CN101006133A - Blends of perfluoroelastomers and fluoroplastics - Google Patents
Blends of perfluoroelastomers and fluoroplastics Download PDFInfo
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- CN101006133A CN101006133A CN 200580015799 CN200580015799A CN101006133A CN 101006133 A CN101006133 A CN 101006133A CN 200580015799 CN200580015799 CN 200580015799 CN 200580015799 A CN200580015799 A CN 200580015799A CN 101006133 A CN101006133 A CN 101006133A
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Abstract
Cured articles are prepared from a composition that comprises a blend of a perfluoroelastomer and 51-300 phr of a semi-crystalline thermoplastic copolymer comprising copolymerized units of tetrafluoroethylene and 5-12 weight percent of a perfluoro(alkyl vinyl ether). The semi-crystalline copolymer is present as particles having an average particle size greater than 100 nm.
Description
Invention field
The present invention relates to perfluoroelastomers and mean particle size curable adulterant greater than the miocrystalline thermoplastic copolymer of 100nm.
Background technology
Perfluoroelastomers is in commercial acquisition immense success, and it is abominable to be widely used in environment, particularly exposes at high temperature and exists in the end-use of corrosive chemical.For example, these polymkeric substance are usually used in sealing, the drilling outfit of aircraft engine, and are used as the high temperature sealing element of the industrial equipments of use down.
The outstanding performance of perfluoroelastomers is mainly based on the unitary stability of copolymerization perfluorinated monomer and the inertia that constitute the major portion of polymer backbone in these compositions.This monomer comprises tetrafluoroethylene and perfluorinated vinyl ether.In order to have given play to elastomeric property fully, perfluoroelastomers is normally crosslinked, i.e. sulfurized.For this reason, a small amount of sulfide site monomer and the copolymerization of perfluorinated monomer unit are arranged.The sulfide site monomer that especially preferably contains at least one cyano group, perfluor-8-cyano group-5-methyl-3 for example, 6-two oxa-s-1-octene.Among the US 4281092,4394489,5789489 and 5789509 this composition has been described.
US 3484503 discloses the single-phase adulterant of the thermoplastic copolymer of the elastocopolymer of perfluoro-ethylene and perfluor (alkyl vinyl ether) and perfluoro-ethylene.Elastic component is the Containing Sulfur position not, so said composition can not be crosslinked.Crosslinked by the sealing agent that this composition is made owing to lacking, make sealing property relatively poor.
US 4713418 discloses the curable perfluoroelastomers composition of the melt blend that contains perfluoroelastomers and 2-50 weight part thermoplastic perfluoropolymer.This thermoplastic polymer generally has at least 300 ℃ fusing point.Because the incorporation of thermoplastic perfluoropolymer is less, the physical strength of the sealing agent shortage high pressure seal application requiring made from these compositions.
US 6710132 B2 disclose the latex adulterant of perfluoroelastomers and 2-90% (weight) miocrystalline nuclear/shell fluoroplastics, and wherein shell polymeric contains bromine and/or iodine in polymer chain.The shell that WO02/79280 discloses perfluoroelastomers and fluoro-resin solidifies the latex adulterant, and wherein the fusing point of fluoro-resin is 230-300 ℃, and mean particle size is less than 100nm.The technical scale of latex adulterant is made complexity or cost height.
Such perfluoroelastomers composition is preferably arranged, when it is crosslinked, can provide excellent sealing performance, the intensity, the favorable chemical resistance that are enough to be applied under the hyperbaric environment are arranged, and said composition can be made in conventional rubberized equipment.
Summary of the invention
One aspect of the present invention is the preparation method of vulcanized article, and described method comprises:
A, be lower than dry type fusion i under 100 ℃ the temperature) perfluoroelastomers, ii) per 100 weight part perfluoroelastomers 51-300 weight parts contain the miocrystalline multipolymer and 5-12% (weight) perfluor (alkyl vinyl ether) of the copolymerization units of tetrafluoroethylene, described miocrystalline multipolymer has mean particle size and the fusing point greater than 100nm, iii) solidifying agent forms curable compositions;
B, vulcanize described composition, form vulcanized article; With
C, under the temperature that is higher than described miocrystalline multipolymer fusing point the described sulfurized goods of after fixing.
