CN101649094A - Flame retarding ABS/PVC/PETG alloy with low cost and high performance and preparation method thereof - Google Patents
Flame retarding ABS/PVC/PETG alloy with low cost and high performance and preparation method thereof Download PDFInfo
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- CN101649094A CN101649094A CN200910164266A CN200910164266A CN101649094A CN 101649094 A CN101649094 A CN 101649094A CN 200910164266 A CN200910164266 A CN 200910164266A CN 200910164266 A CN200910164266 A CN 200910164266A CN 101649094 A CN101649094 A CN 101649094A
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Abstract
The invention discloses a flame retarding ABS/PVC/PETG alloy with low cost and high performance, prepared by mixing 25 to 50 portions of ABS resin, 30 to 70 portions of PVC resin, 5 to 25 portions ofwaste PETG resin, 2 to 5 portions of compatilizer, 1.5 to 4 portions of thermal stabilizer and 0.5 to 2.5 portions of stearic acid lubricant. The invention also discloses a preparation method of the alloy. The PETG with low melting temperature and good fluidity is used in the alloy, thereby improving the processing performance and the flame retarding performance of ABS/PVC alloy, enhancing the extension strength of the alloy, reducing the cost and effectively solving the problem of environmental pollution caused by waste plastics. The alloy can be widely applied to the fields of electronic electric apparatuses, automobiles and the like and has obvious economic benefit and social benefit.
Description
Technical field
The invention belongs to ABS/PVC alloy and preparing technical field thereof, be specifically related to a kind of low-cost and high-performance flame-proof ABS/PVC/PETG Alloy And Preparation Method.
Background technology
Though ABS resin is a kind of have excellent normal temperature and low temperature impact properties and thermotolerance, wear resistance, all good engineering plastics of processing characteristics, be widely used in key areas such as office appliance, electronic apparatus, automobile, yet because its weathering resistance and chemical resistance are poor, inflammable, shortcoming such as cost an arm and a leg has also limited more using in the extensive fields of it.
Though polyvinyl chloride resin has obtained using widely with excellent chemical stability, electrical insulating property and self-extinguishing, but because of its structural defective, under the effect of heat and oxygen, take off HCl easily, and taking off HCl to further degraded, the HCl that takes off has katalysis, thereby caused problems such as PVC goods poor heat stability, notch shock sensitivity, processing fluidity difference, it is used as hard product be subjected to very big restriction.
ABS and PVC are carried out the alloy that blending and modifying obtains not only have the good thermal characteristics of ABS, processing fluidity, the favorable mechanical performance and the flame retardant properties that can also have PVC, and the surface gloss of alloy, tint permanence and can be ornamental etc. all good in appearance, than pure PVC.
Some researchs have been done about the ABS/PVC alloy system both at home and abroad.People generally believe because the solubility parameter of the matrix styrene-acrylonitrile copolymer SAN of ABS and PVC is very close so ABS and PVC are the part compatible polymers, to have the potential quality that reaches fine composite performance.Acrylonitrile content among the SAN has a significant impact (Doo Whan Jin, Kyung Ho Shon, Byung Kyu Kim to consistency and the mechanical property of ABS and PVC, Han Mo Jeong, Compatibility Enhancement of ABS/PVC Blends, J.Appl.Polym.Sci., 1998; 70:705-709), use the ABS of acrylonitrile content 25% of SAN and the alloy of PVC blend, better with respect to the consistency of the ABS of acrylonitrile content 35% and PVC, interfacial thickness is thicker, and impact property is doubled.Research is also found, the component of ABS and PVC is compared to the influence of impact property and the deformation mechanism transformation of system also has relation (C.Zhou, X.Y.Bao, Z.Y.Tan, S.L.Sun, Y.H.Ao, H.D.Yang, H.X.Zhang, Transitionfrom Crazing to Shear Deformation in ABS/PVC Blends, J Polym Sci:Part B, 2006; 44:687-695), generally be increase along with PVC content, the shock strength of alloy increases thereupon.Investigators think that this is that the deformation mechanism of material changes shear yielding into by crazingization, thereby the shock strength of alloy improves thereupon owing to the increase along with PVC content.
