CN105566834B - A kind of low volatilization scratch-resistant automobile interior trim ABS composite material of low smell and preparation method - Google Patents
A kind of low volatilization scratch-resistant automobile interior trim ABS composite material of low smell and preparation method Download PDFInfo
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- CN105566834B CN105566834B CN201410627570.3A CN201410627570A CN105566834B CN 105566834 B CN105566834 B CN 105566834B CN 201410627570 A CN201410627570 A CN 201410627570A CN 105566834 B CN105566834 B CN 105566834B
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- 239000002131 composite material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 67
- 239000000126 substance Substances 0.000 claims abstract description 57
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 33
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000005453 pelletization Methods 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 10
- 239000012745 toughening agent Substances 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 239000004794 expanded polystyrene Substances 0.000 claims description 62
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000012153 distilled water Substances 0.000 claims description 35
- 238000001179 sorption measurement Methods 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 31
- 238000002156 mixing Methods 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 16
- 238000007664 blowing Methods 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 15
- 230000008018 melting Effects 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000005187 foaming Methods 0.000 claims description 13
- 239000004793 Polystyrene Substances 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 229920002223 polystyrene Polymers 0.000 claims description 11
- 235000019399 azodicarbonamide Nutrition 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 10
- 230000003179 granulation Effects 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000011787 zinc oxide Substances 0.000 claims description 10
- 229920005682 EO-PO block copolymer Polymers 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 9
- CASPZMCSNJZQMV-UHFFFAOYSA-N ethane;2-methyloxirane Chemical compound CC.CC1CO1 CASPZMCSNJZQMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004088 foaming agent Substances 0.000 claims description 9
- 238000013329 compounding Methods 0.000 claims description 8
- 238000013461 design Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000005491 wire drawing Methods 0.000 claims description 8
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 8
- 229920000147 Styrene maleic anhydride Polymers 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004156 Azodicarbonamide Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical group NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical group O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical group CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical group C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 3
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- 150000007970 thio esters Chemical class 0.000 claims description 3
- 239000004604 Blowing Agent Substances 0.000 claims description 2
- 238000012662 bulk polymerization Methods 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims 1
- 238000007790 scraping Methods 0.000 abstract description 9
- 238000005034 decoration Methods 0.000 abstract description 8
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 43
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 41
- 230000035943 smell Effects 0.000 description 41
- 238000010438 heat treatment Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 208000016261 weight loss Diseases 0.000 description 14
- 230000004580 weight loss Effects 0.000 description 14
- 229920001400 block copolymer Polymers 0.000 description 13
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 9
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 9
- 229960004756 ethanol Drugs 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- 241000207961 Sesamum Species 0.000 description 6
- 235000003434 Sesamum indicum Nutrition 0.000 description 6
- 229920006248 expandable polystyrene Polymers 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000003463 adsorbent Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 229940040145 liniment Drugs 0.000 description 4
- 239000000865 liniment Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- -1 polysiloxanes Polymers 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- CZIRZNRQHFVCDZ-UHFFFAOYSA-L titan yellow Chemical compound [Na+].[Na+].C1=C(C)C(S([O-])(=O)=O)=C2SC(C3=CC=C(C=C3)/N=N/NC3=CC=C(C=C3)C3=NC4=CC=C(C(=C4S3)S([O-])(=O)=O)C)=NC2=C1 CZIRZNRQHFVCDZ-UHFFFAOYSA-L 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 206010011224 Cough Diseases 0.000 description 1
- 206010019233 Headaches Diseases 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical group [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 208000017574 dry cough Diseases 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 231100000869 headache Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000008447 perception Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention discloses a kind of low volatilization automobile interior decoration ABS composite material of low smell and preparation methods.Composite material is made by following components by weight percent：100 parts of ABS, 0 ~ 30 part of heat-resistant agent, 0 ~ 15 part of toughener, 0.2 ~ 0.8 part of antioxidant, 0.2 ~ 0.8 part of the steady agent of light, 1 ~ 3.5 part of POSS material, removes 0.5 ~ 3.0 part of volatile substance master batch, 0.3 ~ 1.0 part of toner by 0.2 ~ 1 part of lubricant.The present invention, which is added, removes volatile substance master batch, so that material when carrying out double-screw extruding pelletizing, reduces the smell and volatile matter of composite material, so that it is constituted the scraping and wiping resistance performance that inierpeneirating network structure improves composite material with ABS composite material by the way that POSS material is added.The present invention requires the technique and extrusion equipment of extruding pelletization stringent.The poly- ABS composite material of the low low volatilization scratch-resistant automobile interior trim of smell can be finally made in the present invention.
Description
Technical field：
The present invention relates to polymer modification field more particularly to a kind of low volatilization scratch-resistant automobile interior trims of low smell
ABS composite material and preparation method.
Background technique：
Cage modle polysilsesquioxane (abbreviation POSS) is organic/nothing on the real molecular level of one kind emerging in recent years
Machine hybrid nano-material, general molecular formula are (RSiO1.5)n, n is generally 6,8,10,12 etc., wherein being 8 the most typical with n.
POSS while having the advantages of organic polymer with the nano-scale and cage structure of inorganic nano-particle, such as：
1, POSS inorganic silicon oxygen skeleton structure determines it with heat resistance outstanding, anti-flammability and radiation resistance；
2, the toughness of polymer can be improved in POSS, this is because POSS nanoparticle can terminate the hair at micro-crack tip
Exhibition, and crazing or shear band can be caused, or rearrange strand.It can root on the apex angle Si atom of POSS cagelike structure
According to needing to connect reactivity or non-reacted organo-functional group, reach and polymeric matrix reactive compatibilization or molecularly dispersed structure
Purpose, to greatly improve the performance of composite material；
3, the organo-functional group of POSS has it in nanostructure size with polymer and organic monomer compatible well
Property, while making POSS monomer be more easier to graft in polymer, therefore the unique structure of POSS and performance are that enhancing is poly-
Compound composite material, temperature tolerance, inoxidizability, anti-flammability, surface hardness and the mechanical property aspects for improving material provide
Opportunity.
ABS plays an important role in automobile component production always.Polypropylene（PP）Although after in automobile parts production
On occupying, but peerage of the ABS in high-grade car component is that PP can not shake and be completely replaced.The noble of ABS
Position be it is relevant to the good characteristic of ABS, thermoplastic ABS resin is widely recognized as being a kind of engineering material that can freely design
Material has aesthetics, flowing, toughness, dimensional stability and high-fire resistance outstanding.ABS has extensively on the interior exterior part of automobile
General application.On interior trim, ABS can be used for producing door-plate, instrument board escutcheon, glove box, middle control instrument board, air-conditioner air outlet
Deng.On exterior trim, ABS is for manufacturing heat dissipation grid, frame, license plate, decorations mark etc..With the increasingly developed of auto industry and disappear
Expense person's environmental protection and health awareness constantly enhances, and people, which do not require nothing more than car, will spacious interior space, unobscured and carriage
Comfortably, also require in-vehicle air fresh, high-quality.Interior volatile hazardous substances have attracted attention, intuitive anti-
It reflects for the perception to smell, studies have shown that the source of in-car smell is various, the volatile organic from inner-decoration component
Close object（Volatile organic compounds, referred to as " VOC "）One of the main reason for being influence in-car air quality.Greatly
All contain a certain amount of volatile organic compounds in most inner-decoration components, they are mainly alkane, alkene, aromatic hydrocarbons, amine, benzene
Phenol, mercaptan, peroxide, aldehyde, ketone substance, the boiling point of these substances is usually within the scope of 50 ~ 260 DEG C.Work as temperature
When reaching a certain height, under the action of photo-thermal, generate uncomfortable smell, or even cause headache, dry cough and allergy etc.
