CN105315552A - TPV (Thermoplastic Vulcanizate) used in automobile antenna material and preparation method of TPV - Google Patents
TPV (Thermoplastic Vulcanizate) used in automobile antenna material and preparation method of TPV Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L23/12—Polypropene
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
TPV (Thermoplastic Vulcanizate) used in an automobile antenna material is prepared by conducting dynamic vulcanization on a vulcanization mixture. The vulcanization mixture at least comprises the following raw materials in parts by weight: 0.1 to 3 parts of grafted thermoplastic polymer, 100 parts of vulcanizable elastomer, 50 to 200 parts of thermoplastic polyolefin, 0.01 to 10 parts of a cross-linking agent, and 10 to 100 parts of filling oil, wherein the grafted thermoplastic polymer is obtained by modifying a diarylethene compound. The invention relates to the field of TPV, in particular to the TPV used in the automobile antenna material and a preparation method of the TPV.
Description
Technical field
The present invention relates to Thermoplastic Vulcanizate (TPV) field, particularly car antenna material TPV and preparation method thereof.
Background technology
TPV (Thermoplastic Vulcanizate) is a kind of green chemical industry novel material, has the elasticity of rubber and the intensity of engineering plastics, and with rubber phase ratio, it has better processing characteristics and longer work-ing life; Compared with engineering plastics, there is feature that intensity is high equally, snappiness and dynamic properties better.Traditional elastomeric material power consumption of polymer processing is high, not recyclable.TPV material does not need mixing and that sulfuration two energy consumptions are high technological process, can the shaping manufacture rubber product of direct heating.TPV material has high-ductility snappiness, can repeat processing, uses and reclaim.
Automotive industry and mechanical industry are the mainstay industries of China's economy, and the application of TPV material in automobile component is very extensive.Be mainly used in collision bumper, scatterer, chassis, gasket, dw, airbag skin layer, antenna material etc.The features such as the material require as car antenna material has resistance to ultraviolet, resistance to deflection, and feel is dry and comfortable, matte surface is fine and smooth.TPV material can be decomposed gradually under ultraviolet long-term irradiation, and method conventional is at present in TPV, add inorganic UV absorption agent or organic uv absorbers.But the effect that the uv-absorbing agent that the mode of this simple blend adds obtains is also bad, be separated owing to also existing, consistency exists very large problem, and uv-absorbing agent can slowly be separated out after the long period from polymkeric substance, causes the unstable of system.
Summary of the invention
In order to solve the problem, the invention provides a kind of car antenna material TPV, described TPV is prepared through Technology of Dynamic Vulcanized by cured blend, and with parts by weight, described cured blend at least comprises:
Modified thermoplastic polymer 0.1-3 part
Vulcanizable elastomer 100 parts
TPO 50-200 part
Linking agent 0.01-10 part
Extending oil 10-100 part;
Described modified thermoplastic polymer is that diaryl ethylene compounds is polymer-modified,
The structural formula of described diaryl ethylene compounds is as follows:
Wherein E
1for oxygen family element, R is bridged group, and described bridged group is monocycle or condensed ring.
Described diaryl ethylene compounds is selected from dithiazole ethylene compound or two furans ethylene compounds.
Described bridged group is selected from the one in the group shown in following formula:
，
Wherein, E
2for S, NH, O and CH
2in one, X is H or F.
Described bridged group is aromatic group.
Described diaryl ethylene compounds is selected from the one in the dithiazole ethylene compound of aryl bridging or two furans ethylene compounds of aryl bridging.
Described vulcanizable elastomer is ethene
polyene copolymer.
Described
containing 3 to 14 carbon atoms.
Described polyenoid is selected from the one in ethylidene norbornene, dicyclopentadiene and Isosorbide-5-Nitrae-hexadiene.
Described thermoplastic polyolefin hydrocarbon monomer is selected from least one in ethene, propylene, 1-butylene, 2-butylene and iso-butylene.
The present invention also provides a kind of car antenna material, and described car antenna material TPV is prepared from through extrusion process.
Be easier to understand the above-mentioned of the application and other features, aspect and advantage with reference to following detailed description.
Embodiment
Unless otherwise defined, all technology used herein and scientific terminology have the identical implication usually understood with one skilled in the art of the present invention.When there is contradiction, be as the criterion with the definition in this specification sheets.
