Ethylene propylene diene monomer and preparation method and application thereof

Abstract

The invention relates to the field of polymers, and discloses an ethylene propylene diene monomer and a preparation method and application thereof, the content of a third monomer of the ethylene propylene diene monomer is greater than or equal to 7.9 wt%, and the third monomer is non-conjugated diene. The ethylene propylene diene monomer provided by the invention is relatively high in content of a third monomer, and the content of the third monomer can be up to 12.9 wt%.

Description

Technical Field

[0001] The present invention relates to the field of polymers, and particularly to an ethylene-propylene-diene monomer rubber and its preparation method and application. Background Art

[0002] Ethylene-propylene-diene monomer rubber is a copolymer of ethylene, propylene and non-conjugated diene, and is a kind of ethylene-propylene rubber. Because its main chain is composed of chemically stable saturated hydrocarbons and only contains unsaturated double bonds in the side chain, its aging resistance performance such as ozone resistance, heat resistance and weather resistance is excellent. Ethylene-propylene-diene monomer rubber has a wide range of uses and is mainly applied in fields such as building construction, wire and cable, and automotive industry.

[0003] The preparation of ethylene-propylene-diene monomer rubber usually uses ethylene, propylene and non-conjugated diene as raw materials and hexane as a solvent, and is a copolymer synthesized by copolymerization under the action of a vanadium-based or metallocene-based catalyst and an alkylaluminum cocatalyst. When the content of the third monomer in ethylene-propylene rubber is low, the application of ethylene-propylene rubber in the high-end sealing strip field is limited and can only be used as an auxiliary rubber. At present, the situation that high-end ethylene-propylene rubber seriously depends on imports has seriously affected the industrial safety of our country. It is urgent to jointly tackle key problems with upstream and downstream industries, carry out the development of key technologies for the preparation and application of high-performance ethylene-propylene rubber, build an original technology source for ethylene-propylene rubber, achieve high-level scientific and technological innovation and self-reliance, eliminate technical bottleneck problems, build an innovation highland for energy and chemical industry in our country, and comprehensively improve the international level and status of our country's ethylene-propylene rubber industry. Summary of the Invention

[0004] The purpose of the present invention is to overcome the problem of low content of the third monomer in the ethylene-propylene-diene monomer rubber prepared by the prior art, and provide an ethylene-propylene-diene monomer rubber and its preparation method and application. The ethylene-propylene-diene monomer rubber provided by the present invention has a relatively high content of the third monomer, and the content of the third monomer in the ethylene-propylene-diene monomer rubber is ≥ 7.9 wt%, and can reach up to 12.9 wt% at most.

[0005] In order to achieve the above purpose, on the one hand, the present invention provides an ethylene-propylene-diene monomer rubber, wherein the content of the third monomer in the ethylene-propylene-diene monomer rubber is ≥ 7.9 wt%, and the third monomer is a non-conjugated diene.

[0006] On the second hand, the present invention provides a preparation method of the ethylene-propylene-diene monomer rubber described in the present invention. The method includes: carrying out a polymerization reaction of a third monomer and a reaction gas in a solvent in the presence of a main catalyst and a cocatalyst, wherein the main catalyst is a V-based catalyst VOCl n L 3-n , L is a saturated alcohol, 0 < n < 3, and the third monomer is a non-conjugated diene.

[0007] On the third hand, the present invention provides an ethylene-propylene-diene monomer rubber prepared by the preparation method described in the present invention.

[0008] The fourth aspect of this invention provides the application of the EPDM rubber described herein in building materials, wire and cable, and the automotive industry.

[0009] The EPDM rubber provided by this invention is an EPDM rubber with a high content of a third monomer, wherein the content of the third monomer is ≥7.9wt%, and can reach a maximum of 12.9wt%. This invention is the first to discover that by using a self-synthesized V-based main catalyst VOCl... n L 3-n The polymerization process can improve the copolymerization ability of the third monomer, resulting in a higher grafting rate of the third monomer in the prepared EPDM rubber. Detailed Implementation

[0010] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0011] As is known in the art, ethylene propylene diene monomer (EPDM) rubber is usually prepared from ethylene (first monomer), propylene (second monomer), and non-conjugated diene (third monomer). In this invention, the third monomer refers to the non-conjugated diene.

