CN106632793A - A fluoroelastomer resistant to low temperatures and a preparing method thereof - Google Patents
A fluoroelastomer resistant to low temperatures and a preparing method thereof Download PDFInfo
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- CN106632793A CN106632793A CN201610924385.XA CN201610924385A CN106632793A CN 106632793 A CN106632793 A CN 106632793A CN 201610924385 A CN201610924385 A CN 201610924385A CN 106632793 A CN106632793 A CN 106632793A
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- fluorine
- 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
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Abstract
A fluoroelastomer resistant to low temperatures and a preparing method thereof are disclosed. The method includes steps of (a) providing a dispersion of a fluorine-containing silicon-containing monomer having a general formula of CH2=CH(CH2)<m>OSiRR'(CH2)<n>CF3 in water, with the dispersion optionally comprising a surfactant; (b) adding a monomer mixture of vinylidene fluoride and one or more copolymerization monomers into the dispersion; (c) optionally adding a cure site monomer; and (d) adding an initiator to initiate polymerization, and optionally adding a chain transfer to obtain the fluoroelastomer, wherein the copolymerization monomers are selected from vinyl compounds capable of being subjected to free radical copolymerization with the vinylidene fluoride, and vinyl is at least connected to one fluorine atom, fluoroalkyl or fluroalkoxy. The fluoroelastomer prepared by the method is also disclosed.
Description
Technical field
The present invention relates to a kind of low-temperature-resistant elastic body containing fluorine and preparation method thereof, belongs to cryogenic material technical field.
Background technology
Fluoroelastomer is a kind of synthetic rubber of excellent performance, and fluoroelastomer Jing coordinates, processes, product tool made by sulfuration
There are the resistance to medium (being resistant to various fuel oils, artificial oil, lubricating oil, chemicals) and high heat resistance of brilliance, can be using note
The forming method such as penetrate, extrude, being molded and being made into various 0 shape circles, seal, barrier film, packing ring, film, valve block, flexible pipe, rubber roll
Etc. various rubbers.The principal item of fluoroelastomer has vinylidene, hexafluoropropene binary copolymerization fluoroelastomer and inclined fluorine second
Alkene, tetrafluoroethene, hexafluoropropene ternary polymerization fluoroelastomer.But fluoroelastomer (the particularly relatively low fluorine of vinylidene content
Elastomer) vitrification point 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.
Prior art describes many methods to reduce the vitrification point of fluoroelastomer, so as to improve its lower temperature resistance
Energy.First method is the copolymer composition for changing fluoroelastomer, is reduced by the vinylidene content in raising copolymer
The vitrification point of copolymer, because vinylidene fluoride homopolymer --- the vitrification point of Kynoar is -35 DEG C.
For example, United States Patent (USP) US 4,123,603 disclose a kind of vinylidene, tetrafluoroethene, the ternary of hexafluoropropene is total to
Poly- fluoroelastomer, copolymer consists of vinylidene and accounts for 57～61% (weight), tetrafluoroethene and 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
When consisting of vinylidene and accounting for 59% (weight), tetrafluoroethene and account for 12% (weight), hexafluoropropene and account for 29% (weight), convert
To a mole copolymerization consist of vinylidene and account for 74.6% (mole), tetrafluoroethene and account for 9.7% (mole), hexafluoropropene and account for
15.7% (mole).
Chinese patent CN 1,054,778 discloses the ternary polymerization fluorine of a kind of vinylidene, tetrafluoroethene, hexafluoropropene
Elastomer, copolymer consists of vinylidene and accounts for 60.5～64% (weight), tetrafluoroethene and accounts for 5～8% (weight), hexafluoropropene
30～33% (weight) are accounted for, the vitrification point of gained sample is less than or equal to -25 DEG C.When the weight percent of fluoroelastomer is constituted
When accounting for 62% (weight), tetrafluoroethene for vinylidene and accounting for 6.5% (weight), hexafluoropropene and account for 31.5% (weight), convert
To a mole copolymerization consist of vinylidene and account for 77.9% (mole), tetrafluoroethene and account for 5.2% (mole), hexafluoropropene and account for
16.9% (mole).