Discomfort reaction.On March 1st, 2012, GB/T27630-2011《Air Quality Evaluation guide in passenger car》It comes into effect, proposes
Limit value requirement to 8 kinds of substances of benzene class and aldehydes in air in vehicle compartment.Automotive upholstery is main inside automobile bodies
One of air pollution source wanted, and modified ABS be manufacture automotive upholstery one of main material, therefore prepare low smell,
Low volatile organic（8 kinds of substances of benzene class and aldehydes）Modified ABS become one new hot spot of modified plastics.In order to overcome these
Problem, the production and processing person of plastic resin is being dedicated to reducing the grade that distributes of these smells for a long time, and obtains certain
Effect.If patent CN 100580022C and 100506907 C of patent CN are using molecular sieve as adsorbent.Such as patent CN
1730542 B are using Bio-sil as adsorbent.As patent CN 103059409 using active carbon and molecular sieve compounding as
Adsorbent.It can be seen that from the above granted patent, currently as the active charcoal of material, the molecular sieve, porous silicon of volatile matter adsorbent
The materials such as glue.However the above adsorbent material always has an adsorption saturation value, and small molecule does not reach root also inside inside gadget
The purpose removed.
On the other hand, many automobile main frame maker had both required the low smell of automotive interior material, low volatile or had required in recent years
It is with good scraping and wiping resistance performance.The requirement as just having Shanghai Volkswagen.In order to both reach low smell, it is low volatilization with
And good scraping and wiping resistance performance, modified plastics producer is mainly using addition active carbon, molecular sieve or Bio-sil etc. at present
Material improves smell and volatile matter, while it is resistance to improve material that silicone substance, amide substance or polysiloxanes can be added
Scratch performance.Right silicone substance, amide substance or polysiloxanes can all bring the increase of smell and volatile matter.Such as patent CN
102329459 A using silicone or polysiloxanes as scratch resistance liniment, using fatty acid lipoid substance, nano zine oxide,
Nano-titanium oxide is as odor adsorption agent, but the smell of last composite material and scraping and wiping resistance performance are general.Such as patent CN
102532710 A are using nano silicon oxide as scratch resistance liniment, using porous silica or zeolite as odor adsorption agent, but most
The smell of composite material and scraping and wiping resistance performance are general afterwards.The present invention is utilized except volatile substance master batch is poly- by foaming in process
Liquid in styrene is vaporizated into steam and it is partially or completely discharged by double vacuum for the volatile small molecule in material, with
Reach the volatile materials and odoriferous substance eradicated in material.On the other hand POSS material is added and is remarkably improved composite material
Scraping and wiping resistance performance, and smell and volatile substance will not be brought.
Summary of the invention：
The purpose of the present invention is to provide a kind of low volatilization scratch-resistant automobile interior trim ABS composite material of low smell and preparations
Method.
The present invention is for the first time using expanded polystyrene (EPS) as carrier physics adsorption liquid body distilled water+epoxy ethane-epoxy propane
Copolymer has finally prepared one in conjunction with corresponding technique and equipment as the volatile substance master batch that removes during extruding pelletization
The low volatilization automobile interior decoration ABS composite material of the low smell of kind.On the other hand, the present invention makes POSS material as scratch resistance liniment for the first time
With being remarkably improved the scraping and wiping resistance performance of composite material and smell and volatile substance will not be brought.
The low volatilization scratch-resistant automobile interior trim ABS composite material of low smell of the invention, is made by following components by weight percent：
100 parts of ABS,
0 ~ 30 part of heat-resistant agent,
0 ~ 15 part of toughener,
0.2 ~ 0.8 part of antioxidant,
0.2 ~ 0.8 part of the steady agent of light,
0.2 ~ 1 part of lubricant,
1 ~ 3.5 part of POSS material,
Except 0.5 ~ 3.0 part of volatile substance master batch,
0.3 ~ 1.0 part of toner.
Wherein, ABS is acrylonitrile-butadiene-styrene terpolymer；POSS material is polyhedral oligomeric sesquioxyalkane material
Material；Except volatile substance master batch is using expanded polystyrene (EPS) as carrier physics adsorption liquid body distilled water+epoxy ethane-epoxy propane
The mixture of copolymer.
Above-mentioned ABS is the ABS of continuous bulk polymerization method technique production.
Above-mentioned heat-resistant agent is styrene-maleic anhydride copolymer（Referred to as：SMA）, styrene-（N- benzyl maleimide
Amine）Copolymer-maleic anhydride（Referred to as：SMI）One or both of.
Above-mentioned toughener is methyl methacrylate-butadiene-styrene（Referred to as：MBS）.
Above-mentioned antioxidant is that Hinered phenols, phosphorous acid esters, thioesters three are used in compounding.
The above-mentioned steady agent of light is that both hindered amines, benzotriazole are used in compounding.
Above-mentioned lubricant is ethylene bis stearamide.
It is described to remove volatile substance master batch, it is made using following methods step：
The first step：Prepare expanded polystyrene (EPS)
Weigh 100 parts by weight polystyrene, 5 ~ 15 parts by weight of blowing agent, 1 ~ 5 parts by weight blowing promotor, 0.1 ~ 0.3 weight
Part foaming antioxidant carries out mixed at high speed in high-speed mixer（Wherein the temperature of high mixer is 50 ~ 60 DEG C, high mixer revolving speed is
200 ~ 300 revs/min）, then feed the mixture into double screw extruder and carry out melting mixing foaming, wire drawing, pelletizing, cold
But；Above-mentioned foaming agent is azodicarbonamide, and blowing promotor is one or both of zinc oxide and zinc stearate；Above-mentioned foaming
Antioxidant is Hinered phenols, phosphorous acid esters compounding；
Second step：Preparation removes volatile substance master batch
The above-mentioned gained expanded polystyrene (EPS) material for weighing 100 parts by weight is put into distilled water and epoxy ethane-epoxy propane
Sufficient physical absorption is carried out in the mixture of block copolymer, make in the micropore of expanded polystyrene (EPS) hydraulically full distilled water and
Ethylene oxide-propylene oxide block copolymer, obtaining the expanded polystyrene (EPS) of adsorption saturation is of the invention except volatile substance is female
Grain；In the mixture, the weight ratio of liquid distilled water and ethylene oxide-propylene oxide block copolymer is 1：5~5：1.Guarantee
The expanded polystyrene (EPS) of adsorption saturation can reach 50% or more weight-loss ratio in dry 2 hours in 80 DEG C of air dry oven.Wherein
Weight-loss ratio=(（Expanded polystyrene (EPS) quality after expanded polystyrene (EPS) quality-drying of adsorption saturation）The foaming of/adsorption saturation
Polystyrene quality) * 100%.
