CN106496397A - Fluoroelastomer, the resin combination with the fluoroelastomer and preparation method - Google Patents
Fluoroelastomer, the resin combination with the fluoroelastomer and preparation method Download PDFInfo
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- CN106496397A CN106496397A CN201610924380.7A CN201610924380A CN106496397A CN 106496397 A CN106496397 A CN 106496397A CN 201610924380 A CN201610924380 A CN 201610924380A CN 106496397 A CN106496397 A CN 106496397A
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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Abstract
The invention discloses a kind of resistance to extremely low temperature fluoroelastomer and combinations thereof, in the fluoroelastomer, in addition to the two or more monomer of tetrafluoroethene, vinylidene, hexafluoropropene is combined, also alternatively include a kind of cure site monomer, and a kind of fluorine-containing ether monomer containing silene.The fluoroelastomer obtained by each monomer copolymerization, through vulcanization crosslinking after, with splendid cryogenic property, its brittleness temperature be less than 55 DEG C.Additionally, by the surface treatment to filler, improve its compatibility with fluoroelastomer, its consumption can be reduced, so that glue content is improved, enhance the physical and mechanical propertiess of vulcanizate, particularly tearing strength and can be more than 30MPa.Simultaneously as the raising of glue content, its compression set is smaller than 20%.
Description
Technical field
The present invention relates to a kind of resistance to extremely low temperature fluoroelastomer and combinations thereof.It is more particularly related to a kind of
The surface modifying method of filler so as to which the compatibility with resistance to extremely low temperature fluoroelastomer increases, to improve its cross-linking properties.With this
Inventive method can easily improve the cross-linking properties of the fluoroelastomer composition, resulting product have lower temperature resistance excellent,
The features such as compression set rate is low, physical and mechanical propertiess are excellent.
Background technology
Fluoroelastomer refers to that main chain or the carbon atom on side chain are connected to a kind of synthesis bullet of the extremely strong fluorine atom of electronegativity
Gonosome.As C-F bond energys are very big, and the covalent radius of fluorine atom is equivalent to the half of C-C bond distance, and therefore fluorine atom can be
C-C main chains are shielded well so as to superpower stability.This characteristic makes fluoroelastomer have other elastomers incomparable
Excellent properties, such as oil resistant, chemical proofing, good physical and mechanical propertiess and weatherability, electrical insulating property and radiation resistance.
Therefore fluoroelastomer is widely used in the severe rugged environments such as Aeronautics and Astronautics, automobile, oil, is nothing in national defence sophisticated industry
The critical material that method is substituted.
But where fluoroelastomer also has itself deficiency, i.e., cryogenic property is not good enough.January 28 " challenger " in 1986
Number space shuttle goes up to the air 73 seconds after-explosions, and immediate cause is exactly that two viton seal rings between booster afterbody cage connection exist
Fail under low temperature, allow to use temperature low about 6 DEG C than rubber using temperature, and the serious accident for causing.Same the reason for, the U.S.
The time of 2 weeks postponed by National Aeronautics and Space Administration's transmitting " Endea Nour " number space shuttle.With works such as automobile, Aeronautics and Astronautics
Developing rapidly for industry, is continuously increased to the demand of fluorubber, and the performance to fluorubber, particularly resistance to low temperature are proposed more
High requirement.
In recent years, it is the lower temperature resistance that improves fluoroelastomer, has attempted multiple methods both at home and abroad.These methods can be divided into
Two kinds：A kind of is to be used in combination fluorubber and other low temperature resistant excellent blend rubbers；One kind is by copolymerization means, changes molecule
The low-temperature flexibility of chain, introduces low temperature resistant characteristic group on fluorubber molecular backbone or side chain.
External research tendency is introduced on fluorubber main chain or on side chain special mainly by changing copolymerization process at present
Property group is improving low-temperature flexibility.The low temperature resistant fluorubber Viton GLT that Du Pont (Dupont) company develops at first are inclined fluorine
The quaternary of ethylene-tetrafluoroethylene-perfluoro methyl vinyl ether (PMVE) and the bromo- tetra- fluoro- 1-butylene (BTFB) of 3,3,4,4- of 4- is altogether
Polymers, wherein BTFB are crosslinking points monomers.By changing copolymerization composition, the copolymer of different Oil repellents is obtained, so which has
There are different medium-resistances and resistance to low temperature.Common fluorubber is compared, which has more preferable low-temperature flexibility, takes into account again
Excellent physical and mechanical propertiess and processing characteristics.
The open perfluor (alkyl vinyl ether) of patent US 4418186, vinylidene and Third monomer cause in Ammonium persulfate.
Polymerization under agent, in the presence of emulsifying agent.The polymer emulsion for obtaining is chilled, washs drying, obtains fluorine ether rubber
Glue, its vitrification point are -21～-36 DEG C.
