CN109851974B - Strong acid resistant modified chlorosulfonated polyethylene rubber - Google Patents
Strong acid resistant modified chlorosulfonated polyethylene rubber Download PDFInfo
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to the technical field of acid-resistant rubber, and particularly relates to novel strong acid-resistant modified chlorosulfonated polyethylene rubber. Firstly, chlorosulfonated polyethylene and butenedioic acid are connected through covalent bonds by utilizing surface polymerization reaction to prepare polychloroprene-polychlorosulfonated polyethylene copolymer; then modifying the surface of the copolymer by utilizing polydimethylsiloxane to obtain modified chlorosulfonated polyethylene rubber; and finally, uniformly mixing the modified chlorosulfonated polyethylene rubber, the antioxidant, the plasticizer, the filler and the accelerator, and then placing the mixture into a rubber internal mixer for internal mixing to prepare the novel strong acid resistant modified chlorosulfonated polyethylene rubber.
Description
Technical Field
The invention belongs to the technical field of acid-resistant rubber, and particularly relates to strong acid-resistant modified chlorosulfonated polyethylene rubber.
Background
Rubber has excellent chemical stability and relatively low price, and has been widely used for anticorrosion occasions for a long time, such as sealing materials of ion exchange membranes of large-scale chemical reactors and fuel cells. With the development of society, people have higher requirements on the tolerance of materials, and the development of high-acid-resistant rubber has important significance for widening the application field of rubber.
The chlorosulfonated polyethylene rubber is prepared by chlorination and chlorosulfonation of low-density polyethylene or high-density polyethylene. The chlorosulfonated polyethylene rubber is a white or yellow elastomer and has excellent ozone resistance, chemical corrosion resistance, heat resistance, low temperature resistance, oil resistance, flame resistance, wear resistance and electric insulation performance. The molecular chain of the chloroprene rubber contains polar chlorine atom groups, so that on one hand, double bonds can be protected to reduce the activity of the chloroprene rubber; on the other hand, the polymer has good stability to non-polar substances, so that the light resistance, heat resistance, aging resistance, oil resistance and chemical corrosion resistance of the polymer are superior to those of natural rubber, and particularly the heat resistance, aging resistance, weather resistance and flame resistance of the polymer are more outstanding. It has been found that blending neoprene with chlorosulfonated polyethylene can enhance the acid resistance of chlorosulfonated polyethylene. But the preparation of the blended material only prepares the rubber by mixing two polymers in a melting way, and the acid resistance and the mechanical property of the material are not obviously improved, so that the material is difficult to be used in a strong acid environment.
Disclosure of Invention
In order to develop rubber with excellent mechanical property and strong acid resistance, the invention utilizes surface copolymerization reaction to connect chlorosulfonated polyethylene and butenedioic acid through covalent bonds to prepare polychloroprene-polychloroprene sulfonated polyethylene copolymer, and utilizes polysiloxane to further modify the rubber to prepare the high-performance rubber material.
In order to achieve the above object, the present invention provides the following technical solutions:
the strong acid resistant modified chlorosulfonated polyethylene rubber is characterized by comprising the following steps:
(1) dissolving 2-4kg of chlorosulfonated polyethylene in toluene, adding 1-2kg of chloroprene, 30-60g of initiator and 10-20g of catalyst into the solution, degassing for 25-30min by using inert gas, reacting for 6-8h at the temperature of 60-80 ℃, and naturally cooling to obtain a polychloroprene-polychloroprene sulfonated polyethylene copolymer solution;
(2) slowly adding water into the polychloroprene-sulfonated polyethylene copolymer solution obtained in the step (1) to precipitate the copolymer, shearing the polymer for 15-25min by using a high-speed shearing emulsifying machine under the conditions of 10000-12000rpm, centrifugally collecting the precipitate, washing the precipitate for 2-3 times by water, and drying to obtain the polychloroprene-sulfonated polyethylene copolymer;
(3) soaking the polychloroprene-sulfonated polyethylene copolymer obtained in the step (2) in a polydimethylsiloxane solution, performing ultrasonic treatment for 20-30min under the condition of 400-600W, filtering to obtain a solid, and curing the solid for 20-30min at 100 ℃ to obtain modified chlorosulfonated polyethylene rubber;
(4) uniformly mixing the modified chlorosulfonated polyethylene rubber, the antioxidant, the plasticizer, the filler and the accelerator, then placing the mixture into a rubber internal mixer, internally mixing the mixture for 3-5min at the conditions of 180 ℃ and 800rpm of 160-.
