CN103360703A - Fluorine-containing elastomer admixture and composition thereof - Google Patents
Fluorine-containing elastomer admixture and composition thereof Download PDFInfo
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Abstract
The invention relates to a fluorine-containing elastomer admixture and a composition thereof. Provided is the fluorine-containing elastomer admixture, wherein CF3CF2CF2OCF(CF3)CF2OCF(CF3)COONH4 is used as an emulsifier; (A) fluorine-containing elastomers with a low molecular weight having Mn being 5,000 to 100,000 and (B) fluorine-containing elastomers with a high molecular weight having Mn being 130,000 to 3000,000 are obtained through copolymerization by using a method of emulsion polymerization with the use of the emulsifier with a ratio of 0.05 to 0.5 wt% with respect to added water, and (A) and (B) are admixed together with a weight ratio of 70/30 to 30/70; the admixture has a copolymerization of TFE 10-40 mol%, VdF 80-30 mol%, HFP 10-30 mol%, the ratio of Mw/Mn being 2 to 20. The fluorine-containing elastomer admixture and (C) a polyatomic alcohol vulcanizing agent or (D) organic peroxide and poly-functional unsaturated compounds together from the composition.
Description
Technical field
The present invention relates to fluoroelastomer adulterant and composition thereof.Further refer in detail to and have good thermotolerance, solvent resistance, chemical proofing, simultaneously the sulfide that has improved mechanical properties and compression tension set characteristic be can provide, fluoroelastomer adulterant and composition thereof that fuel system parts shaped material, particularly fuel hose shaped material use are suitable as.
Background technology
As employed fuel system parts of fuel such as alcohol, gasoline, light oil, petroleum naphtha such as methyl alcohol, require the excellences such as thermotolerance, solvent resistance, resistance to chemical reagents, therefore, mainly use the fluoroelastomer vulcanization forming product of these various characteristics excellences.
As the fluoroelastomer composition that such vulcanization forming product are provided, the applicant had proposed in the past following fuel system parts and had been shaped with the scheme of fluoroelastomer composition: comprise fluoroelastomer 100 weight parts, at least a 0.1～10 weight part of polyol vulcanized agent and polyamines vulcanizing agent, organo-peroxide 0.05～10 weight part and multi-functional unsaturated compound 0.01～10 weight part, described fluoroelastomer carries out copolymerization in the presence of the emulsifying agents such as ammonium perfluorocaprylate, has 10～40 % by mole in tetrafluoroethylene, the copolymerization that 80～30 % by mole of vinylidenes and R 1216 are 10～30 % by mole forms, its limiting viscosity is 20～180ml/g, the ratio of weight-average molecular weight Mw/ number-average molecular weight Mn is 2～10, and molecular weight distribution is multimodal (patent documentation 1).
Yet, such fluoroelastomer composition needs and with polyol vulcanized agent or polyamines vulcanizing agent and organo-peroxide, sulfuration for the single vulcanization system that only uses any one, aspect normality physical property, compression tension set characteristic, can not satisfy the desired various characteristics of fuel system parts.
Patent documentation 1:WO2008/050588
Patent documentation 2: TOHKEMY 2009-227754
Patent documentation 3: Japanese kokai publication hei 10-212322 communique
Patent documentation 4: Japanese kokai publication hei 11-181032 communique
Patent documentation 5: TOHKEMY 2000-7732 communique
Patent documentation 6: TOHKEMY 2003-165802 communique
Patent documentation 7: TOHKEMY 2007-56215.
Summary of the invention
The purpose of this invention is to provide fluoroelastomer adulterant and composition thereof, by utilizing the sulfuration of single vulcanization system, be suitable as the fuel system parts shaped material and use, can give the fluoroelastomer molding of plasticity, sulfuration physical property, resistance to chemical reagents, light stability and economy excellence.
According to the present invention, the fluoroelastomer adulterant is provided, it all uses 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-, seven fluorine propoxy-) propoxy-]-1-propionic acid ammonium CF
3CF
2CF
2OCF (CF
3) CF
2OCF (CF
3) COONH
4As emulsifying agent, to use emulsifying agent as the ratio of 0.05～0.5 % by weight and undertaken by emulsion polymerization that copolymerization obtains with respect to adding entry (bodyguard Write body water) gross weight, (A) number-average molecular weight Mn is 5,000～100,000 lower molecular weight fluoroelastomer and (B) number-average molecular weight Mn be 130,000～3,000,000 high molecular fluoroelastomer carries out fusion take weight ratio as 70/30～30/70 ratio, adulterant has 10～40 % by mole in tetrafluoroethylene, the copolymerization that 80～30 % by mole of vinylidenes and R 1216 are 10～30 % by mole forms, and the ratio of weight-average molecular weight Mw/ number-average molecular weight Mn is 2～20.Such fluoroelastomer adulterant and (C) polyol vulcanized agent or (D) organo-peroxide and multi-functional unsaturated compound form fluoroelastomer composition jointly.