The present invention is the preparation method of vulcanized article on the other hand, and described method comprises:
A, melt fusion i) perfluoroelastomers and ii) per 100 weight part perfluoroelastomers 51-300 weight parts contain the miocrystalline multipolymer and 5-12% (weight) perfluor (alkyl vinyl ether) of the copolymerization units of tetrafluoroethylene, described miocrystalline multipolymer has mean particle size and the fusing point greater than 100nm, described being blended under the temperature that is higher than described miocrystalline multipolymer fusing point carried out, thereby forms adulterant;
B, in described adulterant, add solidifying agent being lower than under 150 ℃ the temperature; With
C, the described composition of sulfuration form vulcanized article.
The present invention is the vulcanized article with the preparation of one of above two kinds of methods on the other hand.
Detailed Description Of The Invention
Perfluoroelastomers normally has the amorphous polymeric composition of the copolymerization units of at least two main perfluorinated monomer.In general, one of them main monomer is a perfluoroolefine, and another is a perfluorovinyl ether.Representative perfluor alkene comprises tetrafluoroethylene and R 1216.Suitable perfluorinated vinyl ether comprises general formula
CF
2＝CFO(R
f’O)
n(R
f”O)
mR
f (I)
Those, R wherein
F 'And R
F "Be the different straight chains or the 2-6 carbon atom perfluorinated alkylidene of branching, m and n are 0-10 independently, R
fIt is 1-6 carbon atom perfluoroalkyl.
The kind of preferred perfluorinated vinyl ether comprises the composition of following general formula
CF
2＝CFO(CF
2CFXO)
nR
f (II)
Wherein X is F or CF
3, n is 0-5, R
fIt is 1-6 carbon atom perfluoroalkyl.Most preferred perfluorinated vinyl ether is that wherein n is 0 or 1 and R
fContain those of 1-3 carbon atom.The example of this perfluorinated ethers comprises perfluor (ethylene methacrylic ether) and perfluor (propyl vinyl ether).
Other available monomers comprise the compound of following general formula
CF
2＝CFO[(CF
2)
mCF
2CFZO]
nR
f (III)
R wherein
fBe the perfluoroalkyl that has 1-6 carbon atom, m=0 or 1, n=0-5, and Z=F or CF
3Preferred such member is R wherein
fBe C
3F
7, m=0 and n=1 those.
Other perfluorinated vinyl ether monomers comprise the compound of following general formula
CF
2＝CFO[(CF
2CFCF
3O)
n(CF
2CF
2CF
2O)
m(CF
2)
p]C
xF
2x+1 (IV)
Wherein m and n=1-10, p=0-3, and x=1-5.Preferred this type of member comprises the wherein compound of n=0-1, m=0-1 and x=1.
The example of other available perfluorinated vinyl ether comprises
CF
2＝CFOCF
2CF(CF
3)O(CF
2O)
mC
nF
2n+1 (V)
N=1-5 wherein, m=1-3, and n=1 preferably wherein.
Preferred perfluoroelastomers multipolymer is by forming as the unitary tetrafluoroethylene of main monomer and at least one perfluorinated vinyl ether.In this multipolymer, the copolymerization perfluorinated ether units accounts for about 15-50% (mole) of total monomer units in the polymkeric substance.
