CN104774411A - Fluorine-containing elastomer with excellent low temperature and liquid resistance and preparation method thereof - Google Patents
Fluorine-containing elastomer with excellent low temperature and liquid resistance and preparation method thereof Download PDFInfo
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- 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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- 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
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- 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
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Abstract
The invention discloses a fluorine-containing elastomer with excellent low temperature and liquid resistance and a preparation method thereof. The elastomer is prepared by thermally kneading and mixing the following components in parts by weight: 100 parts of fluororubber, 0-30 parts of acid absorbent, 0-35 parts of calcium hydroxide, 0-50 parts of reinforcing filler, 0-10 parts of plasticizer, 0.5-5 parts of vulcanizing agent, 0-5 parts of organic wax, 0.2-2 parts of accelerant, 1-30 parts of fluorosilicone alkane ester and 1-10 parts of multifunctional additive LCA. The fluorine-containing elastomer and the preparation method, which are provided by the invention, have the beneficial effects that the preparation method is simple and practicable and is lower in production cost; by adding fluorosilane ester to the components of the fluorine-containing elastomer and simultaneously matching fluorosilane ester with the multifunctional additive LCA, the low temperature brittleness temperature of an existing fluororubber compound is better decreased (Tg of the fluorine-containing elastomer can be reduced by about 5-10 DEG C) after the existing fluororubber compound undergoes primary or secondary vulcanization; meanwhile, the effects on the liquid resistance of the fluororubber are very small, so that the fluororubber can be more widely applied.
Description
Technical field
The present invention relates to fluoroelastomer of a kind of low temperature resistant, resistance to liquid excellent property and preparation method thereof, belong to field of rubber technology.
Background technology
The carbon atom that viton refers to molecular backbone chain or side chain is connected to the macromolecular elastomer of fluorine atom.In viton molecular structure; the bond energy (435 ~ 485kJ/mol) of C-F key is large; and fluorine atom covalent radius (0.064nm) is equivalent to the half of C-C key bond distance; C-C segment is well protected by fluorine atom; therefore; viton has chemical stability and the thermostability of height, is the one that in current all elastomericss, medium-resistance is best, can be widely used in aerospace, automobile, machinery, petrochemical complex etc.
But, one or more contain the multipolymer of the conventional fluorine-containing ethylene linkage unsaturated monomer of binary or ternary or mixture and there is an outstanding shortcoming by the viton that existing composition technology prepares: its low-temperature performance too poor (general Tg is not less than-21 DEG C), this far can not meet the requirement of market to its performance, especially in Aeronautics and Astronautics.At present, address this problem and mainly contain two kinds of methods: one adopts other materials to replace viton, such as in order to meet the seal request in low cold area, hydrogenated nitrile-butadiene rubber can be adopted to replace viton, but the price comparison of hydrogenated nitrile-butadiene rubber is expensive, its high temperature stability performance is also not ideal enough simultaneously; Another kind method, add the 3rd or the 4th monomer to reduce the Tg of viton at synthesis phase, thus improve the problem of its low temperature flexibility deficiency, on the basis of VDF, TFE monomer, such as introduce new monomer-perfluoro methyl vinyl ether (PMVE) carry out copolymerization, but this method needs to add considerable polymerization single polymerization monomer PMVE, its consumption is usually in 20% ~ 40%(molar fraction) between, not only complex manufacturing, and production cost is also very expensive.In existing production, usually adopt introduce silicone segments or and silicon rubber and mode improve the low-temperature performance of viton; But because silicon rubber and viton are completely inconsistent, linking agent and mechanism of crosslinking are also completely different, are difficult to add and form stable crossover network structure; Equally, because organosilyl resistance to fluidity is poor, although introduce the resistance to low temperature that organosilicon can improve organic fluorine rubber, but can to the energy of resistance to fluidity of organic fluorine rubber, particularly the resistance to fluidity of high temperature can cause very large impact.Therefore, by formula or the improvement of process aspect, make viton under the prerequisite retaining most original superiority, have better resistance to low temperature, this point tool has very great significance.
Summary of the invention
For the deficiencies in the prior art, object of the present invention adopts a kind of simple cost effective method exactly, on the basis of the binary or ternary fluororubber and composition thereof of existing maturation, by adding one or more silicon fluoride esters, coordinate a kind of multifunctional assistant LCA simultaneously, by existing fluorine glue composition through once or after post cure, make its low temperature brittleness temperature have one to float downward preferably, and resistance to fluidity impact is less, thus realize applying widely.