The ABS/PVC alloy is in U.S. Marbon company in 1954 suitability for industrialized production at first, relevant companies such as the U.S., Japan, West Europe also successively release various ABS/PVC alloys, the most famous with U.S. Borg Warner company, hard, semi-rigid wherein arranged, extrude, injection and grade such as fire-retardant, be mainly used in industrial sectors such as instrument, aviation, automobile, light industry, household electrical appliances, especially aspect automobile and electronic apparatus, use cheap fire-retardant ABS/PVC alloy replacing ABS to become trend.But still there is aspect not fully up to expectations in the ABS/PVC alloy: PVC content reaches 50% mobile variation when above in (1) alloy, thereby has reduced the processing characteristics of alloy; (2) flame retardant properties because of alloy is limited by PVC content, after being lower than 50%, PVC content can't reach UL-94 standard V-0 rank, can lost heat stability and improve PVC content, it is fire-retardant good to make it both to have required in manufacturing, require the high goods aspect of thermal characteristics to have difficulties again, limited it and used widely.
Summary of the invention
Primary and foremost purpose of the present invention is the problem that exists at prior art, and a kind of low-cost and high-performance flame-proof ABS/PVC/PETG alloy is provided.
Secondary objective of the present invention provides a kind of method of preparation above-mentioned low-cost and high-performance flame-proof ABS/PVC/PETG alloy.
Low-cost and high-performance flame-proof ABS provided by the invention/PVC/PETG alloy, this alloy are to be formed by following component blend, and each components contents is weight part:
25～50 parts of ABS resin
30～70 parts of polyvinyl chloride resins
5～25 parts of waste PET G resins
2～5 parts of expanding materials
1.5～4 parts of thermo-stabilizers
0.5～2.5 part of stearic acid lubricant
Contained expanding material is at least a in chlorinatedpolyethylene and the acrylonitritrile-styrene resin in the above alloy.
Contained thermo-stabilizer is at least a in sulfuric acid methyl tin, Bis(lauroyloxy)dioctyltin, lead sulfate tribasic, dibasic lead phosphite and the dibasic lead stearate in the above alloy.
Contained waste PET G resin is meant 1,4 waste and old cyclohexanedimethanol modification polyethylene terephthalate in the above alloy.
The method of the above-mentioned low-cost and high-performance flame-proof ABS of preparation provided by the invention/PVC/PETG alloy, the processing step and the condition of this method are as follows:
(1) 25～50 parts of PVC powders, 1.5～4 parts of thermo-stabilizers and 0.5～2.5 part of stearic acid lubricant are put into high-speed mixer, under 40～120 ℃ of temperature, mixed 5～10 minutes;
(2) above-mentioned compound and 25～50 parts of ABS resin, 5～25 parts of waste and old material PETG resins and 2～5 parts of expanding materials are put into cold mixer, under 25～40 ℃ of temperature, mixed 5～10 minutes;
(3) above-mentioned compound is put into twin screw extruder, under 160～180 ℃ of melt temperatures, carries out extruding pelletization and get final product,
The add-on of above material is weight part.
Used expanding material is at least a in chlorinatedpolyethylene and the acrylonitritrile-styrene resin in the aforesaid method.
Used thermo-stabilizer is at least a in sulfuric acid methyl tin, Bis(lauroyloxy)dioctyltin, lead sulfate tribasic, dibasic lead phosphite and the dibasic lead stearate in the aforesaid method.
Used waste PET G resin is meant 1,4 waste and old cyclohexanedimethanol modification polyethylene terephthalate in the above method.
Compared with the prior art the present invention has the following advantages:
1, since component of the present invention in adopted melt temperature very low, flowability is PETG preferably, even if thereby in the alloy PVC content reach more than 50%, also can further improve the processing characteristics of ABS/PVC, see Table 1.
