CN105367911A - Auto part rubber coating TPV and preparation method thereof - Google Patents
Auto part rubber coating TPV and preparation method thereof Download PDFInfo
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- CN105367911A CN105367911A CN201510795286.1A CN201510795286A CN105367911A CN 105367911 A CN105367911 A CN 105367911A CN 201510795286 A CN201510795286 A CN 201510795286A CN 105367911 A CN105367911 A CN 105367911A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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Abstract
The present invention discloses an auto part rubber coating TPV, prepared from the following raw materials in parts by weight: 10-50 parts by weight of a thermoplastic polymer; 20-90 parts by weight of a vulcanizable elastomer; 0.1-20 parts by weight of a crosslinker; 1-50 parts by weight of extender oil; and 0.1-10 parts by weight of organic acid grafted nanoporous carbon, wherein the organic acid grafted nano-porous carbon is loaded with inorganic nanoparticles. The TPV has good demoulding properties and molding effect in the secondary molding.
Description
Technical field
The present invention relates to Thermoplastic Vulcanizate (TPV) field, particularly auto parts machinery encapsulate TPV and preparation method thereof.
Background technology
Thermoplastic dynamic perduren (TPV) refers to that rubber and thermoplastics make the vulcanization of rubber in melt blending process, the macromolecular elastomer material that sulfureted rubber forms in continuous thermoplastic phase as dispersed phase distribution.TPV not only has the good machine-shaping feature of thermoplastics, also has the elastic characteristic that vulcanized rubber is excellent.Compared with traditional elastomeric material, TPV has can be repeatedly shaping, the feature that scrap stock and waste can be recycled, in addition, TPV also has good insulativity, shock-resistance, high thermal resistance, weathering resistance, ultra-violet resistance and good processing performance, therefore, TPV is current tempo one of macromolecular material kind faster.
TPV is widely used in automobile component because of its excellent performance, mainly contains auto parts machinery encapsulate material, hush pipe joint material, antenna material, antiskid pedal, gasket, the outer skin of air bag etc.Along with automotive industry development at a high speed, propose sizing fast to auto parts machinery encapsulate material, the requirement of good forming effect, the easily demoulding, to improve production work efficiency.
Summary of the invention
In order to solve the problem, one aspect of the present invention provides a kind of auto parts machinery encapsulate TPV, is prepared from by the raw material comprising following weight part:
Thermoplastic polymer 10-50 weight part;
Vulcanizable elastomer 20-90 weight part;
Linking agent 0.1-20 weight part;
Extending oil 1-50 weight part;
Organic acid engrafted nanometer porous carbon 0.1-10 weight part,
Wherein, load organic/inorganic nano particle in described organic acid engrafted nanometer porous carbon.
As the preferred technical scheme of one of the present invention, the porosity 50%-80% of described nanoporous carbon, specific surface area is 300m
2/ g-1000m
2/ g.
As the preferred technical scheme of one of the present invention, the charge capacity of described inorganic nano-particle is the 10at%-30at% of described nanoporous carbon.
As the preferred technical scheme of one of the present invention, described inorganic nano-particle is one or more in nano-calcium carbonate, nano silicon oxide, nano manganese oxide, oxide nano rare earth.
As the preferred technical scheme of one of the present invention, described organic acid percentage of grafting is the 0.1at%-10at% of nanoporous carbon.
As the preferred technical scheme of one of the present invention, described organic acid is one or more in the aliphatics of mono carboxylic functional group, alicyclic, aromatic carboxylic acid.
As the preferred technical scheme of one of the present invention, described vulcanizable elastomer is ethene/a-olefin/diene hydrocarbon copolymer.
As the preferred technical scheme of one of the present invention, described a-alkene contains 3-16 carbon atom.
As the preferred technical scheme of one of the present invention, described diolefine is one or more in ethylidene norbornene, dicyclopentadiene, Isosorbide-5-Nitrae-hexadiene.
Another aspect provides a kind of auto parts machinery encapsulate material, described auto parts machinery encapsulate TPV is prepared from through extrusion process.