Patent WO0149758A1 discloses perfluor (methyl vinyl ether) or perfluor (propyl vinyl ether) and inclined fluorine second
The fluoroether rubber that alkene is obtained by radical polymerization, its initiator is peroxide, the vitrification point of the elastomer for obtaining for-
44℃.
Patent US20030670086, EP2002073926319, US20020138069 disclose a kind of elasticity of fluorubber
Body, the unit of its copolymerization is ethylene, tetrafluoroethene and perfluoroether, with excellent cryogenic property, brittleness temperature -25～-30
℃.
Patent US20010009759, EP2001090529616 discloses a kind of elastomer of fluorubber, the list of its copolymerization
Unit is vinylidene and perfluoroalkyl vinyl ether, with excellent cryogenic property, -30～-33 DEG C of brittleness temperature.
Patent US2004236028, US20040800893 discloses a kind of elastomer of fluorubber, its copolymeric structure for-
[CF2CFH-O-Rf-CF2CH2O]n-, with excellent cryogenic property, -35 DEG C or so of brittleness temperature.
Patent US20010956681, US20010956681 discloses a kind of elastomer of fluorubber, the unit of its copolymerization
For vinylidene, tetrafluoroethene and perfluoroalkyl alkylene ether and 2- hydrogen pentafluoropropenes.There is excellent cryogenic property, fragility
- 35～-40 DEG C of temperature.
Patent WO2000US32674 discloses a kind of elastomer of fluorubber, and the unit of its copolymerization is vinylidene, tetrafluoro
Ethylene, perfluoroalkyl alkylene ether, 2- hydrogen pentafluoropropene and I.There is excellent cryogenic property, -45 DEG C of brittleness temperature
Left and right.
Patent US73324396A discloses a kind of elastomer of fluorubber, and the unit of its copolymerization is vinylidene, tetrafluoro second
Alkene, hexafluoropropene and perfluoroalkyl vinyl ether.There is excellent cryogenic property, -40～-45 DEG C of brittleness temperature.
Such patent, though after perfluoroalkyl alkylene ether modification by copolymerization, cryogenic property is improved, perfluor alkane
The monomers such as base alkylene polyethers need to be prepared using electrolytic method, univalent prohibitively expensive and limits throughput.
Also carried out by improving the research of fluorubber resistance to low temperature with other rubber blendings.
CN200910311651.1 discloses fluorubber and formula of inner rubber layer of low-temperature resistant fuel oil rubber tube processed is blended with fluoroether rubber；
CN200920164820.9 discloses fluorubber with butyl rubber compound adhesive tape and the protective garment made using the compound adhesive tape；
CN200810219534.8 discloses a kind of fluorubber and Silicone Rubber Blends and preparation method thereof.The invention is related to a kind of fluorine rubber
Glue and Silicone Rubber Blends and preparation method thereof.By weight percentage, fluorubber constitutes as follows with Silicone Rubber Blends：Fluorine rubber
Glue 12～50%, silicone rubber 12～50%, bulking agent 2.5～10%, acid-acceptor 2.5～10%, reinforcing filler 12～35%,
Constitution controller 0.5～7%, vulcanizing agent 0.5～3% and crosslinking coagent；CN201110253701.2 discloses a kind of low cost
And rubber composite of good performance and preparation method thereof, the composite its be made up of following raw materials according mixture：Fluorubber
60-70 parts (weight, similarly hereinafter), 30～40 parts of butadiene-styrene rubber, 10～15 parts of nitrile rubber.In addition with by add plasticizer come
Improve the lower temperature resistance of fluorubber.
Either add plasticizer or and other rubber blendings improving the lower temperature resistance of fluorubber, have and itself limit to
Property.Improving plasticizer can cause the compression set of fluorubber product to increase, and also result in fluorubber high temperature resistant and grease resistance
Performance reduces；Using with other blend rubbers so that what the local of product was embodied is the performance of other rubber, oil resistant and solvent resistant
Performance can decline.
Therefore, this area remains a need for developing a kind of fluoroelastomer of resistance to extremely low temperature, and the fluoroelastomer main chain is introduced
Monomer containing low temperature resistant group, this raw material monomer are easily made, and copolymerization is controllable, and also have physical and mechanical propertiess excellent, and compression is forever
The advantages of deforming low and easy to process long.
Content of the invention
It is an object of the invention to provide a kind of fluoroelastomer, the resin combination with fluoroelastomer and preparation side
Method, to solve the problems referred to above in the presence of prior art.
A kind of fluoroelastomer, it include the following comonomer by mole percent：
Mix monomer containing vinylidene：55～99%；
Fluorine-containing silicon-containing monomer：1～40%；
Cure site monomer：0～5%.
