CN101065442A - Thermoplastic polymer composition and process for production thereof - Google Patents
Thermoplastic polymer composition and process for production thereof Download PDFInfo
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- CN101065442A CN101065442A CN 200580040561 CN200580040561A CN101065442A CN 101065442 A CN101065442 A CN 101065442A CN 200580040561 CN200580040561 CN 200580040561 CN 200580040561 A CN200580040561 A CN 200580040561A CN 101065442 A CN101065442 A CN 101065442A
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Abstract
The invention provides a melt-moldable thermoplastic polymer composition which is flexible and excellent in heat resistance, chemical resistance and oil resistance; molded articles, laminates, industrial hoses and tubes, and fuel hoses and tubes, which are made by using the composition; and a process for the production of the composition. Specifically, a thermoplastic polymer composition which comprises a fluororesin (A) consisting of a fluorinated ethylene polymer (a) and a crosslinked fluororubber (B) consisting of at least one fluororubber (b) which is at least partially crosslinked at an (A)/(B) weight ratio of 85/15 to 40/60 and which can give molded articles exhibiting fuel transmission coefficients of 40g mm/m<2> day or below and tensile moduli of 400MPa or below.
Description
Technical field
The present invention relates to contain the thermoplastic polymer composition of specific fluoro-resin and specific crosslinked fluororubber.Also relate to the moulding product, laminate, industrial pipe, industrial flexible pipe, fuel tube and the fuel hose that contain this thermoplastic polymer composition in addition.The manufacture method that also relates to thermoplastic polymer composition further.
Background technology
Viton is used for a lot of purposes owing to have characteristics such as excellent thermotolerance, chemical resistant properties, compression set in vehicular field, semiconductor applications, industrial circle etc.
On the other hand, fluoro-resin is excellence aspect characteristics such as sliding, thermotolerance, chemical resistant properties, gasproof marquis property, electrical properties, is used for the field of a wider range such as vehicle, industrial machine, business automation equipment, electric electronic Instrument.
Therefore, give flexibility for the thermotolerance of further improving viton or to fluoro-resin, (for example relevant for the research of the polymer alloy of viton and fluoro-resin, open clear 61-57641 communique with reference to the spy), this polymer alloy is receiving publicity aspect the fuel peripheries such as fuel tube material that are used for the low through performance of requirement fuel and this two specific character of flexibility.
But,, in order to improve the low perviousness of its fuel, need increase the fluoro-resin composition, if the fluoro-resin composition increases the problem that then has the infringement flexibility for the polymer alloy of this viton and fluoro-resin.On the other hand, in order to improve its flexibility, need increase the viton composition, and make rubber more be difficult to be dispersed in the resin as external phase (sea component), consequently, the rubber of disperse phase (island component) forms common external phase, and existence can not obtain the problem of sufficient resin rerum natura.
Therefore, the polymer alloy that contains fluoro-resin and viton that has the low perviousness of fuel and this two specific character of flexibility concurrently is not also arranged now.
Summary of the invention
The object of the present invention is to provide a kind of thermoplastic polymer composition, it has excellent thermotolerance-chemical resistant properties-oil-proofness concurrently, has flexibility, the fuel shielding is higher and can carry out melt molding.The present invention also aims to provide the moulding product, laminate, industrial pipe, industrial flexible pipe, fuel tube and the fuel hose that contain this thermoplastic polymer composition.Further aim of the present invention is to provide the manufacture method of thermoplastic polymer composition.
Promptly, the present invention relates to a kind of thermoplastic polymer composition, this thermoplastic polymer composition contains fluoro-resin (A) and crosslinked fluororubber (B), described fluoro-resin (A) contains vinyl fluoride polymkeric substance (a), and described crosslinked fluororubber (B) is crosslinked the forming of at least a portion by at least a kind of viton (b); The weight ratio of described fluoro-resin (A) and described crosslinked fluororubber (B) is 85/15 to 40/60; The fuel transmission coefficient of the moulding product that obtained by said composition is 40gmm/m
2It following and tensile elasticity rate is below the 400MPa.
Preferred described crosslinked fluororubber (B) carries out the dynamic crosslinking processing to viton (b) and obtains in the presence of fluoro-resin (A), under the melting condition of fluoro-resin (A).
Preferably the 90% sulfuration concluding time T90 of described viton (b) under the dynamic crosslinking temperature is adjusted into 2 minutes～6 minutes.
Preferred described viton (b) is for be selected from by a kind of rubber in vinylidene fluoride/R 1216 class viton, vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene class viton, the group that tetrafluoroethylene/propylene class viton is formed at least.
Preferred describedly contain vinyl fluoride polymkeric substance (a) and/or (a-2) for following (a-1);
Described (a-1) is the multipolymer of tetrafluoroethylene and ethene;
Described (a-2) is the multipolymer of the perfluoro-ethylene unsaturated compound shown in tetrafluoroethylene and the following general formula (1);
CF
2＝CF-R
f 1 (1)
In the general formula (1), R
f 1Expression-CF
3Or-OR
f 2, R
f 2The expression carbonatoms is 1～5 perfluoroalkyl.
Preferred described composition contains polyol as linking agent (C).
Preferred described composition is the structure that fluoro-resin (A) forms external phase and crosslinked fluororubber (B) formation disperse phase.
The average mark shot of preferred described crosslinked fluororubber (B) directly is 0.01 μ m～30 μ m.
In addition, the present invention relates to the manufacture method of thermoplastic polymer composition, described manufacture method contains following operation: in the presence of the fluoro-resin that contains vinyl fluoride polymkeric substance (a) (A), under the melting condition of fluoro-resin (A), make at least a kind of viton (b) carry out dynamic crosslinking, the crosslinked fluororubber (B) that is crosslinked with at least a portion that forms this viton (b); This manufacture method is characterised in that it contains the adjustment operation, in described adjustment operation, the 90% sulfuration concluding time T90 of described viton (b) under the dynamic crosslinking temperature is adjusted into 2 minutes～6 minutes.
Preferably in adjusting operation, contain the further operation of interpolation linking agent (C) and crosslinking accelerator (D) to viton (b) in, and be matched with the linking agent (C) in the viton (b) and the amount of crosslinking accelerator (D) according to following inflation method adjustment;
Described inflation method is:
When linking agent (C) when 90% under 170 ℃ sulfurations concluding time T90 is 2 minutes～6 minutes and crosslinking accelerator (D) are X weight part and Y weight part with respect to the use level of 100 weight part viton (b),
(i) linking agent (C) is adjusted into X weight part and crosslinking accelerator (D) is adjusted into 0.2Y weight part～0.5Y weight part; Perhaps
(ii) linking agent (C) is adjusted into 2X weight part～5X weight part and crosslinking accelerator (D) is adjusted into 0.4Y weight part～2.5Y weight part.
In addition, the present invention relates to the thermoplastic polymer composition that the manufacture method by above-mentioned thermoplastic polymer composition obtains.
The invention further relates to the moulding product that contain above-mentioned thermoplastic polymer composition; Laminate with the layer that contains above-mentioned thermoplastic polymer composition; Laminate with the layer that contains thermoplastic polymer composition and the layer that contains other thermoplastic polymer; Laminate with the layer that contains above-mentioned thermoplastic polymer composition and the layer that contains cross-linked rubber; Contain the industrial pipe of above-mentioned laminate, industrial flexible pipe, fuel tube, fuel hose.
Embodiment
The present invention relates to a kind of thermoplastic polymer composition, this thermoplastic polymer composition contains fluoro-resin (A) and crosslinked fluororubber (B), described fluoro-resin (A) contains vinyl fluoride polymkeric substance (a), and described crosslinked fluororubber (B) is crosslinked the forming of at least a portion by at least a kind of viton (b); The weight ratio of described fluoro-resin (A) and described crosslinked fluororubber (B) is 85/15 to 40/60; The fuel transmission coefficient of the moulding product that obtained by said composition is 40gmm/m
2It following and tensile elasticity rate is below the 400MPa.
As fluoro-resin (A), do not limit especially, can be for containing at least a kind of fluoro-resin that contains vinyl fluoride polymkeric substance (a).Containing vinyl fluoride polymkeric substance (a) preferably has and derives from least a kind and contain the monomeric structural unit of vinyl fluoride.As the above-mentioned vinyl fluoride monomer that contains, for example can enumerate the perfluoroolefines such as perfluoro-ethylene unsaturated compound shown in tetrafluoroethylene, the following general formula (1); Fluoroolefin such as compound shown in chlorotrifluoroethylene, trifluoro-ethylene, hexafluoro-isobutene, vinylidene fluoride, vinyl fluoride, the following general formula (2) etc.,
CF
2＝CF-R
f 1 (1)
In the general formula (1), R
f 1For-CF
3Or-OR
f 2, R
f 2Be that carbonatoms is 1～5 perfluoroalkyl;
CH
2＝CX
1(CF
2)
nX
2 (2)
In the general formula (2), X
1Be hydrogen atom or fluorine atom, X
2Be hydrogen atom, fluorine atom or chlorine atom, n is 1～10 integer.