The technical scheme that technical solution problem of the present invention adopts is: a kind of fluoroelastomer of low temperature resistant, resistance to liquid excellent property, and described fluoroelastomer is mediated by crude fluororubber, acid-acceptor, calcium hydroxide, reinforced filling, softening agent, vulcanizing agent, promotor, multifunctional assistant LCA, organic wax, silicon fluoride ester through heat, mixingly to be formed.
The content of described each component, is by weight:
Crude fluororubber 100 parts
Acid-acceptor 0 ~ 30 part
0 ~ 35 part, calcium hydroxide
Reinforced filling 0 ~ 50 part
0 ~ 10 part, softening agent
Vulcanizing agent 0.5 ~ 5 part
Promotor 0.2 ~ 2 part
Multifunctional assistant LCA 1 ~ 10 part
0 ~ 5 part, organic wax
Silicon fluoride ester 1 ~ 30 part
Described silicon fluoride ester is one or more short chain silicon fluoride esters.
As preferably, the content of described each component, is by weight:
Crude fluororubber 100 parts
Acid-acceptor 8 ~ 12 parts
4 ~ 8 parts, calcium hydroxide
Reinforced filling 15 ~ 30 parts
3 ~ 6 parts, softening agent
Vulcanizing agent 1 ~ 3 part
Promotor 0.3 ~ 0.6 part
Multifunctional assistant LCA 2 ~ 4 parts
0 ~ 2.5 part, organic wax
Silicon fluoride ester 8 ~ 12 parts
In the moiety of above-mentioned low-temperature-resistant elastic body containing fluorine, multifunctional assistant LCA is a kind of auxiliary vulcanizing agent, using the inorganics of one or more vesicular structures as carrier, under the effect of organic fluorine catalyzer, through the low molecule mixture that surface adsorption is polymerized, fusing point lower (65 ~ 85 DEG C), surface is containing part short-chain hydroxyl, carboxyl isoreactivity group, most of polymer can be dissolved under hot melt state, particularly can dissolve unvulcanized viton well at about 90 DEG C.
Further, described silicon fluoride ester is one or more polyfluoro short chain silicon esters, and the silicone content in described polyfluoro short chain silicon ester is greater than 5%.
Further, described polyfluoro short chain silicon ester can be 1,1,8,8-tetramethyl-3,5,7-trifluoro propyl methylsiloxane-1, the two hendecoic acid ethyl ester, 1 of 3-, 1,8,8-tetramethyl--3,5,7-trifluoro propyl methylsiloxane-1, the two hendecoic acid butyl ester or 1 of 3-, 1,8, wherein a kind of or any two kinds and above mixture in 8-tetramethyl--3,5,7-trifluoro propyl methylsiloxane-1-ethyl acetate.
Add described silicon fluoride ester in crude fluororubber after, the Tg of the fluoroelastomer after processing can be made to decline, make this fluoroelastomer have good low temperature flexibility; And with other trifluoropropyl siloxane or add siliceous compound viton compared with there is better resistance to fluidity.
Further, described crude fluororubber comprises by the binary fluorine rubber of two or three monomer polymerization in vinylidene, tetrafluoroethylene, R 1216 or ternary fluororubber.
Further, described acid-acceptor is light magnesium oxide or activated magnesia, and the activity value of described activated magnesia is 50 ~ 180.Acid acceptor (i.e. acid-acceptor) is added, so that the hydrogen fluoride of separating out effectively and in vulcanizable fluororubber process in the cooperation of sizing material.Because hydrofluoric existence can hinder rubber further crosslinked and energy severe corrosion equipment, acid-acceptor can promote the raising of vulcanization crosslinking density, gives cross-linked rubber good thermostability.
Further, described reinforced filling is wherein one or more the mixing in Calucium Silicate powder, carbon black, barium sulfate, diatomite, the beautiful powder of silicon.Viton its cross-linked rubber when not adding weighting agent has higher intensity, though reinforcing and filling system has certain strengthening action to it, but mainly in order to reach improving technique performance, improve thermotolerance, the hardness of goods, the object such as reduce compression set and reduce costs.