Preferably, the fluoroolefin selected from tetrafluoroethene, vinylidene, hexafluoropropene, can be with vinylidene
Carry out at least one in the vinyl compound of free radical copolymerization, and described free radical can be carried out altogether with vinylidene
Be connected with fluorine atom on vinyl in the vinyl compound of polyreaction, containing at least in fluoroalkyl and fluoroalkoxy
Kind.
Used as further preferred scheme, the fluoroolefin includes to carry out free radical copolymerization with vinylidene
At least one in vinyl compound and tetrafluoroethene, vinylidene, hexafluoropropene.
It can be that C1-C8 contains fluoroalkyl containing fluoroalkyl to be connected on vinyl, and preferable C1-C4 contains fluoroalkyl, such as fluorine
Methyl, difluoromethyl, perfluoro-methyl, 1- fluoro ethyls, 2- fluoro ethyls, perfluoro-ethyl, 1- fluoropropyls, bis- fluoropropyls of 1,1-, 1,1,
1- trifluoro propyls, perfluoro propyl.
The fluoroalkoxy being connected on vinyl can be C1-C12 fluoroalkoxy, preferable C1-C6 fluoroalkoxy,
Such as fluorine methoxyl group, difluoro-methoxy, perfluoromethoxy, 1- fluorine ethyoxyls, 2- fluorine ethyoxyls, pentafluoroethoxy, the third oxygen of 1- fluorine
Base, 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,
C2-6 alkene or C3-11 perfluoroalkyl vinyl ethers containing fluoroalkyl or fluoroalkoxy.
In a preferable example of the present invention, the comonomer is selected from fluorothene, trifluoro-ethylene (TrFE), trifluoro chlorine
Ethylene (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 third
Base vinyl ethers (PPVE), perfluor (3- butylene vinyl ethers), perfluor (2,2- dimethyl -1,3- dioxoles)
(PDD), 4- trifluoromethoxies -2,2,5- three fluoro- 1,3- dioxoles (TTD) or its two or more mixture.
Preferably, the general molecular formula of the fluorine-containing silicon-containing monomer is [CH3(CH2)n]2-Si[(CH2)mCF3)]-O
(CH2)pCH=CH2, wherein, n, m, p are no more than 6 integer.
The fluorine-containing silicon-containing monomer can be first CH by formula for chlorosilane and the formula of HClSiRR '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 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 and R ' can also may be used with identical
With difference, n=2～4, generation formula are 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 are 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 bromo- tetra- fluoro- 1-butylene of 3,3,4,4- of fluorine bromine ethylene, trifluoro iodoethylene, 4-, the iodo- tetra- fluoro- 1-butylene of 3,3,4,4- of 4-, 4- bromo- 1,
The iodo- tri- fluoro- 1-butylene of 1,1,2- of tri- fluoro- 1-butylene of 1,2-, 4-, the bromo- perfluorobutyl ethylenes of 6-, the iodo- perfluorobutyl ethylenes of 6-, 8-
The iodo- perfluorohexyl ethylene of bromo- perfluorohexyl ethylene, 8-, 1,2- divinyl hexafluoroethanes, 1,4- divinyl perfluorinated butanes,
1,6- divinylperfluorhexanes, 1,8- divinylperfluorooctanes, perfluor (2- bromoethyl vinyl ethers), perfluor (2- iodine second
Base vinyl ethers), 2- vinyl perfluoro ethyl vinyl ethers, 2- (2- bromoethyls) perfluoroethylvinyl ether, 2- (2- iodine second
Base) perfluoroethylvinyl ether, 2- itrile group perfluoroethylvinyl ethers, 3- itrile group perfluoropropylvinylethers, 4- itrile groups be complete
Fluorine n-butyl vinyl ether, perfluor (2- acetonitrile-base propoxy base ethers), perfluor (2- propionitrile base propoxy base ethers), complete
At least one in fluorine (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.
Which 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, is carried out polyreaction, obtain described fluoroelastomer.
In order to improve dispersibility 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 dispersibility and will not be to subsequent polyreaction
Or the polymer for being formed has a negative impact.
Equally, the type of dispersant is also without particular limitation, if it can improve the dispersibility of monomer and will not to
Polyreaction 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 hydrion 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 hydrion 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, stabilizer is added also optionally in dispersion liquid.The present invention's
In one preferable example, fluorochemical polyether is used as the stabilizer of dispersion liquid.The addition of stabilizer is without particular limitation, as long as
Energy stable dispersions simultaneously have no adverse effects to subsequent polyreaction and the fluoroelastomer for generating.The common skill of this area
Art personnel after present disclosure has been read, in conjunction with the addition that its Professional knowledge is readily determined appropriate stabilizer
Amount.
The polymerization temperature for being applied to the present invention is without particular limitation, 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.