And, contain vinyl fluoride polymkeric substance (a) can have derive from can with the above-mentioned monomeric structural unit that contains the vinyl fluoride monomer copolymerization, as this monomer, can enumerate the not fluorine-containing ethene monomer except that above-mentioned fluoroolefin, perfluoroolefine.As not fluorine-containing ethene monomer, for example can enumerate ethene, propylene or alkyl vinyl ethers etc.Wherein, alkyl vinyl ether refers to and has the alkyl vinyl ether that carbonatoms is 1～5 alkyl.
Wherein, consider from the thermotolerance-chemical resistant properties-oil-proofness excellence of resulting thermoplastic polymer composition and the forming process easy aspect that becomes, contain vinyl fluoride polymkeric substance (a) and be preferably (a-1), (a-2), (a-3) and (a-4) any one, more preferably contain the vinyl fluoride polymkeric substance shown in (a-1), (a-2);
Described (a-1) is for containing the ethylene-tetrafluoroethylene copolymer (ETFE) of tetrafluoroethylene and ethene;
Described (a-2) is for containing tetrafluoroethylene-perfluor (alkyl vinyl ether) multipolymer (PFA) or the tetrafluoraoethylene-hexafluoropropylene copolymer (FEP) of the perfluoro-ethylene unsaturated compound shown in tetrafluoroethylene and the following general formula (1);
Described (a-3) is for containing the ethylene-tetrafluoroethylene-hexafluoropropylene copolymer (Et-TFE-HFP multipolymer) or the ethylene-tetrafluoroethylene-perfluoroalkyl vinyl ether multipolymer of the perfluoro-ethylene unsaturated compound shown in tetrafluoroethylene, ethene and the following general formula (1);
Described (a-4) is poly(vinylidene fluoride) (PVDF);
Described general formula (1) is:
CF
2＝CF-R
f 1 (1)
In the general formula (1), R
f 1For-CF
3Or-OR
f 2, R
f 2Be that carbonatoms is 1～5 perfluoroalkyl.
The vinyl fluoride polymkeric substance that preferably contains to (a-1), (a-2) describes below.
(a-1)ETFE
The described vinyl fluoride polymkeric substance (a) that contains is when the ETFE, and it also shows mechanics rerum natura and low fuel perviousness except having above-mentioned action effect, is preferred therefore.The mol ratio that contains of tetrafluoroethylene units and ethylene unit is preferably 20: 80 to 90: 10, more preferably 62: 38 to 90: 10, is preferably 63: 37 to 80: 20 especially.It can also contain the 3rd composition, as the 3rd composition, so long as can then its kind not limited with the composition of tetrafluoroethylene and ethylene copolymer.As the 3rd composition, use the monomer shown in the following formula usually;
CH
2＝CX
3R
f 3、CF
2＝CFR
f 3、CF
2＝CFOR
f 3、CH
2＝C(R
f 3)
2
(in the formula, X
3Expression hydrogen atom or fluorine atom, R
f 3Expression contains or does not contain the fluoroalkyl of ehter bond Sauerstoffatom), wherein, more preferably CH
2=CX
3R
f 3Shown fluorine-containing vinyl monomer, preferred especially R
f 3Carbonatoms be 1～8 monomer.
As the object lesson of the fluorine-containing vinyl monomer shown in the following formula, can enumerate 1,1-dihydro perfluor-1-propylene, 1,1-dihydro perfluor-1-butylene, 1,1,5-three hydrogen perfluor-1-amylene, 1,1,7-three hydrogen perfluor-1-heptene, 1,1,2-three hydrogen perfluor-1-hexene, 1,1,2-three hydrogen perfluor-1-octene, 2,2,3,3,4,4,5,5-octafluoro amyl group vinyl ether, perfluor (methylvinylether), perfluor (propyl vinyl ether), R 1216, perfluor-1-butylene, 3,3,3-three fluoro-2-(trifluoromethyl)-1-propylene, 2,3,3,4,4,5,5-seven fluoro-1-amylene (CH
2=CFCF
2CF
2CF
2H).
The content of the 3rd composition is preferably 0.1 mole of %～10 mole % with respect to containing vinyl fluoride polymkeric substance (a), and more preferably 0.1 mole of %～5 mole % is preferably 0.2 mole of %～4 mole % especially.
(a-2) PFA or FEP
Described when containing vinyl fluoride polymkeric substance (a) for PFA or FEP, it has excellent thermotolerance especially in above-mentioned action effect, and except that having above-mentioned action effect, also shows the low fuel perviousness, so is preferred.The described vinyl fluoride polymkeric substance (a) that contains more preferably contains the perfluoro-ethylene unsaturated compound unit shown in 90 moles of %～99 mole % tetrafluoroethylene units and the 1 mole of %～10 mole % general formula (1).In addition, contain containing vinyl fluoride polymkeric substance (a) and also can containing the 3rd composition of the perfluoro-ethylene unsaturated compound shown in tetrafluoroethylene and the general formula (1), as the 3rd composition, so long as can then its kind not limited with the composition of the perfluoro-ethylene unsaturated compound copolymerization shown in tetrafluoroethylene and the general formula (1).
In addition, the fusing point that contains vinyl fluoride polymkeric substance (a) is preferably 150 ℃～310 ℃, and more preferably 150 ℃～290 ℃, more preferably 170 ℃～250 ℃.If the fusing point that contains vinyl fluoride polymkeric substance (a) less than 150 ℃ then the thermotolerance of resulting thermoplastic polymer composition the trend of reduction is arranged, if above 310 ℃, then when under the melting condition of fluoro-resin (A), making rubber (b) carry out dynamic crosslinking in the presence of the fluoro-resin (A), melt temperature need be set at the above temperature of fusing point that contains vinyl fluoride polymkeric substance (a), but viton this moment (b) there is the trend of thermal degradation when.
As employed crosslinked fluororubber (B) among the present invention,, then do not limit especially so long as form by at least a portion of at least a kind of viton (b) is crosslinked.
As viton (b), for example can enumerate FFKM (b1), non-FFKM (b2) etc.
As FFKM (b1), can enumerate tetrafluoroethylene (TFE hereinafter referred to as)/perfluor (alkyl vinyl ether) (PAVE hereinafter referred to as) analog copolymer, TFE/ R 1216 (HFP hereinafter referred to as)/PAVE analog copolymer etc.
As non-FFKM (b2), for example can enumerate, vinylidene fluoride (VdF hereinafter referred to as) base polymer, TFE/ propylene copolymers etc., they can distinguish use separately or arbitrary combination use in the scope of not damaging effect of the present invention.
In addition, the example of enumerating as above-mentioned FFKM or non-FFKM is the structure of its principal monomer, also can use the rubber that above-mentioned principal monomer and crosslinkable monomer or modified monomer etc. is carried out copolymerization and obtain aptly.As crosslinkable monomer or modified monomer, can use the known crosslinkable monomers such as monomer that contain iodine atom, bromine atoms, two keys; Modified monomers such as transfer agent, known ethene unsaturated compound etc.
As above-mentioned VdF base polymer, specifically, can enumerate VdF/HFP analog copolymer, VdF/TFE/HFP analog copolymer, VdF/TFE/ propylene copolymers, VdF/ ethene/HFP analog copolymer, VdF/TFE/PAVE analog copolymer, VdF/PAVE analog copolymer, VdF/ chlorotrifluoroethylene (CTFE hereinafter referred to as) analog copolymer etc.More particularly, described VdF base polymer be preferably the VdF that contains 25 moles of %～85 mole % and 75 moles of %～15 mole % can with at least a kind of other monomeric fluorinated copolymer of VdF copolymerization, more preferably contain the VdF of 50 moles of %～80 mole % and 50 moles of %～20 mole % can with at least a kind of other monomeric fluorinated copolymer of VdF copolymerization.
Wherein, as can with at least a kind of other monomer of VdF copolymerization, for example can enumerate fluorochemical monomers such as TFE, CTFE, trifluoro-ethylene, HFP, trifluoro propene, tetrafluoeopropene, five fluorine propylene, trifluoro butylene, tetrafluoro iso-butylene, PAVE, vinyl fluoride; Ethene, propylene, alkyl vinyl ether etc. are fluorochemical monomer not.They can distinguish use separately or arbitrary combination is used.
In the above-mentioned viton, consider, be preferably and contain the unitary viton of VdF more preferably have the unitary viton of VdF unit and HFP from thermotolerance, compression set, processibility, cost aspect.