Preferably, the inert gas in step (1) is one of nitrogen, argon and neon.
Preferably, the initiator in the step (1) is one of azobisisobutyronitrile, azobisisoheptonitrile and tert-butyl hydroperoxide; the catalyst is one of CuBr 2, FeBr 3, CuCl 2 and FeCl 3.
Preferably, the slow dripping speed of the polychloroprene-polychloroprene sulfonated polyethylene copolymer solution in the step (2) is 2-3 mL/min; the particle size of the obtained polychloroprene-polychloroprene sulfonated polyethylene copolymer is not more than 1 μm.
Preferably, the polydimethylsiloxane solution in the step (3) is one of tetrahydrofuran, ethyl acetate and dichloromethane solution of polydimethylsiloxane; the concentration of the polydimethylsiloxane in the polydimethylsiloxane solution is 0.05-0.1 g/mL.
Preferably, the antioxidant in the step (4) is one of tea polyphenol, vitamin E and beta carotene; the plasticizer is an epoxy fatty acid ester antioxidant; the filler is one of titanium dioxide, silicon dioxide and aluminum oxide; the accelerant is phenyl salicylate, calcium sulfate whisker powder and zinc oxide, wherein the mass ratio of the phenyl salicylate to the calcium sulfate whisker powder to the zinc oxide is 1: 1: 1 mass ratio.
Preferably, the chlorosulfonated polyethylene rubber, the antioxidant, the plasticizer, the filler and the accelerator in the step (4) are sequentially calculated according to mass fraction: 90-95 parts, 1-2 parts, 0.5-1 part, 5-10 parts and 1-3 parts.
The rubber prepared by the invention has excellent mechanical property and strong acid resistance. Compared with the prior art, the strong acid resistant modified chlorosulfonated polyethylene rubber provided by the invention has the following beneficial effects: according to the invention, the butenedioic acid is connected to the polychlorosulfonated polyethylene through a covalent bond by utilizing a surface polymerization reaction, so that the acid resistance of the rubber is improved, and the mechanical property of the rubber is enhanced; polysiloxane is adopted to further modify rubber, so that the tolerance and mechanical property of the material are further enhanced. The rubber prepared by the invention has strong tolerance and excellent mechanical property, and can be used as a substrate layer material of various chemical anti-corrosion materials.
Detailed Description
The present invention is further described in detail with reference to the following examples, which are not intended to limit the technical scope of the present invention, and all changes and equivalents made based on the present invention shall fall within the scope of the present invention.
Example one
The strong acid resistant modified chlorosulfonated polyethylene rubber is characterized by comprising the following steps:
(1) dissolving 2kg of chlorosulfonated polyethylene in toluene, adding 1.5kg of chloroprene, 40g of azobisisobutyronitrile and 15g of CuBr 2 into the solution, degassing for 25min by using nitrogen, reacting for 7h at 70 ℃, and naturally cooling to obtain a polychloroprene-polychloroprene sulfonated polyethylene copolymer solution;
(2) slowly adding water into the polychloroprene-sulfonated polyethylene copolymer solution obtained in the step (1) to precipitate the copolymer, shearing the polymer for 20min by using a high-speed shearing emulsifying machine under the condition of 11000rpm, centrifugally collecting the precipitate, washing the precipitate for 3 times by using water, and drying to obtain the polychloroprene-sulfonated polyethylene copolymer;
(3) soaking the polychloroprene-polychlorosulfonated polyethylene copolymer obtained in the step (2) in 0.06g/mL polydimethylsiloxane tetrahydrofuran solution, performing ultrasonic treatment for 20min under the condition of 500W, filtering to obtain a solid, and curing the solid for 25min at the temperature of 100 ℃ to obtain modified chlorosulfonated polyethylene rubber;
(4) uniformly mixing 92 parts of modified chlorosulfonated polyethylene rubber, 1 part of tea polyphenol, 0.5 part of epoxy fatty acid methyl ester, 5 parts of titanium dioxide and 1.5 parts of accelerator, placing the mixture into a rubber internal mixer, internally mixing for 4min at 170 ℃ and 700rpm, heating to 240 ℃ at the speed of 5 ℃/min, internally mixing for 5min, cooling, and discharging to obtain the novel strong acid-resistant modified chlorosulfonated polyethylene rubber.
