CN114621542A - Fluororubber composition containing silane fluorine ester - Google Patents
Fluororubber composition containing silane fluorine ester Download PDFInfo
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- CN114621542A CN114621542A CN202210376073.5A CN202210376073A CN114621542A CN 114621542 A CN114621542 A CN 114621542A CN 202210376073 A CN202210376073 A CN 202210376073A CN 114621542 A CN114621542 A CN 114621542A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/16—Homopolymers or copolymers or vinylidene fluoride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/385—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing halogens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/20—Homopolymers or copolymers of hexafluoropropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a fluororubber composition containing silane fluorine ester, which mainly comprises silane fluorine ester, binary or multi-component fluororubber, filler, vulcanizing agent, accelerator and acid acceptor; the contents of the components are as follows according to parts by weight: 0.5-10 parts of silane fluorine ester, 100 parts of binary or multi-component fluororubber, 1-4 parts of vulcanizing agent, 3-25 parts of acid absorbent, 0.1-2 parts of accelerator and 0-60 parts of filler; the preparation method of the silane fluorine ester comprises the following steps: adding epoxy silicone oil, tetrafluorosuccinic acid and pentafluoropropionic acid into toluene, adding triethylamine catalyst and a proper amount of polymerization inhibitor to carry out esterification reflux reaction on methoxyphenol at 100-120 ℃, stopping the reaction when the acid value is less than 0.5, and removing the solvent to obtain the silane fluorine ester. According to the invention, the silane fluoro-ester with medium and low molecular weight is added into the fluororubber, so that the fluororubber is softened, and the fluidity, the demolding property and the roll separation property of the fluororubber are improved. The fluorine-containing elastomer has better solvent resistance, processing manufacturability, high temperature resistance, corrosion resistance and good mechanical strength.
Description
Technical Field
The invention relates to a fluororubber composition containing silane fluorine ester, belonging to the technical field of rubber materials.
Background
The problems of high rigidity, mold sticking, roller sticking and the like of the fluororubber, and high temperature resistance and oil resistance of the fluororubber are required, so that the problems of no high temperature resistance, great reduction of oil resistance, great reduction of physical and mechanical properties and the like of the traditional scheme of using rubber oil charge as a softening agent are not adopted. Palm wax, organic wax or organic silicon high molecular polymer is usually added as an internal release agent and a plasticizer, the physical and mechanical properties are reduced due to too large addition amount, the effect is not ideal due to too small addition amount, and particularly the problem that fluororubber with large rigidity needs to be softened while maintaining good physical and mechanical properties cannot be well solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to soften the fluororubber and improve the fluidity, the mold release property and the roll separation property of the fluororubber by adding the silane fluorine ester with low and medium molecular weight into the fluororubber. The fluorine-containing elastomer has better solvent resistance, processing manufacturability, high temperature resistance, corrosion resistance and good mechanical strength.
The technical scheme adopted by the invention for solving the technical problem is as follows: a fluororubber composition containing silane fluorine ester, the fluororubber composition mainly comprises silane fluorine ester, binary or multi-component fluororubber, filler, vulcanizing agent, accelerator, acid acceptor; the contents of the components are as follows according to parts by weight:
the preparation method of the silane fluorine ester comprises the following steps: adding epoxy silicone oil, tetrafluorosuccinic acid and pentafluoropropionic acid into toluene, adding triethylamine catalyst and a proper amount of polymerization inhibitor to carry out esterification reflux reaction on methoxyphenol at 100-120 ℃, stopping the reaction when the acid value is less than 0.5, and removing the solvent to obtain the silane fluorine ester.
Further, the content of each component is as follows according to parts by weight:
further, the general structural formula of the silane fluorine ester is as follows:
wherein R is1、R2Is any one of methyl, phenyl and ethyl, R1、R2May be the same or different; n is more than or equal to 1, and m is more than or equal to 1.