Be easier to understand above-mentioned and other features, aspect and advantage of the present invention 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.
One aspect of the present invention provides a kind of auto parts machinery encapsulate TPV, is prepared from by the raw material comprising following weight part:
Thermoplastic polymer 10-50 weight part;
Vulcanizable elastomer 20-90 weight part;
Linking agent 0.1-20 part;
Extending oil 1-10 weight part;
Organic acid engrafted nanometer porous carbon 0.1-10 weight part,
Wherein, load organic/inorganic nano particle in described organic acid engrafted nanometer porous carbon.
thermoplastic polymer
Thermoplastic polymer of the present invention is polypropylene, polyethylene, polystyrene, ethylene-propylene copolymer, ethene-butene-1 copolymer, ethene-1-pentene copolymer, ethene-4 methyl 1 pentene copolymer, ethene-1-hexene copolymer, ethene-1-heptene copolymer, ethylene-l-octane copolymer, ethene-1-nonene multipolymer, ethene-1-decene multipolymer, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polymethylmethacrylate, polybutylene terephthalate, one or more in nylon and polycarbonate.Preferably, described thermoplastic polymer is one or more in polypropylene, polyethylene, polystyrene, ethylene-propylene copolymer, acrylonitrile-butadiene-styrene copolymer, styrene-acrylonitrile copolymer, polymethylmethacrylate, polybutylene terephthalate, nylon and polycarbonate, and add-on is 10-50 weight part.
The said polyethylene of the present invention comprises: high-pressure process low-density polyethylene, high density polyethylene(HDPE), ethene-alpha-olefin copolymer.As high-pressure process low-density polyethylene, can enumerate density is 910 ~ 930kg/m
3high-pressure process low-density polyethylene.In addition, as high density polyethylene(HDPE), include, for example density is 941 ~ 970kg/m
3high density polyethylene(HDPE).Density is the value recorded according to the method specified in JISK6760-1981.
Polyacrylic fusing point of the present invention is 148 DEG C-170 DEG C, and density is 0.87-0.95g/cm
3.Preferably, described polyacrylic fusing point is 150-165 DEG C, and density is 0.88-0.94g/cm
3.
The example of polypropylene manufacture method is included in and is polymerized separately by propylene under known typical polymerization catalyzer exists or by the method for propylene and ethene or alpha-olefin copolymer.
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 nano oxidized degraded relative inertness, but elastomerics can have unsaturated terminal chain for crosslinked at least partly.
As the preferred technical solution of the present invention, vulcanizable elastomer described in the application is ethene/a-olefin/diene hydrocarbon copolymer, and add-on is 20-90 weight part.
A-alkene described in the application contains 3-16 carbon atom, specifically can list such as propylene, 1-butylene, 3-methyl-1-butene, 3,3-dimethyl-1-butylene, 1-amylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 3-methyl-3-ethyl-1-amylene, 3,4-dimethyl-1-hexene, 1-hexene, 5-methyl isophthalic acid-hexene, 4-methyl isophthalic acid-hexene, 3-methyl isophthalic acid-hexene, 3,3-dimethyl-1-hexene, 3,5,5-trimethylammonium-1-hexene, 1-heptene, 4,4-dimethyl-1-amylene, 2-methyl isophthalic acid-hexene, 2，3，3-trimethyl-1-butene, 2,3-dimethyl-1-butylene, 3-ethyl-1-amylene, 1-octene, 6-methyl isophthalic acid-heptene, 2,4,4-trimethylammonium-1-amylene, 3-Ethyl-2-Methyl-1-amylene, 2,5-dimethyl-1-hexene, 