CN103360703B - Fluoroelastomer admixture and combinations thereof - Google Patents
Fluoroelastomer admixture and combinations thereof Download PDFInfo
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Abstract
The present invention relates to fluoroelastomer admixture and combinations thereof.There is provided fluoroelastomer admixture, all using CF3CF2CF2OCF(CF3)CF2OCF(CF3)COONH4As emulsifying agent, blended than 70/30～30/70 ratio with weight with obtained by emulsion polymerization copolymerization using emulsifying agent with respect to the ratio adding water gross weight 0.05～0.5 weight %, (A) Mn 5000～100000 low-molecular-weight fluoroelastomer and (B) Mn 130000～3000000 high molecular fluoroelastomer, admixture has the copolymerization composition of TFE10～40 mole %, VdF80～30 moles of %, HFP10～30 moles of %, and Mw/Mn ratio is 2～20.This fluoroelastomer admixture is collectively forming compositionss with (C) polyol vulcanized agent or (D) organic peroxide and multi-functional unsaturated compound.
Description
Technical field
The present invention relates to fluoroelastomer admixture and combinations thereof.Refer in detail to further have good thermostability,
Solvent resistance, chemical proofing, can provide the sulfide improving mechanical properties and compression resistant permanent set characteristics simultaneously,
Be suitable as fuel system parts moulding material, particularly fuel hose moulding material use fluoroelastomer admixture and its
Compositionss.
Background technology
The fuel system parts that used as fuel such as the alcohol such as methanol, gasoline, light oil, Petroleums are it is desirable to thermostability, resistance to
Solvent borne, resistance to chemical reagents etc. are excellent, therefore, mainly use the fluoroelastomer vulcanization forming product of these various excellents.
As the fluoroelastomer composition providing such vulcanization forming product, before the applicant, propose following fuel
The scheme of systematic part shaping fluoroelastomer composition：Comprise fluoroelastomer 100 weight portion, polyol vulcanized agent and many
At least one 0.1～10 weight portion of amine vulcanizing agent, organic peroxide 0.05～10 weight portion and multi-functional unsaturationization
Compound 0.01～10 weight portion, described fluoroelastomer carries out copolymerization in the presence of the emulsifying agents such as perfluorooctanoic acid, has four
10～40 moles of % of fluorothene, the copolymerization composition of 80～30 moles of % of vinylidene and 10～30 moles of % of hexafluoropropene, its characteristic is glued
Spend for 20～180ml/g, the ratio of weight average molecular weight Mw/ number-average molecular weight Mn is 2～10, molecular weight distribution be multimodal (specially
Sharp document 1).
However, such fluoroelastomer composition needs and uses polyol vulcanized agent or polyamines vulcanizing agent and organic peroxy
Compound, for only using the sulfuration of the single vulcanizing system of any one, in normality physical property, compression resistant permanent set characteristics side
Face is it is impossible to meet the various characteristics required by fuel system parts.
Patent documentation 1：WO2008/050588
Patent documentation 2：Japanese Unexamined Patent Publication 2009-227754
Patent documentation 3：Japanese Unexamined Patent Publication 10-212322 publication
Patent documentation 4：Japanese Unexamined Patent Publication 11-181032 publication
Patent documentation 5：Japanese Unexamined Patent Publication 2000-7732 publication
Patent documentation 6：Japanese Unexamined Patent Publication 2003-165802 publication
Patent documentation 7：Japanese Unexamined Patent Publication 2007-56215.
Content of the invention
It is an object of the invention to provide fluoroelastomer admixture and combinations thereof, by using single vulcanizing system
Sulfuration, is suitable as fuel system parts moulding material and uses, and can give formability, sulfuration physical property, resistance to chemical reagents, light stable
Property and the excellent fluoroelastomer molding of economy.
According to the present invention, provide fluoroelastomer admixture, it is all using 2,3,3,3- tetra- fluoro- 2- [1,1,2,3,3,3-
Hexafluoro -2- (1,1,2,2,3,3,3- seven fluorine propoxyl group) propoxyl group] -1- propanoic acid ammonium CF3CF2CF2OCF(CF3)CF2OCF(CF3)
COONH4As emulsifying agent, with respect to addition water（Bodyguard body water）Gross weight is that the ratio of 0.05～0.5 weight % uses emulsifying
It is fluorine-containing that agent carries out, by emulsion polymerization, the low-molecular-weight that copolymerization obtains, (A) number-average molecular weight Mn is 5,000～100,000
Elastomer and (B) number-average molecular weight Mn be 130,000～3,000,000 high molecular fluoroelastomer with weight than for 70/
30～30/70 ratio is blended, and admixture has 10～40 moles of % of tetrafluoroethene, vinylidene 80～30 moles of % and six
The copolymerization composition of 10～30 moles of % of fluoropropene, the ratio of weight average molecular weight Mw/ number-average molecular weight Mn is 2～20.Such fluorine-containing
Elastomer admixture is collectively forming with (C) polyol vulcanized agent or (D) organic peroxide and multi-functional unsaturated compound
Fluoroelastomer composition.
