CN106632793B - Low-temperature-resistant elastic body containing fluorine and preparation method thereof - Google Patents
Low-temperature-resistant elastic body containing fluorine and preparation method thereof Download PDFInfo
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- CN106632793B CN106632793B CN201610924385.XA CN201610924385A CN106632793B CN 106632793 B CN106632793 B CN 106632793B CN 201610924385 A CN201610924385 A CN 201610924385A CN 106632793 B CN106632793 B CN 106632793B
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- silane
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
Abstract
The invention discloses a kind of low-temperature-resistant elastic body containing fluorines and preparation method thereof, and it is CH that it, which includes the following steps: that (a) provides general formula,2=CH (CH2)mOSiRR’(CH2)nCF3Fluorine-containing silicon-containing monomer dispersion in water, the dispersion optionally contains surfactant；(b) mix monomer of vinylidene and one or more comonomers is added, the comonomer, which is selected from, the vinyl compound of free radical copolymerization is carried out with vinylidene, and a fluorine atom is at least connected on vinyl, containing fluoroalkyl or fluoroalkoxy；(c) it is optionally added into cure site monomer；(d) initiator is added with initiated polymerization, is optionally added into chain-transferring agent, obtains fluoroelastomer.Also disclose the fluoroelastomer made from this method.
Description
Technical field
The present invention relates to a kind of low-temperature-resistant elastic body containing fluorines and preparation method thereof, belong to cryogenic material technical field.
Background technique
Fluoroelastomer is a kind of synthetic rubber haveing excellent performance, and fluoroelastomer has through product made of cooperation, processing, vulcanization
There are brilliant resistance to medium (being resistant to various fuel oils, synthetic oil, lubricating oil, chemicals) and high heat resistance, note can be used
It the forming methods such as penetrates, squeeze out, being molded and being made into various 0 shape circles, sealing element, diaphragm, washer, film, valve block, hose, rubber roller
Etc. various rubber products.The principal item of fluoroelastomer has vinylidene, hexafluoropropene binary copolymerization fluoroelastomer and inclined fluorine second
Alkene, tetrafluoroethene, hexafluoropropene ternary polymerization fluoroelastomer.However fluoroelastomer (the especially lower fluorine of vinylidene content
Elastomer) glass transition temperature it is higher, resistance to low temperature is poor, so the glass of fluoroelastomer must be reduced by various methods
Glass temperature improves its resistance to low temperature.
The glass transition temperature of fluoroelastomer is reduced, prior art describes many methods so as to improve its lower temperature resistance
Energy.First method is the copolymer composition for changing fluoroelastomer, is reduced by improving the vinylidene content in copolymer
The glass transition temperature of copolymer, because of vinylidene fluoride homopolymer --- the glass transition temperature of Kynoar is -35 DEG C.
For example, to disclose a kind of vinylidene, tetrafluoroethene, the ternary of hexafluoropropene total by United States Patent (USP) US 4,123,603
Poly- fluoroelastomer, copolymer group is as vinylidene accounts for 57~61% (weight), tetrafluoroethene accounts for 10~14% (weight), hexafluoro
Propylene accounts for 27~31% (weight), and the average glass transition temperature of gained sample is -24.8 DEG C.When the weight percent of fluoroelastomer
Group converts as when vinylidene accounts for 59% (weight), tetrafluoroethene accounts for 12% (weight), hexafluoropropene accounts for 29% (weight)
To mole copolymerization group become vinylidene accounts for 74.6% (mole), tetrafluoroethene accounts for 9.7% (mole), hexafluoropropene accounts for
15.7% (mole).
Chinese patent CN 1,054,778 discloses the ternary polymerization fluorine of a kind of vinylidene, tetrafluoroethene, hexafluoropropene
Elastomer, copolymer group is as vinylidene accounts for 60.5~64% (weight), tetrafluoroethene accounts for 5~8% (weight), hexafluoropropene
30~33% (weight) are accounted for, the glass transition temperature of gained sample is less than or equal to -25 DEG C.When the weight percent of fluoroelastomer forms
62% (weight) is accounted for for vinylidene, when tetrafluoroethene accounts for 6.5% (weight), hexafluoropropene accounts for 31.5% (weight), convert
To mole copolymerization group become vinylidene accounts for 77.9% (mole), tetrafluoroethene accounts for 5.2% (mole), hexafluoropropene accounts for
16.9% (mole).
The first method reduces the glass of fluoroelastomer by improving the vinylidene molar content in fluoroelastomer
Change temperature, but still the glass transition temperature of fluoroelastomer can not be down to -30 DEG C or less.