Term as used herein " by ... preparation " and " comprising " synonym.Term used herein " comprises ", " comprising ", " having ", " containing " or its other distortion any, be intended to cover the comprising of non-exclusionism.Such as, comprise the composition of listed elements, step, method, goods or device and need not be only limitted to those key elements, but other key element of clearly not listing or the intrinsic key element of this kind of composition, step, method, goods or device can be comprised.
Conjunction " by ... composition " get rid of any key element, step or the component do not pointed out.If in claim, this phrase will make claim be closed, make it not comprise material except those materials described, but except relative customary impurities.When phrase " by ... composition " to appear in the clause of claim main body instead of immediately preceding after theme time, it is only limited to the key element described in this clause; Other key element is not excluded outside described claim as a whole.
During the Range Representation that equivalent, concentration or other value or parameter limit with scope, preferable range or a series of upper limit preferred value and lower preferable values, this is appreciated that all scopes specifically disclosing and formed by arbitrary pairing of any range limit or preferred value and any range lower limit or preferred value, no matter and whether this scope separately discloses.Such as, when disclosing scope " 1 to 5 ", described scope should be interpreted as comprising scope " 1 to 4 ", " 1 to 3 ", " 1-2 ", " 1-2 and 4-5 ", " 1-3 and 5 " etc.When numerical range is described in this article, unless otherwise indicated, otherwise this scope intention comprises its end value and all integers within the scope of this and mark.
In addition, the indefinite article " one " before key element of the present invention or component and " one " are to quantitative requirement (i.e. occurrence number) unrestriction of key element or component.Therefore " one " or " one " should be read as and comprise one or at least one, and the key element of singulative or component also comprise plural form, unless the obvious purport of described quantity refers to singulative.
" polymkeric substance " means the polymerizable compound prepared by the monomer by being polymerized identical or different type.Generic term " polymkeric substance " comprises term " homopolymer ", " multipolymer ", " terpolymer " and " interpolymer ".
" interpolymer " means the polymkeric substance prepared by polymerization at least two kinds of different monomers.Generic term " interpolymer " comprises term " multipolymer " (it is generally in order to refer to the polymkeric substance prepared by two kinds of different monomers) and term " terpolymer " (it is generally in order to refer to the polymkeric substance prepared by three kinds of different monomers).It also comprises plants monomer and the polymkeric substance that manufactures by being polymerized four or more.
The invention provides a kind of car antenna material TPV, described TPV is prepared through Technology of Dynamic Vulcanized by cured blend, and with parts by weight, described cured blend at least comprises:
Modified thermoplastic polymer 0.1-3 part
Vulcanizable elastomer 100 parts
TPO 50-200 part
Linking agent 0.01-10 part
Extending oil 10-100 part;
Described modified thermoplastic polymer is that diaryl ethylene compounds is polymer-modified,
The structural formula of described diaryl ethylene compounds is as follows:
Wherein E
1for oxygen family element, R is bridged group, and described bridged group is monocycle or condensed ring.
diaryl ethylene compounds
The diaryl ethylene compounds structure used in the present invention is as follows:
Wherein E
1for oxygen family element, R is bridged group, and described bridged group is monocycle or condensed ring.
Diaryl ethylene compounds has two kinds of isomer, is open loop isomer and closed loop isomer respectively.Open loop isomer is lower compared with the energy of closed loop isomer molecule, and usual diaryl ethylene compounds is in low-energy open loop situations.There is ring-closure reaction after absorbing high-octane UV-light in open loop isomer, is converted into closed loop isomer from open loop isomer; Closed loop isomer can absorb the relatively low visible ray of energy, and ring-opening reaction occurs, and be converted into open loop isomer from closed loop isomer, reaction formula is as follows:
Open loop and closed loop reacts reversible reaction each other.Diaryl ethylene compounds can absorb UV-light and obtain the higher closed loop product of energy, joins in macromolecular compound and can improve its ultra-violet resistance energy.There is open loop in closed loop isomer, discharged by energy with the form of fluorescence or phosphorescence after the energy absorbing visible region simultaneously.The conversion of diaryl ethylene compounds between open loop isomer and closed loop isomer enables it use as uv-absorbing agent iterative cycles.