In addition, consider from the excellent aspect of compression set, above-mentioned viton is preferably at least a kind of rubber that is selected from the group of being made up of VdF/HFP class viton, VdF/TFE/HFP class viton, TFE/ propylene class viton, more preferably VdF/TFE/HFP class viton.
Employed viton (b) can be by common letex polymerization manufactured among the present invention.Polymerizing conditions such as the temperature during as polymerization, time can suitably determine according to monomeric kind or purpose elastomerics.
Thermoplastic polymer composition of the present invention carries out the dynamic crosslinking processing to rubber (b) and obtains under the melting condition of fluoro-resin (A) in the presence of fluoro-resin (A).Wherein, dynamic crosslinking is handled to refer to and is used Banbury mixer, pressurization kneader, forcing machine etc. that rubber (b) melting mixing is also made its dynamic crosslinking simultaneously.Wherein, consider, preferably use forcing machines such as biaxial extruder from applying the high shear force aspect.Handle by carrying out dynamic crosslinking, can control the phase structure of fluoro-resin (A) and cross-linked rubber (B) and the dispersion of cross-linked rubber (B).
Employed linking agent (C) can suitably be selected according to the kind for the treatment of crosslinked viton (b) or melting mixing condition among the present invention.
When containing crosslinkable groups (sulfide site) in the viton (b), can suitably select employed cross-linking system among the present invention according to the purposes of the kind of sulfide site or resulting moulding product etc.As cross-linking system, can adopt polyol crosslink system, organo-peroxide cross-linking system and polyamines cross-linking system arbitrarily.
Wherein, crosslinked as if being undertaken by the polyol crosslink system, then cross-linking set has carbon-oxygen bond, compression set is less, formability is excellent, sealing characteristics is excellent, owing to have above-mentioned feature, so preferred.
If undertaken crosslinked by the organo-peroxide cross-linking system, then cross-linking set has C-C, thereby compare with the polyamines cross-linking system with the two keys of carbon-nitrogen with the polyol crosslink system that cross-linking set has a carbon-oxygen bond, have the feature of chemical resistant properties and anti-steam excellence.
If undertaken crosslinkedly by polyamines is crosslinked, then cross-linking set has the two keys of carbon-nitrogen, has the feature of dynamic mechanically excellent.But, to carry out comparing when crosslinked with the linking agent that uses polyol crosslink system or organo-peroxide cross-linking system, the compression set rate has the trend of increase.
Therefore, among the present invention, preferably use the linking agent of polyol crosslink system or organo-peroxide cross-linking system, consider from the excellent aspect of stopping property as mentioned above, more preferably use the linking agent of polyol crosslink system.
Linking agent among the present invention can use the linking agent of polyamines system, polyvalent alcohol system, organic peroxide systems.
As the polyamines linking agent, for example can enumerate hexamethylene-diamine carbamate, N, N '-dicinnamylidene-1, polyamine compounds such as 6-hexamethylene-diamine, 4,4 '-two (aminocyclohexyl) methane carbamate.Wherein preferred N, N '-dicinnamylidene-1,6-hexamethylene-diamine.
As the polyol crosslink agent, can use in the past linking agent compound known as viton, for example polyol is considered from the excellent heat resistance aspect, especially preferably uses polyhydroxy aromatic compound.
As above-mentioned polyhydroxy aromatic compound, do not limit especially, for example can enumerate 2,2-two (4-hydroxy phenyl) propane (dihydroxyphenyl propane hereinafter referred to as), 2,2-two (4-hydroxy phenyl) perfluoropropane (bisphenol AF hereinafter referred to as), Resorcinol, 1, the 3-dihydroxy-benzene, 1, the 7-dihydroxy naphthlene, 2, the 7-dihydroxy naphthlene, 1, the 6-dihydroxy naphthlene, 4,4 '-dihydroxybiphenyl, 4,4 '-the dihydroxyl Stilbene, 2, the 6-dihydroxy-anthracene, Resorcinol, pyrocatechol, 2,2-two (4-hydroxy phenyl) butane (bisphenol b hereinafter referred to as), 4,4-two (4-hydroxy phenyl) valeric acid, 2,2-two (4-hydroxy phenyl) tetrafluoro two cyclopropane, 4,4 '-dihydroxy-diphenyl sulfone, 4,4 '-the dihydroxyl diphenylketone, three (4-hydroxy phenyl) methane, 3,3 ', 5,5 '-tetrachlorobisphenol A, 3,3 ', 5,5 '-tetrabromo-bisphenol etc.These polyhydroxy aromatic compounds can be an alkali metal salt, alkaline earth salt etc., but when being to use acid to come the condensation multipolymer, preferably do not use above-mentioned metal-salt.
Linking agent as the organo-peroxide cross-linking system, can be in the presence of heat or redox system, can easily producing the organo-peroxide of peroxy radical, specifically for example can enumerate, 1,1-two (tert-butyl hydroperoxide)-3,5, the 5-trimethyl-cyclohexane, 2,5-dimethylhexane-2,5-peroxidation dihydro, ditertiary butyl peroxide, tert butyl isopropyl benzene peroxide, the diisopropylbenzyl superoxide, α, α-two (tert-butyl hydroperoxide)-to diisopropyl benzene, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide)-3-hexin, benzoyl peroxide, tert-butyl hydroperoxide benzene, the tert-butyl hydroperoxide toxilic acid, tert-butyl hydroperoxide sec.-propyl carbonic ether etc.Wherein, be preferably 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane.
Wherein, less from the compression set of resulting moulding product etc., formability is excellent, the excellent aspect of sealing characteristics is considered, is preferably polyol, consider from the excellent heat resistance aspect, more preferably polyhydroxy aromatic compound, more preferably bisphenol AF.
In addition, in the polyol crosslink system, use crosslinking accelerator (D) usually, this crosslinking accelerator and polyvalent alcohol system linking agent are also used.If use crosslinking accelerator (D), then can promote crosslinking reaction by the formation of the molecule internal double bond in the dehydrogenation fluoric acid reaction that promotes the viton main chain.
Crosslinking accelerator (D) as the polyol crosslink system uses compound usually.Do not limit especially as compound, for example can enumerate, ammonium compounds such as quaternary ammonium salt, season phosphine compound, oxygen compound, sulfonium compound, cyclic amine, 1 functionality amine compound etc. such as phosphonium salt, wherein preferred quaternary ammonium salt, season phosphonium salt.
Do not limit especially as quaternary ammonium salt, for example can enumerate, the 8-methyl isophthalic acid, 8-diazabicyclo [5,4,0]-7-undecylene muriate, the 8-methyl isophthalic acid, 8-diazabicyclo [5,4,0]-7-undecylene iodide, the 8-methyl isophthalic acid, 8-diazabicyclo [5,4,0]-7-undecylene oxyhydroxide, the 8-methyl isophthalic acid, 8-diazabicyclo [5,4,0]-7-undecylene methyl sulfate, the 8-methyl isophthalic acid, 8-diazabicyclo [5,4,0]-7-undecylene bromide, 8-propyl group-1,8-diazabicyclo [5,4,0]-7-undecylene bromide, 8-dodecyl-1,8-diazabicyclo [5,4,0]-7-undecylene muriate, 8-dodecyl-1,8-diazabicyclo [5,4,0]-7-undecylene oxyhydroxide, 8-eicosyl-1,8-diazabicyclo [5,4,0]-7-undecylene muriate, 8-tetracosyl-1,8-diazabicyclo [5,4,0]-7-undecylene muriate, 8-benzyl-1,8-diazabicyclo [5,4,0]-7-undecylene muriate (DBU-B hereinafter referred to as), 8-benzyl-1,8-diazabicyclo [5,4,0]-7-undecylene oxyhydroxide, 8-styroyl-1,8-diazabicyclo [5,4,0]-7-undecylene muriate, 8-(3-phenyl propyl)-1,8-diazabicyclo [5,4,0]-7-undecylene muriate etc.Wherein, consider, be preferably DBU-B from the rerum natura aspect of bridging property, cross-linking agent.
In addition, as the season phosphonium salt, do not limit especially, for example can enumerate, tetrabutylphosphonium chloride, benzyl triphenyl phosphonium chloride phosphine (BTPPC hereinafter referred to as), benzyl trimethyl phosphonium chloride, benzyl tributyl phosphonium chloride, tributyl allyl group chlorination phosphine, tributyl-2-methoxy-propyl phosphonium chloride, benzyl phenyl (dimethylamino) phosphonium chloride etc., wherein, consider, be preferably benzyl triphenyl phosphonium chloride phosphine (BTPPC) from the rerum natura aspect of bridging property, cross-linking agent.