Furthermore, in the silane fluorine ester, n is more than or equal to 50 and more than or equal to 1, and m is more than or equal to 20 and more than or equal to 1.
Preferably, in the silane fluorine ester, 20 is more than or equal to n and more than or equal to 1, and 10 is more than or equal to m and more than or equal to 1.
Further, the binary or multicomponent fluororubber comprises ternary fluororubber polymerized by vinylidene fluoride, tetrafluoroethylene and perfluoropropylene, or binary fluororubber polymerized by vinylidene fluoride and perfluoropropylene.
In the method for preparing the silane fluorine ester, the epoxy silicone oil is generally obtained by polymerizing two or more siloxanes and is blocked by an epoxy group.
Further, the vulcanizing agent is any one or combination of a plurality of phenolic vulcanizing agents, amine vulcanizing agents and phenolic amine vulcanizing agents.
Further, the filler is general filler for fluororubber, and comprises diatomite, silicate, aluminosilicate, aluminum magnesium silicate, carbon black and inert organic filler; the accelerant is universal benzyl triphenyl phosphonium salt and amine accelerant for fluororubber.
Adding silane fluoro ester into fluororubber, adding necessary fluororubber general-purpose vulcanizing agent, acid absorbent, accelerator and a small amount of internal release agent, and mixing by conventional fluororubber mixing process to obtain the fluoroelastomer composition containing silane fluoro ester. The silane fluorine ester is very stable, has good high-temperature and solvent resistance, has good compatibility with fluororubber, plays a good role in softening and plasticizing, achieves a good effect of an internal mold release agent, and greatly improves the roll-separating property. The problem that the common softener is not high-temperature resistant and solvent-intolerant and is difficult to remove during secondary vulcanization, so that negative effects are caused on physical and mechanical properties is solved, and silane fluorine ester is decomposed to generate free radicals after being attacked by high heat energy and the side chain of fluororubber is further subjected to crosslinking cyclization and other effects, so that a certain heat compensation effect is exerted on the fluororubber, and the effect of inhibiting strength reduction is exerted. Meanwhile, the silane fluorine ester is liquid or low-melting-point solid, has excellent compatibility with a vulcanizing agent and an accelerant, plays a good dispersing role for the vulcanizing agent and the accelerant, and also plays a good role in helping physical and mechanical properties.
The invention has the beneficial effects that: compared with the prior art, the invention not only maintains the physical and mechanical properties, better heat-resistant and oil-resistant properties and very good processing property of the fluororubber elastomer by adding the silane fluorine ester into the fluororubber, but also ensures that the properties of the composition can be well exerted by adopting a simple conventional process without adopting a high-mixing-property high-energy-consumption hydraulic internal mixer and a harsh high-thin-pass-rate open mill in the process of producing the fluororubber elastomer composition; simple process, low production cost and easy industrial popularization.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Preparation of methylsilane fluoroester:
396 g of methyl epoxy silicone oil (with an epoxy value of 0.3-0.35) and 78 g of tetrafluorosuccinic acid are put into a three-neck flask filled with toluene, 0.7 g of triethylamine and 0.3 g of p-methoxyphenol are added, after heating reflux dehydration reaction is carried out for half an hour, 6.4 g of pentafluoropropionic acid with the concentration of 10% is slowly dripped, the dripping reaction is carried out for 2 hours, the reaction is stopped when the acid value is less than 1.5mgKOH/g, and the solvent is removed by reduced pressure distillation. Cooling to obtain methylsilane fluoroester for later use.
The method comprises the steps of banburying binary fluororubber FE2601(90 Mooney) polymerized by perfluoropropene and vinylidene fluoride, diatomite, magnesium oxide, calcium hydroxide, carnauba wax, bisphenol AF and BPP and methyl silane fluoro ester prepared by the steps in an internal mixer for 10 minutes at the temperature not higher than 90 ℃, then mixing for 5 times on an open mill according to 1mm thin pass, then discharging rubber sheets with the thickness of 2-2.5 mm, and observing and recording the roll separation effect in the open mill process.