The initiator for being applied to the inventive method is without particular limitation, and 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 solublity 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 sulfur
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.
The chain-transferring agent for being applied to the inventive method 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, butanone；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 ester, 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, dichlorodifluoromethane, F-22, mono- chlorine of 1-, one fluoro- 2- chlorodifluoroethanes, bromomethane, iodomethane, dibromo first
Alkane, diiodomethane, bis- bromo- 2,2- Difluoroethanes of 1,2-, bis- iodo- 2,2- Difluoroethanes of 1,2-, 1,2- dibromotetrafluoroethanes, 1,2-
Diiodo- tetrafluoroethane, 1,4- dibromo Octafluorobutane .s, 1,4- diiodo- Octafluorobutane .s；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 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.In the range of above-mentioned Mooney viscosity, described fluorine-containing
Elastomer has good processing characteristics and cross-linking properties.
A kind of resin combination containing aforementioned fluoroelastomer, it include the following component of percentage：
There is this resin combination containing said components excellent physical and mechanical propertiess, resistance to low temperature and compression resistant to become
Shape performance.
Preferably, described can curable component include at least one in cross-linking agent and crosslinking coagent.
Preferably, the surface treatment method of described filler is：
After described filler is mixed with polyfluoroalkanoyl peroxide, reacted at 0～200 DEG C.
The polyfluoroalkanoyl peroxide is selected from fluorochemical polyether base acyl peroxide, and the formula of wherein fluorochemical polyether base is
X(CF2)aO(CF2O)b(CF2CF2O)c(CF2CF(CF3)O)d(CF2CFClO)e(CF2)f(CF(CF3))g, X be H, Cl or F, a, b,
C, d, e, f, g=0～10；The polyfluoroalkanoyl peroxide is also selected from perfluoroalkyl acyl superoxide, such as perfluor acetyl
Peroxide, Perfluorodipropionyl peroxides, perfluor butyryl peroxide, perfluor hexanoyl peroxide, perfluor oenanthyl peroxide,
Perfluoro-octanoyl peroxide, perfluorocyclohexyl acyl peroxide.
After filler surface treated, microstructure changes, and can improve its compatibility with fluoroelastomer, and minimizing is filled out
The usage amount of material, therefore glue content accordingly improve, its through sulfuration after physical and mechanical propertiess, pressure change performance significantly increases.
Filler surface treatment degree can be characterized by particle diameter, specific surface area.The present invention example in, filler through surface at
After reason, its mean diameter drops to 5 μm by original 20 μm, and specific surface area is by original 55g/m2Increase to 146g/m2.
Preferably, the cross-linking agent be organic peroxide, selected from dibenzoyl peroxide, cumyl peroxide, 1,
Withered dilute, the hydroperoxidation diisopropylbenzene (DIPB) of 3- bis- (tert-butyl group crosses isopropyl) benzene, t-butylcumyl peroxide, hydroperoxidation, excessively benzene first
Tert-butyl acrylate, 2,5- dimethyl -2,5- dibenzoyl peroxyhexanes, di-t-butyl peroxide, two uncles of 2,5- dimethyl -2,5-
At least one in butyl peroxy hexane.Preferably dibenzoyl peroxide, cumyl peroxide, tert-butyl peroxide are withered
Base, 2,5- dimethyl -2,5- dibenzoyl peroxyhexanes, 2,5- dimethyl -2,5- di-t-butyl peroxyhexanes, benzylhydroperoxide
In the tert-butyl ester, di-t-butyl peroxide few one kind.More preferably dibenzoyl peroxide, cumyl peroxide, 1,3-
In two (tert-butyl group crosses isopropyl) benzene, 2,5- dimethyl -2,5- di-t-butyl peroxyhexanes, t-butyl perbenzoate at least one
Kind.
Preferably, the crosslinking coagent is unsaturated polyfunctional compound, and it can effectively improve cross-linking efficiency.Suitable
Unsaturated polyfunctional compound is low selected from triallyl cyanurate, triallyl isocyanurate, triallyl isocyanurate
Polymers, three methallyl of isocyanuric acid, 1,3,5- triacryl hexahydro -1,3,5- triazines, triallyltrimelitate,
Phenylenediamine BMI, p-phthalic acid diine propyl ester, diallyl phthalate, the polysiloxanes comprising vinyl
At least one in oligomer, the polysiloxane oligomers containing vinyl such as Polymethyl methacrylate and poly- first
Base phenylethylene radical siloxane.
Based on 100 mass parts cross-linkable fluoroelastomers in cross-linkable composition of the present invention, the content of the crosslinking coagent
For 1～10 mass parts, preferably preferably 1～7 mass parts, 1～5 mass parts.Within this range, tensile strength can be obtained and breaks
Split the crosslinking rubber that percentage elongation reaches excellent balance.