Perfluoroelastomers also comprises the copolymerization units of at least a cure site monomer, and its content is generally 0.1-5% (mole).The preferred 0.3-1.5% of its scope (mole).Though can there be more than one cure site monomer, the most frequently used is a kind of cure site monomer, and it contains at least one cyanogen substituting group.Suitable cure site monomer comprises cyano-containing fluorinated olefin and cyano-containing fluorinated vinyl ether.Available cyano-containing cure site monomer comprises those of following general formula:
CF
2＝CF-O(CF
2)
n-CN (VI)
N=2-12 wherein, preferred 2-6;
CF
2＝CF-O[CF
2-CF(CF
3)-O]
n-CF
2-CFCF
3-CN (VII)
N=0-4 wherein, preferred 0-2; With
CF
2＝CF-[OCF
2CF(CF
3)]
x-O-(CF
2)
n-CN (VIII)
Wherein x=1-2, and n=1-4.
Those of preferred formula (VIII).Particularly preferred cure site monomer is the perfluorinated polyether that has cyano group and trifluoro-ethylene ether.Most preferred cure site monomer is
CF
2＝CFOCF
2CF(CF
3)OCF
2CF
2CN (IX)
Be perfluor (8-cyano group-5-methyl-3,6-two oxa-s-1-octene) or 8-CNVE.
Other cure site monomer comprise general formula R
1CH=CR
2R
3The alkene of expression, wherein R
1And R
2Independently be selected from hydrogen and fluorine, R
3Independently be selected from hydrogen, fluorine, alkyl and perfluoroalkyl.Perfluoroalkyl can comprise up to about 12 carbon atoms.But preferably have the nearly perfluoroalkyl of 4 carbon atoms.In addition, cure site monomer preferably has and is no more than 3 hydrogen atoms.The example of this alkene comprises ethene, vinylidene fluoride, vinyl fluoride, trifluoro-ethylene, 1-hydrogen five fluorine propylene and 2-hydrogen five fluorine propylene, and such as 4-bromo-3,3,4, the brominated olefins of 4-tetrafluoro butene-1 and bromo trifluoro-ethylene.
Can mix another kind of cure site monomer in the perfluoroelastomers that the present invention adopts and be disclosed relevant monomer among perfluor (2-phenoxy propyl Vinyl Ether) and the US 3467638.
Particularly preferred perfluoroelastomers contains 53.0-79.9% (mole) tetrafluoroethylene, 20.0-46.9% (mole) perfluor (ethylene methacrylic ether) and 0.4-1.5% (mole) cure site monomer, preferred cyano-containing cure site monomer.Molecular fraction is based on the total mole number meter of all comonomer units in the perfluoroelastomers.
As selection, or except that cure site monomer, perfluoroelastomers can contain iodine and/or bromine atoms by terminal position on the perfluoroelastomers polymer chain.This atom can be between polymerization period be introduced by the reaction of the chain-transfer agent that contains iodine or bromine, as the description among the US 4243770.
The miocrystalline fluoropolymer that adopts in the present composition (being the thermoplasticity (per) fluoropolymer) is to comprise the copolymerization units of tetrafluoroethylene and the multipolymer of 5-12% (weight) (based on the multipolymer gross weight) perfluor (alkyl vinyl ether).Perfluor (alkyl vinyl ether) comprises perfluor (ethylene methacrylic ether), perfluor (ethyl vinyl ether) and perfluor (propyl vinyl ether).Preferred perfluor (ethyl vinyl ether) and perfluor (propyl vinyl ether).This fluoropolymer has 285-310 ℃ nominal fusing point (ASTMD3418).The number average particle size of fluoropolymer is preferably greater than 1 μ m greater than 100nm.Preferred miocrystalline fluoropolymer is the Teflon PFA fluoropolymer that obtains from DuPont.Particularly preferred fluoropolymer is the Teflon PFA HP Plus that obtains with the 2.5mm sheet.This miocrystalline fluoropolymer than volume particle size helps on such as the conventional rubber fusion equipment of roller mill, blender and forcing machine and the perfluoroelastomers fusion.
Vulcanized article of the present invention comprises perfluoroelastomers, 51-300 (preferred 60-200, most preferably 75-200) above-mentioned miocrystalline fluoropolymer of phr and solidifying agent.Term " phr " refers to the weight part of each composition in per 100 parts by weight of rubber (being perfluoroelastomers).