Further, described vulcanizing agent is one or both the mixing in bisphenols vulcanizing agent or two amine curing agents; Described bisphenols vulcanizing agent is Resorcinol, dihydroxyphenyl propane, bisphenol AF or bisphenol S, and described two amine curing agentss are two-(4-ammonia hexyl cyclohexyl) methane carbaminate or N, N '-bis-times cinnamyls-1,6-diamines.-CH is there is in viton molecule
2-CF
2-chain link, due to the electronegativity that fluorine atom is extremely strong, make it, when heat and basic cpd (as amine, magnesium oxide etc.) exist, to be easy to the double bond that hydrogen fluoride forms easily polarization, this Fluorine containing olefine structure is easy to nucleophilic reagent as amine, phenols addition, and generates cross-link bond.
Further, described promotor is wherein one or more the mixing in BPP, benzyltriphenylphosphonium bromide phosphorus, quaternary ammonium salt.
The preparation method of the fluoroelastomer of above-mentioned low temperature resistant, resistance to liquid excellent property mainly comprises the following steps:
(1) by for subsequent use after appropriate reinforced filling, softening agent, vulcanizing agent, promotor, multifunctional assistant LCA, organic wax and the mixing of silicon fluoride ester;
(2) in Banbury mixer, add crude fluororubber, plasticate 1 ~ 2 minute, open water coolant, add the standby material in above-mentioned steps 1, mixing 2 ~ 3 minutes, then to proceed in mill thin-pass 10 times, slice cools and parks 24 hours, and back mixing slice cools to obtain finished product.
Because organosilyl low-temperature performance is very good, generally can reach subzero 40 ~ 60 degree, thus usually adopt in organic fluorine rubber introduce organosilane segment or and silicon rubber and mode reach low-temperature performance better.But because silicon rubber and viton are completely inconsistent, linking agent and mechanism of crosslinking are also completely different, are difficult to add and form stable crossover network structure.Meanwhile, because organosilyl resistance to fluidity is poor, although introduce the resistance to low temperature that organosilicon can improve organic fluorine rubber, but can to the energy of resistance to fluidity of organic fluorine rubber, particularly the resistance to fluidity of high temperature can cause very large impact.In order to retain its outstanding energy of resistance to fluidity while the resistance to low temperature improving organic fluorine rubber, the present invention introduces silicon fluoride ester in mixing component, it not only has the distinctive good solvent borne of organic ester, also there is organosilicon and the distinctive low-temperature performance advantage of short chain organic ester simultaneously, greatly compensate for the defect (the common organosilicon of low temperature brittleness Performance Ratio and organic fluorine composition reduce by more than 5 degree) of organic fluorine poor performance at low temperatures.Introduce in organosilicon fluorin radical again can high degree make up organosilicon resistance to fluidity deficiency bring resistance to fluidity not good to fluoro-rubber composite negative impact.The structure that the simultaneously combination of organic fluorinated silicone adds ester also high degree remain the resistant to elevated temperatures characteristic of organic fluorine rubber; Manufacturability overcomes general organosilicon and organic fluorine and not good enough by consistency, disperse the problems such as bad, reach splendid intermiscibility.
The invention has the beneficial effects as follows: compared with prior art, fluoroelastomer provided by the invention, it adopts a kind of preparation method of simple low cost, various advantage property retention is simultaneously better, on the basis of the binary or ternary fluororubber and composition thereof of existing maturation, by adding one or more silicon fluoride esters, coordinate a kind of multifunctional assistant LCA simultaneously, by existing fluorine glue composition through once or after post cure, its low temperature brittleness temperature is made to have splendid float downward (Tg of fluoroelastomer can reduce about 10 DEG C); Also make to minimize (than the resistance to fluidity of trifluoropropyl siloxane superior 40%) the resistance to fluidity impact of viton, it is better that high thermal resistance also keeps, thus make this viton can realize applying widely simultaneously.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
embodiment 1
A fluoroelastomer for low temperature resistant, resistance to liquid excellent property, the content of each component of described fluoroelastomer, is by weight:
Binary fluorine rubber F26 100 parts
4 parts, magnesium oxide (active 120)
6 parts, calcium hydroxide
Calucium Silicate powder 20 parts
Bisphenol AF 2 parts
BPP 0.5 part
Multifunctional assistant LCA 3 parts
1 part, organic wax
The two hendecoic acid ethyl ester 12 parts of 1,1,8,8-tetramethyl-3,5,7-trifluoro propyl methylsiloxane-1,3-
The preparation method of the fluoroelastomer of above-mentioned low temperature resistant, resistance to liquid excellent property mainly comprises the following steps: (1) is by for subsequent use after appropriate reinforced filling, softening agent, vulcanizing agent, promotor, multifunctional assistant LCA, organic wax and the mixing of silicon fluoride ester;
(2) in Banbury mixer, add crude fluororubber, plasticate 1 ~ 2 minute, open water coolant, after adding the standby material in step 1 mixing 2 ~ 3 minutes, then to proceed in mill thin-pass 10 times, slice cools and parks 24 hours, and back mixing slice cools to obtain finished product.