Second method is to be copolymerized fluorochemical monomer and low temperature modification monomer, is total to by the fluorochemical monomer with ether-containing key
The poly- glass transition temperature to reduce fluoroelastomer.For example, Chinese patent CN 1,215,117 discloses a kind of vinylidene, fluorine-containing
Monomer CF2=CF (CF2) mORf binary copolymerization fluoroelastomer, with fluorochemical monomer CF2=CF (CF2) mORf substitution hexafluoropropene
To reduce the glass transition temperature of fluoroelastomer.
Chinese patent CN 1,665,852 disclose a kind of vinylidene, tetrafluoroethene, perfluoro methyl vinyl ether three
Member copolymerization fluoroelastomer replaces hexafluoropropene with perfluoro methyl vinyl ether to reduce the glass transition temperature of fluoroelastomer.
However the synthetic route of low temperature modification monomer is all complex, cost needed for synthon is higher, thus will lead to fluorine bullet
The use cost of property body greatly improves.
Therefore, it is still necessary to develop the fluoroelastomer with low Tg.
Summary of the invention
The object of the present invention is to provide a kind of low-temperature-resistant elastic body containing fluorines and preparation method thereof, to solve institute in the prior art
The existing above problem.
A kind of fluoroelastomer comprising by the following comonomer of mole percent:
Mix monomer containing vinylidene: 55~99%；
Fluorine-containing silicon-containing monomer: 1~40%；
Cure site monomer: 0~5%.
Preferably, the mix monomer containing vinylidene is selected from tetrafluoroethene, vinylidene, hexafluoro third
Alkene, at least one of vinyl compound that free radical copolymerization can be carried out with vinylidene, and it is described can be with inclined fluorine
Ethylene carries out being connected with fluorine atom on the vinyl in the vinyl compound of free radical copolymerization, containing fluoroalkyl and fluorine-containing
At least one of alkoxy.
As further preferred scheme, the mix monomer containing vinylidene includes that can carry out freely with vinylidene
At least one of the vinyl compound and tetrafluoroethene of base copolymerization, vinylidene, hexafluoropropene.
Being connected on vinyl can be C containing fluoroalkyl1-C8Containing fluoroalkyl, preferable C1-C4Containing fluoroalkyl, such as fluorine first
Base, difluoromethyl, perfluoro-methyl, 1- fluoro ethyl, 2- fluoro ethyl, perfluoro-ethyl, 1- fluoropropyl, bis- fluoropropyl of 1,1-, 1,1,1-
Trifluoro propyl, perfluoro propyl.
The fluoroalkoxy being connected on vinyl can be C1-C12Fluoroalkoxy, preferable C1-C6Fluoroalkoxy, example
As fluorine methoxyl group, difluoro-methoxy, perfluoromethoxy, 1- fluorine ethyoxyl, 2- fluorine ethyoxyl, pentafluoroethoxy, 1- fluorine propoxyl group,
1,1- difluoro propoxyl group, perfluor propoxyl group.
In of the invention one preferable example, the comonomer be at least be connected on vinyl a fluorine atom,
C containing fluoroalkyl or fluoroalkoxy2~C6Alkene or C3~C11Perfluoroalkyl vinyl ether.
In of the invention one preferable example, the comonomer is selected from vinyl fluoride, trifluoro-ethylene (TrFE), trifluoro chlorine
Ethylene (CTFE), tetrafluoroethene (TFE), 3,3,3- trifluoro propene, perfluoroethyl vinyl, perfluorJustButylethylene, hexafluoropropene
(HFP), perfluoroalkyl vinyl ether: just such as perfluoro methyl vinyl ether (PMVE), perfluoroethylvinyl ether (PEVE), perfluor
Propyl vinyl ether (PPVE), perfluor (3- butylene vinyl ethers), perfluor (2,2- dimethyl -1,3- dioxole)
(PDD), at least one of fluoro- 1,3- dioxole (TTD) of 4- trifluoromethoxy -2,2,5- three.
Preferably, the general molecular formula of the fluorine-containing silicon-containing monomer is CH2=CH (CH2)mOSiRR’(CH2)nCF3, m
=1 or 2, R, R ' it is methyl, ethyl, methoxy or ethoxy, R and R ' can be the same or different, n=2~4.
The fluorine-containing silicon-containing monomer can be first CH by chlorosilane and general formula that general formula is HClSi RR '2=CH (CH2)n-2CF3
Vinyl compound reaction, R, R ' be methyl, ethyl, methoxy or ethoxy, R and R ' can be the same or different, n=
2~4, generation general formula is ClSi RR ' (CH2)nCF3Chlorosilane, R, R ' be methyl, ethyl, methoxy or ethoxy, R and R '
It can be the same or different, n=2~4；The general formula is ClSi RR ' (CH2)nCF3Chlorosilane and general formula be CH2=CH
(CH2)mThe compound of OH reacts, and m=1 or 2, R, R ' is methyl, ethyl, methoxy or ethoxy, R and R ' can it is identical can also
With difference, n=2~4, generation general formula is CH2=CH (CH2)mOSiRR’(CH2)nCF3Fluorine-containing silicon-containing monomer, m=1 or 2, R,
R ' is methyl, ethyl, methoxy or ethoxy, and R and R ' can be the same or different, n=2~4.