The curable compositions that is used to make vulcanized article of the present invention can pass through melt fusion miocrystalline fluoropolymer and perfluoroelastomers, or dry type fusion miocrystalline fluoropolymer and perfluoroelastomers are made under the temperature that is lower than miocrystalline fluoropolymer fusing point.Yet importantly this miocrystalline fluoropolymer is melted at some the some place in this vulcanized article manufacturing processed.
" melt fusion " refers to fusion dry ingredients under the temperature that is higher than miocrystalline fluoropolymer fusing point (promptly not being latex or liquid dispersion).Melt fusion temperature should remain below during the fusion perfluoroelastomers or obvious pyrolysated temperature may take place the miocrystalline fluoropolymer.Preferred melt fusion temperature is 300-350 ℃.Behind melt fusion perfluoroelastomers and the miocrystalline fluoropolymer, under the temperature that is lower than 150 ℃ (preferably being lower than 100 ℃), in adulterant, add solidifying agent.Importantly solidifying agent does not add under comparatively high temps, and sulfuration (promptly crosslinked) can not taken place before composition is configured as goods.Then by not necessarily the latter's composition being shaped, crosslinked then (i.e. sulfuration) and make vulcanized article by said composition.These goods also can not necessarily carry out postcure.
Vulcanized article preferably of the present invention is made by curable compositions, said composition is passed through at the fusing point far below the miocrystalline fluoropolymer, also be lower than the obvious crosslinked temperature of generation and (promptly be lower than 100 ℃, preferably be lower than 50 ℃ temperature) under, dry type fusion perfluoroelastomers, miocrystalline fluoropolymer and solidifying agent preparation." dry type fusion " refers to for the latex that has big water gaging or solvent, liquid dispersion or solution blending, will contain each composition fusion together of a small amount of (if any) water or solvent.Dry type fusion process can not necessarily be carried out in two steps, i.e. fusion perfluoroelastomers and miocrystalline fluoropolymer (carrying out under far below the temperature of miocrystalline fluoropolymer fusing point) in advance before adding solidifying agent.Usually preferably under the temperature that is lower than miocrystalline fluoropolymer fusing point, said composition is shaped and sulfuration then, promptly crosslinked.In postcure resulting product under the temperature that is higher than miocrystalline fluoropolymer fusing point (i.e. postcure under 300-350 ℃ of temperature), the postcure time reaches the fusing miocrystalline needed time of fluoropolymer at least then.General these goods of postcure 5-30 hour in inert atmosphere (for example nitrogen) or air are with fusing miocrystalline fluoropolymer and further cross-linked perfluorinated elastomerics.The postcure condition should keep below perfluoroelastomers or the miocrystalline fluoropolymer during these goods of postcure obvious pyrolysated temperature may take place.The physicals of the vulcanized article of unexpectedly, making by this method is better than the goods of making by the melt blend composition of perfluoroelastomers and miocrystalline fluoropolymer.
When perfluoroelastomers has the copolymerization units of cyano-containing cure site monomer, can utilize vulcanization system based on organo-tin compound.Suitable organo-tin compound comprise allyl group-, propargyl-, triphenyl-and propadiene base tin solidifying agent.Tetraalkyl tin compound or four tin aryl SnAr2 compounds are to be used for the preferred consolidation agent that is connected with cure site that nitrile replaces.The consumption of solidifying agent will depend on the degree of crosslinking that the finished product require, and the type and the concentration of active part in the perfluoroelastomers.Generally can adopt per about 0.5-10 weight parts of 100 parts of elastomericss (phr) solidifying agent, 1-4phr can satisfy most purposes.Believe that itrile group trimerization in the presence of such as the solidifying agent of organotin forms the s-triazine ring, thus cross-linked perfluorinated elastomerics.This crosslinked be heat-staple, even also stable under 275 ℃ and above temperature.