As the preferred technical scheme of one of the present invention, described diaryl ethylene compounds is selected from dithiazole ethylene compound or two furans ethylene compounds.
More preferably, described diaryl ethylene compounds is dithiazole ethylene compound.
Thiophene is for furans, and the radius of its sulphur atom is larger, and the 3p electronics of sulphur atom is easier than the 2p electronics of Sauerstoffatom to polarize, and in addition, the electronegativity of sulphur atom is less than Sauerstoffatom, in furans
understand more localization on oxygen, and in thiophene
tend to delocalization in whole five-ring.In sum, in thiophene
easilier compared with furans to flow in whole aromatic nucleus.The aromaticity of thiophene is better than furans, and also just make dithiazole ethylene compound relative to two furans ethylene compounds, the thermostability of corresponding closed loop isomer is higher.After the thermostability raising of closed loop isomer, the energy barrier that open loop isomer transforms to closed loop isomer can be reduced, also just can increase the absorption region of UV-light, improve uv absorption rate.
As the preferred technical scheme of one of the present invention, described bridged group is selected from the one in the group shown in following formula:
，
Wherein, E
2for S, NH, O and CH
2in one, X is H or F.
As the preferred technical scheme of one of the present invention, described bridged group is aromatic group.
When middle bridged group is the isolated alkene without aromaticity, in sulfidation, the double bond of isolated alkene can be destroyed, and can produce crosslinked with other double bond, will have influence on the assimilation effect of diaryl ethylene compounds to ultraviolet.When middle bridged group is phenolic compound, regular owing to meeting you 4n+2 of shock, double bond now no longer shows the character of isolated double bond, but between singly-bound and double bond, can not react in sulfidation with linking agent.Therefore, when only having middle bridged group to have aromaticity, diaryl ethylene compounds can not be destroyed by holding structure in sulfidation, still has the activity absorbing ultraviolet.
More preferably, described diaryl ethylene compounds is selected from the one in the dithiazole ethylene compound of aryl bridging or two furans ethylene compounds of aryl bridging.
When bridged group in diaryl ethylene compounds is aromatic group, electron delocalization degree also exists close associating with the energy of closed loop isomer.When diaryl ethylene compounds is in open loop situations, aryl is connected by rotatable singly-bound with middle bridged group, and whole molecule does not have aromaticity.After open loop isomer absorption UV-light changes closed loop isomer into, whole molecule forms the rigid plane that has aromaticity, and in closed loop isomer, the size of aromaticity determines its Thermodynamically stable degree.Aromaticity after diaryl ethylene compounds generation closed loop, can reduce the energy of closed loop isomer, improves the transformation efficiency of open loop isomer, ring-closure reaction is more easily occurred, and also just improves the rate of absorbing UV of diaryl ethylene compounds accordingly.
More preferably, described bridged group is selected from the one in the group shown in following formula:
, wherein, E
2for the one in S, NH and O.
When described bridged group is
time, described diaryl ethylene compounds structure is as follows:
Wherein E
1for oxygen family element, be preferably O or S; X is H or F.
When X is H, synthetic method reference Chemistry-AEuropeanJournal, 1999,5,3285-3292.
When X is F, synthetic method reference InorganicChemistry, 2007,46,10470-10472.
Described bridged group is
, E
2for S, NH, O, CH
2time, described diaryl ethylene compounds is that organic solvent and water are as mixed solvent, and reflux obtains in the basic conditions by the chloro thing of aryl boric acid and bridged group using palladium complex as catalyzer.The chloro thing mol ratio of aryl boric acid, alkali, catalyzer and bridged group is (2-2.5): (0.5-2): (0.01-0.03): 1.
Described palladium complex can be zeroth order palladium complex, such as, and tetrakis triphenylphosphine palladium.Also can be non-zero valence palladium complex, such as, palladium, palladium chloride, [1,1 '-bis-(diphenylphosphino) ferrocene] palladium chloride.
Described organic solvent can be the one in ethanol, Isosorbide-5-Nitrae-dioxane, DMF, toluene, tetrahydrofuran (THF).
Described alkali can be the one in hydrated barta, sodium carbonate, salt of wormwood, cesium carbonate, cesium fluoride, potassiumphosphate.