In addition, as crosslinking accelerator (D), also can use quaternary ammonium salt, season phosphonium salt and the sosoloid of bisphenol AF; Disclosed no chlorine crosslinking accelerator in the Te Kaiping 11-147891 communique.
As organo-peroxide crosslinking accelerator (D), for example can enumerate, triallyl cyanurate, triallyl isocyanurate (TAIC), three vinylformic acid methylals (tracryl formal), triallyl trimellitate, N, N '-metaphenylene dimaleimide, the dipropargyl terephthalate, diallyl phthalate, the tetraallyl terephthalamide, the triallyl phosphoric acid ester, bismaleimides, fluoridize cyanacrylate (1,3,5-three (2,3,3-three fluoro-2-propenyl)-1,3,5-triazine-2,4, the 6-triketone), three (diallyl amine)-S-triazines, triallyl phosphite, N, N-diallyl acrylamide, 1,6-divinyl ten difluoro hexanes, six allyl group phosphamides, N, N, N ', N '-tetraallyl phthalic diamide, N, N, N ', N '-tetraallyl Malonamide, the trivinyl isocyanuric acid ester, 2,4,6-trivinyl methyl trisiloxanes, three (5-norbornylene-2-methylene radical) cyanurate, triallyl phosphorous acid ester etc.Wherein, consider, be preferably triallyl isocyanurate (TAIC) from the rerum natura aspect of bridging property, cross-linking agent.
Addition as linking agent (C) and crosslinking accelerator (D), be preferably the 90% sulfuration concluding time T90 that will carry out under the temperature of dynamic crosslinking when handling and be adjusted into 2 minutes～6 minutes amount, more preferably 90% sulfuration concluding time T90 is adjusted into 3 minutes～5 minutes amount.If optimum sulfurating time T90 is less than 2 minutes amount, the trend that is dispersed with heterogeneity and thickization of cross-linked rubber then; If surpass 6 minutes amount, then rubber cross needs the long time and crosslinked incomplete trend is arranged.
Wherein, 90% sulfuration concluding time T90 refers to, when viton (b) is carried out 1 press vulcanization, use JSR type vulkameter (Curelastometer) II type and V-type, try to achieve the vulcanization curve under the dynamic vulcanization temperature, with time of 90% the value that arrives maximum torque be 90% sulfuration concluding time (T90).
As the concrete grammar of the addition of determining linking agent (C) and crosslinking accelerator (D), at first obtain 90% when making 170 ℃ to vulcanize concluding time T90 be 2 minutes～6 minutes, be preferably 3 minutes～the use level X weight part of 5 minutes the linking agent with respect to 100 weight part viton (C), the use level Y weight part of crosslinking accelerator (D).
Then, linking agent of the present invention (C) and crosslinking accelerator (D) are as follows based on the preferred addition of the amount of above-mentioned X and Y:
(i) amount of linking agent (C) is the X weight part, and the amount of crosslinking accelerator (D) is 0.2Y weight part～0.5Y weight part and is preferably 0.3Y weight part～0.4Y; Perhaps
(ii) the amount of linking agent (C) is 2X weight part～5X weight part, and the amount of crosslinking accelerator (D) is 0.4Y weight part～2.5Y weight part.
If crosslinking accelerator (D) is less than the 0.2Y weight part, crosslinked carry out insufficient of viton (b) then, the thermotolerance of resulting thermoplastic polymer composition and oil-proofness have the trend of reduction; If surpass the 2.5Y weight part, then the physical strength of resulting thermoplastic polymer composition has the trend of reduction.
In addition, referring to fluoro-resin (A) and viton (b) under the melting condition takes place under the fused temperature.Fused temperature different and different according to the second-order transition temperature of various fluoro-resin (A) and viton (b) and/or fusing point are taken place, but melt temperature is preferably 120 ℃～330 ℃, more preferably 130 ℃～320 ℃.Be lower than 120 ℃ as if temperature, then the trend that is dispersed with thickization between fluoro-resin (A) and the viton (b); If surpass 330 ℃, then rubber (b) has the trend of thermal degradation when.
Resulting thermoplastic polymer composition can have the structure that fluoro-resin (A) forms external phase and cross-linked rubber (B) formation disperse phase, or have fluoro-resin (A) and cross-linked rubber (B) and form the structure of external phase altogether, wherein preferably have fluoro-resin (A) and form the structure that external phase and cross-linked rubber (B) form disperse phase.
Even viton (b) is disperseing to form at first matrix, be accompanied by the carrying out of crosslinking reaction, viton (b) forms cross-linked rubber (B), and melt viscosity also can increase, thereby makes cross-linked rubber (B) form the common external phase of disperse phase or formation and fluoro-resin (A).
If form this structure, thermoplastic polymer composition then of the present invention shows excellent thermotolerance, chemical resistant properties and oil-proofness, has lower fuel perviousness and excellent forming process simultaneously.At this moment, the average mark shot of crosslinked fluororubber (B) directly is preferably 0.01 μ m～30 μ m.If average mark shot footpath is less than the then mobile trend that reduction is arranged of 0.01 μ m, if surpass 30 μ m then the intensity of resulting thermoplastic polymer composition the trend of reduction is arranged.
In addition, for thermoplastic polymer composition of the present invention, in the part of the structure that fluoro-resin (A) formation external phase and cross-linked rubber (B) as its preferred mode form disperse phase, also can contain the common continuous structure of fluoro-resin (A) and crosslinked fluororubber (B).
The average mark shot footpath of the crosslinked fluororubber in the thermoplastic polymer composition of the present invention (B) can be determined by any one mode among use AFM, SEM, the TEM or their array mode.For example, when using AFM, obtain, can carry out 2 systemizations by this shading value being carried out Hue distinguishes by the resulting difference of surface information of the crosslinked fluororubber (B) of the fluoro-resin (A) of external phase and disperse phase form with the different picture of light and shade.By with the position of 2 systemizations as the central horizontal in the Hue distinguishes, can obtain having the picture of clear and definite contrast gradient, can read the cross-linked rubber particle diameter of disperse phase.In addition, when using SEM, by emphasize contrast gradient or to picture implement the adjustment of shading value or carry out above-mentioned two kinds adjust so that the crosslinked fluororubber of disperse phase (B) in the picture that looks like to obtain by reflection electronic for clearly, thereby can similarly read the cross-linked rubber particle diameter of disperse phase with AFM.For TEM, also with SEM similarly, the contrast gradient by emphasizing resulting picture or picture implemented the adjustment of shading value or carry out above-mentioned two kinds of adjustment then can similarly read the cross-linked rubber particle diameter of disperse phase with AFM or SEM.Wherein, for various thermoplastic polymer compositions, can select the method for easier affirmation.
The weight ratio of fluoro-resin (A) and crosslinked fluororubber (B) is 85/15 to 40/60, is preferably 80/2 to 50/50, more preferably 80/20 to 60/40.If fluoro-resin (A) is less than 40 weight %, the mobile variation of resulting thermoplastic polymer composition then, forming process has the trend of reduction; If surpass 85 weight %, then the balance of the flexibility of resulting thermoplastic polymer composition and fuel perviousness has the trend of variation.
The fuel transmission coefficient that contains the moulding product of thermoplastic compounds of the present invention can be 40gmm/m
2Below it, be preferably 20gmm/m
2Below it, 10gmm/m more preferably
2Below it.Lower value to the fuel transmission coefficient does not limit especially, and is low more preferred more.If the fuel transmission coefficient surpasses 40gmm/m
2My god,,, not preferred economically then in order to suppress the thickness that the fuel transit dose must thicken the moulding product because anti-fuel perviousness is lower.And the fuel transmission coefficient is low more to prevent that then the ability that fuel sees through is high more, on the contrary if the fuel transmission coefficient more then fuel easily see through thereby moulding product such as the pipe that is not suitable for acting as a fuel.
It is that the method for benchmark is implemented that the mensuration of fuel transmission coefficient adopts with the agar diffusion method in the Water Vapour Permeability test method of damp proof wrapping material (Cup method).Wherein, agar diffusion method refers to the Water Vapour Permeability test method of regulation among the JIS Z 0208, is the method for measuring the steam vapour amount of the membranaceous material that passes through unit surface in the set time.Among the present invention, measure the fuel transmission coefficient according to this agar diffusion method.As concrete method, (the opening portion area is 1.26 * 10 at the volumetrical SUS container made with 20mL
-3m
2) the middle CE10 (toluene/octane-iso/ethanol=45/45/10 capacity %) that adds 18mL as analog fuel, the sheet test film is installed on container opening portion and sealing, make the test body thus.Should test body and put into thermostat (60 ℃), the weight of determination test body, the weight of unit time reduce when constant tries to achieve the fuel perviousness by following mathematical expression.