2,4-dimethyl-1-hexene, 2-methyl isophthalic acid-heptene, 4,4-dimethyl-1-hexene, 6-methyl isophthalic acid-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 3-methyl isophthalic acid-heptene, 2,3-dimethyl-1-hexene, 4,5-dimethyl-1-hexene, 1-nonene, 7-methyl isophthalic acid-octene, 2-methyl isophthalic acid-octene, 2,6-dimethyl-1-heptene, 2,4-dimethyl-1-heptene, 3,3-dimethyl-1-heptene, 2,4,4-trimethylammonium-1-hexene, 1-decene, 2-butyl-1-hexene, 2-methyl isophthalic acid-nonene, 3,7-dimethyl-1-octene, 2-methyl-3-ethyl-1-heptene, 3-ethyl-1-octene, 3,3-dimethyl-1-octene, 2-ethyl-1-octene, 2-ethyl-5-methyl isophthalic acid-heptene, 1-hendecene, 2-methyl isophthalic acid-decene, 4-methyl isophthalic acid-decene, 5-methyl isophthalic acid-decene, 2-sec.-propyl-1-octene, 1-laurylene, 2-butyl-1-octene, 2-methyl isophthalic acid-hendecene, 2-ethyl-1-decene, 2,4,4,6,6-pentamethyl--1-heptene, 10-methyl isophthalic acid-hendecene, 4-methyl isophthalic acid-hendecene, 3,4-dimethyl-1-decene, 9-methyl isophthalic acid-hendecene, 2,4-dimethyl-1-decene, 7-methyl isophthalic acid-hendecene, 1-tridecylene, 2-methyl isophthalic acid-laurylene, 1-tetradecylene, 2-butyl-1-decene, 2-ethyl-1-laurylene, 2-hexyl-1-octene, 2-methyl isophthalic acid-tridecylene, 1-ten pentaene, 3,7,11-trimethylammonium-1-laurylene, 2-methyl isophthalic acid-tetradecene, 1-hexadecylene, 14-methyl isophthalic acid-ten pentaene, 2-methyl isophthalic acid-ten pentaene, one or more in 2,4,4,6,6,8,8-, seven methyl isophthalic acids-nonene, preferably, described a-alkene is propylene, 1-butylene, 3-methyl-1-butene, 3,3-dimethyl-1-butylene, 1-amylene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 1-hexene, 5-methyl isophthalic acid-hexene, 1-heptene, 2-methyl isophthalic acid-hexene, 1-octene, 6-methyl isophthalic acid-heptene, 2-methyl isophthalic acid-heptene, 6-methyl isophthalic acid-hexene, 4-methyl isophthalic acid-hexene, 3-methyl isophthalic acid-heptene, 1-nonene, 7-methyl isophthalic acid-octene, 2-methyl isophthalic acid-octene, one or more in 1-decene.
Diolefine described in the application is the material containing two carbon-carbon double bonds in molecule, include, for example out ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, isoprene, 1,5-cyclooctadiene, bicycloheptadiene, 2,5-dimethyl-2,4-hexadiene, tetrahydrochysene Dicyclopentadiene (DCPD), 1, one or more in 3-divinyl, preferably, described diolefine is non-conjugated diene, such as, be one or more in ethylidene norbornene, dicyclopentadiene, Isosorbide-5-Nitrae-hexadiene, more preferably, described diolefine is ethylidene norbornene.
In vulcanizable elastomer described in the application, with parts by weight, the ratio that ethene and a-alkene add is between 1:1-4:1, the add-on of diolefine accounts for the 0.1at%-15at% of vulcanizable elastomer, mooney viscosity is between 40-90, and preferably, the ratio that described ethene and a-alkene add is between 2:1-3:1, the add-on of diolefine accounts for the 0.5at%-10at% of vulcanizable elastomer, and mooney viscosity is between 50-70.In the application, represent elastomeric molecular weight with mooney viscosity, probe temperature is 125 DEG C.
organic acid engrafted nanometer porous carbon
Organic acid Grafted Nano-scale porous carbon described in the application is the organic/inorganic composite material generated by mono carboxylic organic acid and nanoporous carbon generation esterification, wherein, and load organic/inorganic nano particle in described nanoporous carbon.