The structural formula of described aryl boric acid is as follows:
Wherein E
1for oxygen family element, be preferably O or S.
The structural formula of the chloro thing of described bridged group is as follows:
, wherein, E
2for S, NH, O and CH
2in one,
The building-up reactions equation of described diaryl ethylene compounds is:
Wherein E
1for oxygen family element, be preferably O or S.
aryl boric acid
The structural formula of described aryl boric acid is as follows:
Wherein E
1for oxygen family element, be preferably O or S.
Described aryl boric acid obtains via following steps synthesis:
Step a: dissolve presoma with enough polar solvents in flask, described polar solvent is preferably chloroform.0
time drip excessive bromine, under ice bath, stir 15h after dropwising.Add aqueous sodium carbonate after completion of the reaction, then add extracted with diethyl ether.Collect diethyl ether solution, recrystallization after suction filtration.
Step b: solvent is aprotic solvent,
condition under drip lithium reagent, then add boric acid ester, under agitation return to room temperature gradually, then be hydrolyzed in acid condition, extract after hydrolysis.Described aprotic solvent is preferably tetrahydrofuran (THF), and described lithium reagent is the one in n-Butyl Lithium or tert-butyl lithium, and described lithium reagent is preferably n-Butyl Lithium.Described boric acid ester can be trimethyl borate, triethyl borate, tripropoxy-boron and tributyl borate.
the chloro thing of bridged group
The chloro thing structural formula of described bridged group is:
R is selected from
in one, wherein E
2for S, NH, O, CH
2.
When R is
time, the chloro thing of described bridged group obtains via following step synthesis:
Step a: take DMF as solvent, at room temperature adds bromo-1, the 1-glycol dimethyl ether of 2-and the backflow of carbonate post-heating of stoichiometry.Cool after completion of the reaction, filter, extract.Described carbonate is preferably the one in salt of wormwood or sodium carbonate, and Heating temperature is greater than 130
, be preferably 135
, return time is greater than 5h, is preferably 7h.
Step b: add chlorobenzene and Vanadium Pentoxide in FLAKES, reflux.Cool after completion of the reaction, filter, extract.Heating temperature is greater than 100
, be preferably 130
, return time is greater than 7h, is preferably 10h, cooling, recrystallization.
When R is selected from
in one, wherein E
2for NH, O, CH
2, the chloro thing of described bridged group can from buying on the market.
R is
time, the chloro thing of described bridged group can be obtained by traditional Chinese medicines group 80045926.
R is
time, described bridged group can be obtained by HEChemical0055121.
R is
time, described bridged group can by finishing medical BD158633 obtains.
R is
time, described bridged group can be obtained by AuroraFineChemicalsA18.378.805.
R is
time, described bridged group can be obtained by AquilaPharmatechLLCAP09790.
modified thermoplastic polymer
Modified thermoplastic polymer described in the present invention is by diaryl ethylene compounds modification, and described modification is first by above-mentioned diaryl ethylene compounds and polymer monomer generation esterification, and then polymerization occurs obtains modified thermoplastic polymer.The condition of described esterification and polymerization is well known to those skilled in the art.The monomer of described polymkeric substance is selected from containing those of carboxyl, such as: vinylformic acid, 2-methacrylic acid, 2-methyl-2-butenoic acid, butenoic acid, toxilic acid, fumaric acid, 10 hendecenoic acid, oleic acid, erucic acid, phenylacrylic acid, 2-phenylacrylic acid, 3-phenylacrylic acid, citraconic acid, methylfumaric acid, 4-hydroxycinnamic acid, 9-eicosenoic acid, 2-furfuracrylic acid, 3, 3-dimethacrylate, 4-pentenoic acid, butyl maleate, to vinyl benzoic acid, 3-(3-pyridine) vinylformic acid, the acid of 3-phenyl but-2-ene, 2-methyl-3-phenylacrylic acid, 3-indole acrylic acid, 3-hexenoic acid, 2, 4-dimethyl styracin, propene dicarboxylic acid, 4-phenyl-3-butenoic acid, 3, 4-dimethoxy-cinnamic acid, 2-tolyl acrylic acid, monomethyl maleate, 2-methyl-2-pentenoic acid, 2-butylene acid, pyridine-4-vinylformic acid, 2 benzyl acrylic acid.
vulcanizable elastomer
The vulcanizable elastomer of any appropriate can form the elastomerics phase of TPV of the present invention.Preferred vulcanizable elastomer has basic stable hydrocarbon main chain, and this main chain makes multipolymer to ozone attack and oxidative degradation relative inertness, but elastomerics can have unsaturated terminal chain for crosslinked at least partly.