The first method reduces the glass of fluoroelastomer by the vinylidene molar content in raising fluoroelastomer
Change temperature, but still the vitrification point of fluoroelastomer cannot be down to less than -30 DEG C.
Second method is by fluorochemical monomer and low temperature modification monomer copolymerization, by carrying out altogether with the fluorochemical monomer of ether-containing key
The poly- vitrification point to reduce fluoroelastomer.For example, Chinese patent CN 1,215,117 disclose a kind of vinylidene, fluorine-containing
Monomer CF2=CF (CF2) mORf binary copolymerization fluoroelastomer, with fluorochemical monomer CF2=CF (CF2) mORf replacement hexafluoropropenes
So as to reduce the vitrification point of fluoroelastomer.
Chinese patent CN 1,665,852 disclose a kind of vinylidene, tetrafluoroethene, the three of perfluoro methyl vinyl ether
First copolymerization fluoroelastomer, hexafluoropropene is replaced so as to reduce the vitrification point of fluoroelastomer with perfluoro methyl vinyl ether.
But the synthetic route of low temperature modification monomer is all complex, cost is higher needed for synthon, thus can cause fluorine bullet
The use cost of gonosome is greatly improved.
Therefore, it is still necessary to fluoroelastomer of the exploitation with low Tg.
The content of the invention
It is an object of the invention to provide a kind of low-temperature-resistant elastic body containing fluorine and preparation method thereof, to solve prior art in institute
The problems referred to above of presence.
A kind of fluoroelastomer, it is included 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 that can be carried out with vinylidene in the vinyl compound of free radical copolymerization, and it is described can be with inclined fluorine
Fluorine atom is connected with the vinyl that ethene carries out in the vinyl compound of free radical copolymerization, containing fluoroalkyl and fluorine-containing
At least one in alkoxyl.
Used as further preferred scheme, the mix monomer containing vinylidene includes that freedom can be carried out with vinylidene
At least one in vinyl compound and tetrafluoroethene, vinylidene, the hexafluoropropene of base copolymerization.
It can be C containing fluoroalkyl to be connected on vinyl1-C8Containing fluoroalkyl, preferable C1-C4Containing fluoroalkyl, such as fluorine first
Base, difluoromethyl, perfluoro-methyl, 1- fluoro ethyls, 2- fluoro ethyls, perfluoro-ethyl, 1- fluoropropyls, the fluoropropyls of 1,1- bis-, 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 ethyoxyls, 2- fluorine ethyoxyls, pentafluoroethoxy, 1- fluorine propoxyl group,
1,1- difluoro propoxyl group, perfluor propoxyl group.
The present invention a preferable example in, the comonomer be at least be connected with vinyl a fluorine atom,
C containing fluoroalkyl or fluoroalkoxy2～C6Alkene or C3～C11Perfluoroalkyl vinyl ether.
In a preferable example of the present invention, the comonomer is selected from PVF, trifluoro-ethylene (TrFE), trifluoro chlorine
Ethene (CTFE), tetrafluoroethene (TFE), 3,3,3- trifluoro propenes, perfluoroethyl vinyl, perfluorJustButylethylene, hexafluoropropene
(HFP), perfluoroalkyl vinyl ether：Such as perfluoro methyl vinyl ether (PMVE), perfluoroethylvinyl ether (PEVE), perfluor just
Propyl vinyl ether (PPVE), perfluor (3- butylene vinyl ethers), perfluor (2,2- dimethyl -1,3- dioxoles)
(PDD), at least one in the fluoro- 1,3- dioxoles (TTD) of 4- trifluoromethoxies -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 the chlorosilane that formula is HClSi RR ' and formula2=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 formula is ClSi RR ' (CH2)nCF3Chlorosilane, R, R ' be methyl, ethyl, methoxy or ethoxy, R and R '
Can be the same or different, n=2～4；The formula is ClSi RR ' (CH2)nCF3Chlorosilane and formula be CH2=CH
(CH2)mThe compound reaction of OH, m=1 or 2, R, R ' it is methyl, ethyl, methoxy or ethoxy, R can be with identical with R '
With difference, n=2～4, generation 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 propyls) silane, dimethallyl epoxide (3,3,3- trifluoro propyls) silane, dimethoxy
Base allyloxy (4,4,4- trifluoro normal-butyls) silane, methyl methoxy base allyloxy (4,4,4- trifluoro normal-butyls) silane, two
Methyl allyloxy (4,4,4- trifluoro normal-butyls) silane, diethoxy allyloxy (3,3,3- trifluoro propyls) silane, ethyl
Ethyoxyl allyloxy (3,3,3- trifluoro propyls) silane, diethyl allyloxy (3,3,3- trifluoro propyls) silane, diethoxy
Base allyloxy (4,4,4- trifluoro normal-butyls) silane, ethyl ethyoxyl allyloxy (4,4,4- trifluoro normal-butyls) silane, two
At least one in allyl epoxide (4,4,4- trifluoro normal-butyls) silane.
