CN102532787B - ABS resin of a kind of high heat resistance high tenacity and preparation method thereof - Google Patents
ABS resin of a kind of high heat resistance high tenacity and preparation method thereof Download PDFInfo
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- CN102532787B CN102532787B CN201010609498.3A CN201010609498A CN102532787B CN 102532787 B CN102532787 B CN 102532787B CN 201010609498 A CN201010609498 A CN 201010609498A CN 102532787 B CN102532787 B CN 102532787B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92561—Time, e.g. start, termination, duration or interruption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92904—Die; Nozzle zone
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses ABS resin of a kind of high heat resistance high tenacity and preparation method thereof.Its component and parts by weight are: ABS resin 30 ~ 90 parts, heat-resistant agent 10 ~ 50 parts, toughner 5 ~ 30 parts, compatilizer 5 ~ 20 parts, anti-oxidant auxiliary agent 0.5 ~ 1 part, processing aid 1 part.The ABS resin of high heat resistance high tenacity of the present invention, prepared by employing twin screw extrusion process, have that flow process is simple, continuously, production efficiency is high, can increase substantially the heat resisting temperature of ABS, and well possess the toughness of general ABS, part can replace PC/ABS alloy material.
Description
Technical field
The invention belongs to technical field of macromolecules, relate to a kind of ABS resin and preparation method thereof.
Background technology
ABS resin is the thermoplastic engineering plastic that a kind of purposes is extremely wide, its shock resistance, thermotolerance, lower temperature resistance, chemical proofing and excellent electrical properties, also there is easy processing, product size is stablized, the features such as surface luster property is good, easy application, painted, surface metallization can also be carried out, plating, welding, hot pressing and the secondary processing such as bonding, be widely used in machinery, automobile, electronic apparatus, instrument, the industrial circles such as weaving and building, but general ABS resin heat resisting temperature is 80 ~ 90 DEG C, in some occasion, its product heat resisting temperature made will not reach requirement, under this just needs us to make to possess the prerequisite of ABS fundamental property to it, improve its resistance toheat, now heat-proof ABS on the market, while the heat resisting temperature improving general ABS, it is obvious that its impelling strength also declines.
Summary of the invention
The object of the present invention is to provide ABS resin of a kind of high heat resistance high tenacity and preparation method thereof.To overcome the above-mentioned defect that currently available products exists, meet the needs of electronic enterprises development to it.
The object of the invention is achieved through the following technical solutions:
A kind of high heat resistance high tenacity ABS resin, comprises following raw material and parts by weight thereof:
ABS resin 30 ~ 90 parts
Heat-resistant agent 10 ~ 50 parts
Toughner 5 ~ 30 parts
Compatilizer 5 ~ 20 parts
Anti-oxidant auxiliary agent 0.5 ~ 1 part
Processing aid 1 part
Described ABS resin comprises one or more in acrylonitrile-butadiene-phenylethene grafted copolymer (ABS), acrylonitrile-ethylenepropylene elastomerics-phenylethene grafted copolymer (AES), acrylonitrile-styrene-acrylic terpolymer (ASA) or MBS graft copolymer (MBS), acrylonitritrile-styrene resin (SAN).Commodity are as the acrylonitrile-butadiene-phenylethene grafted copolymer ABS750 of Jin Hu company of Korea S, the strange beautiful acrylonitrile-styrene-acrylic terpolymer ASA957 in Taiwan, the MBS graft copolymer MBS521 of middle deep pool chemistry, acrylonitritrile-styrene resin SAN80HF etc.
Described heat-resistant agent is one or more of the polymkeric substance of substituted phenylethylene, substituted maleimide amine or maleic anhydride.
Described substituted phenylethylene polymkeric substance is alpha-methyl styrene, 2-methyl styrene, one or more in 2,5-dimethyl styrene or 4-butylstyrene.
Described replacement maleinamide is one or more in N-N-cyclohexylmaleimide, N-phenylmaleimide, N-isopropylmaleimide or N-ethylomaleimide.
Described toughner is one or more in the acrylonitrile-butadiene-phenylethene grafted copolymer of acryl-butadiene-styrol copolymer, methyl or ethylacrylate copolymer, ethyl or butyl propyleneglycol acid ester copolymer or high rubber content.
The acrylonitrile-butadiene-phenylethene grafted copolymer of described high rubber content to be butadiene content be 50 ~ 70% acrylonitrile-butadiene-phenylethene grafted copolymer, particularly butadiene content be 60 ~ 65% to be advisable.
Described compatilizer is maleic anhydride graft acrylonitrile-butadiene-phenylethene grafted copolymer, one or more in maleic anhydride and cinnamic multipolymer or styrene-butadiene-styrene block copolymer etc.