The tensile elasticity rate that contains the moulding product of thermoplastic compounds of the present invention is below the 400MPa, is preferably below the 350MPa, more preferably below the 300MPa, more preferably below the 250MPa.Lower value to tensile elasticity rate does not limit especially, is preferably more than the 5MPa, more preferably more than the 10MPa.If tensile elasticity rate surpasses 400MPa, then may be unsuitable for needing the moulding product of flexibility.
In addition, in the scope that does not influence effect of the present invention, can in thermoplastic polymer composition of the present invention, add other polymkeric substance such as polyethylene, polypropylene, polymeric amide, polyester, urethane; Inorganic filling materials such as lime carbonate, talcum, cerite, clay, titanium oxide, carbon black, barium sulfate; Pigment, fire retardant, lubricant, photostabilizer, weather-proof stablizer, static inhibitor, UV light absorber, antioxidant, releasing agent, whipping agent, spices, oil, tenderizer etc.
In addition, the present invention relates to the manufacture method of thermoplastic polymer composition, described manufacture method contains following operation: in the presence of the fluoro-resin that contains vinyl fluoride polymkeric substance (a) (A), under the melting condition of fluoro-resin (A), make at least a kind of viton (b) carry out dynamic crosslinking, the crosslinked fluororubber (B) that is crosslinked with at least a portion that forms this viton (b); This manufacture method is characterised in that it contains the adjustment operation, in described adjustment operation, described viton (b) is being adjusted into 2 minutes dynamically to carry out 90% sulfuration concluding time T90 under the temperature (dynamic crosslinking temperature) when crosslinked～6 minutes.
Preferably in adjusting operation, contain the operation of further in viton (b), adding linking agent (C) and crosslinking accelerator (D).
For fluoro-resin (A), linking agent (C) and crosslinking accelerator (D), if then can preferably use any one as mentioned above.In addition, for dynamic crosslinking condition, ratio of mixture, addition etc., can adopt above-mentioned condition suitably.
In addition, adjust operation also as mentioned above.
Thermoplastic polymer composition of the present invention can use general shaping operation method or shaping and processing device etc. to carry out forming process.As method for processing forming, for example, can adopt arbitrary method such as injection molding, extrusion moulding, compressed moulding, blow molding, calendering formation, vacuum forming, thermoplastic polymer composition of the present invention is shaped to the formed body of arbitrary shape according to application target.
Further relate to the moulding product that use thermoplastic polymer composition of the present invention and obtain among the present invention, as these moulding product, comprise the formed body of sheet or film, and comprise the laminated structure body that has the layer that contains thermoplastic polymer composition of the present invention and contain the layer of other material.
One deck at least contain the layer of thermoplastic polymer composition of the present invention and at least one deck contain in the laminated structure body of layer of other material, above-mentioned other material can be according to desired characteristic, the suitable materials of selection such as purposes be scheduled to.As other material, for example can enumerate polyolefine (for example: high density polyethylene(HDPE), medium-density polyethylene, new LDPE (film grade), straight chain shape new LDPE (film grade), ethylene-propylene copolymer, polypropylene etc.), nylon, polyester, vinyl chloride resin (PVC), vinylidene resin thermoplastic polymers such as (PVDC); Cross-linked rubbers such as ethylene-propylene-dience rubber, isoprene-isobutylene rubber, nitrile rubber, silicone rubber, acrylic rubber; Metal; Glass; Timber; Pottery etc.
In having the moulding product of this laminated structure, can and contain between the substrate layer of other material at the layer that contains thermoplastic polymer composition of the present invention and insert binder layer.Engage the formation one securely by inserting this binder layer, can make layer that contains thermoplastic polymer composition of the present invention and the substrate layer that contains other material.As employed tackiness agent in the binder layer, can use the anhydride modified thing of alkadiene polymkeric substance; Polyolefinic anhydride modified thing; Macromolecule polyol is (for example, with diprotic acid polycondensations such as diatomic alcohol compounds such as ethylene glycol, propylene glycol and hexanodioic acids and the polyester polyol that obtains; The partly-hydrolysed thing of the multipolymer of vinyl-acetic ester and vinylchlorid etc.) with polyisocyanate compound (for example, 1, diatomic alcohol compounds and 2 such as 6-hexamethylene glycol, the mol ratio of diisocyanate cpds such as 4-tolylene vulcabond are 1 to 2 reaction product; Trivalent alcohol compounds and 2 such as TriMethylolPropane(TMP), the mol ratio of diisocyanate cpds such as 4-tolylene vulcabond are 1 to 3 reaction product etc.) mixture etc.And, in order to form laminated structure, can use coextrusion, altogether injection, known method such as extrusion coated.
Thermoplastic polymer composition of the present invention can be used for for example semi-conductor association areas such as semiconductor-fabricating device, liquid crystal panel manufacturing installation, plasma panel manufacturing installation, PALC panel, field emission display panel, solar cell substrate suitably with the moulding product that contain said composition; Vehicular field; Field of aircraft; The rocket field; Ship domain; Field of chemicals such as chemical industry equipment; Medicine fields such as pharmaceuticals; Visualizers etc. are taken the photograph the phase field; Print fields such as printing instrument; Field of coating such as coating equipment; Analysis-physics and chemistry is learned instrument field; The food apparatus instrument field; The atomic power device instrument field; Iron and steel domains such as iron plate processing units; The general industry field; Electric field; In the fields such as fuel cell field, wherein more preferably be used for vehicular field.
In vehicular field, pad, axle envelope, valve rod sealing member, sealing material and flexible pipe can be used for engine and peripheral device, flexible pipe and sealing material can be used for the AT device, and circle (side) shape ring, pipe, filler, spool material, flexible pipe, sealing material and barrier film can be used for fuel system and peripheral device.Specifically, can be used as the motor head pad, metallic gasket, the food tray pad, the crank axle sealing member, the camshaft sealing, valve rod sealing member, manifold seal, shore installation hose, the oxygen sensor sealing member, the ATF flexible pipe, the injector circular rings, injector seal, the petrolift circular rings, barrier film, fuel hose, the crank axle sealing member, the wheel casing sealing member, the power piston sealing member, the sealing member of steam jacket, the sealing member of valve rod, the preceding pump seal of automatic transmission, rear axle pinion(gear) sealing member, the pad of universal joint, the pinion(gear) sealing member of velometer, the piston cup of foot brake, the circular rings of transmission of torque, oil seal, the sealing member of exhausting recombustion device, bearing seal, the EGR pipe, the twin carburettor pipe, the transmitter barrier film of vaporizer, vibration-proof rubber (engine mount, exhaust portion etc.), reignition device flexible pipe, oxygen sensor lining etc.
Moulding product of the present invention can be used for above-mentioned various uses suitably, are suitable as industrial flexible pipe, industrial pipe, fuel with flexible pipe, fuel tube particularly.
Embodiment
The present invention will be described then to enumerate embodiment below, but the present invention is not limited in following embodiment.
＜vulcanization characteristics 〉
Use JSR type vulkameter (Curelastometer) II type is tried to achieve the vulcanization curve under 170 ℃ and 260 ℃, tries to achieve MV minium viscosity (ML), sulphidity (MH), induction time (T10) and optimum sulfurating time (T90) by the variation of moment of torsion.Even if under heated condition through not seeing more than 30 minutes that moment of torsion changes yet, think that then vulcanization reaction does not carry out.
The manufacturing of＜sheet test film 〉
To be installed on mould by the thermoplastic polymer composition of embodiment, comparative example manufacturing, utilize the high 60 ℃ temperature (280 ℃) of fusing point (220 ℃) of heat extruder employed fluoro-resin (A) in to keep 15 minutes～30 minutes than composition, make the dynamic vulcanization composition be in molten state, apply the load of 3MPa then, application time is 1 minute, carry out compressed moulding, make the sheet test film of defined thickness.
＜tensile break strength, tension fracture elongation rate and tensile elasticity rate are measured 〉
Making thickness with aforesaid method is the sheet test film of 2mm, uses ASTM V-type dumbbell, is die-cut into distance between bench marks from being the dumbbell shaped test film of 3.18mm.Utilize resulting dumbbell shaped test film, use Autograph (the system AGS-J 5kN of (strain) Shimadzu Seisakusho Ltd.), with ASTM-D638 is benchmark, measures tension fracture elongation rate, tensile break strength and tension fracture spring rate in the time of 25 ℃ under the 50mm/min condition.
＜fuel perviousness 〉
Making thickness with aforesaid method is the sheet test film of 0.5mm.(the opening portion area is 1.26 * 10 having 20mL volumetrical SUS container made
-3m
2) the middle CE10 (toluene/octane-iso/ethanol=45/45/10 capacity %) that adds 18mL as analog fuel, above-mentioned sheet test film is installed on container opening portion and sealing, make the test body thus.Should test body and put into thermostat (60 ℃), the weight of determination test body, the weight of unit time reduce when constant tries to achieve the fuel perviousness by following mathematical expression.
