阅读说明：本技术 乙烯共聚物及其生产方法 (Ethylene copolymer and process for producing the same ) 是由 P·纽特布姆 D·M·卡斯塔内达祖尼加 J·N·E·达查特奥 F·P·H·施鲁尔斯 J·瓦尚 于 2018-11-19 设计创作，主要内容包括：本发明涉及通过高压法由自由基聚合获得的乙烯共聚物,其包含(i)≥78.0且≤99.99摩尔％的衍生自乙烯的重复单元；(ii)≥0.01且≤22.0摩尔％的衍生自根据式(I)的共聚单体A的重复单元：<Image he="275" wi="565" file="DDA0002547074100000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中R1由包含5-40个碳原子的饱和脂族结构部分构成,或R1由饱和脂族结构部分构成并且由氢原子和5-40个碳原子组成；R2选自-H或-CH<Sub>3</Sub>；R3选自-O-、-(CO)-(NH)-或-(CO)-O-；n＝0或1该乙烯共聚物具有降低的峰值熔融温度和降低的熔合焓,表明这些乙烯共聚物具有降低的结晶度和改进的清明度,同时具有令人期望的熔体质量流动速率。(The invention relates to an ethylene copolymer obtained by free-radical polymerization by a high-pressure process, comprising (i) 78.0 or more and 99.99 mol% or less of recurring units derived from ethylene; (ii) 0.01 and 22.0 mol% of recurring units derived from a comonomer A according to formula (I): wherein R1 consists of a saturated aliphatic moiety containing from 5 to 40 carbon atoms,or R1 consists of a saturated aliphatic moiety and consists of hydrogen atoms and 5 to 40 carbon atoms; r2 is selected from-H or-CH 3 (ii) a R3 is selected from-O-, - (CO) - (NH) -or- (CO) -O-; n-0 or 1 the ethylene copolymers have reduced peak melting temperatures and reduced enthalpy of fusion, indicating that these ethylene copolymers have reduced crystallinity and improved clarity while having desirable melt mass flow rates.)

1. An ethylene copolymer obtained by free-radical polymerization by a high pressure process comprising:

(i) (ii) from > 78.0 to < 99.99 mol% of recurring units derived from ethylene;

(ii) 0.01 and 22.0 mol% of recurring units derived from a comonomer A according to formula (I):

wherein

R1 consists of a saturated aliphatic moiety containing from 5 to 40 carbon atoms or R1 consists of a saturated aliphatic moiety and consists of hydrogen atoms and from 5 to 40 carbon atoms;

r2 is selected from-H or-CH₃；

R3 is selected from-O-, - (CO) - (NH) -or- (CO) -O-;

n is 0 or 1.

2. The ethylene copolymer of claim 1, wherein the ethylene copolymer comprises

(iii) 0 and 2.00 mol% of recurring units derived from a comonomer B according to formula (II):

wherein

R4 is a moiety comprising 1 to 30 carbon atoms;

each R2 is independently selected from-H or-CH₃；

Each R3 is independently selected from-O-, - (CO) - (NH) -or- (CO) -O-;

n is 0 or 1;

p is 0 or 1; and

m is more than or equal to 1 and less than or equal to 10.

3. The ethylene copolymer of claim 1, wherein the ethylene copolymer comprises

(iii) >0 and ≦ 2.00 mol% of recurring units derived from comonomer B according to formula (II):

wherein

R4 is a moiety comprising 1 to 30 carbon atoms;

each R2 is independently selected from-H or-CH₃；

Each R3 is independently selected from-O-, - (CO) - (NH) -or- (CO) -O-;

n is 0 or 1;

p is 0 or 1; and

m is more than or equal to 1 and less than or equal to 10.

4. An ethylene copolymer as claimed in any one of claims 1 to 3, wherein comonomer A is a compound according to formula (III):

wherein

R1 consists of a saturated aliphatic moiety containing from 5 to 40 carbon atoms, or R1 consists of a saturated aliphatic moiety consisting of hydrogen atoms and from 5 to 40 carbon atoms,

r2 is selected from-H or-CH₃。

5. The ethylene copolymer of claim 1 or claim 4 wherein R1 consists of a saturated aliphatic moiety comprising 5-12 carbon atoms, or wherein R1 consists of a saturated aliphatic moiety and consists of hydrogen atoms and 5-12 carbon atoms.

