Olefin coordination polymerization catalyst, and preparation method and application thereof

Patent metadata

Field	Value
Publication number	US-11014994-B2
Application number	US-201816161894-A
Country	US
Kind code	B2
Filing date	Oct 16, 2018
Priority date	May 4, 2016
Publication date	May 25, 2021
Grant date	May 25, 2021

Abstract

The present invention relates to an olefin coordination polymerization catalyst and a preparation method and application thereof. The olefin polymerization catalyst consists of a primary catalyst mainly prepared from a magnesium compound, a transition metal halide, a C2-C15 alcohol and an electron donor in a molar ratio of 1:1-40:0.01-10:0.001-10, and a co-catalyst which is an organoaluminum compound; and the molar ratio of the transition metal halide to the co-catalyst is 1:10-500. The catalyst of the present invention has a good particle morphology, and a spherical shape, and the catalyst particles do not stick to the vessel wall; the catalyst has high activity and excellent hydrogen regulation performance, and the melt index MFR of polyethylene may be adjusted within 0.01 g/10 min-550 g/10 min; and the catalyst is applicable in slurry polymerization process, loop reactor polymerization process, gas phase polymerization process or combined polymerization process.

First claim

What is claimed is:

1. An olefin coordination polymerization catalyst having a primary catalyst prepared from a magnesium compound, a transition metal halide, a C 2 -C 15 alcohol and an electron donor in a molar ratio of 1:1-40:0.01-10:0.001-10, and a co-catalyst which is an organoaluminum compound; and the molar ratio of the transition metal halide to the co-catalyst is 1:10-500;
wherein the electron donor is a four-arm organoheteroether compound having the following structure.

2. The olefin coordination polymerization catalyst according to claim 1 , wherein the magnesium compound is selected from at least one of the compounds of Formula MgR a X b ; in the formula, R is a C 1 -C 20 aliphatic hydrocarbon group, a C 1 -C 20 aliphatic alkoxy group, a C 3 -C 20 alicyclic group or a C 6 -C 20 aromatic hydrocarbon group; X is halogen; a=0, 1 or 2; b=0, 1 or 2, and a+b=2.

3. The olefin coordination polymerization catalyst according to claim 2 , wherein the magnesium compound is selected from at least one of magnesium dichloride, magnesium dibromide, magnesium diiodide, methoxy magnesium chloride, ethoxy magnesium chloride, propoxy magnesium chloride, butoxy magnesium chloride, phenoxy magnesium chloride, magnesium ethoxide, magnesium isopropoxide, magnesium butoxide, isopropoxy magnesium chloride, butyl magnesium chloride, magnesium diethoxide, magnesium dipropoxide and magnesium dibutoxide.

4. The olefin coordination polymerization catalyst according to claim 1 , wherein the transition metal halide is selected from at least one of the compounds of Formula MR 1 4-m X m ; in the formula, M is Ti, Zr, Hf, Fe, Co or Ni; X is Cl, Br or F; m is an integer of 0 to 4; R 1 is a C 1 -C 20 aliphatic hydrocarbon group, a C 1 -C 20 aliphatic alkoxy group, a C 1 -C 20 cyclopentadienyl group, a C 1 -C 20 aromatic hydrocarbon group, COR′ or COOR′, wherein R′ is a C 1 -C 10 aliphatic group or a C 1 -C 10 aromatic group.

5. The olefin coordination polymerization catalyst according to claim 4 , wherein the transition metal halide is selected from at least one of titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, titanium tetrabutoxide, titanium tetraethoxide, chlorotitanium triethoxide, dichlorotitanium diethoxide, trichlorotitanium ethoxide, n-butyl titanate, isopropyl titanate, methoxytitanium trichloride, dibutoxytitanium dichloride, tributoxytitanium chloride, titanium tetraphenoxide, chlorotitanium triphenoxide, dichlorotitanium diphenoxide and trichlorotitanium phenoxide.

6. The olefin coordination polymerization catalyst according to claim 1 , wherein the molar ratio of the transition metal halide to the magnesium compound is 8-40:1.

7. The olefin coordination polymerization catalyst according to claim 1 , wherein the C 2 -C 15 alcohol is selected from at least one of ethanol, propanol, butanol, pentanol, heptanol, isooctanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol and pentadecanol.

8. The olefin coordination polymerization catalyst according to claim 1 , wherein the organoaluminum compound is selected from at least one of triethyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, monochlorodiethyl aluminum and methyl aluminoxane.