Fluoroelastomer adulterant and the composition thereof that the present invention relates to, only use in patent documentation 1 illustrative 2 with specified amount, 3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-, seven fluorine propoxy-) propoxy-]-1-propionic acid ammonium prepares the fluoroelastomer adulterant of lower molecular weight fluoroelastomer and high molecular fluoroelastomer as emulsifying agent, by using this fluoroelastomer adulterant, do not need in the past the also usefulness of necessary polyol vulcanized agent when used ammonium perfluorocaprylate made to prepare fluoroelastomer as emulsifying agent usually or polyamines vulcanizing agent and organo-peroxide, by utilizing the sulfuration of single vulcanization system, performance can make the normality physical property, the good also improved excellent effect of compression set characteristic and binding property balance.
In addition, when using the polyol vulcanized agent, compare the effect of performance compression set excellent during with the use organo-peroxide.
Embodiment
As the fluoroelastomer adulterant, use following substances: all use 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-, seven fluorine propoxy-) propoxy-]-1-propionic acid ammonium is as emulsifying agent, to use emulsifying agent as the ratio of 0.05～0.5 % by weight and undertaken by emulsion polymerization that copolymerization obtains with respect to adding the entry gross weight, (A) number-average molecular weight Mn is 5,000～100,000 lower molecular weight fluoroelastomer and (B) number-average molecular weight Mn be 130,000～3,000,000 high molecular fluoroelastomer carries out fusion take weight ratio as 70/30～30/70 ratio, and the ratio of weight-average molecular weight Mw/ number-average molecular weight Mn is 2～20.
This adulterant has 10～40 % by mole in tetrafluoroethylene [TFE], preferred 15～35 % by mole; 80～30 % by mole of vinylidenes [VdF], 10～30 % by mole of preferred 70～40 % by mole and R 1216s [HFP], preferred 15～25 % by mole copolymerization forms.The copolymerization ratio of TFE its when many, then winter hardiness worsens, and the elasticity of the fluoroelastomer adulterant that obtains reduces, and is therefore not preferred, on the other hand the copolymerization ratio of TFE its when few, then oil-proofness, resistance to chemical reagents reduce, and be therefore not preferred.In addition, the copolymerization ratio of VdF its when few, then winter hardiness extremely worsens.And then, the copolymerization ratio of HFP its when many, then the deterioration of compression tension set characteristic is remarkable, on the other hand the copolymerization ratio of HFP its when few, then cause the caoutchouc elasticity of fluoroelastomer adulterant to reduce.
In addition, the ratio Mw/Mn of the expression weight-average molecular weight Mw of molecular weight distribution and number-average molecular weight Mn is more than it the time, molecular weight distribution is wide, contain low molecular weight compositions and ultra-high molecular weight composition much more relatively, processibility, particularly extrude processibility and extrudate surface property (extrusion thing flesh characteristic) and physical property and be difficult to be met simultaneously.This be because, when low molecular weight compositions was many, then processibility improved but can cause the reduction of physical property, and the ultra-high molecular weight composition then causes relation contrary to the above when many.On the other hand, the Mw/Mn ratio is below it the time, then causes processibility, particularly extrudes processibility and significantly worsen.
Such lower molecular weight and high molecular fluoroelastomer can prepare by emulsion polymerization.In emulsion polymerization, with the redox system of the water-soluble inorganic peroxide such as ammonium persulphate or itself and reductive agent as catalyzer, take with respect to adding the entry gross weight as 0.05～0.5 % by weight, the ratio of preferred 0.1～0.3 % by weight, use is as 2,3 of emulsifying agent, 3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-, seven fluorine propoxy-) propoxy-]-1-propionic acid ammonium.When using with its few ratio of emulsification dose ratio, the stability of milk sap variation extremely then, when using with the ratio of Duo than it on the contrary, then binding property significantly worsens, so not preferred.In addition, in patent documentation 2, disclose the preparation method of the fluorinated copolymer that has used this emulsifying agent, but it only is the invention about the aqueous liquid dispersion of the fluorinated copolymer of mechanical stability excellence, copolymerization form also from the present invention in preferred copolymerization form different.
The adjusting of the number-average molecular weight Mn of high molecular and low-molecular-weight fluoroelastomer is mainly undertaken by kind and the usage quantity of regulating chain-transfer agent and polymerization starter.
As chain-transfer agent, can enumerate for example dme, methyl tertiary butyl ether, C
1～C
6Alkanes, methyl alcohol, ethanol, Virahol, hexanaphthene, tetracol phenixin, chloroform, methylene dichloride, ethyl acetate, propanedioic acid diethyl ester, acetone etc.