The film was cured once in a 120x100x2 mold at 175 ℃ x10min and then cured once at 230 ℃ x24 h. The demolding property experiment and the adhesion oil seal experiment adopt vulcanization at 175 ℃ for 6 min. The mold release performance was evaluated by continuously pressing 100 times with 100O-rings Φ 2.0 × 8 (inside diameter) and recording the number of times that the sheets could not be automatically released.
Example 2
Preparation of phenylsilane fluorine ester:
adding 405 g of phenyl epoxy silicone oil (with an epoxy value of 0.28-0.32) and 59 g of tetrafluorosuccinic acid into a three-neck flask filled with toluene, adding 0.5 g of triethylamine and 0.2 g of p-methoxyphenol, heating, refluxing, dehydrating, reacting for 40 minutes, slowly dropwise adding 4.7 g of pentafluoropropionic acid with the concentration of 10%, reacting for about 3 hours dropwise, stopping the reaction when the acid value is less than 1.0mgKOH/g, distilling under reduced pressure to remove the solvent and the like, and cooling to obtain the phenylsilane fluorine ester for later use.
The rest of the procedure was the same as in example 1, and the amount of phenylsilane fluoride added was 3 parts.
Example 3
Preparation of methyl phenyl silane fluoro ester:
412 g of methyl phenyl epoxy silicone oil (with an epoxy value of 0.3-0.35) and 64 g of tetrafluorosuccinic acid are put into a three-neck flask filled with toluene, 0.6 g of triethylamine and 0.25 g of p-methoxyphenol are added, after heating reflux dehydration reaction is carried out for 40 minutes, 5.3 g of pentafluoropropionic acid with the concentration of 10% is slowly dripped, the reaction is stopped when the dropwise addition reaction lasts for 2.5-3 hours and the acid value is less than 1.0mgKOH/g, the solvent and the like are removed by reduced pressure distillation, and the methyl phenyl silane fluorine ester is obtained for standby application.
The other steps are the same as example 1, and the amount of the methylphenylsilane fluoride ester added is 2.6 parts.
Example 4
The fluororubber is replaced by FE2461 polymerized from vinylidene fluoride, tetrafluoroethylene and perfluoropropylene, and the Mooney index is 85. The rest is the same as example 1.
Example 5
The procedure of example 2 was repeated except that the fluororubber vulcanizing agent was changed to hexamethylenediamine 3# vulcanizing agent in an amount of 2.5 parts and no BPP was added.
Example 6
The amount of methylsilane fluoroester used was changed to 4 parts. The rest is the same as example 1.
Comparative example 1
Methyl silane fluoro ester was not added. The rest is the same as example 1.
Comparative example 2
Methyl silane fluoro ester was not added. The rest is the same as example 4.
The following table shows the results of various performance tests of the fluoroelastomers obtained in examples 1-6 and comparative examples 1-2.
The roller separation property is excellent when the film naturally droops and falls off, the film is excellent when the film follows half of the fast roller, the film wrapping fast roller is poor, and the fast and slow rollers are poor when the rubber materials are all in the range.
The experimental results show that the physical and mechanical properties of the fluororubber composition are maintained after the silane fluoroester prepared by the invention is added, the processing manufacturability is greatly improved, and the key is that the oil resistance is also maintained.
The above embodiments are only for illustrating the invention and are not to be construed as limiting the invention, and those skilled in the art can make various modifications and improvements without departing from the spirit and scope of the invention, therefore, all equivalent technical solutions also fall into the scope of the invention, and the scope of the invention is defined by the claims.
