阅读说明：本技术 一种改性助剂epbm的制备方法 (Preparation method of modification auxiliary agent EPBM ) 是由 李秀国 于 2021-08-12 设计创作，主要内容包括：本发明属于三元乙丙橡胶技术领域,公开了一种改性助剂EPBM的制备方法,用于解决现有三元乙丙橡胶存在着机械强度差、动态性能差以及硫化速度慢的问题。本发明的改性助剂EPBM由如下重量份的原料组成：三元乙丙橡胶生胶80-95份,甲基丙烯酸2-10份,硫磺0.6-3份,氧化锌1-4份,阻燃剂4-7份,超支化丙烯酸酯3-5份,对苯二甲酸3-7份,双季无四醇0.6-1.2份,引发剂0.5-1份,表面活性剂2-3.5份。本发明相比于现有技术具有更好的机械性能和耐寒性能。(The invention belongs to the technical field of ethylene propylene diene monomer, and discloses a preparation method of a modification auxiliary agent EPBM, which is used for solving the problems of poor mechanical strength, poor dynamic performance and low vulcanization speed of the existing ethylene propylene diene monomer. The modification auxiliary agent EPBM of the invention is composed of the following raw materials in parts by weight: 80-95 parts of ethylene propylene diene monomer crude rubber, 2-10 parts of methacrylic acid, 0.6-3 parts of sulfur, 1-4 parts of zinc oxide, 4-7 parts of flame retardant, 3-5 parts of hyperbranched acrylate, 3-7 parts of terephthalic acid, 0.6-1.2 parts of double-season no-tetrol, 0.5-1 part of initiator and 2-3.5 parts of surfactant. Compared with the prior art, the invention has better mechanical property and cold resistance.)

1. The preparation method of the modification aid EPBM is characterized in that the modification aid EPBM consists of the following raw materials in parts by weight:

80-95 parts of ethylene propylene diene monomer crude rubber, 2-10 parts of methacrylic acid, 0.6-3 parts of sulfur, 1-4 parts of zinc oxide, 4-7 parts of flame retardant, 3-5 parts of hyperbranched acrylate, 3-7 parts of terephthalic acid, 0.6-1.2 parts of double-season no-tetrol, 0.5-1 part of initiator and 2-3.5 parts of surfactant.

2. The preparation method of the modification assistant EPBM of claim 1, wherein the hyperbranched acrylate is prepared as follows: under the condition of normal pressure, dissolving tannic acid, a catalyst and a polymerization inhibitor in a reaction solvent; heating the mixed system to 80-90 ℃ under stirring, and dropwise adding the epoxy monomer within 0.5-1 h; sealing the reaction container, keeping stirring, heating the mixed solution to 80-85 ℃, and carrying out heat preservation reaction for 25-30 hours; obtaining a dark brown viscous product after the reaction is finished, namely the tannin-based hyperbranched acrylic ester; the catalyst is triphenylphosphine and titanium dioxide powder, the dosage of the catalyst is 0.5-1.5% of the mass sum of the tannin and the epoxy monomer, and the weight ratio of the triphenylphosphine to the titanium dioxide powder is 1: 0.05-0.1.

3. The preparation method of the EPBM as claimed in claim 2, wherein the polymerization inhibitor is one of p-hydroxyanisole, hydroquinone, resorcinol, and 2, 6-di-tert-butyl-p-ethylphenol, and the amount of the polymerization inhibitor is 0.05-0.15% of the sum of the mass of the tannin and the epoxy monomer.

4. The preparation method of the EPBM of claim 1, wherein the flame retardant is one or a combination of aluminum hydroxide and magnesium hydroxide.

5. The method for preparing the EPBM of claim 1, wherein the initiator is dicumyl peroxide.

6. The method for preparing the modification assistant EPBM of claim 1, wherein the surfactant is one of an anionic surfactant, a zwitterionic surfactant and a nonionic surfactant, and the anionic surfactant is sodium stearate; the zwitterionic active agent is betaine; the non-ionic active agent is tween.