In addition, peroxide crosslinking point also can by copolymerization system coexist saturated contain iodine compound or contain the iodine bromine compounds import, these compounds also play a role as chain-transfer agent.As the record of patent documentation 3～6 as can be known these compounds are known compounds, for example can enumerate general formula R In or InBrmR (wherein, R is fluorocarbon based, Chlorofluorocarbons (CFCs) base, chlorocarbon base or alkyl, and n, m are 1 or 2) represented saturated iodine compound or aliphatics or the aromatic iodine bromine compounds that contains of containing.
In these fluoroelastomers, also can make the unsaturated compound that contains iodine or bromine with approximately below 1 % by mole, preferred approximately 0.1～0.5 % by mole carry out copolymerization, form the peroxide crosslinking point.As such unsaturated compound that contains iodine or bromine, can enumerate for example iodine trifluoro-ethylene, perfluor (2-iodine ethyl vinyl ether), 2-bromo-vinylidene fluoride, bromotrifluoethylene, 4-bromo-3,3,4,4-tetrafluoro butene-1, perfluor (2-bromotrifluoromethane vinyl ether) etc.
On the other hand, preferred 2 kinds of fluoroelastomers are prepared as aqueous liquid dispersion (milk sap) respectively, with the each other fusion and form the fusion method of fluoroelastomer adulterant of the aqueous liquid dispersion of fluoroelastomer, from this viewpoint, preferred each fluoroelastomer prepares by emulsion polymerization, therefore as polymerization starter, can use separately water-soluble inorganic peroxide, such as ammonium persulphate, Potassium Persulphate or water-soluble azo compounds etc., or use the redox system of the reductive agents such as they and sodium bisulfite, S-WAT.
The chain-transfer agent that uses in the emulsion polymerization and the usage quantity of polymerization starter become fewer, the large trend of number-average molecular weight Mn change of fluoroelastomer generally more can occur generating.For example, in order to obtain the high molecular fluoroelastomer, use Virahol as chain-transfer agent with the ratio that is about 0.05～0.15 % by weight with respect to reaction raw materials total amount (following same datum), the saturated iodine compound that contains, and to be about the ratio use polymerization starter of 0.01～0.1 % by weight with respect to reaction raw materials total amount (following same datum), in addition, in order to obtain the lower molecular weight fluoroelastomer, use the saturated iodine compound that contains as chain-transfer agent with the ratio of about 7～12 % by weight, and use polymerization starter with the ratio of about 0.1～0.5 % by weight, carry out copolyreaction.But these numerical value are examples, and other polymerizing conditions beyond can forming according to copolymerization change.
Emulsion polymerization is generally at the about 0～10MPa of pressure, preferred approximately 0.5～4MPa; Approximately 0～100 ℃ of temperature is preferably approximately carried out under 20～80 ℃ the condition.At this moment, preferably the fluorochemical monomer mixture of supplying with is supplied with the substep addition manner, so that reaction pressure remains on certain limit.And, in order to regulate the pH in the polymerization system, also can add Na
2HPO
4, NaH
2PO
4, KH
2PO
4In the electrolyte substance with surge capability or sodium hydroxide.
The high molecular fluoroelastomer that obtains like this and the fusion of lower molecular weight fluoroelastomer, preferably have high molecular fluoroelastomer composition that essentially identical copolymerization forms and lower molecular weight fluoroelastomer composition take weight ratio as 70/30～30/70, carry out under preferred 60/40～40/60 such ratio.The ratio of high molecular fluoroelastomer its when many, then the polymkeric substance mooney viscosity after the fusion rises and mobile the reduction, when lacking than it on the other hand, it is large that the adhesivity of adulterant becomes, the polymkeric substance mooney viscosity can not become practical viscosity.
There is no particular limitation for the fusion method of high molecular fluoroelastomer and lower molecular weight fluoroelastomer, after for example mixing, stir with required ratio by the aqueous liquid dispersion (milk sap) with them, add sodium-chlor, calcium chloride, Repone K etc. and carry out condensation, carry out through washing, dry etc.
The elastomerics shape fluorinated copolymer adulterant (fluoroelastomer adulterant) that obtains, add polyol vulcanized agent or organo-peroxide and multi-functional unsaturated compound and vulcanize, shaping etc., can obtain cured article or processed goods.In addition, in patent documentation 7, the fluoroelastomer composition that adds organo-peroxide and multi-functional unsaturated compound is disclosed, specifically illustrate prepare as fluoroelastomer the time emulsifying agent, only limit to following comparative example 1 and 5 used ammonium perfluorocaprylates.
