CN109354809A - A kind of fluoro-rubber composite of high Shao Er hardness - Google Patents
A kind of fluoro-rubber composite of high Shao Er hardness Download PDFInfo
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- CN109354809A CN109354809A CN201811342339.4A CN201811342339A CN109354809A CN 109354809 A CN109354809 A CN 109354809A CN 201811342339 A CN201811342339 A CN 201811342339A CN 109354809 A CN109354809 A CN 109354809A
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- vulcanizing agent
- rubber composite
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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
- 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
Abstract
The invention discloses a kind of fluoro-rubber composites of high Shao Er hardness, the content of each component in the fluoro-rubber composite, in parts by weight are as follows: 100 parts of crude fluororubber, 3~10 parts of acid absorbent, 2~10 parts of calcium hydroxide, 1~3 part of organic wax, 0.5~6 part of polyphenol amine vulcanizing agent, 0.2~2 part of promotor, 10~40 parts of filler, 1~10 part of LCA；Phenolic hydroxyl group and an amino are contained at least two in the structure of the polyphenol amine vulcanizing agent.The present invention uses polyphenol amine curing agents system, by increasing more crosslinking points in sulfidation and forming cross-linked network, greatly improve the hardness and strength of fluorubber, the traditional bis-phenol vulcanizing system of very good solution improves poor fluidity caused by hardness by increasing filler and is difficult the problem of accomplishing 90 degree or more hardness, ensure that the fluorubber product under high-temperature liquid gas medium environment to the endurance of high pressure.And simple production process of the present invention, lower production costs, it is convenient for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of fluoro-rubber composites of high Shao Er hardness, belong to field of rubber technology.
Background technique
Fluorubber refers to the macromolecular elastomer that fluorine atom is connected on the carbon atom of molecular backbone or side chain.In fluorubber point
In minor structure, greatly, and fluorine atom covalent radius (0.064nm) is equivalent to C-C key key to the bond energy (435~485kJ/mol) of C-F key
Long half, C-C segment are protected well by fluorine atom, and therefore, fluorubber has the chemical stability of height and heat steady
It is qualitative, it is one kind that medium-resistance is best in current all elastic body, can be widely used for aerospace, automobile, machinery, petrochemical industry
Deng.
Under some particular surroundings, need very high hardness meet with some special camera oil, lubricating oil,
The high temperature and high pressure environment of the oil gas mediums such as fuel oil and sulfur dioxide, it usually needs be just able to satisfy using fluorubber material product.
The sealed loop-pad etc. on packing element and some high-temperature services for bearing larger pressure especially used on oil gas field packer, needs
Bear 70Mpa pressure above, but compression ratio require be not it is too high, be typically necessary hardness and reach 90 degree or more, even as high as
95 degree or more.Therefore, it is necessary to be exactly to increase more benefit to general fluorubber material raising intensity and hardness, common practice
Strong filler and limited vulcanizing agent, but such method is difficult to make the hardness of fluorubber material to accomplish 90 degree or more, and due to
It is excessive to add filler, causes mobility very poor, intensity is also extremely difficult to require, and product rejection rate is very high or even cannot be closed
Lattice product.
In the prior art, there are also methods to be used to prepare the relatively high fluorubber material of hardness.Such as application No. is
Disclose a kind of high rigidity fluorubber and preparation method thereof in 201310170083.4 patent application, the composition of the fluorubber at
Divide as follows according to parts by weight: 100 parts of fluorubber, 13~18 parts of magnesia, 50~70 parts of carbon black N990, low molecular weight are poly-
1 part of ethylene (617A), 0.2~0.7 part of dibutyl ester, 2~4 parts of vulcanizing agent, 0.2~0.7 part of stearic acid.It is adopted in foregoing invention
With the fluorubber of high molecular weight, vulcanized using bisphenol AF/BPP, and being equipped with ligh structure SRF is reinforcing agent, can be produced
High rigidity sizing material.However, testing through experiment, the maximum pressure range that can be born by fluorubber material obtained by the above method is
18~20Mpa, hardness number range are 85~90shore.For another example application No. is public in 201210048315.4 patent application
It has opened a kind of High-strength fluorine rubber and preparation method, fluorine rubber seal element, its component of above-mentioned fluorubber and content is as follows: fluorubber
80~120 parts, 10~50 parts of carbon black, 0.5~1.5 part of -2.5 bis(t-butylperoxy) hexane of 2.5- dimethyl, triolefin
1.5~2.5 parts of propyl fulminuric acid ester, 3~7 parts of indirect process zinc oxide, 0.5~1 part of palm wax.To synthesis in foregoing invention
Hardness, intensity and the elongation of fluorubber detected, hardness is 75 ± 5 degree, intensity >=16MPa, elongation >=
180% synthetic rubber is qualified synthetic rubber.
