CN114656736A - Oil-resistant easy-to-process fluorine-containing elastomer composition - Google Patents
Oil-resistant easy-to-process fluorine-containing elastomer composition Download PDFInfo
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- CN114656736A CN114656736A CN202210376077.3A CN202210376077A CN114656736A CN 114656736 A CN114656736 A CN 114656736A CN 202210376077 A CN202210376077 A CN 202210376077A CN 114656736 A CN114656736 A CN 114656736A
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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
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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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 an oil-resistant easy-to-process fluorine-containing elastomer composition, which comprises 0.1-5 parts of high-fluoroalkyl ester, 100 parts of binary or multi-component fluororubber, 0-50 parts of filler, 1-5 parts of vulcanizing agent, 0.1-3 parts of accelerator, 4-25 parts of acid absorbent and 0.5-3 parts of internal mold release agent; the high-fluorine alkyl ester is polyhexafluoropropylene oxide methyl pentafluoropropionate. The preparation method of the polyhexafluoropropylene oxide methyl pentafluoropropionate comprises the following steps: the polyhexafluoropropylene oxide methyl pentafluoropropionate is obtained by carrying out reflux esterification dehydration reaction on polyhexafluoropropylene oxide monomethyl alcohol and pentafluoropropionic acid for 3-4 hours under the action of catalyst phosphoric acid. The invention achieves the purposes of softening the fluororubber and improving the fluidity, the demolding property and the roll separation property of the fluororubber by adding the fluoroalkyl ester with medium and low molecular weight into the fluororubber. The fluorine-containing elastomer has good solvent resistance, processing manufacturability, high temperature resistance, corrosion resistance and good mechanical strength.
Description
Technical Field
The invention relates to an oil-resistant easy-to-process fluorine-containing elastomer composition, and belongs 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 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 fluoroalkyl ester with medium and low molecular weight into the fluororubber. The fluorine-containing elastomer has good 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: an oil-resistant easy-to-process fluorine-containing elastomer composition, which mainly comprises high-fluorine alkyl ester, binary or multi-element fluorine rubber, a filler, a vulcanizing agent, an accelerator, an acid-absorbing agent and an internal release agent;
the contents of the components are as follows according to parts by weight:
the high-fluorine alkyl ester is polyhexafluoro epoxypropane pentafluoride methyl propionate, and the structural formula is as follows:
the preparation method of the polyhexafluoropropylene oxide methyl pentafluoropropionate comprises the following steps: the method comprises the steps of carrying out reflux esterification dehydration reaction on polyhexafluoropropylene oxide monomethyl alcohol and pentafluoropropionic acid for 3-4 hours under the action of catalyst phosphoric acid, and adding organic amine tetramethyl ammonium hydroxide to neutralize the phosphoric acid to obtain polyhexafluoropropylene oxide methyl pentafluoropropionate.
Further, the content of each component is as follows according to parts by weight:
furthermore, in the polyhexafluoropropylene oxide pentafluoropropionic acid methyl ester, n is more than or equal to 20 and is more than 2.
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.
Furthermore, the polyhexafluoropropylene oxide single methanol is polymerized by more than two pieces of hexafluoropropylene oxide, and the end capping is a methanol group; the high-fluorine alkyl ester is polyhexafluoropropylene oxide single methanol with the same polymerization degree or a mixture consisting of polyhexafluoropropylene oxide single methanol with a plurality of different polymerization degrees.
Further, the vulcanizing agent is any one or a combination of a plurality of phenolic vulcanizing agents, amine vulcanizing agents and phenolic amine vulcanizing agents.
Furthermore, the filler is general filler for fluororubber, and comprises diatomite, silicate, aluminosilicate, aluminum magnesium silicate, carbon black and inert organic filler.
Furthermore, the accelerator is a universal benzyl triphenyl phosphonium salt and amine accelerator for fluororubber.