Preferably, the fluorine-containing silicon-containing monomer is selected from dimethoxy allyloxy (3,3,3- trifluoro propyl) silane, methyl
Methoxyl group allyloxy (3,3,3- trifluoro propyl) silane, dimethallyl oxygroup (3,3,3- trifluoro propyl) silane, dimethoxy
Base allyloxy (4,4,4- trifluoro normal-butyl) silane, methyl methoxy base allyloxy (4,4,4- trifluoro normal-butyl) silane, two
Methyl allyloxy (4,4,4- trifluoro normal-butyl) silane, diethoxy allyloxy (3,3,3- trifluoro propyl) silane, ethyl
Ethyoxyl allyloxy (3,3,3- trifluoro propyl) silane, diethyl allyloxy (3,3,3- trifluoro propyl) silane, diethoxy
Base allyloxy (4,4,4- trifluoro normal-butyl) silane, ethyl ethyoxyl allyloxy (4,4,4- trifluoro normal-butyl) silane, two
At least one of allyl oxygroup (4,4,4- trifluoro normal-butyl) silane.
Preferably, the general molecular formula of the cure site monomer is CX2=CX (Z), wherein X be H or F, Z Br,
I, Cl or RfU, U Br, I, Cl, CN or-CX=CX2, the general formula of Rf is-(OCF2CF(CF3))nO(CF2) m-, n=0~3,
M=1~8.
Preferably, the cure site monomer is selected from the bromo- vinylidene fluoride of 2-, the iodo- vinylidene fluoride of 2-, three
The fluoro- 1- butylene of the bromo- 3,3,4,4- tetra- of fluorine vinyl bromide, trifluoro iodoethylene, 4-, the fluoro- 1- butylene of the iodo- 3,3,4,4- tetra- of 4-, 4- bromo- 1,
The fluoro- 1- butylene of 1,2- tri-, the fluoro- 1- butylene of the iodo- 1,1,2- tri- of 4-, the bromo- perfluoro-n-butyl group ethylene of 4-, the iodo- perfluoro-n-butyl group second of 4-
The bromo- perfluor n-hexyl vinyl of alkene, 6-, the iodo- perfluor n-hexyl vinyl of 6-, 1,2- divinyl hexafluoroethane, 1,4- divinyl
It is perfluorinated butane, 1,6- divinylperfluorhexane, 1,8- divinylperfluorooctane, perfluor (2- bromoethyl vinyl ether), complete
Fluorine (2- iodine ethyl vinyl ether), 2- vinyl perfluoro ethyl vinyl ether, 2- (2- bromoethyl) perfluoroethylvinyl ether, 2-
(2- iodine ethyl) perfluoroethylvinyl ether, 2- itrile group perfluoroethylvinyl ether, 3- itrile group perfluoropropylvinylether, 4-
Itrile group perfluoro-n-butyl group vinyl ethers, perfluor (2- acetonitrile-base propoxy base ether), perfluor (2- propionitrile base propoxy base
Ether), at least one of perfluor (2- n-Butyronitrile base propoxy base ether).
A kind of preparation method of fluoroelastomer as the aforementioned, including one in emulsion polymerization, polymerisation in solution, suspension polymerisation
Kind.Preferably emulsion polymerization, because emulsion polymerization can easily adjust molecular weight and copolymer composition.
It includes the following steps: after being dispersed in water fluorine-containing silicon-containing monomer, and the mix monomer containing vinylidene is added；
Initiator is added, is optionally added into chain-transferring agent, carries out polymerization reaction, obtains the fluoroelastomer.
In order to improve the dispersibility of the fluorine-containing silicon-containing monomer in water, dispersion is also added optionally into dispersion
Agent.The additional amount of dispersing agent is without particular limitation, as long as the dispersibility of monomer can be improved and will not be to subsequent polymerization reaction
Or the polymer formed has an adverse effect.
Equally, the type of dispersing agent is also without particular limitation, if it can improve the dispersibility of monomer and will not to
The polymer of polymerization reaction or formation afterwards has an adverse effect.