Claims (9)
1. A fluororubber composition containing a silane fluorine ester, characterized in that: the fluororubber composition mainly comprises silane fluorine ester, binary or multi-component fluororubber, filler, vulcanizing agent, accelerator and acid absorbent; the contents of the components are as follows according to parts by weight:
the preparation method of the silane fluorine ester comprises the following steps: adding epoxy silicone oil, tetrafluorosuccinic acid and pentafluoropropionic acid into toluene, adding triethylamine catalyst and a proper amount of polymerization inhibitor to carry out esterification reflux reaction on methoxyphenol at 100-120 ℃, stopping the reaction when the acid value is less than 0.5, and removing the solvent to obtain the silane fluorine ester.
2. The fluororubber composition according to claim 1, which comprises the following components: the contents of the components are as follows according to parts by weight:
3. the fluororubber composition according to claim 1 or 2, which contains a silane fluorine ester, characterized in that: the general structural formula of the silane fluorine ester is as follows:
wherein R is1、R2Is any one of methyl, phenyl and ethyl, R1、R2May be the same or different; n is more than or equal to 1, and m is more than or equal to 1.
4. The fluororubber composition according to claim 3, which comprises the following components: in the silane fluorine ester, n is more than or equal to 50 and more than or equal to 1, and m is more than or equal to 20 and more than or equal to 1.
5. The fluororubber composition according to claim 4, which comprises the following components: in the silane fluorine ester, n is more than or equal to 20 and more than or equal to 1, and m is more than or equal to 10 and more than or equal to 1.
6. The fluororubber composition according to claim 1, which comprises the following components: the binary or multicomponent fluororubber comprises ternary fluororubber polymerized by vinylidene fluoride, tetrafluoroethylene and perfluoropropylene, or binary fluororubber polymerized by vinylidene fluoride and perfluoropropylene.
7. The fluororubber composition according to claim 1, which comprises the following components: in the preparation method of the silane fluorine ester, the epoxy silicone oil is generally obtained by polymerizing two or more siloxanes, and the end of the epoxy silicone oil is blocked to be an epoxy group.
8. The fluororubber composition according to claim 1, which comprises the following components: the vulcanizing agent is any one or combination of a plurality of phenolic vulcanizing agents, amine vulcanizing agents and phenol amine vulcanizing agents.
9. A fluororubber composition containing silane fluorine ester according to claim 1, characterized in that: the filler is general filler for fluororubber and comprises diatomite, silicate, aluminosilicate, aluminum magnesium silicate, carbon black and inert organic filler; the accelerant is universal benzyl triphenyl phosphonium salt and amine accelerant for fluororubber.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005015711A (en) * | 2003-06-27 | 2005-01-20 | Toyo Seal Kogyo Kk | Fluororubber composition |
| CN104774411A (en) * | 2015-04-25 | 2015-07-15 | 江苏千富之丰科技有限公司 | Fluorine-containing elastomer with excellent low temperature and liquid resistance and preparation method thereof |
| CN109467855A (en) * | 2018-11-13 | 2019-03-15 | 江苏奥纳森弹性体技术研究院有限公司 | A kind of fluorubber of high temperature and pressure contracting ratio |
| CN112318972A (en) * | 2020-11-17 | 2021-02-05 | 王向 | Preparation method of non-woven fabric composite board |
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- 2022-04-11 CN CN202210376073.5A patent/CN114621542B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005015711A (en) * | 2003-06-27 | 2005-01-20 | Toyo Seal Kogyo Kk | Fluororubber composition |
| CN104774411A (en) * | 2015-04-25 | 2015-07-15 | 江苏千富之丰科技有限公司 | Fluorine-containing elastomer with excellent low temperature and liquid resistance and preparation method thereof |
| CN109467855A (en) * | 2018-11-13 | 2019-03-15 | 江苏奥纳森弹性体技术研究院有限公司 | A kind of fluorubber of high temperature and pressure contracting ratio |
| CN112318972A (en) * | 2020-11-17 | 2021-02-05 | 王向 | Preparation method of non-woven fabric composite board |
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