Fluoroelastomer admixture according to the present invention and combinations thereof, with ormal weight using example only in patent documentation 1
The fluoro- 2- of 2,3,3,3- tetra- [1,1,2,3,3,3- hexafluoro -2- (1,1,2,2,3,3,3- seven fluorine propoxyl group) the propoxyl group] -1- third showing
Sour ammonium prepares the fluoroelastomer admixture of low-molecular-weight fluoroelastomer and high molecular fluoroelastomer as emulsifying agent,
By using this fluoroelastomer admixture it is not necessary in the past conventionally used perfluorooctanoic acid uses as emulsifying agent and to prepare
During fluoroelastomer, necessary polyol vulcanized agent or polyamines vulcanizing agent and organic peroxide is used in combination, by using single
Vulcanizing system sulfuration, performance can make normality physical property, compression set characteristic and bonding sexual balance good and improved
Excellent effect.
In addition, using during polyol vulcanized agent, with using compared with during organic peroxide, playing compression set characteristic
Excellent effect.
Specific embodiment
As fluoroelastomer admixture, using following substances：All using the fluoro- 2- [1,1,2,3,3,3- of 2,3,3,3- tetra-
Hexafluoro -2- (1,1,2,2,3,3,3- seven fluorine propoxyl group) propoxyl group] -1- propanoic acid ammonium as emulsifying agent, with total with respect to adding water
Weight is that the ratio of 0.05～0.5 weight % carries out copolymerization obtains, the equal molecule of (A) number using emulsifying agent by emulsion polymerization
Measuring the low-molecular-weight fluoroelastomer that Mn is 5,000～100,000 and (B) number-average molecular weight Mn is 130,000～3,000,000
High molecular fluoroelastomer blended with weight than the ratio for 70/30～30/70, weight average molecular weight Mw/ number is divided equally
The ratio of son amount Mn is 2～20.
This admixture has 10～40 moles of % of tetrafluoroethene [TFE], preferably 15～35 moles %；Vinylidene [VdF] 80
～30 moles of %, preferably 70～40 moles % and 10～30 moles of % of hexafluoropropene [HFP], the preferably copolymerization group of 15～25 moles of %
Become.The copolymerization ratios of TFE than its many when, then tolerance to cold deteriorate, and the fluoroelastomer admixture obtaining elasticity reduction, because
This is not preferred, the copolymerization ratios of another aspect TFE than its few when, then oil resistivity, resistance to chemical reagents reduce, therefore not preferred.In addition,
The copolymerization ratios of VdF than its few when, then tolerance to cold extreme degradation.And then, the copolymerization ratios of HFP than its many when, then compression resistant is forever
Long the deterioration of deformation characteristic is notable, the copolymerization ratios of another aspect HFP than its few when, then lead to the rubber of fluoroelastomer admixture
Glue elasticity reduces.
In addition, when ratio Mw/Mn of weight average molecular weight Mw of expression molecular weight distribution and number-average molecular weight Mn is more than it,
How molecular weight distribution width, contain low molecular weight compositions and super high molecular weight composition relatively, processability, particularly extrudes processability
With extrudate surface characteristic（Extrusion thing flesh characteristic）It is difficult to be met with physical property simultaneously.This is because, low-molecular-weight becomes
When dividing many, then processability improves but can cause the reduction of physical property, and when super high molecular weight composition is many, then causes contrary to the above
Relation.On the other hand, when Mw/Mn ratio is below it, then processability, particularly extrusion processability is led to significantly to deteriorate.
Such low-molecular-weight and high molecular fluoroelastomer can be prepared by emulsion polymerization.Anti- in emulsion polymerization
Ying Zhong, using the water-soluble inorganic peroxide such as Ammonium persulfate. or its redox system with reducing agent as catalyst, with phase
For adding water gross weight to be 0.05～0.5 weight %, the ratio of preferably 0.1～0.3 weight %, as emulsifying agent 2 are used, 3,
The fluoro- 2- of 3,3- tetra- [1,1,2,3,3,3- hexafluoro -2- (1,1,2,2,3,3,3- seven fluorine propoxyl group) propoxyl group] -1- propanoic acid ammonium.With
When its few ratio of emulsifying dose ratio uses, then the stability of emulsion is extremely deteriorated, when being used with the ratio more than it on the contrary,
Then cohesive significantly deteriorates, therefore not preferred.Additionally, in patent documentation 2, disclosing the fluorine-containing copolymerization employing this emulsifying agent
The preparation method of thing, but it is only about the invention of the aqueous liquid dispersion of the excellent fluorinated copolymer of mechanical stability, copolymerization group
Become also different from copolymerization composition preferred in the present invention.
The regulation of number-average molecular weight Mn of the fluoroelastomer of high molecular and low-molecular-weight is mainly passed through to adjust chain-transferring agent
To carry out with the species of polymerization initiator and usage amount.