2, because PETG and PVC that the present invention uses have the cooperative flame retardant effect, thus the PETG that adds, can partly substitute PVC and keep excellent flame-retardant, see Table 1.
3, since among the present invention the PETG that uses have than high tensile, thereby it does not obviously reduce the shock strength of alloy in the tensile strength that improves alloy, see Table 1.
4, because the selected raw material PETG of alloy provided by the invention is a waste PET G reclaimed materials, thereby both can reduce product cost significantly, have considerable economic, also can solve the problem of environmental pollution that waste or used plastics brings effectively.
Embodiment
Provide embodiment below so that the present invention will be described in more detail; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field must belong to protection scope of the present invention according to the invention described above content to some nonessential improvement and the adjustment that the present invention did.
In addition, also what deserves to be explained is, below in each embodiment and the Comparative Examples the used umber of material be weight part; The Izod notched Izod impact strength of products therefrom is tested according to GB/T 1834-1996, tensile strength is then tested according to the GB/T1040-92 standard, the combustionproperty test is tested according to the UL94 standard, melt index determination is tested according to ASTM D1238-82 standard, and concrete data see Table 1.
Embodiment 1
Put into high-speed mixer earlier with 50 parts of polyvinyl chloride resin powders, by weight 1: 1 composite lead sulfate tribasic and 4 parts and 2.5 parts stearic acid lubricant of dibasic lead phosphite of ratio, under 100 ℃ of temperature, mixed 5 minutes; Above-mentioned compound and 45 parts of ABS resin, 5 parts of waste and old material PETG resins and 3 parts of chlorinatedpolyethylenees are put into cold mixer, under 30 ℃ of temperature, mixed 10 minutes; Above-mentioned compound is put into twin screw extruder, under 160～180 ℃ of melt temperatures (160 ℃ of twin screw extruder one district's temperature, 170 ℃ of two district's temperature, 180 ℃ of three district's temperature, 180 ℃ of four district's temperature), carry out obtaining behind the extruding pelletization screw speed 30rpm.
Embodiment 2
60 parts of polyvinyl chloride resin powders, 3.5 parts of lead sulfate tribasics and 1.5 parts of stearic acid lubricants are put into high-speed mixer earlier, under 80 ℃ of temperature, mixed 8 minutes; Above-mentioned compound and 25 parts of ABS resin, 15 parts of waste and old material PETG resins and each 1.5 parts chlorinatedpolyethylene and acrylonitritrile-styrene resin are put into cold mixer, under 40 ℃ of temperature, mixed 5 minutes; Above-mentioned compound is put into twin screw extruder, under 160～180 ℃ of melt temperatures (respectively distinguishing temperature), carry out obtaining behind the extruding pelletization screw speed 30rpm with embodiment 1.
Embodiment 3
Put into high-speed mixer earlier with 70 parts of polyvinyl chloride resin powders, by weight 1: 1 composite dibasic lead stearate and 3 parts and 1 part stearic acid lubricant of sulfuric acid methyl tin of ratio, under 100 ℃ of temperature, mixed 5 minutes; Above-mentioned compound and 25 parts of ABS resin, 5 parts of waste and old material PETG resins and each 2.5 parts chlorinatedpolyethylene and acrylonitritrile-styrene resin are put into cold mixer, under 25 ℃ of temperature, mixed 8 minutes; Above-mentioned compound is put into twin screw extruder, under 160～180 ℃ of melt temperatures (respectively distinguishing temperature), carry out obtaining behind the extruding pelletization screw speed 30rpm with embodiment 1.
Embodiment 4
50 parts of polyvinyl chloride resin powders, 4 parts of sulfuric acid methyl tin and 2 parts of stearic acid lubricants are put into high-speed mixer earlier, under 120 ℃ of temperature, mixed 5 minutes; Above-mentioned compound and 40 parts of ABS resin, 10 parts of waste and old material PETG resins and 2.5 parts of acrylonitritrile-styrene resins are put into cold mixer, under 33 ℃ of temperature, mixed 8 minutes; Above-mentioned compound is put into twin screw extruder, under 160～180 ℃ of melt temperatures (respectively distinguishing temperature), carry out obtaining behind the extruding pelletization screw speed 30rpm with embodiment 1.