The preferred vulcanization system that can be used for comprising the perfluoroelastomers that contains the nitrile cure sites utilizes two (amino-phenol) and two (aminothiophenol) of following general formula
With
Tetramine with following general formula
Wherein A is SO
2, O, CO, 1-6 carbon atom alkylidene group, 1-10 carbon atom perfluorinated alkylidene or connect the C-C of two aromatic rings.Above general formula (X) and (XI) in amino and hydroxyl or thio group on phenyl ring, adjoin each other, and can in a position and contraposition, exchange with basic A respectively.Preferred solidifying agent is to be selected from 4,4 '-[2,2,2-three fluoro-1-(trifluoromethyl) ethylidene] two (2-amino-phenols), 4,4 '-alkylsulfonyl two (2-amino-phenol), 3,3 '-diaminobenzidine and 3,3 ', 4, the compound of 4 '-tetramino benzophenone.Wherein first kind of compound most preferably will be called two (amino-phenol) AF.Solidifying agent can be as disclosed method preparation among the US 3332907 (Angelo).Two (amino-phenol) AF can be by 4,4 '-[2,2,2-three fluoro-1-(trifluoromethyl) ethylidene] biphenol (being bisphenol AF), preferably carry out nitrated with saltpetre and trifluoroacetic acid, by catalytic hydrogenation, preferably prepare as catalyzer then with the palladium of ethanol as catalytic amount on solvent and the carbon.The selection of hardener dose should make the best performance of vulcanized rubber expectation.Generally make the consumption of solidifying agent be slightly more than with perfluoroelastomers in the consumption of all cure sites reaction needed of existing.The per 100 parts of elastomerics 0.5-5 weight part solidifying agent of general requirement.Preferable range is 1-2phr.
Superoxide also can be used as solidifying agent, particularly when cure sites is nitrile, iodine or bromo.The available superoxide is the superoxide that produces free radical under solidification value.Particularly preferably in being higher than dialkyl peroxide or two (dialkyl peroxides) that decompose under 50 ℃ the temperature.The preferred in many cases ditertiary butyl peroxide that has the tertiary carbon atom that is connected with peroxide oxygen that adopts.In this type of superoxide the most usefully 2,5-dimethyl-2,5-two (t-butylperoxy) hexin-3 and 2,5-2.Other superoxide can be selected from such as dicumyl peroxide, dibenzoyl peroxide, t-butylperoxyl benzoate and two [1,3-dimethyl-3-(t-butylperoxy) butyl] carbonic ether.Usually the about 1-3 part superoxide of per 100 parts of perfluoroelastomers.Be usually used in the composition fusion as the another kind of material of a peroxide firming agent system part by can with the collaborative available solidified coagent that polyunsaturated compounds is formed (coagent) that provides of superoxide.The addition of these coagents can be per 100 parts of perfluoroelastomers 0.1-10 parts, preferred 2-5phr.This coagent can be following one or more compounds: triallyl cyanurate, triallyl isocyanurate, three (methacrylic) chlorinated isocyanurates, three (diallyl amine)-s-triazines, triallyl phosphite, N, N-diallyl acrylamide, six allyl group phosphamides, N, N, N ', N '-tetraalkyl tetraphthalamide, N, N, N ', N '-tetraalkyl Malonamide, tricarbimide trivinyl ester, 2,4,6-trivinyl methyl trisiloxanes, and three (5-norbornylene-2-methylene radical) cyanurate.Useful especially is triallyl isocyanurate.
Other be fit to solidifying agent that sulfuration has the perfluoroelastomers of nitrile cure sites comprise ammonia, as disclosed inorganic or organic acid ammonium salt (for example ammonium perfluorocaprylate) among the US 5565512, and as the disclosed compound (for example urea) for preparing ammonia that under curing temperature, decomposes among US 6281296 B1.
Cure sites difference according to existing also can adopt dual cure systems.For example, the perfluoroelastomers that has a copolymerization units that contains the nitrile cure site monomer can combine curing with organotin solidifying agent and coagent with the solidifying agent of the mixture that comprises superoxide.General 0.3-5 part superoxide, 0.3-5 part coagent and the 0.1-10 part organotin solidifying agent of adopting.