As a kind of preferred technical scheme of the present invention, vulcanizable elastomer is ethene
polyenoid terpolymer.Vulcanizable elastomer has ethylene content, the about 10wt% of about 10wt% to about 90wt% to about 80wt%'s
content and about 0.5wt% are to the polyene content of about 20wt%, and all wt is based on the gross weight of polymkeric substance.
Described
containing 3 to 14 carbon atoms.These
example be propylene, iso-butylene, 1-butylene, 1-amylene, 1-octene, 2-ethyl-1-hexene, 1-laurylene etc.
Described polyenoid can be: conjugated diolefine, as isoprene, divinyl, chloroprene etc.; Non-conjugated diene; Triolefin, or the polyenoid of higher number.The example of triolefin is Isosorbide-5-Nitrae, 9-triolefin in the last of the ten Heavenly stems, 5,8-dimethyl-Isosorbide-5-Nitrae, 9-triolefin in the last of the ten Heavenly stems, 4,9-dimethyl-Isosorbide-5-Nitrae, 9-triolefin in the last of the ten Heavenly stems etc.More preferably non-conjugated diene.Non-conjugated diene contains 5 to 25 carbon atoms.Example is: non-conjugated diene, as Isosorbide-5-Nitrae-pentadiene, Isosorbide-5-Nitrae-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadienes, Isosorbide-5-Nitrae-octadiene etc.; Cyclisation diene, as cyclopentadiene, cyclohexadiene, cyclooctadiene, Dicyclopentadiene (DCPD) etc.; Vinyl cycloolefin, as 1-vinyl-1-cyclopentenes, 1-vinyl-1-tetrahydrobenzene etc.; Alkyl two cyclonoadiene, as 3-methyl-two ring (4,2,1) diene in the ninth of the ten Heavenly Stems-3,7-, 3-ethyl two cyclonoadiene etc.; Indenes, as methyltetrahydro indenes etc.; Alkenyl norbornene, as 5-ethylidene-2-norbornene, 5-butylidene-2-norbornylene, 2-methylallyl-5-norbornylene, 2-pseudoallyl-5-norbornylene, 5-(1,5-hexadienyl)-2-norbornylene, 5-(3,7-octadienyl)-2-norbornylene etc.
As the preferred technical scheme of one of the present invention, described in
be selected from least one in propylene and 1-butylene.
As the preferred technical scheme of one of the present invention, described polyenoid is selected from the one in ethylidene norbornene, dicyclopentadiene, Isosorbide-5-Nitrae-hexadiene.
tPO
Any suitable thermoplastic material can be used as the thermoplasticity phase of TPV of the present invention.Thermoplastic material normally can at least at the softening temperature of material or the material of melting temperature molding or shaping and reprocessing.Polyolefine is preferred thermoplastic material.Polyolefine is the fundamental building block of polymer science and engineering, because the thermoplastic material low cost of producing based on petroleum chemistry and high-throughput.
TPO includes but not limited to homopolymer and the multipolymer of following monomer:
as 1-butylene, 1-amylene, 1-hexene, 2-methyl-1-propylene, 3-Methyl-1-pentene, 4-methyl-1-pentene and 5-methyl isophthalic acid-hexene, and ethene, butylene and propylene, but the homopolymer of preferred propylene and multipolymer.
linking agent
Any substantially do not degrade and/or to solidify under the thermoplastic polymer that is used in TPV can the linking agent of curing elastomer, all can be used in the specific embodiment of the present invention.Preferred linking agent is resol.Other solidifying agent comprises, but be not restricted to superoxide, nitrine, aldehyde-amine reaction product, the xanthate of the urea of vinyl silanes graft, replacement, the guanidine of replacement, replacement, the dithiocarbamate of replacement, thiazole, imidazoles, sulfinyl amine, thiuram disulfide, paraquinonedioxime, dibenzo paraquinonedioxime, sulphur.Certainly, more than one combination can also to be selected in above-mentioned solidifying agent.