The POSS material is prepared by the following method to obtain：Monomer A and monomer B are weighed in three-necked flask, thereto plus
Enter ethyl alcohol to be uniformly mixed, the pH value 2 ~ 4 that concentrated hydrochloric acid adjusts mixed solution is added dropwise, it is small to be then warming up to 80 ~ 90 DEG C of reactions 100 ~ 200
When, distilled water is cleaned and is filtered, and is filtered product in 80-90 DEG C of vacuum drying and is obtained POSS material for 24 hours；The monomer A is phenyl three
Methoxy silane, monomer B are methacryloxypropyl trimethoxy silane, and the mass ratio of A and B are 1：3~3：1, A, B is total
The mass ratio of quality and ethyl alcohol is 1：1~1：3.
Above-mentioned toner is titanium dioxide, carbon black, iron oxide red, titan yellow are used in compounding.
The preparation method of the low automobile interior decoration composite material that volatilizees of above-mentioned low smell is as follows：
One or more of network structures of kind improve the scraping and wiping resistance performance of composite material, weigh 100 parts of ABS, 0 ~ 30 first
Part heat-resistant agent, 0 ~ 15 part of toughener, 1 ~ 3.5 part of POSS material mix 3 ~ 5 minutes in high-speed mixer, wherein high-speed mixer
Revolving speed be 200 ~ 300 revs/min；Then weigh 0.2 ~ 0.8 part of antioxidant, the steady agent of 0.2 ~ 0.8 part of light, 0.2 ~ 1 part of lubricant,
0.3 ~ 1.0 part of toner, which is added in high-speed mixer, to be mixed 3 ~ 5 minutes, and wherein the revolving speed of high-speed mixer is 200 ~ 300 revs/min
Clock；0.5 ~ 3.0 part is finally weighed except volatile substance master batch carries out crawl mixing 3 ~ 5 times in high-speed mixer；By above-mentioned mixing
Good particle, which adds twin-screw extrude, carries out melting extrusion, granulation, drying, cooling, dress packet.The temperature of double screw extruder
Room temperature is followed successively by from feeding section to head（Heating is not opened）, room temperature（Heating is not opened）,200℃,210℃,210℃,210℃,215
℃,215℃,215℃,215℃.Double vacuum designs, and vacuum level requirements≤- 0.07MPa.
The invention has the beneficial effects that：
1, the present invention is for the first time using expanded polystyrene (EPS) as carrier physics adsorption liquid body distilled water+ethylene oxide-epoxy third
Alkyl copolymer is finally prepared as the volatile substance master batch that removes during extruding pelletization in conjunction with corresponding technique and equipment
A kind of low volatilization automobile interior decoration ABS composite material of low smell.
2, the low volatilization automobile interior decoration composite material of this low smell of the invention is stringent to technique and equipment requirement, such as double spiral shells
The processing temperature of bar extruder first segment and second segment cannot be opened, and the temperature remains within the normal range.If having opened heating, temperature is more than 100
DEG C liquid distilled water vaporizes in advance, and devolatilization effect is unobvious；Double vacuum designs, and vacuum level requirements≤- 0.07MPa, vacuum
Not enough, vapor and small molecule volatile matter detach not completely degree, and devolatilization effect is also unobvious.
3, the present invention is used POSS material as the scratch resistance liniment of composite material for the first time, significant effect.And it will not bring
Smell and volatile matter, resistance to precipitation.
Specific embodiment：
Below with reference to some embodiments, the invention will be further described with comparative example.Following embodiment is of the invention
Typical case, scope of protection of the present invention is not limited thereto.The smell of following embodiment and comparative example is according to Shanghai Volkswagen's
PV3900《Components smell is tested in automobile bodies》Standard is tested：1,20g granulation material is placed in 1L odor test bottle；
2,2h is placed in 80 DEG C of baking ovens, is taken out after bottle is cooled to 60 DEG C, starts to evaluate smell；3, odor gradings method, smell are commented
The fixed oder levels made according to table -1 are demarcated.
- 1 oder levels of table
| Grade | Smell description |
| 1 | It is imperceptible |
| 2 | It can feel, not disturb people |
| 3 | It can be clearly felt that but not disturb people also |
| 4 | Disturb people |
| 5 | Strong dislike |
| 6 | It is difficult to tolerate |
Organic volatile according to Shanghai Volkswagen PV3341《Organic compound emission》Standard carries out test total carbon content
（TVOC）, unit is μ gC/g.Scraping and wiping resistance performance according to Shanghai Volkswagen PV3952《The test of plastics inside gadget scratch resistant》Standard into
As a result row test tests the size with △ L before and after color difference meter test experiments wherein using the load of 20N.
The main raw material(s) used in embodiment and comparative example is as follows：
ABS：
Continuous bulk ABS model：8391 producers：Middle petrochemical industry Gaoqiao Petrochemical Company；
Continuous bulk ABS model：8434 producers：Middle petrochemical industry Gaoqiao Petrochemical Company；
Heat-resistant agent：
Styrene-maleic anhydride copolymer model：26080 producer of SMA：Dutch Polyscope Polymers company；
Styrene-（N-phenylmaleimide）Copolymer-maleic anhydride model：MS-NB producer：U.S. electric
It learns；
Toughener：
Methyl methacrylate-butadiene-styrene model：MBS E2620 producer：U.S.'s ROHM AND HAAS；
Antioxidant：
Hinered phenols model：1076 producers：Yixing City angel synthesizes chemistry；
Phosphorous acid esters model：168 producers：Yixing City angel synthesizes chemistry；
Thioesters model：DSTDP producer：Yixing City angel synthesizes chemistry；
The steady agent of light：
Hindered amines model：770DF producer：German BASF；
Benzotriazole model：UV-P producer：German BASF；
Lubricant：
Ethylene bis stearamide model：500 mesh producer of EBS：The prosperous chemical industry of Guangzhou wound brocade；
Monomer：
Monomer A：Phenyl-trimethylsilicane model：Analyze pure producer：Aladdin reagent；
Monomer B：Methacryloxypropyl trimethoxy silane model：Analyze pure producer：Aladdin reagent；
Foaming agent：
Azodicarbonamide model：Azodicarbonamide producer：Zhengzhou Kang Ding chemical industry；
Blowing promotor：
Zinc oxide model：Environmentally friendly zinc oxide producer：The grand zinc industry in Jiangsu Shen；
Zinc stearate model：Environmentally friendly zinc stearate producer：The grand zinc industry in Jiangsu Shen.
