[특허]Monovinylarene/conjugated diene copolymers having lower glass transition temperatures

Chevron Phillips Chemical Company, LP

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Monovinylarene/conjugated diene copolymers having lower glass transition temperatures

특허상세정보
국가/구분	United States(US) Patent 등록
국제특허분류(IPC7판)	C08F-297/04 C08F-297/00
미국특허분류(USC)	525/314; 525/271
출원번호	US-0705704 (2003-11-10)
발명자 / 주소	Stacy,Nathan E. Nash,Larry L. Hottovy,John D.
출원인 / 주소	Chevron Phillips Chemical Company, LP
인용정보	피인용 횟수 : 21 인용 특허 : 32

초록
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We disclose a monovinylarene/conjugated diene block copolymer, comprising: (i) a random (conjugated dienex /monovinylareney)m block, wherein x is about 2.5 wt % to about 10 wt %, y is from about 90 wt % to about 97.5 wt %, and x+y is about 97.5 wt % to 100 wt %; and (ii) a (conjugated diene)n block; wherein n is from about 20 wt % to about 30 wt %, m is from about 70 wt % to about 80 wt %, and m+n is from about 90 wt % to 100 wt %. We also disclose a method of forming the block copolymer and a method for fabricating an article from the block copolymer. The block copolymer typically exhibits a Tg at least about 10째 C. less than the T g of a reference polymer differing only in that x is about 0 wt % and y is about 100 wt %.