embodiment 2
A fluoroelastomer for low temperature resistant, resistance to liquid excellent property, the silicon fluoride ester in each component of described fluoroelastomer replaces with the two hendecoic acid butyl ester of 1,1,8,8-tetramethyl--3,5,7-trifluoro propyl methylsiloxane-1,3-, adds number and becomes 12.2.All the other components and preparation method are all with embodiment 1.
embodiment 3
A fluoroelastomer for low temperature resistant, resistance to liquid excellent property, the silicon fluoride ester in each component of described fluoroelastomer replaces with 1,1,8,8-tetramethyl--3,5,7-trifluoro propyl methylsiloxane-1-ethyl acetate, and content becomes 10.3.All the other components and preparation method are all with embodiment 1.
embodiment 4
A fluoroelastomer for low temperature resistant, resistance to liquid excellent property, the content of each component of described fluoroelastomer is with above-described embodiment 1, and difference is: by the silicon fluoride ester in embodiment 1 with 5 part 1,1,8,8-tetramethyl--3,5,7-trifluoro propyl methylsiloxane-1-ethyl acetate and 6 part 1,1,8,8-tetramethyl--3, the mixture of the two hendecoic acid butyl ester of 5,7-trifluoro propyl methylsiloxane-1,3-substitutes; Binary fluorine rubber F26 ternary fluororubber F246 in embodiment 1 is substituted.Above-mentioned method for producing elastomers is with embodiment 1.
embodiment 5
A kind of fluoroelastomer of low temperature resistant, resistance to liquid excellent property, the content of each component of described fluoroelastomer is with above-described embodiment 4, difference is: change the ternary fluororubber F246 in embodiment 4 into binary fluorine rubber F26 and ternary fluororubber F246 and use, and its ratio is 1:1; Change the bisphenol AF in embodiment 4 into N, N '-bis-cinnamylidenes-1,6-diamines, does not add BPP by 3 parts.Above-mentioned method for producing elastomers is with embodiment 1.
comparative example 1:
Contrast difference with embodiment 1 to be not add silicon fluoride ester, all the other components and technique are all constant.
comparative example 2:
In order to embody the advantage of viton on the energy of resistance to fluidity obtained in above-described embodiment further, in this comparative example, rubber adopts the better trifluoropropyl siloxane of low-temperature performance, instead of the silicon fluoride ester in embodiment with fluorosilicon oil, counts by weight:
Methyl ethylene crude rubber of fluorinated silicone rubber 100 parts
Fluorosilicon oil 4.5 parts
White carbon black 45 parts
Two 253 parts
TAIC 1.2 parts
Following table is the performance test results of the sulphur sex change energy of fluoroelastomer in embodiment 1 ~ 5 and comparative example 1 ~ 2, cured properties and viton goods.
From above embodiment 1 ~ 5, it is good that the physical and mechanical properties of each fluoroelastomer all keeps, major embodiment is following 2 points: (1) low temperature brittleness: add after silicon fluoride ester, the low temperature brittleness of viton lowers all greatly, best reaches-30 DEG C (embodiments 1), 10 DEG C are reduced nearly than common fluorine glue formula (comparative example 1, Tg is for about-20 DEG C); (2) resistance to fluidity (resistance to ASTM3 standard oil): can find out from comparative example 2, although trifluoropropyl siloxane has good low temperature brittleness (-52 DEG C), but because rubber is fluorine silicon composition, and with the addition of fluorosilicon oil, it is very large to resistance to liquid performance impact, as can be seen from the above table, the mass change of comparative example 2 increases 10 times nearly than embodiment 1 ~ 5, volume change increases nearly 3 times, and comparative example 2 is compared with the viton (comparative example 1) of usually filling a prescription, and resistance to liquid performance variation is larger; And relatively under, introduce silicon fluoride ester (embodiment 1 ~ 5) in viton after, it is compared with the viton of usually fill a prescription, and the reduction degree of resistance to fluidity energy is very little.In summary, introduce silicon fluoride ester component in viton after, the resistance to low temperature of viton is well improved, simultaneously very little again on the impact of the resistance to fluidity energy of viton, solve the problem that existing trifluoropropyl siloxane and auxiliary agent cannot be taken into account both the resistance to low temperature of viton and the energy of resistance to fluidity, make the viton after improvement have application space more widely.