As chain-transferring agent, such as dimethyl ether, methyl tertiary butyl ether(MTBE), C can be enumerated1～C6Alkanes, methanol, ethanol, isopropyl
Alcohol, hexamethylene, carbon tetrachloride, chloroform, dichloromethane, ethyl acetate, diethyl malonate, acetone etc..
In addition, peroxide crosslinking point also can contain iodine compound or bromine containing iodine by the saturation that copolymerization system is coexisted
Compound and import, these compounds also serve as chain-transferring agent and play a role.Record as patent documentation 3～6 understands these changes
Compound is known compound, can enumerate such as general formula R In or InBrmR (wherein, R be fluorohydrocarbon base, Chlorofluorocarbons (CFCs) base, chlorocarbon base or
Alkyl, n, m are 1 or 2) represented by saturation contain iodine compound or aliphatic or aromatic bromine compoundss containing iodine.
In these fluoroelastomers, also can make the unsaturated compound containing iodine or bromine with about 1 mole of below %, preferably
About 0.1～0.5 mole of % carries out copolymerization, forms peroxide crosslinking point.As such unsaturated chemical combination containing iodine or bromine
Thing, can enumerate such as iodine trifluoro-ethylene, perfluor (2- iodine ethyl vinyl ether), the bromo- vinylidene fluoride of 2-, bromotrifluoethylene,
4- bromo- 3,3,4,4- tetrafluoro butene-1, perfluor (2- bromoethyl vinyl ether) etc..
On the other hand, preferably 2 kinds fluoroelastomers are prepared respectively as aqueous liquid dispersion (emulsion), by fluorine-containing bullet
The aqueous liquid dispersion of gonosome blends each other and forms the blending procedure of fluoroelastomer admixture, from the point of view of this viewpoint, preferably respectively
Fluoroelastomer is prepared by emulsion polymerization, and therefore as polymerization initiator, can be used alone water-soluble inorganic peroxidating
Thing, such as Ammonium persulfate., potassium peroxydisulfate or water-soluble azo compounds etc., or use they and sodium sulfite, sodium sulfite
Redox system Deng reducing agent.
Used in emulsion polymerization, the usage amount of chain-transferring agent and polymerization initiator becomes fewer, typically more occurs
Number-average molecular weight Mn generating fluoroelastomer becomes big trend.For example, in order to obtain high molecular fluoroelastomer, with relatively
Isopropyl as chain-transferring agent is used in the ratio that reaction raw materials total amount (following same datum) is about 0.05～0.15 weight %
Alcohol, saturation contain iodine compound, and to be about 0.01～0.1 weight % with respect to reaction raw materials total amount (following same datum)
Ratio uses polymerization initiator, in addition, in order to obtain low-molecular-weight fluoroelastomer, with the ratio of about 7～12 weight % using full
And polymerization initiator is used with the ratio of about 0.1～0.5 weight % with containing iodine compound as chain-transferring agent, carry out copolymerization anti-
Should.But, these numerical value are examples, can be changed according to other polymerizing conditions beyond copolymerization composition.
Emulsion polymerization is typically in pressure about 0～10MPa, preferably from about 0.5～4MPa；About 0～100 DEG C of temperature, preferably
Carry out under conditions of about 20～80 DEG C.Now, preferably the fluorochemical monomer mixture of supply is supplied with substep addition manner,
So that reaction pressure is maintained at certain limit.And, in order to adjust the pH in polymerization system, Na also can be added2HPO4、
NaH2PO4、KH2PO4Etc. the electrolyte substance with buffer capacity or sodium hydroxide.
The high molecular fluoroelastomer so obtaining and the blending of low-molecular-weight fluoroelastomer, preferably have basic phase
With the high molecular fluoroelastomer composition of copolymerization composition and low-molecular-weight fluoroelastomer composition with weight than for 70/30～
30/70, carry out under ratio as preferably 60/40～40/60.The ratio of high molecular fluoroelastomer than its many when, then mix
Polymer Mooney viscosity after conjunction rises and mobility reduces, on the other hand than its few when, the adhesiveness of admixture becomes big, polymerization
Thing Mooney viscosity nor the viscosity becoming practicality.
There is no particular limitation for the blending procedure of high molecular fluoroelastomer and low-molecular-weight fluoroelastomer, for example logical
Cross after their aqueous liquid dispersion (emulsion) is carried out in a desired proportion mixing, stirs, add sodium chloride, calcium chloride, chlorine
Change potassium etc. and carry out condensation, to carry out through washing, being dried etc..
Elastomer shape fluorinated copolymer admixture (fluoroelastomer admixture) obtaining, add polyol vulcanized agent or
Organic peroxide and multi-functional unsaturated compound and carry out vulcanizing, shape, can get solidfied material or processed goods.This
Outward, in patent documentation 7, disclose the fluoroelastomer combination adding organic peroxide and multi-functional unsaturated compound
Thing, emulsifying agent when preparing as fluoroelastomer specifically illustrating, it is only limitted to the perfluoro caprylic acid used by following comparative examples 1 and 5
Ammonium.
