CN101724209B - Resin composition and preparation method thereof - Google Patents
Resin composition and preparation method thereof Download PDFInfo
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- CN101724209B CN101724209B CN2008102248735A CN200810224873A CN101724209B CN 101724209 B CN101724209 B CN 101724209B CN 2008102248735 A CN2008102248735 A CN 2008102248735A CN 200810224873 A CN200810224873 A CN 200810224873A CN 101724209 B CN101724209 B CN 101724209B
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Abstract
The invention provides a resin composition, which contains the following constituents in part by weight: 100 parts of polrvinyl chloride resin, 3 to 50 parts of ABS resin and 3 to 30 parts of composite compatilizer which are blended, wherein the composite compatilizer consists of a thermoplastic elastomer graft and chlorinated polyethylene; the thermoplastic elastomer graft is the graft of styrene-butadiene-styrene block copolymer or styrene-pentadiene-styrene block copolymer and a polar monomer; and the mass ratio of the thermoplastic elastomer graft to the chlorinated polyethylene in the composite compatilizer is 10:90 to 60:40. The resin composition has extremely high shock resistance, excellent low temperature resistance, superior stretching resistance, good rigidity and good thermodynamic property. A method for preparing the composition of the invention is simple in process and easy in operation.
Description
Technical field
The present invention relates to a kind of resin combination and preparation method thereof.Specifically, relate to a kind of PVC/acrylonitrile-butadiene-styrene copolymer alloy resin composition and preparation method thereof.
Technical background
Polyvinyl chloride resin is the thermal plasticity high polymer that is formed by polymerization of vinyl choride monomer, belongs to the indefiniteness polymkeric substance, contains the microcrystal of degree of crystallinity 5-10%.The outstanding advantage of PVC is exactly difficult combustion, has excellent abrasive, resistance to chemical corrosion, the low property revealed of gas aqueous vapor.Comprehensive mechanical performance, the goods transparency, electrical insulating property, heat insulation, noise elimination in addition, weakening are also better, are the most superior versatility materials of the ratio of performance to price.Its shortcoming is that thermostability, tensile property, shock resistance are relatively poor.The notched Izod impact strength of pure rigid polyvinyl chloride has only 3～5KJ/m
2, elongation at break is also very low, belongs to hard and fragile material.
ABS resin is made up of the mixture of the free multipolymer (SAN) of the vinyl cyanide (A) of polyhutadiene and the monomeric graft copolymer of vinylbenzene (S) and vinylbenzene-vinyl cyanide.ABS resin promptly has the high gloss and the processing fluidity of polystyrene resin (PS), has good shock resistance again, and the introducing of vinyl cyanide makes material have favorable rigidity and chemical resistance again, so ABS resin has the excellent comprehensive performance.But simultaneously because the existence of the two keys of divinyl makes its ageing-resistant performance relatively poor.
The solubility parameter of polyvinyl chloride resin is 9.5, and the solubility parameter of the SAN among the ABS is 9.3～9.8, and therefore two kinds of resins can form the macroscopical homogeneous phase of a kind of macroscopic view and the alloy material of microcosmic phase-splitting fully.Along with the expansion of the application of development of science and technology and ABS resin, polyvinyl chloride resin, people are no matter be for to the reduction of material cost or for the exploration to modification technology, and are all underway always to the research of PVC/ABS alloy material.U.S. Marbon company had at first realized suitability for industrialized production to the PVC/ABS alloy in 1954.The company of state such as the U.S., Japan, West Europe has successively released various PVC/ABS alloy materials to the sixties in 20th century, and is widely used in instrument, aviation, automobile, light industry, industry such as powers up.Present PVC/ABS alloy mainly shows as material aspect modification rigidity, shock strength, winter hardiness, elongation at break can not be taken into account.The PVC/ABS alloy that for example Guangzhou Synthetic Materials Inst produced, though the modulus in flexure of material up to 2.7GPa, the IZOD of material impacts and to have only 9.5KJ/m
2, elongation at break has only 10%.The graft copolymer that former East Germany Buna company adopts vinyl acetate between to for plastic and ABS also only reaches 49.1 and 9.6KJ/m as its material of compatilizer of PVC/ABS alloy 23 ℃ of IZOD shock strengths with-20 ℃
2Application number is 94117372 the described a kind of health of Chinese invention patent, flame-proof PVC/ABS alloy, and its notched Izod impact strength has only 7-22KJ/m
2, tensile strength also has only 35-45MPa.