As the polyol vulcanized agent, can use the polyhydroxy aromatic compounds linking agent, can and use this moment to comprise at least a vulcanization accelerator that is selected from quaternary ammonium salt, quaternary alkylphosphonium salt and the inferior amine salt (イ ミ ニ ウ ム salt), and then preferred the use comprises oxide compound or at least a acid acceptor in oxyhydroxide and the hydrotalcite (being subjected to sour drug) that is selected from the divalent metal.
As polyhydroxy aromatic compounds, can be take per 100 weight part fluoroelastomer adulterants as 0.1～10 weight part, the ratio example of preferred 0.6～5 weight part such as Resorcinol, 2, two (4-hydroxy phenyl) propane [dihydroxyphenyl propane], 2 of 2-, two (4-hydroxy phenyl) perfluoropropane [bisphenol AF], 4 of 2-, 4 '-dihydroxyl ditan, 2, at least a in two (4-hydroxy phenyl) butane of 2-etc.
In addition, as quaternary ammonium salt quaternary alkylphosphonium salt and inferior amine salt, can be take per 100 weight part fluoroelastomer adulterants as 0.05～2 weight part, ratio example such as the tetramethyl ammonium chloride of preferred 0.1～1 weight part, etamon chloride, 4-propyl ammonium chloride, tetrabutylammonium chloride, Tetrabutyl amonium bromide, 4-butyl phosphonium chloride, Bian base triphenyl phosphonium chloride, benzyl trioctylphosphine phosphonium chloride, two (benzyl phenyl phosphino-) chlorimide (PVC ス (ベ Application ジ Le Off ェ ニ Le ホ ス Off ィ Application) イ ミ ニ ウ system Network ロ ラ イ De), at least a in the imines positively charged ion (イ ミ ニ ウ system カ チ オ Application) etc.
And then, oxide compound or oxyhydroxide as the divalent metal, but at least a in the oxide compound of the metals such as example such as magnesium, calcium, zinc, lead, the oxyhydroxide, its usage quantity is identical with the situation of hydrotalcite, be 1～30 weight part at per 100 weight part fluoroelastomer adulterants, select in the scope of preferred 2～20 weight parts.In addition, as required, in order to improve the effect of vulcanization accelerator, also can add various sulfurations and promote promoting agent.Promote the representation compound of promoting agent as this sulfuration, can enumerate 1,8-diazabicyclo [5.4.0] hendecene-7[DBU], the sulphones such as dimethyl sulfone, dichloro diphenylsulfone.
As organo-peroxide, preferably easily produce the organo-peroxide of peroxy radical owing to being heated, but example is such as 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3,2, at least a in the dialkyl peroxides such as 5-2，5-dimethyl-2，5-di(t-butyl peroxy)2，5-hexane etc.Infer these organo-peroxides and produce free radical owing to being heated when sulfuration, the iodine/bromo of this Free Radical in polymkeric substance produces free radical in polymkeric substance, and mutually combines by 2 free radicals in the polymkeric substance, can cause crosslinked.
The addition of organo-peroxide can suitably be selected according to active oxygen amount, decomposition temperature etc., is 0.05～10 weight part at per 100 weight part fluoroelastomer adulterants usually, selects in the scope of preferred 0.05～5 weight part.When using organo-peroxide with the ratio of lacking than it, then the generation of free radical is too few, can not make and crosslinkedly carry out fully, when being used with the ratio of Duoing than it on the other hand, can not show the raising of effect, it is unfavorable not only can to cause economically, and owing to the decomposition gas of superoxide causes foaming, can be observed the trend that mechanical properties reduces, therefore not preferred.
As multi-functional unsaturated compound, can be take per 100 weight part elastomerics adulterants as 0.01～10 weight part, at least a in the ratio example of preferred 0.1～5 weight part such as cyanuric acid triallyl ester, tricarbimide triallyl ester, three (the diallyl amine)-s-triazine etc., preferred tricarbimide triallyl ester.
Except above essential component, in fluoroelastomer composition of the present invention, can add various additives as required, toughener or weighting agents such as carbon black, silicon-dioxide, clay, talcum, the processing aids such as wax class etc., comprise above each composition fluoroelastomer composition can by mix with roller, Banbury etc., the mixing preparation.
The fluoroelastomer composition that obtains thus can be after fully mixing, and in long way is cut to band shape, obtains the flexible pipe of tubulose by using extrusion shaper, then, can be as required carries out post cure by steam etc., obtains thus desired sulfide.
Embodiment
Then, the present invention will be described according to embodiment.