As polyol vulcanized agent, polyhydroxy aromatic compounds cross-linking agent can be used, now can and with comprising selected from quaternary ammonium
Salt, quaternary salt and inferior amine salt（イ ミ ニ ウ system）In at least one vulcanization accelerator, and then preferably use and comprise selected from 2
At least one acid acceptor in the oxide of valency metal or hydroxide and hydrotalcite（By acid）.
As polyhydroxy aromatic compounds, can be with every 100 weight portion fluoroelastomer admixtures for 0.1～10 weight
Part, the ratio of preferably 0.6～5 weight portion using double (4- hydroxy phenyl) propane [bisphenol-A] of such as hydroquinone, 2,2-, 2,2-
Double (4- hydroxy phenyl) butane of double (4- hydroxy phenyl) perfluoropropane [bisphenol AF], 4,4 '-dihydroxydiphenyl methane, 2,2- etc.
In at least one.
In addition, as quaternary ammonium salt, quaternary salt and inferior amine salt, with every 100 weight portion fluoroelastomer admixtures can be
0.05～2 weight portion, the ratio of preferably 0.1～1 weight portion uses such as tetramethyl ammonium chloride, tetraethylammonium chloride, tetrapropyl
Ammonium chloride, tetrabutylammonium chloride, tetrabutyl ammonium bromide, tetrabutyl chlorination, benzyl triphenyl phosphonium chloride, benzyl trioctylphosphine chlorination
, double (benzyl phenyl phosphino-) chlorimide（ビス(ベンジルフェニルホスフィン)イミニウムクロライ
ド）, iminium cations（イミニウムカチオン）Deng at least one.
And then, the oxide as divalent metal or hydroxide, the oxidation of the such as metal such as magnesium, calcium, zinc, lead can be used
At least one in thing, hydroxide, its usage amount is identical with the situation of hydrotalcite, in every 100 weight portion fluoroelastomers
Admixture is 1～30 weight portion, selects in the range of preferably 2～20 weight portions.In addition, as needed, promote to improve sulfuration
Enter the effect of agent it is also possible to add various sulfurations to promote activating agent.Promote the representation compound of activating agent as this sulfuration, can arrange
Lift the sulphones such as 1,8- diazabicyclo [5.4.0] hendecene -7 [DBU], dimethylsulfone, dichloro diphenylsulfone.
As organic peroxide, preferably easily produce the organic peroxide of peroxy radical due to being heated, can make
With such as 2,5- dimethyl -2,5- two (t-butylperoxy) hexin -3,2,5- dimethyl -2,5- two (t-butylperoxy)
At least one in dialkyl peroxides such as hexane etc..Estimate these organic peroxides to produce due to being heated in sulfuration
Free radical, iodine/bromo in polymer for this Free Radical, produce free radical in the polymer, and by polymer
2 free radicals be combined with each other, crosslinking can be caused.
The addition of organic peroxide suitably can select according to active oxygen amount, decomposition temperature etc., generally in every 100 weight
Part fluoroelastomer admixture is 0.05～10 weight portion, selects in the range of preferably 0.05～5 weight portion.With ratio fewer than its
When example is using organic peroxide, then the yield of free radical is excessively less it is impossible to make crosslinking be sufficiently carried out, on the other hand with than
When its many ratio is used, nor show the raising of effect, it is unfavorable not only economically to cause, and due to peroxide
The decomposition gas of compound and cause foaming, can be observed mechanical properties reduction trend, therefore not preferred.
As multi-functional unsaturated compound, can be with every 100 weight parts of elastomer admixtures for 0.01～10 weight
Part, the ratio of preferably 0.1～5 weight portion uses such as triallyl cyanurate, isocyanuric acid triallyl ester, three (diene
Propyl group amine) at least one in-s- triazine etc., preferably isocyanuric acid triallyl ester.
In addition to above essential component, in the fluoroelastomer composition of the present invention, various adding can be added as needed
Plus agent, the such as reinforcing agent such as carbon black, silicon dioxide, clay, Talcum or filler, processing aid such as wax class etc., comprise above each
The fluoroelastomer composition of composition can be prepared by mixing, being kneaded with roller, Banbury etc..
Thus obtained fluoroelastomer composition can be cut to banding, by using extrusion after abundant kneading in long way
Forming machine and obtain the flexible pipe of tubulose, then, post-cure can be carried out as desired by steam etc., thus obtain desired
Sulfide.
Embodiment
Then, according to embodiment, the present invention will be described.