Summary of the invention
The inventor finds by great deal of experimental, adopt a kind of special thermoplastic elastomer grafts to mix to make to be used for modified PVC/ABS matrix material, make this matrix material have high shock resistance, excellent resistance to low temperature, excellent stretch-proof performance, favorable rigidity (flexural strength, modulus in flexure), good thermomechanical property with halogenated olefin polymer.This matrix material has remedied the problem that the rigidity of PVC/ABS alloy material, shock strength, winter hardiness, elongation at break can not be taken into account in the prior art.
The purpose of this invention is to provide above-mentioned a kind of PVC/ABS resin combination, it has excellent elongation at break, high/low-temperature impact performance, has rigidity and thermomechanical property preferably simultaneously.
The present invention further provides the preparation method of above-mentioned resin combination.
Resin combination of the present invention includes the following component of blend:
Polyvinyl chloride (PVC) RESINS, 100 weight parts;
ABS resin, 3～50 weight parts;
Compound compatilizer, 3～30 weight parts.
Wherein said polyvinyl chloride (PVC) RESINS can be selected the various types of polyvinyl chloride (PVC) RESINS in the existing production technology, the polyvinyl chloride (PVC) RESINS of preferred degree of polymerization 〉=700 for use.
Wherein said ABS resin is made up of the vinyl cyanide of polyhutadiene and the graft copolymer and the vinylbenzene-acrylonitrile copolymer (SAN) of styrene monomer, san copolymer content in ABS resin is high more, the consistency of ABS resin and polyvinyl chloride (PVC) RESINS is good more, and preferred SAN content is greater than 10% ABS; The ABS resin consumption is 100 weight parts in polyvinyl chloride (PVC) RESINS, is preferably 5～30 weight parts.
Wherein said compound compatilizer is made up of thermoplastic elastomer grafts and chlorinatedpolyethylene (CPE).In compound compatilizer, the weight ratio of thermoplastic elastomer grafts and chlorinatedpolyethylene is 10:90～60:40, is preferably 20:80～50:50, more preferably 30:70～40:60.Compound compatilizer consumption is 100 weight parts in polyvinyl chloride (PVC) RESINS, is preferably 3～15 weight parts, more preferably 3～10 weight parts.
Above-described thermoplastic elastomer grafts is styrene-butadiene-styrene block copolymer (SBS) or vinylbenzene-pentadiene-styrene block copolymer (SIS) and the grafts of polar monomer, and described polar monomer is selected from least a in the pyridine of 2-vinyl arsenic, the arsenic pyridine of 4-vinyl or its isomer.Preferred percentage of grafting is 1～10% thermoplastic elastomer grafts, and more preferably percentage of grafting is 3～5% thermoplastic elastomer grafts.
Described SBS or SIS and polar monomer grafts can adopt the SDS according to the prepared a kind of polar of Chinese patent ZL200410023077.7.SDS is a kind of Tetrablock copolymer, its structure can be represented with SDSP, wherein S represents polystyrene block, D represents polybutadiene block or polyisoprene blocks, P represents polar block, polar block comprises that by pyridine of vinyl arsenic and derivative thereof the polar monomer polymerization of the pyridine of 2-vinyl arsenic, the arsenic pyridine of 4-vinyl or its isomer obtains.
Wherein said thermoplastic elastomer grafts is as main compatilizer, and chlorinatedpolyethylene is as auxiliary compatilizer.Described thermoplastic elastomer grafts and chlorinatedpolyethylene are mixed and made into compound compatilizer.The use of this compound compatilizer can make between PVC in the PVC/ABS alloy and ABS has appropriate consistency, thereby makes the PVC/ABS alloy have high shock resistance, excellent resistance to low temperature, excellent stretch-proof performance, favorable rigidity (flexural strength, modulus in flexure), good thermomechanical property.
