CN103044818B - PVC/ASA (polyvinyl chloride/ acrylic-styrene-acrylonitrile copolymer) alloy material and preparation method thereof - Google Patents
PVC/ASA (polyvinyl chloride/ acrylic-styrene-acrylonitrile copolymer) alloy material and preparation method thereof Download PDFInfo
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 110
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 109
- 239000000956 alloy Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920002877 acrylic styrene acrylonitrile Polymers 0.000 title abstract 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 34
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 16
- 239000004902 Softening Agent Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- -1 [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester Chemical class 0.000 claims description 9
- 239000004615 ingredient Substances 0.000 claims description 8
- 239000004801 Chlorinated PVC Substances 0.000 claims description 7
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 7
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 239000003112 inhibitor Substances 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical group CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 235000006708 antioxidants Nutrition 0.000 claims 4
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 239000000155 melt Substances 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000012745 toughening agent Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 10
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000002596 correlated effect Effects 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101100257124 Caenorhabditis elegans sma-10 gene Proteins 0.000 description 1
- 101100257136 Caenorhabditis elegans sma-5 gene Proteins 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- 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
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- 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
- B29C2948/92514—Pressure
-
- 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
Abstract
The invention discloses a PVC/ASA (polyvinyl chloride/ acrylic-styrene-acrylonitrile copolymer) alloy material and a preparation method thereof. The PVC/ASA alloy material comprises the following components in weight percentage: 55-65% of PVC, 15-20% of ASA, 5-7% of toughening agent, 5-20% of heat-resistant agent, 2-3% of plasticizer, 0.2-0.6% of antioxidant and 0.2-0.3% of other auxiliary agents. The PVC/ASA alloy material takes PVC and ASA as base materials, and the heat-resistant agent is synergistic with other components in a melt extrusion process to endow the PVC/ASA alloy material with excellent heat resistance, so that the PVC/ASA alloy material has good processability and excellent mechanical properties. The preparation method is simple in process, easy to control conditions, low in cost and low in equipment requirement and is applicable to industrial production.
Description
Technical field
The invention belongs to technical field of polymer materials, particularly a kind of PVC/ASA alloy material and preparation method thereof.
Background technology
Polyvinyl chloride (PVC) true qualities are that micro-yellow is translucent, glossy.Different with auxiliary dosage, be divided into soft, rigid polyvinyl chloride, soft goods is soft and tough, and feel is glued, and the hardness of boardy product is higher than Low Density Polyethylene, PVC is with its good dimension stability, low cost, the advantage that hardness is high makes its usage quantity occupy the second in general-purpose plastics, but it also has, and chemical resistant properties is poor, the not shortcoming such as crisp, easy decomposition of heatproof, matter and make it use to be restricted, this just need us can make up the resin of PVC shortcoming with other and PVC blended, improve the performance of PVC itself.
There is the fire retardant material that PVC/ABS is novel at present, there is very high cost performance, be applied in every field now, but due to PVC/ABS poor heat resistance, heat-resistant deforming temperature, generally below 70 DEG C, which has limited its very many-sided application.
Summary of the invention
The object of the invention is to the above-mentioned deficiency overcoming prior art, a kind of high heat-resisting PVC/ASA alloy material is provided.
It is simple that another object of the present invention is to provide a kind of technique, and condition is easily controlled, the PVC/ASA alloy material preparation method that production cost is low.
In order to realize foregoing invention object, technical scheme of the present invention is as follows:
A kind of PVC/ASA alloy material, comprises the recipe ingredient of following weight percent:
And a kind of preparation method of PVC/ASA alloy material, comprises the following steps:
Each component is taken respectively according to above-mentioned PVC/ASA alloy material formula;
Take each component carry out mixing treatment by described, obtain mixture;
Described mixture is melt extruded, granulation, obtain described PVC/ASA alloy material.
Above-mentioned PVC/ASA alloy material with PVC, ASA for body material, act synergistically melt extruding in process in heat-resistant agent and other components, give the resistance toheat of this PVC/ASA alloy material excellence, also make this PVC/ASA alloy material have good processing characteristics and excellent mechanical property simultaneously.