Embodiment 1
(preparation of high molecular fluoroelastomer emulsion)
Enter line replacement in the stainless steel autoclave of internal volume 10L with nitrogen, add after degassing：
Surfactant [CF3CF2CF2OCF(CF3)CF2OCF(CF3)COONH4] 8.5g
(being 0.15 weight % with respect to deionized water)
Disodium hydrogen phosphate 12 hydrate 10g
Deionized water 5.8L
Internal volume is de-gassed after fully being replaced with nitrogen again.Then add wherein：
Vinylidene [VdF] 90g
Tetrafluoroethene [TFE] 77g
Hexafluoropropene [HFP] 760g
2- bromo- 1,1- difluoroethylene [BDFE] 8g
After making to be warming up to 80 DEG C in autoclave, add：
Ammonium persulfate. [APS；Using 0.3 weight % aqueous solution] 1.8g
Polyreaction is made to cause.Now intrinsic pressure is for 2.2MPa.In the way of keeping intrinsic pressure 2.15～2.25MPa, add：
VdF 786g
TFE 673g
HFP 520g
Reaction cools down after terminating, and discharges residual gas and obtains emulsion I (solid constituent concentration 31.5 weight %) 8,524g.
Additionally, carrying out condensation, washing, being dried using 1 weight % calcium chloride water and separate VdF-TFE-HFP3 unit from this emulsion
Copolymer, measuring its number-average molecular weight Mn (measuring according to following methods) is 161,000.
(preparation of low-molecular-weight fluoroelastomer emulsion)
In the preparation of aforementioned high molecular fluoroelastomer emulsion, BDFE is replaced to use octafluoro-Isosorbide-5-Nitrae-two iodobutane
[DIOFB] 34.0g, and by APS quantitative change more 6g, obtain emulsion II (solid constituent concentration 31.8 weight %) 8,534g.This
Outward, polyreaction cause when intrinsic pressure for 2.2MPa.And, the Mn of the VdF-TFE-HFP3 membered copolymer obtaining is 18,000.
(preparation of elastomer shape copolymer blend)
By the emulsion obtaining I and emulsion II mixing, so that respective solid weight ratio of constituents is 50：After 50, utilize 1
Weight % calcium chloride water carries out condensation, washing, is dried, and obtains elastomer shape copolymer blend A 5,344g.
Comparative example 1
In embodiment 1, in the system of high molecular fluoroelastomer emulsion and low-molecular-weight fluoroelastomer emulsion
In standby, as surfactant, CF is used with identical amount3CF2CF2CF2CF2CF2CF2COONH4When (perfluorooctanoic acid), respectively
Obtain high molecular fluoroelastomer emulsion III (solid constituent concentration 32.1 weight %, Mn144,000) 8,521g and low point
Son amount fluoroelastomer emulsion IV (solid constituent concentration 31.8 weight %, Mn18,000) 8,537g, by them with solid composition
Weight compares 50：50, to use, obtain elastomer shape copolymer blend B 5,419g.
Comparative example 2
In embodiment 1, in the system of high molecular fluoroelastomer emulsion and low-molecular-weight fluoroelastomer emulsion
In standby, as surfactant, CHF is used with identical amount2CF2CF2CF2CF2CF2CF2CF2COONH4(9H- ten hexafluoro n-nonanoic acid
Ammonium) when, respectively obtain high molecular fluoroelastomer emulsion V (solid constituent concentration 31.4 weight %, Mn151,000) 8,
512g and low-molecular-weight fluoroelastomer emulsion VI (solid constituent concentration 32.2 weight %, Mn19,000) 8,531g, by them
With solid weight ratio of constituents 50：50, to use, obtain elastomer shape copolymer blend C 5,321g.
Comparative example 3
In embodiment 1, in the system of high molecular fluoroelastomer emulsion and low-molecular-weight fluoroelastomer emulsion
In standby, when amount of surfactant is changed to 1.7g (0.03 weight %) to use, respectively obtain high molecular fluoroelastomer breast
Shape liquid VII (solid constituent concentration 31.7 weight %, Mn138,000) 8,528g and low-molecular-weight fluoroelastomer emulsion VIII
(solid constituent concentration 31.8 weight %, Mn16,000) 8,551g, by them with solid weight ratio of constituents 50：50, to use, obtain
Elastomer shape copolymer blend D 5,326g.
Comparative example 4
In embodiment 1, in the system of high molecular fluoroelastomer emulsion and low-molecular-weight fluoroelastomer emulsion
In standby, amount of surfactant be changed to 40.6g (0.7 weight %) to use, respectively obtain high molecular fluoroelastomer emulsus
Liquid IX (solid constituent concentration 31.1 weight %, Mn168,000) (solid becomes 8,542g with low-molecular-weight fluoroelastomer emulsion X
Point concentration 31.4 weight %, Mn17,000) 8,555g, by them with solid weight ratio of constituents 50：50, to use, obtain elastomer
Shape copolymer blend E 5,331g.
For the elastomer shape copolymer blend A～E obtaining in above embodiment and each comparative example, carry out following
The mensure of project.
Copolymer forms [mole %]：Measured using Jeol JMN-LA300 Fourier-transform nuclear magnetic resonance instrument.
Oil repellent [weight %]：F content is calculated according to molecular weight.
Polymer Mooney viscosity (ML1+10)：Under 121 DEG C of test temperature, after preheating 1 minute, rotary head is made to rotate immediately,
Value after measuring 10 minutes.