Suitable superoxide as linking agent comprises, but be not limited to aromatics diacyl peroxide, aliphatics diacyl peroxide, dibasic acid peroxides, ketone peroxide, alkyl peroxyesters, alkyl hydroperoxide (such as diacetyl peroxide, dibenzoyl peroxide, two-2, 4-dichlorobenzoyl peroxide, two-tert-butyl peroxide, dicumyl peroxide, TBPB tertiary butyl perbenzoate, tert-butyl cumyl peroxide, 2, 5-bis(t-butylperoxy)-2, 5-dimethylhexane, 2, 5-bis(t-butylperoxy)-2, 5-dimethylhexyne-3, 4, 4, 4 ', 4 '-four-(t-butylperoxy)-2, 2-dicyclohexyl propane, 1, 4-pair-(tert butylperoxyisopropyl)-benzene, 1, 1-pair-(t-butylperoxy)-3, 3, 5-trimethyl-cyclohexane, lauroyl peroxide, succinic acid peroxide, Cyclohexanone peroxides, t-butyl peracetate ester, butyl hydroperoxide etc.
extending oil
Described extending oil can select aromatics mineral oil, naphthenic mineral oils, paraffin class mineral oil, preferred paraffin class mineral oil.In addition, preferred molecular-weight average is 300 ~ 1500.Add extending oil amount depend on required character, its upper limit depends on the consistency of concrete oil and blend composition, when the extending oil of excessive outflow occurs, namely beyond this restriction.
other
Various additive can be contained within the scope without prejudice to the object of the present invention.Additive comprises antioxidant; Surface tension improvers; Anti blocking agent; Lubricant; Antiseptic-germicide, such as organometallic compound, isothiazolinone, organosulfur and mercaptan; Antioxidant, such as phenoplast, secondary amine, phosphite and thioesters; Static inhibitor, such as quaternary ammonium compound, amine and ethoxylation, propoxylation or glycerol compounds; Filler and toughener, such as carbon black, glass, metal carbonate (such as calcium carbonate), metal sulfate (such as calcium sulfate), talcum, clay or graphite fibre; Hydrolysis stabilizer; Lubricant (such as lipid acid, fatty alcohol, ester, fatty amide, metallic stearate, paraffin and Microcrystalline Wax, siloxanes and ortho-phosphoric acid ester; Acid neutralizing agent or halogen scavenger, such as zinc oxide; Releasing agent, such as particulate or powdery solid, soap, wax, siloxanes, polyoxyethylene glycol and mixed ester, such as trimethylolpropane tris stearate or four stearic acid tetramethylolmethanes; Pigment, dyes and dyestuffs; Softening agent, the ester of such as diprotic acid (or its acid anhydride) and monohydroxy-alcohol, such as phthalic ester, adipic acid ester and benzoic ether; Thermo-stabilizer, the octyl group ester of such as organo-tin mercaptide, Thiovanic acid and carboxylic acid barium or carboxylic acid cadmium.Those skilled in the art can easily according to the amount of involved purposes determination desired additives.
technology of Dynamic Vulcanized
Dynamic vulcanization is technique as described below: the blend of plasticated by this technique when curing rubber plastics, rubber and Cure of Rubber agent.Term " dynamically " refers to that mixture stands shearing force during vulcanisation step, and " static state " sulfuration of its motionless with vulcanisable compound during wherein vulcanisation step (correlation space fixing) is contrary.An advantage of dynamic vulcanization is, when blend contains plastics and the rubber of suitable proportion, can obtain thermoplastic elastomer composition.
TPV general dynamic vulcanization, is prepared by fusion plasticity and curing rubber.Cured blend is prepared, as mixed in the mixing equipment such as Banbury mixer, forcing machine by any method for mixed rubber polymkeric substance suitably.In the step coordinated, fusion tradition ancillary component.This type of ancillary component can comprise carbon black and other filler of one or more types, such as clay, silicon-dioxide etc., tackifier, wax etc., zinc oxide, antioxidant, antiozonant, processing aid and solidification activator.By heating solidification in about 5 minutes to about 60 minutes at about 150 DEG C to about 200 DEG C, to form TPV.