Each component mixing only also need melt extrude and can obtain product by formula by above-mentioned PVC/ASA alloy material preparation method at a proper temperature, and its preparation method technique is simple, and condition is easily controlled, with low cost, and feature low for equipment requirements, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing:
Fig. 1 is the process flow diagram of embodiment of the present invention PVC/ASA alloy material preparation method.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearly understand, below in conjunction with embodiment and accompanying drawing, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The embodiment of the present invention provides a kind of high heat-resisting PVC/ASA alloy material.This PVC/ASA alloy material comprises the recipe ingredient of following weight percent:
Particularly, above-mentioned PVC is preferably the polyvinyl chloride that number-average molecular weight is preferably 56000 ~ 65000, and wherein, PVC can be PVC SG-6.Therefore, this PVC can be the PVC etc. that Ning Botai moulds.
Above-mentioned ASA is acrylate rubber like body and vinyl cyanide, cinnamic graft copolymer, and ASA has good mechanical-physical, the structural similitude of ASA and ABS, and it remains the splendid mechanical and physical performance that ABS has as engineering plastics.ASA has very strong weathering resistance, and according to test result, the ageing resistance of ASA is more than 10 times of ABS.ASA has reasonable resistance to elevated temperatures, is a kind of antistatic material, can make the few dust stratification dirt in surface.In a preferred embodiment, the relative density of ASA is 1.05 ~ 1.07.Therefore, this ASA can select strange beautiful PW-978B, the LI913 etc. of Korea S LG.
Above-mentioned PVC and ASA, as the matrix component of PVC/ASA alloy material, is melt extruding in process, and its molecule and other components such as components such as heat-resistant agent act synergistically, thus realizes the modification to PVC.Above-mentioned preferred PVC and ASA can give embodiment of the present invention PVC/ASA alloy material more excellent mechanical property.
Above-mentioned toughner is preferably the terpolymer of the methyl methacrylate (M) of chlorinated polyvinyl chloride CPE-6000, MBS(nucleocapsid structure, divinyl (B) and vinylbenzene (S)), the acrylic acid esters co-polymer of ACR(nucleocapsid structure) at least one, be more preferably polyvinyl chloride CPE-6000.This preferred chlorinated polyvinyl chloride CPE-6000 as toughner and other each components particularly PVC and ASA component have good consistency, while PVC/ASA alloy material toughness can be improved, the flame retardant resistance of PVC/ASA alloy material can also be given.
Above-mentioned heat-resistant agent is preferably heat-resistant agent SMA, and it is the random copolymers of vinylbenzene and maleic anhydride, and the model as Dutch Polysope production import is the SMA of SZ26120.This preferred heat-resistant agent SMA not only can improve the thermotolerance of PVC/ASA alloy material, can also improve the rigidity of PVC/ASA alloy material, little to other mechanical impact of this PVC/ASA alloy material.If do not consider the performance impact to PVC/ASA alloy material machinery, this heat-resistant agent can also select other heat-resistant agents well known in the art.
Above-mentioned softening agent is preferably trioctyl trimellitate (TOTM), and this preferred softening agent significantly can promote the heat-drawn wire of above-described embodiment PVC/ASA alloy material.
Above-mentioned antioxidant component effectively can improve the antioxidant property of PVC/ASA alloy material in the various embodiments described above, extends its work-ing life.In a preferred embodiment, the composite antioxidant that this oxidation inhibitor is made up of primary antioxidant and auxiliary antioxidant, wherein, the weight (or other unit) of primary antioxidant and auxiliary antioxidant is than being 1:2 ~ 1:1, primary antioxidant is preferably four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester is or/and β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, auxiliary antioxidant is tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester).
Other auxiliary agents above-mentioned are at least one in processing aid, thermo-stabilizer, lubricant.Wherein, processing aid can select epoxy soybean oil, organotin etc., and thermo-stabilizer can select calcium-zinc composite stabilizing agent, and lubricant can select Zinc Stearate, EBS(ethylene bis stearamide).