Preferably, the dispersing agent generally uses fluorine-containing surfactant, and not limiting example has: XRfCOOM, wherein
X is fluorine atom or hydrogen atom or chlorine atom, RfIt is C3-C11Contain fluoroalkyl or fluoroalkoxy, M be hydrogen ion or alkali metal from
Son or ammonium ion or substituted ammonium ion or polyether segment, such as C7F15COOK；Or general formula is RfC6H4SO3The substituted benzene sulphur of M
Acid, benzene sulfonate or benzene sulfonate, wherein RfIt is C3-C12Contain fluoroalkyl or fluoroalkoxy, M be hydrogen ion or alkali metal from
Son or ammonium ion or substituted ammonium ion or polyether segment, such as C6F13C6H4SO3K。
Preferably, based on fluoroelastomer described in 100 parts by weight, the additional amount of dispersing agent is 0.01~4 parts by weight.
In order to improve the stability of monomer dispersion liquid, stabilizer is also optionally added into dispersion liquid.Of the invention
In one preferable example, use fluorochemical polyether as the stabilizer of dispersion liquid.The additional amount of stabilizer is without particular limitation, as long as
Energy stable dispersions simultaneously have no adverse effects to the fluoroelastomer of subsequent polymerization reaction and generation.The common skill of this field
Art personnel can easily determine the addition of stabilizer appropriate in conjunction with its professional knowledge after having read present disclosure
Amount.
It is without particular limitation to be suitable for the invention polymerization temperature, it is preferable that the polymerization temperature is 20~110 DEG C, excellent
It is selected as 30~100 DEG C.
The polymerization pressure of two methods of the present invention is without particular limitation, it is preferable that the polymerization pressure be 0.5~
6.0MPa, preferably 0.5~4.0MPa.
Initiator suitable for the method for the present invention is without particular limitation, it can be polymerization initiator commonly used in the art.
The initiator is generally water-soluble peroxide, and example includes: persulfate, such as ammonium persulfate, sodium peroxydisulfate, persulfuric acid
Potassium；Oxidation-reduction trigger system, wherein oxidant can be persulfate, such as ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate；
Water-soluble organic peroxide, such as hydrogen peroxide, tert-butyl hydroperoxide, isopropyl benzene hydroperoxide, p-Methylisopropylbenzene peroxide
Change hydrogen, tert-butyl cumyl peroxide hydrogen peroxide；Reducing agent can be sulphite, bisulfites, thiosulfate, formaldehyde time sulphur
Hydrochlorate, ferrous salt etc..
Based on fluoroelastomer described in 100 parts by weight, 0.005 can be for polymerizeing the additional amount of initiator of fluoroelastomer
~2 parts by weight.
The method of the present invention is optionally added chain-transferring agent.
Chain-transferring agent suitable for the method for the present invention can be any compound that can continue fluoroelastomer copolymerization,
Its illustrative example includes: alcohols, such as methanol, isopropanol；Ethers, such as dimethyl ether, diethyl ether, diη-propyl ether, methyl- tert
Butyl ether；Ketone, such as acetone, methyl ethyl ketone；Esters, such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, acetic acid
N-butyl, isobutyl acetate, tert-butyl acetate, trifluoro-acetate, Trifluoroacetic Acid Ethyl Ester, trifluoroacetic acid n-propyl, trifluoro second
Isopropyl propionate, trifluoroacetic acid N-butyl, trifluoroacetic acid isobutyl ester, the trifluoroacetic acid tert-butyl ester, perfluorinated acid methyl esters, perfluorinated acid second
Ester, perfluorinated acid n-propyl, perfluorinated acid isopropyl ester, perfluorinated acid N-butyl, perfluorinated acid isobutyl ester, the tertiary fourth of perfluorinated acid
Ester, diethyl malonate, dimethyl carbonate, diethyl carbonate；Halogen alkane, such as chloroform, carbon tetrachloride, trichloro-monofluoro first
Alkane, dicholorodifluoromethane, F-22, the fluoro- 2- chlorodifluoroethane of mono- chlorine of 1- one, bromomethane, iodomethane, dibromo first
Alkane, diiodomethane, the bromo- 2,2- Difluoroethane of 1,2- bis-, the iodo- 2,2- Difluoroethane of 1,2- bis-, 1,2- dibromotetrafluoroethane, 1,2-
Diiodo- tetrafluoroethane, 1,4- dibromo octafluorobutane, 1,4- diiodo- octafluorobutane；Aliphatic alkane, such as methyl cyclopentane, methyl ring
Hexane etc.；Bromide, iodide, such as lithium bromide, sodium bromide, potassium bromide, lithium iodide, sodium iodide, potassium iodide.
Based on fluoroelastomer described in 100 parts by weight, the additional amount of chain-transferring agent can be 0.001~20 parts by weight.