The porosity of nanoporous carbon of the present invention is at 50%-80%, and specific surface area is at 300m
2/ g-1000m
2/ g, preferably, the porosity of described nanoporous carbon is at 60%-75%, and specific surface area is at 600m
2/ g-800m
2/ g.
Inorganic particulate of the present invention is nano-calcium carbonate, nano silicon, nano titanium oxide, nano-manganese dioxide, nano ferriferrous oxide, nano lanthanum oxide, nano-cerium oxide, nano oxidized praseodymium, Nanometer-sized Neodymium Oxide, nano oxidized promethium, nano oxidized samarium, nano europium oxide, nano oxidized gadolinium, nano oxidized terbium, nano oxidized dysprosium, nano oxidized holmium, nano oxidized erbium, nano oxidized thulium, nano oxidized ytterbium, nano oxidized lutetium, nano scandium oxide, in nano yttrium oxide one or more, preferably, described inorganic particulate is nano lanthanum oxide, nano-cerium oxide, nano oxidized praseodymium, Nanometer-sized Neodymium Oxide, nano oxidized terbium, one or more in nano oxidized dysprosium.
Organic acid Grafted Nano-scale porous carbon of the present invention adopts two step synthesis to obtain, and the first step is adopt coprecipitation method to prepare the porous carbon that described load has nano inoganic particle, and second step is the porous carbon having nano inoganic particle with organic acid grafting load.
The present invention's adopt coprecipitation method to prepare porous carbon that described load has nano inoganic particle.Concrete preparation method is: a certain amount of carbonated rare earth or rare earth oxide are added in appropriate nitric acid, adjusted to ph is 2-3, stir, removal of impurities, add nanoporous carbon, add-on is 0.5-10 times of carbonated rare earth or rare earth oxide weight, stir, slowly add carbon ammonium, consumption is 1.5-1.6 times of carbonated rare earth or rare earth oxide weight, pH value to solution is 6-7,40 DEG C-60 DEG C ageing 2-5 hour, centrifugation, cleaning post-drying, vacuum calcination at 600-800 DEG C again, obtains the porous carbon that described load has nano inoganic particle.
In a preferred embodiment, the charge capacity of described inorganic nano-particle is the 10at%-30at% of described nanoporous carbon, and preferably, the charge capacity of described inorganic nano-particle is the 15at%-20at% of described nanoporous carbon.
Organic acid of the present invention is the aliphatics of mono carboxylic functional group, alicyclic, one or more in aromatic carboxylic acid, specifically can list formic acid, acetic acid, propionic acid, 2 Methylpropionic acid, butyric acid, valeric acid, 3 Methylbutanoic acid, cyclobutyl formate, Cyclopropylacetic acid, chaulmoogric acid, 2 Ethylbutanoic acid, 3 methylvaleric acid, caproic acid, 4-methylvaleric acid, 3,3-dimethyl-1-butyric acid, 2 methyl valeric acid, heptanaphthenic acid, cyclopentaneacetic acid, hexamethylene propionic acid, enanthic acid, 2 methyl caproic acid, 2-Ethyl-2-Methyl butyric acid, 4-methyl acetic acid, 5-methylhexanoic acid, 3-cyclopentanepropanoiacid acid, ring formic acid in heptan, 4-cyclohexanecarboxylic acid, cyclohexyl acetic acid, 2-methyl isophthalic acid-cyclohexane carboxylic, valproic acid, sad, isocaprylic acid, 2-methyl enanthic acid, isocaprylic acid, ring acetic acid in heptan, the acid of 4-cyclohexyl, n-nonanoic acid, 3,5,5 Trimethylhexanoic acid, different n-nonanoic acid, 4-methyloctanoic acid, cyclohexane butyric acid, capric acid, 4-ethyl is sad, neodecanoic acid, di-n-butylacetic acid, 2-propyl-heptanoic acid, hexamethylene valeric acid, undeeanoic acid, 2-methyl capric acid, 6-methyl capric acid, 3-methyl capric acid, 3-butyl enanthic acid, 2,2-dimethyl nonanoic, 2-ethyl nonanoic acid, 4-sec.-propyl is sad, 4-isopropylcyclohexyl-acetic acid, laurostearic acid, 2,2-dimethyl capric acid, 2-ethyl capric acid, 2-pentaacetic acid, 2-propyl group n-nonanoic acid, 2-butyl is sad, 10-methyl undecanoic acid, 11-methyidodecanoic acid, 2-methyidodecanoic acid, tridecylic acid, TETRADECONIC ACID, pentadecanoic acid, palmitic acid, margaric acid, stearic acid, nonadecanoic acid, 20 acid, phenylformic acid, toluylic acid, 2-phenylbutyric acid, 3-phenylpropionic acid, to methylphenyl acetic acid, benzenebutanoic acid, 5-phenylpentanoic acid, 6-toluylic acid, 3-phenylbutyric acid, 3-(4-toluene) propionic acid, 4-p-methylphenyl butyric acid, m-Tolylacetic acid, one or more in ibufenac, preferably, described organic acid is capric acid, undeeanoic acid, laurostearic acid, TETRADECONIC ACID, palmitic acid, stearic acid, one or more in 20 acid.