Polystyrene：
Polystyrene model：GPPS PG-383 producer：The odd beauty in Zhenjiang；
Ethyl alcohol：
Dehydrated alcohol model：Analyze pure producer：Aladdin reagent；
Hydrochloric acid：
Concentrated hydrochloric acid model：Analyze pure producer：Shenzhen Cambridge science；
Toner：
Titanium dioxide model：CR826 producer：Australia Ke Meiji；
Carbon black model：660R producer：U.S.'s Cabot；
Iron oxide red model：RO-3097 producer：U.S.'s Lockwood；
Titan yellow model：K2001 producer：German BASF.
Embodiment 1
The first step：Preparation removes volatile substance master batch
（1）Prepare expanded polystyrene (EPS)
Weigh 100 parts of polystyrene PG-383,5 parts of foaming agent azodicarbonamides, 1 part of blowing promotor zinc oxide, 0.05
Mixed at high speed is carried out in part antioxidant 1076,0.05 part of irgasfos 168 and high-speed mixer（Wherein the temperature of high mixer is 50
DEG C, high mixer revolving speed be 200 revs/min）, the mixture mixed is then added twin-screw extrude into carry out melting mixing
Foaming, wire drawing, pelletizing, cooling.
（2）Preparation removes volatile substance master batch
Weigh liquid distilled water and ring that the expanded polystyrene (EPS) material that 100 parts of above-mentioned first steps prepare is put into sufficient amount
Oxidative ethane-propylene oxide block copolymer mixture（Liquid distilled water：Ethylene oxide-propylene oxide block copolymer quality
Than 1：5）It is middle to carry out sufficient physical absorption, make hydraulically full distilled water and ethylene oxide-in the micropore of expanded polystyrene (EPS)
Propylene oxide block copolymer, finally obtaining the expanded polystyrene (EPS) of adsorption saturation is of the invention except volatile substance master batch.It protects
The expanded polystyrene (EPS) for demonstrate,proving adsorption saturation can reach 50% or more weight-loss ratio in dry 2 hours in 80 DEG C of air dry oven.Its
Middle weight-loss ratio=(（Expanded polystyrene (EPS) quality after expanded polystyrene (EPS) quality-drying of adsorption saturation）The hair of/adsorption saturation
Foamed polystyrene quality) * 100%.The expanded polystyrene (EPS) of this preparation dry 2 hours weightlessness in 80 DEG C of air dry oven
Rate 58%.
Second step：Prepare POSS material
It is weighed in 1 part of monomer A and 3 parts of monomer B and three mouthfuls of sesame seed cakes first, then is slowly added to 4 parts of ethyl alcohol mixing thereto
It is even；Then concentrated hydrochloric acid is slowly added dropwise into aforementioned mixed solution, the pH value for adjusting mixed solution is 2, is then warming up to 80 DEG C instead
It answers 100 hours；Benefit wash with distilled water and filters after reaction, filters product in 85 DEG C and is dried in vacuo 24 hours to obtain POSS material
Material.
Third step：Prepare the low volatilization scratch-resistant automobile interior trim ABS composite material of low smell
It weighs and is mixed 3 minutes in the POSS material and high-speed mixer of 100 parts of ABS, 8391,1 parts of second steps preparation first,
Wherein the revolving speed of high-speed mixer is 200 revs/min；Then weigh 0.06 part of antioxidant 1076,0.06 part of irgasfos 168,
0.08 part of antioxidant DSTDP, the steady agent 770DF of 0.1 part of light, the steady agent UV-P of 0.1 part of light, 0.2 part of Lubricate EBS, 0.15 part of toner
CR826,0.02 part of toner 660R, 0.03 part of toner RO-3097,0.10 part of toner K2001 are added in high-speed mixer and mix 3 points
Clock, wherein the revolving speed of high-speed mixer is 200 revs/min；Finally, then weigh the preparation of 0.5 part of first step except volatile substance
It is carried out crawl mixing 3 times in master batch and high-speed mixer.The above-mentioned particle mixed is added twin-screw extrude and is melted
Melt extrusion, granulation, drying, cooling, dress packet.The temperature of double screw extruder is followed successively by room temperature from feeding section to head（It does not open and adds
Heat）, room temperature（Heating is not opened）,200℃,210℃,210℃,210℃,215℃,215℃,215℃,215℃.Double vacuum are set
Meter, and vacuum level requirements≤- 0.07MPa.Performance such as table -2.
Comparative example 1（It is not added except volatile substance master batch）
The first step：Prepare POSS material
It is weighed in 1 part of monomer A and 3 parts of monomer B and three mouthfuls of sesame seed cakes first, then is slowly added to 4 parts of ethyl alcohol mixing thereto
It is even；Then concentrated hydrochloric acid is slowly added dropwise into aforementioned mixed solution, the pH value for adjusting mixed solution is 2, is then warming up to 80 DEG C instead
It answers 100 hours；Benefit wash with distilled water and filters after reaction, filters product in 85 DEG C and is dried in vacuo 24 hours to obtain POSS material
Material.
Second step：Prepare the low volatilization scratch-resistant automobile interior trim ABS composite material of low smell
It weighs and is mixed 3 minutes in the POSS material and high-speed mixer of 100 parts of ABS, 8391,1 parts of first steps preparation first,
Wherein the revolving speed of high-speed mixer is 200 revs/min；Then weigh 0.06 part of antioxidant 1076,0.06 part of irgasfos 168,
0.08 part of antioxidant DSTDP, the steady agent 770DF of 0.1 part of light, the steady agent UV-P of 0.1 part of light, 0.2 part of Lubricate EBS, 0.15 part of toner
CR826,0.02 part of toner 660R, 0.03 part of toner RO-3097,0.10 part of toner K2001 are added in high-speed mixer and mix 3 points
Clock, wherein the revolving speed of high-speed mixer is 200 revs/min.The above-mentioned particle mixed is added twin-screw extrude into progress
Melting extrusion, granulation, drying, cooling, dress packet.The temperature of double screw extruder is followed successively by room temperature from feeding section to head（It does not open
Heating）, room temperature（Heating is not opened）,200℃,210℃,210℃,210℃,215℃,215℃,215℃,215℃.Double vacuum are set
Meter, and vacuum level requirements≤- 0.07MPa.Performance such as table -2.
Comparative example 2（POSS material is not added）
The first step：Preparation removes volatile substance master batch
（1）Prepare expanded polystyrene (EPS)
Weigh 100 parts of polystyrene PG-383,5 parts of foaming agent azodicarbonamides, 1 part of blowing promotor zinc oxide, 0.05
Mixed at high speed is carried out in part antioxidant 1076,0.05 part of irgasfos 168 and high-speed mixer（Wherein the temperature of high mixer is 50
DEG C, high mixer revolving speed be 200 revs/min）, the mixture mixed is then added twin-screw extrude into carry out melting mixing
Foaming, wire drawing, pelletizing, cooling.
