Functionalized block copolymers, method for making same, and various uses for such block copolymers
View Patent ↗The present invention is a, solid block copolymer comprising at least two polymer end blocks A and at least one polymer interior block B wherein each A block is a polymer block resistant to lithiation and each B block is a polymer block susceptible to lithiation, and wherein said A and B blocks do not contain any significant levels of olefinic unsaturation. After lithiation, the lithiated polymer is reacted with at least one graftable functional molecule selected from the group consisting of an electrophilic graftable molecule containing a functional group and an electrophile. Preferred are carbon monoxide and ethylene oxide. Also claimed are processes for making such block copolymers, and the various end uses and applications for such block copolymers.
1. A carboxylated block copolymer that is solid in water comprising at least two polymer end blocks A and at least one polymer interior block B wherein:
a. each A block is a polymer block resistant to lithiation and each B block is a polymer block susceptible to lithiation, said A and B blocks containing no significant levels of olefinic unsaturation;
b. each A block independently having a number average molecular weight between 1,000 and 60,000 and each B block independently having a number average molecular weight between 10,000 and 300,000;
c. each A block is a segment consisting of one or more polymerized para-substituted styrene monomers;
d. each B block comprising segments of one or more vinyl aromatic monomers selected from polymerized (i) unsubstituted styrene monomers, (ii) ortho-substituted styrene monomers, (iii) meta-substituted styrene monomers, (iv) alpha-methylstyrene, (v) para-substituted styrene having hydrogen on a para benzylic carbon center,
(vi) 1,1-diphenylethylene, (vii) 1,2-diphenylethylene and (viii) mixtures thereof;
e. said B blocks are carboxylated to the extent of 10 to 100 mol percent, based on the units of vinyl aromatic monomer in said B blocks;
f. the mol percent of vinyl aromatic monomers which are unsubstituted styrene monomers, ortho-substituted styrene monomers, meta-substituted styrene monomers, alpha-methylstyrene, para-substituted styrene having hydrogen on a para benzylic carbon center, 1,1-diphenylethylene and 1,2-diphenylethylene in each B block being between 10 mol percent and 100 mol percent; and
g. said carboxylated block copolymer is solid and non-dispersible in water and has a tensile strength greater than 100 psi in the presence of water according to ASTM D412 after immersion in water for 24 hours.
2. The carboxylated block copolymer according to claim 1 , further comprising at least one polymer block D having a glass transition temperature of less than 20° C. and a number average molecular weight of between 1,000 and 50,000.
3. The carboxylated block copolymer according to claim 1 , wherein said A block comprises polymerized para-t-butylstyrene monomers.
4. The carboxylated block copolymer according to claim 3 , wherein said A block is a polymerized segment of para-t-butylstyrene and said B block is a polymerized segment of unsubstituted styrene.
5. The carboxylated block copolymer according to claim 3 , wherein the block copolymer is present in a solution of an aliphatic hydrocarbon, having a solids content of 0.1 to 20 weight percent.
6. The carboxylated block copolymer according to claim 1 , having the general configuration A-B-A, A-B-A-B-A, (A-B-A) n X, (A-B) n X, and mixtures thereof, where n is an integer from 2 to about 30, and X is coupling agent residue.
7. The carboxylated block copolymer according to claim 6 , wherein said B blocks are carboxylated to the extent of 20 to 90 mol percent, based on the units of vinyl aromatic monomer in said B blocks.
8. The carboxylated block copolymer according to claim 1 , wherein the interior block B is a hydrogenated copolymer of one or more unsubstituted styrene monomers, and monomers of conjugated dienes having a vinyl content of 20 to 80 mol percent prior to hydrogenation.