Embodiment 1
(preparation of high molecular fluoroelastomer milk sap)
Replace degassed rear adding in the stainless steel autoclave to internal volume 10L with nitrogen:
Tensio-active agent [CF
3CF
2CF
2OCF (CF
3) CF
2OCF (CF
3) COONH
4] 8.5g
(be 0.15 % by weight with respect to deionized water)
Sodium phosphate dibasic 12 hydrate 10g
Deionized water 5.8L
Carry out degassed after the internal space replaced fully with nitrogen again.Then add therein:
Vinylidene [VdF] 90g
Tetrafluoroethylene [TFE] 77g
R 1216 [HFP] 760g
2-bromo-vinylidene fluoride [BDFE] 8g
Make be warming up to 80 ℃ in the autoclave after, add:
Ammonium persulphate [APS; Use the 0.3 % by weight aqueous solution] 1.8g
Polyreaction is caused.The interior pressure of this moment is 2.2MPa.To keep the mode of interior pressure 2.15～2.25MPa, add:
VdF 786g
TFE 673g
HFP 520g
Cooling after reaction finishes is discharged residual gas and is obtained milk sap I (solid constituent concentration 31.5 % by weight) 8,524g.In addition, utilize 1 % by weight calcium chloride water to carry out condensation, washing, drying and separate the VdF-TFE-HFP3 membered copolymer from this milk sap, measuring its number-average molecular weight Mn (measuring according to following method) is 161,000.
(preparation of lower molecular weight fluoroelastomer milk sap)
In the preparation of aforementioned high molecular fluoroelastomer milk sap, replace BDFE to use octafluoro-Isosorbide-5-Nitrae-two butyl iodide [DIOFB] 34.0g, and with APS quantitative change 6g more, obtain milk sap II (solid constituent concentration 31.8 % by weight) 8,534g.Interior pressure when in addition, polyreaction causes is 2.2MPa.And the Mn of the VdF-TFE-HFP3 membered copolymer that obtains is 18,000.
(preparation of elastomerics shape multipolymer adulterant)
The milk sap I that obtains and milk sap II are mixed, so that after solid weight ratio of constituents separately is 50:50, utilize 1 % by weight calcium chloride water to carry out condensation, washing, drying, obtain elastomerics shape multipolymer adulterant A 5,344g.
Comparative example 1
In embodiment 1, in the preparation of high molecular fluoroelastomer milk sap and lower molecular weight fluoroelastomer milk sap, use CF as tensio-active agent with identical amount
3CF
2CF
2CF
2CF
2CF
2CF
2COONH
4When (ammonium perfluorocaprylate), obtain respectively high molecular fluoroelastomer milk sap III (solid constituent concentration 32.1 % by weight, Mn144,000) 8,521g and lower molecular weight fluoroelastomer milk sap IV (solid constituent concentration 31.8 % by weight, Mn18,000) 8,537g uses them with solid weight ratio of constituents 50:50, obtain elastomerics shape multipolymer adulterant B 5,419g.
Comparative example 2
In embodiment 1, in the preparation of high molecular fluoroelastomer milk sap and lower molecular weight fluoroelastomer milk sap, use CHF as tensio-active agent with identical amount
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2COONH
4When (9H-ten hexafluoro n-nonanoic acid ammoniums), obtain respectively high molecular fluoroelastomer milk sap V (solid constituent concentration 31.4 % by weight, Mn151,000) 8,512g and lower molecular weight fluoroelastomer milk sap VI (solid constituent concentration 32.2 % by weight, Mn19,000) 8,531g uses them with solid weight ratio of constituents 50:50, obtain elastomerics shape multipolymer adulterant C 5,321g.
Comparative example 3
In embodiment 1, in the preparation of high molecular fluoroelastomer milk sap and lower molecular weight fluoroelastomer milk sap, amount of surfactant is changed to 1.7g (0.03 % by weight) when using, obtain respectively high molecular fluoroelastomer milk sap VII (solid constituent concentration 31.7 % by weight, Mn138,000) 8,528g and lower molecular weight fluoroelastomer milk sap VIII (solid constituent concentration 31.8 % by weight, Mn16,000) 8,551g uses them with solid weight ratio of constituents 50:50, obtain elastomerics shape multipolymer adulterant D 5,326g.
Comparative example 4
In embodiment 1, in the preparation of high molecular fluoroelastomer milk sap and lower molecular weight fluoroelastomer milk sap, amount of surfactant is changed to 40.6g (0.7 % by weight) to be used, obtain respectively high molecular fluoroelastomer milk sap IX (solid constituent concentration 31.1 % by weight, Mn168,000) 8,542g and lower molecular weight fluoroelastomer milk sap X (solid constituent concentration 31.4 % by weight, Mn17,000) 8,555g uses them with solid weight ratio of constituents 50:50, obtain elastomerics shape multipolymer adulterant E 5,331g.
For the elastomerics shape multipolymer adulterant A～E that obtains in above embodiment and each comparative example, carry out the following purpose and measure.
The multipolymer composition [% by mole]: use Jeol JMN-LA300 Fourier transform nuclear magnetic resonance instrument to measure.
Fluorine content [% by weight]: calculate F content according to molecular weight.