Above-mentioned PVC/ASA alloy material with PVC, ASA for body material, act synergistically melt extruding in process in heat-resistant agent and other components, give the resistance toheat of this PVC/ASA alloy material excellence, also make this PVC/ASA alloy material have good processing characteristics and excellent mechanical property simultaneously.Wherein, the correlated performance such as resistance toheat and mechanical property of this PVC/ASA alloy material refers to hereafter data in table 1.Therefore, this PVC/ASA alloy material effectively overcomes the deficiency that existing PVC alloy material product exists.In addition, by the content of each component and the adjustment of kind, further increasing thermotolerance and the mechanical property of this PVC/ASA alloy material.
Correspondingly, the embodiment of the present invention additionally provides the preparation method of above-mentioned PVC/ASA alloy material, and its technical process as shown in Figure 1.The method comprises the steps:
S01. recipe ingredient is taken: take each component according to the formula of above-mentioned PVC/ASA alloy material;
S02. mixture is prepared: carrying out mixing treatment by taking each component in step S01, obtaining mixture;
S03. the melt extruding of mixture: the mixture in step S02 is melt extruded, obtains described PVC/ASA alloy material.
Particularly, each component preferred content in the formula of the PVC/ASA alloy material in above-mentioned steps S01 and formula and kind as described above, in order to save length, do not repeat them here.
In above-mentioned steps S02, the time that each component carries out mixing treatment can adjust flexibly according to actual production conditions, as long as each component premix fully, the equipment as mixing can be mixing machine etc.
In order to make each component fully mix, in a preferred embodiment, each component preferably mixes by the mixing treatment of this step S02 under the condition of 80 DEG C, until PVC powder is taken out, as mixed 10 ~ 15 minutes in after loose shape.
In further preferred embodiment, first by the 80 DEG C of dryings 2 ~ 4 hours in vacuum drying oven of the component such as ASA, heat-resistant agent, fully remove moisture.
In above-mentioned steps S03, mixture melt extrude the technique that can adopt this area routine.Better act synergistically in melt extruding to make each component, give the more excellent thermotolerance of above-mentioned PVC/ASA alloy material and mechanical property, in a preferred embodiment, it is adopt twin screw extruder to melt extrude that mixture melt extrudes, and expressing technique condition is:
One district's temperature 120 ~ 140 DEG C, two district's temperature 150 ~ 170 DEG C, three district's temperature 140 ~ 160 DEG C, four district's temperature 140 ~ 160 DEG C, head 170 ~ 190 DEG C, the residence time 2 ~ 3min, pressure is 12 ~ 18MPa.
Wherein, twin screw rotating speed can be set to 130 ~ 150 revs/min.
Each component mixing only also need melt extrude and can obtain product by formula by above-mentioned PVC/ASA alloy material preparation method at a proper temperature, melt extruding the temperature and time that only need control in process to melt extrude, therefore, its preparation method technique is simple, condition is easily controlled, with low cost, feature low for equipment requirements, is suitable for suitability for industrialized production.
Now for the formula of concrete PVC/ASA alloy material and preparation method, the present invention is further elaborated.
Embodiment 1
The weight percent recipe ingredient of the present embodiment PVC/ASA alloy material is see following table 1, wherein, PVC is the PVC SG-6 that Ning Botai moulds, ASA is strange beautiful PW-978B, toughner is chlorinated polyvinyl chloride CPE-6000, heat-resistant agent is the model that Dutch Polysope produces is the SMA of SZ26120, softening agent is TOTM, oxidation inhibitor is weight ratio is the primary antioxidant of 1:1 and the composite antioxidant of auxiliary antioxidant formation, primary antioxidant is four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2, 4-6-di-tert-butyl phenyl ester), Ciba company is selected to produce, trade names are respectively Irganox1010 and Irganox168, weight ratio is the organotin processing aid of 1:1:1, Ca-Zn composite heat stabilizer and Zinc Stearate lubricant.
