Alternating crystalline-amorphous multiblock copolymer compositions and methods of production thereof

Patent metadata

Field	Value
Publication number	US-9963553-B2
Application number	US-201615259079-A
Country	US
Kind code	B2
Filing date	Sep 8, 2016
Priority date	Oct 30, 2015
Publication date	May 8, 2018
Grant date	May 8, 2018

Abstract

Alternating crystalline-amorphous polyolefin based multiblock copolymer compositions and methods for producing these multiblock copolymer compositions are disclosed. Also disclosed is the use of these multiblock copolymer compositions as additives to high density polyethylene (HDPE) resins in order to form polymer blends having improved ductility and toughness over that of the HDPE resins while retaining high mechanical strength, and the use of these polymer blends in films.

First claim

The invention claimed is:

1. An alternating crystalline-amorphous multiblock copolymer comprising:
one or more blocks of a polyolefin A and one or more blocks of an amorphous polyolefin B,
wherein polyolefin A comprises ethylene and polyolefin B comprises ethylene and a C 3 to C 10 alpha-olefin,
and wherein at least 90% of crystallites in the multiblock copolymer have a thickness of 15 nm or less.

2. The multiblock copolymer of claim 1 , wherein polyolefin A comprises units derived from cyclooctene, and wherein polyolefin B comprises units derived from butadiene.

3. The multiblock copolymer of claim 1 , wherein the polyolefin A has a melt index ranging from 0.10 g/10 min to 45 g/10 min, as measured in accordance with ASTM-131238 condition E.

4. The multiblock copolymer of claim 3 , wherein polyolefin A has an ethylene content of greater than 99 mol % based on the total moles of the monomers of polyolefin A.

5. The multiblock copolymer of claim 1 , wherein the alpha-olefin of polyolefin B is 1-butene.

6. The multiblock copolymer of claim 1 , wherein polyolefin B has an ethylene content ranging from 30 mol % to 70 mol % based on the total moles of the monomers of polyolefin B.

7. The multiblock copolymer of claim 1 , wherein the one or more blocks of polyolefin A form 5 wt % to 90 wt % of the multiblock copolymer.

8. The multiblock copolymer of claim 1 ,
wherein the one or more blocks of polyolefin A have a weight average molecular weight ranging from 1,000 to 250,000 g/mol, and
wherein the one or more blocks of polyolefin B have a weight average molecular weight ranging from 1,000 to 250,000 g/mol.

9. A method of synthesizing an alternating crystalline-amorphous multiblock copolymer comprising one or more blocks of a crystalline polyolefin A and one or more blocks of an amorphous polyolefin B, the method comprising:
(a) coupling a polyolefin A prepolymer and a polyolefin B prepolymer via at least one of (i) click chemistry, (ii) condensation chemistry, and/or (iii) Williamson ether synthesis, wherein the polyolefin A prepolymer comprises polycyclooctene, and wherein the polyolefin B prepolymer comprises polybutadiene; and
(b) hydrogenating the coupled polyolefin A and polyolefin B prepolymers.

10. The method of claim 9 , wherein the polyolefin A prepolymer is synthesized via Ring Opening Metathesis Polymerization (ROMP) of cyclooctene in the presence of a chain transferring agent (CTA).

11. The method of claim 10 , wherein the CTA is a halogenated C 3 to C 10 bi-functional alkene.

12. The method of claim 11 , wherein the polyolefin A prepolymer comprises telechelic bromo-terminated polycyclooctene.

13. The method of claim 9 , wherein the polyolefin B prepolymer comprises dilithium initiated, anionic polymerized polybutadiene.

14. The method of claim 9 ,
wherein the coupling is performed via Williamson ether synthesis in a solvent under basic conditions at a temperature ranging from 30° C. to 150° C., and
wherein the solvent is selected from the group consisting of C 6 to C 8 aliphatic hydrocarbons, C 6 to C 20 aryls, halogenated C 6 to C 20 aryls, and heterocyclic hydrocarbons.

15. A method of forming a polymer blend, comprising blending:
a) high density polyethylene (HDPE); and
b) an alternating crystalline-amorphous multiblock copolymer comprising:
one or more blocks of a crystalline polyolefin A and one or more blocks of an amorphous polyolefin B,
wherein polyolefin A comprises ethylene and polyolefin B comprises ethylene and a C 3 to C 10 alpha-olefin, and
wherein at least 90% of crystallites in the multiblock copolymer have a thickness of 15 nm or less,
wherein the multiblock copolymer is present at from 2.5 wt % to 60 wt % based on the weight of the polymer blend.

16. The method of claim 15 , wherein the blending comprises extrusion mixing of the HDPE and the multiblock copolymer at a temperature ranging from 120° C. to 300° C.

17. A polymer blend comprising:
a) HDPE; and
b) an alternating crystalline-amorphous multiblock copolymer comprising:
one or more blocks of a crystalline polyolefin A and one or more blocks of an amorphous polyolefin B,
wherein polyolefin A comprises ethylene and polyolefin B comprises ethylene and a C 3 to C 10 alpha-olefin,
wherein the multiblock copolymer is present at from 2.5 wt % to 60 wt % based on the weight of the polymer blend, and
wherein at least 15% of crystallites in the polymer blend have a thickness of 15 nm or less.

18. The polymer blend of claim 17 , wherein polyolefin A comprises HDPE.

19. The polymer blend of claim 18 , wherein polyolefin A has an ethylene content of greater than 99 mol % based on the total moles of the monomers of polyolefin A.

20. The polymer blend of claim 17 , wherein the alpha-olefin of polyolefin B is 1-butene, and wherein polyolefin B has a degree of crystallinity of less than 10%.

21. The polymer blend of claim 17 , wherein the blend has a yield stress greater than 15 MPa.

22. The polymer blend of claim 17 , wherein the blend has an elongation at break greater than 400%.

23. The polymer blend of claim 17 , wherein the blend has a Young's modulus greater than 350 MPa.

24. A film having one or more layers, wherein at least one layer comprises the polymer blend of claim 17 .

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Tsou Andy H
• Peretti Kathryn L
• Luo Shuji
• Yablon Dalia
• Vadlamudi Madhavi

Classifications

• C08J5/18 Primary

  Manufacture of films or sheets · CPC title

• C08G81/024 Primary

  Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G · CPC title

• C08L23/06

  Polyethylene · CPC title

• C08J2453/00

  Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers · CPC title

• C08L87/005

  Block or graft polymers not provided for in groups C08L1/00 - C08L85/04 · CPC title