7. The preparation method of the EPBM of any one of claims 1 to 6, wherein the EPBM is prepared from the following raw materials in parts by weight: 88 parts of ethylene propylene diene monomer crude rubber, 5 parts of methacrylic acid, 1.4 parts of sulfur, 2.3 parts of zinc oxide, 5 parts of a flame retardant, 3.7 parts of hyperbranched acrylate, 4 parts of terephthalic acid, 0.6 part of double-season no-tetrol, 0.8 part of an initiator and 3.5 parts of a surfactant.

8. The preparation method of the EPBM of any one of claims 1 to 6, wherein the EPBM is prepared from the following raw materials in parts by weight: 92 parts of ethylene propylene diene monomer crude rubber, 2 parts of methacrylic acid, 3 parts of sulfur, 2 parts of zinc oxide, 5 parts of a flame retardant, 4.5 parts of hyperbranched acrylate, 6 parts of terephthalic acid, 1 part of double-season no-tetrol, 0.5 part of an initiator and 2 parts of a surfactant.

9. The preparation method of the EPBM of any one of claims 1 to 6, wherein the EPBM is prepared from the following raw materials in parts by weight: 85 parts of ethylene propylene diene monomer crude rubber, 8 parts of methacrylic acid, 2 parts of sulfur, 4 parts of zinc oxide, 7 parts of a flame retardant, 3 parts of hyperbranched acrylate, 7 parts of terephthalic acid, 1.2 parts of double-season no-tetrol, 1 part of an initiator and 3 parts of a surfactant.

10. The preparation method of the modification aid EPBM according to claim 1, comprising the steps of:

(1) preparing raw ethylene propylene diene monomer rubber 80-95 parts, methacrylic acid 2-10 parts, sulfur 0.6-3 parts, zinc oxide 1-4 parts, flame retardant 4-7 parts, hyperbranched acrylate 3-5 parts, terephthalic acid 3-7 parts, double-season no-tetrol 0.6-1.2 parts, initiator 0.5-1 part and surfactant 2-3.5 parts for backup;

(2) pretreatment: adding a surfactant, sulfur and zinc oxide into deionized water and uniformly mixing to obtain a mixture;

(3) heating the mixture in the step (2), preserving heat for 1-3h, and then adding terephthalic acid;

(4) stirring raw ethylene propylene diene monomer rubber, methacrylic acid and an initiator at a high speed, and heating to 50-55 ℃;

(5) adding the hyperbranched acrylic ester and the double-quaternary alcohol-free mixture into the step (4), stirring and mixing to 58-60 ℃;

(6) adding a flame retardant into the mixture obtained in the step (5) and keeping the temperature for 0.5-1 h; and (4) adding the mixture obtained in the step (3), stirring and preserving heat for 0.5-1 h.

Technical Field

The invention belongs to the technical field of ethylene propylene diene monomer preparation, and particularly relates to a preparation method of a modification auxiliary agent EPBM.

Background

Ethylene-propylene-diene monomer is a copolymer of ethylene, propylene and a small amount of non-conjugated diene, is one of ethylene-propylene rubbers, has excellent ozone resistance, heat resistance, weather resistance and other aging resistance because the main chain of the ethylene-propylene-diene monomer is composed of chemically stable saturated hydrocarbon and only contains unsaturated double bonds in the side chain, and can be widely used in the fields of automobile parts, waterproof materials for buildings, wire and cable sheaths, heat-resistant rubber tubes, adhesive tapes, automobile sealing parts and the like.

The ethylene propylene diene monomer is synthetic rubber with excellent comprehensive performance, and has excellent aging resistance, excellent chemical resistance and excellent insulating property at normal temperature. However, because of its low strength and poor cold resistance, the mechanical strength is generally poor at about-30 ℃, and the application range is greatly limited.

Although the performance of ethylene propylene diene monomer is improved by adding various additives into the ethylene propylene diene monomer in the prior art, the problems of poor dynamic performance and low vulcanization speed exist in the preparation process.