The preparation method of organic acid engrafted nanometer porous carbon of the present invention is: a certain amount of load had the nanoporous carbon of inorganic particulate to add in the appropriate vitriol oil, 2-4 hour is incubated at 70-80 DEG C, be cooled to 60-70 DEG C, slowly add organic acid, add-on is that load has the 0.1-1 of the nanoporous carbon of inorganic particulate doubly, and the reaction times is 1-3 hour, filter, cleaning, dry, obtain described organic acid engrafted nanometer porous carbon.
In a preferred embodiment, described organic acid percentage of grafting is the 0.1at%-10at% of nanoporous carbon, and preferably, described organic acid percentage of grafting is the 0.5at%-5at% of nanoporous carbon.
Organic acid engrafted nanometer porous carbon of the present invention not only can promote thermoplastic elastomer Quick uniform nucleation, improve its release property, and good consistency can be had with TPV system, toughened and reinforced effect can also be played, because herein is provided beneficial effect of the present invention simultaneously.
linking agent
Solidifying agent of the present invention to be kick off temperature be those of more than 90 DEG C, comprising the organosilicon systems etc. of composite peroxide systems, resol resin system, platinum catalysis.Composite peroxide systems specifically can list as peroxidation butyl alcohol-tert, hydrogen phosphide cumene, dicumyl peroxide, dibenzoyl peroxide, the two lauroyl of peroxidation, peroxidation tert-butyl isobutyrate, di-t-butyl peroxide, urea peroxide, 2, 4-dichlorobenzoperoxide, peroxidized t-butyl perbenzoate, peroxidation tert-pentyl-2-ethylhexanoate, tert-Butyl peroxypivalate, 4, 4-bis-(tert-butyl hydroperoxide) n-butyl pentanoate, methylethyl ketone peroxide, 2, two (tert-butyl peroxide) butane of 2-, peroxidation (2 ethyl hexanoic acid) tert-butyl ester, 1, 1-cyclohexane di-tert-butyl peroxide, cyclohexanone peroxide, 3, 5, 5-tri-methyl hexanoic acid ester, peroxidation two (hexadecyl) two carbonic ether, cumyl peroxyneodecanoate, peroxy dicarbonate two (2-phenoxy group second) ester, one or more in benzoyl peroxide, resol resin can list one or more in octyl phenolic, heptyl resol, hexyl resol, amyl phenolic resin, butylphenol urea formaldehyde, propyl phenoxy urea formaldehyde, ethyl phenol urea formaldehyde, sylvan urea formaldehyde, phenol formaldehyde (PF) resol, the polymerization degree of described phenolic resin crosslinking agent is 1-20, preferably, described linking agent is phenolic resin crosslinking agent, more preferably, described linking agent is octyl phenolic linking agent, number of repeat unit is 1-5, and add-on is 0.1-20 weight part.