The present invention also provides a kind of car antenna material, is prepared from through extrusion process by aforesaid TPV.
Hereinafter, by embodiment, the present invention is explained in more detail, but should be understood that these embodiments are only illustrative and nonrestrictive.If do not have other to illustrate, raw materials used is all commercially available.
The present invention is described in detail referring to several example.
Component A is diaryl ethylene compounds modified thermoplastic polymer, and B component is vulcanizable elastomer, and component C is TPO.
The structural formula of above-mentioned diaryl ethylene compounds is as follows:
Wherein E
1for oxygen family element, R is bridged group, is selected from the one in monocycle or condensed ring.
A1E
1for O, R are
, modification polymaleic acid
A2E
1for O, R are
, modified polyacrylic acid
A3E
1for S, R are
, modification polymaleic acid
A4E
1for S, R are
, modified polyacrylic acid
A5E
1for S, R are
, modified polyacrylic acid
A6E
1for S, R are
, modified polyacrylic acid
A7E
1for S, R are
, modified polyacrylic acid
A8E
1for O, R are
, modified polyacrylic acid
A9E
1for O, R are
, modified polyacrylic acid
A10E
1for O, R are
, modified polyacrylic acid
A11E
1for S, R are
, modified polyacrylic acid
A12E
1for S, R are
, modified polyacrylic acid
A13E
1for S, R are
, modified polyacrylic acid
B1 Dupont NDR2744
B2 Dupont NDR3722
B3 Japan synthesis commercial firm JSREP87
C Exxon Mobil PP7032KN
Linking agent: reactive octyl phenolic, chemical industry SP-1045 takes in the U.S. ten
Extending oil: Kelamayi company KP6030
Other: tin protochloride;
(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three (2,4-di-t-butyl) phenyl-phosphite composite (mass ratio 1:1); Zinc oxide selects rubber grade zinc oxide, purity 99.7%, comes from Hengshan Mountain, Anqiu chemical company; Zinic stearas selected by lubricant, middle vast and boundless chemical industry YT-500.
By the thermoplastic polymer of the grafting of the vulcanizable elastomer of 100 weight parts, 0.1-3 weight part, the TPO of 50-200 weight part, weigh up and pour agitator into, stir.Add the linking agent of 0.01-10 weight part again, the zinc oxide of 1.5 weight part tin protochlorides, 1 weight part, the stablizer of 0.5 weight part, the Zinic stearas of 2 weight parts, pours agitator into and stirs.Join in the hopper of twin screw extruder by the material mixed, the extending oil of 10-100 weight part joins forcing machine by microprocessor pump drive from the fluxing zone of forcing machine, and through melt blending, extruding pelletization becomes matrix material.Wherein, screw rod each heating region temperature arranges and is respectively: district's temperature: 160 DEG C; 2nd district: 170 DEG C; 3rd district: 180 DEG C; 4th district: 170 DEG C; Head: 180 DEG C; The residence time 2 ~ 3min.Pressure is 14MPa.
Detection method
Weathering resistance is tested by GB/T3511-2008 standard.Artificial weathering exposure test is undertaken by the regulation of GB/T16422.1, GB/T16422.2, GB/T16422.3 or GB/T16422.4.Ranking is in table 1.
The rating of table 1 artificial weathering exposure test and corresponding phenomenon
Embodiment
The above, be only preferred embodiment of the present invention, be not intended to limit protection scope of the present invention.Every equalization done according to content of the present invention changes and modifies, and is all encompassed in the scope of the claims of the present invention.
Claims (10)
1. a car antenna material TPV, is characterized in that, described TPV is prepared through Technology of Dynamic Vulcanized by cured blend, and with parts by weight, described cured blend at least comprises:
Modified thermoplastic polymer 0.1-3 part
Vulcanizable elastomer 100 parts
TPO 50-200 part
Linking agent 0.01-10 part
Extending oil 10-100 part;
Described modified thermoplastic polymer is that diaryl ethylene compounds is polymer-modified,
The structural formula of described diaryl ethylene compounds is as follows:
Wherein E
1for oxygen family element, R is bridged group, and described bridged group is monocycle or condensed ring.