（2）Preparation removes volatile substance master batch
Weigh liquid distilled water and ring that the expanded polystyrene (EPS) material that 100 parts of above-mentioned first steps prepare is put into sufficient amount
Oxidative ethane-propylene oxide block copolymer mixture（Liquid distilled water：Ethylene oxide-propylene oxide block copolymer quality
Than 1：5）It is middle to carry out sufficient physical absorption, make hydraulically full distilled water and ethylene oxide-in the micropore of expanded polystyrene (EPS)
Propylene oxide block copolymer, finally obtaining the expanded polystyrene (EPS) of adsorption saturation is of the invention except volatile substance master batch.It protects
The expanded polystyrene (EPS) for demonstrate,proving adsorption saturation can reach 50% or more weight-loss ratio in dry 2 hours in 80 DEG C of air dry oven.Its
Middle weight-loss ratio=(（Expanded polystyrene (EPS) quality after expanded polystyrene (EPS) quality-drying of adsorption saturation）The hair of/adsorption saturation
Foamed polystyrene quality) * 100%.The expanded polystyrene (EPS) of this preparation dry 2 hours weightlessness in 80 DEG C of air dry oven
Rate 58%.
Second step：Prepare the low volatilization scratch-resistant automobile interior trim ABS composite material of low smell
100 parts of ABS, 8391,0.06 parts of antioxidant 1076s, 0.06 part of irgasfos 168,0.08 part of antioxidant are weighed first
DSTDP, the steady agent 770DF of 0.1 part of light, the steady agent UV-P of 0.1 part of light, 0.2 part of Lubricate EBS, 0.15 part of toner CR826,0.02 part
Toner 660R, 0.03 part of toner RO-3097,0.10 part of toner K2001 are added in high-speed mixer and mix 3 minutes, high speed
The revolving speed of mixing machine is 200 revs/min；Finally, then weighing the except volatile substance master batch and mixed at a high speed of 0.5 part of first step preparation
It is carried out crawl mixing 3 times in conjunction machine.By the above-mentioned particle mixed add twin-screw extrude carry out melting extrusion, granulation,
Dry, cooling, dress packet.The temperature of double screw extruder is followed successively by room temperature from feeding section to head（Heating is not opened）, room temperature（It does not open
Heating）,200℃,210℃,210℃,210℃,215℃,215℃,215℃,215℃.Double vacuum designs, and vacuum level requirements
≤-0.07MPa.Performance such as table -2.
- 2 embodiment 1 of table and 1 ~ 2 performance of comparative example
| Test item | Embodiment 1 | Comparative example 1 | Comparative example 2 |
| Smell/grade | 4.5 | 5.5 | 4.5 |
| TVOC (< C16)/(μ gC/g) | 120 | 269 | 132 |
| Scratch-resistant/△ L | 1.3 | 1.2 | 2.6 |
From above embodiments 1 and comparative example 1 ~ 2 it will be evident that this mode of the invention to prepare the low volatilization of low smell resistance to
Automobile interior trim ABS composite material significant effect is scraped, can obviously improve the smell, volatile matter and scratch resistance of composite material
Energy.
Embodiment 2
The first step：Preparation removes volatile substance master batch
（1）Prepare expanded polystyrene (EPS)
Weigh 100 parts of polystyrene PG-383,15 parts of foaming agent azodicarbonamides, 3 parts of blowing promotor zinc oxide, 2 parts
Mixed at high speed is carried out in blowing promotor zinc stearate, 0.2 part of antioxidant 1076,0.1 part of irgasfos 168 and high-speed mixer（Its
The temperature of middle high mixer is 60 DEG C, high mixer revolving speed is 300 revs/min）, then the mixture mixed addition twin-screw is squeezed
Melting mixing foaming, wire drawing, pelletizing, cooling are carried out in machine out.
（2）Preparation removes volatile substance master batch
Weigh liquid distilled water and ring that the expanded polystyrene (EPS) material that 100 parts of above-mentioned first steps prepare is put into sufficient amount
Oxidative ethane-propylene oxide block copolymer mixture（Liquid distilled water：Ethylene oxide-propylene oxide block copolymer quality
Than 5：1）It is middle to carry out sufficient physical absorption, make hydraulically full distilled water and ethylene oxide-in the micropore of expanded polystyrene (EPS)
Propylene oxide block copolymer, finally obtaining the expanded polystyrene (EPS) of adsorption saturation is of the invention except volatile substance master batch.It protects
The expanded polystyrene (EPS) for demonstrate,proving adsorption saturation can reach 50% or more weight-loss ratio in dry 2 hours in 80 DEG C of air dry oven.Its
Middle weight-loss ratio=(（Expanded polystyrene (EPS) quality after expanded polystyrene (EPS) quality-drying of adsorption saturation）The hair of/adsorption saturation
Foamed polystyrene quality) * 100%.The expanded polystyrene (EPS) of this preparation dry 2 hours weightlessness in 80 DEG C of air dry oven
Rate 62%.
Second step：Prepare POSS material
It is weighed in 3 parts of monomer A and 1 part of monomer B and three mouthfuls of sesame seed cakes first, then is slowly added to 12 parts of ethyl alcohol mixing thereto
It is even；Then concentrated hydrochloric acid is slowly added dropwise into aforementioned mixed solution, the pH value for adjusting mixed solution is 4, is then warming up to 90 DEG C instead
It answers 200 hours；Benefit wash with distilled water and filters after reaction, filters product in 85 DEG C and is dried in vacuo 24 hours to obtain POSS material
Material.
Third step：Prepare the low volatilization scratch-resistant automobile interior trim ABS composite material of low smell
It is weighed in the POSS material and high-speed mixer of 100 parts of ABS, 8434,3.5 parts of second steps preparation first and mixes 5 points
Clock, wherein the revolving speed of high-speed mixer is 300 revs/min；Then weigh 0.25 part of antioxidant 1076,0.3 part of irgasfos 168,
0.25 part of antioxidant DSTDP, the steady agent 770DF of 0.35 part of light, the steady agent UV-P of 0.45 part of light, 1 part of Lubricate EBS, 0.46 part of toner
CR826,0.03 part of toner 660R, 0.04 part of toner RO-3097,0.47 part of toner K2001 are added in high-speed mixer and mix 5 points
Clock, wherein the revolving speed of high-speed mixer is 300 revs/min；Finally, then weigh the preparation of 3.0 parts of first steps except volatile substance
It is carried out crawl mixing 5 times in master batch and high-speed mixer.The above-mentioned particle mixed is added twin-screw extrude and is melted
Melt extrusion, granulation, drying, cooling, dress packet.The temperature of double screw extruder is followed successively by room temperature from feeding section to head（It does not open and adds
Heat）, room temperature（Heating is not opened）,200℃,210℃,210℃,210℃,215℃,215℃,215℃,215℃.Double vacuum are set
Meter, and vacuum level requirements≤- 0.07MPa.Performance such as table -3.