Preferably, the general molecular formula of the cure site monomer is CX2=CX (Z), wherein, X be H or F, Z be Br,
I, Cl or RfU, U is Br, I, Cl, CN or-CX=CX2, the formula of Rf is-(OCF2CF(CF3))nO(CF2) m-, n=0～3,
M=1～8.
Preferably, the cure site monomer selected from the bromo- vinylidene fluorides of 2-, the iodo- vinylidene fluorides of 2-, three
The fluoro- 1- butylene of the bromo- 3,3,4,4- tetra- of fluorine bromine ethene, 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 ethene 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 vinyls of 6-, 1,2- divinyl hexafluoroethanes, 1,4- divinyl
It is perfluorinated butane, 1,6- divinylperfluorhexanes, 1,8- divinylperfluorooctanes, perfluor (2- bromoethyl vinyl ethers), complete
Fluorine (2- iodine ethyl vinyl ethers), 2- vinyl perfluoro ethyl vinyl ethers, 2- (2- bromoethyls) perfluoroethylvinyl ether, 2-
(2- iodine ethyls) perfluoroethylvinyl ether, 2- itrile group perfluoroethylvinyl ethers, 3- itrile group perfluoropropylvinylethers, 4-
Itrile group perfluoro-n-butyl group vinyl ethers, perfluor (2- acetonitrile-base propoxy base ethers), perfluor (2- propionitrile base propoxy bases
Ether), at least one in perfluor (2- n-Butyronitrile base propoxy base ethers).
A kind of preparation method of fluoroelastomer as the aforementioned, including in emulsion polymerization, polymerisation in solution, suspension polymerisation
Kind.Preferably emulsion polymerization, because emulsion polymerization can easily adjust molecular weight and copolymer composition.
It comprises the steps：After fluorine-containing silicon-containing monomer is dispersed in water, the mix monomer containing vinylidene is added；
Initiator is added, chain-transferring agent is optionally added into, polymerisation is carried out, described fluoroelastomer is obtained.
In order to improve dispersiveness of the fluorine-containing silicon-containing monomer in water, dispersion is added also optionally in dispersion
Agent.The addition of dispersant is without particular limitation, if can improve monomer dispersiveness and will not be to subsequent polymerisation
Or the polymer for being formed has a negative impact.
Equally, the type of dispersant is also without particular limitation, if it can improve monomer dispersiveness and will not to
Polymerisation or the polymer of formation afterwards has a negative impact.
Preferably, the dispersant typically adopts fluorine-containing surfactant, its not limiting example to have：XRfCOOM, wherein
X is fluorine atom or hydrogen atom or chlorine atom, RfIt is C3-C11Containing 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 formula is RfC6H4SO3The substituted benzene sulphur of M
Acid, benzene sulfonate or benzene sulfonate, wherein RfIt is C3-C12Containing 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 weight portions, the addition of dispersant is 0.01～4 weight portion.
