Production method of olefin (co)polymer containing constituent unit derived from 1-butene

Patent metadata

Field	Value
Publication number	US-9944728-B2
Application number	US-201515509382-A
Country	US
Kind code	B2
Filing date	Sep 10, 2015
Priority date	Sep 11, 2014
Publication date	Apr 17, 2018
Grant date	Apr 17, 2018

Abstract

The purpose of the present invention is to provide a method for efficiently producing an olefin (co)polymer containing a constituent unit derived from 1-butene, the (co)polymer having a molecular weight that is sufficiently high even for high temperature conditions that are beneficial for industrial production methods. This purpose can be achieved by means of a method for producing an olefin (co)polymer containing a constituent unit derived from 1-butene, wherein at least 1-butene and, if necessary, an α-olefin having 2 or more carbon atoms (excluding 1-butene) and other monomers are (co)polymerized in the presence of an olefin polymerization catalyst that contains (A) a crosslinked metallocene compound represented by general formula [I] and (B) at least one type of compound selected from among (b-1) an organic aluminum oxy compound, (b-2) a compound that forms an ion pair upon a reaction with the crosslinked metallocene compound (A), and (b-3) an organic aluminum compound, at a polymerization temperature of 55-200° C. and a polymerization pressure of 0.1-5.0 MPaG.

First claim

The invention claimed is:

1. A production method of an olefin copolymer containing structural units derived from 1-butene, comprising
a step of copolymerizing at least a 1-butene and a propylene, optionally an α-olefin having 2 or more carbon atoms (excluding 1-butene and propylene) and optionally (an)other monomer(s) under the conditions of a polymerization temperature of not less than 55° C. and not more than 200° C. and a polymerization pressure of not less than 0.1 MPaG and not more than 5.0 MPaG in the presence of an olefin polymerization catalyst containing
(A) a crosslinked metallocene compound represented by General Formula [I] below, and
(B) at least one compound selected from
(b-1) an organoaluminum oxy-compound,
(b-2) a compound that forms an ion pair by reacting with the crosslinked metallocene compound (A), and
(b-3) an organoaluminum compound;
wherein the olefin copolymer includes at least structural units derived from 1-butene, includes the total content of structural units derived from ethylene and an α-olefin having 4 or more carbon atoms (including 1-butene) in the range of not less than 8 mol % and not more than 50 mol %, and includes the content of structural units derived from propylene in the range of not less than 50 mol % and not more than 92 mol % (provided that the total of the content of structural units derived from ethylene and the α-olefin having 4 or more carbon atoms (including 1-butene) and the content of structural units derived from propylene is 100 mol %), and
wherein a peak melting point (Tm) obtained from the differential scanning calorimetry (DSC) is not less than 50° C. and less than 110° C., or the peak melting point is not observed from DSC,

(In the formula, R 1 is an adamantyl group derivative; R 2 and R 7 are selected from a hydrocarbon group, a silicon-containing group, and a halogen-containing hydrocarbon group; R 3 and R 6 are hydrogen atoms; R 4 , R 5 , R 8 , R 9 , R 10 , R 11 , and R   are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group and may be the same or different from each other, and adjacent substituents among R 4 , R 5 , R 8 , R 9 , R 10 , R 11 , and R 12 may combine to form a ring; M is a Group 4 transition metal; Q is a halogen atom, a hydrocarbon group, an anionic ligand, or a neutral ligand that is bondable with a lone pair and may be the same or different from each other; and j is an integer between 1 and 4).

2. The production method of an olefin copolymer containing structural units derived from 1-butene according to claim 1 , wherein in General Formula [I], R 1 is a 1-adamantyl group.

3. The production method of an olefin copolymer containing structural units derived from 1-butene according to claim 1 , wherein in General Formula [I], R 2 and R 7 are hydrocarbon groups having 4 to 10 carbon atoms.

4. The production method of an olefin copolymer containing structural units derived from 1-butene according to claim 1 , wherein in General Formula [I], R 4 and R 5 are hydrogen atoms.

5. The production method of an olefin copolymer containing structural units derived from 1-butene according to claim 1 , wherein in General Formula [I], R 12 is a hydrocarbon group having 1 to 20 carbon atoms.

6. The production method of an olefin copolymer containing structural units derived from 1-butene according to claim 1 , wherein in General Formula [I], R 8 to R 11 are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms.