The Mooney viscosity of the fluoroelastomer prepared in the present invention need to reach 20~200 [ML (1+10), 121 DEG C, similarly hereinafter],
Preferably 20~150, more preferably 30~100, most preferably 30~80.The Mooney viscosity is an index of molecular weight,
Mooney viscosity is bigger, and molecular weight is higher, and Mooney viscosity is smaller, and molecular weight is lower.It is described fluorine-containing within the scope of above-mentioned Mooney viscosity
Elastomer has good processing performance and cross-linking properties.
Compared with prior art, the present invention have it is following the utility model has the advantages that
After the fluorine-containing modification by copolymerization of ether monomer containing silene, had been equipped with after fluoroelastomer is crosslinked excellent low temperature resistant
Performance, glass transition temperature are not higher than -35 DEG C.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Indices detection method in the present invention is respectively as follows:
1, F is used19NMR, HNMR measure the copolymerization composition of fluoroelastomer, and solvent is deuterated acetone.
2, by the glass transition temperature Tg of ASTM D3418 standard test fluoroelastomer.Heating rate is 10 DEG C/min.
3, by the Mooney viscosity of ASTM D1646 standard test fluoroelastomer, measuring temperature is 121 DEG C.
4, by the low temperature retraction temperature TR10 of ASTM D1329 standard test fluoroelastomer vulcanized rubber.
5, by the strength character of ASTM D412 standard test fluoroelastomer vulcanized rubber.
Embodiment 1
The present embodiment is related to a kind of preparation method of fluoroelastomer, specifically comprises the following steps:
In 10 liters of vertical response kettles, be added 4358 grams of deionized waters, 70 grams of Sodium perfluorooctanoates and its homologous mixture,
108 grams of dipotassium hydrogen phosphates, 2642 grams of dimethallyl oxygroup (3,3,3- trifluoro propyl) silane.Closed reaction kettle, vacuumizes simultaneously
It is replaced with nitrogen, until oxygen content is less than or equal to 10ppm in reaction kettle.Then start to be stirred with the rate of 800rpm, it will
Reaction kettle internal temperature rises to 50 DEG C, and absolute pressure reaches 1.5MPa, the copolymerization in supplement copolymerization mix monomer to reaction kettle
Mix monomer mol ratio accounts for 55%, hexafluoropropene for vinylidene and accounts for 45%.18 grams of sodium peroxydisulfates, 10 grams of bisulfites are added
Sodium, 14 grams of diethyl malonates start polymerization reaction.Absolute pressure in reaction kettle is maintained by adding copolymerization mix monomer
1.5MPa, the copolymerization mix monomer mol ratio added account for 78%, hexafluoropropene for vinylidene and account for 22%.Work as reaction kettle
When interior emulsion solid content reaches 20%, terminate polymerization reaction.
Through F19Mole copolymerization group of NMR, HNMR measurement, gained fluoroelastomer becomes VDF:HFP: dimethallyl oxygroup
(3,3,3- trifluoro propyl) silane=54.7%:15.4%:29.9%.
Fluoroelastomer vulcanized rubber is obtained by formula vulcanization shown in table 1, the performance of the fluoroelastomer measured, as a result
It is listed in table 2.
Embodiment 2
The present embodiment is related to a kind of preparation method of fluoroelastomer, specifically comprises the following steps:
In 10 liters of vertical response kettles, be added 4358 grams of deionized waters, 70 grams of Sodium perfluorooctanoates and its homologous mixture,
108 grams of dipotassium hydrogen phosphates, 2642 grams of dimethallyl oxygroup (3,3,3- trifluoro propyl) silane.Closed reaction kettle, vacuumizes simultaneously
It is replaced with nitrogen, until oxygen content is less than or equal to 10ppm in reaction kettle.Then start to be stirred with the rate of 800rpm, it will
Reaction kettle internal temperature rises to 50 DEG C, and absolute pressure reaches 1.5MPa, the copolymerization in supplement copolymerization mix monomer to reaction kettle
Mix monomer mol ratio accounts for 55%, hexafluoropropene for vinylidene and accounts for 45%.18 grams of sodium peroxydisulfates, 10 grams of bisulfites are added
Sodium, 9.5 grams of diiodomethanes start polymerization reaction.Absolute pressure in reaction kettle is maintained by adding copolymerization mix monomer
1.5MPa, the copolymerization mix monomer mol ratio added account for 77%, hexafluoropropene for vinylidene and account for 22%, 2- iodo- 1,
1- difluoroethylene accounts for 1%.When emulsion solid content reaches 20% in reaction kettle, terminate polymerization reaction.
Through F19Mole copolymerization group of NMR, HNMR measurement, gained fluoroelastomer becomes VDF:HFP: dimethallyl oxygroup
(3,3,3- trifluoro propyl) silane: the iodo- 1,1- difluoroethylene of 2- accounts for=54.6%:15.1%:29.6%:0.7%.