In order to improve the stability of monomer dispersion liquid, also optionally stabilizer is added in dispersion liquid.The present invention's
In one preferable example, using fluorochemical polyether as dispersion liquid stabilizer.The addition of stabilizer is without particular limitation, as long as
Energy stable dispersions simultaneously have no adverse effects to subsequent polymerisation and the fluoroelastomer for generating.The common skill of this area
Art personnel are readily determined the addition of appropriate stabilizer after present disclosure has been read with reference to its professional knowledge
Amount.
It is without particular limitation suitable for the polymerization temperature of the present invention, it is preferable that the polymerization temperature is 20～110 DEG C, excellent
Elect 30～100 DEG C as.
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.
Without particular limitation suitable for the initiator of the inventive method, it can be polymerization initiator commonly used in the art.
The initiator is generally water-soluble peroxide, and its example includes：Persulfate, such as ammonium persulfate, sodium peroxydisulfate, persulfuric acid
Potassium；Oxidation-reduction trigger system, wherein oxidant can be persulfates, such as ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate；
Water-soluble organic peroxide, such as hydrogen peroxide, TBHP, 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 weight portions, the addition for the initiator of the fluoroelastomer that is polymerized can be 0.005
～2 weight portions.
The inventive method is optionally added chain-transferring agent.
Can be any compound that can continue fluoroelastomer copolymerization suitable for the chain-transferring agent of the inventive method,
Its illustrative example includes：Alcohols, such as methyl alcohol, isopropanol；Ethers, such as dimethyl ether, diethyl ether, diη-propyl ether, methyl- tert
Butyl ether；Ketone, such as acetone, MEK；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- chlorodifluoroethanes of mono- chlorine of 1- one, bromomethane, iodomethane, dibromo first
The bromo- 2,2- Difluoroethanes of alkane, diiodomethane, 1,2- bis-, the iodo- 2,2- Difluoroethanes of 1,2- bis-, 1,2- dibromotetrafluoroethanes, 1,2-
Diiodo- HFC-134a, 1,4- dibromo octafluorobutanes, 1,4- diiodo- octafluorobutanes；Aliphatic alkane, such as methyl cyclopentane, methyl ring
Hexane etc.；Bromide, iodide, such as lithium bromide, sodium bromide, KBr, lithium iodide, sodium iodide, KI.
Based on fluoroelastomer described in 100 weight portions, the addition of chain-transferring agent can be 0.001～20 weight portion.
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 less, and molecular weight is lower.It is described fluorine-containing in the range of above-mentioned Mooney viscosity
Elastomer has good processing characteristics and cross-linking properties.
Compared with prior art, the present invention has following beneficial effect：
After using the fluorine-containing modification by copolymerization of ether monomer containing silene, have been equipped with after fluoroelastomer is crosslinked excellent low temperature resistant
Performance, not higher than -35 DEG C of vitrification point.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill to this area
For personnel, without departing from the inventive concept of the premise, some deformations and improvement can also be made.These belong to the present invention
Protection domain.
Indices detection method in the present invention is respectively：
1st, F is used19NMR, HNMR determine the copolymerization composition of fluoroelastomer, and solvent is deuterated acetone.
2nd, by vitrification point Tg of ASTM D3418 standard test fluoroelastomers.Heating rate is 10 DEG C/min.
3rd, by the Mooney viscosity of ASTM D1646 standard test fluoroelastomers, temperature of the measurement is 121 DEG C.
4th, by the low temperature retraction temperature TR10 of ASTM D1329 standard test fluoroelastomer vulcanized rubbers.
5th, by the strength character of ASTM D412 standard test fluoroelastomer vulcanized rubbers.