Above embodiment is only for illustration of the present invention; and be not limitation of the present invention; the those of ordinary skill of relevant technical field; without departing from the spirit and scope of the present invention; various amendment and improvement can also be made; therefore all equivalent technical schemes also belong to category of the present invention, and scope of patent protection of the present invention should be defined by the claims.
Claims (10)
1. a fluoroelastomer for low temperature resistant, resistance to liquid excellent property, is characterized in that: described fluoroelastomer is mediated by crude fluororubber, acid-acceptor, calcium hydroxide, reinforced filling, softening agent, vulcanizing agent, promotor, multifunctional assistant LCA, organic wax and silicon fluoride ester through heat, mixingly to be formed; The content of described each component, is by weight:
Crude fluororubber 100 parts
Acid-acceptor 0 ~ 30 part
0 ~ 35 part, calcium hydroxide
Reinforced filling 0 ~ 50 part
0 ~ 10 part, softening agent
Vulcanizing agent 0.5 ~ 5 part
Promotor 0.2 ~ 2 part
Multifunctional assistant LCA 1 ~ 10 part
0 ~ 5 part, organic wax
Silicon fluoride ester 1 ~ 30 part;
Described silicon fluoride ester is one or more short chain silicon fluoride esters.
2. according to the fluoroelastomer of a kind of low temperature resistant, the resistance to liquid excellent property described in claim 1, it is characterized in that: the content of described each component, is by weight:
Crude fluororubber 100 parts
Acid-acceptor 8 ~ 12 parts
4 ~ 8 parts, calcium hydroxide
Reinforced filling 15 ~ 30 parts
3 ~ 6 parts, softening agent
Vulcanizing agent 1 ~ 3 part
Promotor 0.3 ~ 0.6 part
Multifunctional assistant LCA 2 ~ 4 parts
0 ~ 2.5 part, organic wax
Silicon fluoride ester 8 ~ 12 parts.
3. the fluoroelastomer of a kind of low temperature resistant, resistance to liquid excellent property according to claim 1, is characterized in that: described silicon fluoride ester is one or more polyfluoro short chain silicon esters, and the silicone content in described polyfluoro short chain silicon ester is greater than 5%.
4. according to the fluoroelastomer of a kind of low temperature resistant, the resistance to liquid excellent property described in claim 3, it is characterized in that: described polyfluoro short chain silicon ester can be 1,1,8,8-tetramethyl-3,5, the two hendecoic acid ethyl ester, 1 of 7-trifluoro propyl methylsiloxane-1,3-, 1,8,8-tetramethyl--3,5,7-trifluoro propyl methylsiloxane-1, the two hendecoic acid butyl ester or 1 of 3-, 1,8,8-tetramethyl--3, wherein a kind of or any two kinds and above mixture in 5,7-trifluoro propyl methylsiloxane-1-ethyl acetate.
5. according to the fluoroelastomer of a kind of low temperature resistant, the resistance to liquid excellent property described in claim 1, it is characterized in that: described crude fluororubber comprises by the binary fluorine rubber of two or three monomer polymerization in vinylidene, tetrafluoroethylene, R 1216 or ternary fluororubber.
6. the fluoroelastomer of a kind of low temperature resistant, resistance to liquid excellent property according to claim 1, is characterized in that: described acid-acceptor is light magnesium oxide or activated magnesia, and the activity value of described activated magnesia is 50 ~ 180.
7. the fluoroelastomer of a kind of low temperature resistant, resistance to liquid excellent property according to claim 1, is characterized in that: described reinforced filling is wherein one or more the mixing in Calucium Silicate powder, carbon black, barium sulfate, diatomite, the beautiful powder of silicon.