Can mix the additive such as filler (for example carbon black, barium sulfate, silicon oxide, aluminum oxide, pure aluminium silicate and titanium dioxide), stablizer, softening agent, lubricant and processing material commonly used in the perfluoroelastomers prescription in the composition of the present invention, as long as they have enough stability to the application conditions of expecting.Preferably under being lower than 150 ℃ temperature, mix any additives that exists in the present composition.Yet, in the preferred embodiment of the invention, in the present composition, do not mix carbon black, metallic stuffing, metal-salt, metal oxide or metal hydroxides.Therefore, this embodiment of the present invention contains the low-down metal that extracts, and is particularly suitable for requiring such as semi-conductor manufacturing and pharmacy etc. the environment of high purity sealing.
Sulfuration perfluoroelastomers goods of the present invention have excellent sealing performance, sufficient intensity is used for high-voltage applications, creep resistance, snappiness, and excellent chemical resistant properties." excellent sealing performance " refer to 25 ℃, 200% the elongation under tensile-permanent set (% retraction) be at least 25%." sufficient intensity is used for high-voltage applications " refers to that 100% modulus under stretching is 5.5MPa at least." excellent chemical resistant properties " refer to when sulfuration perfluoroelastomers goods under 90 ℃ of quadrols or 225 ℃ of steam the volume swelling of exposure after 70 hours less than 12%.
These goods can be used for and will be exposed to such as the many application such as sealing, packing ring, pipe, steel wire chuck and roller under high temperature, harsh chemical and the highly compressed environment.Concrete end-use comprises semiconductor manufacturing facility, chemical process, food and pharmaceutical industry, and business machine (being duplicating machine and printer roller).
Embodiment
Test method
Vulcanization characteristics
Vulcanization characteristics is measured under the following conditions with Monsanto MDR 2000 instruments:
Mobile shape of the mouth as one speaks frequency: 1.66Hz
Amplitude: 1.0
Temperature: 190 ℃, except as otherwise noted
Specimen size: the dish of diameter 45mm, thickness 5mm
Test period: 20 minutes
Write down following curing parameter:
M
H: maximum button square, the N.m of unit
M
L: minimum button square, the N.m of unit
t
s1: from M
LUpwards increase the number of minutes of 0.04N.m
t
c90: the number of minutes that reaches maximum button square 90%
Test sample use according to the prescription of enumerating in following examples and fusion the elastomerics preparation of appropriate addn.Batching is carried out on rubber mill or Banbury mixer.The composition that grinds is made sheet, will form test sample in the 10g sample incision dish.
Vulcanization characteristics is by placing test sample the seal test groove of instrument, and keeps malleation and high temperature to measure.A biconical dish is embedded in the test sample, and with the radian swing of assigned frequency by 0.5 °, thereby shear-stress on test sample, applied.The power (button square) at the peak swing place that the rotation plate needs is directly proportional with the stiffness (shearing modulus) of rubber.Write down the function of this button square as the time.Because the stiffness of rubber sample increases between curing time, this test just provides the measurement of curability.When the button square of record when reaching balance or maximum value, or when reaching the scheduled time, off-test.Obtaining the curve required time is the function of test temperature and rubber compound characteristic.
Tensile property
Except as otherwise noted, the stress/strain performance, is measured on 10 hours the test sample of postcure in 305 ℃ of air 190 ℃ of following press vulcanizations 4 minutes then.Physical property measurement obtains according to the method for describing among the ASTM D 412.Write down following parameter:
M
100: the modulus under 100% elongation, units MPa
T
B: fracture tensile strength, units MPa
E
B: extension at break, the % of unit
Shore hardness, Shore A
The compression set of O shape circle test is measured according to ASTM D 395.
25 ℃ and 200% elongation tensile-permanent set (% of unit retraction) down are according to ASTM D 412 mensuration.