Adding polyhexafluoropropylene oxide methyl pentafluoropropionate into fluororubber, and mixing with necessary general fluororubber vulcanizing agent, acid absorbent, accelerator and a small amount of internal mold release agent by a conventional fluororubber mixing process to obtain the oil-resistant easy-to-process fluorine-containing elastomer composition. Because only a small amount of C-H weak bonds are arranged on the molecular chain of the polyhexafluoropropylene oxide pentafluoropropionic acid methyl ester, and the rest are high-bond-energy F-C bonds and ether bonds, the polyhexafluoropropylene oxide pentafluoropropionic acid methyl ester is very stable, has good compatibility with fluororubber, plays a good role in softening and plasticizing, is surrounded by fluorine atoms in the molecular chain, is matched with a small amount of internal mold release agent for use, can achieve a good effect of the internal mold release agent, and greatly improves the roll-separating property. In the vulcanization process of the fluororubber, one HF is removed from H on the polyhexafluoropropylene oxide methyl pentafluoropropionate and F beside the polyhexafluoropropylene oxide methyl pentafluoropropionate under the action of alkali and an accelerator, a vacancy bond is formed, bisphenol or amine vulcanizing agents can easily perform a grafting reaction with the polyhexafluoropropylene oxide methyl pentafluoropropionate, and cross-linking with a fluororubber molecular chain is formed, so that the problems that a common softening agent does not have activity and the physical and mechanical properties are greatly influenced are solved, because the polyhexafluoropropylene oxide methyl pentafluoropropionate is cross-linked to the fluororubber molecular chain side chain, the polyhexafluoropropylene oxide methyl pentafluoropropionate is damaged after being attacked by high heat energy, a certain protection effect is realized on a main chain, and the high temperature resistance is not reduced but slightly improved. Meanwhile, the melting point of the polyhexafluoropropylene oxide methyl pentafluoropropionate is low, the polyhexafluoropropylene oxide methyl pentafluoropropionate has excellent compatibility with a vulcanizing agent and an accelerator, plays a good role in dispersing the vulcanizing agent and the accelerator, and also plays a good role in improving physical and mechanical properties.
The invention has the beneficial effects that: compared with the prior art, the invention adds the polyhexafluoropropylene oxide pentafluoropropionic acid methyl ester into the fluororubber, thereby not only improving the physical and mechanical properties of the fluororubber elastomer, but also ensuring that the fluororubber has excellent heat-resistant and oil-resistant properties and excellent processing technological properties, and the process for producing the fluororubber elastomer composition does not need to adopt a hydraulic internal mixer with high mixing performance and high energy consumption and a harsh open mill with high thin-pass rate, can ensure that the composition can well exert the properties by adopting a simple conventional process, has simple production process, low requirement on production equipment and easy industrial popularization.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
Preparation of polyhexafluoropropylene oxide methyl pentafluoropropionate:
454 g of hexafluoropropylene oxide dimer alcohol and 164 g of pentafluoropropionic acid are put into a three-neck flask, 0.98 g of phosphoric acid is added, the mixture is heated to reflux and is subjected to dehydration reaction for 3.5 hours, 2.73 g of tetramethylammonium hydroxide is dropwise added after the materials are transparent to react for 10 minutes, the distillate at 96-98 ℃ is removed by distillation, the acid value is less than 0.5, and the polyhexafluoropropylene oxide pentafluoropropionic acid methyl ester is obtained by cooling.
The method comprises the steps of internally mixing binary fluororubber FE2601(80 Mooney) polymerized by perfluoropropene and vinylidene fluoride, diatomite, magnesium oxide, calcium hydroxide, carnauba wax, bisphenol AF and BPP and the prepared polyhexafluoropropylene oxide pentafluoropropionic acid methyl ester in an internal mixer for 10 minutes at the temperature of not more than 90 ℃ according to the following proportion, then mixing for 5 times on an open mill according to 1mm thickness, then producing a film with the thickness of 2-2.5mm, and observing and recording the roll-off effect in the open mill process.
The rubber sheet is subjected to primary vulcanization in a mold of 120x100x2 at 175 ℃ x10min, and then subjected to secondary vulcanization 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
In the same manner as in example 1, the fluororubber was replaced with FE2461 (Mooney 75) obtained by polymerizing vinylidene fluoride, tetrafluoroethylene, and perfluoropropylene.
Example 3
In the same manner as in example 1, the fluororubber was changed to FEG2461, the fluorine content was 70%, the Mooney was 79, the amount of vulcanizing agent bisphenol AF added was 2.5 parts, and the bpp was 0.9 part.
Example 4
In the same manner as in example 1, the amount of methyl polyhexafluoropropyleneoxide pentafluoropropionate added was changed to 4 parts.
Example 5
In the same manner as in example 1, the vulcanization system was changed to hexamethylenediamine 3# vulcanizer in an amount of 2.5 parts without BPP.
Comparative example 1
In the same manner as in example 1, methyl polyhexafluoropropyleneoxide pentafluoropropionate was not added.
Comparative example 2
In the same manner as in example 2, methyl polyhexafluoropropyleneoxide pentafluoropropionate was not added.
Comparative example 3
In the same manner as in example 3, methyl polyhexafluoropropyleneoxypropane pentafluoropropionate was not added, and 2.2 parts of vulcanizing agent bisphenol AF and 0.8 part of bpp were added.