[0012] The present invention provides a EPDM rubber, wherein the content of the third monomer in the EPDM rubber is ≥7.9wt%, and the third monomer is a non-conjugated diene.

[0013] According to a preferred embodiment of the present invention, the content of the third monomer of the EPDM rubber is 10-13 wt%, preferably 12-13 wt%.

[0014] According to a preferred embodiment of the present invention, the weight-average molecular weight of EPDM rubber is 3.9 × 10⁻⁶. 5 ~5×10 5 Preferably, the weight-average molecular weight is 4.1 × 10⁻⁶. 5 ~4.9×10 5 .

[0015] According to a preferred embodiment of the present invention, the molecular weight distribution of the EPDM rubber is 2.9 to 4.2, preferably 3.0 to 4.0.

[0016] In the ethylene-propylene-diene monomer (EPDM) rubber of the present invention, there are no special requirements for the type of the third monomer. The following is a demonstration, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the third monomer is one or more of 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, and vinyl norbornene, and preferably ethylidene norbornene.

[0017] The EPDM rubber having the foregoing characteristics can achieve the purpose of the present invention. There are no special requirements for its preparation method. The following is a demonstration, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the preparation method of the EPDM rubber includes: carrying out a polymerization reaction of the third monomer and a reaction gas in a solvent in the presence of a main catalyst and a co-catalyst. The main catalyst is a V-based catalyst VOCl n L 3-n , where L is a saturated alcohol, 0 < n < 3, and the third monomer is a non-conjugated diene.

[0018] It should be noted that the preparation method of the main catalyst in the present invention can refer to Patent CN105732699B.

[0019] According to a preferred embodiment of the present invention, in the V-based catalyst VOCl n L 3-n of the main catalyst, the L is a saturated alcohol having 5 to 10 carbon atoms, and 1.1 ≤ n ≤ 1.5. Preferably, L is octanol.

[0020] In the present invention, in order to improve the performance of the EPDM rubber, the polymerization reaction is carried out under an anhydrous and oxygen-free condition. There are no special requirements for the anhydrous and oxygen-free environment. According to a preferred embodiment of the present invention, the polymerization reaction is carried out under an inert atmosphere. For example, the inert atmosphere can be nitrogen, and the polymerization kettle can be replaced with nitrogen 3 to 5 times by a method of vacuum pumping - gas raw material replacement to maintain an anhydrous and oxygen-free environment.

[0021] In the present invention, the concentration range of the main catalyst in the solvent is relatively wide. The following is a demonstration, but it does not limit the scope of the present invention. According to a preferred embodiment of the present invention, the concentration of the main catalyst in the solvent is 0.1 to 0.5 mmol / L, and preferably 0.2 to 0.4 mmol / L.

[0022] By adopting the foregoing preferred scheme, since the main catalyst has a strong copolymerization ability with the third monomer, it can improve the copolymerization ability of the third monomer during the polymerization reaction, so that the EPDM rubber has a high grafting rate of the third monomer.

[0023] In this invention, there are no special requirements for the type of co-catalyst. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the co-catalyst is an Al compound, preferably one or more of sesquiethylaluminum chloride, ethylaluminum dichloride, diethylaluminum monochloride, and triethylaluminum, and more preferably sesquiethylaluminum chloride.

[0024] In this invention, the molar ratio of the co-catalyst to the main catalyst can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the molar ratio of the co-catalyst to the main catalyst is 5 to 50:1, preferably 5 to 20:1.

[0025] In this invention, there are no special requirements for the type of solvent. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the solvent is a C5-C10 saturated straight-chain alkane and / or a C5-C10 saturated cycloalkanes, preferably hexane.

[0026] In this invention, there are no special requirements for the type of the third monomer. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the third monomer is one or more of 1,4-hexadiene, dicyclopentadiene, ethylene norbornene, and vinyl norbornene, preferably ethylene norbornene.