Embodiment 1
The present embodiment is related to a kind of preparation method of fluoroelastomer, specifically includes following steps：
In 10 liters of vertical response kettles, addition 4358 grams of deionized waters, 70 grams of Sodium perfluorooctanoates and its homologous mixtures,
108 grams of dipotassium hydrogen phosphates, 2642 grams of dimethallyl epoxide (3,3,3- trifluoro propyls) silane.Closed reaction kettle, vacuumizes simultaneously
With nitrogen displacement, until oxygen content is less than or equal to 10ppm in reactor.Then start to be stirred with the speed of 800rpm, will
Reactor internal temperature rises to 50 DEG C, supplements copolymerization mix monomer to absolute pressure in reactor and reaches 1.5MPa, the copolymerization
Mix monomer mol ratio accounts for 55%, hexafluoropropene and accounts for 45% for vinylidene.Add 18 grams of sodium peroxydisulfates, 10 grams of bisulfites
Sodium, 14 grams of diethyl malonates, start polymerisation.Absolute pressure in reactor is maintained by adding copolymerization mix monomer
1.5MPa, the copolymerization mix monomer mol ratio added accounts for 78%, hexafluoropropene and accounts for 22% for vinylidene.Work as reactor
When interior emulsion solid content reaches 20%, terminate polymerisation.
Jing F19NMR, HNMR are determined, and a mole copolymerization for gained fluoroelastomer consists of VDF:HFP:Dimethallyl epoxide
(3,3,3- trifluoro propyls) silane=54.7%:15.4%:29.9%.
Formula sulfuration as shown in table 1 obtains fluoroelastomer vulcanized rubber, determines the performance of the fluoroelastomer for obtaining, 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 includes following steps：
In 10 liters of vertical response kettles, addition 4358 grams of deionized waters, 70 grams of Sodium perfluorooctanoates and its homologous mixtures,
108 grams of dipotassium hydrogen phosphates, 2642 grams of dimethallyl epoxide (3,3,3- trifluoro propyls) silane.Closed reaction kettle, vacuumizes simultaneously
With nitrogen displacement, until oxygen content is less than or equal to 10ppm in reactor.Then start to be stirred with the speed of 800rpm, will
Reactor internal temperature rises to 50 DEG C, supplements copolymerization mix monomer to absolute pressure in reactor and reaches 1.5MPa, the copolymerization
Mix monomer mol ratio accounts for 55%, hexafluoropropene and accounts for 45% for vinylidene.Add 18 grams of sodium peroxydisulfates, 10 grams of bisulfites
Sodium, 9.5 grams of diiodomethanes, start polymerisation.Absolute pressure in reactor is maintained by adding copolymerization mix monomer
1.5MPa, the copolymerization mix monomer mol ratio added accounts for 77%, hexafluoropropene and accounts for 22%, 2- iodo- 1 for vinylidene,
1- difluoroethylenes account for 1%.When emulsion solid content reaches 20% in reactor, terminate polymerisation.
Jing F19NMR, HNMR are determined, and a mole copolymerization for gained fluoroelastomer consists of VDF:HFP:Dimethallyl epoxide
(3,3,3- trifluoro propyls) silane:The iodo- 1,1- difluoroethylenes of 2- account for=54.6%:15.1%:29.6%:0.7%.
Formula sulfuration as shown in table 1 obtains fluoroelastomer vulcanized rubber, determines the performance of the fluoroelastomer for obtaining, 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 includes following steps：
In 10 liters of vertical response kettles, addition 4276 grams of deionized waters, 70 grams of Sodium perfluorooctanoates and its homologous mixtures,
108 grams of dipotassium hydrogen phosphates, 2724 grams of dimethallyl epoxide (3,3,3- trifluoro propyls) silane.Closed reaction kettle, vacuumizes simultaneously
With nitrogen displacement, until oxygen content is less than or equal to 10ppm in reactor.Then start to be stirred with the speed of 800rpm, will
Reactor internal temperature rises to 50 DEG C, supplements copolymerization mix monomer to absolute pressure in reactor and reaches 1.5MPa, the copolymerization
Mix monomer mol ratio accounts for 65%, tetrafluoroethene and accounts for 10%, hexafluoropropene and accounts for 25% for vinylidene.Add 18 grams of persulfuric acid
Sodium, 10 grams of sodium hydrogensulfites, 12.4 grams of Trifluoroacetic Acid Ethyl Esters, start polymerisation.Reaction is made by adding copolymerization mix monomer
Absolute pressure maintains 1.5MPa in kettle, and the copolymerization mix monomer mol ratio added accounts for 78%, tetrafluoro for vinylidene
Ethene accounts for 10%, hexafluoropropene and accounts for 12%.When emulsion solid content reaches 20% in reactor, terminate polymerisation.