Polymkeric substance mooney viscosity (ML
1+10): under 121 ℃ test temperature, preheating makes the rotary head rotation after 1 minute immediately, measures the value after 10 minutes.
Molecular weight determination: use Japanese light splitting industry 851-AS type intelligence processed self-actuated sampler, ガ ス Network ロ industry MODEL 576 type LC pumps processed, possess clear and electrician Shodex KF-801 processed, KF-802, the ガ ス Network ロ industry MODEL 556 type HPLC column ovens processed that the pillar of KF-802.5 and KF-805 is 4 and Japanese light splitting industry detector JASCO 830RI differential refractometer processed, make tetrahydrofuran (THF) as developing solvent, sample concentration 0.5 % by weight, flow 1.0ml/ minute, 40 ℃ of lower mensuration of temperature.
The シ ス テ system イ Application ス Star Le メ Application SIC ラ processed of Star society Block チ ャ ー ト 180 is used in the parsing of molecular weight, and as molecular weight calibration curve standard polymers, uses the various monodisperse polystyrenes [Mw/Mn=1.1 (MAX)] of Japan Cao Da goods.
Measurement result is shown in the following table 1.
Embodiment 2
Elastomerics shape multipolymer adulterant A 100 weight parts
MT carbon black (キ ャ Application キ ャ Block goods サ ー マ ッ Network ス N990) 20 weight parts
Multi-functional unsaturated compound 5 weight parts
(Japan changes into goods TAIC M60; The tricarbimide triallyl ester)
Organo-peroxide (Japanese oil product パ ー ヘ キ サ 25B-40) 3.5 weight parts
ZnO 5 weight parts
Above each composition is mixed with end runner mill, make the solidification compound that obtains under 180 ℃, carry out sheet material and O ring (P24) that thickness 2mm is made in compression molding in 10 minutes (once sulfuration), further under 230 ℃, carry out 22 hours oven cure (post cure).When once vulcanizing, be cured test, the material after the post cure is carried out about normality physical property, compression set and fusible mensuration and evaluation.
Solidity test: use all plate rheometers of Meng Shan, 121 ℃ of lower values of measuring MH, Tc90.
Normality physical property: according to JIS K6250,6253.
Compression set: according to ASTM D395 Method B, for P24 O ring, measure 150 ℃, 70 hours value.
Binding property: make separately approximately sheet material and the not sheet material applying of sulfurized nitrile rubber of the not sulfuration fluoroelastomer (above-mentioned solidification compound) of 1.5mm of thickness, carry out 160 ℃, 30 minutes press vulcanizations, after then letting cool, die-cut test film uses TOYOSEIKI STROGRAPH E II with enforcement stripping test in trial speed 100mm/ minute to thickness 2mm, wide 12.5mm, long 100mm.
Damaged situation occurs evaluation which side rubber before peeling off is that binding property is good, and rubber is damaged and situation that peel off is that binding property is bad.
In addition, as sulfurized nitrile rubber not, can use following title complex
Paracril (southern Supreme Being's chemical industry goods NANCAR1051) 100 weight parts
HAF carbon black (Xu カ ー ボ Application goods) 50 weight parts
Zinc oxide 5 weight parts
Stearic acid 1 weight part
Anti-aging agent (Seiko chemical preparations ノ Application Off レ ッ Network ス RD) 3 weight parts
Sulphur 2 weight parts
Vulcanization accelerator (three new chemical industry goods サ Application セ ラ ー TS) 3 weight parts.
Comparative example 5
In embodiment 2, replace elastomerics shape multipolymer adulterant A, use elastomerics shape multipolymer adulterant B with identical amount.
Comparative example 6
In embodiment 2, replace elastomerics shape multipolymer adulterant A, use elastomerics shape multipolymer adulterant C with identical amount.
Comparative example 7
In embodiment 2, replace elastomerics shape multipolymer adulterant A, use elastomerics shape multipolymer adulterant D with identical amount.
Comparative example 8
In embodiment 2, replace elastomerics shape multipolymer adulterant A, use elastomerics shape multipolymer adulterant E with identical amount.
What obtain in above embodiment 2 and the comparative example 5～8 the results are shown in following table 2.
Embodiment 3
(preparation of high molecular fluoroelastomer milk sap)
Replace degassed rear adding in the steel autoclave to internal volume 10L with nitrogen:
Tensio-active agent [CF
3CF
2CF
2OCF (CF
3) CF
2OCF (CF
3) COONH
4] 15g (0.26 % by weight)
Sodium phosphate dibasic 12 hydrate 10g
Deionized water 5.8L
Carry out degassed after the internal space replaced fully with nitrogen again.Then add therein:
Vinylidene [VdF] 83g
Tetrafluoroethylene [TFE] 67g
R 1216 [HFP] 640g
Virahol [IPA] 1.0g
Make be warming up to 80 ℃ in the autoclave after, add:
Ammonium persulphate [APS] 1.0g
Polyreaction is caused.The interior pressure of this moment is 2.2MPa.To keep the mode of interior pressure 2.15～2.25MPa, add:
VdF 932g
TFE 673g
HFP 520g
Cooling after reaction finishes is discharged residual gas and is obtained milk sap I ' (solid constituent concentration 31.6 % by weight, Mn173,000) 8,473g.
