adhesive composition comprising 100 parts by weight of at least one hydrogenated block copolymer, about 25 to about 300 parts by weight of a compatible styrene/isoprene unhydrogenated block copolymer, about 25 to about 300 parts by weight of at least one tackifying resin and about zero to about 200 parts by weight of an extending oil, wherein said hydrogenated block copolymer has at least one polymer block A and at least one polymer block B, and wherein:
a. prior to hydrogenation each A block is a mono alkenyl arene homopolymer block and each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene;
b. subsequent to hydrogenation about 0–10% of the arene double bonds have been reduced, and at least about 90% of the conjugated diene double bonds have been reduced;
c. each A block having a number average molecular weight between about 3,000 and about 60,000 and each B block having a number average molecular weight between about 20,000 and about 300,000;
d. each B block comprises terminal regions adjacent to the A blocks that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono alkenyl arene units;
e. the total amount of mono alkenyl arene in the hydrogenated block copolymer is about 20 percent weight to about 80 percent weight; and
f. the weight percent of mono alkenyl arene in each B block is between about 10 percent and about 75 percent.
2. The adhesive composition according to claim 1 wherein said mono alkenyl arene is styrene and said conjugated diene is selected from the group consisting of isoprene and butadiene.
3. The adhesive composition according to claim 2 wherein said conjugated diene is butadiene, and wherein about 20 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration.
4. The adhesive composition according to claim 3 wherein the styrene blockiness of the block B is less than about 40 mol percent.
5. The adhesive composition according to claim 4 wherein the polymer is an ABA polymer and each block B has a center region with a minimum ratio of butadiene units to styrene units.
6. The adhesive composition according to claim 3 wherein the weight percent of styrene in each B block is between about 10 percent and about 30 percent, and the styrene blockiness index of each block B is less than about 10 percent, said styrene blockiness index being defined to be the proportion of styrene units in the block B having two styrene neighbors on the polymer chain.
7. The adhesive composition according to claim 3 wherein said hydrogenated block copolymer is an ABA, (A-B) n , (A-B) n A, or (A-B) n X block copolymer where n is an integer from 2 to about 30, X is the coupling agent residue, said block copolymer having a total number average molecular weight of about 40,000 to about 140,000 and wherein each B block has between 10 and 30 weight percent styrene.
8. The adhesive composition according to claim 7 comprising 100 parts by weight of said hydrogenated block copolymer, about 75 to about 200 parts by weight of a tackifying resin and 0 to about 150 parts by weight of a polymer extending oil.
9. The adhesive composition according to claim 8 also comprising 0 to about 50 parts by weight of an end block resin.
10. 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, resins esters, resin derivatives and mixtures thereof.
11. 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.
12. 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.
13. The adhesive composition according to claim 1 also comprising additional components selected from the groups consisting of antioxidants, stabilizers, fillers, and additional auxiliaries.
14. A hot melt, pressure sensitive adhesive comprising the composition of claim 8 .
15. The hot melt, pressure sensitive composition according to claim 14 also comprising an end block resin.
16. A solvent based adhesive composition comprising the composition of claim 1 and a compatible solvent selected from the group consisting of aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, polar solvents and mixtures thereof.
17. The solvent based adhesive composition according to claim 16 wherein said solvent is an aromatic hydrocarbon solvent.
18. A pressure sensitive adhesive composition comprising 100 parts by weight of at least one hydrogenated block copolymer, about 25 to about 300 parts by weight of a compatible styrene/isoprene unhydrogenated block copolymer, about 50 to about 500 parts by weight of a tackifying resin, and about 0 to about 200 parts by weight of a polymer extending oil, wherein said hydrogenated block copolymer has the general configuration
A-B,
A-B-A,
(A-B) n
(A-B) n -A
(A-B-A) n X
or
(A-B) n X,
where n is an integer from 2 to about 30, and X is coupling agent residue and wherein:
a. prior to hydrogenation each A block is a mono alkenyl arene homopolymer block and each B block is a controlled distribution copolymer block of at least one conjugated diene and at least one mono alkenyl arene;
b. subsequent to hydrogenation about 0–10% of the arene double bonds have been reduced, and at least about 90% of the conjugated diene double bonds have been reduced;
c. each A block having a number average molecular weight between about 3,000 and about 60,000 and each B block having a number average molecular weight between about 20,000 and about 300,000;
d. each B block comprises terminal regions adjacent to the A blocks that are rich in conjugated diene units and one or more regions not adjacent to the A blocks that are rich in mono alkenyl arene units;
e. the total amount of mono alkenyl arene in the hydrogenated block copolymer is about 20 percent weight to about 80 percent weight; and
f. the weight percent of mono alkenyl arene in each B block is between about 10 percent and about 75 percent.
