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 PDF

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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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composite material
low
abs
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automobile interior
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CN105566834A (en
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杨桂生
俞飞
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Hefei Genius New Materials Co Ltd
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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

A kind of low volatilization scratch-resistant automobile interior trim ABS composite material of low smell and preparation Method
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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