Fluoroelastomer vulcanized rubber is obtained by formula vulcanization shown in table 1, the performance of the fluoroelastomer measured, as a result
It is listed in table 2.
Embodiment 3
The present embodiment is related to a kind of preparation method of fluoroelastomer, specifically comprises the following steps:
In 10 liters of vertical response kettles, be added 4276 grams of deionized waters, 70 grams of Sodium perfluorooctanoates and its homologous mixture,
108 grams of dipotassium hydrogen phosphates, 2724 grams of dimethallyl oxygroup (3,3,3- trifluoro propyl) silane.Closed reaction kettle, vacuumizes simultaneously
It is replaced with nitrogen, until oxygen content is less than or equal to 10ppm in reaction kettle.Then start to be stirred with the rate of 800rpm, it will
Reaction kettle internal temperature rises to 50 DEG C, and absolute pressure reaches 1.5MPa, the copolymerization in supplement copolymerization mix monomer to reaction kettle
Mix monomer mol ratio is that vinylidene accounts for 65%, tetrafluoroethene and accounts for 10%, hexafluoropropene and accounts for 25%.18 grams of persulfuric acid are added
Sodium, 10 grams of sodium hydrogensulfites, 12.4 grams of Trifluoroacetic Acid Ethyl Esters start polymerization reaction.Make to react by adding copolymerization mix monomer
Absolute pressure maintains 1.5MPa in kettle, and the copolymerization mix monomer mol ratio added is that vinylidene accounts for 78%, tetrafluoro
Ethylene accounts for 10%, hexafluoropropene and accounts for 12%.When emulsion solid content reaches 20% in reaction kettle, terminate polymerization reaction.
Through F19Mole copolymerization group of NMR, HNMR measurement, gained fluoroelastomer becomes VDF:TFE:HFP: dimethallyl oxygen
Base (3,3,3- trifluoro propyl) silane=54.7%:7.1:8.5%:29.7%.
Fluoroelastomer vulcanized rubber is obtained by formula vulcanization shown in table 1, the performance of the fluoroelastomer measured, as a result
It is listed in table 2.
Embodiment 4
The present embodiment is related to a kind of preparation method of fluoroelastomer, specifically comprises the following steps:
In 10 liters of vertical response kettles, be added 4677 grams of deionized waters, 70 grams of Sodium perfluorooctanoates and its homologous mixture,
108 grams of dipotassium hydrogen phosphates, 2323 grams of dimethallyl oxygroup (3,3,3- trifluoro propyl) silane.Closed reaction kettle, vacuumizes simultaneously
It is replaced with nitrogen, until oxygen content is less than or equal to 10ppm in reaction kettle.Then start to be stirred with the rate of 800rpm, it will
Reaction kettle internal temperature rises to 50 DEG C, and absolute pressure reaches 1.3MPa, the copolymerization in supplement copolymerization mix monomer to reaction kettle
Mix monomer mol ratio accounts for 63.1%, PMVE for vinylidene and accounts for 36.9%.18 grams of sodium peroxydisulfates, 10 grams of bisulfites are added
Sodium, 9.5 grams of diiodomethanes start polymerization reaction.Absolute pressure in reaction kettle is maintained by adding copolymerization mix monomer
1.3MPa, the copolymerization mix monomer mol ratio added account for 81%, PMVE for vinylidene and account for iodo- 1, the 1- bis- of 18%, 2-
Vinyl fluoride accounts for 1%.When emulsion solid content reaches 20% in reaction kettle, terminate polymerization reaction.
Through F19Mole copolymerization group of NMR, HNMR measurement, gained fluoroelastomer becomes VDF:PMVE: dimethallyl oxygroup
(3,3,3- trifluoro propyl) silane: the iodo- 1,1- difluoroethylene of 2- accounts for=61%:13.4%:24.8%:0.8%.
Fluoroelastomer vulcanized rubber is obtained by formula vulcanization shown in table 1, the performance of the fluoroelastomer measured, as a result
It is listed in table 2.
Comparative example 1
This comparative example is related to a kind of preparation method of fluoroelastomer, specifically comprises the following steps:
In 10 liters of vertical response kettles, be added 7000 grams of deionized waters, 70 grams of Sodium perfluorooctanoates and its homologous mixture,
108 grams of dipotassium hydrogen phosphates.Closed reaction kettle is vacuumized and is replaced with nitrogen, until oxygen content is less than or equal in reaction kettle
10ppm.Then start to be stirred with the rate of 800rpm, reaction kettle internal temperature is risen to 50 DEG C, supplement copolymerization mixing is single
Absolute pressure reaches 1.5MPa in body to reaction kettle, and the copolymerization mix monomer mol ratio is that vinylidene accounts for 55%, hexafluoro
Propylene accounts for 45%.18 grams of sodium peroxydisulfates, 10 grams of sodium hydrogensulfites, 14 grams of diethyl malonates are added, start polymerization reaction.Pass through
Adding copolymerization mix monomer makes absolute pressure in reaction kettle maintain 1.5MPa, the copolymerization mix monomer mol ratio added
78%, hexafluoropropene, which is accounted for, for vinylidene accounts for 22%.When emulsion solid content reaches 20% in reaction kettle, terminate polymerization reaction.