Embodiment 5
45 parts of polyvinyl chloride resin powders, 3.5 parts of Bis(lauroyloxy)dioctyltins and 1.5 parts of stearic acid lubricants are put into high-speed mixer earlier, under 80 ℃ of temperature, mixed 10 minutes; Above-mentioned compound and 30 parts of ABS resin, 25 parts of waste and old material PETG resins and each 1.5 parts chlorinatedpolyethylene and acrylonitritrile-styrene resin are put into cold mixer, under 40 ℃ of temperature, mixed 7 minutes; Above-mentioned compound is put into twin screw extruder, under 160～180 ℃ of melt temperatures (respectively distinguishing temperature), carry out obtaining behind the extruding pelletization screw speed 30rpm with embodiment 1.
Embodiment 6
40 parts of polyvinyl chloride resin powders, 2 parts of dibasic lead phosphites and 1 part of stearic acid lubricant are put into high-speed mixer earlier, under 60 ℃ of temperature, mixed 8 minutes; Above-mentioned compound and 50 parts of ABS resin, 10 parts of waste and old material PETG resins and 2 parts of acrylonitritrile-styrene resins are put into cold mixer, under 35 ℃ of temperature, mixed 5 minutes; Above-mentioned compound is put into twin screw extruder, under 160～180 ℃ of melt temperatures (respectively distinguishing temperature), carry out obtaining behind the extruding pelletization screw speed 30rpm with embodiment 1.
Embodiment 7
30 parts of polyvinyl chloride resin powders, 2 parts of dibasic lead stearates and 0.5 part of stearic acid lubricant are put into high-speed mixer earlier, under 40 ℃ of temperature, mixed 10 minutes; Above-mentioned compound and 50 parts of ABS resin, 20 parts of waste and old material PETG resins and 5 parts of chlorinated polyethylene alkene copolymers are put into cold mixer, under 25 ℃ of temperature, mixed 8 minutes; Above-mentioned compound is put into twin screw extruder, under 160～180 ℃ of melt temperatures (respectively distinguishing temperature), carry out obtaining behind the extruding pelletization screw speed 30rpm with embodiment 1.
Comparative Examples 1
50 parts of polyvinyl chloride resin powders, 4 parts of lead sulfate tribasics and 2 parts of stearic acid lubricants are put into high-speed mixer earlier, under 100 ℃ of temperature, mixed 5 minutes; Above-mentioned compound and 50 parts of ABS resin are put into cold mixer, under 30 ℃ of temperature, mixed 10 minutes; Above-mentioned compound is put into twin screw extruder, under 160～180 ℃ of melt temperatures (respectively distinguishing temperature), carry out obtaining behind the extruding pelletization screw speed 30rpm with embodiment 1.
Comparative Examples 2
40 parts of polyvinyl chloride resin powders, 4 parts of sulfuric acid methyl tin and 1.5 parts of stearic acid lubricants are put into high-speed mixer earlier, under 100 ℃ of temperature, mixed 5 minutes; Above-mentioned compound and 60 parts of ABS resin are put into cold mixer, under 30 ℃ of temperature, mixed 10 minutes; Above-mentioned compound is put into twin screw extruder, under 160～180 ℃ of melt temperatures (respectively distinguishing temperature), carry out obtaining behind the extruding pelletization screw speed 30rpm with embodiment 1.
Table 1
Claims (6)
1, a kind of low-cost and high-performance flame-proof ABS/PVC/PETG alloy, this alloy is to be formed by following component blend, each components contents is weight part:
25～50 parts of ABS resin
30～70 parts of polyvinyl chloride resins
5～25 parts of waste PET G resins
2～5 parts of expanding materials
1.5～4 parts of thermo-stabilizers
0.5～2.5 part of stearic acid lubricant
2, low-cost and high-performance flame-proof ABS according to claim 1/PVC/PETG alloy is characterized in that expanding material contained in this alloy is at least a in chlorinatedpolyethylene and the acrylonitritrile-styrene resin.
