Process for preparing graft copolymer comprising polyethylene

Patent metadata

Field	Value
Publication number	US-10975186-B2
Application number	US-201716067890-A
Country	US
Kind code	B2
Filing date	Jan 2, 2017
Priority date	Jan 5, 2016
Publication date	Apr 13, 2021
Grant date	Apr 13, 2021

Abstract

The invention relates to a process for preparing a graft copolymer comprising polyethylene, comprising the steps of: A) providing an ethylene copolymer comprising side chains having C≡C bond and B) reacting the ethylene copolymer of step A) with an azide at an elevated temperature in the absence of a catalyst to obtain the graft copolymer, wherein the azide compound is an azide compound having a functional group or a polymer having an azide group.

First claim

The invention claimed is:

1. A process for preparing a graft copolymer comprising polyethylene, comprising the steps of:
A) providing an ethylene copolymer comprising side chains having C≡C bond and
B) reacting the ethylene copolymer of step A) with an azide at an elevated temperature in the absence of a catalyst to obtain the graft copolymer,
wherein the azide is an azide compound having a functional group or a polymer having an azide group,
wherein step B) is performed at a temperature between the melting point of the ethylene copolymer having C≡C bond and 300° C.

2. The process according to claim 1 , wherein the ethylene copolymer of step A) is reacted with the azide compound in step B) and the azide compound is represented by
N 3 -spacer 1 -FG 1   (I)

wherein
FG 1 is selected from the group consisting of —OH, —OR 5 , —NH 2 , —NHR, —NR 5 2 , —SH, —CH═CH 2 ,

—COOH, —SO 3 H, —NH—COR 5 , —N 3 , —Si(OR 5 ) 3 ,

—I, —Br, —Cl, —F, —COOR 5 , —COR 5 , —CN, -phenyl, —C 6 H 4 R 5 , —S—C 6 H 5 and —CO—C 6 H 5 , where R 5 is a C 1 -C 10 linear or branched alkyl,
spacer 1 is selected from the group consisting of —(CH 2 ) p —, —(CH 2 ) p —C 6 H 4 —, —C 6 H 4 —(CH 2 ) p —, —(CHR 6 ) p —, —(CR 6 2 ) p —, —(O—CH 2 —CH 2 ) p —, —(O—CH 2 —CHCH 3 ) p —, —SO 2 —, —SO 2 —C 6 H 4 —, —SO 2 —C 6 H 2 R 6 2 —, —C 6 H 4 —, —C 6 H 2 R 6 2 —,
where p is an integer from 1 to 20 and where R 6 is C 1 -C 10 a linear or branched alkyl.

3. A process for preparing a graft copolymer comprising polyethylene, the process comprising the steps of:
A) providing an ethylene copolymer comprising side chains having C≡C bond and
B) reacting the ethylene copolymer of step A) with an azide at an elevated temperature in the absence of a catalyst to obtain the graft copolymer,
wherein the azide is an azide compound having a functional group or a polymer having an azide group,
wherein step A) involves preparing the ethylene copolymer in the presence of free-radical polymerization initiator at pressures in the range of from 150 MPa to 350 MPa and temperatures in the range of from 100° C. to 350° C. by copolymerizing ethylene and a comonomer having a C≡C bond and optionally further comonomers, wherein the comonomer having the C≡C bond is represented by formula

wherein
R 1 is hydrogen or methyl;
X 1 is —CO—O— or —CO—NH—;
R 2 is —CH 2 —O—, —O—CO—, —Si(CH 3 ) 2 —, —Si(CH 3 ) 2 —O— or —CR 5 R 6 — wherein R 5 and R 6 are independently selected from hydrogen, methyl, ethyl and hydroxyl;
n is an integer from 1 to 32 and R 2 is same or different from each other when n is 2 to 32; and
R 3 is —C≡C— and R 4 is hydrogen, C 1 -C 10 linear or branched alkyl, C 1 -C 10 linear or branched hydroxyalkyl or phenyl
or
the unit R 3 -R 4 stands for

wherein X 2 is F, Cl, Br or I.