Jing F19NMR, HNMR are determined, and a mole copolymerization for gained fluoroelastomer consists of VDF:TFE:HFP:Dimethallyl oxygen
Base (3,3,3- trifluoro propyls) silane=54.7%:7.1:8.5%:29.7%.
Formula sulfuration as shown in table 1 obtains fluoroelastomer vulcanized rubber, determines the performance of the fluoroelastomer for obtaining, 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 includes following steps：
In 10 liters of vertical response kettles, addition 4677 grams of deionized waters, 70 grams of Sodium perfluorooctanoates and its homologous mixtures,
108 grams of dipotassium hydrogen phosphates, 2323 grams of dimethallyl epoxide (3,3,3- trifluoro propyls) silane.Closed reaction kettle, vacuumizes simultaneously
With nitrogen displacement, until oxygen content is less than or equal to 10ppm in reactor.Then start to be stirred with the speed of 800rpm, will
Reactor internal temperature rises to 50 DEG C, supplements copolymerization mix monomer to absolute pressure in reactor and reaches 1.3MPa, the copolymerization
Mix monomer mol ratio accounts for 63.1%, PMVE and accounts for 36.9% for vinylidene.Add 18 grams of sodium peroxydisulfates, 10 grams of bisulfites
Sodium, 9.5 grams of diiodomethanes, start polymerisation.Absolute pressure in reactor is maintained by adding copolymerization mix monomer
1.3MPa, the copolymerization mix monomer mol ratio added accounts for 81%, PMVE and accounts for iodo- 1, the 1- bis- of 18%, 2- for vinylidene
PVF accounts for 1%.When emulsion solid content reaches 20% in reactor, terminate polymerisation.
Jing F19NMR, HNMR are determined, and a mole copolymerization for gained fluoroelastomer consists of VDF:PMVE:Dimethallyl epoxide
(3,3,3- trifluoro propyls) silane:The iodo- 1,1- difluoroethylenes of 2- account for=61%:13.4%:24.8%:0.8%.
Formula sulfuration as shown in table 1 obtains fluoroelastomer vulcanized rubber, determines the performance of the fluoroelastomer for obtaining, 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 includes following steps：
In 10 liters of vertical response kettles, addition 7000 grams of deionized waters, 70 grams of Sodium perfluorooctanoates and its homologous mixtures,
108 grams of dipotassium hydrogen phosphates.Closed reaction kettle, vacuumizes and uses nitrogen displacement, until oxygen content is less than or equal in reactor
10ppm.Then start to be stirred with the speed of 800rpm, reactor internal temperature is risen to into 50 DEG C, supplement copolymerization mixing single
Body to absolute pressure in reactor reaches 1.5MPa, and the copolymerization mix monomer mol ratio accounts for 55%, hexafluoro for vinylidene
Propylene accounts for 45%.18 grams of sodium peroxydisulfates, 10 grams of sodium hydrogensulfites, 14 grams of diethyl malonates are added, starts polymerisation.Pass through
Adding copolymerization mix monomer makes absolute pressure in reactor maintain 1.5MPa, the copolymerization mix monomer mol ratio added
78%, hexafluoropropene is accounted for for vinylidene account for 22%.When emulsion solid content reaches 20% in reactor, terminate polymerisation.
Jing F19NMR, HNMR are determined, and a mole copolymerization for gained fluoroelastomer consists of VDF:HFP=77.6%:22.4%.