(preparation of lower molecular weight fluoroelastomer milk sap)
In the preparation of aforementioned high molecular fluoroelastomer milk sap, replace IPA to use propanedioic acid diethyl ester 70g, and with APS quantitative change 5g more, obtain milk sap II ' (solid constituent concentration 31.4 % by weight, Mn18,000) 8,489g.Interior pressure when in addition, polyreaction causes is 2.2MPa.
(preparation of elastomerics shape multipolymer adulterant)
The milk sap I ' that obtains and milk sap II ' are mixed, so that after solid weight ratio of constituents separately is 50:50, utilize 1 % by weight calcium chloride water to carry out condensation, washing, drying, obtain elastomerics shape multipolymer adulterant F 5,342g.
Comparative example 9
In embodiment 3, in the preparation of high molecular fluoroelastomer milk sap and lower molecular weight fluoroelastomer milk sap, use CF as tensio-active agent with identical amount
3CF
2CF
2CF
2CF
2CF
2CF
2COONH
4When (ammonium perfluorocaprylate), obtain respectively high molecular fluoroelastomer milk sap III ' (solid constituent concentration 32.2 % by weight, Mn166,000) 8,397g and lower molecular weight fluoroelastomer milk sap IV ' (solid constituent concentration 31.6 % by weight, Mn19,000) 8,518g uses them and obtains elastomerics shape multipolymer adulterant G 5,318g.
Comparative example 10
In embodiment 3, in the preparation of high molecular fluoroelastomer milk sap and lower molecular weight fluoroelastomer milk sap, use CHF as tensio-active agent with identical amount
2CF
2CF
2CF
2CF
2CF
2CF
2CF
2COONH
4When (9H-ten hexafluoro n-nonanoic acid ammoniums), obtain respectively high molecular fluoroelastomer milk sap V ' (solid constituent concentration 31.5 % by weight, Mn162,000) 8,452g and lower molecular weight fluoroelastomer milk sap VI ' (solid constituent concentration 31.6 % by weight, Mn17,000) 8,522g uses them and obtains elastomerics shape multipolymer adulterant H 5,347g.
Comparative example 11
In embodiment 3, in the preparation of high molecular fluoroelastomer milk sap and lower molecular weight fluoroelastomer milk sap, amount of surfactant is changed to 1.7g (0.03 % by weight) when using, obtain respectively high molecular fluoroelastomer milk sap VII ' (solid constituent concentration 30.6 % by weight, Mn154,000) 8,402g and lower molecular weight fluoroelastomer milk sap VIII ' (solid constituent concentration 30.8 % by weight, Mn16,000) 8,542g uses them and obtains elastomerics shape multipolymer adulterant I 5,389g.
Comparative example 12
In embodiment 3, in the preparation of high molecular fluoroelastomer milk sap and lower molecular weight fluoroelastomer milk sap, amount of surfactant is changed to 40.6g (0.7 % by weight) when using, obtain respectively high molecular fluoroelastomer milk sap IX ' (solid constituent concentration 32.2 % by weight, Mn172,000) 8,440g and lower molecular weight fluoroelastomer milk sap X ' (solid constituent concentration 31.9 % by weight, Mn18,000) 8,542g uses them and obtains elastomerics shape multipolymer adulterant J 5,316g.
For the elastomerics shape multipolymer adulterant F～J that obtains in above embodiment 3 and the comparative example 9～12, carry out the following purpose and measure.Measurement result is shown in the following table 3.
Embodiment 4
In embodiment 2, use following solidification compound, similarly measure and estimate.Wherein, to compression set, measure 200 ℃, 70 hours value.
Elastomerics shape multipolymer adulterant F 100 weight parts
MT carbon black (サ ー マ ッ Network ス N990) 25 weight parts
Vulcanizing agent (PVC ス Off ェ ノ ー Le AF) 2 weight parts
Vulcanization accelerator (Bian base triphenyl phosphonium chloride) 1 weight part
Acid acceptor (republicanism chemical preparations キ ョ ウ ワ マ グ #150) 3 weight parts
Acid acceptor (near river chemical preparations Caldic#2000) 6 weight parts.
Comparative example 13
In embodiment 4, replace elastomerics shape multipolymer adulterant F, use elastomerics shape multipolymer adulterant G with identical amount.