3, low-cost and high-performance flame-proof ABS according to claim 1 and 2/PVC/PETG alloy is characterized in that thermo-stabilizer contained in this alloy is at least a in sulfuric acid methyl tin, Bis(lauroyloxy)dioctyltin, lead sulfate tribasic, dibasic lead phosphite and the dibasic lead stearate.
4, a kind of method for preparing each described low-cost and high-performance flame-proof ABS/PVC/PETG alloy of claim 1～3, the processing step and the condition of this method are as follows:
(1) 25～50 parts of polyvinyl chloride resin powders, 1.5～4 parts of thermo-stabilizers and 0.5～2.5 part of stearic acid lubricant are put into high-speed mixer, under 40～120 ℃ of temperature, mixed 5～10 minutes;
(2) above-mentioned compound and 25～50 parts of ABS resin, 5～25 parts of waste PET G resins and 2～5 parts of expanding materials are put into cold mixer, under 25～40 ℃ of temperature, mixed 5～10 minutes;
(3) above-mentioned compound is put into twin screw extruder, under 160～180 ℃ of melt temperatures, carries out extruding pelletization and get final product,
The add-on of above material is weight part.
5, the method for preparing low-cost and high-performance flame-proof ABS/PVC/PETG alloy according to claim 4 is characterized in that the used expanding material of this method is at least a in chlorinatedpolyethylene and the acrylonitritrile-styrene resin.
6,, it is characterized in that the used thermo-stabilizer of this method is at least a in sulfuric acid methyl tin, Bis(lauroyloxy)dioctyltin, lead sulfate tribasic, dibasic lead phosphite and the dibasic lead stearate according to claim 4 or the 5 described methods that prepare low-cost and high-performance flame-proof ABS/PVC/PETG alloy.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101831136A (en) * | 2010-04-21 | 2010-09-15 | 深圳市科聚新材料有限公司 | High-strength high-toughness flame-resistant ABS (Acrylonitrile Butadiene Styrene) composite material and preparation method thereof |
| CN102040786A (en) * | 2010-12-30 | 2011-05-04 | 佛山市顺德区圆融新材料有限公司 | Antiflaming PVC (poly vinyl chloride)/ABS (acrylonitrile butadiene styrene) alloy material and preparation method thereof |
| CN102108181A (en) * | 2010-12-30 | 2011-06-29 | 金发科技股份有限公司 | Thermoplastic alloy and preparation method thereof |
| CN102786769A (en) * | 2012-08-31 | 2012-11-21 | 上海瀚氏模具成型有限公司 | Aging-resistant ABS (acrylonitrile-butadiene-styrene) /PVC (polyvinyl chloride) /PETG (polyethylene terephthalate glycol) alloy and preparation method thereof |
| CN102786770A (en) * | 2012-08-31 | 2012-11-21 | 上海瀚氏模具成型有限公司 | Scratch-resistant ABS (acrylonitrile-butadiene-styrene) /PVC (polyvinyl chloride) /PETG (polyethylene terephthalate glycol) alloy and preparation method thereof |
| CN102807727A (en) * | 2012-08-31 | 2012-12-05 | 上海瀚氏模具成型有限公司 | Antistatic ABS (acrylonitrile butadiene styrene)/PVC (polyvinyl chloride)/PETG (polyethylene terephthalate glycol) alloy and preparation method thereof |
| CN102807728A (en) * | 2012-08-31 | 2012-12-05 | 上海瀚氏模具成型有限公司 | Flame-retardant ABS/PVC/PETG alloy and manufacturing method thereof |
| CN103525000A (en) * | 2013-10-16 | 2014-01-22 | 上海瀚氏模具成型有限公司 | Low-odor ABS (acrylonitrile butadiene styrene)/PVC (polyvinyl chloride)/PETG (polyethylene terephthalate glycol) alloy material and preparation method thereof |