Described antioxidative stabilizer is alkyl substituted phenol, alkyl replaces polyphenol, four (β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, β-(4-hydroxy phenyl-3, 5-di-t-butyl) the positive octadecanol ester of propionic acid, N, N '-1, 6-hexylidene-bis-[3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid amide, thio-2 acid two (18) ester, diphenyl phosphite, triphenyl phosphite, one or more in two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites or hydroxybenzotriazole, the trade mark produced as vapour Bagong department is antioxidant 1010, irgasfos 168, the product of antioxidant 1076.
Described processing aid is lubricant, process and shaping time effectively can improve each component disperses, reduce harmful friction.Comprise the mixture of some soap, fatty acid amide and/or these compounds, specifically comprise solid paraffin, whiteruss, low molecular weight polyethylene, calcium stearate, Zinic stearas, stearic amide, methylene bis stearic amide or N, N-ethylene bis stearic acid amide (EBS) etc.
A preparation method for the ABS resin of above-mentioned high heat resistance high tenacity, comprises step:
(1) ABS resin, toughner, compatilizer, antioxidant and processing aid is taken according to the above ratio;
(2) ABS resin, toughner, compatilizer, antioxidant and the processing aid that take in step (1) are put into high-speed mixer fully to mix, high mixer rotating speed 1 ~ 200 turn/min, mixing time 1 ~ 15min.
(3) with singe screw metering material conveying device, mixed for second step raw material is sent in twin screw extruder, through the shearing action of screw rod according to the speed of coupling forcing machine extruded velocity, sufficient mixing, through extruding, tie rod, cooling, pelletizing, is packaged into finished product.
Described high speed machine mixing process, optimum high mixer rotating speed is 50 ~ 150 turns/min, and optimum high mixer mixing time is 3 ~ 5min;
The processing condition of described forcing machine are: the length-to-diameter ratio of twin screw extruder is 40: 1 ~ 45: 1, screw speed is at 150 ~ 600 revs/min, twin-screw extrusion working temperature interval is, one 170 ~ 190 DEG C, district, two 190 ~ 200 DEG C, districts, three 200 ~ 220 DEG C, districts, four 210 ~ 220 DEG C, districts, head 210 ~ 220 DEG C, stops 1 ~ 2 minute.
The present invention has the following advantages:
The ABS resin of high heat resistance high tenacity of the present invention, adopts twin screw extrusion process preparation, have flow process simple, continuously, the advantage of high, the constant product quality of production efficiency.While maintenance ABS performance, improve heat resisting temperature and the toughness of product, expand the use range of product, may be used for, to heat resisting temperature and the more harsh occasion of toughness reguirements, having broad application prospects.
Embodiment
ABS resin of high heat resistance high tenacity of the present invention and preparation method thereof and physicals see attached list 1 and 2.
Wherein
ABS resin is 750 of Jin Hu company of Korea S;
ASA resin is 957 of Taiwan Qi Mei company;
MBS resin is 521 of middle deep pool chemistry;
SAN resin is the 80HF of LG chemistry
Heat-resistant agent is the MS-NB of NEC chemistry;
Toughner is the EM-500 of LG chemistry;
Toughner is the DP60N of new lake petrochemical industry;
Compatilizer is the SMA218 of Jie Shijie company ABS-G or oil of SPC;
Antioxidative stabilizer is antioxidant 1010 and the irgasfos 168 of CIBA (vapour Bagong department);
Processing aid is domestic EBS (ethylene bis stearamide).
Embodiment 1
A kind of preparation method of ABS resin of high heat resistance high tenacity is:
(1) ABS resin, toughner, compatilizer, antioxidant and processing aid is taken by the proportioning in table 2;
(2) each component in step (1) is put into high-speed mixer, high mixer rotating speed is that 50 turns/min fully mixes 5min;
(3) with metering material conveying device, material mixed in step (2) is sent in twin screw extruder, through the shearing action of screw rod, sufficient mixing, wherein the major diameter of twin screw extruder is 40: 1, and screw speed is at 150 revs/min, twin-screw extrusion working temperature interval is, 180 DEG C, a district, two 200 DEG C, districts, three 215 DEG C, districts, four 215 DEG C, districts, head 220 DEG C, stop 1 ~ 2 minute, through extruding, tie rod, cooling, pelletizing; Be packaged into finished product.
Embodiment 2
(1) ABS resin, toughner, compatilizer, antioxidant and processing aid is taken by the proportioning in table 2;
(2) each component in step (1) is put into high-speed mixer, high mixer rotating speed is that 80 turns/min fully mixes 4min;
(3) with metering material conveying device, material mixed in step (2) is sent in twin screw extruder, through the shearing action of screw rod, sufficient mixing, wherein the major diameter of twin screw extruder is 40: 1, and screw speed is at 300 revs/min, twin-screw extrusion working temperature interval is, 180 DEG C, a district, two 195 DEG C, districts, three 205 DEG C, districts, four 215 DEG C, districts, head 210 DEG C, stop 1 ~ 2 minute, through extruding, tie rod, cooling, pelletizing; Be packaged into finished product.
