Ethylene copolymers and process for the production thereof

Patent metadata

Field	Value
Publication number	US-11198746-B2
Application number	US-201816766018-A
Country	US
Kind code	B2
Filing date	Nov 19, 2018
Priority date	Nov 24, 2017
Publication date	Dec 14, 2021
Grant date	Dec 14, 2021

Abstract

The present invention relates to an ethylene copolymer obtained by radical polymerisation through a high-pressure process comprising (i) ≥78.0 and ≤99.99 mole % of recurring units derived from ethylene; (it) ≥0.01 and ≤22.0 mole % of recurring units derived from comonomer A according to Formula (I), wherein R1 is composed of a saturated aliphatic moiety comprising 5-40 carbon atoms or R1 is composed of a saturated aliphatic moiety and consists of hydrogen atoms and 5-40 carbon atoms; R2 is selected from —H or —CH 3 ; R3 is selected from —O—, —(CO)—(NH)— or —(CO)—O—; n=0 or 1 The ethylene copolymers have a reduced peak melting temperature and reduced enthalpy of fusion, indicating that these ethylene copolymers have a reduced degree of crystallinity and improved clarity, combined with a desired melt mass-flow rate.

First claim

The invention claimed is:

1. Ethylene copolymer obtained by radical polymerisation through a high-pressure process comprising:
(i) ≥78.0 and ≤99.99 mole % of recurring units derived from ethylene;
(ii) ≥0.01 and ≤22.0 mole % of recurring units derived from comonomer A according to Formula (I):

wherein
R1 is composed of a saturated aliphatic moiety comprising 5-40 carbon atoms or R1 is composed of a saturated aliphatic moiety and consists of hydrogen atoms and 5-40 carbon atoms;
R2 is —H or —CH3;
R3 is —O—, —(CO)—(NH)— or —(CO)—O—; and
n=0 or 1,
wherein the ethylene copolymer has a melt mass-flow rate as determined in accordance with ISO 1133-1 (2011), at a temperature of 190° C. and a load of 2.16 kg, of ≥0.1 and ≤150.0 g/10 min.

2. Ethylene copolymer according to claim 1 wherein the ethylene copolymer comprises
(iii) ≥0 and ≤2.00 mole % of recurring units derived from comonomer B according to Formula (II):

wherein
R4 is a moiety comprising 1-30 carbon atoms;
each of R2 is independently —H or —CH3;
each of R3 is independently —O—, —(CO)—(NH)— or —(CO)—O—;
n=0 or 1;
p=0 or 1; and
m≥1 and ≤10.

3. Ethylene copolymer according to claim 2 wherein the copolymer comprises
≥78.0 and ≤99.99 mole % of recurring units derived from ethylene;
≥0.01 and ≤22.0 mole % of recurring units derived from comonomer A wherein comonomer A is selected from the group consisting of lauryl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, 10-undecenyl acrylate, behenyl acrylate, stearyl methacrylate, lauryl acrylate, isodecyl acrylate, isooctyl acrylate, octyl acrylate, tridecyl acrylate, 3,5,5-trimethylhexyl acrylate and isobornyl methacrylate and
≥0 and ≤2.00 mole % of recurring units derived from comonomer B wherein comonomer B is 1,4-butanediol dimethacrylate, hexanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, dodecanediol dimethacrylate, glycerol dimethacrylate, 1,4-butanediol diacrylate, hexanediol diacrylate, 1,3-butylene glycol diacrylate, dodecanediol diacrylate, poly(ethylene glycol) dimethacrylate, or poly(propylene glycol) dimethacrylate.

4. Ethylene copolymer according to claim 1 wherein comonomer A is a compound according to Formula (III):

wherein
R1 is composed of a saturated aliphatic moiety comprising 5-40 carbon atoms or R1 is composed of a saturated aliphatic moiety consisting of hydrogen atoms and 5-40 carbon atoms,
R2 is —H or —CH3.

5. Ethylene copolymer according to claim 1 wherein R1 is composed of a saturated aliphatic moiety comprising 5-12 carbon atoms or wherein R1 is composed of a saturated aliphatic moiety and consists of hydrogen atoms and 5-12 carbon atoms.

6. Ethylene copolymer according to claim 1 wherein the ethylene copolymer is produced in a tubular reactor.

7. Article comprising an ethylene copolymer according to claim 1 wherein the article is an extrusion coated article, a film, a foam, an adhesive, a bitumen modifier, a moulded article, a 3D printed article or a polymer alloy.

