Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof

Patent metadata

Field	Value
Publication number	US-11530281-B2
Application number	US-201916279677-A
Country	US
Kind code	B2
Filing date	Feb 19, 2019
Priority date	Aug 19, 2016
Publication date	Dec 20, 2022
Grant date	Dec 20, 2022

Abstract

An ultra-high molecular weight, ultra-fine particle size polyethylene has a viscosity average molecular weight (Mv) greater than 1×106. The polyethylene is spherical or are sphere-like particles having a mean particle size of 10-100 μm, having a standard deviation of 2-15 μm and a bulk density of 0.1-0.3 g/mL. Using the polyethylene as a basic polyethylene, a grafted polyethylene can be obtained by means of a solid-phase grafting method; and a glass fiber-reinforced polyethylene composition comprising the polyethylene and glass fibers, and a sheet or pipe prepared therefrom; a solubilized ultra-high molecular weight, ultra-fine particle size polyethylene; and a fiber and a film prepared from the solubilized ultra-high molecular weight, ultra-fine particle size polyethylene may also be obtained. The method has simple steps, is easy to control, has a relatively low cost and a high repeatability, and can realize industrialisation.

First claim

The invention claimed is:

1. A method for preparing an ultra-high molecular weight, ultra-fine particle size polyethylene powder, comprising:
carrying out ethylene polymerization in presence of a catalyst at a polymerization temperature of −20° C. to 100° C., wherein, in the ethylene, a content of carbon monoxide is not higher than 5 ppm, a content of carbon dioxide is not higher than 15 ppm, and a content of conjugated diene is not higher than 10 ppm,
wherein the catalyst is prepared by a method comprising steps of:
(a) mixing magnesium halide, an alcohol compound, a titanate compound, a first portion of an internal electron donor compound, and a solvent to prepare a mixture I;
(b) adding the mixture I into a reactor, preheating to −30° C.-30° C., and adding a first portion of a titanium compound to form a reaction mixture; or adding the first portion of the titanium compound into the reactor, preheating to −30° C.-30° C., and adding the mixture I to form the reaction mixture;
(c) raising the temperature of the reaction mixture and maintaining the temperature at 90° C.-130° C. for 0.5-3 hours, adding a second portion of the internal electron donor compound to the reaction mixture, and continuously reacting;
(d) filtering the reaction mixture to remove liquid, adding a second portion of the titanium compound, and continuously reacting; and
(e) obtaining the catalyst after post-treatment.

2. The method according to claim 1 , wherein the polyethylene powder has a viscosity average molecular weight (Mv) of greater than 1×10 6 , a mean particle size of 10-100 μm, a standard deviation of 2 μm-15 μm, and a bulk density of 0.1 g/mL-0.3 g/mL, and a particle size distribution that is substantially a normal distribution.

3. A method for preparing an ultra-high molecular weight, ultra-fine particle size grafted polyethylene, comprising:
preparing a polyethylene powder according to the method of claim 1 ;
mixing the polyethylene powder, a grafting monomer, an initiator and an interface agent to form a mixture;
heating the mixture to carry out a solid-phase grafting reaction to form the grafted polyethylene.

4. The method according to claim 3 , wherein the solid-phase grafting reaction is carried out at a temperature of 60-120° C. for 0.5-5 hours, wherein
the grafting monomer is a siloxane-based compound or a vinyl-based unsaturated compound, and said initiator is an azo initiator or a peroxide initiator.

5. The method according to claim 3 , wherein an effective grafting rate of the grafting monomer is ≥0.5%, the polyethylene powder is spherical or substantially spherical particles having a mean particle size of 10 μm-100 μm, a standard deviation of 2 μm-15 μm and, a bulk density of 0.1 g/mL-0.3 g/mL, and a viscosity average molecular weight (Mv) of greater than 1×10 6 .

6. The method according to claim 5 , wherein,
the effective grafting rate is 1.0-3.0%, the mean particle size of said polyethylene powder is 20 μm-80 μm, the standard deviation of said polyethylene powder is 5 μm-15 μm,
a water contact angle of said grafted polyethylene is 80°-88°,
the bulk density of said polyethylene is 0.15 g/mL-0.25 g/mL,
the viscosity average molecular weight (Mv) of said polyethylene is greater than or equal to 1.5×10 6 , and
said polyethylene is an ethylene homopolymer having a molecular weight distribution (Mw/Mn) of 2-15.