Embodiment 3
(1) ABS resin, toughner, compatilizer, antioxidant and processing aid is taken by the proportioning in table 2;
(2) each component in step (1) is put into high-speed mixer, high mixer rotating speed is that 120 turns/min fully mixes 4min;
(3) with metering material conveying device, material mixed in step (2) is sent in twin screw extruder, through the shearing action of screw rod, sufficient mixing, wherein the major diameter of twin screw extruder is 42: 1, and screw speed is at 350 revs/min, twin-screw extrusion working temperature interval is, 180 DEG C, a district, two 195 DEG C, districts, three 200 DEG C, districts, four 210 DEG C, districts, head 205 DEG C, stop 1 ~ 2 minute, through extruding, tie rod, cooling, pelletizing; Be packaged into finished product.
Embodiment 4
(1) MBS resin, toughner, compatilizer, antioxidant and processing aid is taken by the proportioning in table 2;
(2) each component in step (1) is put into high-speed mixer, high mixer rotating speed is that 150 turns/min fully mixes 3min;
(3) with metering material conveying device, material mixed in step (2) is sent in twin screw extruder, through the shearing action of screw rod, sufficient mixing, wherein the major diameter of twin screw extruder is 44: 1, and screw speed is at 400 revs/min, twin-screw extrusion working temperature interval is, 180 DEG C, a district, two 195 DEG C, districts, three 205 DEG C, districts, four 215 DEG C, districts, head 210 DEG C, stop 1 ~ 2 minute, through extruding, tie rod, cooling, pelletizing; Be packaged into finished product.
Embodiment 5
(1) ASA resin, toughner, compatilizer, antioxidant and processing aid is taken by the proportioning in table 2;
(2) each component in step (1) is put into high-speed mixer, high mixer rotating speed is that 100 turns/min fully mixes 4min;
(3) with metering material conveying device, material mixed in step (2) is sent in twin screw extruder, through the shearing action of screw rod, sufficient mixing, wherein the major diameter of twin screw extruder is 42: 1, and screw speed is at 350 revs/min, twin-screw extrusion working temperature interval is, 180 DEG C, a district, two 195 DEG C, districts, three 205 DEG C, districts, four 215 DEG C, districts, head 210 DEG C, stop 1 ~ 2 minute, through extruding, tie rod, cooling, pelletizing; Be packaged into finished product.
Embodiment 6
(1) ASA resin, toughner, compatilizer, antioxidant and processing aid is taken by the proportioning in table 2;
(2) each component in step (1) is put into high-speed mixer, high mixer rotating speed is that 120 turns/min fully mixes 3min;
(3) with metering material conveying device, material mixed in step (2) is sent in twin screw extruder, through the shearing action of screw rod, sufficient mixing, wherein the major diameter of twin screw extruder is 40: 1, and screw speed is at 400 revs/min, twin-screw extrusion working temperature interval is, 180 DEG C, a district, two 195 DEG C, districts, three 200 DEG C, districts, four 215 DEG C, districts, head 210 DEG C, stop 1 ~ 2 minute, through extruding, tie rod, cooling, pelletizing; Be packaged into finished product.
Embodiment 7
(1) SAN resin, toughner, compatilizer, antioxidant and processing aid is taken by the proportioning in table 2;
(2) each component in step (1) is put into high-speed mixer, high mixer rotating speed is that 100 turns/min fully mixes 4min;
(3) with metering material conveying device, material mixed in step (2) is sent in twin screw extruder, through the shearing action of screw rod, sufficient mixing, wherein the major diameter of twin screw extruder is 40: 1, and screw speed is at 300 revs/min, twin-screw extrusion working temperature interval is, 180 DEG C, a district, two 195 DEG C, districts, three 205 DEG C, districts, four 215 DEG C, districts, head 210 DEG C, stop 1 ~ 2 minute, through extruding, tie rod, cooling, pelletizing; Be packaged into finished product.
Embodiment 8
(1) SAN resin, toughner, compatilizer, antioxidant and processing aid is taken by the proportioning in table 2;
(2) each component in step (1) is put into high-speed mixer, high mixer rotating speed is that 120 turns/min fully mixes 3min;
(3) with metering material conveying device, material mixed in step (2) is sent in twin screw extruder, through the shearing action of screw rod, sufficient mixing, wherein the major diameter of twin screw extruder is 44: 1, and screw speed is at 380 revs/min, twin-screw extrusion working temperature interval is, 180 DEG C, a district, two 200 DEG C, districts, three 205 DEG C, districts, four 210 DEG C, districts, head 215 DEG C, stop 1 ~ 2 minute, through extruding, tie rod, cooling, pelletizing; Be packaged into finished product.