Its preparation method is as follows:
S11: take PVC 65.3%(weight percent according to embodiment 1 formula in hereafter table 1, lower with), ASA 20%, heat-resistant agent SMA 5%, toughner 5%, heat-resistant agent 5%, softening agent 3%, antioxidant 1010/168 0.2/0.2%, other auxiliary agents 0.3%;
S12: by ASA, heat-resistant agent SMA 80 DEG C of dryings 2 ~ 4 hours in vacuum drying oven;
S13: by PVC, toughner, high-speed mixer mixing 10 ~ 15 minutes put into by softening agent, keeps mixing temperature at 80 DEG C, treats that PVC powder is that loose shape takes out;
S14: carry out mixing treatment to mixing by other component mixing machines taken in step S12, step S13 and step S11;
S15: the mixture in step S14 is placed in twin screw extruder and melt extrudes, granulation, wherein, screw rod each district temperature arranges and is respectively: district's temperature 120 ~ 140 DEG C, two district's temperature 150 ~ 170 DEG C, three district's temperature 140 ~ 160 DEG C, four district's temperature 140 ~ 160 DEG C, head 170 ~ 190 DEG C, the residence time 2 ~ 3min, pressure is 12 ~ 18MPa.Wherein, twin screw rotating speed can be set to 130 ~ 150 revs/min.
Embodiment 2
The weight percent recipe ingredient of the present embodiment PVC/ASA alloy material is see following table 1, wherein, PVC is the PVC SG-6 that Ning Botai moulds, ASA is strange beautiful PW-978B, toughner is chlorinated polyvinyl chloride CPE-6000, heat-resistant agent is the model that Dutch Polysope produces is the SMA of SZ26120, softening agent is TOTM, oxidation inhibitor is weight ratio is the primary antioxidant of 1:1 and the composite antioxidant of auxiliary antioxidant formation, primary antioxidant is four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2, 4-6-di-tert-butyl phenyl ester), Ciba company is selected to produce, trade names are respectively Irganox1010 and Irganox168, weight ratio is the organotin processing aid of 1:1:1, Ca-Zn composite heat stabilizer and Zinc Stearate lubricant.
Its preparation method is as follows:
S21: take PVC 62.3%, ASA 18%, heat-resistant agent SMA 10%, toughner 5%, softening agent 3%, antioxidant 1010/168 0.2/0.2%, other auxiliary agents 0.3% according to embodiment 2 formula in hereafter table 1;
S22: with reference to embodiment 1 step S12;
S23: with reference to embodiment 1 step S13;
S24: with reference to embodiment 1 step S14;
S25: the mixture in step S24 is placed in twin screw extruder and melt extrudes, granulation, wherein, screw rod each district temperature arranges and is respectively: district's temperature 120 ~ 140 DEG C, two district's temperature 150 ~ 170 DEG C, three district's temperature 140 ~ 160 DEG C, four district's temperature 140 ~ 160 DEG C, head 170 ~ 190 DEG C, the residence time 2 ~ 3min, pressure is 12 ~ 18MPa.Wherein, twin screw rotating speed can be set to 130 ~ 150 revs/min.
Embodiment 3
The weight percent recipe ingredient of the present embodiment PVC/ASA alloy material is see following table 1, wherein, PVC is the PVC SG-6 that Ning Botai moulds, ASA is strange beautiful PW-978B, toughner is chlorinated polyvinyl chloride CPE-6000, heat-resistant agent is the model that Dutch Polysope produces is the SMA of SZ26120, softening agent is TOTM, oxidation inhibitor is weight ratio is the primary antioxidant of 1:1 and the composite antioxidant of auxiliary antioxidant formation, primary antioxidant is four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2, 4-6-di-tert-butyl phenyl ester), Ciba company is selected to produce, trade names are respectively Irganox1010 and Irganox168, weight ratio is the organotin processing aid of 1:1:1, Ca-Zn composite heat stabilizer and Zinc Stearate lubricant.