Amount of filler based on 100 mass parts fluoroelastomers in cross-linkable composition of the present invention, after institute's surface treated
For 1～20 mass parts, more preferably preferably 5～20 mass parts, 5～15 mass parts.
The preparation method of cross-linkable composition of the present invention is without particular limitation, can be arbitrary method of the invention.At this
In one example of invention, the preparation method of cross-linkable composition of the present invention is included following components mix homogeneously：Fluorine-containing elasticity
Body, cross-linking agent, crosslinking coagent, filler.Can be mixed with conventional mixing arrangement, such as mill, kneader or banburying
Machine.The working condition for mixing is not particularly limited, is generally mixed at about 30～80 DEG C about 5～20 minutes.
Cross-linkable composition of the present invention can heat cross-linking under stress.Heating-up temperature is usually 80～260 DEG C, preferably
100～200 DEG C.Heat time heating time usually not limits, but according to the species that cross-linking agent is organic peroxide, heat time heating time is usual
For 1 minute～2 hours, preferably 5 minutes～1 hour.
The cross-linking products obtained after heating are carried out secondary cross-linking, physical property can be so efficiently modified.For example, it is possible to
The post bake for carrying out at 100～300 DEG C, preferably 150～250 DEG C about 2～30 hours is processed.
Based on 100 mass parts fluoroelastomers in the cross-linkable composition, the content of the cross-linking agent is preferably 0.1～
10 mass parts, preferably 0.3～5 mass parts, more preferably 0.5～3 mass parts.Within this range, tensile strength can be obtained and breaks
Split the crosslinking rubber that percentage elongation reaches excellent balance.
A kind of preparation method of resin combination as the aforementioned, which comprises the steps：
After fluoroelastomer is plasticated, surface treated filler is added at 60～140 DEG C；
Mix homogeneously, adds cross-linking agent and crosslinking coagent, pelletize after mixing, discharging at less than 100 DEG C.
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.In the inventive method after white carbon black surface treated, compare with non-surface treated, as which is improved with rubber compatibility,
Consumption reduces, and in a disguised form puies forward high-glue content.Therefore through sulfuration after, the physical and mechanical propertiess of rubber are significantly improved, and brittleness temperature enters one
Step reduces, then its resistance to low temperature is more excellent, and compression set also accordingly reduces.
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, packing material size test
White carbon black is placed under laser particle analyzer, the mean diameter after test surfaces before processing is contrasted respectively.
2nd, packing specific area test
According to GB/T3780.5-2008, determine before and after surface treatment the specific surface area of white carbon black respectively and contrast.
3rd, thing machinery reason performance test
According to the standard of GB-528-1998, the physical and mechanical propertiess that tests after fluoroelastomer composition crosslinking.
4th, thing machinery reason performance test
According to the standard of GB-528-1998, the physical and mechanical propertiess that tests after fluoroelastomer composition crosslinking.
5th, cryogenic property test
According to《The many SAMPLE METHODs of the measure of GB-T15256-1994 vulcanite black brittleness》Standard, test fluorine-containing elasticity
Brittleness temperature after the crosslinking of body compositionss.
6th, pressure change performance test
According to《The assay method of GB1683-81 vulcanite constant deformation compression sets》Standard, test fluorine-containing
Compression set rate after elastic composition crosslinking.
7th, the copolymerization composition of fluoroelastomer is determined with F19NMR, HNMR, and solvent is deuterated acetone.
8th, vitrification point Tg of ASTM D3418 standard test fluoroelastomer is pressed.Heating rate is 10 DEG C/min.
9th, the low temperature retraction temperature TR10 of ASTM D1329 standard test fluoroelastomer is pressed.
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, evacuation is 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 and reaches 1.5MPa to absolute pressure in reactor, the copolymerization
Mix monomer mol ratio accounts for 55%, hexafluoropropene for vinylidene and accounts for 45%.Add 18 grams of sodium peroxydisulfates, 10 grams of bisulfites
Sodium, 14 grams of diethyl malonates, start polyreaction.Maintain absolute pressure in reactor by adding copolymerization mix monomer
1.5MPa, the copolymerization mix monomer mol ratio that adds account for 78%, hexafluoropropene for vinylidene and account for 22%.Work as reactor
When interior emulsion solid content reaches 20%, terminate polyreaction.
Determine through F19NMR, a mole copolymerization for gained fluoroelastomer consists of VDF:HFP:Dimethallyl epoxide (3,3,
3- trifluoro propyls) silane=54.7%:15.4%:29.9%.
The performance of the fluoroelastomer for obtaining is determined, table 1 is as a result listed in.