6. Ethylene copolymer according to any one of claims 1 to 5, wherein the comonomer B is a compound according to formula (IV):

wherein

R4 is a moiety selected from:

-CH₂-；

-[CH₂]_x-CH(CH₃) -, where x is not less than 1 and not more than 10;

-CH₂-CH(OH)-CH₂-；

-CH₂-CHR5-[O-CH₂-CHR5]_q-, where q.gtoreq.1 and.ltoreq.10, and each R5 is independently selected from CH₃And H; and

m is greater than or equal to 1 and less than or equal to 10, and

each R2 is independently selected from-H or-CH₃。

7. Ethylene copolymer according to any one of claims 1 to 6, wherein

Comonomer a is a compound selected from the list consisting of: lauryl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, 10-undecylenyl 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 list consisting of: 1, 4-butanediol dimethacrylate, hexanediol dimethacrylate, ethylene glycol dimethacrylate, 1, 3-butanediol dimethacrylate, dodecanediol dimethacrylate, glycerol dimethacrylate, 1, 4-butanediol diacrylate, hexanediol diacrylate, ethylene glycol diacrylate, 1, 3-butanediol diacrylate, dodecanediol diacrylate, glycerol 1, 3-diglyceride dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, poly (ethylene glycol propylene glycol) dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, 1, 4-butanediol divinyl ether, poly (ethylene glycol) divinyl ether, di (ethylene glycol) divinyl ether, 1, 5-hexadiene, 1, 7-octadiene, 1, 9-decadiene and 1, 13-tetradecadiene.

8. Ethylene copolymer according to any one of claims 1 to 7, wherein the copolymer comprises

At least 78.0 and at most 99.99 mol% or at least 78.0 and at most 99.98 mol% of recurring units derived from ethylene;

0.01 and 22.0 mol% of recurring units derived from comonomer A, wherein comonomer A is selected from the list consisting of: lauryl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, 10-undecylenyl 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 to 2.00 mol% or >0 to 2.00 mol% of recurring units derived from comonomer B, wherein comonomer B is selected from 1, 4-butanediol dimethacrylate, hexanediol dimethacrylate, 1, 3-butanediol dimethacrylate, dodecanediol dimethacrylate, glycerol dimethacrylate, 1, 4-butanediol diacrylate, hexanediol diacrylate, 1, 3-butanediol diacrylate, dodecanediol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate.

9. Ethylene copolymer according to any one of claims 1 to 8, wherein the ethylene copolymer has a melt mass flow rate, determined according to ISO 1133-1(2011) at a temperature of 190 ℃ and a load of 2.16kg, of ≥ 0.1 and ≤ 150.0g/10 min.

10. Ethylene copolymer according to any one of claims 1 to 9, wherein the ethylene copolymer has a peak melting temperature of ≤ 110 ℃ determined according to ISO 11357-3(2011) and a fusion enthalpy of the melting peak of ≤ 120J/g determined according to ISO 11357-3 (2011).

11. Ethylene copolymer according to any one of claims 1 to 10, wherein the ethylene copolymer is prepared in a tubular reactor.

12. Process for the preparation of an ethylene copolymer in a tubular reactor, wherein:

the method is carried out at a pressure of more than or equal to 200 and less than or equal to 350MPa and at a temperature of more than or equal to 100 and less than or equal to 350 ℃;

the process is carried out in the presence of one or more radical initiators selected from organic peroxides and/or azo compounds;

introducing into the reactor a mixture of reactants comprising:

(a) more than or equal to 78.0 and less than or equal to 99.99 mol percent or more than or equal to 78.0 and less than or equal to 99.98 mol percent of ethylene;

(b) not less than 0.01 and not more than 22.0 mol% of a comonomer A according to formula (III):

wherein

R1 consists of a saturated aliphatic moiety containing from 5 to 40 carbon atoms;

r2 is selected from-H or-CH₃；

(c) More than or equal to 0 and less than or equal to 2.0 mol% or more than 0 and less than or equal to 2.0 mol% of a comonomer B according to formula (IV):

wherein

R4 is a moiety selected from:

-CH₂-；

-[CH₂]_x-CH(CH₃) -, where x is not less than 1 and not more than 10;

-CH₂-CH(OH)-CH₂-；

-CH₂-CHR5-[O-CH₂-CHR5]_q-, where q.gtoreq.1 and.ltoreq.10, and each R5 is independently selected from CH₃And H; and

m is more than or equal to 1 and less than or equal to 10; and

each R2 can be independently selected from-H or-CH₃。

13. The method of claim 12, wherein

Comonomer A is selected from lauryl methacrylate, lauryl acrylate, hexyl methacrylate, hexyl acrylate, octyl acrylate and decyl acrylate, and

comonomer B is selected from 1, 4-butanediol dimethacrylate, polyethylene glycol dimethacrylate and polypropylene glycol dimethacrylate.

14. Use of an ethylene copolymer according to any one of claims 1 to 11 or an ethylene copolymer prepared according to the process of any one of claims 12 to 13 for the manufacture of extrusion coated articles, films, foams, adhesives, asphalt modifiers, moulded articles, 3D printed articles and/or polymer alloys.

15. An article comprising an ethylene copolymer according to any one of claims 1 to 11 or prepared according to the process of any one of claims 12 to 14, wherein the article is an extrusion coated article, a film, a foam, an adhesive, an asphalt modifier, a molded article, a 3D printed article or a polymer alloy.

Examples

The following materials were used as comonomers in the examples.