Its preparation method is as follows:
S31: take PVC 59.3%, ASA 16%, heat-resistant agent SMA 15%, softening agent 3%, toughner 5%, antioxidant 1010/168 0.2/0.2%, other auxiliary agents 0.3% according to embodiment 3 formula in hereafter table 1;
S32: with reference to embodiment 1 step S12;
S33: with reference to embodiment 1 step S13;
S34: with reference to embodiment 1 step S14;
S35: the mixture in step S34 is placed in twin screw extruder and melt extrudes, granulation, wherein, screw rod each district temperature arranges and is respectively: district's temperature 120 ~ 140 DEG C, two district's temperature 150 ~ 170 DEG C, three district's temperature 140 ~ 160 DEG C, four district's temperature 140 ~ 160 DEG C, head 170 ~ 190 DEG C, the residence time 2 ~ 3min, pressure is 12 ~ 18MPa.Wherein, twin screw rotating speed can be set to 130 ~ 150 revs/min.
Embodiment 4
The weight percent recipe ingredient of the present embodiment PVC/ASA alloy material is see following table 1, wherein, PVC is the PVC SG-6 that Ning Botai moulds, ASA is strange beautiful PW-978B, toughner is chlorinated polyvinyl chloride CPE-6000, heat-resistant agent is the model that Dutch Polysope produces is the SMA of SZ26120, softening agent is TOTM, oxidation inhibitor is weight ratio is the primary antioxidant of 1:1 and the composite antioxidant of auxiliary antioxidant formation, primary antioxidant is four [3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2, 4-6-di-tert-butyl phenyl ester), Ciba company is selected to produce, trade names are respectively Irganox1010 and Irganox168, weight ratio is the epoxy soybean oil processing aid of 1:1:1, Ca-Zn composite heat stabilizer and EBS lubricant.
Its preparation method is as follows:
S41: take PVC 55.3%(weight percent according to embodiment 4 formula in hereafter table 1, lower with), ASA 15%, heat-resistant agent SMA 20%, softening agent 3%, toughner 5%, antioxidant 1010/1680.2/0.2%, other auxiliary agents 0.3%;
S42: with reference to embodiment 1 step S12;
S43: with reference to embodiment 1 step S13;
S44: with reference to embodiment 1 step S14;
S45: the mixture in step S44 is placed in twin screw extruder and melt extrudes, granulation, wherein, screw rod each district temperature arranges and is respectively: district's temperature 120 ~ 140 DEG C, two district's temperature 150 ~ 170 DEG C, three district's temperature 140 ~ 160 DEG C, four district's temperature 140 ~ 160 DEG C, head 170 ~ 190 DEG C, the residence time 2 ~ 3min, pressure is 12 ~ 18MPa.Wherein, twin screw rotating speed can be set to 130 ~ 150 revs/min.
Performance test:
PVC/ASA alloy material above-described embodiment 1 to embodiment 4 prepared carries out correlated performance test.Wherein, each correlated performance testing method is as follows:
By the particle in the convection oven of 80 ~ 100 DEG C dry 4 ~ 6 hours respectively completing granulation in above-described embodiment 1 ~ 4, then by the injection moulding sample preparation on 80T injection moulding machine of the particle of drying, in sample making course, keep mould temperature between 50 ~ 70 DEG C.
Tensile strength: test by GB/T 1040 standard.Specimen types is I type, and batten size (mm): 170(is long) × (20 ± 0.2) (end portion width) × (4 ± 0.2) (thickness), draw speed is 50mm/min;
Flexural strength and modulus in flexure: test by GB 9341/T standard, specimen types is specimen size (mm): (80 ± 2) × (10 ± 0.2) × (4 ± 0.2), and rate of bending is 20mm/min;
Notched Izod impact strength: test by GB/T 1043 standard.Specimen types is I type, specimen size (mm): (80 ± 2) × (10 ± 0.2) × (4 ± 0.2); Breach type is category-A, and breach residual thickness is 3.2mm;
Heat-drawn wire: test by ASTM D648 standard, batten size (mm) is the load of (128 ± 2) × (13 ± 0.2) × (6.4 ± 0.2) is 1.85MPa.