Mixture prepared by each embodiment is injection molded into the standard batten of test by standard size, the physicals in each embodiment is respectively according to China's national standard test, as shown in table 1.
Table 1 performance test methods
Formula, in table 2, is parts by weight.
The concrete formula that table 2 embodiment is corresponding
Detected result is in table 3.
The properties of sample that table 3 embodiment is corresponding
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (1)
1. a high heat resistance high tenacity ABS resin, is characterized in that: comprise following raw material and parts by weight thereof:
Described toughner is the composite of the acrylonitrile-butadiene-phenylethene grafted copolymer DP60N of alkylmethacrylate polymer EM500 and high rubber content;
The acrylonitrile-butadiene-phenylethene grafted copolymer of described high rubber content to be butadiene content be 50 ~ 70% acrylonitrile-butadiene-phenylethene grafted copolymer DP60N;
Described ABS resin is one or more in acrylonitrile-styrene-acrylic terpolymer ASA957, MBS graft copolymer MBS521 or acrylonitritrile-styrene resin SAN80HF;
Described compatilizer is maleic anhydride graft acrylonitrile-butadiene-phenylethene grafted copolymer;
Described anti-oxidant auxiliary agent is that antioxidant 1010 and irgasfos 168 are composite;
Described heat-resistant agent is substituted maleimide amine; Described substituted maleimide amine is one or more in N-N-cyclohexylmaleimide, N-phenylmaleimide, N-isopropylmaleimide or N-ethylomaleimide;
Described processing aid is lubricant;
Described lubricant is selected from solid paraffin, low molecular weight polyethylene, calcium stearate, Zinic stearas, stearic amide, methylene bis stearic amide or N, N-ethylene bis stearic acid amide;
The preparation method of the ABS resin of described high heat resistance high tenacity comprises step:
(1) ABS resin, heat-resistant agent, toughner, compatilizer, anti-oxidant auxiliary agent and processing aid is taken according to the above ratio;
(2) ABS resin taken in step (1), heat-resistant agent, toughner, compatilizer, anti-oxidant auxiliary agent and processing aid are put into high-speed mixer fully to mix, high mixer rotating speed 1 ~ 200 turn/min, mixing time 1 ~ 15min;
(3) with singe screw metering material conveying device, mixed for second step raw material is sent in twin screw extruder, through the shearing action of screw rod according to the speed of coupling forcing machine extruded velocity, sufficient mixing, through extruding, tie rod, cooling, pelletizing, is packaged into finished product;
The processing condition of described forcing machine are the length-to-diameter ratio of twin screw extruder is 40:1 ~ 45:1, screw speed is at 150 ~ 600 revs/min, twin-screw extrusion working temperature interval is, one 170 ~ 190 DEG C, district, two 190 ~ 200 DEG C, districts, three 200 ~ 220 DEG C, districts, four 210 ~ 220 DEG C, districts, head 210 ~ 220 DEG C, stops 1 ~ 2 minute.
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| CN102532787B true CN102532787B (en) | 2016-04-20 |
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| CN102827453B (en) * | 2012-09-20 | 2014-04-02 | 南华大学 | Dust-proof anti-aging black high-gloss ABS (acrylonitrile-butadiene-styrene) alloy and preparation method thereof |
| CN103013025A (en) * | 2012-11-21 | 2013-04-03 | 合肥杰事杰新材料股份有限公司 | ABS (Acrylonitrile Butadiene Styrene) resin composition available for blow moulding and having excellent comprehensive properties and preparation method thereof |
| CN103044847A (en) * | 2012-12-30 | 2013-04-17 | 苏州旭光聚合物有限公司 | ABS (Acrylonitrile Butadiene Styrene) composite material and preparation method thereof |
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| CN105504652A (en) * | 2015-12-30 | 2016-04-20 | 上海普利特复合材料股份有限公司 | Thermo-oxidative-aging-resistance illumination-aging-resistance ABS/ASA blending material and preparation method thereof |
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| CN111690227A (en) * | 2020-06-16 | 2020-09-22 | 廊坊兴联新材料有限公司 | Heat-resistant ABS material and preparation method thereof |
| CN112063097A (en) * | 2020-09-07 | 2020-12-11 | 海信（山东）冰箱有限公司 | Refrigerator, refrigerator drawer, injection molding material for refrigerator and preparation method of injection molding material |
| CN114316503A (en) * | 2021-12-29 | 2022-04-12 | 浙江普利特新材料有限公司 | High-heat-resistance modified ABS material strongly bonded with PUR and preparation method thereof |
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