Disclosure of Invention

The invention provides a preparation method of a modification aid EPBM (ethylene propylene rubber) in order to solve the problems of poor mechanical strength, poor dynamic performance and low vulcanization speed of the conventional ethylene propylene diene monomer.

In order to solve the technical problem, the technical scheme adopted by the invention is as follows:

the preparation method of the modification aid EPBM is characterized in that the modification aid EPBM is used as an aid in the production process of ethylene propylene diene monomer, and the modification aid EPBM comprises the following raw materials in parts by weight:

80-95 parts of ethylene propylene diene monomer crude rubber, 2-10 parts of methacrylic acid, 0.6-3 parts of sulfur, 1-4 parts of zinc oxide, 4-7 parts of flame retardant, 3-5 parts of hyperbranched acrylate, 3-7 parts of terephthalic acid, 0.6-1.2 parts of double-season no-tetrol, 0.5-1 part of initiator and 2-3.5 parts of surfactant.

Further, the preparation method of the hyperbranched acrylic ester comprises the following steps: under the condition of normal pressure, dissolving tannic acid, a catalyst and a polymerization inhibitor in a reaction solvent; heating the mixed system to 80-90 ℃ under stirring, and dropwise adding the epoxy monomer within 0.5-1 h; sealing the reaction container, keeping stirring, heating the mixed solution to 80-85 ℃, and carrying out heat preservation reaction for 25-30 hours; obtaining a dark brown viscous product after the reaction is finished, namely the tannin-based hyperbranched acrylic ester; the catalyst is triphenylphosphine and titanium dioxide powder, the dosage of the catalyst is 0.5-1.5% of the mass sum of the tannin and the epoxy monomer, and the weight ratio of the triphenylphosphine to the titanium dioxide powder is 1: 0.05-0.1.

Further, the polymerization inhibitor is one of p-hydroxyanisole, hydroquinone, resorcinol and 2, 6-di-tert-butyl-p-ethylphenol, and the dosage of the polymerization inhibitor is 0.05-0.15% of the sum of the mass of the tannic acid and the mass of the epoxy monomer. The reaction solvent is any one of N, N-dimethylformamide, water, ethyl acetate, ethanol, butyl acetate and acetone or a mixture of the N, N-dimethylformamide, the water, the ethyl acetate, the ethanol, the butyl acetate and the acetone, and the dosage of the reaction solvent is 20-60% of the total mass of the reaction system; the epoxy monomer consists of an epoxy monomer containing a photosensitive double bond and an epoxy monomer without the photosensitive double bond, wherein the amount of the substance of the epoxy monomer containing the photosensitive double bond is 20-100% of the total epoxy monomer.

Further, the epoxy monomer containing the photosensitive double bond is one of glycidyl methacrylate, allyl glycidyl ether and glycidyl acrylate; the epoxy monomer without photosensitive double bonds is one of tertiary carbonic acid glycidyl ester, n-butyl glycidyl ether, octyl glycidyl ether, glycidyl butyl ester and ethylene glycol diglycidyl ether.

Further, the molar group ratio of the tannic acid to the epoxy monomer is 1:2 to 2: 1.

Further, the flame retardant is one or a combination of more of aluminum hydroxide or magnesium hydroxide.

Further, the initiator is dicumyl peroxide.

Further, the surfactant is one of an anionic active agent, a zwitterionic active agent and a nonionic active agent, and the anionic active agent is sodium stearate; the zwitterionic active agent is betaine; the non-ionic active agent is tween.

Further, the modification auxiliary agent EPBM consists of the following raw materials in parts by weight: 88 parts of ethylene propylene diene monomer crude rubber, 5 parts of methacrylic acid, 1.4 parts of sulfur, 2.3 parts of zinc oxide, 5 parts of a flame retardant, 3.7 parts of hyperbranched acrylate, 4 parts of terephthalic acid, 0.6 part of double-season no-tetrol, 0.8 part of an initiator and 3.5 parts of a surfactant.