Comparative example 3（It is not added except volatile substance master batch）
The first step：Prepare POSS material
It is weighed in 3 parts of monomer A and 1 part of monomer B and three mouthfuls of sesame seed cakes first, then is slowly added to 12 parts of ethyl alcohol mixing thereto
It is even；Then concentrated hydrochloric acid is slowly added dropwise into aforementioned mixed solution, the pH value for adjusting mixed solution is 4, is then warming up to 90 DEG C instead
It answers 200 hours；Benefit wash with distilled water and filters after reaction, filters product in 85 DEG C and is dried in vacuo 24 hours to obtain POSS material
Material.
Second step：Prepare the low volatilization scratch-resistant automobile interior trim ABS composite material of low smell
It is weighed in the POSS material and high-speed mixer of 100 parts of ABS, 8434,3.5 parts of first steps preparation first and mixes 5 points
Clock, wherein the revolving speed of high-speed mixer is 300 revs/min；Then weigh 0.25 part of antioxidant 1076,0.3 part of irgasfos 168,
0.25 part of antioxidant DSTDP, the steady agent 770DF of 0.35 part of light, the steady agent UV-P of 0.45 part of light, 1 part of Lubricate EBS, 0.46 part of toner
CR826,0.03 part of toner 660R, 0.04 part of toner RO-3097,0.47 part of toner K2001 are added in high-speed mixer and mix 5 points
Clock, wherein the revolving speed of high-speed mixer is 300 revs/min.The above-mentioned particle mixed is added twin-screw extrude into progress
Melting extrusion, granulation, drying, cooling, dress packet.The temperature of double screw extruder is followed successively by room temperature from feeding section to head（It does not open
Heating）, room temperature（Heating is not opened）,200℃,210℃,210℃,210℃,215℃,215℃,215℃,215℃.Double vacuum are set
Meter, and vacuum level requirements≤- 0.07MPa.Performance such as table -3.
Comparative example 4（POSS material is not added）
The first step：Preparation removes volatile substance master batch
（1）Prepare expanded polystyrene (EPS)
Weigh 100 parts of polystyrene PG-383,15 parts of foaming agent azodicarbonamides, 3 parts of blowing promotor zinc oxide, 2 parts
Mixed at high speed is carried out in blowing promotor zinc stearate, 0.2 part of antioxidant 1076,0.1 part of irgasfos 168 and high-speed mixer（Its
The temperature of middle high mixer is 60 DEG C, high mixer revolving speed is 300 revs/min）, then the mixture mixed addition twin-screw is squeezed
Melting mixing foaming, wire drawing, pelletizing, cooling are carried out in machine out.
（2）Preparation removes volatile substance master batch
Weigh liquid distilled water and ring that the expanded polystyrene (EPS) material that 100 parts of above-mentioned first steps prepare is put into sufficient amount
Oxidative ethane-propylene oxide block copolymer mixture（Liquid distilled water：Ethylene oxide-propylene oxide block copolymer quality
Than 5：1）It is middle to carry out sufficient physical absorption, make hydraulically full distilled water and ethylene oxide-in the micropore of expanded polystyrene (EPS)
Propylene oxide block copolymer, finally obtaining the expanded polystyrene (EPS) of adsorption saturation is of the invention except volatile substance master batch.It protects
The expanded polystyrene (EPS) for demonstrate,proving adsorption saturation can reach 50% or more weight-loss ratio in dry 2 hours in 80 DEG C of air dry oven.Its
Middle weight-loss ratio=(（Expanded polystyrene (EPS) quality after expanded polystyrene (EPS) quality-drying of adsorption saturation）The hair of/adsorption saturation
Foamed polystyrene quality) * 100%.The expanded polystyrene (EPS) of this preparation dry 2 hours weightlessness in 80 DEG C of air dry oven
Rate 62%.
Second step：Prepare the low volatilization scratch-resistant automobile interior trim ABS composite material of low smell
100 parts of ABS, 8434,0.25 parts of antioxidant 1076s, 0.3 part of irgasfos 168,0.25 part of antioxidant are weighed first
DSTDP, the steady agent 770DF of 0.35 part of light, the steady agent UV-P of 0.45 part of light, 1 part of Lubricate EBS, 0.46 part of toner CR826,0.03 part
Toner 660R, 0.04 part of toner RO-3097,0.47 part of toner K2001 are added in high-speed mixer and mix 5 minutes, high speed
The revolving speed of mixing machine is 300 revs/min；Finally, then weighing the except volatile substance master batch and mixed at a high speed of 3.0 parts of first step preparations
It is carried out crawl mixing 5 times in conjunction machine.By the above-mentioned particle mixed add twin-screw extrude carry out melting extrusion, granulation,
Dry, cooling, dress packet.The temperature of double screw extruder is followed successively by room temperature from feeding section to head（Heating is not opened）, room temperature（It does not open
Heating）,200℃,210℃,210℃,210℃,215℃,215℃,215℃,215℃.Double vacuum designs, and vacuum level requirements
≤-0.07MPa.Performance such as table -3.
Embodiment 3
The first step：Preparation removes volatile substance master batch
（1）Prepare expanded polystyrene (EPS)
Weigh 100 parts of polystyrene PG-383,8 parts of foaming agent azodicarbonamides, 1.4 parts of blowing promotor zinc oxide, 0.3
Mixed at high speed is carried out in part blowing promotor zinc stearate, 0.12 part of antioxidant 1076,0.1 part of irgasfos 168 and high-speed mixer
（Wherein the temperature of high mixer is 53 DEG C, high mixer revolving speed is 245 revs/min）, double spiral shells then are added in the mixture mixed
Melting mixing foaming, wire drawing, pelletizing, cooling are carried out in bar extruder.
（2）Preparation removes volatile substance master batch
Weigh liquid distilled water and ring that the expanded polystyrene (EPS) material that 100 parts of above-mentioned first steps prepare is put into sufficient amount
Oxidative ethane-propylene oxide block copolymer mixture（Liquid distilled water：Ethylene oxide-propylene oxide block copolymer quality
Than 1：1）It is middle to carry out sufficient physical absorption, make hydraulically full distilled water and ethylene oxide-in the micropore of expanded polystyrene (EPS)
Propylene oxide block copolymer, finally obtaining the expanded polystyrene (EPS) of adsorption saturation is of the invention except volatile substance master batch.It protects
The expanded polystyrene (EPS) for demonstrate,proving adsorption saturation can reach 50% or more weight-loss ratio in dry 2 hours in 80 DEG C of air dry oven.Its
Middle weight-loss ratio=(（Expanded polystyrene (EPS) quality after expanded polystyrene (EPS) quality-drying of adsorption saturation）The hair of/adsorption saturation
Foamed polystyrene quality) * 100%.The expanded polystyrene (EPS) of this preparation dry 2 hours weightlessness in 80 DEG C of air dry oven
Rate 55%.