[0027] In this invention, the concentration of the third monomer in the solvent can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the concentration of the third monomer in the solvent is 20 to 50 mmol / L, preferably 33 to 40 mmol / L.

[0028] In this invention, the reaction gas includes ethylene, propylene, and optionally hydrogen. The molar ratio of propylene to ethylene in the reaction gas can be selected within a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the molar ratio of propylene to ethylene in the reaction gas is 1 to 3.5:1, preferably 1.5 to 3:1.

[0029] In this invention, the volume fraction of hydrogen in the reaction gas can be selected from a wide range. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the volume fraction of hydrogen in the reaction gas is 0 to 10%, preferably 1 to 7%.

[0030] In the polymerization reaction of this invention, there are no special requirements for the reaction temperature. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the reaction temperature is 30-60°C, preferably 40-50°C.

[0031] In the polymerization reaction of this invention, there are no special requirements for the reaction pressure. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the reaction pressure is 0.3 to 0.6 MPa, preferably 0.4 to 0.5 MPa.

[0032] In the polymerization reaction of this invention, there are no special requirements for the reaction time. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the reaction time is 10 to 90 minutes, preferably 30 to 60 minutes.

[0033] According to a preferred embodiment of the present invention, the preparation method of the EPDM rubber further includes: after the polymerization reaction is completed, adding a terminator to deactivate the polymerization system, and then removing the solvent and drying.

[0034] In this invention, there are no special requirements for the type of terminating agent. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the terminating agent is one or more of ethanol, methanol, and propanol.

[0035] In this invention, there are no special requirements for the amount of the terminator. The following is an illustrative description, but it does not limit the scope of the invention. According to a preferred embodiment of the invention, the amount of the terminator is 1 to 10 wt% of the mass of the polymerized adhesive, preferably 3 to 6 wt%.

[0036] In this invention, there are no special requirements for the solvent removal method. Commonly used solvent removal methods are applicable to this invention and can be selected according to actual needs. For example, solvent removal can be achieved by evaporation.

[0037] In this invention, there are no special requirements for the drying process. The drying method and drying instrument can be selected according to actual needs, which will not be elaborated here.

[0038] In this invention, there are no special requirements for the apparatus used in the polymerization reaction. Any apparatus that can achieve the purpose of this invention can be used in this invention, and can be selected according to actual needs. For example, the polymerization reaction can be carried out in a polymerization reactor.

[0039] This invention provides EPDM rubber prepared by the preparation method described herein.

[0040] The EPDM rubber provided by this invention is an EPDM rubber with a high third monomer content, wherein the third monomer content is ≥7.9wt%, and can reach up to 12.9wt%. This invention improves the copolymerization ability of the third monomer during the polymerization reaction by using a self-synthesized V-based main catalyst, so that the prepared EPDM rubber has a high third monomer grafting rate.

[0041] This invention provides the application of the EPDM rubber described herein in building materials, wire and cable, and the automotive industry.

[0042] In this invention, the weight-average molecular weight and molecular weight distribution of EPDM rubber were determined using high-temperature gel permeation chromatography (GPC).

[0043] Polymerization activity calculation formula: Polymerization activity = Amount of polymer obtained (kg) / Amount of catalyst added (mol).

[0044] Ethylene content calculation formula: Ethylene content is tested using infrared spectroscopy, based on the ratio of the absorbance of the sample film (at approximately 1155 cm⁻¹). -1 Absorbance at approximately 721 cm⁻¹ due to transverse deformation vibration of the methyl plane of propylene -1 The absorbance of the transverse deformation vibration of the ethylene methylene plane at the reference curve is used to determine the corresponding ethylene content.

[0045] The formula for calculating the content of the third monomer, such as ethylene norbornene, is as follows: The ethylene norbornene content is tested using infrared spectroscopy, based on the ratio of the absorbance of the sample film (at approximately 1685 cm⁻¹). -1 Absorbance at approximately 4330 cm⁻¹ due to outward bending vibrations of the outer double bond of the ENB ring -1 The absorbance of the combined frequency of the methylene bending vibration at a given location was used to determine the corresponding ethylene norbornene content from the baseline curve.

