CN-121991271-A - Ethylene propylene diene monomer rubber and preparation method and application thereof

Abstract

The invention relates to the field of polymers, and discloses ethylene propylene diene monomer, a preparation method and application thereof, wherein the content of a third monomer of the ethylene propylene diene monomer is more than or equal to 7.9wt%, and the third monomer is non-conjugated diene. The ethylene propylene diene monomer provided by the invention has higher content of the third monomer which can reach 12.9wt% at the highest.

Inventors

• YANG BO
• DONG ZHAOYONG
• LU SHULAI
• SUN JUHUA
• LIU ZHENGUO
• ZHANG GUANYING
• DONG SHENGKUI

Assignees

• 中国石油天然气股份有限公司

Dates

Publication Date

20260508

Application Date

20241108

Claims (19)

1. 1. The ethylene propylene diene monomer is characterized in that the content of a third monomer of the ethylene propylene diene monomer is more than or equal to 7.9wt%, and the third monomer is non-conjugated diene.
2. 2. Ethylene propylene diene monomer according to claim 1, characterized in that it comprises, The content of the third monomer is 10-13wt%, and/or Weight average molecular mass of 3.9X10 5 ～5×10 5 , and/or Molecular mass distribution of 2.9-4.2, and/or The third monomer is one or more of 1, 4-hexadiene, dicyclopentadiene, ethylidene norbornadiene and vinyl norbornene.
3. 3. Ethylene propylene diene monomer according to claim 2, characterized in that it: The content of the third monomer is 12-13wt%, and/or Weight average molecular mass of 4.1X10 5 ～4.9×10 5 , and/or Molecular mass distribution of 3.0-4.0, and/or The third monomer is ethylidene norbornylene.
4. 4. The preparation method of the ethylene propylene diene monomer rubber is characterized by comprising the following steps: And (2) in the presence of a main catalyst and a cocatalyst, carrying out polymerization reaction on a third monomer and reaction gas in a solvent, wherein the main catalyst is a V-system catalyst VOCl n L 3-n , L is saturated alcohol, 0< n <3, and the third monomer is non-conjugated diene.
5. 5. The method according to claim 4, wherein, The L is saturated alcohol with the carbon number of 5-10, n is more than or equal to 1.1 and less than or equal to 1.5, and/or The concentration of the main catalyst in the solvent is 0.1-0.5 mmol/L.
6. 6. The method according to claim 5, wherein, The L is octanol, and/or The concentration of the main catalyst in the solvent is 0.2-0.4 mmol/L.
7. 7. The method according to claim 4, wherein, The promoter is Al compound, and/or The molar ratio of the cocatalyst to the main catalyst is 5-50:1.
8. 8. The method according to claim 7, wherein, The promoter is one or more of sesquiethylaluminum chloride, ethylaluminum dichloride, diethylaluminum chloride and triethylaluminum, and/or The molar ratio of the cocatalyst to the main catalyst is 5-20:1.
9. 9. The method according to claim 4, wherein, The solvent is C5-C10 saturated straight-chain alkane and/or C5-C10 saturated cycloalkane.
10. 10. The method according to claim 4, wherein, The third monomer is one or more of 1, 4-hexadiene, dicyclopentadiene, ethylidene norbornadiene and vinyl norbornene, and/or The concentration of the third monomer in the solvent is 20-50 mmol/L.
11. 11. The method according to claim 10, wherein, The third monomer is ethylidene norbornadiene and/or The concentration of the third monomer in the solvent is 33-40 mmol/L.
12. 12. The method according to claim 4, wherein, The reaction gas comprises ethylene, propylene and optionally hydrogen; the mol ratio of propylene to ethylene in the reaction gas is 1-3.5:1, and/or The volume fraction of hydrogen in the reaction gas is 0-10%.
13. 13. The method according to claim 12, wherein, The mol ratio of propylene to ethylene in the reaction gas is 1.5-3:1, and/or The volume fraction of hydrogen in the reaction gas is 1-7%.
14. 14. The method of claim 4, wherein the polymerization conditions include: At a temperature of 30-60 ℃, and/or The pressure is 0.3-0.6 MPa, and/or The time is 10-90 min.
15. 15. The method of claim 14, wherein the polymerization conditions comprise: At a temperature of 40-50 ℃ and/or The pressure is 0.4-0.5 MPa, and/or The time is 30-60 min.
16. 16. The method of manufacturing according to claim 4, further comprising: After the polymerization reaction is finished, adding a terminator to inactivate a polymerization system, removing a solvent and drying.
17. 17. The method of claim 16, wherein the process comprises, The terminator is one or more of ethanol, methanol, and propanol, and/or The consumption of the terminator is 1-10wt% of the mass of the glue solution obtained after polymerization.
18. 18. Ethylene propylene diene monomer prepared by the preparation method of any one of claims 4 to 17.
19. 19. Use of the ethylene propylene diene monomer rubber according to any one of claims 1-3, 18 in building materials, wire and cable, automotive industry.