Resin combination of the present invention can also comprise acrylic polymer (ACR) modifier general in the existing P VC processing technology, and its consumption is a conventional amount used, is that 100 weight parts can be 1～10 weight part in polyvinyl chloride resin generally.
Resin combination of the present invention can also comprise general stablizer in the existing P VC processing technology, comprises organic tin, calcium zinc class, barium zinc class or lead salts stablizer.Its consumption is a conventional amount used.The consumption of calcium zinc class stablizer can be that 100 weight parts are counted 5～15 weight parts with polyvinyl chloride resin preferably in the present invention.Resin combination of the present invention in addition can comprise thermo-stabilizer and photostabilizer general in the existing ABS processing technology, and its consumption is a conventional amount used.
In addition, can also include common used lubricant (as G60, oxidic polyethylene, polyethylene wax etc.), mineral filler, tinting material and other processing aid etc. of PVC processing in the prior art in the resin combination of the present invention.Its consumption is conventional amount used, or adjusts according to practical requirements.
The preparation method of resin combination of the present invention comprises and will include the step of the component of described polyvinyl chloride (PVC) RESINS, ABS resin, compound compatilizer by melt blending, and makes resin combination.
In preparation process, the blending temperature of material is the common processing temperature of polyvinyl chloride, should select not only guaranteeing the complete fusion of polyvinyl chloride but also can not make in the scope of its decomposition, generally at 165～220 ℃, is preferably 180～220 ℃.In addition, according to the processing needs, can in the blend material, add conventional auxiliary agent such as lubricant (oxidic polyethylene, polyethylene wax, G60 etc.), mineral filler, tinting material and other processing aid etc. of polyvinyl chloride processing in right amount.Its consumption is conventional amount used, or adjusts according to practical requirements.In order to guarantee ABS resin stablizing in processing and in using, need to add ABS thermo-stabilizer and photostabilizer simultaneously, its consumption is a conventional amount used.
Employed melt blending equipment can be disclosed mill, Banbury mixer, single screw extrusion machine or twin screw extruder etc. in the rubber plastic blend technology among this preparation method.
PVC/ABS alloy composite of the present invention is mainly used in industries such as automobile, electronic apparatus.This material has high shock resistance, excellent resistance to low temperature, excellent stretch-proof performance, favorable rigidity (flexural strength, modulus in flexure), good thermomechanical property.Preparation method's technology of the present composition is simple, easy handling, is suitable for industrial applications.
Embodiment
The invention will be further described below in conjunction with specific embodiment.Scope of the present invention is not subjected to the restriction of these embodiment, and scope of the present invention proposes in claims.
Embodiment 1～3:
With SDS (Ba Ling petrochemical complex limited liability company, percentage of grafting is 3.0%, the grafted polar monomer is the pyridine of 2-vinyl arsenic, the arsenic pyridine of 4-vinyl and mixture of isomers thereof) even with chlorinatedpolyethylene CPE (homemade) by weight the mixed that is 38:62, make compound compatible phase.
With polyvinyl chloride resin (group of Beijing Chemical Plant Two, the trade mark is SG-5, five types, the polymerization degree is 800), calcium zinc stabilizer (Dalian Kai Misen company), lubricant (homemade) be warming up to 100 ℃ under high-speed stirring, put into cold mixing and be cooled to room temperature, with ABS resin (Taiwan Qi Mei company, the trade mark is 777), compound compatilizer stirs.Specifically forming in polyvinyl chloride (PVC) RESINS is that 100 parts by weight see Table 1.Adopt two roller mill mixings, melting temperature is 180-200 ℃.Through compression molding instrument compressing tablet, the compressing tablet temperature is 190-210 ℃.Be processed into test bars through milling machine, carry out the test of various mechanical properties, its result is as shown in table 1.