Formula sulfuration as shown in table 1 obtains fluoroelastomer vulcanized rubber, determines the performance of the fluoroelastomer for obtaining, 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 includes following steps：
In 10 liters of vertical response kettles, addition 7000 grams of deionized waters, 70 grams of Sodium perfluorooctanoates and its homologous mixtures,
108 grams of dipotassium hydrogen phosphates.Closed reaction kettle, vacuumizes and uses nitrogen displacement, until oxygen content is less than or equal in reactor
10ppm.Then start to be stirred with the speed of 800rpm, reactor internal temperature is risen to into 50 DEG C, supplement copolymerization mixing single
Body to absolute pressure in reactor reaches 1.3MPa, the copolymerization mix monomer mol ratio accounts for 63.1% for vinylidene,
PMVE accounts for 36.9%.18 grams of sodium peroxydisulfates, 10 grams of sodium hydrogensulfites, 9.5 grams of diiodomethanes are added, starts polymerisation.Pass through
Adding copolymerization mix monomer makes absolute pressure in reactor maintain 1.3MPa, the copolymerization mix monomer mol ratio added
81%, hexafluoropropene being accounted for for vinylidene and accounting for the iodo- 1,1- difluoroethylenes of 18%, 2- account for 1%..When emulsion solid content in reactor
When reaching 20%, terminate polymerisation.
Jing F19NMR, HNMR are determined, and a mole copolymerization for gained fluoroelastomer consists of VDF:PMVE:The iodo- 1,1- difluoros second of 2-
Alkene=81.1%:18.3%:0.6%.
Formula sulfuration as shown in table 1 obtains fluoroelastomer vulcanized rubber, determines the performance of the fluoroelastomer for obtaining, 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
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can within the scope of the claims make various modifications or modification, this not shadow
Ring the flesh and blood of the present invention.
Claims (9)
1. a kind of low-temperature-resistant elastic body containing fluorine, it is characterised in that include 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%.
2. low-temperature-resistant elastic body containing fluorine as claimed in claim 1, it is characterised in that the mix monomer containing vinylidene
Selected from tetrafluoroethene, vinylidene, hexafluoropropene, vinyl compound that free radical copolymerization can be carried out with vinylidene
In at least one, and described can carry out on the vinyl in the vinyl compound of free radical copolymerization with vinylidene
Be connected with fluorine atom, containing at least one in fluoroalkyl and fluoroalkoxy.
3. low-temperature-resistant elastic body containing fluorine as claimed in claim 2, it is characterised in that described to carry out free radical with vinylidene
The vinyl compound of copolymerization is selected from PVF, trifluoro-ethylene, CTFE, tetrafluoroethene, 3,3,3- trifluoropropyls
Alkene, perfluoroethyl vinyl, perfluoro-n-butyl group ethene, hexafluoropropene, perfluoroalkyl vinyl ether：As perfluoro methyl vinyl ether,
Perfluoroethylvinyl ether, perfluoropropylvinylether, perfluor (3- butylene vinyl ethers), perfluor (2,2- dimethyl -1,3-
Dioxole), at least one in the fluoro- 1,3- dioxoles of 4- trifluoromethoxies -2,2,5- three.
4. low-temperature-resistant elastic body containing fluorine as claimed in claim 1, it is characterised in that the general molecular formula of the fluorine-containing silicon-containing monomer
For CH2=CH (CH2)mOSiRR’(CH2)nCF3, m=1 or 2, R, R ' and it is methyl, ethyl, methoxy or ethoxy, R and R ' can be with
It is identical can also be different, n=2～4.
5. low-temperature-resistant elastic body containing fluorine as claimed in claim 4, it is characterised in that the fluorine-containing silicon-containing monomer is selected from dimethoxy
Base allyloxy (3,3,3- trifluoro propyls) silane, methyl methoxy base allyloxy (3,3,3- trifluoro propyls) silane, dimethyl
Allyloxy (3,3,3- trifluoro propyls) silane, dimethoxy allyloxy (4,4,4- trifluoro normal-butyls) silane, methyl methoxy
Base allyloxy (4,4,4- trifluoro normal-butyls) silane, dimethallyl epoxide (4,4,4- trifluoro normal-butyls) silane, diethoxy
Base allyloxy (3,3,3- trifluoro propyls) silane, ethyl ethyoxyl allyloxy (3,3,3- trifluoro propyls) silane, diethyl
Allyloxy (3,3,3- trifluoro propyls) silane, diethoxy allyloxy (4,4,4- trifluoro normal-butyls) silane, ethyl ethoxy
In base allyloxy (4,4,4- trifluoro normal-butyls) silane, diethyl allyloxy (4,4,4- trifluoro normal-butyls) silane at least
It is a kind of.