＜flowability 〉
The particle of the thermoplastic polymer composition that use is made by embodiment, comparative example is measured melt flow rate (MFR) (MFR) by melt flow determinator (the smart mechanism of (strain) Japan is done made) under 297 ℃, the condition of 5000g load.
＜compounding process 〉
The mixing use LABOPLASTOMIL of fluoro-resin (A) and viton (B) (the smart mechanism of (strain) Japan is done made) carries out.Adjust the total amount of mixing fluoro-resin (A) and viton (B) so that their cumulative volume is 77 volume % of the kneading part cubic capacity of LABOPLASTOMIL.The temperature of LABOPLASTOMIL is configured to the temperature than the fusing point (220 ℃) high 40 ℃ (260 ℃) of employed fluoro-resin (A) in the composition.Behind the temperature-stable of LABOPLASTOMIL, add fluoro-resin (A), stirred 5 minutes～10 minutes, make fluoro-resin (A) fusion with 10rpm.In the fluoro-resin (A) of molten state, add fluoro-rubber composite (b-1), (b-2), (b-3), (b-4) or (b-5), add the back and be about to stirred for several and increase to 80rpm.(corresponding to the T90 of Curelastometer II type) back continues to stir 10 minutes when torque meter reveals maximum value, obtains the dynamic vulcanization composition of fluoro-resin (A)/viton (B).
In embodiment and the comparative example, use following vinyl fluoride polymkeric substance (a), viton (b), linking agent (C) and the crosslinking accelerator (D) of containing.
＜fluoro-resin (A) 〉
(EP-610 Daikin Industries (strain) system, fusing point is 218 ℃～228 ℃ to tetrafluoroethylene-ethylene copolymer, is MFR=25g/10min during for 5000g of 297 ℃, load～35g/10min) in temperature
＜viton (b) 〉
2 yuan of system rubber that form by vinylidene fluoride (VdF) and R 1216 (HFP) (VdF: HFP=78mol%: 22mol%, the mooney viscosity in the time of 121 ℃=41 are 297 ℃, the load MFR=28g/10min during for 5000g in temperature)
＜viton (b2) 〉
The 3 yuan of system rubber (VdF: TFE: HFP=50mol%: 20mol%: 30mol%, the mooney viscosity in the time of 100 ℃=88) that form by vinylidene fluoride (VdF), tetrafluoroethylene (TFE) and R 1216 (HFP)
＜linking agent (C) 〉
Polyvalent alcohol system linking agent: 2,2-two (4-hydroxy phenyl) perfluoropropane (Daikin Industries (strain) system " bisphenol AF ")
＜crosslinking accelerator (D) 〉
Benzyl triphenyl phosphonium chloride phosphine (BTPPC, industry (strain) system is learned in northern Xinghua)
Reference example 1 (preparation of fluoro-rubber composite (b-1)～(b-3))
In 100 weight part viton (b), add 2.17 weight parts (X) linking agents (C), 0.11 weight part (Y) crosslinking accelerator (D), 3 weight part magnesium oxide (Kyowamag150, consonance chemical industry (strain)), it is mixing to use 8 inches open roll to carry out, and obtains fluoro-rubber composite (b-1).
In 100 weight part viton (b), add 8.68 weight parts (X) linking agents (C), 0.44 weight part (Y) crosslinking accelerator (D), 3 weight part magnesium oxide (Kyowamag150, consonance chemical industry (strain)), it is mixing to use 8 inches open roll to carry out, and obtains fluoro-rubber composite (b-2).
In 100 weight part viton (b), add 2.17 weight parts (X) linking agents (C), 0.43 weight part (Y) crosslinking accelerator (D), 3 weight part magnesium oxide (Kyowamag150, consonance chemical industry (strain)) and 6 weight part calcium hydroxide (CALDIC2000, nearly river chemical industry (strain) system), it is mixing to use 8 inches open roll to carry out, and obtains fluoro-rubber composite (b-3).
Cooperate fluoro-rubber composite (b-1)～(b-3) with the use level shown in the table 1 respectively, carry out mixing.Vulcanization characteristics when 170 ℃ of being measured by Curelastometer II type of these fluoro-rubber composites and 260 ℃ is as shown in table 1.Fluoro-rubber composite (b-1), (b-2) do not carry out vulcanization reaction in the time of 170 ℃, the curing time T90 during with 260 ℃ is adjusted into 4 minutes.In addition, for fluoro-rubber composite (b-3), in 4 minutes, finish at 170 ℃ owing to its vulcanization reaction being adjusted under general vulcanization rate, thereby its curing time T90 in the time of 260 ℃ is 0.4 minute.
Table 1
| Fluoro-rubber composite (b-1) | Fluoro-rubber composite (b-2) | Fluoro-rubber composite (b-3) | |||||
| Use level (weight part) | Viton (b) | 100 | 100 | 100 | |||
| Bisphenol AF | 2.17 | 8.68 | 2.17 | ||||
| BTPPC | 0.11 | 0.44 | 0.43 | ||||
| Magnesium oxide | 3 | 3 | 3 | ||||
| Calcium hydroxide | 0 | 0 | 6 | ||||
| Vulcanization characteristics | Curelastometer II type | ||||||
| Temperature (℃) | 170 | 260 | 170 | 260 | 170 | 260 | |
| ML(N) | - | 0.3 | - | 0.1 | 1.2 | 1.7 | |
| MH(N) | - | 7.8 | - | 6.7 | 28.5 | 29.1 | |
| T10 (minute) | - | 1.7 | - | 2.1 | 2.9 | 0.2 | |
| T90 (minute) | - | 4.0 | - | 4.0 | 3.8 | 0.4 | |
Reference example 2 (preparation of fluoro-rubber composite (b-4)～(b-5))
In 100 weight part viton (b2), add 2.00 weight parts (X) linking agents (C), 1.00 weight parts (Y) crosslinking accelerators (D), 3 weight part magnesium oxide (Kyowamag150, consonance chemical industry (strain)), it is mixing to use 8 inches open roll to carry out, and obtains fluoro-rubber composite (b-4).
In 100 weight part viton (b2), add 2.00 weight parts (X) linking agents (C), 2.00 weight parts (Y) crosslinking accelerators (D), 3 weight part magnesium oxide (Kyowamag150, consonance chemical industry (strain)) and 6 weight part calcium hydroxide (CALDIC2000, nearly river chemical industry (strain) system), it is mixing to use 8 inches open roll to carry out, and obtains fluoro-rubber composite (b-5).
Cooperate fluoro-rubber composite (b-4)～(b-5) with the use level shown in the table 2 respectively, carry out mixing.The vulcanization characteristics when 170 ℃ and 260 ℃ that these fluoro-rubber composites are measured by Curelastometer II type is as shown in table 1.Fluoro-rubber composite (b-4) does not carry out vulcanization reaction in the time of 170 ℃, the curing time T90 during with 260 ℃ is adjusted into 3.6 minutes.In addition, for fluoro-rubber composite (b-5), in 4 minutes, finish at 170 ℃ owing to its vulcanization reaction being adjusted under general vulcanization rate, thereby its curing time T90 in the time of 260 ℃ is 0.5 minute.
Table 2
| Fluoro-rubber composite (b-4) | Fluoro-rubber composite (b-5) | ||||
| Use level (weight part) | Viton (b2) | 100 | 100 | ||
| Bisphenol AF | 2.00 | 2.00 | |||
| BTPPC | 1.00 | 2.00 | |||
| Magnesium oxide | 3 | 3 | |||
| Calcium hydroxide | 0 | 6 | |||
| Vulcanization characteristics | Curelastometer II type | ||||
| Temperature (℃) | 170 | 260 | 170 | 260 | |
| ML(N) | - | 0.1 | 1.2 | 1.1 | |
| MH(N) | - | 4.9 | 22.3 | 24.5 | |
| T10 (minute) | - | 1.6 | 2.5 | 0.4 | |
| T90 (minute) | - | 3.6 | 4.0 | 0.5 | |
＜tensile break strength is measured 〉
Embodiment 1
Use the method for defined, with the ratio of 80/20,70/30,60/40,50/50 (weight ratio) that fluoro-resin (A) and fluoro-rubber composite (b-1) is mixing respectively, obtain the dynamic vulcanization composition.Make the sheet test film of resulting dynamic vulcanization composition, measure tensile break strength.Measurement result is as shown in table 3.
Embodiment 2
Except using fluoro-rubber composite (b-2) to come the replacement fluorine rubber combination (b-1), use the method identical with embodiment 1, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 3.