crosslinking accelerator
Crosslinking accelerator of the present invention is use the material that can improve rate of crosslinking and crosslinking degree with described crosslinker compounding.The crosslinking accelerator of composite superoxide is multi-functional active substance, such as, can be esters of acrylic acid, methyl acrylic ester, bismaleimide amine, cyanuric acid tripropylene, cyanacrylate, triallyl phosphoric acid ester, Vinylstyrene; Be tin protobromide, iron bromide, zinc bromide etc. with the crosslinking accelerator of resol.The add-on of described crosslinking accelerator is 0.01-1 weight part.
extending oil
Described extending oil can select aromatics mineral oil, naphthenic mineral oils, paraffin class mineral oil, preferred paraffin class mineral oil, more preferably white oil.In addition, preferred molecular-weight average is 300 ~ 1500.Described extending oil consumption is 1-50 weight part.
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
In Technology of Dynamic Vulcanized, 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.
Present invention also offers a kind of auto parts machinery encapsulate material, be prepared from through extrusion process by aforesaid TPV.
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Be to be understood that; following examples are only for the present invention will be further described; can not limiting the scope of the invention be interpreted as, some nonessential amendment and adjustment that the professional and technical personnel in this field makes according to the content of the invention described above, still belong to protection scope of the present invention.
In addition, if do not have other to illustrate, all raw materials are all commercially available, and described number is weight part.
Raw material:
A1: polypropylene, fusing point is 165 DEG C.
B1: vulcanizable elastomer, DSM, keltan512, wherein ethylene content is 55%, and propylene content is 42%, and Third monomer kind is ethylidene norbornene
B2: vulcanizable elastomer, DSM, keltan512, wherein ethylene content is 67%, and propylene content is 29%, and Third monomer kind is ethylidene norbornene
B3: vulcanizable elastomer, DSM, keltan512, wherein ethylene content is 67%, and propylene content is very low, and Third monomer kind is ethylidene norbornene
C1: octyl phenolic, number of repeat unit is 3.
D1: white oil
E1: (synthesize by described method, wherein, described inorganic nano-particle is nano lanthanum oxide to organic acid engrafted nanometer porous carbon, content is the 10at% of described nanoporous carbon, the porosity of nanoporous carbon is 70%, and organic acid is stearic acid, and percentage of grafting is the 3at% of nanoporous carbon)
E2: (synthesize by described method, wherein, described inorganic nano-particle is nano lanthanum oxide to organic acid engrafted nanometer porous carbon, content is the 17at% of described nanoporous carbon, the porosity of nanoporous carbon is 70%, and organic acid is stearic acid, and percentage of grafting is the 3at% of nanoporous carbon)
E3: (synthesize by described method, wherein, described inorganic nano-particle is nano lanthanum oxide to organic acid engrafted nanometer porous carbon, content is the 30at% of described nanoporous carbon, the porosity of nanoporous carbon is 70%, and organic acid is stearic acid, and percentage of grafting is the 3at% of nanoporous carbon)
E4: (synthesize by described method, wherein, described inorganic nano-particle is nano lanthanum oxide to organic acid engrafted nanometer porous carbon, content is the 17at% of described nanoporous carbon, the porosity of nanoporous carbon is 50%, and organic acid is stearic acid, and percentage of grafting is the 3at% of nanoporous carbon)
E5: (synthesize by described method, wherein, described inorganic nano-particle is nano lanthanum oxide to organic acid engrafted nanometer porous carbon, content is the 17at% of described nanoporous carbon, the porosity of nanoporous carbon is 80%, and organic acid is stearic acid, and percentage of grafting is the 3at% of nanoporous carbon)
E6: (synthesize by described method, wherein, described inorganic nano-particle is nano lanthanum oxide to organic acid engrafted nanometer porous carbon, content is the 17at% of described nanoporous carbon, the porosity of nanoporous carbon is 70%, and organic acid is stearic acid, and percentage of grafting is the 0.1at% of nanoporous carbon)