Description

Ethylene propylene diene monomer rubber and preparation method and application thereof Technical Field The invention relates to the field of polymers, in particular to ethylene propylene diene monomer rubber and a preparation method and application thereof. Background Ethylene propylene diene monomer is a copolymer of ethylene, propylene and non-conjugated diene, and is one of ethylene propylene rubbers, and because the main chain of the ethylene propylene diene monomer consists of chemically stable saturated hydrocarbon and only contains unsaturated double bonds in side chains, the ethylene propylene diene monomer has excellent ageing resistance such as ozone resistance, heat resistance and weather resistance. The ethylene propylene diene monomer is widely used and is mainly applied to the fields of house construction, wires and cables, automobile industry and the like. Ethylene, propylene and non-conjugated diene are generally used as raw materials, hexane is used as a solvent, and the ethylene propylene diene monomer is a copolymer synthesized by copolymerization under the action of a vanadium-based or metallocene-based catalyst and an aluminum alkyl cocatalyst. When the content of the third monomer in the ethylene propylene rubber is low, the ethylene propylene rubber is limited in application in the field of high-end sealing strips and can only be used as auxiliary rubber. At present, the situation that the high-end ethylene propylene rubber is seriously depended on import has seriously influenced the industrial safety of China, and the development of key technology for preparing and applying the high-performance ethylene propylene rubber by cooperating with the upstream and downstream joint is urgently needed, so that the original technical policy and source place of the ethylene propylene rubber are created, the self-standing and self-strengthening of high-level technological innovation is realized, the technical bottleneck problem is solved, the energy and chemical innovation high place of China is built, and the international level and position of the ethylene propylene rubber industry of China are improved in all aspects. Disclosure of Invention The invention aims to solve the problem of low content of a third monomer of ethylene propylene diene monomer prepared by the prior art, and provides ethylene propylene diene monomer, and a preparation method and application thereof. The ethylene propylene diene monomer provided by the invention has higher third monomer content, and the third monomer content in the ethylene propylene diene monomer is more than or equal to 7.9wt% and can reach 12.9wt% at most. In order to achieve the above purpose, in one aspect, the invention provides an ethylene propylene diene monomer, wherein the content of a third monomer of the ethylene propylene diene monomer is more than or equal to 7.9wt%, and the third monomer is non-conjugated diene. The second aspect of the invention provides a preparation method of ethylene propylene diene monomer, which comprises the steps of carrying out polymerization reaction on a third monomer and reaction gas in a solvent in the presence of a main catalyst and a cocatalyst, wherein the main catalyst is a V-series catalyst VOCl nL3-n, L is saturated alcohol, 0< n <3, and the third monomer is non-conjugated diene. The third aspect of the invention provides the ethylene propylene diene monomer prepared by the preparation method. The fourth aspect of the invention provides application of the ethylene propylene diene monomer rubber in building materials, wires and cables and automobile industry. The ethylene propylene diene monomer provided by the invention is ethylene propylene diene monomer with high third monomer content, wherein the third monomer content is more than or equal to 7.9wt% and can reach 12.9wt% at most. The invention discovers for the first time that the copolymerization capability of the third monomer can be improved in the polymerization reaction process by using the self-synthesized V-based main catalyst VOCl nL3-n, so that the prepared ethylene propylene diene monomer has higher grafting rate of the third monomer. Detailed Description The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. Ethylene propylene diene monomer is generally prepared from ethylene (first monomer), propylene (second monomer) and a non-conjugated diene (third monomer), the third monomer being referred to herein as a non-conjugated diene, as is known in the art. The invention provides ethylene propylene diene monomer, wherein th