Second step：Prepare POSS material
It is weighed in 1 part of monomer A and 1 part of monomer B and three mouthfuls of sesame seed cakes first, then is slowly added to 4 parts of ethyl alcohol mixing thereto
It is even；Then concentrated hydrochloric acid is slowly added dropwise into aforementioned mixed solution, the pH value for adjusting mixed solution is 3, is then warming up to 84 DEG C instead
It answers 148 hours；Benefit wash with distilled water and filters after reaction, filters product in 90 DEG C and is dried in vacuo 24 hours to obtain POSS material
Material.
Third step：Prepare the low volatilization scratch-resistant automobile interior trim ABS composite material of low smell
8434,30 parts of 70 parts of ABS, 8391,30 parts of ABS heat-resistant agent SMA, 26080,15 parts of toughener MBS are weighed first
E2620, the preparation of 2.4 parts of second steps POSS material and high-speed mixer in mix 3.7 minutes, the wherein revolving speed of high-speed mixer
It is 259 revs/min；Then 0.17 part of antioxidant 1076,0.12 part of irgasfos 168,0.16 part of antioxidant DSTDP, 0.21 are weighed
The steady agent 770DF of part light, the steady agent UV-P of 0.14 part of light, 0.36 part of Lubricate EBS, 0.42 part of toner CR826,0.03 part of toner
660R, 0.04 part of toner RO-3097,0.41 part of toner K2001 are added in high-speed mixer and mix 3.9 minutes, and high speed is mixed
The revolving speed of conjunction machine is 253 revs/min；Finally, then weigh the preparation of 1.9 parts of first steps except volatile substance master batch and mixed at high speed
It is carried out crawl mixing 4 times in machine.The above-mentioned particle mixed is added twin-screw extrude and carries out melting extrusion, granulation, do
Dry, cooling, dress packet.The temperature of double screw extruder is followed successively by room temperature from feeding section to head（Heating is not opened）, room temperature（It does not open and adds
Heat）,200℃,210℃,210℃,210℃,215℃,215℃,215℃,215℃.Double vacuum designs, and vacuum level requirements
≤-0.07MPa.Performance such as table -3.
Embodiment 4
The first step：Preparation removes volatile substance master batch
（1）Prepare expanded polystyrene (EPS)
Weigh 100 parts of polystyrene PG-383,9.8 parts of foaming agent azodicarbonamides, 1.6 parts of blowing promotor zinc oxide,
It is mixed that high speed is carried out in 0.4 part of blowing promotor zinc stearate, 0.13 part of antioxidant 1076,0.1 part of irgasfos 168 and high-speed mixer
It closes（Wherein the temperature of high mixer is 56 DEG C, high mixer revolving speed is 276 revs/min）, then the mixture mixed is added double
Melting mixing foaming, wire drawing, pelletizing, cooling are carried out in screw extruder.
（2）Preparation removes volatile substance master batch
Weigh liquid distilled water and ring that the expanded polystyrene (EPS) material that 100 parts of above-mentioned first steps prepare is put into sufficient amount
Oxidative ethane-propylene oxide block copolymer mixture（Liquid distilled water：Ethylene oxide-propylene oxide block copolymer quality
Than 1：1）It is middle to carry out sufficient physical absorption, make hydraulically full distilled water and ethylene oxide-in the micropore of expanded polystyrene (EPS)
Propylene oxide block copolymer, finally obtaining the expanded polystyrene (EPS) of adsorption saturation is of the invention except volatile substance master batch.It protects
The expanded polystyrene (EPS) for demonstrate,proving adsorption saturation can reach 50% or more weight-loss ratio in dry 2 hours in 80 DEG C of air dry oven.Its
Middle weight-loss ratio=(（Expanded polystyrene (EPS) quality after expanded polystyrene (EPS) quality-drying of adsorption saturation）The hair of/adsorption saturation
Foamed polystyrene quality) * 100%.The expanded polystyrene (EPS) of this preparation dry 2 hours weightlessness in 80 DEG C of air dry oven
Rate 59%.
Second step：Prepare POSS material
It is weighed in 1 part of monomer A and 1 part of monomer B and three mouthfuls of sesame seed cakes first, then is slowly added to 6 parts of ethyl alcohol mixing thereto
It is even；Then concentrated hydrochloric acid is slowly added dropwise into aforementioned mixed solution, the pH value for adjusting mixed solution is 4, is then warming up to 88 DEG C instead
It answers 178 hours；Benefit wash with distilled water and filters after reaction, filters product in 80 DEG C and is dried in vacuo 24 hours to obtain POSS material
Material.
Third step：Prepare the low volatilization scratch-resistant automobile interior trim ABS composite material of low smell
8434,60 parts of 40 parts of ABS, 8391,8 parts of ABS heat-resistant agent SMA 26080,5 parts of heat-resistant agent MS-NB, 7 are weighed first
3.8 minutes are mixed in POSS material and high-speed mixer prepared by part toughener MBS E2620,2.9 parts of second steps, high speed
The revolving speed of mixing machine is 279 revs/min；Then 0.18 part of antioxidant 1076,0.14 part of irgasfos 168,0.16 part of antioxygen are weighed
Agent DSTDP, the steady agent 770DF of 0.21 part of light, the steady agent UV-P of 0.15 part of light, 0.37 part of Lubricate EBS, 0.43 part of toner CR826,
0.04 part of toner 660R, 0.03 part of toner RO-3097,0.26 part of toner K2001 are added in high-speed mixer and mix 4.7 minutes,
Wherein the revolving speed of high-speed mixer is 258 revs/min；Finally, then weigh the preparation of 2.7 parts of first steps except volatile substance master batch
It is carried out crawl mixing 5 times with high-speed mixer.The above-mentioned particle mixed is added twin-screw extrude melt and is squeezed
Out, it is granulated, is dry, is cooling, dress packet.The temperature of double screw extruder is followed successively by room temperature from feeding section to head（Heating is not opened）,
Room temperature（Heating is not opened）,200℃,210℃,210℃,210℃,215℃,215℃,215℃,215℃.Double vacuum designs, and
Vacuum level requirements≤- 0.07MPa.Performance such as table -3.
- 3 embodiment 2 ~ 4 of table and 3 ~ 4 performance of comparative example
| Test item | Embodiment 2 | Comparative example 3 | Comparative example 4 | Embodiment 3 | Embodiment 4 |
| Smell/grade | 2.5 | 5.5 | 2.5 | 3.0 | 3.0 |
| TVOC (< C16)/(μ gC/g) | 29 | 248 | 25 | 35 | 32 |
| Scratch-resistant/△ L | 0.6 | 0.5 | 2.3 | 0.8 | 0.8 |
From above embodiments 2 ~ 4 and comparative example 3 ~ 4 it will be evident that this mode of the invention prepares the low volatilization of low smell
Scratch-resistant automobile interior trim ABS composite material significant effect, can obviously improve the smell, volatile matter and scratch-resistant of composite material
Performance.Such as embodiment 2,2.5 grades of oder levels（The requirement of Shanghai Volkswagen is≤3.0 grades）, TVOC be 29 μ gC/g（Shanghai is big
Many requirements are≤50 μ gC/g）, scratch-resistant be L=0.6 △（The requirement of Shanghai Volkswagen is L≤1.5 △）.