E7: (synthesize by described method, wherein, described inorganic nano-particle is nano lanthanum oxide to organic acid engrafted nanometer porous carbon, content is the 17at% of described nanoporous carbon, the porosity of nanoporous carbon is 70%, and organic acid is stearic acid, and percentage of grafting is the 10at% of nanoporous carbon)
E8: (synthesize by described method, wherein, described inorganic nano-particle is nano lanthanum oxide to organic acid engrafted nanometer porous carbon, content is the 17at% of described nanoporous carbon, the porosity of nanoporous carbon is 70%, and organic acid is stearic acid, and percentage of grafting is the 0.5at% of nanoporous carbon)
E9: (synthesize by described method, wherein, described inorganic nano-particle is nano lanthanum oxide to organic acid engrafted nanometer porous carbon, content is the 17at% of described nanoporous carbon, the porosity of nanoporous carbon is 70%, and organic acid is stearic acid, and percentage of grafting is the 5at% of nanoporous carbon)
E10: (synthesize by described method, wherein, described inorganic nano-particle is nano-calcium carbonate to organic acid engrafted nanometer porous carbon, content is the 17at% of described nanoporous carbon, the porosity of nanoporous carbon is 70%, and organic acid is stearic acid, and percentage of grafting is the 3at% of nanoporous carbon)
E11: (synthesize by described method, wherein, described inorganic nano-particle is nano lanthanum oxide to organic acid engrafted nanometer porous carbon, content is the 10at% of described nanoporous carbon, the porosity of nanoporous carbon is 70%, and organic acid is stearic acid, and percentage of grafting is the 0at% of nanoporous carbon)
E12: (synthesize by described method, wherein, described inorganic nano-particle is nano lanthanum oxide to organic acid engrafted nanometer porous carbon, content is the 0at% of described nanoporous carbon, the porosity of nanoporous carbon is 70%, and organic acid is stearic acid, and percentage of grafting is the 3at% of nanoporous carbon)
F1: tin protobromide
The preparation method of TPV described in embodiment 1-14 and comparative example 1-3 for: the vulcanizable elastomer measured described in each example, thermoplastic polymer are joined agitator, stir.Again the linking agent of metered amount, crosslinking accelerator, organic acid engrafted nanometer porous carbon are joined agitator, stir.Join in the hopper of twin screw extruder by the material mixed, join forcing machine by the extending oil of metered amount by microprocessor pump drive from the fluxing zone of forcing machine, through melt blending, extruding pelletization becomes matrix material.Wherein, screw rod each heating region temperature arranges and is respectively feeding section temperature: 175 DEG C; Back segment: 180 DEG C; Stage casing: 190 DEG C; Leading portion: 195 DEG C; Head: 190 DEG C; The residence time 2 ~ 3min.Pressure is 14MPa.
Performance test:
Demolding performace is tested: the described TPV prepared is adopted injection molding process, observes its molding effect.Result evaluation:
◎: stripping result is very good, and module departs from automatically from mould
Zero: stripping result is good, module is easier to depart from from mould,
△: stripping result is general, and module need depart from from mould by external force
×: stripping result is poor, and module can not depart from from mould
Molding effect is tested: observe the module after the demoulding, evaluate its surface forming effect.
Result evaluation:
◎: module surface decorative pattern is very clear
Zero: module surface decorative pattern is clear
△: module surface pattern blurring
×: module surface decorative pattern is very fuzzy
Prepare the raw material of auto parts machinery encapsulate TPV, consumption and test result as shown in table 1.
Table 1 prepares the raw material of auto parts machinery encapsulate TPV, consumption and test result
Above data can be found out, compared with the auto parts machinery encapsulate TPV not using organic acid engrafted nanometer porous carbon, auto parts machinery encapsulate TPV prepared by the application has better stripping result and better molding effect, therefore constitutes beneficial effect of the present invention.