The following table shows the results of various performance tests of the fluoroelastomers obtained in examples 1 to 5 and comparative examples 1 to 3.
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.
Experimental results show that the fluorine-containing elastomer composition added with the polyhexafluoropropylene oxide methyl pentafluoropropionate prepared by the invention has the advantages of improving the physical and mechanical properties, greatly improving the processing manufacturability and improving the oil resistance.
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 (8)
1. An oil-resistant easy-to-process fluorine-containing elastomer composition is characterized in that: the fluorine-containing elastomer composition mainly comprises high-fluorine alkyl ester, binary or multi-element fluorine rubber, a filler, a vulcanizing agent, an accelerator, an acid acceptor and an internal release agent;
the contents of the components are as follows according to parts by weight:
the high-fluorine alkyl ester is polyhexafluoro epoxypropane pentafluoride methyl propionate, and the structural formula is as follows:
the preparation method of the polyhexafluoropropylene oxide methyl pentafluoropropionate comprises the following steps: the method comprises the steps of carrying out reflux esterification dehydration reaction on polyhexafluoropropylene oxide monomethyl alcohol and pentafluoropropionic acid for 3-4 hours under the action of catalyst phosphoric acid, and adding organic amine tetramethyl ammonium hydroxide to neutralize the phosphoric acid to obtain polyhexafluoropropylene oxide methyl pentafluoropropionate.
2. The oil resistant easy processing fluoroelastomer composition of claim 1, wherein: the contents of the components are as follows according to parts by weight:
3. the oil resistant easy processing fluoroelastomer composition of claim 1, wherein: in the polyhexafluoropropylene oxide pentafluoropropionic acid methyl ester, n is more than or equal to 20 and is more than 2.
4. The oil resistant easy processing fluoroelastomer composition of claim 1, wherein: the binary or multicomponent fluororubber comprises ternary fluororubber polymerized by vinylidene fluoride, tetrafluoroethylene and perfluoropropylene, or binary fluororubber polymerized by vinylidene fluoride and perfluoropropylene.
5. The oil resistant easy processing fluoroelastomer composition of claim 1, wherein: the polyhexafluoropropylene oxide single methanol is polymerized by more than two pieces of hexafluoropropylene oxide, and the end capping is a methanol group; the high-fluorine alkyl ester is polyhexafluoropropylene oxide single methanol with the same polymerization degree or a mixture consisting of polyhexafluoropropylene oxide single methanol with a plurality of different polymerization degrees.
6. The oil resistant easy processing fluoroelastomer composition of claim 1, wherein: the vulcanizing agent is any one or a combination of a plurality of phenolic vulcanizing agents, amine vulcanizing agents and phenolic amine vulcanizing agents.
7. The oil resistant easy processing fluoroelastomer composition of claim 1, wherein: the filler is general filler for fluororubber, and comprises diatomite, silicate, aluminosilicate, aluminum magnesium silicate, carbon black and inert organic filler.
8. The oil resistant easy processing fluoroelastomer composition of claim 1, wherein: the accelerant is universal benzyl triphenyl phosphonium salt and amine accelerant for fluororubber.
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| CN202210376077.3A CN114656736A (en) | 2022-04-11 | 2022-04-11 | Oil-resistant easy-to-process fluorine-containing elastomer composition |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06306241A (en) * | 1993-04-23 | 1994-11-01 | Asahi Glass Co Ltd | Fluorubber composition having improved vulcanizing property |
| CN104672724A (en) * | 2015-03-11 | 2015-06-03 | 江苏千富之丰科技有限公司 | Low temperature-resistant fluoroelastomer and preparation method thereof |
| 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 |
| CN109354809A (en) * | 2018-11-13 | 2019-02-19 | 江苏奥纳森弹性体技术研究院有限公司 | A kind of fluoro-rubber composite of high Shao Er hardness |
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2022
- 2022-04-11 CN CN202210376077.3A patent/CN114656736A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06306241A (en) * | 1993-04-23 | 1994-11-01 | Asahi Glass Co Ltd | Fluorubber composition having improved vulcanizing property |
| CN104672724A (en) * | 2015-03-11 | 2015-06-03 | 江苏千富之丰科技有限公司 | Low temperature-resistant fluoroelastomer and preparation method thereof |
| 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 |
| CN109354809A (en) * | 2018-11-13 | 2019-02-19 | 江苏奥纳森弹性体技术研究院有限公司 | A kind of fluoro-rubber composite of high Shao Er hardness |
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