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, evacuation is 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 and reaches 1.5MPa to absolute pressure in reactor, the copolymerization
Mix monomer mol ratio accounts for 55%, hexafluoropropene for vinylidene and accounts for 45%.Add 18 grams of sodium peroxydisulfates, 10 grams of bisulfites
Sodium, 9.5 grams of diiodomethanes, start polyreaction.Maintain absolute pressure in reactor by adding copolymerization mix monomer
1.5MPa, the copolymerization mix monomer mol ratio that adds account for 77%, hexafluoropropene for vinylidene and account for 22%, 2- iodo- 1,
1- difluoroethylenes account for 1%.When emulsion solid content reaches 20% in reactor, terminate polyreaction.
Determine through F19NMR, 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%.
The performance of the fluoroelastomer for obtaining is determined, table 1 is as a result listed in.
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, evacuation simultaneously use 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 50 DEG C, supplement copolymerization mixing single
Body reaches 1.5MPa to absolute pressure in reactor, 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 sulfitees, 14 grams of diethyl malonates are added, starts polyreaction.Pass through
Adding copolymerization mix monomer makes absolute pressure in reactor maintain 1.5MPa, the copolymerization mix monomer mol ratio that adds
78%, hexafluoropropene is accounted for for vinylidene and accounts for 22%.When emulsion solid content reaches 20% in reactor, terminate polyreaction.
Determine through F19NMR, a mole copolymerization for gained fluoroelastomer consists of VDF:HFP=77.6%:22.4%.
The performance of the fluoroelastomer for obtaining is determined, table 1 is as a result listed in.
Table 1
Embodiment 3
The present embodiment is related to a kind of preparation method of the resin combination containing fluoroelastomer, specifically includes following step
Suddenly：
By 100 parts of fluoroelastomers (vinylidene fluoride/hexafluoropropene/fluorine-containing ether monomer containing silene/cure site monomer copolymerization
Thing, Mooney viscosity 60, similarly hereinafter), banbury (ML5L, one hundred is great mechanical, similarly hereinafter) is placed in, when temperature reaches 70 DEG C, 20 parts is added
White carbon black after surface treated.Closed-smelting machine rotor rotating speed, pressure are adjusted by frequency conversion motor, cooling water inlet and outlet piping valve is adjusted
Open degree, makes banburying room temperature be maintained at 80 DEG C.After 15 minutes, 1 part of 2,5- dimethyl -2,5- di-t-butyl peroxyhexanes is added
With 5 parts of TAIC, temperature control is less than 100 DEG C.Total mixing time is more than 20 minutes.
Crosslinkable fluoroelastomer composition, sulfuration according to above-mentioned each testing standard is obtained as stated above, tests
The physical and mechanical propertiess of fluoroelastomer, resistance to low temperature, pressure change performance, as a result as shown in table 2 below.
Embodiment 4
The present embodiment is related to a kind of preparation method of the resin combination containing fluoroelastomer, specifically includes following step
Suddenly：
100 parts of fluoroelastomers are placed in banbury, when temperature reaches 70 DEG C, the charcoal after 15 parts of surface treateds is added
Black.Closed-smelting machine rotor rotating speed, pressure are adjusted by frequency conversion motor, cooling water inlet and outlet piping valve opening degree is adjusted, is made banburying chamber
Temperature is maintained at 80 DEG C.After 15 minutes, 1 part of 2,5- dimethyl -2,5- di-t-butyls peroxyhexane and 5 parts of TAIC, temperature is added
Control is being less than 100 DEG C.Total mixing time is more than 20 minutes.
Crosslinkable fluoroelastomer composition, sulfuration according to above-mentioned each testing standard is obtained as stated above, tests
The physical and mechanical propertiess of fluoroelastomer, resistance to low temperature, pressure change performance, as a result as shown in table 2 below.
Embodiment 5
The present embodiment is related to a kind of preparation method of the resin combination containing fluoroelastomer, specifically includes following step
Suddenly：
100 parts of fluoroelastomers are placed in banbury, when temperature reaches 70 DEG C, the charcoal after 10 parts of surface treateds is added
Black.Closed-smelting machine rotor rotating speed, pressure are adjusted by frequency conversion motor, cooling water inlet and outlet piping valve opening degree is adjusted, is made banburying chamber
Temperature is maintained at 80 DEG C.After 15 minutes, 1 part of 2,5- dimethyl -2,5- di-t-butyls peroxyhexane and 5 parts of TAIC, temperature is added
Control is being less than 100 DEG C.Total mixing time is more than 20 minutes.
Crosslinkable fluoroelastomer composition, sulfuration according to above-mentioned each testing standard is obtained as stated above, tests
The physical and mechanical propertiess of fluoroelastomer, resistance to low temperature, pressure change performance, as a result as shown in table 2 below.