Example two
The strong acid resistant modified chlorosulfonated polyethylene rubber is characterized by comprising the following steps:
(1) dissolving 3kg of chlorosulfonated polyethylene in toluene, adding 2kg of chloroprene, 45g of azobisisoheptonitrile and 18g of FeCl 3 into the solution, degassing for 30min by using argon, reacting for 7h at 75 ℃, and naturally cooling to obtain a polychloroprene-polychloroprene sulfonated polyethylene copolymer solution;
(2) slowly adding water into the polychloroprene-sulfonated polyethylene copolymer solution obtained in the step (1) to precipitate the copolymer, shearing the polymer for 20min by using a high-speed shearing emulsifying machine under the condition of 12000rpm, centrifugally collecting the precipitate, washing the precipitate for 3 times by using water, and drying to obtain the polychloroprene-sulfonated polyethylene copolymer;
(3) soaking the polychloroprene-polychlorosulfonated polyethylene copolymer obtained in the step (2) in 0.07g/mL polydimethylsiloxane ethyl acetate solution, performing ultrasonic treatment for 25min under the condition of 500W, filtering to obtain a solid, and curing the solid for 25min at the temperature of 100 ℃ to obtain modified chlorosulfonated polyethylene rubber;
(4) uniformly mixing 90 parts of modified chlorosulfonated polyethylene rubber, 1 part of vitamin E, 0.5 part of epoxy fatty acid ethyl ester, 6.5 parts of aluminum oxide and 2 parts of accelerator, placing the mixture into a rubber internal mixer, internally mixing for 4min at 170 ℃ and 700rpm, heating to 240 ℃ at the speed of 5 ℃/min, internally mixing for 5min, cooling, and discharging to obtain the novel strong acid resistant modified chlorosulfonated polyethylene rubber.
Comparative example 1
The strong acid resistant modified chlorosulfonated polyethylene rubber is characterized by comprising the following steps:
uniformly mixing 45 parts of chlorosulfonated polyethylene rubber, 45 parts of chloroprene rubber, 1 part of tea polyphenol, 0.5 part of epoxy fatty acid ethyl ester, 5.5 parts of aluminum oxide and 2 parts of accelerator, placing the mixture into a rubber internal mixer, internally mixing for 4min at the temperature of 170 ℃ and the rpm of 700, heating to 240 ℃ at the speed of 5 ℃/min, internally mixing for 5min, cooling, and discharging to obtain the strong acid resistant modified chlorosulfonated polyethylene rubber.
Performance testing
The rubbers prepared in examples 1 to 3 and comparative example were soaked in 0.1mol, 0.5mol, 1mol, 2mol of hydrochloric acid solution at 150 ℃ for 12 hours, and then dried to measure the mechanical properties and quality change of the rubbers prepared in examples 1 to 3 and comparative example.
The tensile strength and the elongation at break are tested according to GB/T528-1998, and the tensile speed is 500mm/min
TABLE 1 mechanical Properties and Mass changes after soaking examples 1-3 and comparative example 1 under different acidic conditions
As can be seen from Table 1, materials prepared by covalently bonding chlorosulfonated polyethylene and butenedioic acid and further modifying the rubber with polysiloxane have stronger mechanical properties and acid resistance.
It is obvious to those skilled in the art that the present invention is not limited to the above embodiments, and it is within the scope of the present invention to adopt various insubstantial modifications of the method concept and technical scheme of the present invention, or to directly apply the concept and technical scheme of the present invention to other occasions without modification.