8. the fluoroelastomer of a kind of low temperature resistant, resistance to liquid excellent property according to claim 1, is characterized in that: described vulcanizing agent is one or both the mixing in bisphenols vulcanizing agent or two amine curing agents; Described bisphenols vulcanizing agent is Resorcinol, dihydroxyphenyl propane, bisphenol AF or bisphenol S, and described two amine curing agentss are two-(4-ammonia hexyl cyclohexyl) methane carbaminate or N, N '-bis-times cinnamyls-1,6-diamines.
9. the fluoroelastomer of a kind of low temperature resistant, resistance to liquid excellent property according to claim 1, is characterized in that: described promotor is wherein one or more the mixing in BPP, benzyltriphenylphosphonium bromide phosphorus, quaternary ammonium salt.
10. a preparation method for the fluoroelastomer of low temperature resistant, the resistance to liquid excellent property according to any one in claim 1 to 9, is characterized in that: described preparation method mainly comprises the following steps:
(1) by for subsequent use after appropriate reinforced filling, softening agent, vulcanizing agent, promotor, multifunctional assistant LCA, organic wax and the mixing of silicon fluoride ester;
(2) in Banbury mixer, add crude fluororubber, plasticate 1 ~ 2 minute, open water coolant, then standby material in above-mentioned steps 1 is added mixing 2 ~ 3 minutes, then to proceed in mill thin-pass 10 times, slice cools and parks 24 hours, and back mixing slice cools to obtain finished product.
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| CN106380752A (en) * | 2016-08-31 | 2017-02-08 | 江苏千富之丰科技有限公司 | Super-high wear-resistant fluorine-containing elastomer and preparation method thereof |
| CN106674829A (en) * | 2016-12-12 | 2017-05-17 | 芜湖集拓橡胶技术有限公司 | Strong acid and alkali resistant red ternary fluorine rubber seal ring material formula |
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| CN108276710A (en) * | 2018-01-19 | 2018-07-13 | 合肥净龙环保科技有限公司 | A kind of low temperature resistant fluorubber composite material and preparation method and application |
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| CN107142807A (en) * | 2015-08-11 | 2017-09-08 | 孙欣 | A kind of low temperature resistant fast spreading road |
| CN105419034A (en) * | 2015-12-31 | 2016-03-23 | 崇夕山 | Motorcycle engine rubber gasket with excellent heat stability |
| CN106380755A (en) * | 2016-08-31 | 2017-02-08 | 江苏千富之丰科技有限公司 | Fluorine-containing elastomer having ultrahigh abrasion resistance and preparation method thereof |
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| CN106674829A (en) * | 2016-12-12 | 2017-05-17 | 芜湖集拓橡胶技术有限公司 | Strong acid and alkali resistant red ternary fluorine rubber seal ring material formula |
| CN107163708B (en) * | 2017-06-07 | 2019-05-07 | 浙江宏利汽车零部件有限公司 | A kind of fluorubber of high temperature-resistant acid-resistant alkali |
| CN107163708A (en) * | 2017-06-07 | 2017-09-15 | 浙江宏利汽车零部件有限公司 | A kind of fluorubber of high temperature-resistant acid-resistant alkali |
| CN109575483B (en) * | 2017-09-29 | 2021-10-08 | 氟乐泰科（厦门）新材料有限公司 | Anti-explosion decompression fluororubber compound and preparation method thereof |
| CN109575483A (en) * | 2017-09-29 | 2019-04-05 | 氟乐泰科（厦门）新材料有限公司 | A kind of anti-burst decompression fluororubber compounded rubber and preparation method thereof |
| CN108276710A (en) * | 2018-01-19 | 2018-07-13 | 合肥净龙环保科技有限公司 | A kind of low temperature resistant fluorubber composite material and preparation method and application |
| CN115216250A (en) * | 2022-01-06 | 2022-10-21 | 广东硕成科技股份有限公司 | High-stability coating adhesive 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 |
| CN114621542A (en) * | 2022-04-11 | 2022-06-14 | 江苏千富之丰科技有限公司 | Fluororubber composition containing silane fluorine ester |
| 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 |
| CN114621542B (en) * | 2022-04-11 | 2023-04-07 | 江苏千富之丰科技有限公司 | Fluororubber composition containing silane fluorine ester |
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