6. low-temperature-resistant elastic body containing fluorine as claimed in claim 1, it is characterised in that the general molecular formula of the cure site monomer is
CX2=CX (Z), wherein, X is H or F, Z are Br, I, Cl or RfU, and U is Br, I, Cl, CN or-CX=CX2, the formula of Rf for-
(OCF2CF(CF3))nO(CF2) m-, n=0～3, m=1～8.
7. low-temperature-resistant elastic body containing fluorine as claimed in claim 6, it is characterised in that the cure site monomer is selected from 2- bromo- 1,
The iodo- 1,1- difluoroethylenes of 1- difluoroethylenes, 2-, bromotrifluoroethylene, trifluoro iodoethylene, the fluoro- 1- butylene of the bromo- 3,3,4,4- tetra- of 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 ethene of perfluoro-n-butyl group ethene, 4-, the bromo- perfluor n-hexyl vinyls of 6-, the iodo- perfluor n-hexyl vinyls of 6-, 1,
2- divinyl hexafluoroethanes, 1,4- divinyl perfluorinated butanes, 1,6- divinylperfluorhexanes, 1,8- divinyl perfluors
Octane, perfluor (2- bromoethyl vinyl ethers), perfluor (2- iodine ethyl vinyl ethers), 2- vinyl perfluoro ethyl vinyl ethers,
2- (2- bromoethyls) perfluoroethylvinyl ether, 2- (2- iodine ethyls) perfluoroethylvinyl ether, 2- itrile group perfluoroethyl vinyls
Base ether, 3- itrile group perfluoropropylvinylethers, 4- itrile group perfluoro-n-butyl group vinyl ethers, perfluor (2- acetonitrile-base propoxyl group second
Alkene ether), perfluor (2- propionitrile base propoxy base ethers), in perfluor (2- n-Butyronitrile base propoxy base ethers) at least one
Kind.
8. a kind of preparation method of the low-temperature-resistant elastic body containing fluorine as described in any one in Claims 1 to 5, its feature exists
In comprising the steps：
After fluorine-containing silicon-containing monomer is dispersed in water, the mix monomer containing vinylidene, cure site monomer are added；
Initiator is added, polymerisation is carried out, described fluoroelastomer is obtained.
9. a kind of preparation method of the low-temperature-resistant elastic body containing fluorine as described in any one in Claims 1 to 5, its feature exists
In comprising the steps：
After fluorine-containing silicon-containing monomer is dispersed in water, the mix monomer containing vinylidene, cure site monomer are added；
Initiator, chain-transferring agent are added, polymerisation is carried out, described fluoroelastomer is obtained.
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| CN109762092A (en) * | 2019-01-25 | 2019-05-17 | 常熟三爱富中昊化工新材料有限公司 | A kind of synthetic method of novel low temperature resistant fluorine silicone rubber |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1336938A (en) * | 1999-11-12 | 2002-02-20 | 阿托费纳化学股份有限公司 | Fluoropolymers containing organo-silanes and methods of making the same |
| US20060160972A1 (en) * | 2003-03-11 | 2006-07-20 | Solvay (Societe Anonyme) | Functionalized fluoromonomers and their copolymers with vinylidende fluoride |
| 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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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1336938A (en) * | 1999-11-12 | 2002-02-20 | 阿托费纳化学股份有限公司 | Fluoropolymers containing organo-silanes and methods of making the same |
| US20060160972A1 (en) * | 2003-03-11 | 2006-07-20 | Solvay (Societe Anonyme) | Functionalized fluoromonomers and their copolymers with vinylidende fluoride |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| J. GUIOT等: "Original Crosslinking of Poly(vinylidene fluoride) via Trialkoxysilane-Containing Cure-Site Monomers", 《JOURNAL OF POLYMER SCIENCE: PART A: POLYMER CHEMISTRY》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762092A (en) * | 2019-01-25 | 2019-05-17 | 常熟三爱富中昊化工新材料有限公司 | A kind of synthetic method of novel low temperature resistant fluorine silicone rubber |
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