| CN103627133A (en) * | 2013-11-12 | 2014-03-12 | 上海瀚氏模具成型有限公司 | Flame retardant ABS/PVC/PETG (Acrylonitrile Butadiene Styrene/Polyvinyl Chloride/Polyethylene Terephthalate Glycol) alloy plastic and preparation method thereof |
| CN104231501A (en) * | 2014-09-30 | 2014-12-24 | 句容金猴机械研究所有限公司 | Synthesized resin tile and preparing method thereof |
| CN105968630A (en) * | 2016-05-18 | 2016-09-28 | 深圳市志海实业股份有限公司 | High-temperature plastic alloy material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101831136A (en) * | 2010-04-21 | 2010-09-15 | 深圳市科聚新材料有限公司 | High-strength high-toughness flame-resistant ABS (Acrylonitrile Butadiene Styrene) composite material and preparation method thereof |
| CN102040786A (en) * | 2010-12-30 | 2011-05-04 | 佛山市顺德区圆融新材料有限公司 | Antiflaming PVC (poly vinyl chloride)/ABS (acrylonitrile butadiene styrene) alloy material and preparation method thereof |
| CN102108181A (en) * | 2010-12-30 | 2011-06-29 | 金发科技股份有限公司 | Thermoplastic alloy and preparation method thereof |
| CN102108181B (en) * | 2010-12-30 | 2013-02-20 | 金发科技股份有限公司 | Thermoplastic alloy and preparation method thereof |
| CN102807728A (en) * | 2012-08-31 | 2012-12-05 | 上海瀚氏模具成型有限公司 | Flame-retardant ABS/PVC/PETG alloy and manufacturing method thereof |
| CN102807727A (en) * | 2012-08-31 | 2012-12-05 | 上海瀚氏模具成型有限公司 | Antistatic ABS (acrylonitrile butadiene styrene)/PVC (polyvinyl chloride)/PETG (polyethylene terephthalate glycol) alloy and preparation method thereof |
| CN102786770A (en) * | 2012-08-31 | 2012-11-21 | 上海瀚氏模具成型有限公司 | Scratch-resistant ABS (acrylonitrile-butadiene-styrene) /PVC (polyvinyl chloride) /PETG (polyethylene terephthalate glycol) alloy and preparation method thereof |
| CN102786769A (en) * | 2012-08-31 | 2012-11-21 | 上海瀚氏模具成型有限公司 | Aging-resistant ABS (acrylonitrile-butadiene-styrene) /PVC (polyvinyl chloride) /PETG (polyethylene terephthalate glycol) alloy and preparation method thereof |
| CN103525000A (en) * | 2013-10-16 | 2014-01-22 | 上海瀚氏模具成型有限公司 | Low-odor ABS (acrylonitrile butadiene styrene)/PVC (polyvinyl chloride)/PETG (polyethylene terephthalate glycol) alloy material and preparation method thereof |
| CN103525000B (en) * | 2013-10-16 | 2015-10-14 | 上海瀚氏模具成型有限公司 | A kind of low smell ABS/PVC/PETG alloy material and preparation method thereof |
| CN103627133A (en) * | 2013-11-12 | 2014-03-12 | 上海瀚氏模具成型有限公司 | Flame retardant ABS/PVC/PETG (Acrylonitrile Butadiene Styrene/Polyvinyl Chloride/Polyethylene Terephthalate Glycol) alloy plastic and preparation method thereof |
| CN104231501A (en) * | 2014-09-30 | 2014-12-24 | 句容金猴机械研究所有限公司 | Synthesized resin tile and preparing method thereof |
| CN105968630A (en) * | 2016-05-18 | 2016-09-28 | 深圳市志海实业股份有限公司 | High-temperature plastic alloy material |
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Assignee: HANGZHOU DAHUA PLASTICS INDUSTRY CO., LTD. Assignor: Sichuan University Contract record no.: 2011330000804 Denomination of invention: Flame retardant ABS/PVC/PETG alloy and preparation method thereof Granted publication date: 20110330 License type: Exclusive License Open date: 20100217 Record date: 20110624 |
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