Comparative Examples 1:
Except that not adding compound compatilizer, all the other compositions and preparation condition are all identical with embodiment 1.Concrete prescription and batten test result are as shown in table 1.
Comparative Examples 2:
Removing and changing compound compatilizer into percentage of grafting is 3% SDS, and all the other compositions and preparation condition are all identical with embodiment 1.Concrete prescription and batten test result are as shown in table 1.
Comparative Examples 3:
Remove and change compound compatilizer into chlorinatedpolyethylene (CPE), all the other compositions and preparation condition are all identical with embodiment 1.Concrete prescription and batten test result are as shown in table 1.
Table 1 set of dispense is the mechanical property result of material when
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Testing standard | |
| PVC | 100 | 100 | 100 | 100 | 100 | 100 | ——— |
| ABS | 15 | 15 | 10 | 15 | 15 | 15 | ——— |
| Calcium zinc stabilizer | 5 | 5 | 5 | 5 | 5 | 5 | ——— |
| ACR | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | ——— |
| Compound compatilizer | 5 | 10 | 10 | 0 | 0 | 0 | ——— |
| Polarity grafting SDS | 0 | 0 | 0 | 0 | 10 | 0 | ——— |
| CPE | 0 | 0 | 0 | 0 | 0 | 10 | ——— |
| Oxidation inhibitor | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| Tensile strength (MPa) | 30.2 | 34.3 | 38 | 42.3 | 34.6 | 40.8 | GB/T1040-1992 |
| Elongation at break (%) | 141 | 182 | 136 | 15 | 53 | 38 | GB/T1040-1992 |
| Simply supported beam notched Izod impact strength (23 ℃) (KJ/m 2) | 119 | 141 | 133 | 20.4 | 92.4 | 82.5 | GB/T1043-1993 |
| Simply supported beam notched Izod impact strength (20 ℃) (KJ/m 2) | 44.6 | 75.2 | 21.9 | 5.0 | 18.6 | 13.0 | GB/T1043-1993 |
| Flexural strength (MPa) | 51.4 | 49.0 | 52.8 | 59.4 | 48.8 | 58.2 | GB/T9341-2000 |
| The bending amount of touching (GPa) | 1.97 | 1.86 | 2.05 | 2.51 | 1.76 | 2.15 | GB/T9341-2000 |
| Vicat softening point (℃) | 89.0 | 88.3 | 88.5 | 90 | 81.0 | 80.4 | GB/T1633-2000 |
The PVC/ABS alloy composite of the embodiment of the invention and comparative example 1,2,3, in the PVC/ABS alloy composite compare, visible PVC/ABS alloy composite of the present invention has high shock resistance, excellent resistance to low temperature, excellent stretch-proof performance, favorable rigidity (flexural strength, modulus in flexure), good thermomechanical property.
Claims (10)
1. resin combination includes the following component of blend:
Polyvinyl chloride (PVC) RESINS, 100 weight parts;
ABS resin, 3～50 weight parts;
Compound compatilizer, 3～30 weight parts;
Wherein said ABS resin is made up of the vinyl cyanide of polyhutadiene and the graft copolymer and the vinylbenzene-acrylonitrile copolymer of styrene monomer;
Wherein said compound compatilizer is made up of thermoplastic elastomer grafts and chlorinatedpolyethylene, described thermoplastic elastomer grafts is the grafts of styrene-butadiene-styrene block copolymer or vinylbenzene-pentadiene-styrene block copolymer and polar monomer, and described polar monomer is at least a in the pyridine of 2-vinyl arsenic, the arsenic pyridine of 4-vinyl or its isomer; Wherein in compound compatilizer, the weight ratio of thermoplastic elastomer grafts and chlorinatedpolyethylene is 10:90～60:40.
2. resin combination according to claim 1 is characterized in that in described compound compatilizer, the weight ratio of thermoplastic elastomer grafts and chlorinatedpolyethylene is 20:80～50:50.