8. Ethylene copolymer obtained by radical polymerisation through a high-pressure process comprising:
≥78.0 and ≤99.99 mole % of recurring units derived from ethylene;
iii) ≥0.01 and ≤22.0 mole % of recurring units derived from comonomer A according to Formula (I):

wherein
R1 is composed of a saturated aliphatic moiety comprising 5-40 carbon atoms or R1 is composed of a saturated aliphatic moiety and consists of hydrogen atoms and 5-40 carbon atoms;
R2 is —H or —CH3;
R3 is —O—, —(CO)—(NH)— or —(CO)—O—; and
n=0 or 1,
wherein the ethylene copolymer further comprises
(iii) >0 and ≤2.00 mole % of recurring units derived from comonomer B according to Formula (II):

wherein
R4 is a moiety comprising 1-30 carbon atoms;
each of R2 is independently —H or —CH3;
each of R3 is independently —O—, —(CO)—(NH)— or —(CO)—O—;
n=0 or 1;
p=0 or 1; and
m≥1 and ≤10.

9. Ethylene copolymer according to claim 8 wherein the comonomer B is a compound according to Formula (IV):

wherein
R4 is a moiety selected from the group consisting of:
—CH2—;
—[CH2]x-CH(CH3)—, wherein x≥1 and ≤10;
—CH2—CH(OH)—CH2—; and
—CH2—CHR5—[—CH2—CHR5]q-, wherein q≥1 and ≤10, and each R5 individually is selected from CH3 and H; and
m≥1 and ≤10 and
each R2 is independently —H or —CH3.

10. Ethylene copolymer according to claim 8 wherein
comonomer A is a compound selected from the group consisting of lauryl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, 10-undecenyl acrylate, behenyl acrylate, stearyl methacrylate, lauryl acrylate, isodecyl acrylate, isooctyl acrylate, octyl acrylate, tridecyl acrylate, 3,5,5-trimethylhexyl acrylate and isobornyl methacrylate and/or
comonomer B is a compound selected from the group consisting of 1,4-butanediol dimethacrylate, hexanediol dimethacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, dodecanediol dimethacrylate, glycerol dimethacrylate, 1,4-butanediol diacrylate, hexanediol diacrylate, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, dodecanediol diacrylate, glycerol diacrylate, glycerol 1,3-diglycerolate diacrylate, glycerol 1,3-diglycerolate dimethacrylate, poly(ethylene glycol) dimethacrylate, poly(propylene glycol) dimethacrylate, poly(ethylenepropyleneglycol) dimethacrylate, trimethylol propane trimethacrylate, trimethylol propane triacrylate, 1,4-butanediol divinyl ether, poly(ethylene glycol) divinyl ether, di(ethyleneglycol) divinyl ether, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene and 1,13-tetradecadiene.

11. Ethylene copolymer according to claim 8 wherein the ethylene copolymer has a melt mass-flow rate as determined in accordance with ISO 1133-1 (2011), at a temperature of 190° C. and a load of 2.16 kg, of ≥0.1 and ≤150.0 g/10 min.

12. Ethylene copolymer according to claim 8 , wherein the copolymer comprises
≥78.0 and ≤99.99 mole % of recurring units derived from ethylene;
≥0.01 and ≤22.0 mole % of recurring units derived from comonomer A wherein comonomer A is selected from the group consisting of lauryl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, 10-undecenyl acrylate, behenyl acrylate, stearyl methacrylate, lauryl acrylate, isodecyl acrylate, isooctyl acrylate, octyl acrylate, tridecyl acrylate, 3,5,5-trimethylhexyl acrylate and isobornyl methacrylate and
≥0 and ≤2.00 mole % of recurring units derived from comonomer B wherein comonomer B is 1,4-butanediol dimethacrylate, hexanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, dodecanediol dimethacrylate, glycerol dimethacrylate, 1,4-butanediol diacrylate, hexanediol diacrylate, 1,3-butylene glycol diacrylate, dodecanediol diacrylate, poly(ethylene glycol) dimethacrylate, or poly(prop

Assignees

• Sabic Global Technologies Bv

Inventors

• Neuteboom Peter
• Castaneda Zuniga Diego Mauricio
• Duchateau Jan Nicolaas Eddy
• Schreurs Franciscus Petrus Hermanus
• Vachon Jerome
• Toloza Porras Carolina De Los Angeles

Classifications

• C08F220/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title

• C08F2/02

  Polymerisation in bulk · CPC title

• C08F210/02 Primary

  Ethene · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title

• C08F2800/10

  as molar percentages · CPC title