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What is claimed is: 1. A monovinylarene/conjugated diene block copolymer, comprising: a random (conjugated dienex/monovinylareney) m block, wherein x is about 2.5 wt % to about 10 wt %, y is from about 90 wt % to about 97.5 wt %, and x+y is about 97.5 wt % to 100 wt %; and a (conjugated diene)n block; wherein n is from about 20 wt % to about 30 wt %, m is from about 70 wt % to about 80 wt %, and m+n is from about 90 wt % to 100 wt %. 2. The monovinylarene/conjugated diene block copolymer of claim 1, wherein x is about 5 wt % to about 10 wt %. 3. The monovinylarene/conjugated diene block copolymer of claim 1, wherein y is about 90 wt % to about 95 wt %. 4. The monovinylarene/conjugated diene block copolymer of claim 1, wherein n is about 25 wt % and m is about 75 wt %. 5. The monovinylarene/conjugated diene block copolymer of claim 1, wherein the Tg is at least about 10째 C. less than the Tg of a reference polymer differing only in x being about 0 wt % and y being about 100 wt %. 6. The monovinylarene/conjugated diene block copolymer of claim 5, wherein the Tg is at least about 20째 C. less than the Tg of the reference polymer. 7. The monovinylarene/conjugated diene block copolymer of claim 6, wherein the Tg is at least about 30째 C. less than the Tg of the reference polymer. 8. The monovinylarene/conjugated diene block copolymer of claim 1, further comprising a monovinylarene/conjugated diene block. 9. The monovinylarene/conjugated diene block copolymer of claim 1, further comprising a monovinylarene block. 10. An article, comprising the monovinylarene/conjugated diene block copolymer of claim 1. 11. The article of claim 10, wherein the article is a shrink film. 12. A method of preparing a monovinylarene/conjugated diene block copolymer comprising: (a) charging a monovinylarene monomer, a conjugated diene monomer, an initiator, and a randomizer, allowing polymerizing to occur, to produce a random (conjugated dienex/monovinylareney) m block; wherein x is about 2.5 wt % to about 10 wt %, y is from about 90 wt % to about 97.5 wt %, and x+y is about 97.5 wt % to 100 wt %, and m is from about 70 wt % to about 80 wt %; (b) charging a monovinylarene monomer, a conjugated diene monomer, and an initiator, allowing polymerization to occur, to produce a monovinylarene/conjugated diene block; (c) charging a conjugated diene monomer, and allowing polymerization to occur, to produce a (conjugated diene)n block, wherein n is from about 20 wt % to about 30 wt % and m+n is from about 90 wt % to 100 wt %; and (d) charging the reaction mixture with a coupling agent, to form monovinylarene/conjugated diene block copolymer. 13. A monovinylarene/conjugated diene block copolymer, produced according to the method of claim 12. 14. A method of preparing a monovinylarene/conjugated diene block copolymer comprising: (a) charging an initiator and a monovinylarene monomer and allowing polymerization to occur, to produce a monovinylarene block; (b) charging a randomizer, an initiator, and a conjugated diene/monovinylarene monomer mixture and allowing polymerization to occur, to produce a random (conjugated dienex/monovinylareney) m block, wherein x is about 2.5 wt % to about 10 wt %, y is from about 90 wt % to about 97.5 wt %, x+y is about 97.5 wt % to 100 wt %, and m is from about 70 wt % to about 80 wt %; (c) charging a conjugated diene monomer and allowing polymerization to occur, to produce a conjugated diene block; (d) charging a randomizer, an initiator, and a conjugated diene/monovinylarene monomer mixture and allowing polymerization to occur, to produce a random (conjugated dienex/monovinylareney) m1 block, wherein x1 is about 2.5 wt % to about 10 wt %, y1 is from about 90 wt % to about 97.5 wt %. x1+y1 is about 97.5 wt % to 100 wt %, and m1 is from about 70 wt % to about 80 wt %; (e) charging a conjugated diene monomer and allowing polymerization to occur, to produce a conjugated diene block; and (f) charging the reaction mixture with a coupling agent, to form monovinylarene/conjugated diene block copolymer. 15. A monovinylarene/conjugated diene block copolymer, produced according to the method of claim 14. 16. A method of fabricating an article, comprising: forming a monovinylarene/conjugated diene block copolymer into the article, wherein the monovinylarene/conjugated diene block copolymer comprises (i) a random (conjugated dienex /monovinylareney)m block, wherein x is about 2.5 wt % to about 10 wt %, y is from about 90 wt % to about 97.5 wt %, and x+y is about 97.5 wt % to 100 wt %; and (ii) a (conjugated diene)n block; wherein n is from about 20 wt % to about 30 wt %, m is from about 70 wt % to about 80 wt %, and m+n is from about 90 wt % to 100 wt %. 17. The method of claim 16, wherein forming comprises sheet extrusion, thermoforming, injection molding, blow molding, film blowing, or film casting. 18. A monovinylarene/conjugated diene block copolymer, comprising the structure: (B/S)-B-CA, wherein (B/S) is a random monovinylarene/conjugated diene block; B is a conjugated diene block; CA is a coupling agent residue; and--is a covalent linkage between blocks, and wherein the monovinylarene/conjugated diene block copolymer further comprises a second structure selected from the group consisting of (a) a (B/S) block covalently linked to the (B/S) block of the (B/S)-B-CA structure, (b) a (B/S)-(B/S)-B structure covalently linked to the (B/S) block of the (B/S)-B-CA structure, (c) a (B/S)-B structure covalently linked to the (B/S) block of the (B/S)-B-CA structure, and (d) an S-(B/S)-B-structure covalently linked to the (B/S) block of the (B/S)-B-CA structure, wherein S is a monovinylarene block. 19. The monovinylarene/conjugated diene block copolymer of claim 18, wherein the second structure is a (B/S) block covalently linked to the (B/S) block of the (B/S)-B-CA structure. 20. The monovinylarene/conjugated diene block copolymer of claim 18, wherein the second structure is a (B/S)-(B/S)-B structure covalently linked to the (B/S) block of the (B/S)-B-CA structure. 21. The monovinylarene/conjugated diene block copolymer of claim 18, wherein the second structure is a (B/S)-B structure covalently linked to the (B/S) block of the (B/S)-B-CA structure. 22. The monovinylarene/conjugated diene block copolymer of claim 18, wherein the second structure is a S-(B/S)-B-structure covalently linked to the (B/S) block of the (B/S)-B-CA structure, wherein S is a monovinylarene block. 23. A monovinylarene/conjugated diene block copolymer, comprising the structure: <B/S>2-<B/S>3-<B/S>4-<B/S>5-CA, wherein <B/S> is a tapered monovinylarene/conjugated diene block; <B/S>2 has a conjugated diene content from about 2.5 wt % to about 10 wt %, <B/S>3, <B/S>4, and <B/S>5 have a conjugated diene content from about 30 wt % to about 70 wt %, and CA is a coupling agent residue. 24. The monovinylarene/conjugated diene block copolymer of claim 23, further comprising a <B/S>1 block covalently linked to the <B/S>2 block of the <B/S>2-<B/S>3-<B/S>4-< B/S>5-CA structure, wherein <B/S>1 has a conjugated diene content from about 2.5 wt % to about 10 wt %. 25. A monovinylarene/conjugated diene block copolymer, comprising the structure: (B/S)1-(B/S)2-<B/S>3-<B/S>4-<B/S>5-CA, wherein (B/S) is a random monovinylarene/conjugated diene block; <B/S> is a tapered monovinylarene/conjugated diene block; CA is a coupling agent residue;--is a covalent linkage between blocks; (B/S) 1 and (B/S)2 each have a conjugated diene content from about 2.5 wt % to about 10 wt %; and <B/S>3, <B/S>4, and <B/S>5 each have a conjugated diene content from about 30 wt % to about 70 wt %. 26. A monovinylarene/conjugated diene block copolymer, comprising the structure: (B/S)1-(B/S)2-(B/S)3-(B/S)4-(B/S)5-CA, wherein (B/S) is a random monovinylarene/conjugated diene block; CA is a coupling agent residue;--is a covalent linkage between blocks; (B/S)1 and (B/S)2 each have a conjugated diene content from about 2.5 wt % to about 10 wt %; and (B/S)3, (B/S)4, and (B/S)5 each have a conjugated diene content from about 30 wt % to about 70 wt %.

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Monovinylarene/conjugated diene copolymers having lower glass transition temperatures

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