COPOLYMER OF 1,3,7-OCTATRIENE AND ISOPRENE, HYDRIDE THEREOF, AND METHOD FOR PRODUCING SAID COPOLYMER

• US 20190315899A1
• Filed: 12/28/2017
• Published: 10/17/2019
• Est. Priority Date: 12/28/2016
• Status: Active Grant

• Current Assignee: Kuraray Company Limited
• Original Assignee: Kuraray Company Limited
• Inventors: SUNAGA, Shuichi, TSUJI, Tomoaki, HORI, Takashi, INUBUSHI, Yasutaka
• Granted Patent: US 11,091,578 B2
• Time in Patent Office: Days
• CPC Class Codes: C08F 2/38 Polymerisation using regulators, e.g. chain terminating agents , e.g. telomerisation
• CPC Class Codes: C08F 236/08 Isoprene
• CPC Class Codes: C08F 236/22 the radical having three or more carbon-to-carbon double bonds
• CPC Class Codes: C08F 2800/10 as molar percentages
• CPC Class Codes: C08F 4/48 selected from lithium, rubidium, caesium or francium C08F4/461 takes precedence
• CPC Class Codes: C08F 8/04 Reduction, e.g. hydrogenation

Abstract

The present invention provides a copolymer of 1,3,7-octatriene and isoprene having a narrow molecular weight distribution (Mw/Mn) and a hydride thereof. Furthermore, in a production method of a copolymer containing a structural unit derived from 1,3,7-octatriene and a structural unit derived from isoprene, high raw material conversions are achieved for a short polymerization time. Specifically, the copolymer is a copolymer containing a structural unit derived from 1,3,7-octatriene and a structural unit derived from isoprene and is a copolymer having a molecular weight distribution (Mw/Mn) of less than 1.44, or the like.

Claims

1. :

A copolymer comprising a structural unit derived from 1,3,7-octatriene and a structural unit derived from isoprene, the copolymer having a molecular weight distribution (Mw/Mn) of less than 1.44.

4. :

The copolymer according to claim 1, having a weight average molecular weight (Mw) of 5,000 to 500,000.

5. :

The copolymer according to claim 1, having a weight average molecular weight (Mw) of 20,000 to 500,000.

6. :

The copolymer according to claim 1, having a weight average molecular weight (Mw) of 50,000 to 500,000.

7. :

The copolymer according to claim 1, having a weight average molecular weight (Mw) of 210,000 to 500,000.

8. :

The copolymer according to claim 1, not having a living anionic active species at a molecular end thereof.

9. :

The copolymer according to claim 1, having a living anionic active species at a molecular end thereof.

12. :

The copolymer according to claim 1, further comprising a structural unit derived from a conjugated diene compound having 6 or more carbon atoms.

13. :

The copolymer according to claim 12, wherein the conjugated diene compound having 6 or more carbon atoms is at least one selected from the group consisting of 2,3-dimethyl-1,3-butadiene, 4,5-diethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2-hexyl-1,3-butadiene, 2-benzyl-1,3-butadiene, 2-p-toluyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2,3-diethyl-1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-hexadiene, 2,3-diethyl-1,3-heptadiene, 3-butyl-1,3-octadiene, 2,3-dimethyl-1,3-octadiene, 4,5-diethyl-1,3-octadiene, 1,3-cyclohexadiene, and myrcene.

14. :

A hydride of the copolymer according to claim 1.

2. :

A copolymer comprising a structural unit derived from 1,3,7-octatriene and a structural unit derived from isoprene, the copolymer having a molecular weight distribution (Mw/Mn) smaller than a value determined according to the following formula (i);

3.1569×

10<sup>−

6</sup>×

[Weight average molecular weight (Mw)]+1.1945 

 

(i).

3. :

A copolymer comprising a structural unit derived from 1,3,7-octatriene and a structural unit derived from isoprene, the copolymer having not only a content of the structural unit derived from 1,3,7-octatriene of more than 21.0 mol % relative to a total amount of the structural unit derived from 1,3,7-octatriene and the structural unit derived from isoprene, but also a molecular weight distribution (Mw/Mn) thereof of less than 2.06.

10. :

A copolymer comprising a structural unit derived from 1,3,7-octatriene and a structural unit derived from isoprene, the copolymer having a living anionic active species at a molecular end thereof and having a molecular weight distribution (Mw/Mn) of 2.50 or less.

11. :

The copolymer according to claim 10, having a weight average molecular weight (Mw) of 5,000 to 500,000.

15. :

A method of producing a copolymer containing a structural unit derived from 1,3,7-octatriene and a structural unit derived from isoprene, the method comprising subjecting 1,3,7-octatriene having a purity, as determined by gas chromatography, of more than 98.0% and isoprene to anionic polymerization, wherein

impurities which may be contained in the 1,3,7-octatriene include at least one selected from the group consisting of a peroxide and its decomposition product, and a total content of the peroxide and its decomposition product in the 1,3,7-octatriene is 0.30 mmol/kg or less; and

the copolymer satisfies at least one of the following conditions I to III;

Condition I;

a molecular weight distribution (Mw/Mn) is less than 1.44;

Condition II;

a molecular weight distribution (Mw/Mn) is smaller than a value determined according to the following formula (i);

3.1569×

10<sup>−

6</sup>×

[Weight average molecular weight (Mw)]+1.1945 

 

(i); and

Condition III;

not only a content of the structural unit derived from 1,3,7-octatriene is more than 21.0 mol % relative to a total amount of the structural unit derived from 1,3,7-octatriene and the structural unit derived from isoprene, but also a molecular weight distribution (Mw/Mn) thereof is less than 2.06.

16. :

The method of claim 15, wherein the 1,3,7-octatriene has a purity, as determined by gas chromatography, of 98.5% or more.

17. :

The method of claim 15, wherein the anionic polymerization is carried out in the presence of a Lewis base.

18. :

The method of claim 17, wherein a molar ratio of the Lewis base to a polymerization initiator used for the anionic polymerization [(Lewis base)/(polymerization initiator)] is from 0.01 to 1,000.

19. :

The method of claim 17, wherein the Lewis base is a compound having at least one selected from the group consisting of an ether bond and a tertiary amino group in a molecule thereof.

20. :

The method of claim 17, wherein the Lewis base is a compound having one atom having an unshared electron pair.

21. :

The method of claim 17, wherein the Lewis base is a compound having two or more atoms having an unshared electron pair.

22. :

The method of claim 21, wherein the Lewis base has multidentate properties.

23. :

The method of claim 15, wherein a solid content concentration of a reaction liquid obtained after completion of the anionic polymerization is from 10 to 80% by mass.

24. :

The method of claim 15, wherein the anionic polymerization is carried out at −

50 to 200°

C.

25. :

The method of claim 15, wherein a conversion of the 1,3,7-octatriene after completion of the anionic polymerization, as determined by gas chromatography, is 80.0% or more.

26. :

The method of claim 15, wherein a conversion of the 1,3,7-octatriene after completion of the anionic polymerization, as determined by gas chromatography, is 88.0% or more.