Embodiment 3
Except using fluoro-rubber composite (b-4) to come the replacement fluorine rubber combination (b-1), use the method identical with embodiment 1, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 3.
Comparative example 1
Except using fluoro-rubber composite (b-3) to come the replacement fluorine rubber combination (b-1), use the method identical with embodiment 1, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 3.
Comparative example 2
Except using fluoro-rubber composite (b-5) to come the replacement fluorine rubber combination (b-1), use the method identical with embodiment 1, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 3.
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | ||
| Fluoro-resin/viton (weight ratio) | 80/20 | 27 | 32 | 28 | 14 | 15 |
| 70/30 | 22 | 28 | 22 | 13 | 14 | |
| 60/40 | 20 | 26 | 17 | 12 | 11 | |
| 50/50 | 19 | 23 | 13 | 10 | 10 |
(unit: MPa)
Compare with the dynamic vulcanization composition (comparative example 1,2) that uses fluoro-rubber composite (b-3), fluoro-rubber composite (b-5), use the tensile break strength of the dynamic vulcanization composition (embodiment 1,2,3) of fluoro-rubber composite (b-1), fluoro-rubber composite (b-2) and fluoro-rubber composite (b-4) to improve a lot.This has hinted by adjusting vulcanization rate, can be more effectively be scattered in the fluoro-resin viton is little.In addition as can be known, on the basis of the fixed ratio of vulcanizing agent/vulcanization accelerator, carry out increment (embodiment 2), can further improve tensile break strength.
＜tension fracture elongation rate is measured 〉
Embodiment 4
Use the method for defined, with the ratio of 80/20,70/30,60/40,50/50 (weight ratio) that fluoro-resin (A) and fluoro-rubber composite (b-1) is mixing respectively, obtain the dynamic vulcanization composition.Make the sheet test film of resulting dynamic vulcanization composition, measure tension fracture elongation rate.Measurement result is as shown in table 4.
Embodiment 5
Except using fluoro-rubber composite (b-2) to come the replacement fluorine rubber combination (b-1), use the method identical with embodiment 4, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 4.
Embodiment 6
Except using fluoro-rubber composite (b-4) to come the replacement fluorine rubber combination (b-1), use the method identical with embodiment 4, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 4.
Comparative example 3
Except using fluoro-rubber composite (b-3) to come the replacement fluorine rubber combination (b-1), use the method identical with embodiment 4, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 4.
Comparative example 4
Except using fluoro-rubber composite (b-5) to come the replacement fluorine rubber combination (b-1), use the method identical with embodiment 4, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 4.
Table 4
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 3 | Comparative example 4 | ||
| Fluoro-resin/viton (weight ratio) | 80/20 | 450 | 400 | 430 | 300 | 320 |
| 70/30 | 470 | 360 | 420 | 290 | 300 | |
| 60/40 | 420 | 350 | 410 | 280 | 290 | |
| 50/50 | 430 | 330 | 410 | 240 | 260 |
(unit: %)
Compare with the dynamic vulcanization composition (comparative example 3,4) that uses fluoro-rubber composite (b-3), fluoro-rubber composite (b-5), use the bigger value of tension fracture elongation rate performance of the dynamic vulcanization composition (embodiment 4,5,6) of fluoro-rubber composite (b-1), fluoro-rubber composite (b-2) and fluoro-rubber composite (b-4).This has hinted by adjusting vulcanization rate, can be more effectively be scattered in the fluoro-resin viton is little.
<MFR>
Embodiment 7
Use the method for defined, with the ratio of 80/20,70/30,60/40 (weight ratio) that fluoro-resin (A) and fluoro-rubber composite (b-2) is mixing respectively, obtain the dynamic vulcanization composition.Measure the MFR of resulting dynamic vulcanization composition.Measurement result is as shown in table 5.
Embodiment 8
Except using fluoro-rubber composite (b-1) to come the replacement fluorine rubber combination (b-2), use the method identical with embodiment 7, manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 5.
Embodiment 9
Except using fluoro-rubber composite (b-4) to come the replacement fluorine rubber combination (b-2), use the method identical with embodiment 7, manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 5.
Comparative example 5
Except using fluoro-rubber composite (b-3) to come the replacement fluorine rubber combination (b-2), use the method identical with embodiment 7, manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 5.
Comparative example 6
Except using fluoro-rubber composite (b-5) to come the replacement fluorine rubber combination (b-2), use the method identical with embodiment 7, manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 5.
Table 5
| Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative example 5 | Comparative example 6 | ||
| Fluoro-resin/viton (weight ratio) | 80/20 | 13.4 | 12.4 | 15.0 | 11.9 | 12.0 |
| 70/30 | 7.5 | 1.6 | 9.0 | 1.4 | 7.0 | |
| 60/40 | 2.8 | 0.8 | 5.6 | 0.6 | 3.5 |
(unit: g/10 minute)
As can be known, compare with the dynamic vulcanization composition (comparative example 5,6) that uses fluoro-rubber composite (b-3), (b-5), use the MFR of the dynamic vulcanization composition (embodiment 7,8,9) of the fluoro-rubber composite (b-2) of having adjusted vulcanization rate, (b-1), (b-4) to increase.In addition as can be known, on the basis of the fixed ratio of vulcanizing agent/vulcanization accelerator, carry out increment (embodiment 7), MFR significantly is improved.
＜tensile elasticity rate is measured 〉
Embodiment 10
Use the method for defined, the weight ratio that makes fluoro-resin/viton is 50/50 fluoro-resin (A) and fluoro-rubber composite (b-1), fluoro-resin (A) and fluoro-rubber composite (b-2), fluoro-resin (A) and fluoro-rubber composite (b-3), fluoro-resin (A) and fluoro-rubber composite (b-4) and fluoro-resin (A) and fluoro-rubber composite (b-5) is mixing, obtains the dynamic vulcanization composition.Make the sheet test film of resulting dynamic vulcanization composition, measure the tension fracture spring rate.Measurement result is as shown in table 6.
Embodiment 11
Except the weight ratio that makes fluoro-resin/viton is 60/40, use the method identical with embodiment 10, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 6.
Embodiment 12
Except the weight ratio that makes fluoro-resin/viton is 70/30, use the method identical with embodiment 10, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 6.
Embodiment 13
Except the weight ratio that makes fluoro-resin/viton is 83/17, use the method identical with embodiment 10, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 6.
Comparative example 7
Except the weight ratio that makes fluoro-resin/viton is 87/13, use the method identical with embodiment 10, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 6.
Table 6
| Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Comparative example 7 | ||
| The kind of fluoro-rubber composite | b-1 | 125 | 210 | 270 | 365 | 405 |
| b-2 | 133 | 201 | 278 | 370 | 410 | |
| b-3 | 117 | 200 | 270 | 360 | 405 | |
| b-4 | 103 | 173 | 265 | 365 | 410 | |
| b-5 | 104 | 175 | 272 | 368 | 408 |
(unit: MPa)
As can be known, the tensile elasticity rate of resulting dynamic vulcanization composition determined by the ratio of fluoro-resin/viton, and irrelevant with the vulcanization rate and the sulfuration density of viton.In order to make tensile elasticity rate is below the 400MPa, and the weight ratio that must make fluoro-resin is (viton is more than 15%) below 85%.
＜fuel transmission coefficient is measured 〉
Embodiment 14
Use the method for defined, the weight ratio that makes fluoro-resin/viton is 80/20 fluoro-resin (A) and fluoro-rubber composite (b-1), fluoro-resin (A) and fluoro-rubber composite (b-2), fluoro-resin (A) and fluoro-rubber composite (b-3), fluoro-resin (A) and fluoro-rubber composite (b-4) and fluoro-resin (A) and fluoro-rubber composite (b-5) is mixing, obtains the dynamic vulcanization composition.Method by defined is that thickness is the film of 0.5mm with resulting dynamic vulcanization composition molding.Measure the fuel perviousness of this film.Measurement result is shown in table 7,8.
Embodiment 15
Except the weight ratio that makes fluoro-resin/viton is 70/30, use the method identical with embodiment 14, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is shown in table 7, table 8.
Embodiment 16
Except the weight ratio that makes fluoro-resin/viton is 60/40, use the method identical with embodiment 14, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is shown in table 7, table 8.
Comparative example 8
Except the weight ratio that makes fluoro-resin/viton is 50/50, use the method identical with embodiment 14, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 7.
Embodiment 17
Except the weight ratio that makes fluoro-resin/viton is 42/58, use the method identical with embodiment 14, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is shown in table 7, table 8.
Comparative example 9
Except the weight ratio that makes fluoro-resin/viton is 38/62, use the method identical with embodiment 14, the sheet test film of manufacturing dynamic vulcanization composition is measured.Measurement result is as shown in table 7.