Further, the modification auxiliary agent EPBM consists of the following raw materials in parts by weight: 92 parts of ethylene propylene diene monomer crude rubber, 2 parts of methacrylic acid, 3 parts of sulfur, 2 parts of zinc oxide, 5 parts of a flame retardant, 4.5 parts of hyperbranched acrylate, 6 parts of terephthalic acid, 1 part of double-season no-tetrol, 0.5 part of an initiator and 2 parts of a surfactant.

Further, the modification auxiliary agent EPBM consists of the following raw materials in parts by weight: 85 parts of ethylene propylene diene monomer crude rubber, 8 parts of methacrylic acid, 2 parts of sulfur, 4 parts of zinc oxide, 7 parts of a flame retardant, 3 parts of hyperbranched acrylate, 7 parts of terephthalic acid, 1.2 parts of double-season no-tetrol, 1 part of an initiator and 3 parts of a surfactant.

In some embodiments, the modification assistant EPBM is used as one of the assistants in the ethylene propylene diene monomer production process, when the assistants added in the ethylene propylene diene monomer production process comprise the modification assistants EPBM, CPE and ACR, the ratio of the addition amount of the modification assistant EPBM to the addition amount of ACR + CPE (calculated by weight) is 1:1-2, and the weight of the lubricant added in the ethylene propylene diene monomer production process is 10-12% of the weight of the added modification assistant EPBM; when the addition additives in the ethylene propylene diene monomer production process comprise modification additives EPBM and ACR, the ratio of the addition amount of the modification additives EPBM to the addition amount of the ACR (calculated according to weight) is 1:1, and the weight of the lubricant added in the ethylene propylene diene monomer production process is 10-15% of the weight of the addition modification additives EPBM.

The invention discloses a preparation method of a modification auxiliary agent EPBM, which comprises the following steps:

(1) preparing raw ethylene propylene diene monomer rubber 80-95 parts, methacrylic acid 2-10 parts, sulfur 0.6-3 parts, zinc oxide 1-4 parts, flame retardant 4-7 parts, hyperbranched acrylate 3-5 parts, terephthalic acid 3-7 parts, double-season no-tetrol 0.6-1.2 parts, initiator 0.5-1 part and surfactant 2-3.5 parts for backup;

(2) pretreatment: adding a surfactant, sulfur and zinc oxide into deionized water and uniformly mixing to obtain a mixture;

(3) heating the mixture in the step (2), preserving heat for 1-3h, and then adding terephthalic acid;

(4) stirring raw ethylene propylene diene monomer rubber, methacrylic acid and an initiator at a high speed, and heating to 50-55 ℃;

(5) adding the hyperbranched acrylic ester and the double-quaternary alcohol-free mixture into the step (4), stirring and mixing to 58-60 ℃;

(6) adding a flame retardant into the mixture obtained in the step (5) and keeping the temperature for 0.5-1 h; and (4) adding the mixture obtained in the step (3), stirring and preserving heat for 0.5-1 h.

Compared with the prior art, the invention has the following beneficial effects:

in the production process of the ethylene propylene diene monomer, the modification auxiliary agent EPBM is added, and the raw ethylene propylene diene monomer in the modification auxiliary agent EPBM is grafted with a methacrylic acid monomer and then chemically crosslinked with an active functional group of an external long chain of the hyperbranched acrylate, so that the mechanical strength of the rubber is greatly improved; meanwhile, when the hyperbranched acrylic ester is chemically crosslinked with the active functional group of the external long chain of the hyperbranched acrylic ester, the added double-quaternary alcohol-free can promote and accelerate the speed of chemical crosslinking. Meanwhile, after the ethylene propylene diene monomer raw rubber is chemically crosslinked with active functional groups of external long chains of the hyperbranched acrylic ester, the flame retardant, the surfactant, the sulfur and the zinc oxide are added, so that on one hand, the chemical crosslinking cannot be influenced in the vulcanization process, the chemical correlation strength is guaranteed, on the other hand, the dynamic performance can be improved, the vulcanization speed is improved, and the ethylene propylene diene monomer raw rubber has better mechanical performance and cold resistance compared with the prior art.