19. The adhesive composition according to claim 18 wherein said compatible styrene/isoprene unhydrogenated block copolymer is an S-I-S block copolymer having a number average molecular weight of about 100,000 to about 350,000, and a styrene content of between about 12 and about 20 weight percent.
20. The adhesive composition according to claim 19 wherein said hydrogenated block copolymer is a linear hydrogenated styrene/butadiene block copolymer having a total number average molecular weight of about 25,000 to about 150,000.
21. The adhesive composition according to claim 20 wherein the amount of styrene/isoprene unhydrogenated block copolymer is between about 50 and about 200 parts by weight.
22. The adhesive composition according to claim 18 wherein said styrene/isoprene unhydrogenated block copolymer comprises a linear S-I-S block copolymer and an S-I diblock copolymer.
23. The adhesive composition according to claim 1 wherein said hydrogenated block copolymer is a functionalized selectively hydrogenated block copolymer wherein the block copolymer has been grafted with an acid compound or its derivative.
24. The adhesive composition according to claim 23 wherein said acid compound or its derivative is selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, and their derivatives.
25. The adhesive composition according to claim 1 wherein said hydrogenated block copolymer is a functionalized selectively hydrogenated block copolymer wherein the block copolymer has a sulfonic acid or sulfonate functional group.
26. The adhesive composition according to claim 25 wherein at least 50 percent of the sulfonic functional groups are present as zinc salts.
27. The adhesive composition according to claim 25 wherein the block copolymer has from about one (1) sulfonic acid or sulfonate group per molecule of the block copolymer to about (1) sulfonic acid or sulfonate group per aromatic ring of the block copolymer.
28. The adhesive composition according to claim 27 wherein the block copolymer has from about three (3) sulfonic acid or sulfonate groups per molecule of the block copolymer to about (1) sulfonic acid or sulfonate group per two (2) aromatic rings of the block copolymer.
29. The adhesive composition according to claim 28 wherein the mono alkenyl arene is styrene and the conjugated diene is selected from the group consisting of isoprene and butadiene.
30. The adhesive composition according to claim 29 wherein the conjugated diene is butadiene, and wherein about 20 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration prior to hydrogenation.
31. The adhesive composition according to claim 30 wherein the weight percentage of styrene in the B block is between about 10 percent and about 40 percent, and the styrene blockiness index of the block B is less than about 10 percent, the styrene blockiness index being the proportion of styrene units in the block B having two styrene neighbors on the polymer chain.
32. The adhesive composition according to claim 25 comprising 100 parts by weight of said block copolymer, about 75 to about 200 parts by weight of a tackifying resin and 0 to about 150 parts by weight of a polymer extending oil.
33. The adhesive composition according to claim 32 wherein the block copolymer has from about one (1) sulfonic acid or sulfonate group per molecule of the block copolymer to about (1) sulfonic acid or sulfonate group per aromatic ring of the block copolymer.
34. The adhesive composition according to claim 33 wherein the mono alkenyl arene is styrene and the conjugated diene is selected from the group consisting of isoprene and butadiene.
35. The adhesive composition according to claim 33 wherein the conjugated diene is butadiene, and wherein about 20 to about 80 mol percent of the condensed butadiene units in block B have 1,2-configuration prior to hydrogenation.
36. The adhesive composition according to claim 34 wherein the weight percentage of styrene in the B block is between about 20 percent and about 80 percent.