Unhydrogenated block copolymer compositions
View Patent ↗The present invention relates to novel compositions comprising (a) anionic block copolymers having at least two blocks of a mono alkenyl arene and at least one block of a conjugated diene and mono alkenyl arene having a specific arrangement of the monomers in the copolymer block, and (b) tailored softening modifiers have a particular structure that results in a surprising improvement in properties for the composition. Also included are processes for the manufacturing such novel compositions and various end-uses and applications for such compositions.
1. A block copolymer composition comprising:
(a) 100 parts by weight of a solid block copolymer wherein:
(i) said block copolymer comprises at least two A blocks and at least one B block, each A block independently selected from mono alkenyl arene polymer blocks and each B block independently selected from
(1) polymer blocks having at least one conjugated diene and at least one mono alkenyl arene and having a random distribution; and
(2) polymer blocks having at least one conjugated diene and at least one mono alkenyl arene and having a controlled distribution;
(ii) each A block having a peak molecular weight between about 3,000 and about 60,000 and each B block having a peak molecular weight (MW 1 ) between about 20,000 and about 200,000;
(iii) the total amount of mono alkenyl arene in the block copolymer is about 30 percent weight to about 85 percent weight; and
(iv) the weight percent of mono alkenyl arene in each B block (S 1 ) is between about 5 percent and about 75 percent; and
(b) 5 to 250 parts by weight of a tailored softening modifier which comprises a conjugated diene and is structurally related to the character of the B block of said block copolymer wherein:
(i) the ratio (MW 2 )/(MW 1 ) of the peak molecular weight of said softening modifier (MW 2 ) to the peak molecular weight of said B block of said block copolymer (MW 1 ) is 0.01 to 1.0, with a minimum molecular weight (MW 2 ) of 2,000;
(ii) the weight percent of mono alkenyl arene in each softening modifier (S 2 ) is between about 5 percent and about 75 percent and the ratio of S 2 /S 1 is between 0.5 and 1.5; and
(c) wherein said softening modifier is polymerized in solution in the presence of a solvent in a second reactor to form a second solution and combined with a first solution prepared in a first reactor having a solvent to form a common solution, wherein said block copolymer is polymerized in said first solution or common solution, and
(d) the solvent is removed from the common solution after polymerization of said block copolymer, providing an intimate mixture of said block copolymer and said tailored softening modifier.
2. The composition according to claim 1 wherein said mono alkenyl arene for the block copolymer and the softening modifier is styrene and said conjugated diene for the block copolymer and the softening modifier is selected from the group consisting of isoprene, 1,3-butadiene and mixtures thereof.
3. The composition according to claim 2 wherein said conjugated diene is 1,3-butadiene and wherein about 5 to about 80 mol percent of the condensed butadiene units in block B and in the softening modifier have 1,2-configuration.
4. The composition according to claim 3 wherein the weight percentage of styrene in the B block and in the softening modifier is between about 40 percent and about 75 percent.
5. The composition according to claim 4 wherein said block A has a molecular weight of between 5,000 and 45,000, said block B is a controlled distribution block and has a molecular weight of between 20,000 and 200,000, said softening modifier has a molecular weight of between 2,000 and 60,000 and has a controlled distribution structure, and said softening modifier and said B block have a blockiness index of between about 0 percent and 80 percent.
6. The composition according to claim 5 wherein said first solution and second solutions are combined after polymerization of both the block copolymer and the tailored softening modifier, and prior to finishing.
7. The composition according to claim 5 wherein said second solution is added to said first solution prior to polymerization of said block copolymer.
8. The composition according to claim 5 wherein said second solution is added to said first solution during the polymerization of said block copolymer.
9. A block copolymer composition comprising:
(a) 100 parts by weight of a solid block copolymer wherein:
(i) said block copolymer comprises at least two A blocks and at least one B block, each A block independently selected from mono alkenyl arene polymer blocks and each B block independently selected from
(1) polymer blocks having at least one conjugated diene and at least one mono alkenyl arene and having a random distribution; and
(2) polymer blocks having at least one conjugated diene and at least one mono alkenyl arene and having a controlled distribution;
(ii) each A block having a peak molecular weight between about 3,000 and about 60,000 and each B block having a peak molecular weight (MW 1 ) between about 20,000 and about 200,000;
(iii) the total amount of mono alkenyl arene in the block copolymer is about 30 percent weight to about 85 percent weight; and
(iv) the weight percent of mono alkenyl arene in each B block (S 1 ) is between about 5 percent and about 75 percent; and
(b) 5 to 250 parts by weight of a tailored softening modifier which comprises a conjugated diene and is structurally related to the character of the B block of said block copolymer wherein:
(i) the ratio (MW 2 )/(MW 1 ) of the peak molecular weight of said softening modifier (MW 2 ) to the peak molecular weight of said B block of said block copolymer (MW 1 ) is 0.01 to 1.0, with a minimum molecular weight (MW 2 ) of 2,000;
(ii) the weight percent of mono alkenyl arene in each softening modifier (S 2 ) is between about 5 percent and about 75 percent and the ratio of S 2 /S 1 is between 0.5 and 1.5; and
(c) wherein said block copolymer is formed in solution in a reactor in the presence of a solvent and said tailored softening modifier is formed in the same solution in the same reactor; and
(d) the solvent is removed from the solution, providing an intimate mixture of said block copolymer and said tailored softening modifier.
10. The composition according to claim 9 wherein said mono alkenyl arene for the block copolymer and the softening modifier is styrene and said conjugated diene for the block copolymer and the softening modifier is selected from the group consisting of isoprene, 1,3-butadiene and mixtures thereof.
11. The composition according to claim 10 wherein said conjugated diene is 1,3-butadiene and wherein about 5 to about 80 mol percent of the condensed butadiene units in block B and in the softening modifier have 1,2-configuration.
12. The composition according to claim 11 wherein the weight percentage of styrene in the B block and in the softening modifier is between about 40 percent and about 75 percent.
13. A formulated composition comprising the composition of claim 1 and at least one component selected from the group consisting of fillers, reinforcements, polymer extending oils, tackifying resins, lubricants, stabilizers, styrene polymers, antioxidants, styrene/diene block copolymers and polyolefins.
14. A formulated composition comprising the composition of claim 9 and at least one component selected from the group consisting of fillers, reinforcements, polymer extending oils, tackifying resins, lubricants, stabilizers, styrene polymers, antioxidants, styrene/diene block copolymers and polyolefins.
15. An article comprising the composition of claim 13 , wherein said article is formed in a process selected from the group consisting of injection molding, over molding, dipping, extrusion, roto molding, slush molding, fiber spinning, film making or foaming.
16. An article comprising the composition of claim 13 , wherein said article is selected from the group consisting of closures, synthetic corks, cap seals, tubing, food containers, beverage containers, interior automotive parts, window gaskets, elastic films, foamed products, bicomponent fibers, monofilaments, adhesives, cosmetics and medical goods.
17. The composition according to claim 1 wherein said second solution is added to said first solution after polymerization of said block copolymer.