Molecular weight determination：Using Japanese light splitting industry 851-AS type Intelligent Auto Sampler processed, ガ ス Network ロ industry system
MODEL 576 type LC pump, possess Showa electrician Shodex KF-801,4, the pillar of KF-802, KF-802.5 and KF-805
ガ ス Network ロ industry MODEL 556 type HPLC column incubator processed and Japanese light splitting industry detector JASCO 830RI differential processed roll over
Penetrate meter, make oxolane as developing solvent, sample concentration 0.5 weight %, flow 1.0ml/ minute, measure at 40 DEG C of temperature.
The parsing of molecular weight uses シ ス テ system イ Application ス ツルメン Star society SIC ラ Block チ ャ ト 180, Er Qiezuo
For molecular weight calibration curve standard polymers, using the various monodisperse polystyrene [Mw/Mn=1.1 of Japan's Cao Da product
(MAX)].
Measurement result is shown in table 1 below.
Embodiment 2
Elastomer shape copolymer blend A 100 weight portion
MT carbon black (キ ャ Application キ ャ Block product サ マ ッ Network ス N990) 20 weight portions
Multi-functional unsaturated compound 5 weight portion
(Japan chemical conversion product TAIC M60；Isocyanuric acid triallyl ester)
Organic peroxide (Japanese oil product パ ヘ キ サ 25B-40) 3.5 weight portions
ZnO 5 weight portion
By each composition above with end runner mill mixing so as to get solidification compound carry out at 180 DEG C 10 minutes
Compression molding (once vulcanizing) makes sheet material and the O ring (P24) of thickness 2mm, carries out the baker of 22 hours further at 230 DEG C
Sulfuration (post-cure).Carry out solidity test when once vulcanizing, the material after post-cure is carried out with regard to normality physical property, pressure
The mensure of compression permanent deformation and cohesive and evaluation.
Solidity test：Using Meng's santoprene plate rheometer, measure the value of MH, Tc90 at 121 DEG C.
Normality physical property：According to JIS K6250,6253.
Compression set：According to ASTM D395 Method B, for P24 O ring, measure 150 DEG C, the value of 70 hours.
Cohesive：Make respective thickness about 1.5mm the sheet material of unvulcanized fluoroelastomer (above-mentioned solidification compound) and
The sheet material laminating of unvulcanized nitrile rubber, carries out 160 DEG C, 30 minutes press cures, after then letting cool, shocking experiment piece is to thickness
2mm, wide 12.5mm, long 100mm, implement to peel off with test speed 100mm/ minute using TOYOSEIKI STROGRAPH E II
Test.
Evaluate which side rubber before stripping damaged situation occurring is that cohesive is good, and rubber is damaged and the feelings peeled off
Condition is that cohesive is bad.
Additionally, as unvulcanized nitrile rubber, following coordination compound can be used
Nitrile rubber (southern Supreme Being chemical industry product NANCAR1051) 100 weight portions
HAF carbon black (rising sun カ ボ Application product) 50 weight portions
Zinc oxide 5 weight portion
Stearic acid 1 weight portion
Age resistor (Seiko chemicalss ノ Application Off レ ッ Network ス RD) 3 weight portions
Sulfur 2 weight portion
Vulcanization accelerator (three new chemical industry product サ Application セ ラ TS) 3 weight portions.
Comparative example 5
In example 2, replace elastomer shape copolymer blend A, mixed using elastomer shape copolymer with identical amount
Compound B.
Comparative example 6
In example 2, replace elastomer shape copolymer blend A, mixed using elastomer shape copolymer with identical amount
Compound C.
Comparative example 7
In example 2, replace elastomer shape copolymer blend A, mixed using elastomer shape copolymer with identical amount
Compound D.
Comparative example 8
In example 2, replace elastomer shape copolymer blend A, mixed using elastomer shape copolymer with identical amount
Compound E.
The result obtaining in above example 2 and comparative example 5～8 is shown in table 2 below.
Embodiment 3
(preparation of high molecular fluoroelastomer emulsion)
Enter line replacement in the steel autoclave of internal volume 10L with nitrogen, add after degassing：
Surfactant [CF3CF2CF2OCF(CF3)CF2OCF(CF3)COONH4] 15g (0.26 weight %)
Disodium hydrogen phosphate 12 hydrate 10g
Deionized water 5.8L
Internal volume is de-gassed after fully being replaced with nitrogen again.Then add wherein：
Vinylidene [VdF] 83g
Tetrafluoroethene [TFE] 67g
Hexafluoropropene [HFP] 640g
Isopropanol [IPA] 1.0g
After making to be warming up to 80 DEG C in autoclave, add：
Ammonium persulfate. [APS] 1.0g
Polyreaction is made to cause.Now intrinsic pressure is for 2.2MPa.In the way of keeping intrinsic pressure 2.15～2.25MPa, add：
VdF 932g
TFE 673g
HFP 520g
Reaction terminate after cooling, discharge residual gas obtain emulsion I ' (solid constituent concentration 31.6 weight %, Mn173,
000)8,473g.