7. A method for preparing a glass-fiber enforced polyethylene sheet, comprising:
preparing a polyethylene powder according to the method of claim 1 ;
mixing the polyethylene powder with and glass fibers; and
extruding the mixture through a sheet die.

8. A method for preparing a glass-fiber enforced polyethylene pipe, comprising:
preparing a polyethylene powder according to the method of claim 1 ;
mixing the polyethylene powder and glass fibers; and
extruding the mixture through a pipe mold.

9. The method according to claim 2 , wherein the polymerization temperature is 30° C.-80° C.

10. The method according to claim 2 , wherein the polymerization temperature is 50° C.-80° C.

11. An ultra-high molecular weight, ultra-fine particle size polyethylene powder prepared by the method according to claim 1 , having a viscosity average molecular weight (Mv) of greater than 1×10 6 , a standard deviation of 2 μm-15 μm, and a bulk density of 0.1 g/mL-0.3 g/mL, having a particle size distribution that is substantially a normal distribution, and a mean particle size of 20 μm-80 μm.

12. The ultra-high molecular weight, ultra-fine particle size polyethylene powder according to claim 11 , wherein the mean particle size of said polyethylene powder is 50 μm-80 μm.

13. The method according to claim 4 , wherein an amount of said grafting monomer is 0.2-15 wt % by weight of the polyethylene powder and an amount of said initiator is 0.1-10 wt % by weight of the polyethylene powder,
wherein the vinyl-based unsaturated compound is selected from a styrene-based compound, a vinyl-based unsaturated organic acid, a vinyl-based unsaturated organic ester, a vinyl-based unsaturated organic acid anhydride, acrylic acid (AA), methacrylic acid (MAA), methyl acrylate (MA), methyl methacrylate (MMA), ethyl acrylate (EA), ethyl methacrylate (MEA), butyl acrylate (BA), butyl methacrylate (BMA), maleic anhydride (MAH), maleic acid, styrene (St), and pentaerythritol triacrylate (PETA), and mixtures thereof,
the siloxane-based compound is selected from vinyltrimethylsilane, vinyltriethylsilane, divinyldimethylsilane, (triethylsilyl)acetylene, allyltrimethylsilane, and mixtures thereof, and said initiator is an azo initiator or a peroxide initiator.

14. An ultra-high molecular weight, ultra-fine particle size grafted polyethylene, comprising the polyethylene powder prepared according to the method of claim 1 , and a grafting monomer grafted on the polyethylene powder, wherein the grafting monomer is a siloxane-based compound or a vinyl-based unsaturated compound, and an amount of said grafting monomer is 0.2-15 wt % by weight of the polyethylene powder.

15. An ultra-high molecular weight, ultra-fine particle size grafted polyethylene of claim 14 , wherein the vinyl-based unsaturated compound is selected from a styrene-based compound, a vinyl-based unsaturated organic acid, a vinyl-based unsaturated organic ester, a vinyl-based unsaturated organic acid anhydride, acrylic acid (AA), methacrylic acid (MAA), methyl acrylate (MA), methyl methacrylate (MMA), ethyl acrylate (EA), ethyl methacrylate (MEA), butyl acrylate (BA), butyl methacrylate (BMA), maleic anhydride (MAH), maleic acid, styrene (St), and pentaerythritol triacrylate (PETA), and mixtures thereof, the siloxane-based compound is selected from vinyltrimethylsilane, vinyltriethylsilane, divinyldimethylsilane, (triethylsilyl)acetylene, allyltrimethylsilane, and mixtures thereof, and said initiator is an azo initiator or a peroxide initiator.

Assignees

• Inst Chemistry Cas

Inventors

• Li Huayi
• Li Qian
• Sun Tongbing
• Zhu Caizhen
• Liu Ruigang
• Zhao Ning
• Xu Jian

Classifications

• C08K2201/004

  Additives being defined by their length · CPC title

• C08K3/40

  Glass · CPC title

• C08F4/658

  with metals or metal-containing compounds, not provided for in a single group of groups C08F4/653 - C08F4/657 · CPC title

• B29C48/07

  Flat, e.g. panels · CPC title

• C08J2323/06

  Polyethene · CPC title