Comparative example 2
This comparative example is related to a kind of preparation method of the resin combination containing fluoroelastomer, specifically includes following step
Suddenly：
100 parts of fluoroelastomers are placed in banbury, when temperature reaches 70 DEG C, after adding 20 parts of non-surface treateds
White carbon black.Closed-smelting machine rotor rotating speed, pressure are adjusted by frequency conversion motor, cooling water inlet and outlet piping valve opening degree is adjusted, is made banburying
Room temperature is maintained at 80 DEG C.After 15 minutes, 1 part of 2,5- dimethyl -2,5- di-t-butyls peroxyhexane and 5 parts of TAIC, temperature is added
Degree control is being less than 100 DEG C.Total mixing time is more than 20 minutes.
Crosslinkable fluoroelastomer composition, sulfuration according to above-mentioned each testing standard is obtained as stated above, tests
The physical and mechanical propertiess of fluoroelastomer, resistance to low temperature, pressure change performance, as a result as shown in table 2 below.
Comparative example 3
This comparative example is related to a kind of preparation method of the resin combination containing fluoroelastomer, specifically includes following step
Suddenly：
100 parts of fluoroelastomers are placed in banbury, when temperature reaches 70 DEG C, after adding 15 parts of non-surface treateds
White carbon black.Closed-smelting machine rotor rotating speed, pressure are adjusted by frequency conversion motor, cooling water inlet and outlet piping valve opening degree is adjusted, is made banburying
Room temperature is maintained at 80 DEG C.After 15 minutes, 1 part of 2,5- dimethyl -2,5- di-t-butyls peroxyhexane and 5 parts of TAIC, temperature is added
Degree control is being less than 100 DEG C.Total mixing time is more than 20 minutes.
Crosslinkable fluoroelastomer composition, sulfuration according to above-mentioned each testing standard is obtained as stated above, tests
The physical and mechanical propertiess of fluoroelastomer, resistance to low temperature, pressure change performance, as a result as shown in table 2 below.
Comparative example 4
This comparative example is related to a kind of preparation method of the resin combination containing fluoroelastomer, specifically includes following step
Suddenly：
100 parts of fluoroelastomers are placed in banbury, when temperature reaches 70 DEG C, after adding 10 parts of non-surface treateds
White carbon black.Closed-smelting machine rotor rotating speed, pressure are adjusted by frequency conversion motor, cooling water inlet and outlet piping valve opening degree is adjusted, is made banburying
Room temperature is maintained at 80 DEG C.After 15 minutes, 1 part of 2,5- dimethyl -2,5- di-t-butyls peroxyhexane and 5 parts of TAIC, temperature is added
Degree control is being less than 100 DEG C.Total mixing time is more than 20 minutes.
Crosslinkable fluoroelastomer composition, sulfuration according to above-mentioned each testing standard is obtained as stated above, tests
The physical and mechanical propertiess of fluoroelastomer, resistance to low temperature, pressure change performance, as a result as shown in table 2 below.
Table 2
Above the specific embodiment of the present invention is described.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various modifications or modification within the scope of the claims, this not shadow
Ring the flesh and blood of the present invention.
Claims (11)
1. a kind of fluoroelastomer, it is characterised in that include the following comonomer by mole percent：
Mix monomer containing vinylidene：55～99%；
Fluorine-containing silicon-containing monomer：1～40%；
Cure site monomer：0～5%.
2. fluoroelastomer as claimed in claim 1, it is characterised in that the fluoroolefin is selected from tetrafluoroethene, inclined fluorine second
Alkene, hexafluoropropene, at least one that can be carried out with vinylidene in the vinyl compound of free radical copolymerization, and described
Can carry out on the vinyl in the vinyl compound of free radical copolymerization, being connected with fluorine atom with vinylidene, contain halothane
At least one in base and fluoroalkoxy.
3. fluoroelastomer as claimed in claim 1, it is characterised in that the fluorine-containing general molecular formula containing silene ether is [CH3
(CH2)n]2-Si[(CH2)mCF3)]-O(CH2)pCH=CH2, wherein, n, m, p are no more than 6 integer.
4. fluoroelastomer 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 is-(OCF2CF
(CF3))nO(CF2) m-, n=0～3, m=1～8.