9. A method for preparing the olefin coordination polymerization catalyst according to claim 1 , wherein the method for preparing the primary catalyst comprises:
a) dispersing the magnesium compound in an organic solvent, adding the C 2 -C 15 alcohol, and stirring at 90 to 150° C. for 1-5 hours;
b) cooling the mixture of a) to 30-80° C., adding the electron donor, and reacting for 1-5 hours; and
c) cooling the mixture of b) to −20-30° C., contacting the mixture of b) with the transition metal halide, reacting at −20-30° C. for 0.5-5 hours, then warming to 50-120° C., reacting for 0.5-5 hours, after the completion of the reaction, washing, filtering, and vacuum drying, to obtain the primary catalyst.

10. The method for preparing the olefin coordination polymerization catalyst according to claim 9 , wherein in a), the organic solvent is at least one of a C 5 -C 15 saturated hydrocarbon, a C 5 -C 10 alicyclic hydrocarbon, and a C 6 -C 15 aromatic hydrocarbon.

11. The method for preparing the olefin coordination polymerization catalyst according to claim 9 , wherein in c), the vacuum drying temperature is 40-90° C. and the vacuum drying time is 0.5-5 hours.

12. A method for ethylene polymerization, propylene polymerization, copolymerization of ethylene with α-olefin or copolymerization of propylene with α-olefin comprising using the olefin coordination polymerization catalyst according to claim 1 .

13. The method according to claim 12 , wherein α-olefin is a C 3 -C 20 olefin.

14. An olefin coordination polymerization catalyst having a primary catalyst is prepared from a magnesium compound, a transition metal halide, a C 2 -C 15 alcohol, an electron donor and a silicon-containing substance in a molar ratio of 1:1-40:0.01-10:0.001-10:0.00005-1, and a co-catalyst which is an organoaluminum compound; and the molar ratio of the transition metal halide to the co-catalyst is 1:10-500;
wherein the electron donor is a four-arm organoheteroether compound having the following structure

15. The method for preparing the olefin coordination polymerization catalyst according to claim 14 , wherein when the primary catalyst is prepared from the magnesium compound, the transition metal halide, the C 2 -C 15 alcohol, the electron donor and a silicon-containing substance, the method for preparing the primary catalyst comprises:
a) dispersing the magnesium compound in an organic solvent, adding the C 2 -C 15 alcohol, and stirring at 90 to 150° C. for 1-5 hours;
b) cooling the mixture of a) to 30-80° C., adding the electron donor and the silicon-containing substance, and reacting for 1-5 hours; and
c) cooling the mixture of b) to −20-30° C., contacting the mixture of b) with the transition metal halide, reacting at −20-30° C. for 0.5-5 hours, then warming to 50-120° C., reacting for 0.5-5 hours, after the completion of the reaction, washing, filtering, and vacuum drying, to obtain the primary catalyst.

16. An olefin coordination polymerization catalyst having a primary catalyst prepared from a magnesium compound, a transition metal halide, a C 2 -C 15 alcohol, an electron donor and a succinic acid ester in a molar ratio of 1:1-40:0.01-10:0.001-10:0.001-1, and a co-catalyst which is an organoaluminum compound; and the molar ratio of the transition metal halide to the co-catalyst is 1:10-500;
wherein the electron donor is a four-arm organoheteroether compound having the following structure

17. The method for preparing the olefin coordination polymerization catalyst according to claim 16 , wherein when the primary catalyst is prepared from the magnesium compound, the transition metal halide, the C 2 -C 15 alcohol, the electron donor and a succinic acid ester, the method for preparing the primary catalyst comprises:
a) dispersing the magnesium compound in an organic solvent, adding the C 2 -C 15 alcohol, and stirring at 90 to 150° C. for 1-5 hours;
b) cooling the mixture of a) to 30-80° C., adding the electron donor and the succinic acid ester, and reacting for 1-5 hours; and
c) cooling the mixture of b) to −20-

Assignees

• Petrochina Co Ltd

Inventors

• Zhang Mingge
• Li Dianjun
• Wang Shuo
• Li Hongming
• Yuan Yuan
• Yi Jianjun
• Sun Tianxu
• Mao Jing
• Men Lin
• Huang Qigu
• Zhang Runcong
• Wang Jing
• Nie Yanpei

Classifications

• C08F10/00 Primary

  Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond · CPC title

• C08F210/16

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

• C08F4/6497

  containing phosphorus · CPC title

• C08F4/651

  Pretreating with non-metals or metal-free compounds · CPC title

• C08F4/6495

  containing nitrogen · CPC title