3. resin combination according to claim 2 is characterized in that in described compound compatilizer, the weight ratio of thermoplastic elastomer grafts and chlorinatedpolyethylene is 30:70～40:60.
4. resin combination according to claim 1 is characterized in that comprising the following component of blend:
Polyvinyl chloride (PVC) RESINS, 100 weight parts;
ABS resin, 5～30 weight parts;
Compound compatilizer, 3～15 weight parts.
5. resin combination according to claim 4 is characterized in that in polyvinyl chloride (PVC) RESINS 100 weight parts, described compound compatilizer is 3～10 weight parts.
6. resin combination according to claim 1, the percentage of grafting of described thermoplastic elastomer grafts are 1～10%.
7. resin combination according to claim 6, the percentage of grafting of described thermoplastic elastomer grafts are 3～5%.
8. resin combination according to claim 1, wherein said polyvinyl chloride (PVC) RESINS are the polyvinyl chloride of the polymerization degree 〉=700.
9. resin combination according to claim 1, the weight percent of wherein said vinylbenzene-acrylonitrile copolymer in ABS resin is greater than 10%wt.
10. as the preparation method of each described resin combination in the claim 1-9, comprising: will include polyvinyl chloride (PVC) RESINS, ABS resin and the compound compatilizer be made up of described thermoplastic elastomer grafts and chlorinatedpolyethylene compares melt blending by described set of dispense.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102492256A (en) * | 2011-12-12 | 2012-06-13 | 湖北众联塑业有限公司 | Processing modifier for acrylonitrile butadiene styrene (ABS)/polyvinyl chloride (PVC) alloy waste board material and use method thereof |
| CN104017323A (en) * | 2014-03-31 | 2014-09-03 | 浙江方明塑胶管道有限公司 | ABS/PVC blend alloy and preparation method thereof |
| CN104277355A (en) * | 2014-08-15 | 2015-01-14 | 辽宁工程技术大学 | Flame-retardant toughening HPVC (polyvinyl with high degree of polymerization)/ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
| CN107987421A (en) * | 2017-12-11 | 2018-05-04 | 浙江金华天开电子材料有限公司 | A kind of medical anti-iodine PVC roll material and preparation method thereof |
| CN108586983A (en) * | 2018-05-07 | 2018-09-28 | 南京思甲宁新材料科技有限公司 | The dispensing and make of plastics hardware |
| CN111004457B (en) * | 2019-12-19 | 2021-11-26 | 广州雷诺丽特塑料有限公司 | Solvent-resistant and scratch-resistant PVC (polyvinyl chloride) film and preparation method thereof |
| CN111100413B (en) * | 2019-12-27 | 2022-05-06 | 东莞市正新包装制品有限公司 | PE shrink film |
| CN113462115B (en) * | 2021-06-29 | 2022-07-15 | 上海艾镇新材料有限公司 | High-weather-resistance spraying-free ABS (acrylonitrile butadiene styrene) composite material and preparation method thereof |
| CN114395090A (en) * | 2022-02-18 | 2022-04-26 | 海信（山东）冰箱有限公司 | SBS-g-PS material, preparation method thereof and application thereof in low-temperature toughening modification of PP |
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| EP0704482A1 (en) * | 1994-10-01 | 1996-04-03 | Alkor Gmbh Kunststoffe | Plastic film for furniture or their parts and process for their application |
| CN1191232A (en) * | 1997-02-17 | 1998-08-26 | 上海氯碱化工股份有限公司 | PVC/ABS alloy material having low content of ABS |
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- 2008-10-24 CN CN2008102248735A patent/CN101724209B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0704482A1 (en) * | 1994-10-01 | 1996-04-03 | Alkor Gmbh Kunststoffe | Plastic film for furniture or their parts and process for their application |
| CN1191232A (en) * | 1997-02-17 | 1998-08-26 | 上海氯碱化工股份有限公司 | PVC/ABS alloy material having low content of ABS |
Non-Patent Citations (1)
| Title |
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| 吴波震等.PVC/ABS合金性能研究.《塑料科技》.2007,第35卷(第8期),70-73. * |
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