[0046] Example 1

[0047] The polymerization system is purged with nitrogen 3-5 times using a vacuum-gas feedstock replacement method to maintain an anhydrous and oxygen-free environment. Then, the main catalyst, co-catalyst, solvent, and ethylene norbornene are added to the polymerization reactor. Once the required polymerization pressure is reached, the polymerization reaction is initiated. The main catalyst is VOCl. n L 3-n The polymerization reaction mixture consisted of a catalyst, n = 1.2, L = octanol, and 0.20 mmol / L hexane. The molar ratio of the co-catalyst sesquiethylaluminate chloride to the main catalyst was 7:1. The amount of ethylene norbornene added was 38 mmol / L hexane, and the total hexane volume was 1 L. The molar ratio of propylene to ethylene in the gaseous feedstock was 2:1, and the volume fraction of hydrogen was 3%. The polymerization time was controlled by the hexane feed rate to 45 min. During the polymerization reaction, the temperature was kept stable at 45℃, and the polymerization pressure was kept stable at 0.5 MPa. After the polymerization reaction was completed, ethanol was added as a terminator to deactivate the polymerization system. The amount of ethanol was 5 wt% of the mass of the resulting polymer. After solvent removal and drying, ethylene-propylene rubber was obtained. The results are shown in Table 1.

[0048] Example 2

[0049] The difference from Example 1 is that the amount of ethylene norbornene added is 36 mmol / L hexane solution.

[0050] Example 3

[0051] The difference from Example 1 is that the amount of ethylene norbornene added is 34 mmol / L hexane solution.

[0052] Example 4

[0053] The difference compared to Example 3 is that the molar ratio of the co-catalyst sesquiethylaluminate to the main catalyst is 10:1.

[0054] Example 5

[0055] The difference compared to Example 3 is that the molar ratio of the co-catalyst sesquiethylaluminate to the main catalyst is 15:1.

[0056] Example 6

[0057] The difference compared to Example 3 is that the molar ratio of the co-catalyst sesquiethylaluminate to the main catalyst is 20:1.

[0058] Example 7

[0059] The difference from Example 1 is that the amount of ethylene norbornene added is 32 mmol / L hexane solution.

[0060] Example 8

[0061] The difference from Example 1 is that the amount of ethylene norbornene added is 30 mmol / L hexane solution.

[0062] Example 9

[0063] The difference from Example 1 is that the amount of ethylene norbornene added is 28 mmol / L hexane solution.

[0064] Example 10

[0065] The difference from Example 1 is that the amount of ethylene norbornene added is 26 mmol / L hexane solution.

[0066] Example 11

[0067] The difference compared to Example 1 is that the molar ratio of propylene to ethylene in the gaseous feedstock is 2.5:1.

[0068] Example 12

[0069] The difference compared to Example 1 is that the molar ratio of propylene to ethylene in the gaseous feedstock is 3:1.

[0070] Example 13

[0071] The difference compared to Example 1 is that the main catalyst is VOCl. n L 3-n , where n = 1.1.

[0072] Example 14

[0073] The difference compared to Example 1 is that the main catalyst is VOCl. n L 3-n , where n = 1.5.

[0074] Example 15

[0075] The difference compared to Example 1 is that the main catalyst is VOCl. n L 3-n , where n = 2.

[0076] Example 16

[0077] The difference from Example 1 is that L is hexanol.

[0078] Example 17

[0079] The difference from Example 1 is that L is pentanol.

[0080] Comparative Example 1

[0081] The difference from Example 1 is that VOCl3 is used as the main catalyst.

[0082] Comparative Example 2

[0083] The difference from Example 3 is that VOCl3 was used as the main catalyst.

[0084] Comparative Example 3

[0085] The difference from Example 9 is that the main catalyst used is VOCl3.

[0086] Table 1

[0087]

[0088] The preferred embodiments of the present invention have been described above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various specific technical features in any suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A EPDM rubber, characterized in that, The content of the third monomer in the EPDM rubber is ≥7.9wt%, and the third monomer is a non-conjugated diene.