9. A carboxylated block copolymer that is solid in water and having the general configuration A-D-B-D-A, A-B-D-B-A, (A-D-B) n X, (A-B-D) n X, or mixtures thereof, where n is an integer from 2 to about 30, and X is a coupling agent residue wherein
a. each A block and each D block is a polymer block resistant to lithiation and each B block is a polymer block susceptible to lithiation, said A, B and D blocks containing no significant levels of olefinic unsaturation;
b. each A block independently having a number average molecular weight between 1,000 and 60,000 and each B block independently having a number average molecular weight between 10,000 and 300,000;
c. each A block is a segment consisting of one or more polymerized para-substituted styrene monomers;
d. each B block comprising segments of one or more vinyl aromatic monomers selected from polymerized (i) unsubstituted styrene monomers, (ii) ortho-substituted styrene monomers, (iii) meta-substituted styrene monomers, (iv) alpha-methylstyrene, (v) para-substituted styrene having hydrogen on a para benzylic carbon center, (vi) 1,1-diphenylethylene, (vii) 1,2-diphenylethylene and (viii) mixtures thereof;
e. each D block comprises polymers having a glass transition temperature less than 20° C. and a number average molecular weight of between 1,000 and 50,000, said D block being selected from the group consisting of (i) a polymerized or copolymerized conjugated diene selected from isoprene, 1,3-butadiene having a vinyl content prior to hydrogenation of between 20 and 80 mol percent, (ii) polymerized isobutylene and (iii) mixtures thereof, wherein any segments containing polymerized 1,3-butadiene or isoprene are subsequently hydrogenated;
f. said B blocks are carboxylated to the extent of 10 to 100 mol percent, based on the units of vinyl aromatic monomer in said B blocks; and
g. the mol percent of vinyl aromatic monomers which are unsubstituted styrene monomers, ortho-substituted styrene monomers, meta-substituted styrene monomers, alpha-methylstyrene, para-substituted styrene having hydrogen on a para benzylic carbon center, 1,1-diphenylethylene and 1,2-diphenylethylene in each B block being between 10 mol percent and 100 mol percent.
10. The carboxylated block copolymer according to claim 9 , wherein said D block prior to hydrogenation is polymer block of 1,3-butadiene wherein 20 to 80 mol percent of the condensed butadiene units in block D have 1,2-configuration prior to hydrogenation.
11. The carboxylated block copolymer according to claim 1 , wherein a portion of the resulting carboxyl functional groups in said block B have been neutralized.
12. The carboxylated block copolymer according to claim 11 , wherein a portion of said carboxyl functional groups have been neutralized with an ionizable metal compound to form metal salts.
13. The carboxylated block copolymer according to claim 12 , wherein the ionizable metal compound contains Na + , K + , Li + , Cs + , Ag + , Hg + , Cu + , Mg + , Ca + , Sr + , Ba 2+ , Cu 2+ , Cd 2+ , Hg 2+ , Sn 2+ , Pb 2+ , Fe 2+ , Co 2+ , Ni 2+ , Zn 2+ , Al 3+ , Sc 3+ , Fe 3+ , La 3+ or Y 3+ .
14. The carboxylated block copolymer according to claim 12 , wherein the ionizable metal compound comprises a hydroxide, an oxide, an alcoholate, a carboxylate, a formate, an acetate, a methoxide, an ethoxide, a nitrate, a carbonate or a bicarbonate.
15. A composition comprising the carboxylated block copolymer of claim 1 and additional components selected from the group consisting of pigments, antioxidants, stabilizers, surfactants, waxes, flow promoters, particulates, fillers, and oils.
16. A composition comprising the carboxylated block copolymer of claim 1 and additional components selected from the group consisting of other polymers, polymer liquids and fillers.
17. The composition according to claim 16 , wherein the other polymers are selected from the group consisting of olefin polymers, styrene polymers, tackifying resins, hydrophilic polymers and engineering thermoplastic polymers.
18. A functionalized block copolymer comprising at least two polymer end blocks A and at least one polymer interior block B wherein:
a. each A block is a polymer block resistant to lithiation and each B block is a polymer block susceptible to lithiation, said A and B blocks containing no significant levels of olefinic unsaturation;
b. each A block independently having a number average molecular weight between 1,000 and 60,000 and each B block independently having a number average molecular weight between 10,000 and 300,000;
c. each A block is a segment consisting of one or more polymerized para-substituted styrene monomers;
d. each B block comprising segments of one or more vinyl aromatic monomers selected from polymerized (i) unsubstituted styrene monomers, (ii) ortho-substituted styrene monomers, (iii) meta-substituted styrene monomers, (iv) alpha-methylstyrene, (v) para-substituted styrene having hydrogen on a para benzylic carbon center, (vi) 1,1-diphenylethylene, (vii) 1,2-diphenylethylene and (viii) mixtures thereof;
e. each B blocks are lithiated to the extend of 10 to 100 mol percent, based on the units of vinyl aromatic monomer in said B blocks;
f. the mol percent of vinyl aromatic monomers which are unsubstituted styrene monomers, ortho-substituted styrene monomers, meta-substituted styrene monomers, alpha-methylstyrene, para-substituted styrene having hydrogen on a para benzylic carbon center, 1,1-diphenylethylene and 1,2-diphenylethylene in each B block being between 10 mol percent and 100 mol percent; and
g. each B block after lithiation is reacted with at least one graftable functional molecule selected from the group consisting of (i) carbon dioxide, (ii) ethylene oxide, (iii) aldehydes, (iv) ketones, (v) carboxylic acids, salts, esters and (vi) halides.