Through F19Mole copolymerization group of NMR, HNMR measurement, gained fluoroelastomer becomes VDF:HFP=77.6%:22.4%.
Fluoroelastomer vulcanized rubber is obtained by formula vulcanization shown in table 1, the performance of the fluoroelastomer measured, as a result
It is listed in table 2.
Comparative example 2
This comparative example is related to a kind of preparation method of fluoroelastomer, specifically comprises the following steps:
In 10 liters of vertical response kettles, be added 7000 grams of deionized waters, 70 grams of Sodium perfluorooctanoates and its homologous mixture,
108 grams of dipotassium hydrogen phosphates.Closed reaction kettle is vacuumized and is replaced with nitrogen, until oxygen content is less than or equal in reaction kettle
10ppm.Then start to be stirred with the rate of 800rpm, reaction kettle internal temperature is risen to 50 DEG C, supplement copolymerization mixing is single
Absolute pressure reaches 1.3MPa in body to reaction kettle, the copolymerization mix monomer mol ratio be vinylidene account for 63.1%,
PMVE accounts for 36.9%.18 grams of sodium peroxydisulfates, 10 grams of sodium hydrogensulfites, 9.5 grams of diiodomethanes are added, start polymerization reaction.Pass through
Adding copolymerization mix monomer makes absolute pressure in reaction kettle maintain 1.3MPa, the copolymerization mix monomer mol ratio added
81%, hexafluoropropene is accounted for for vinylidene account for the iodo- 1,1- difluoroethylene of 18%, 2- account for 1%.When emulsion solid content in reaction kettle
When reaching 20%, terminate polymerization reaction.
Through F19Mole copolymerization group of NMR, HNMR measurement, gained fluoroelastomer becomes iodo- 1, the 1- difluoro second of VDF:PMVE:2-
Alkene=81.1%:18.3%:0.6%.
Fluoroelastomer vulcanized rubber is obtained by formula vulcanization shown in table 1, the performance of the fluoroelastomer measured, as a result
It is listed in table 2.
Table 1
BPP: benzyltriphenyl phosphonium phosphonium chloride
Double 2,5:2,5- dimethyl -2,5- exane-tert-butyl peroxides
TAIC: triallyl isocyanurate
Table 2
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited to above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring substantive content of the invention.
Claims (9)
1. a kind of low-temperature-resistant elastic body containing fluorine, which is characterized in that the following comonomer including pressing mole percent:
Mix monomer containing vinylidene: 55~99%；
Fluorine-containing silicon-containing monomer: 1~40%；
Cure site monomer: 0~5%；
The general molecular formula of the fluorine-containing silicon-containing monomer is CH2=CH (CH2)mOSiRR’(CH2)nCF3, m=1 or 2, R, R ' is first
Base, ethyl, methoxy or ethoxy, R and R ' can be the same or different, n=2~4.
2. low-temperature-resistant elastic body containing fluorine as described in claim 1, which is characterized in that the mix monomer containing vinylidene
By vinylidene and can with vinylidene carry out free radical copolymerization vinyl compound form, and it is described can be with inclined fluorine
Ethylene carries out being connected with fluorine atom on the vinyl in the vinyl compound of free radical copolymerization, containing fluoroalkyl and fluorine-containing
At least one of alkoxy.
3. low-temperature-resistant elastic body containing fluorine as claimed in claim 2, which is characterized in that described to carry out free radical with vinylidene
The vinyl compound of copolymerization be selected from vinyl fluoride, trifluoro-ethylene, chlorotrifluoroethylene, tetrafluoroethene, perfluoroethyl vinyl,
Perfluoro-n-butyl group ethylene, perfluoroalkyl vinyl ether.
4. low-temperature-resistant elastic body containing fluorine as claimed in claim 3, which is characterized in that the perfluoroalkyl vinyl ether includes complete
Methyl fluoride vinyl ethers, perfluoroethylvinyl ether, perfluoropropylvinylether, perfluor (3- butylene vinyl ethers), perfluor
In (2,2- dimethyl -1,3- dioxole), the fluoro- 1,3- dioxole of 4- trifluoromethoxy -2,2,5- three
At least one.