7. The production method of an olefin copolymer containing structural units derived from 1-butene according to claim 1 , wherein in General Formula [I], R 10 and R 11 are hydrogen atoms.

8. The production method of an olefin copolymer containing structural units derived from 1-butene according to claim 1 , wherein in General Formula [I], R 8 and R 9 are hydrocarbon groups having 1 to 20 carbon atoms.

9. The production method of an olefin copolymer containing structural units derived from 1-butene according to claim 1 , wherein copolymerization is performed in the presence of hydrogen.

10. The production method of an olefin copolymer containing structural units derived from 1-butene according to claim 1 ,
wherein the olefin copolymer is obtained by copolymerization of at least a 1-butene and propylene and optionally (an)other monomer(s), and satisfies both of the requirements (i) and (ii) below:
(i) the structural units derived from propylene (P) are 51 mol % ≤P ≤90 mol %, and the structural units derived from 1-butene (B) are 10 mol % ≤B ≤49 mol % (provided that (P) +(B) =100 mol %), and
(ii) the intrinsic viscosity [η] in decalin at 135° C. is 1.3 (dl/g) ≤[η] ≤10 (dl/g).

11. The production method of an olefin copolymer containing structural units derived from 1-butene according to claim 1 ,
wherein the olefin copolymer is obtained by copolymerization of at least a 1-butene, propylene and ethylene and optionally (an)other monomer(s), and satisfies both of the requirements (i) and (ii) below:
(i) the structural units derived from propylene (P) are 51 mol % ≤P ≤92 mol %, the structural units derived from 1-butene (B) are 4 mol % ≤B ≤45 mol %, and the structural units derived from ethylene (E) are 4 mol % ≤E ≤45 mol % (provided that (P) +(B) +(E) =100 mol %), and
(ii) the intrinsic viscosity [η] in decalin at 135° C. is 1.3 (dl/g) ≤[η] ≤10 (dl/g).

12. A production method of an olefin (co)polymer containing structural units derived from 1-butene, comprising
a step of (co)polymerizing at least a 1-butene, optionally an α-olefin having 2 or more carbon atoms (excluding 1-butene) and optionally (an)other monomer(s) under the conditions of a polymerization temperature of not less than 55° C. and not more than 200° C. and a polymerization pressure of not less than 0.1 MPaG and not more than 5.0 MPaG in the presence of an olefin polymerization catalyst containing
(A) a crosslinked metallocene compound represented by General Formula [I] below, and
(B) at least one compound selected from
(b-1) an organoaluminum oxy-compound,
(b-2) a compound that forms an ion pair by reacting with the crosslinked metallocene compound (A), and
(b-3) an organoaluminum compound;
wherein the olefin (co)polymer includes at least structural units derived from 1-butene, includes the content of structural units derived from 1-butene in the range of more than 50 mol % and 100 mol % or less, and includes the total content of structural units derived from an α-olefin having 2 or more carbon atoms (excluding 1-butene) in the range of 0 mol % or more and less than 50 mol % (provided that the total of the content of structural units derived from 1-butene and the content of structural units derived from the α-olefin having 2 or more carbon atoms (excluding 1-butene) is 100 mol %),

(In the formula, R 1 is an adamantyl group derivative; R 2 and R 7 are selected from a hydrocarbon group, a silicon-containing group, and a halogen-containing hydrocarbon group; R 3 and R 6 are hydrogen atoms; R 4 , R 5 , R 8 , R 9 , R 10 , R 11 , and R 12 are selected from a hydrogen atom, a hydrocarbon group, a silicon-containing group, a halogen atom, and a halogen-containing hydrocarbon group and may be the same or different from each other, and adjacent substituents among R 4 , R 5 , R 8 , R 9 , R 10 , R 11 , and R 12 may combine to form a ring; M is a Group 4 transition metal; Q is a halogen atom, a hydrocarbon group, an

Assignees

• Mitsui Chemicals Inc

Inventors

• Ebisawa Ikuko
• Yamashita Masahiro
• Yukita Takashi
• Mohri Junichi
• Tanaka Junpei
• Kai Noriko

Classifications

• C08F4/64003

  the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond · CPC title

• C08F4/65922

  containing at least two cyclopentadienyl rings, fused or not · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F10/08 Primary

  Butenes · CPC title

• C08F4/6428

  with an aluminoxane, i.e. a compound containing an Al-O-Al- group · CPC title