Claims (10)
1. a kind of low volatilization scratch-resistant automobile interior trim ABS composite material of low smell, which is characterized in that by following components by weight percent system
?：
100 parts of ABS,
0 ~ 30 part of heat-resistant agent,
0 ~ 15 part of toughener,
0.2 ~ 0.8 part of antioxidant,
0.2 ~ 0.8 part of the steady agent of light,
0.2 ~ 1 part of lubricant,
1 ~ 3.5 part of POSS material,
Except 0.5 ~ 3.0 part of volatile substance master batch,
0.3 ~ 1.0 part of toner;
Wherein POSS material is polyhedral oligomeric silsesquioxane materials；Except volatile substance master batch is using expanded polystyrene (EPS) as load
The mixture of body physical absorption liquid distilled water and ethylene oxide-propylene oxide copolymer.
2. the low volatilization scratch-resistant automobile interior trim ABS composite material of a kind of low smell as described in claim 1, which is characterized in that
The ABS is the ABS of continuous bulk polymerization method technique production.
3. the low volatilization scratch-resistant automobile interior trim ABS composite material of a kind of low smell as described in claim 1, which is characterized in that
The heat-resistant agent is styrene-maleic anhydride copolymer, styrene-（N-phenylmaleimide）In copolymer-maleic anhydride
One or two.
4. the low volatilization scratch-resistant automobile interior trim ABS composite material of a kind of low smell as described in claim 1, which is characterized in that
The toughener is methyl methacrylate-butadiene-styrene.
5. the low volatilization scratch-resistant automobile interior trim ABS composite material of a kind of low smell as described in claim 1, which is characterized in that
The antioxidant is that Hinered phenols, phosphorous acid esters, thioesters three are used in compounding.
6. the low volatilization scratch-resistant automobile interior trim ABS composite material of a kind of low smell as described in claim 1, which is characterized in that
The steady agent of light is that both hindered amines, benzotriazole are used in compounding.
7. the low volatilization scratch-resistant automobile interior trim ABS composite material of a kind of low smell as described in claim 1, which is characterized in that
The lubricant is ethylene bis stearamide.
8. the low volatilization scratch-resistant automobile interior trim ABS composite material of a kind of low smell as described in claim 1, which is characterized in that
It is described to remove volatile substance master batch, it is made using following methods step：
The first step：Prepare expanded polystyrene (EPS)
Weigh 100 parts by weight polystyrene, 5 ~ 15 parts by weight of blowing agent, 1 ~ 5 parts by weight blowing promotor, 0.1 ~ 0.3 parts by weight hair
Bubble antioxidant carries out mixed at high speed in high-speed mixer, then feeds the mixture into and carries out melting mixing in double screw extruder
Foaming, wire drawing, pelletizing, cooling；Above-mentioned foaming agent is azodicarbonamide, and blowing promotor is one in zinc oxide and zinc stearate
Kind or two kinds；Above-mentioned foaming antioxidant is Hinered phenols, phosphorous acid esters compounding；
Second step：Preparation removes volatile substance master batch
The above-mentioned gained expanded polystyrene (EPS) material for weighing 100 parts by weight is put into distilled water and epoxy ethane-epoxy propane block
Sufficient physical absorption is carried out in the mixture of copolymer, the expanded polystyrene (EPS) for obtaining adsorption saturation is to remove volatile substance mother
Grain；In the mixture, the weight ratio of liquid distilled water and ethylene oxide-propylene oxide block copolymer is 1：5~5：1.
9. the low volatilization scratch-resistant automobile interior trim ABS composite material of a kind of low smell as described in claim 1, which is characterized in that
The POSS material is prepared by the following method to obtain：Monomer A and monomer B are weighed in three-necked flask, it is mixed that ethyl alcohol is added thereto
It closes uniformly, the pH value 2 ~ 4 that concentrated hydrochloric acid adjusts mixed solution is added dropwise, be then warming up to 80 ~ 90 DEG C and react 100 ~ 200 hours, distillation
Water is cleaned and is filtered, and is filtered product and is dried in vacuo to obtain POSS material in 80-90 DEG C；The monomer A is phenyltrimethoxysila,e,
Monomer B is methacryloxypropyl trimethoxy silane, and the mass ratio of A and B are 1：3~3：1, A, B gross mass and ethyl alcohol
Mass ratio be 1：1~1：3.
10. a kind of preparation of the low scratch-resistant automobile interior trim ABS composite material of volatilizing of any one of claim 1 ~ 9 low smell
Method, which is characterized in that steps are as follows：
100 parts of ABS, 0 ~ 30 part of heat-resistant agent, 0 ~ 15 part of toughener, 1 ~ 3.5 part of POSS material are weighed first in high-speed mixer
Mixing 3 ~ 5 minutes, wherein the revolving speed of high-speed mixer is 200 ~ 300 revs/min；Then weigh 0.2 ~ 0.8 part of antioxidant, 0.2 ~
The steady agent of 0.8 part of light, 0.2 ~ 1 part of lubricant, 0.3 ~ 1.0 part of toner are added in high-speed mixer and mix 3 ~ 5 minutes, and high speed is mixed
The revolving speed of conjunction machine is 200 ~ 300 revs/min；0.5 ~ 3.0 part is finally weighed except volatile substance master batch carries out in high-speed mixer
Crawl mixing 3 ~ 5 times；The above-mentioned particle mixed is added twin-screw extrude and carries out melting extrusion, granulation, drying, cold
But, dress packet；The temperature of double screw extruder is followed successively by room temperature, room temperature, 200 DEG C, 210 DEG C, 210 DEG C, 210 from feeding section to head
℃,215℃,215℃,215℃,215℃;Double vacuum designs, and vacuum level requirements≤- 0.07MPa.
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| CN108047633A (en) * | 2017-12-19 | 2018-05-18 | 会通新材料股份有限公司 | A kind of automobile-used low smell ABS alloy material of negative pressure of vacuum and preparation method thereof |
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| CN110982238B (en) * | 2019-12-18 | 2022-01-07 | 万华化学（宁波）有限公司 | Polycarbonate alloy material and preparation method thereof |
| CN111138798A (en) * | 2019-12-30 | 2020-05-12 | 上海金发科技发展有限公司 | PBT/ABS resin composition for automotive interior and preparation method thereof |
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| CN114573944B (en) * | 2022-03-31 | 2023-11-03 | 金发科技股份有限公司 | High-gloss high-surface-hardness ABS composite material and preparation method and application thereof |
| CN119529468A (en) * | 2024-11-27 | 2025-02-28 | 万华化学集团股份有限公司 | A foaming agent-resistant and scratch-resistant acrylonitrile-butadiene-styrene copolymer material and its preparation method and application |
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