5. low-temperature-resistant elastic body containing fluorine as claimed in claim 4, which is characterized in that the fluorine-containing silicon-containing monomer is selected from dimethoxy
Base allyloxy (3,3,3- trifluoro propyl) silane, methyl methoxy base allyloxy (3,3,3- trifluoro propyl) silane, dimethyl
Allyloxy (3,3,3- trifluoro propyl) silane, dimethoxy allyloxy (4,4,4- trifluoro normal-butyl) silane, methyl methoxy
Base allyloxy (4,4,4- trifluoro normal-butyl) silane, dimethallyl oxygroup (4,4,4- trifluoro normal-butyl) silane, diethoxy
Base allyloxy (3,3,3- trifluoro propyl) silane, ethyl ethyoxyl allyloxy (3,3,3- trifluoro propyl) silane, diethyl
Allyloxy (3,3,3- trifluoro propyl) silane, diethoxy allyloxy (4,4,4- trifluoro normal-butyl) silane, ethyl ethoxy
In base allyloxy (4,4,4- trifluoro normal-butyl) silane, diethyl allyloxy (4,4,4- trifluoro normal-butyl) silane at least
It is a kind of.
6. low-temperature-resistant elastic body containing fluorine as described in claim 1, which is characterized in that the general molecular formula of the cure site monomer is
CX2=CX (Z), wherein X is H or F, Z Br, I, Cl or RfU, U Br, I, Cl, CN or-CX=CX2, the general formula of Rf is-
(OCF2CF(CF3))nO(CF2) m-, n=0~3, m=1~8.
7. low-temperature-resistant elastic body containing fluorine as claimed in claim 6, which is characterized in that the cure site monomer is selected from 2- bromo- 1,
The fluoro- 1- butylene of the bromo- 3,3,4,4- tetra- of the iodo- 1,1- difluoroethylene of 1- difluoroethylene, 2-, bromotrifluoroethylene, trifluoro iodoethylene, 4-,
The fluoro- 1- butylene of the iodo- 3,3,4,4- tetra- of 4-, the fluoro- 1- butylene of the bromo- 1,1,2- tri- of 4-, the fluoro- 1- butylene of the iodo- 1,1,2- tri- of 4-, 4- are bromo-
The iodo- perfluoro-n-butyl group ethylene of perfluoro-n-butyl group ethylene, 4-, the bromo- perfluor n-hexyl vinyl of 6-, the iodo- perfluor n-hexyl vinyl of 6-, 1,
2- divinyl hexafluoroethane, 1,4- divinyl perfluorinated butane, 1,6- divinylperfluorhexane, 1,8- divinyl perfluor
Octane, perfluor (2- bromoethyl vinyl ether), perfluor (2- iodine ethyl vinyl ether), 2- vinyl perfluoro ethyl vinyl ether,
2- (2- bromoethyl) perfluoroethylvinyl ether, 2- (2- iodine ethyl) perfluoroethylvinyl ether, 2- itrile group perfluoroethyl vinyl
Base ether, 3- itrile group perfluoropropylvinylether, 4- itrile group perfluoro-n-butyl group vinyl ethers, perfluor (2- acetonitrile-base propoxyl group second
Alkene ether), perfluor (2- propionitrile base propoxy base ether), at least one in perfluor (2- n-Butyronitrile base propoxy base ether)
Kind.
8. a kind of preparation method of the low-temperature-resistant elastic body containing fluorine as described in any one of Claims 1 to 5, feature exist
In including the following steps:
After fluorine-containing silicon-containing monomer is dispersed in water, the mix monomer containing vinylidene, cure site monomer is added；
Initiator is added, carries out polymerization reaction, obtains the fluoroelastomer.
9. a kind of preparation method of the low-temperature-resistant elastic body containing fluorine as described in any one of Claims 1 to 5, feature exist
In including the following steps:
After fluorine-containing silicon-containing monomer is dispersed in water, the mix monomer containing vinylidene, cure site monomer is added；
Initiator, chain-transferring agent is added, carries out polymerization reaction, obtains the fluoroelastomer.
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| CN106496397A (en) * | 2016-10-24 | 2017-03-15 | 内蒙古奥特普氟化学新材料开发有限公司 | Fluoroelastomer, the resin combination with the fluoroelastomer and preparation method |
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| CN106496397A (en) * | 2016-10-24 | 2017-03-15 | 内蒙古奥特普氟化学新材料开发有限公司 | Fluoroelastomer, the resin combination with the fluoroelastomer and preparation method |
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| Original Crosslinking of Poly(vinylidene fluoride) via Trialkoxysilane-Containing Cure-Site Monomers;J. GUIOT等;《Journal of Polymer Science: Part A: Polymer Chemistry》;20061231;第44卷;第3896-3910页 |
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