Detailed Description

The present invention will be further described with reference to the following examples, which are intended to illustrate only some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, other embodiments obtained by persons of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

The invention relates to a preparation method of a modification aid EPBM, which comprises the following raw materials in parts by weight: the composition is characterized by comprising the following raw materials in parts by weight:

80-95 parts of ethylene propylene diene monomer crude rubber, 2-10 parts of methacrylic acid, 0.6-3 parts of sulfur, 1-4 parts of zinc oxide, 4-7 parts of flame retardant, 3-5 parts of hyperbranched acrylate, 3-7 parts of terephthalic acid, 0.6-1.2 parts of double-season no-tetrol, 0.5-1 part of initiator and 2-3.5 parts of surfactant.

Further, the preparation method of the hyperbranched acrylic ester comprises the following steps: under the condition of normal pressure, dissolving tannic acid, a catalyst and a polymerization inhibitor in a reaction solvent; heating the mixed system to 80-90 ℃ under stirring, and dropwise adding the epoxy monomer within 0.5-1 h; sealing the reaction container, keeping stirring, heating the mixed solution to 80-85 ℃, and carrying out heat preservation reaction for 25-30 hours; obtaining a dark brown viscous product after the reaction is finished, namely the tannin-based hyperbranched acrylic ester; the catalyst is triphenylphosphine and titanium dioxide powder, the dosage of the catalyst is 0.5-1.5% of the mass sum of the tannin and the epoxy monomer, and the weight ratio of the triphenylphosphine to the titanium dioxide powder is 1: 0.05-0.1.

Further, the polymerization inhibitor is one of p-hydroxyanisole, hydroquinone, resorcinol and 2, 6-di-tert-butyl-p-ethylphenol, and the dosage of the polymerization inhibitor is 0.05-0.15% of the sum of the mass of the tannic acid and the mass of the epoxy monomer. The reaction solvent is any one of N, N-dimethylformamide, water, ethyl acetate, ethanol, butyl acetate and acetone or a mixture of the N, N-dimethylformamide, the water, the ethyl acetate, the ethanol, the butyl acetate and the acetone, and the dosage of the reaction solvent is 20-60% of the total mass of the reaction system; the epoxy monomer consists of an epoxy monomer containing a photosensitive double bond and an epoxy monomer without the photosensitive double bond, wherein the amount of the substance of the epoxy monomer containing the photosensitive double bond is 20-100% of the total epoxy monomer.

The photosensitive double bond-containing epoxy monomer is one of glycidyl methacrylate, allyl glycidyl ether and glycidyl acrylate; the epoxy monomer without photosensitive double bonds is one of tertiary carbonic acid glycidyl ester, n-butyl glycidyl ether, octyl glycidyl ether, glycidyl butyl ester and ethylene glycol diglycidyl ether.

Further, the molar group ratio of the tannic acid to the epoxy monomer is 1:2 to 2: 1.

Compared with the prior art, in the preparation process of the hyperbranched acrylic ester, titanium dioxide powder is added into the catalyst, so that the production reaction time of the hyperbranched acrylic ester can be greatly shortened, and the temperature of the production process is reduced, thereby achieving the purpose of improving the production efficiency of the hyperbranched acrylic ester.

Further, the flame retardant is one or a combination of more of aluminum hydroxide or magnesium hydroxide. The invention adopts inorganic metal compound as flame retardant, which has obvious flame retardant effect, good stability, no volatilization, no toxicity, little corrosivity and low price.

Further, the initiator is dicumyl peroxide.

Further, the surfactant is one of an anionic active agent, a zwitterionic active agent and a nonionic active agent, and the anionic active agent is sodium stearate; the zwitterionic active agent is betaine; the non-ionic active agent is tween.