2. The EPDM rubber according to claim 1, characterized in that, The EPDM rubber, The content of the third monomer is 10–13 wt%; and / or The weight-average molecular weight is 3.9 × 10⁻⁶. 5 ~5×10 5 ; and / or Molecular weight distribution is 2.9–4.2; and / or The third monomer is one or more of 1,4-hexadiene, dicyclopentadiene, ethylidene norbornene, and vinyl norbornene.

3. The EPDM rubber according to claim 2, characterized in that, The EPDM rubber: The content of the third monomer is 12–13 wt%; and / or The weight-average molecular weight is 4.1 × 10⁻⁶. 5 ~4.9×10 5 ; and / or Molecular weight distribution is 3.0–4.0; and / or The third monomer is ethylidene norborneol.

4. A method for preparing ethylene propylene diene monomer (EPDM) rubber, characterized in that, The method includes: In the presence of a main catalyst and a cocatalyst, a third monomer and a reaction gas are subjected to a polymerization reaction in a solvent. The main catalyst is a V-based catalyst VOCl n L 3-n , where L is a saturated alcohol, 0 < n < 3, and the third monomer is a non-conjugated diene.

5. The preparation method according to claim 4, characterized in that, The L is a saturated alcohol with 5 to 10 carbon atoms, 1.1 ≤ n ≤ 1.5; and / or The concentration of the main catalyst in the solvent is 0.1–0.5 mmol / L.

6. The preparation method according to claim 5, characterized in that, The L is octanol; and / or The concentration of the main catalyst in the solvent is 0.2–0.4 mmol / L.

7. The preparation method according to claim 4, characterized in that, The cocatalyst is an Al compound; and / or The molar ratio of the co-catalyst to the main catalyst is 5 to 50:

1.

8. The preparation method according to claim 7, characterized in that, The co-catalyst is one or more of sesquiethylaluminum chloride, ethylaluminum dichloride, diethylaluminum monochlorochloride, and triethylaluminum; and / or The molar ratio of the co-catalyst to the main catalyst is 5 to 20:

1.

9. The preparation method according to claim 4, characterized in that, The solvent is a C5-C10 saturated straight-chain alkane and / or a C5-C10 saturated cycloalkanes.

10. The preparation method according to claim 4, characterized in that, The third monomer is one or more of 1,4-hexadiene, dicyclopentadiene, ethylene norbornene, and vinyl norbornene; and / or The concentration of the third monomer in the solvent is 20–50 mmol / L.

11. The preparation method according to claim 10, characterized in that, The third monomer is ethylidene norborneol; and / or The concentration of the third monomer in the solvent is 33–40 mmol / L.

12. The preparation method according to claim 4, characterized in that, The reaction gas includes ethylene, propylene, and optionally hydrogen; The molar 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. The preparation method according to claim 12, characterized in that, The molar ratio of propylene to ethylene in the reaction gas is 1.5 to 3:1; and / or The volume fraction of hydrogen in the reaction gas is 1-7%.

14. The preparation method according to claim 4, characterized in that, Polymerization reaction conditions include: Temperature is 30–60℃; and / or The pressure is 0.3–0.6 MPa; and / or The time is 10 to 90 minutes.

15. The preparation method according to claim 14, characterized in that, Polymerization reaction conditions include: The temperature is 40–50°C; and / or The pressure is 0.4–0.5 MPa; and / or The time is 30 to 60 minutes.

16. The preparation method according to claim 4, characterized in that, The method also includes: After the polymerization reaction is complete, a terminator is added to deactivate the polymerization system, followed by solvent removal and drying.

17. The preparation method according to claim 16, characterized in that, The terminating agent is one or more of ethanol, methanol, and propanol; and / or The amount of the terminator is 1 to 10 wt% of the mass of the polymerized solution.

18. The EPDM rubber prepared by the preparation method according to any one of claims 4-17.

19. The application of EPDM rubber according to any one of claims 1-3 and 18 in building materials, wire and cable, and automotive industries.

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