Chemical resistant properties (% volume swelling) is measured by ASTM D 471.
Embodiment 1-7 and contrast A-E
The perfluoroelastomers that adopts in embodiment and the contrast contains 68.2mol% tetrafluoroethylene, 31.0mol% perfluor (ethylene methacrylic ether) and 0.80mol% perfluor (8-cyano group-5-methyl-3,6-two oxa-s-1-octene) copolymerization units is according to the general method preparation of describing among the US 5789489.
The miocrystalline fluoropolymer that adopts is the Teflon PFA grade 940,945 or 950 that obtains from DuPont-Mitsui Fluorochemicals Co..
The composition of the present invention (embodiment 1-6) and contrast D and E is by preparing in 40 ℃ of following fusion perfluoroelastomers and miocrystalline fluoropolymer on the open type roller mill.In roller mill, add solidifying agent and other compositions then under the same conditions.Contrast composition (contrast A-C) is by preparing in each composition of 40 ℃ of following fusion on the open type roller mill.Composition and proportioning are shown in table 1.Vulcanization characteristics, chemical resistant properties and tensile property also are shown in table 1 according to above-mentioned test method measuring.
Another kind of composition of the present invention (embodiment 7) is by preparing in 320 ℃ of following melt fusion perfluoroelastomers and miocrystalline fluoropolymer in Laboplasto mill (Toyo-Seiki).Then on two rollers mill in this adulterant, adding solidifying agent and other compositions under 40 ℃.Composition and proportioning are shown in table 1.Vulcanization characteristics and tensile property also are shown in table 1 according to above-mentioned test method measuring.
Table 1
| Prescription (phr) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Contrast A | Contrast B | Contrast C | Contrast D | Contrast E |
| Perfluoroelastomers | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 0 | 100 | 100 |
| PFA940 | 51 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| PFA945 | 0 | 51 | 0 | 100 | 200 | 300 | 51 | 0 | 0 | 100 | 40 | 45 |
| PFA950 | 0 | 0 | 51 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
| Urea | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0 | 0.3 | 0.3 |
| The MT carbon black | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 30 | 0 | 0 | 0 |
| Vulcanization characteristics | ||||||||||||
| M L，N·m | 1.10 | 1.09 | 1.15 | 1.60 | 1.95 | 2.46 | 0.88 | NT | 0.98 | NT | NT | NT |
| M H，N·m | 2.09 | 2.23 | 2.25 | 2.52 | 2.70 | 3.44 | 2.54 | NT | 2.48 | NT | NT | NT |
| Ts1, minute | 0.2 | 0.2 | 0.2 | 0.1 | 0.2 | 0.2 | 0.2 | NT | 0.2 | NT | NT | NT |
| T 90, minute | 4.0 | 5.2 | 4.3 | 5.6 | 2.6 | 3.0 | 1.1 | NT | 5.9 | NT | NT | NT |
| Tensile property | ||||||||||||
| T B，MPa | 16.2 | 18.7 | 18.0 | 22.0 | 27.6 | 26.1 | 17.7 | 10.6 | 17.3 | 41.3 | NT | NT |
| E B，％ | 316 | 318 | 336 | 332 | 327 | 228 | 330 | 358 | 242 | NT | NT | NT |
| M 100，MPa | 5.9 | 6.3 | 5.8 | 8.8 | 11.9 | 15.3 | 6.2 | 1.5 | 7.5 | 17.3 | 5.4 | NT |
| Hardness, Shore A | 76 | 77 | 78 | 89 | 95 | 97 | 78 | 54 | 73 | 97 | NT | NT |
Table 1 (continuing)
| Contrast (phr) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Contrast A | Contrast B | Contrast C | Contrast D | Contrast E |
| Chemical resistant properties | ||||||||||||
| Quadrol, 90 ℃, 70 hours, the % volume swelling | 9.4 | NT | NT | NT | NT | NT | NT | NT | NT | NT | 15.7 | 17.5 |
| Steam, 225 ℃, 70 hours, the % volume swelling | 11.4 | NT | NT | NT | NT | NT | NT | NT | NT | NT | 32.5 | 27.3 |
| Compression set, 204 ℃， 70 hours | ||||||||||||
| 10% compression | 55 | 51 | 56 | 60 | 67 | NT | NT | NT | NT | NT | NT | NT |
| 25% compression | 40 | 38 | 39 | 50 | 62 | NT | NT | 80 | 12 | 100 | NT | NT |
| Tensile-permanent set, 25 ℃， 200% elongation | ||||||||||||
| Retraction, % | NT | 70 | NT | 48 | 33 | 26 | NT | NT | NT | 0 | NT | NT |
NT refers to not test.