Fluorubber material obtained in above-mentioned two patent application all has higher compared with conventional fluorubber material
Hardness and strength, but its hardness is unable to reach 90 degree of shore hardness or more, is unable to satisfy the use demand of some special occasions.
Application No. is disclosed in 201310542847.8 patent of invention a kind of high-temperature and high-presure resistent fluoroelastomer glue stock and
Preparation method and application.The high-temperature and high-presure resistent fluoroelastomer glue stock includes the fluorubber of 100 mass parts, 3~15 mass parts
Acid absorbent, the filler of 0~30 mass parts, the processing aid of 0~3 mass parts, the vulcanizing agent of 0.1~0.6 mass parts, 1~6
The Fanglun slurry cake of mass parts and 1~6 mass parts spray carbon black.High temperature high voltage resistant fluorubber glue is also disclosed in foregoing invention patent
The preparation method of material.The fluoroelastomer glue stock that the above method is prepared, with resistance to 180~225 DEG C or more of high temperature, Yi Jinai
The characteristics of high pressure of 100~150MPa, product can satisfy the use under harsh working condition, and have very high hardness,
Modulus and stress at definite elongation；It may infer that crosslinking points are less from the invention using the vulcanizing agent of 0.1~0.6 part of mass fraction, very
Hardness is done height by difficulty, and the invention is also without illustrating that can specific hardness reach 90 degree or more, while its preparation process is complicated, work
Sequence is various.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is by the way that a kind of polyphenol amine is added in existing fluorubber
Vulcanizing agent obtains fluorubber group of the Shao Er hardness at 95 degree or more by the cladodification crosslinking rate during raising vulcanizable fluororubber
Object is closed, the high intensity and high rigidity use demand of fluorubber product are met；And fluoro-rubber composite provided by the invention its production
Simple process, lower production costs are convenient for large-scale industrial production.
The technical proposal for solving the technical problem of the invention is: a kind of fluoro-rubber composite of high Shao Er hardness, institute
Fluoro-rubber composite is stated mainly by crude fluororubber, acid absorbent, calcium hydroxide, organic wax, polyphenol amine vulcanizing agent, promotor, more
Function additive LCA, filler are process；
The content of each component, in parts by weight are as follows:
100 parts of crude fluororubber
3~10 parts of acid absorbent
2~10 parts of calcium hydroxide
1~3 part of organic wax
0.5~6 part of polyphenol amine vulcanizing agent
0.2~2 part of promotor
10~40 parts of filler
1~10 part of LCA；
Phenolic hydroxyl group and an amino are contained at least two in the structure of the polyphenol amine vulcanizing agent.
Further, the content of each component, in parts by weight are as follows:
100 parts of crude fluororubber
3~7 parts of acid absorbent
2~8 parts of calcium hydroxide
1~3 part of organic wax
0.5~5 part of polyphenol amine vulcanizing agent
0.2~2 part of promotor
20~30 parts of filler
2~8 parts of LCA.
Further, the crude fluororubber includes by one of vinylidene, tetrafluoroethene, perfluoropropene or two
Kind or more monomer synthesis.
Further, the polyphenol amine vulcanizing agent can be 5- amino-Resorcinol, 6- amino -1,3,5- benzene three
Phenol, 4- ethylamino -1,3- benzenediol, 5- ethylamino -1,3- benzenediol or 4- ethylamino -1,3,5- benzenetriol.
The fluoro-rubber composite of above-mentioned high Shao Er hardness is processed using general purpose rubber processing technology.The specific method is as follows: fluorine
Rubber raw rubber mastication 1~after five minutes in mixer, other raw materials are put into together, and mixing is to after 80~120 degree, in mill
Thin pass-out piece is cooling on machine, thin 3~8 times logical after parking curing 24 hours or more, slice cooling packing.