(preparation of low-molecular-weight fluoroelastomer emulsion)
In the preparation of aforementioned high molecular fluoroelastomer emulsion, IPA is replaced to use diethyl malonate 70g,
And by APS quantitative change more 5g, obtain emulsion II ' (solid constituent concentration 31.4 weight %, Mn18,000) 8,489g.Additionally,
Polyreaction cause when intrinsic pressure for 2.2MPa.
(preparation of elastomer shape copolymer blend)
By the emulsion obtaining I ' and emulsion II ' mixing, so that respective solid weight ratio of constituents is 50：After 50, profit
Carry out condensation, washing with 1 weight % calcium chloride water, be dried, obtain elastomer shape copolymer blend F 5,342g.
Comparative example 9
In embodiment 3, in the system of high molecular fluoroelastomer emulsion and low-molecular-weight fluoroelastomer emulsion
In standby, as surfactant, CF is used with identical amount3CF2CF2CF2CF2CF2CF2COONH4When (perfluorooctanoic acid), respectively
Obtain high molecular fluoroelastomer emulsion III ' (solid constituent concentration 32.2 weight %, Mn166,000) 8,397g and low point
Son amount fluoroelastomer emulsion IV ' (solid constituent concentration 31.6 weight %, Mn19,000) 8,518g, obtained using them
Elastomer shape copolymer blend G 5,318g.
Comparative example 10
In embodiment 3, in the system of high molecular fluoroelastomer emulsion and low-molecular-weight fluoroelastomer emulsion
In standby, as surfactant, CHF is used with identical amount2CF2CF2CF2CF2CF2CF2CF2COONH4(9H- ten hexafluoro n-nonanoic acid
Ammonium) when, respectively obtain high molecular fluoroelastomer emulsion V ' (solid constituent concentration 31.5 weight %, Mn162,000) 8,
452g and low-molecular-weight fluoroelastomer emulsion VI ' (solid constituent concentration 31.6 weight %, Mn17,000) 8,522g, use
They and obtain elastomer shape copolymer blend H 5,347g.
Comparative example 11
In embodiment 3, in the system of high molecular fluoroelastomer emulsion and low-molecular-weight fluoroelastomer emulsion
In standby, when amount of surfactant is changed to 1.7g (0.03 weight %) to use, respectively obtain high molecular fluoroelastomer breast
Shape liquid VII ' (solid constituent concentration 30.6 weight %, Mn154,000) 8,402g and low-molecular-weight fluoroelastomer emulsion
VIII ' (solid constituent concentration 30.8 weight %, Mn16,000) 8,542g, elastomer shape copolymerization polymer blends are obtained using them
Thing I 5,389g.
Comparative example 12
In embodiment 3, in the system of high molecular fluoroelastomer emulsion and low-molecular-weight fluoroelastomer emulsion
In standby, when amount of surfactant is changed to 40.6g (0.7 weight %) to use, respectively obtain high molecular fluoroelastomer breast
Shape liquid IX ' (solid constituent concentration 32.2 weight %, Mn172,000) 8,440g and low-molecular-weight fluoroelastomer emulsion X ' (Gu
Shape constituent concentration 31.9 weight %, Mn18,000) 8,542g, elastomer shape copolymer blend J 5 is obtained using them,
316g.
For the elastomer shape copolymer blend F～J obtaining in above embodiment 3 and comparative example 9～12, carry out with
The mensure of lower projects.Measurement result is shown in table 3 below.
Embodiment 4
In example 2, using following solidification compounds, similarly it is measured and evaluates.Wherein, permanent to compressing
Deformation, measures 200 DEG C, the value of 70 hours.
Elastomer shape copolymer blend F 100 weight portion
MT carbon black (サ マ ッ Network ス N990) 25 weight portions
Vulcanizing agent (PVC ス Off ェ ノ Le AF) 2 weight portions
Vulcanization accelerator (benzyl triphenyl phosphonium chloride) 1 weight portion
Acid acceptor (republicanism chemicalss キ ョ ウ ワ マ グ #150) 3 weight portions
Acid acceptor (nearly river chemicalss Caldic#2000) 6 weight portions.
Comparative example 13
In example 4, replace elastomer shape copolymer blend F, mixed using elastomer shape copolymer with identical amount
Compound G.
Comparative example 14
In example 4, replace elastomer shape copolymer blend F, mixed using elastomer shape copolymer with identical amount
Compound H.
Comparative example 15
In example 4, replace elastomer shape copolymer blend F, mixed using elastomer shape copolymer with identical amount
Compound I.
Comparative example 16
In example 4, replace elastomer shape copolymer blend F, mixed using elastomer shape copolymer with identical amount
Compound J.
The result obtaining in above embodiment 4 and comparative example 13～16 is shown in table 4 below.
According to result above, it is summarized as follows.