Further, the modification auxiliary agent EPBM consists of the following raw materials in parts by weight: 88 parts of ethylene propylene diene monomer crude rubber, 5 parts of methacrylic acid, 1.4 parts of sulfur, 2.3 parts of zinc oxide, 5 parts of a flame retardant, 3.7 parts of hyperbranched acrylate, 4 parts of terephthalic acid, 0.6 part of double-season no-tetrol, 0.8 part of an initiator and 3.5 parts of a surfactant.

Further, the modification auxiliary agent EPBM consists of the following raw materials in parts by weight: 92 parts of ethylene propylene diene monomer crude rubber, 2 parts of methacrylic acid, 3 parts of sulfur, 2 parts of zinc oxide, 5 parts of a flame retardant, 4.5 parts of hyperbranched acrylate, 6 parts of terephthalic acid, 1 part of double-season no-tetrol, 0.5 part of an initiator and 2 parts of a surfactant.

Further, the modification auxiliary agent EPBM consists of the following raw materials in parts by weight: 85 parts of ethylene propylene diene monomer crude rubber, 8 parts of methacrylic acid, 2 parts of sulfur, 4 parts of zinc oxide, 7 parts of a flame retardant, 3 parts of hyperbranched acrylate, 7 parts of terephthalic acid, 1.2 parts of double-season no-tetrol, 1 part of an initiator and 3 parts of a surfactant.

The invention discloses a preparation method of a modification auxiliary agent EPBM, which comprises the following steps:

(1) preparing raw ethylene propylene diene monomer rubber 80-95 parts, methacrylic acid 2-10 parts, sulfur 0.6-3 parts, zinc oxide 1-4 parts, flame retardant 4-7 parts, hyperbranched acrylate 3-5 parts, terephthalic acid 3-7 parts, double-season no-tetrol 0.6-1.2 parts, initiator 0.5-1 part and surfactant 2-3.5 parts for backup;

(2) pretreatment: adding a surfactant, sulfur and zinc oxide into deionized water and uniformly mixing to obtain a mixture;

(3) heating the mixture in the step (2), preserving heat for 1-3h, and then adding terephthalic acid;

(4) stirring raw ethylene propylene diene monomer rubber, methacrylic acid and an initiator at a high speed, and heating to 50-55 ℃;

(5) adding the hyperbranched acrylic ester and the double-quaternary alcohol-free mixture into the step (4), stirring and mixing to 58-60 ℃;

(6) adding a flame retardant into the mixture obtained in the step (5) and keeping the temperature for 0.5-1 h; and (4) adding the mixture obtained in the step (3), stirring and preserving heat for 0.5-1 h.

Example 1

The modification assistant EPBM of this example was prepared according to the following steps:

(1) preparing raw rubber of ethylene propylene diene monomer 80 parts, methacrylic acid 2 parts, sulfur 0.6 part, zinc oxide 1 part, flame retardant 4 parts, hyperbranched acrylate 3 parts, terephthalic acid 3 parts, double-season no-tetrol 0.6 part, initiator 0.5 part and surfactant 2 parts for backup;

(2) pretreatment: adding a surfactant, sulfur and zinc oxide into deionized water and uniformly mixing to obtain a mixture;

(3) heating the mixture in the step (2), preserving heat for 1-3h, and then adding terephthalic acid;

(4) stirring raw ethylene propylene diene monomer rubber, methacrylic acid and an initiator at a high speed, and heating to 50-55 ℃;

(5) adding the hyperbranched acrylic ester and the double-quaternary alcohol-free mixture into the step (4), stirring and mixing to 58-60 ℃;

(6) adding a flame retardant into the mixture obtained in the step (5) and keeping the temperature for 0.5-1 h; and (4) adding the mixture obtained in the step (3), stirring and preserving heat for 0.5-1 h.