Claims (9)
1. the preparation method of vulcanized article, described method comprises:
A, be lower than dry type fusion i under 100 ℃ the temperature) perfluoroelastomers, ii) per 100 weight part perfluoroelastomers 51-300 weight parts contain the miocrystalline multipolymer and the 5-12 weight % perfluor (alkyl vinyl ether) of the copolymerization units of tetrafluoroethylene, described miocrystalline multipolymer has greater than the mean particle size of 100nm and a certain fusing point, iii) solidifying agent forms curable compositions;
B, the described composition of sulfuration form vulcanized article; With
C, under the temperature that is higher than described miocrystalline multipolymer fusing point the described sulfurized goods of after fixing.
2. the process of claim 1 wherein vulcanisation step B) occur under the temperature that is lower than described miocrystalline multipolymer fusing point.
3. the process of claim 1 wherein described dry type fusion steps A) carry out being lower than under 50 ℃ the temperature.
4. the preparation method of vulcanized article, described method comprises:
A, melt fusion i) perfluoroelastomers and ii) per 100 weight part perfluoroelastomers 51-300 weight parts contain the miocrystalline multipolymer and the 5-12 weight % perfluor (alkyl vinyl ether) of the copolymerization units of tetrafluoroethylene, described miocrystalline multipolymer has greater than the mean particle size of 100nm and a certain fusing point, described being blended under the temperature that is higher than described miocrystalline multipolymer fusing point carried out, thereby forms adulterant;
B, in described adulterant, add solidifying agent being lower than under 150 ℃ the temperature; With
C, the described composition of sulfuration form vulcanized article.
5. the method for claim 4, wherein said melt fusion steps A) under 300-350 ℃ of temperature, carry out.
6. the method for claim 4, wherein said solidifying agent adds in the described adulterant under being lower than 100 ℃ of temperature.
7. any one method of claim 1-6, wherein said curable compositions contains the described miocrystalline multipolymer of per 100 weight part perfluoroelastomers 60-200 weight parts.
8. the method for claim 7, wherein said curable compositions contains the described miocrystalline multipolymer of per 100 weight part perfluoroelastomers 75-200 weight parts.
9. any one method of claim 1-8, wherein said perfluoroelastomers contains the copolymerization units of 53.0-79.9 mole % tetrafluoroethylene, 20.0-46.9 mole % perfluor (methylvinylether) and 0.4-1.5 mole % cure site monomer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US57281004P | 2004-05-20 | 2004-05-20 | |
| US60/572,810 | 2004-05-20 | ||
| US11/114,627 | 2005-04-26 |
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| CN101006133A true CN101006133A (en) | 2007-07-25 |
| CN100484996C CN100484996C (en) | 2009-05-06 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103242611A (en) * | 2007-04-16 | 2013-08-14 | 特拉华格林托德有限公司 | Perfluoroelastomer compositions and methods of preparing same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242611A (en) * | 2007-04-16 | 2013-08-14 | 特拉华格林托德有限公司 | Perfluoroelastomer compositions and methods of preparing same |
| CN103242611B (en) * | 2007-04-16 | 2016-08-31 | 特拉华格林托德有限公司 | perfluoroelastomer composition and preparation method thereof |
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| CN100484996C (en) | 2009-05-06 |
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