Polyphenol amine curing agents is used in the present invention and replaces traditional bisphenols vulcanizing agent, and curingprocess rate is fast, due to one
A polyphenol amine can provide three or three or more crosslinking points, and same amount of molecular number will provide at least 1.5 times of friendship
Join density, to improve the hardness and strength of product, the Shao Er hardness of obtained fluorubber material can be to 95 degree or more；Due to not
It is to improve hardness by adding more fillers, filler is less, and mobility is unaffected, while compensating for filler and excessively cause
Defect probability increase, intensity decline the problem of, job efficiency can reach 100%.
The beneficial effects of the present invention are: compared with prior art, the present invention is led to by using polyphenol amine curing agents system
It crosses and increases more crosslinking points during vulcanizable fluororubber and form non-linear cross-linked network, greatly improve fluoro-rubber composite
Crosslink density achieve the purpose that improve hardness and strength, the traditional bis-phenol vulcanizing system crosslinking points of very good solution are limited,
And be linearly to be crosslinked, improve hardness mainly by filler is increased, so as to cause poor fluidity, be difficult to accomplish 90 degree or more it is hard
Degree, can not guarantee fluorubber product under high-temperature liquid gas medium environment to the endurance of high pressure.In addition, fluorine rubber provided by the invention
Glue composition curingprocess rate is fast, and simple production process, lower production costs are convenient for large-scale industrial production.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Embodiment 1
A kind of fluoro-rubber composite of high Shao Er hardness, the content of the fluoroelastomer each component, in parts by weight are as follows:
100 parts of binary fluorine rubber raw rubber F26
5 parts of acid absorbent (magnesia)
6 parts of calcium hydroxide
1 part of organic wax
2.5 parts of benzenediol of 5- amino -1,3-
0.4 part of promotor (bpp)
30 parts of filler (carbon black N990)
3 parts of LCA
Above-mentioned fluoro-rubber composite the preparation method is as follows:
Fluorubber is plasticated 3 minutes in mixer, and put into every other powder (can put into) mixing to after 80~120 degree twice,
Thin pass-out piece is cooling on a mill, thin 3~8 times logical after parking curing 24 hours or more, slice cooling packing.
Embodiment 2
A kind of fluoro-rubber composite of high Shao Er hardness, the binary fluorine rubber raw rubber F26 in the composition each component are substituted for
Ternary fluororubber F246, remaining component and preparation method are the same as embodiment 1.
Embodiment 3
A kind of fluoro-rubber composite of high Shao Er hardness, polyphenol amine vulcanizing agent in the composition each component by amino -1 5-,
3- benzenediol is changed to 4- ethylamino-Resorcinol, and dosage is 3 parts.Remaining component and preparation method are the same as embodiment 1.
Comparative example 1
100 parts of binary fluorine rubber raw rubber F26
4 parts of magnesia
6 parts of calcium hydroxide
50 parts of carbon black N990
1.8 parts of bisphenol AF
0.5 part of promotor (bpp)
1 part of organic wax
3 parts of LCA
The preparation method is the same as that of Example 1.
Comparative example 2
100 parts of ternary fluororubber raw rubber F246
4 parts of magnesia
6 parts of calcium hydroxide
50 parts of carbon black N990
1.8 parts of bisphenol AF
0.5 part of promotor (bpp)
1 part of organic wax
3 parts of LCA
The preparation method is the same as that of Example 1.
Following table is the performance test results of composition described in Examples 1 to 3 and comparative example 1~2 and its product.
As it can be seen that the intensity of obtained each fluoro-rubber composite is high from above embodiments 1~3, qualification rate reaches 100%, Shao
That hardness is up to 95 degree or more.
The above embodiments are only used to illustrate the present invention, and not limitation of the present invention, in relation to the common of technical field
Technical staff can also make various modifications and improvements, therefore all without departing from the spirit and scope of the present invention
Equivalent technical solution also belongs to scope of the invention, and scope of patent protection of the invention should be defined by the claims.