5. fluoroelastomer as claimed in claim 4, it is characterised in that the cure site monomer is selected from bromo- 1, the 1- difluoros of 2-
The bromo- tetra- fluoro- 1-butylene of 3,3,4,4- of the iodo- 1,1- difluoroethylenes of ethylene, 2-, bromotrifluoroethylene, trifluoro iodoethylene, 4-, 4- iodo- 3,
The bromo- tri- fluoro- 1-butylene of 1,1,2- of tetra- fluoro- 1-butylene of 3,4,4-, 4-, the iodo- tri- fluoro- 1-butylene of 1,1,2- of 4-, the bromo- perfluoro butyls of 6-
The iodo- perfluorobutyl ethylene of ethylene, 6-, the bromo- perfluorohexyl ethylenes of 8-, the iodo- perfluorohexyl ethylenes of 8-, 1,2- divinyl perfluor second
Alkane, 1,4- divinyl perfluorinated butanes, 1,6- divinylperfluorhexanes, 1,8- divinylperfluorooctanes, perfluor (2- bromine second
Base vinyl ethers), perfluor (2- iodine ethyl vinyl ethers), 2- vinyl perfluoro ethyl vinyl ethers, 2- (2- bromoethyls) perfluor
Ethyl vinyl ether, 2- (2- iodine ethyls) perfluoroethylvinyl ether, 2- itrile group perfluoroethylvinyl ethers, 3- itrile groups perfluor are just
Propyl vinyl ether, 4- itrile group perfluoro-n-butyl group vinyl ethers, perfluor (2- acetonitrile-base propoxy base ethers), perfluor (2- third
Itrile group propoxy base ether), at least one in perfluor (2- n-Butyronitrile base propoxy base ethers).
6. a kind of preparation method of the fluoroelastomer as described in any one in Claims 1 to 5, it is characterised in that include
Following steps：
After fluorine-containing silicon-containing monomer is dispersed in water, the mix monomer containing vinylidene is added；
Initiator, chain-transferring agent is added, polyreaction is carried out, described fluoroelastomer is obtained.
7. a kind of resin combination containing fluoroelastomer described in claim 1, it is characterised in that including weight percent
The following component of meter：
8. resin combination as claimed in claim 7, it is characterised in that described can curable component include that cross-linking agent and crosslinking are helped
At least one in agent.
9. resin combination as claimed in claim 7, it is characterised in that the surface treatment method of the mineral filler is：
After described filler is mixed with polyfluoroalkanoyl peroxide, reacted at 0～200 DEG C.
10. resin combination as claimed in claim 7, it is characterised in that the polyfluoroalkanoyl peroxide is selected from fluorine-containing poly-
Ether acyl peroxide, the wherein formula of fluorochemical polyether base are X (CF2)aO(CF2O)b(CF2CF2O)c(CF2CF(CF3)O)d
(CF2CFClO)e(CF2)f(CF(CF3)) g, X is H, Cl or F, a, b, c, d, e, f, g=0～10；The perfluoroalkyl acyl mistake
Oxide is selected from perfluor acetyl pexoxide, Perfluorodipropionyl peroxides, perfluor butyryl peroxide, perfluor hexanoyl peroxidating
At least one in thing, perfluor oenanthyl peroxide, perfluoro-octanoyl peroxide, perfluorocyclohexyl acyl peroxide.
A kind of 11. preparation methoies of the resin combination as described in any one in claim 7～10, it is characterised in that bag
Include following steps：
After fluoroelastomer is plasticated, surface treated filler is added at 60～140 DEG C；
Mix homogeneously, adds cross-linking agent and crosslinking coagent, pelletize after mixing, discharging at less than 100 DEG C.
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Cited By (4)
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| CN106632793A (en) * | 2016-10-24 | 2017-05-10 | 内蒙古奥特普氟化学新材料开发有限公司 | A fluoroelastomer resistant to low temperatures and a preparing method thereof |
| 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 |
| CN112812566A (en) * | 2021-01-22 | 2021-05-18 | 航天材料及工艺研究所 | Low-pressure-change high-temperature-resistant silicon rubber and preparation method thereof |
| CN116041878A (en) * | 2023-02-14 | 2023-05-02 | 苏州巨友新能源科技有限公司 | Fluororubber with excellent low-temperature performance and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632793A (en) * | 2016-10-24 | 2017-05-10 | 内蒙古奥特普氟化学新材料开发有限公司 | A fluoroelastomer resistant to low temperatures and a preparing method thereof |
| CN106632793B (en) * | 2016-10-24 | 2019-01-08 | 内蒙古奥特普氟化学新材料开发有限公司 | Low-temperature-resistant elastic body containing fluorine and preparation method thereof |
| 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 |
| CN112812566A (en) * | 2021-01-22 | 2021-05-18 | 航天材料及工艺研究所 | Low-pressure-change high-temperature-resistant silicon rubber and preparation method thereof |
| CN116041878A (en) * | 2023-02-14 | 2023-05-02 | 苏州巨友新能源科技有限公司 | Fluororubber with excellent low-temperature performance and preparation method thereof |
| CN116041878B (en) * | 2023-02-14 | 2023-09-15 | 苏州巨友新能源科技有限公司 | Fluororubber with excellent low-temperature performance and preparation method thereof |
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| CN106496397B (en) | 2019-01-08 |
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