Aforesaid example is only illustrative, for explaining some features of feature of the present disclosure.Appended claim is intended to the scope wide as far as possible that requirement it is contemplated that, and the embodiment presented herein is only the explanation of the embodiment of the selection of combination according to all possible embodiment.Therefore, the purpose of applicant is the selectional restriction that appended claim is not illustrated the example of feature of the present invention.And progress in science and technology is not replaced to be formed due to the inaccurate reason of language performance by the possible equivalent considered at present or son, and these changes also should be interpreted as being covered by appended claim in the conceived case.
Claims (10)
1. an auto parts machinery encapsulate TPV, is prepared from by the raw material comprising following weight part:
Thermoplastic polymer 10-50 weight part;
Vulcanizable elastomer 20-90 weight part;
Linking agent 0.1-20 weight part;
Extending oil 1-50 weight part;
Organic acid engrafted nanometer porous carbon 0.1-10 weight part,
Wherein, load organic/inorganic nano particle in described organic acid engrafted nanometer porous carbon.
2. a kind of auto parts machinery encapsulate TPV according to claim 1, it is characterized in that, the porosity 50%-80% of described nanoporous carbon, specific surface area is 300m
2/ g-1000m
2/ g.
3. a kind of auto parts machinery encapsulate TPV according to claim 1, is characterized in that, the charge capacity of described inorganic nano-particle is the 10at%-30at% of described nanoporous carbon.
4. a kind of auto parts machinery encapsulate TPV according to claim 3, it is characterized in that, described inorganic nano-particle is one or more in nano-calcium carbonate, nano silicon oxide, nano manganese oxide, oxide nano rare earth.
5. a kind of auto parts machinery encapsulate TPV according to claim 1, is characterized in that, described organic acid percentage of grafting is the 0.1at%-10at% of nanoporous carbon.
6. a kind of auto parts machinery encapsulate TPV according to claim 5, is characterized in that, described organic acid is one or more in the aliphatics of mono carboxylic functional group, alicyclic, aromatic carboxylic acid.
7. a kind of auto parts machinery encapsulate TPV according to claim 1, is characterized in that, described vulcanizable elastomer is ethene/a-olefin/diene hydrocarbon copolymer.
8. a kind of auto parts machinery encapsulate TPV according to claim 7, it is characterized in that, described a-alkene contains 3-16 carbon atom.
9. a kind of auto parts machinery encapsulate TPV according to claim 8, is characterized in that, described diolefine is one or more in ethylidene norbornene, dicyclopentadiene, Isosorbide-5-Nitrae-hexadiene.
10. an auto parts machinery encapsulate material, is prepared from through extrusion process by the auto parts machinery encapsulate TPV described in any one of claim 1-9 claim.
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| CN201510795286.1A CN105367911A (en) | 2015-11-18 | 2015-11-18 | Auto part rubber coating TPV and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553868A (en) * | 2018-12-05 | 2019-04-02 | 袁进 | Encapsulated material in the floor a kind of high abrasion TPV and preparation method thereof |
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| CN101027357A (en) * | 2004-07-27 | 2007-08-29 | 陶氏环球技术公司 | Thermoplastic vulcanizates and process to prepare them |
| CN102924828A (en) * | 2012-11-07 | 2013-02-13 | 安徽万朗磁塑集团有限公司 | Thermoplastic vulcanizate (TPV) magnetic door seal and manufacture method thereof |
| CN103044737A (en) * | 2012-12-17 | 2013-04-17 | 广东天安新材料股份有限公司 | TPV material for automobile interior trim and preparation method thereof |
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| CN101027357A (en) * | 2004-07-27 | 2007-08-29 | 陶氏环球技术公司 | Thermoplastic vulcanizates and process to prepare them |
| CN102924828A (en) * | 2012-11-07 | 2013-02-13 | 安徽万朗磁塑集团有限公司 | Thermoplastic vulcanizate (TPV) magnetic door seal and manufacture method thereof |
| CN103044737A (en) * | 2012-12-17 | 2013-04-17 | 广东天安新材料股份有限公司 | TPV material for automobile interior trim and preparation method thereof |
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Application publication date: 20160302 |