Comparative example 14
In embodiment 4, replace elastomerics shape multipolymer adulterant F, use elastomerics shape multipolymer adulterant H with identical amount.
Comparative example 15
In embodiment 4, replace elastomerics shape multipolymer adulterant F, use elastomerics shape multipolymer adulterant I with identical amount.
Comparative example 16
In embodiment 4, replace elastomerics shape multipolymer adulterant F, use elastomerics shape multipolymer adulterant J with identical amount.
What obtain in above embodiment 4 and the comparative example 13～16 the results are shown in the following table 4.
According to above result, be summarized as follows.
(1) in embodiment 2 and 4, breaking tenacity and compression tension set characteristic all demonstrate good value.
(2) in the preparation of elastomerics shape multipolymer adulterant, use ammonium perfluorocaprylate as comparative example 5 and the 13 resulting sulfide of tensio-active agent, breaking tenacity is poor.
(3) in the preparation of elastomerics shape multipolymer adulterant, use 9H-ten hexafluoro n-nonanoic acid ammoniums as comparative example 6 and the 14 resulting sulfide of tensio-active agent, compression tension set characteristic is poor.
(4) in the preparation of elastomerics shape multipolymer adulterant, even when using the used tensio-active agent of each embodiment, the comparative example 7 that its use level is few and 15 resulting sulfide, the stability of milk sap is also poor, can be observed low viscosity milk sap and separates out.
(5) in the preparation of elastomerics shape multipolymer adulterant, even when using the used tensio-active agent of each embodiment, comparative example 8 and 16 resulting sulfide that its use level is many, also poor with the binding property of NBR.
Industrial applicability
The fluoroelastomer composition that the present invention relates to has the normality physical property owing to providing, the sulfide of the physical property of compression set excellent, therefore can be suitable as fuel system parts, the particularly vulcanization forming such as fuel hose, pipe materials'use.
Claims (6)
1. fluoroelastomer adulterant, it all uses 2,3,3,3-tetrafluoro-2-[1,1,2,3,3,3-hexafluoro-2-(1,1,2,2,3,3,3-, seven fluorine propoxy-) propoxy-]-1-propionic acid ammonium CF
3CF
2CF
2OCF (CF
3) CF
2OCF (CF
3) COONH
4As emulsifying agent, to use emulsifying agent as the ratio of 0.05～0.5 % by weight and undertaken by emulsion polymerization that copolymerization obtains with respect to adding the entry gross weight, (A) number-average molecular weight Mn is 5,000～100,000 lower molecular weight fluoroelastomer and (B) number-average molecular weight Mn be 130,000～3,000,000 high molecular fluoroelastomer carries out fusion take weight ratio as 70/30～30/70 ratio, adulterant has 10～40 % by mole in tetrafluoroethylene, the copolymerization that 80～30 % by mole of vinylidenes and R 1216 are 10～30 % by mole forms, and the ratio of weight-average molecular weight Mw/ number-average molecular weight Mn is 2～20.
2. fluoroelastomer adulterant according to claim 1, its with (A) lower molecular weight fluoroelastomer and (B) the high molecular fluoroelastomer all be prepared as aqueous liquid dispersion, with each other fusion and form the fluoroelastomer adulterant of aqueous liquid dispersion.
3. fluoroelastomer composition, it comprises claim 1 or 2 described fluoroelastomer adulterants, (C) polyol vulcanized agent or (D) organo-peroxide and multi-functional unsaturated compound.
4. fluoroelastomer composition according to claim 3, per 100 weight part fluoroelastomer adulterants, respectively the ratio take the agent of (C) polyol vulcanized as 0.1～10 weight part or take (D) organo-peroxide as 0.05～10 weight part, multi-functional unsaturated compound uses as the ratio of 0.01～10 weight part.
5. the fuel system parts that fluoroelastomer composition vulcanization forming claimed in claim 4 is obtained.
6. fuel system parts according to claim 5, it is fuel hose.
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| JP2012083675A JP5998588B2 (en) | 2012-04-02 | 2012-04-02 | Fluorine-containing elastomer blend and composition thereof |
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| CN106432987A (en) * | 2016-08-31 | 2017-02-22 | 河南汇龙液压科技股份有限公司 | 200-DEG C high-temperature-resistant steel wire enhanced dynamic hose inner rubber and preparation method thereof |
| CN107787348A (en) * | 2015-07-27 | 2018-03-09 | 阿科玛法国公司 | Fluorinated polymer compositions |
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| JP2021075662A (en) * | 2019-11-12 | 2021-05-20 | ユニマテック株式会社 | Fluorine elastomer-blended matter for crosslinking polyol, crosslinked molded body using the same, and method of producing the same |
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| CN103360703B (en) | 2017-03-01 |
| JP5998588B2 (en) | 2016-09-28 |
| JP2013213130A (en) | 2013-10-17 |
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