Claims (4)
1. a kind of fluoro-rubber composite of high Shao Er hardness, it is characterised in that: the fluoro-rubber composite is mainly given birth to by fluorubber
Glue, acid absorbent, calcium hydroxide, organic wax, polyphenol amine vulcanizing agent, promotor, multifunctional assistant LCA, filler are process；
The content of each component, in parts by weight are as follows:
100 parts of crude fluororubber
3~10 parts of acid absorbent
2~10 parts of calcium hydroxide
1~3 part of organic wax
0.5~6 part of polyphenol amine vulcanizing agent
0.2~2 part of promotor
10~40 parts of filler
1~10 part of LCA；
Phenolic hydroxyl group and an amino are contained at least two in the structure of the polyphenol amine vulcanizing agent.
2. the fluoro-rubber composite of a kind of high Shao Er hardness according to claim 1, it is characterised in that: each component
Content, in parts by weight are as follows:
100 parts of crude fluororubber
3~7 parts of acid absorbent
2~8 parts of calcium hydroxide
1~3 part of organic wax
0.5~5 part of polyphenol amine vulcanizing agent
0.2~2 part of promotor
20~30 parts of filler
2~8 parts of LCA.
3. according to claim 1 or a kind of fluoro-rubber composite of high Shao Er hardness described in 2, it is characterised in that: described
Crude fluororubber includes being synthesized by one or more of vinylidene, tetrafluoroethene, perfluoropropene monomer.
4. according to claim 1 or a kind of fluoro-rubber composite of high Shao Er hardness described in 2, it is characterised in that: described
Polyphenol amine vulcanizing agent can be 5- amino -1,3- benzenediol, 6- amino -1,3,5- benzenetriol, 4- ethylamino -1,3- benzenediol,
5- ethylamino -1,3- benzenediol or 4- ethylamino -1,3,5- benzenetriol.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811342339.4A CN109354809B (en) | 2018-11-13 | 2018-11-13 | high-Shore-hardness fluororubber composition |
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| CN201811342339.4A CN109354809B (en) | 2018-11-13 | 2018-11-13 | high-Shore-hardness fluororubber composition |
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| CN109354809B CN109354809B (en) | 2021-01-08 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851958A (en) * | 2019-03-20 | 2019-06-07 | 成都菁尚科技有限公司 | A kind of high rigidity fluorubber and preparation method thereof |
| CN114621541A (en) * | 2022-04-11 | 2022-06-14 | 江苏千富之丰科技有限公司 | High-temperature-resistant oil-resistant fluorine-containing elastomer composition |
| CN114656736A (en) * | 2022-04-11 | 2022-06-24 | 江苏千富之丰科技有限公司 | Oil-resistant easy-to-process fluorine-containing elastomer composition |
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| US4525539A (en) * | 1982-12-02 | 1985-06-25 | E. I. Du Pont De Nemours And Company | Vulcanizable nitrile-containing perfluoroelastomer |
| CN1946793A (en) * | 2004-04-28 | 2007-04-11 | 大金工业株式会社 | Fluorine-containing elastomer composition and molded article formed therefrom |
| CN101296989A (en) * | 2005-10-27 | 2008-10-29 | 大金工业株式会社 | Crosslinkable composition and molded article made of same |
| CN104672491A (en) * | 2015-03-11 | 2015-06-03 | 江苏千富之丰科技有限公司 | Novel fluororubber vulcanizer and preparation method thereof |
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2018
- 2018-11-13 CN CN201811342339.4A patent/CN109354809B/en active Active
Patent Citations (4)
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|---|---|---|---|---|
| US4525539A (en) * | 1982-12-02 | 1985-06-25 | E. I. Du Pont De Nemours And Company | Vulcanizable nitrile-containing perfluoroelastomer |
| CN1946793A (en) * | 2004-04-28 | 2007-04-11 | 大金工业株式会社 | Fluorine-containing elastomer composition and molded article formed therefrom |
| CN101296989A (en) * | 2005-10-27 | 2008-10-29 | 大金工业株式会社 | Crosslinkable composition and molded article made of same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109851958A (en) * | 2019-03-20 | 2019-06-07 | 成都菁尚科技有限公司 | A kind of high rigidity fluorubber and preparation method thereof |
| CN114621541A (en) * | 2022-04-11 | 2022-06-14 | 江苏千富之丰科技有限公司 | High-temperature-resistant oil-resistant fluorine-containing elastomer composition |
| CN114656736A (en) * | 2022-04-11 | 2022-06-24 | 江苏千富之丰科技有限公司 | Oil-resistant easy-to-process fluorine-containing elastomer composition |
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