4. The process according to claim 3 , wherein the comonomer having the C≡C bond is compound (I) or (III).

5. The process according to claim 3 , wherein the comonomer having the C≡C bond is compound (I) wherein X 1 is —CO—O—, R 2 is —CH 2 —, n is from 1 to 22, and R 3 is —C≡C— and R 4 is methyl or hydrogen or R 3 -R 4 stands for

6. The process according to claim 3 , wherein the comonomer having the C≡C bond is selected from the group consisting of propargyl acrylate, propargyl methacrylate, 2-methyl-acrylic acid 3-(cyclooct-2-ynyloxy)-propyl ester, 6-hepten-3-yn-1-ol, 3-methyl-1-penten-4-yn-3-ol, 2-methyl-6-hepten-3-yn-2-ol, 1-phenyl-4-penten-1-yne, 5-hexen-2-yn-1-ol, 3-(allyloxy)-1-propyne, allyl propiolate, 2-Nonynoic acid, 2-propen-1-yl ester, 2-methyl-1-hexen-3-yne and 2-methyl-1-buten-3-yne.

7. The process according to claim 3 , wherein the comonomer having the C≡C bond is propargyl methacrylate or propargyl acrylate.

8. The process according to claim 3 , wherein the amount of the comonomer having the C≡C bond is 0.1-10 mol % of the total weight of ethylene and all comonomers in step A).

9. The process according to claim 1 , wherein step A) involves grafting a compound having a C≡C bond to a base ethylene polymer which is an ethylene homopolymer or a copolymer of ethylene and α-olefins with 3-12 C atoms.

10. The process according to claim 3 , wherein step B) is performed at a temperature between the melting point of the ethylene copolymer having C≡C bond and 300° C.

11. The process according to claim 1 , wherein the ethylene copolymer of step A) has a number average molecular weight M n of at least 5.0 kg/mol and/or a weight average molecular weight M w of at least 50 kg/mol.

12. The graft copolymer obtained by the process according to claim 1 ,
wherein the ethylene copolymer comprising side chains having C≡C bond of step A) is provided by copolymerizing ethylene and a comonomer having a C≡C bond and optionally further comonomers, wherein the comonomer having the C≡C bond is represented by formula

wherein
R 1 is hydrogen or methyl;
X 1 is —CO—O— or —CO—NH—;
R 2 is —CH 2 —O—, —O—CO—, —Si(CH 3 ) 2 —, —Si(CH 3 ) 2 —O— or —CR 5 R 6 — wherein R 5 and R 6 are independently selected from hydrogen, methyl, ethyl and hydroxyl;
n is an integer from 1 to 32 and R 2 is same or different from each other when n is 2 to 32; and
R 3 is —C≡C— and R 4 is hydrogen, C 1 -C 10 linear or branched alkyl, C 1 -C 10 linear or branched hydroxyalkyl or phenyl
or
the unit R 3 -R 4 stands for

wherein X 2 is F, Cl, Br or I.

13. An article comprising the graft copolymer according to claim 12 .

14. The article according to claim 13 , wherein the article is a film; a molded article; an extruded article; an article made by 3D printing; an article made by compounding; a foam; a profile; an adhesive; a bitumen modifier; a sealant; a disposable diaper; a textile; or a polymer alloy.

15. The article according to claim 14 , wherein the film is packaging of bakery items, snack foods, consumer durables, an agricultural film, a shrink film, medical packaging, upholstery wrap, a disposable glove or a film made by encapsulation.

16. The graft copolymer according to claim 12 , wherein the comonomer having the C≡C bond is compound (I) or (III).

17. The graft copolymer according to claim 12 , wherein the comonomer having the C≡C bond is compound (I) wherein X 1 is —CO—O—, R 2 is —CH 2 —, n is from 1 to 22, and R 3 is —C≡C— and R 4 is methyl or hydrogen or R 3 -R 4 stands for

18. The graft copolymer according to claim 12 , wherein the comonomer having the C≡C bond is selected from the group consisting of propargyl acrylate, propargyl methacrylate, 2-methyl-acrylic acid 3-(cyclooct-2-ynyloxy)-propyl ester, 6-hepten-3-yn-1-ol, 3-methyl

Assignees

• Sabic Global Technologies Bv

Inventors

• Castaneda Zuniga Diego Mauricio
• Neuteboom Peter
• Duchateau Jan Nicolaas Eddy
• Busch Markus
• Fries Sebastian Bruno

Classifications

• C08G81/027

  containing polyester or polycarbonate sequences · CPC title

• C08F8/30 Primary

  Introducing nitrogen atoms or nitrogen-containing groups · CPC title

• C08F238/00

  Copolymers of compounds having one or more carbon-to-carbon triple bonds · CPC title

• C08F255/026 Primary

  on to ethylene-vinylester copolymers · CPC title

• C08G81/021

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