Example 2

The modification assistant EPBM of this example was prepared according to the following steps:

(1) preparing raw rubber of Ethylene Propylene Diene Monomer (EPDM) 95 parts, methacrylic acid 10 parts, sulfur 3 parts, zinc oxide 4 parts, flame retardant 7 parts, hyperbranched acrylate 5 parts, terephthalic acid 7 parts, double-quaternary alcohol-free 1.2 parts, initiator 1 part and surfactant 3.5 parts for backup;

(2) pretreatment: adding a surfactant, sulfur and zinc oxide into deionized water and uniformly mixing to obtain a mixture;

(3) heating the mixture in the step (2), preserving heat for 1-3h, and then adding terephthalic acid;

(4) stirring raw ethylene propylene diene monomer rubber, methacrylic acid and an initiator at a high speed, and heating to 50-55 ℃;

(5) adding the hyperbranched acrylic ester and the double-quaternary alcohol-free mixture into the step (4), stirring and mixing to 58-60 ℃;

(6) adding a flame retardant into the mixture obtained in the step (5) and keeping the temperature for 0.5-1 h; and (4) adding the mixture obtained in the step (3), stirring and preserving heat for 0.5-1 h.

Example 3

The modification assistant EPBM of this example was prepared according to the following steps:

(1) preparing raw ethylene propylene diene monomer rubber 90 parts, methacrylic acid 6 parts, sulfur 2.2 parts, zinc oxide 2.5 parts, flame retardant 5.5 parts, hyperbranched acrylate 4 parts, terephthalic acid 5 parts, double-season no-tetrol 0.8 part, initiator 0.6 part and surfactant 2.8 part for backup;

(2) pretreatment: adding a surfactant, sulfur and zinc oxide into deionized water and uniformly mixing to obtain a mixture;

(3) heating the mixture in the step (2), preserving heat for 1-3h, and then adding terephthalic acid;

(4) stirring raw ethylene propylene diene monomer rubber, methacrylic acid and an initiator at a high speed, and heating to 50-55 ℃;

(5) adding the hyperbranched acrylic ester and the double-quaternary alcohol-free mixture into the step (4), stirring and mixing to 58-60 ℃;

(6) adding a flame retardant into the mixture obtained in the step (5) and keeping the temperature for 0.5-1 h; and (4) adding the mixture obtained in the step (3), stirring and preserving heat for 0.5-1 h.

Example 4

The modification assistant EPBM of this example was prepared according to the following steps:

(1) preparing raw ethylene propylene diene monomer rubber 88 parts, methacrylic acid 5 parts, sulfur 1.4 parts, zinc oxide 2.3 parts, flame retardant 5 parts, hyperbranched acrylate 3.7 parts, terephthalic acid 4 parts, double-season no-tetrol 0.6 part, initiator 0.8 part and surfactant 3.5 parts for backup;

(2) pretreatment: adding a surfactant, sulfur and zinc oxide into deionized water and uniformly mixing to obtain a mixture;

(3) heating the mixture in the step (2), preserving heat for 1-3h, and then adding terephthalic acid;

(4) stirring raw ethylene propylene diene monomer rubber, methacrylic acid and an initiator at a high speed, and heating to 50-55 ℃;

(5) adding the hyperbranched acrylic ester and the double-quaternary alcohol-free mixture into the step (4), stirring and mixing to 58-60 ℃;

(6) adding a flame retardant into the mixture obtained in the step (5) and keeping the temperature for 0.5-1 h; and (4) adding the mixture obtained in the step (3), stirring and preserving heat for 0.5-1 h.

Example 5

The modification assistant EPBM of this example was prepared according to the following steps:

(1) preparing raw ethylene propylene diene monomer rubber 92 parts, methacrylic acid 2 parts, sulfur 3 parts, zinc oxide 2 parts, flame retardant 5 parts, hyperbranched acrylate 4.5 parts, terephthalic acid 6 parts, double-season no-tetrol 1 part, initiator 0.5 part and surfactant 2 parts for backup;

(2) pretreatment: adding a surfactant, sulfur and zinc oxide into deionized water and uniformly mixing to obtain a mixture;

(3) heating the mixture in the step (2), preserving heat for 1-3h, and then adding terephthalic acid;

(4) stirring raw ethylene propylene diene monomer rubber, methacrylic acid and an initiator at a high speed, and heating to 50-55 ℃;

(5) adding the hyperbranched acrylic ester and the double-quaternary alcohol-free mixture into the step (4), stirring and mixing to 58-60 ℃;

(6) adding a flame retardant into the mixture obtained in the step (5) and keeping the temperature for 0.5-1 h; and (4) adding the mixture obtained in the step (3), stirring and preserving heat for 0.5-1 h.