(1) in embodiment 2 and 4, fracture strength and compression resistant permanent set characteristics all show good value.
(2) in the preparation of elastomer shape copolymer blend, perfluorooctanoic acid is used as the comparison of surfactant
Sulfide obtained by example 5 and 13, fracture strength is poor.
(3) in the preparation of elastomer shape copolymer blend, 9H- ten hexafluoro n-nonanoic acid ammonium is used as surfactant
Comparative example 6 and 14 obtained by sulfide, compression resistant permanent set characteristics are poor.
(4) in the preparation of elastomer shape copolymer blend, even if using the surfactant used by each embodiment
When, the sulfide obtained by the few comparative example of its use level 7 and 15, the stability of emulsion is also poor, and low viscosity breast can be observed
Shape liquation goes out.
(5) in the preparation of elastomer shape copolymer blend, even if using the surfactant used by each embodiment
When, the sulfide obtained by comparative example 8 and 16 more than its use level, also poor with the cohesive of NBR.
Industrial applicability
Fluoroelastomer composition according to the present invention has normality physical property, compression set excellent due to providing
Physical property sulfide, therefore can be suitable as fuel system parts, the particularly vulcanization forming material such as fuel hose, pipe makes
With.
Claims (6)
1. fluoroelastomer admixture, its all using 2,3,3,3- tetra- fluoro- 2- [1,1,2,3,3,3- hexafluoro -2- (1,1,2,2,3,
3,3- seven fluorine propoxyl group) propoxyl group] -1- propanoic acid ammonium CF3CF2CF2OCF(CF3)CF2OCF(CF3)COONH4As emulsifying agent, only
By copolymerization is carried out by emulsion polymerization with respect to the ratio that addition water gross weight is 0.05～0.5 weight % using emulsifying agent
Obtain, (A) number-average molecular weight Mn be 5,000～100,000 low-molecular-weight fluoroelastomer and (B) number-average molecular weight Mn be
130,000～3,000,000 high molecular fluoroelastomer is blended with weight than the ratio for 70/30～30/70, mixes
Compound has 10～40 moles of % of tetrafluoroethene, the copolymerization group of 80～30 moles of % of vinylidene and 10～30 moles of % of hexafluoropropene
Become, the ratio of weight average molecular weight Mw/ number-average molecular weight Mn is 2～20.
2. fluoroelastomer admixture according to claim 1, it is by (A) low-molecular-weight fluoroelastomer and (B) high score
Son amount fluoroelastomer is all prepared as aqueous liquid dispersion, aqueous liquid dispersion is blended each other and forms fluoroelastomer and mix
Compound.
3. fluoroelastomer composition, it comprises fluoroelastomer admixture and following (C) or (D) described in claim 1 or 2
One of, wherein (C) be polyol vulcanized agent, (D) be organic peroxide and multi-functional unsaturated compound.
4. fluoroelastomer composition according to claim 3, every 100 weight portion fluoroelastomer admixtures, respectively with
(C) polyol vulcanized agent be 0.1～10 weight portion ratio or with (D) organic peroxide be 0.05～10 weight portion, many officials
Can property unsaturated compound be the ratio of 0.01～10 weight portion using.
5. by the fuel system parts obtained from fluoroelastomer composition vulcanization forming described in claim 4.
6. fuel system parts according to claim 5, it is fuel hose.
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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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| US3845024A (en) * | 1972-11-22 | 1974-10-29 | Du Pont | Continuous process for production of fluoroelastomers |
| JPH06271734A (en) * | 1993-03-24 | 1994-09-27 | Asahi Chem Ind Co Ltd | Fluoroelastomer composition |
| DE19542501A1 (en) * | 1995-11-15 | 1997-05-22 | Bayer Ag | Peroxidically crosslinkable fluororubbers, a process for their production and their use |
| JP4304841B2 (en) * | 2000-07-28 | 2009-07-29 | ユニマテック株式会社 | Gel component-containing fluorine-containing elastomer with excellent extrudability |
| JP3900883B2 (en) * | 2001-10-05 | 2007-04-04 | ダイキン工業株式会社 | Method for producing fluoropolymer latex |
| EP1762594B1 (en) * | 2004-06-28 | 2012-10-10 | Daikin Industries, Ltd. | Fluorine-containing elastomer composition and molded article made therefrom |
| US20060105179A1 (en) * | 2004-11-17 | 2006-05-18 | Hofman Gerald R A | Elastomeric dental article with a protective fluoropolymer layer |
| US20100068436A1 (en) * | 2006-10-25 | 2010-03-18 | Unimatec CO. Ltd | Fluorine-containing elastomer for molding fuel system parts and composition thereof |
| US7989566B2 (en) * | 2008-01-22 | 2011-08-02 | Dupont Performance Elastomers Llc | Process for producing fluoropolymers |
| JP5433962B2 (en) * | 2008-03-21 | 2014-03-05 | ユニマテック株式会社 | Fluorine-containing copolymer and aqueous dispersion thereof |
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