Polymers of 4-substituted hexadiene and processes for production thereof

Patent metadata

Field	Value
Publication number	US-12503529-B2
Application number	US-202217678822-A
Country	US
Kind code	B2
Filing date	Feb 23, 2022
Priority date	Feb 26, 2021
Publication date	Dec 23, 2025
Grant date	Dec 23, 2025

Abstract

This invention relates to polymers comprising: one or more that include 1) at least 11 wt % 4 substituted 1,4 hexadiene and less than 20 wt % 5-methyl-1,4-hexadiene, based upon the weight of the polymer, and 2) optionally, one or more olefins; and processes to produces such polymers using metallocene or post-metallocene catalyst compounds.

First claim

What is claimed is:

1 . A polymer comprising: 1) one or more dienes that include at least 11 wt % 4-substituted 1,4 hexadiene and less than 1 wt % 5-methyl-1,4-hexadiene based upon a weight of the polymer, and 2) one or more olefins comprising ethylene, ethylene and propylene, or ethylene, propylene and styrene, and the polymer has a glass transition temperature of −40° C. or less.

2 . The polymer of claim 1 , wherein the one or more dienes is represented by the formula:
H 2 C≡CH—CH 2 —C(R # )═CH—CH 3

wherein R # is a C 1 to C 20 hydrocarbyl group.

3 . The polymer of claim 2 , wherein R″ is one or more of phenyl, benzyl, naphthyl, styryl, xylyl, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or an isomer thereof.

4 . The polymer of claim 1 , wherein the one or more dienes is 4-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 4-n-propyl-1,4-hexadiene, 4-n-butyl-1,4-hexadiene, 4-phenyl-1,4-hexadiene, or 4-methylphenyl-1,4-hexadiene.

5 . The polymer of claim 1 , wherein the one or more olefins comprise ethylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, styrene, methylstyrene, substituted derivatives thereof, or isomers thereof.

6 . The polymer of claim 1 , wherein the polymer is a copolymer of at least one C 2 to C 40 alpha olefin, a vinyl aromatic, and one or more dienes represented by the formula:
H 2 C≡CH—CH 2 —C(R # )═CH—CH 3

wherein R # is a C 1 to C 20 hydrocarbyl group.

7 . A polymer comprising: 1) one or more dienes that include 11-30 wt % 4-substituted 1,4 hexadiene and less than 20 wt % 5-methyl-1,4-hexadiene based upon the weight of the polymer, and 2) one or more olefins, wherein propylene is not included in the polymer unless there are at least two olefins in the polymer and the polymer is a terpolymer of ethylene, propylene, and 4-substituted 1,4 hexadiene, the polymer has a Mw of 70,000 g/mol or more, the polymer has a Mooney (ML 1+4, 125° C.) value greater than 20 MU, the polymer has a glass transition temperature of −40° C. or less.

8 . A polymer comprising: 1) one or more dienes that include 0.1 to 10 wt % 4-substituted 1,4 hexadiene and less than 0.5 wt % 5-methyl-1,4-hexadiene based upon a weight of the polymer, and 2) one or more olefins that at least includes propylene.

9 . The polymer of claim 8 , wherein the polymer is a copolymer of the propylene and the 4-substituted 1,4 hexadiene, the copolymer has an isotactic propylene backbone, the copolymer has a melting point ranging from 140° C. to 160° C. as measured according to DSC-2, and the isotactic propylene backbone has a meso pentad ranging from 0.650 to 0.985 as measured by 13 C NMR spectroscopy.

10 . A process to produce polymer comprising: contacting 1) diene comprising 4-substituted 1,4 hexadiene and 1 wt % or less of 5-methyl-1,4-hexadiene, and 2) one or more olefins, with 3) a catalyst system comprising single site coordination polymerization catalyst and activator and the contacting includes using propylene as the one or more olefins, and the contacting is performed in solution, gas phase, slurry, or bulk-slurry, and wherein the polymer is a copolymer of the propylene and the 4-substituted 1,4 hexadiene, the copolymer has an isotactic propylene backbone, the copolymer has a melting point ranging from 80° C. to 155° C., the isotactic propylene backbone has a meso pentad ranging from 0.650 to 0.985 as measured by 13 C NMR spectroscopy, and the polymer includes 0.1-10 wt % of the 4-substituted 1,4 hexadiene based upon weight of the polymer.

11 . The process of claim 10 , wherein the polymer is a terpolymer of ethylene, propylene and 4-substituted 1,4 hexadiene, the terpolymer is amorphous, the polymer has a Tg of less than −40° C., Mooney (M+L 125° C.) greater than 20, and the polymer contains 4-substituted 1,4 hexadiene content between 11-30% by weight.