Example 6

The modification assistant EPBM of this example was prepared according to the following steps:

(1) preparing raw ethylene propylene diene monomer rubber 85 parts, methacrylic acid 8 parts, sulfur 2 parts, zinc oxide 4 parts, flame retardant 7 parts, hyperbranched acrylate 3 parts, terephthalic acid 7 parts, double-quaternary alcohol-free 1.2 parts, initiator 1 part and surfactant 3 parts for backup;

(2) pretreatment: adding a surfactant, sulfur and zinc oxide into deionized water and uniformly mixing to obtain a mixture;

(3) heating the mixture in the step (2), preserving heat for 1-3h, and then adding terephthalic acid;

(4) stirring raw ethylene propylene diene monomer rubber, methacrylic acid and an initiator at a high speed, and heating to 50-55 ℃;

(5) adding the hyperbranched acrylic ester and the double-quaternary alcohol-free mixture into the step (4), stirring and mixing to 58-60 ℃;

(6) adding a flame retardant into the mixture obtained in the step (5) and keeping the temperature for 0.5-1 h; and (4) adding the mixture obtained in the step (3), stirring and preserving heat for 0.5-1 h.

Example 7

The modification assistant EPBM of this example was prepared according to the following steps:

(1) preparing raw rubber of ethylene propylene diene monomer 80 parts, methacrylic acid 2 parts, sulfur 3 parts, zinc oxide 4 parts, flame retardant 6 parts, hyperbranched acrylate 2.5 parts, terephthalic acid 5 parts, double-season no-tetrol 0.6 parts, initiator 0.5-1 part and surfactant 2 parts for backup;

(2) pretreatment: adding a surfactant, sulfur and zinc oxide into deionized water and uniformly mixing to obtain a mixture;

(3) heating the mixture in the step (2), preserving heat for 1-3h, and then adding terephthalic acid;

(4) stirring raw ethylene propylene diene monomer rubber, methacrylic acid and an initiator at a high speed, and heating to 50-55 ℃;

(5) adding the hyperbranched acrylic ester and the double-quaternary alcohol-free mixture into the step (4), stirring and mixing to 58-60 ℃;

(6) adding a flame retardant into the mixture obtained in the step (5) and keeping the temperature for 0.5-1 h; and (4) adding the mixture obtained in the step (3), stirring and preserving heat for 0.5-1 h.

Example 8

The modification assistant EPBM of this example was prepared according to the following steps:

(1) preparing raw ethylene propylene diene monomer rubber 95 parts, methacrylic acid 10 parts, sulfur 0.6 part, zinc oxide 1 part, flame retardant 4-7 parts, hyperbranched acrylate 5 parts, terephthalic acid 3-7 parts, double-season no-tetrol 0.6 part, initiator 0.5-1 part and surfactant 2-3.5 parts for backup;

(2) pretreatment: adding a surfactant, sulfur and zinc oxide into deionized water and uniformly mixing to obtain a mixture;

(3) heating the mixture in the step (2), preserving heat for 1-3h, and then adding terephthalic acid;

(4) stirring raw ethylene propylene diene monomer rubber, methacrylic acid and an initiator at a high speed, and heating to 50-55 ℃;

(5) adding the hyperbranched acrylic ester and the double-quaternary alcohol-free mixture into the step (4), stirring and mixing to 58-60 ℃;

(6) adding a flame retardant into the mixture obtained in the step (5) and keeping the temperature for 0.5-1 h; and (4) adding the mixture obtained in the step (3), stirring and preserving heat for 0.5-1 h.