Table 7
| Embodiment 14 | Embodiment 15 | Embodiment 16 | Comparative example 8 | ||
| The kind of fluoro-rubber composite | b-1 | 6.5 | 15.0 | 39.0 | 120 |
| b-2 | 7.0 | 14.1 | 39.5 | 130 | |
| b-3 | 8.0 | 13.5 | 38.5 | 125 |
(unit: gmm/m
2My god)
Table 8
| Embodiment 14 | Embodiment 15 | Embodiment 16 | Comparative example 8 | Embodiment 17 | Comparative example 9 | ||
| The kind of fluoro-rubber composite | b-4 | 6.0 | 8.0 | 13.0 | 23.5 | 38.5 | 41.0 |
| b-5 | 6.0 | 7.5 | 12.5 | 23.5 | 38.0 | 41.5 |
(unit: gmm/m
2My god)
The fuel transmission coefficient of dynamic vulcanization composition is determined by the ratio of fluoro-resin/viton as can be known, and irrelevant with the vulcanization rate and the sulfuration density of viton.In order to make the fuel transmission coefficient is 40gmm/m
2Below it, the weight ratio that must make fluoro-resin is (viton is below 60%) more than 40%.
To utilize scanning electron microscope (NEC (strain) system) to carry out morphological observation by the resulting thermoplastic polymer composition of fluoro-rubber composite (b-1, b-2 and b-4) that vulcanization rate has obtained adjusting, it has the structure that fluoro-resin (A) forms external phase and crosslinked fluororubber (B) formation disperse phase as can be known.The average mark shot of crosslinked fluororubber (B) directly is respectively 0.01 μ m～30 μ m.
To utilize scanning electron microscope (NEC (strain) system) to carry out morphological observation by the resulting thermoplastic polymer composition of the unjustified fluoro-rubber composite of vulcanization rate (b-3 and b-5), it has the structure that fluoro-resin (A) forms external phase and crosslinked fluororubber (B) formation disperse phase or common external phase as can be known.
Utilizability on the industry
Fuel transmission coefficient by the resulting products formed of thermoplastic polymer composition of the present invention is 40gmm/m2It following and tensile elasticity rate is below the 400MPa, thus its to have excellent anti-fuel permeability and flexibility and processing and forming concurrently excellent.
Claims (19)
1. thermoplastic polymer composition, it contains fluoro-resin (A) and crosslinked fluororubber (B), described fluoro-resin (A) contains vinyl fluoride polymkeric substance (a), and described crosslinked fluororubber (B) is crosslinked the forming of at least a portion by at least a kind of viton (b); The weight ratio of described fluoro-resin (A) and described crosslinked fluororubber (B) is 85/15 to 40/60; The fuel transmission coefficient of the moulding product that obtained by said composition is 40gmm/m
2It following and tensile elasticity rate is below the 400MPa.
2. thermoplastic polymer composition as claimed in claim 1, wherein, described crosslinked fluororubber (B) carries out the dynamic crosslinking processing to viton (b) and obtains in the presence of fluoro-resin (A), under the melting condition of fluoro-resin (A).
3. thermoplastic polymer composition as claimed in claim 2 is characterized in that, the 90% sulfuration concluding time T90 of described viton (b) under the dynamic crosslinking temperature is adjusted into 2 minutes～6 minutes.
4. as any described thermoplastic polymer composition of claim 1～3, wherein, described viton (b) is for be selected from by a kind of rubber in vinylidene fluoride/R 1216 class viton, vinylidene fluoride/tetrafluoroethylene/hexafluoropropylene class viton, the group that tetrafluoroethylene/propylene class viton is formed at least.
5. as any described thermoplastic polymer composition of claim 1～4, wherein, describedly contain vinyl fluoride polymkeric substance (a) and/or (a-2) for following (a-1);
Described (a-1) is the multipolymer of tetrafluoroethylene and ethene;
Described (a-2) is the multipolymer of the perfluoro-ethylene unsaturated compound shown in tetrafluoroethylene and the following general formula (1);
CF
2＝CF-R
f 1 (1)
In the general formula (1), R
f 1Expression-CF
3Or-OR
f 2, R
f 2The expression carbonatoms is 1～5 perfluoroalkyl.
6. as any described thermoplastic polymer composition of claim 1～5, wherein, described composition contains polyol as linking agent (C).
7. as any described thermoplastic polymer composition of claim 1～6, wherein, described composition is the structure that fluoro-resin (A) forms external phase and crosslinked fluororubber (B) formation disperse phase.
8. thermoplastic polymer composition as claimed in claim 7, wherein, the average mark shot of described crosslinked fluororubber (B) directly is 0.01 μ m～30 μ m.
9. the manufacture method of a thermoplastic polymer composition, described manufacture method contains following operation: under the melting condition of the fluoro-resin that contains vinyl fluoride polymkeric substance (a) (A), make at least a kind of viton (b) carry out dynamic crosslinking, the crosslinked fluororubber (B) that is crosslinked with at least a portion that forms this viton (b); This manufacture method is characterised in that it contains the adjustment operation, in described adjustment operation, the 90% sulfuration concluding time T90 of described viton (b) under the dynamic crosslinking temperature is adjusted into 2 minutes～6 minutes.
10. the manufacture method of thermoplastic polymer composition as claimed in claim 9, it is characterized in that, in adjusting operation, contain the further operation of interpolation linking agent (C) and crosslinking accelerator (D) to viton (b) in, and be matched with the linking agent (C) in the viton (b) and the amount of crosslinking accelerator (D) according to following inflation method adjustment;
Described inflation method is:
When linking agent (C) when 90% under 170 ℃ sulfurations concluding time T90 is 2 minutes～6 minutes and crosslinking accelerator (D) are X weight part and Y weight part with respect to the use level of 100 weight part viton (b),
(i) linking agent (C) is adjusted into X weight part and crosslinking accelerator (D) is adjusted into 0.2Y weight part～0.5Y weight part; Perhaps
(ii) linking agent (C) is adjusted into 2X weight part～5X weight part and crosslinking accelerator (D) is adjusted into 0.4Y weight part～2.5Y weight part.
11. a thermoplastic polymer composition, it is that manufacture method by claim 9 or 10 described thermoplastic polymer compositions obtains.
12. moulding product, it contains claim 1～8,11 any described thermoplastic polymer compositions.
13. a laminate, it has the layer that contains right requirement 1～8,11 any described thermoplastic polymer compositions.
14. a laminate, it has layer that contains right requirement 1～8,11 any described thermoplastic polymer compositions and the layer that contains other thermoplastic polymer.
15. a laminate, it has layer that contains right requirement 1～8,11 any described thermoplastic polymer compositions and the layer that contains cross-linked rubber.
16. an industrial pipe, it contains any described laminate of claim 13～15.
17. an industrial flexible pipe, it contains any described laminate of claim 13～15.
18. a fuel tube, it contains any described laminate of claim 13～15.
19. a fuel hose, it contains any described laminate of claim 13～15.
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| JP2004342771 | 2004-11-26 | ||
| JP342771/2004 | 2004-11-26 | ||
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102858870A (en) * | 2010-09-29 | 2013-01-02 | 东海橡塑工业株式会社 | Rubber composition for water hose, and water hose obtained using same |
| CN106147091A (en) * | 2015-04-21 | 2016-11-23 | 江苏美亚塑胶科技有限公司 | A kind of preparation method of dynamic vulcanization type thermoplastic fluoroelastomer |
| CN112409731A (en) * | 2020-10-21 | 2021-02-26 | 浙江巨化技术中心有限公司 | Special fluorine-containing resin composition for 3D printing and preparation method thereof |
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- 2005-11-25 CN CN200580040551XA patent/CN101065440B/en active Active
- 2005-11-25 CN CN 200580040561 patent/CN101065442A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102858870A (en) * | 2010-09-29 | 2013-01-02 | 东海橡塑工业株式会社 | Rubber composition for water hose, and water hose obtained using same |
| CN102858870B (en) * | 2010-09-29 | 2014-01-08 | 东海橡塑工业株式会社 | Rubber composition for water hose, and water hose obtained using same |
| CN106147091A (en) * | 2015-04-21 | 2016-11-23 | 江苏美亚塑胶科技有限公司 | A kind of preparation method of dynamic vulcanization type thermoplastic fluoroelastomer |
| CN112409731A (en) * | 2020-10-21 | 2021-02-26 | 浙江巨化技术中心有限公司 | Special fluorine-containing resin composition for 3D printing and preparation method thereof |
| CN112409731B (en) * | 2020-10-21 | 2023-02-24 | 浙江巨化技术中心有限公司 | Fluorine-containing resin composition for 3D printing and preparation method thereof |
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|---|---|
| CN101065440A (en) | 2007-10-31 |
| CN101065440B (en) | 2012-01-18 |
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