2. car antenna material TPV as claimed in claim 1, it is characterized in that, described diaryl ethylene compounds is selected from dithiazole ethylene compound or two furans ethylene compounds.
3. car antenna material TPV as claimed in claim 1, it is characterized in that, described bridged group is selected from the one in the group shown in following formula:
，
Wherein, E
2for S, NH, O and CH
2in one, X is H or F.
4. car antenna material TPV as claimed in claim 1, it is characterized in that, described bridged group is aromatic group.
5. car antenna material TPV as claimed in claim 1, it is characterized in that, described diaryl ethylene compounds is selected from the one in the dithiazole ethylene compound of aryl bridging or two furans ethylene compounds of aryl bridging.
6. car antenna material TPV as claimed in claim 1, it is characterized in that, described vulcanizable elastomer is ethene
polyene copolymer.
7. car antenna material TPV as claimed in claim 6, is characterized in that, described in
containing 3 to 14 carbon atoms.
8. car antenna material TPV as claimed in claim 6, it is characterized in that, described polyenoid is selected from the one in ethylidene norbornene, dicyclopentadiene and Isosorbide-5-Nitrae-hexadiene.
9. car antenna material TPV as claimed in claim 1, it is characterized in that, the monomer of described TPO is selected from least one in ethene, propylene, 1-butylene, 2-butylene and iso-butylene.
10. a car antenna material, is prepared from through extrusion process by the car antenna material TPV described in any one of claim 1-9 claim.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510751439.2A CN105315552A (en) | 2015-11-06 | 2015-11-06 | TPV (Thermoplastic Vulcanizate) used in automobile antenna material and preparation method of TPV |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510751439.2A CN105315552A (en) | 2015-11-06 | 2015-11-06 | TPV (Thermoplastic Vulcanizate) used in automobile antenna material and preparation method of TPV |
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| CN105315552A true CN105315552A (en) | 2016-02-10 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118757A (en) * | 2017-04-24 | 2017-09-01 | 上海电力学院 | A kind of diarylethene organic photochromic material based on furans and its preparation method and application |
| CN107383569A (en) * | 2017-03-28 | 2017-11-24 | 安徽雄亚塑胶科技有限公司 | A kind of TPV applied to automatic foot-mat |
| CN107383568A (en) * | 2017-03-28 | 2017-11-24 | 安徽雄亚塑胶科技有限公司 | A kind of low smell TPV and its application in triangular groove sealing strip |
| CN107383629A (en) * | 2017-03-28 | 2017-11-24 | 安徽雄亚塑胶科技有限公司 | A kind of low smell TPV and its cut the application of sealing strip in water |
| CN107383628A (en) * | 2017-03-28 | 2017-11-24 | 安徽雄亚塑胶科技有限公司 | A kind of low smell TPV and its application in glass guide groove sealing strip |
| CN107383627A (en) * | 2017-03-28 | 2017-11-24 | 安徽雄亚塑胶科技有限公司 | A kind of TPV applied to air conditioning for automobiles pipe fitting |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107383569A (en) * | 2017-03-28 | 2017-11-24 | 安徽雄亚塑胶科技有限公司 | A kind of TPV applied to automatic foot-mat |
| CN107383568A (en) * | 2017-03-28 | 2017-11-24 | 安徽雄亚塑胶科技有限公司 | A kind of low smell TPV and its application in triangular groove sealing strip |
| CN107383629A (en) * | 2017-03-28 | 2017-11-24 | 安徽雄亚塑胶科技有限公司 | A kind of low smell TPV and its cut the application of sealing strip in water |
| CN107383628A (en) * | 2017-03-28 | 2017-11-24 | 安徽雄亚塑胶科技有限公司 | A kind of low smell TPV and its application in glass guide groove sealing strip |
| CN107383627A (en) * | 2017-03-28 | 2017-11-24 | 安徽雄亚塑胶科技有限公司 | A kind of TPV applied to air conditioning for automobiles pipe fitting |
| CN107118757A (en) * | 2017-04-24 | 2017-09-01 | 上海电力学院 | A kind of diarylethene organic photochromic material based on furans and its preparation method and application |
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Application publication date: 20160210 |