12 . The process of claim 10 , wherein the diene is represented by the formula:
H 2 C═CH—CH 2 —C(R # )═CH—CH 3

wherein R # is a C to C 20 hydrocarbyl group.

13 . The process of claim 10 , wherein the diene is one or more of 4-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 4-n-propyl-1,4-hexadiene, 4-n-butyl-1,4-hexadiene, 4-phenyl-1,4-hexadiene, and 4-methyl-phenyl-1,4-hexadiene; and the one or more olefins are selected from the group consisting of: ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, styrene, methyl-styrene, and isomers thereof.

14 . The process of claim 10 , wherein the single site coordination polymerization catalyst includes a metallocene complex, pyridyldiamido complex, quinolinyldiamido complex, phenoxyimine complex, bisphenolate complex, cyclopentadienyl-amidinate complex, iron pyridyl bis(imine) complex, FI catalyst, or PI catalyst.

15 . The process of claim 10 , wherein the single site coordination polymerization catalyst is one or more of:
dimethylsilyl (tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl; dimethylsilyl (tetramethylcyclopentadienyl)(t-butylamido)titanium dimethyl; μ-(CH 3 ) 2 Si(cyclopentadienyl)(1-adamantylamido)titanium dimethyl; μ-(CH 3 ) 2 Si(3-tertbutylcyclopentadienyl)(1-adamantylamido)titanium dimethyl; μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl; μ-(CH 3 ) 2 C(tetramethylcyclopentadienyl)(1-adamantylamido)titanium dimethyl; μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-tertbutylamido)titanium dimethyl; μ-(CH 3 ) 2 Si(fluorenyl)(1-tertbutylamido)titanium dimethyl; μ-(CH 3 ) 2 Si(tetramethylcyclopentadienyl)(1-cyclododecylamido)titanium dimethyl; μ-(C 6 H 5 ) 2 C(tetramethylcyclopentadienyl)(1-cyclododecylamido)titanium dimethyl; μ-(CH 3 ) 2 Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tertbutylamido)titanium dimethyl; bis(1-methyl, 3-n-butyl cyclopentadienyl)hafnium dimethyl; bis(1-methyl, 3-n-butyl cyclopentadienyl)zirconium dimethyl; dimethylsilyl bis(indenyl)zirconium dimethyl; dimethylsilyl bis(indenyl)hafnium dimethyl; bis(indenyl)zirconium dimethyl; bis(indenyl)hafnium dimethyl; dimethylsilyl bis(tetrahydroindenyl)zirconium dimethyl; bis(n-propylcyclopentadienyl)zirconium dimethyl; dimethylsilylbis(tetrahydroindenyl)hafnium dimethyl; dimethylsilyl bis(2-methylindenyl)zirconium dimethyl; dimethylsilyl bis(2-methylfluorenyl)zirconium dimethyl; dimethylsilyl bis(2-methylindenyl)hafnium dimethyl; dimethylsilyl bis(2-methylfluorenyl)hafnium dimethyl; dimethylsilyl bis(2-methyl-4-phenylindenyl)zirconium dimethyl; dimethylsilyl bis(2-ethyl-5-phenylindenyl)zirconium dimethyl; dimethylsilyl bis(2-methyl-4-biphenylindenyl)zirconium dimethyl; dimethylsilylene bis(2-methyl-4-carbazolylindenyl)zirconium dimethyl; rac-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benz[f]indenyl)hafnium dimethyl; diphenylmethylene (cyclopentadienyl)(fluorenyl)hafnium dimethyl; bis(methylcyclopentadienyl)zirconium dimethyl; rac-dimethylsiylbis(2-methyl,3-propyl indenyl)hafnium dimethyl; rac/meso-diphenylsilyl-bis(n-propylcyclopentadienyl)hafnium dimethyl; 1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tertiary-butyl-1-fluorenyl)hafnium Cl 2 (bridge is considered the 1 position); 1,1′-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tertiary-butyl-1-fluorenyl)hafnium Me 2 (bridge is considered the 1 position)

Assignees

• Exxonmobil Chemical Patents Inc

Inventors

• Carpenter Alex E
• Lin Tzu-Pin
• Rohde Brian J
• Mattler Sarah J
• Lambic Nikola S
• Chiang Hsu
• Jiang Peijun
• Cai Irene C
• Culcu Gursu
• Younker Jarod M

Classifications

• C08F2500/36

  Terpolymer with exactly three olefinic monomers · CPC title

• C08F210/18

  with non-conjugated dienes, e.g. EPT rubbers · CPC title

• C08F236/20

  unconjugated · CPC title

• C08L23/14

  Copolymers of propene (C08L23/16 takes precedence) · CPC title

• C08F4/76

  selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum · CPC title