Claims (7)
1. The strong acid resistant modified chlorosulfonated polyethylene rubber is characterized by comprising the following steps:
(1) dissolving 2-4kg of chlorosulfonated polyethylene in toluene, adding 1-2kg of chloroprene, 30-60g of initiator and 10-20g of catalyst into the solution, degassing for 25-30min by using inert gas, reacting for 6-8h at the temperature of 60-80 ℃, and naturally cooling to obtain a polychloroprene-polychloroprene sulfonated polyethylene copolymer solution;
(2) slowly adding the polychloroprene-sulfonated polyethylene copolymer solution obtained in the step (1) into water to precipitate the copolymer, shearing the polymer for 15-25min by using a high-speed shearing emulsifying machine under the conditions of 10000-12000rpm, centrifugally collecting the precipitate, washing the precipitate for 2-3 times by water, and drying to obtain the polychloroprene-sulfonated polyethylene copolymer;
(3) soaking the polychloroprene-sulfonated polyethylene copolymer obtained in the step (2) in a polydimethylsiloxane solution, performing ultrasonic treatment for 20-30min under the condition of 400-600W, filtering to obtain a solid, and curing the solid for 20-30min at 100 ℃ to obtain modified chlorosulfonated polyethylene rubber;
(4) uniformly mixing the modified chlorosulfonated polyethylene rubber, the antioxidant, the plasticizer, the filler and the accelerator, then placing the mixture into a rubber internal mixer, internally mixing the mixture for 3 to 5min at the conditions of 180 ℃ and 800rpm of 160-;
wherein the accelerant is phenyl salicylate, calcium sulfate whisker powder and zinc oxide, and the mass ratio of the accelerant to the calcium sulfate whisker powder is 1: 1: 1 mass ratio.
2. The strong acid resistant modified chlorosulfonated polyethylene rubber of claim 1, wherein the inert gas in step (1) is one of nitrogen, argon and neon.
3. The strong acid resistant modified chlorosulfonated polyethylene rubber of claim 1, wherein the initiator in step (1) is one of azobisisobutyronitrile, azobisisoheptonitrile, and tert-butyl hydroperoxide; the catalyst is one of CuBr 2, FeBr 3, CuCl 2 and FeCl 3.
4. The strong acid resistant modified chlorosulfonated polyethylene rubber of claim 1, wherein the particle size of the polychloroprene-polychloroprene sulfonated polyethylene copolymer obtained in step (2) is not more than 1 μm.
5. The strong acid resistant modified chlorosulfonated polyethylene rubber according to claim 1, wherein the polydimethylsiloxane solution of step (3) is one of tetrahydrofuran, ethyl acetate and dichloromethane solution of polydimethylsiloxane; the concentration of the polydimethylsiloxane in the polydimethylsiloxane solution is 0.05-0.1 g/mL.
6. The strong acid resistant modified chlorosulfonated polyethylene rubber of claim 1, wherein the antioxidant of step (4) is one of tea polyphenol, vitamin E, beta carotene; the plasticizer is an epoxy fatty acid ester antioxidant; the filler is one of titanium dioxide, silicon dioxide and aluminum oxide.
7. The strong acid resistant modified chlorosulfonated polyethylene rubber according to claim 1, wherein the chlorosulfonated polyethylene rubber in the step (4), the antioxidant, the plasticizer, the filler and the accelerator are sequentially calculated according to mass fractions: 90-95 parts, 1-2 parts, 0.5-1 part, 5-10 parts and 1-3 parts.
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Citations (3)
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|---|---|---|---|---|
| US3594451A (en) * | 1967-10-26 | 1971-07-20 | Du Pont | Chlorosulfonated polyethylene graft polymers |
| CN1165831A (en) * | 1997-03-13 | 1997-11-26 | 华东理工大学 | Method for prepn. of rubber and vinyl monomer graft polymer |
| CN101550256A (en) * | 2009-05-08 | 2009-10-07 | 尤建义 | Preparation method of environmental protection chlorosulfonated polyethylene rubber |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3594451A (en) * | 1967-10-26 | 1971-07-20 | Du Pont | Chlorosulfonated polyethylene graft polymers |
| CN1165831A (en) * | 1997-03-13 | 1997-11-26 | 华东理工大学 | Method for prepn. of rubber and vinyl monomer graft polymer |
| CN101550256A (en) * | 2009-05-08 | 2009-10-07 | 尤建义 | Preparation method of environmental protection chlorosulfonated polyethylene rubber |
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| CN109851974A (en) | 2019-06-07 |
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Effective date of registration: 20210715 Address after: 317 200 Daheng Village, Sanhe Town, Tiantai County, Taizhou City, Zhejiang Province Applicant after: Tiantai Pengyu Rubber Co.,Ltd. Address before: 6C, Xiangjiang garden, 108 Jiahe Road, Siming District, Xiamen City, Fujian Province, 361000 Applicant before: Wang Dexiu |
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