After tested, the PVC/ASA alloy material correlated performance test result of above-described embodiment 1 to embodiment 4 preparation is as shown in table 1 respectively.
Table 1
| Composition (% by weight) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| PVC | 65.3 | 62.3 | 59.3 | 55.3 |
| ASA | 20 | 18 | 16 | 15 |
| Toughner | 5 | 5 | 5 | 5 |
| Heat-resistant agent | 5 | 10 | 15 | 20 |
| Softening agent | 3 | 3 | 3 | 3 |
| Oxidation inhibitor | 0.4 | 0.4 | 0.4 | 0.4 |
| Other auxiliary agents | 0.3 | 0.3 | 0.3 | 0.3 |
| Notched Izod impact strength (J/m) | 115 | 108 | 112 | 105 |
| Tensile strength (MPa) | 40 | 43 | 48 | 47 |
| Elongation at break (%) | 23 | 46 | 36 | 41 |
| Flexural strength (MPa) | 53 | 54 | 59 | 61 |
| Modulus in flexure (MPa) | 2200 | 2400 | 2500 | 2500 |
| Fire-retardant UL94 | V0 | V0 | V0 | V2 |
| Heat-drawn wire (DEG C) | 67 | 69 | 73 | 72 |
As can be seen from above-mentioned table 1, ASA content is in 15% ~ 16% scope, toughner is 5%, heat-resistant agent SMA is in 15% ~ 20% scope, and softening agent is within the scope of 2% ~ 3% part, and the heat-drawn wire test result of high heat-resistant PVC/ASA alloy is best, with the increase of heat-resisting SMA content, high heat-resistant PVC/ASA alloy can lose its flame retardant resistance, but stretches all at more than 45MPa, impacts at more than 100MPa.The consideration of comprehensive cost and performance, the optimum addition of ASA is 15 ~ 20%.The present invention can obtain the splendid high heat-resistant PVC/ASA alloy of mechanical property by selecting suitable heat-resistant agent, and add heat-resistant agent in 15 ~ 20% scopes, can meet materials hot deformation test condition is under 1.85MPa, the requirement of heat-drawn wire up to 73 DEG C.And existing PVC/ABS and PVC/ASA all cannot reach this performance.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. a PVC/ASA alloy material, comprises the recipe ingredient of following weight percent:
2. PVC/ASA alloy material according to claim 1, is characterized in that: the relative density of described ASA is 1.05 ~ 1.07.
3., according to the arbitrary described PVC/ASA alloy material of claim 1 ~ 2, it is characterized in that: described PVC is the polyvinyl chloride of number-average molecular weight 56000 ~ 65000.
4., according to the arbitrary described PVC/ASA alloy material of claim 1 ~ 2, it is characterized in that: described toughner is at least one in chlorinated polyvinyl chloride CPE-6000, MBS, ACR.
5., according to the arbitrary described PVC/ASA alloy material of claim 1 ~ 2, it is characterized in that: described softening agent is trioctyl trimellitate.
6. according to the arbitrary described PVC/ASA alloy material of claim 1 ~ 2, it is characterized in that: described oxidation inhibitor is mass ratio is the primary antioxidant of 1:1 ~ 2 and the compound of auxiliary anti-oxidant, described primary antioxidant is four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester is or/and β-(3,5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, described auxiliary antioxidant is tricresyl phosphite (2,4-6-di-tert-butyl phenyl ester).
7., according to the arbitrary described PVC/ASA alloy material of claim 1 ~ 2, it is characterized in that: other auxiliary agents described are at least one in processing aid, thermo-stabilizer, lubricant.
8. a preparation method for PVC/ASA alloy material, comprises the following steps:
Each component is taken respectively according to PVC/ASA alloy material formula described in claim 1 ~ 7;
Take each component carry out mixing treatment by described, obtain mixture;
Described mixture is melt extruded, granulation, obtain described PVC/ASA alloy material.
9. PVC/ASA alloy material according to claim 8, is characterized in that: described in melt extrude be adopt twin-screw extrusion, its expressing technique condition is:
One district's temperature 120 ~ 140 DEG C, two district's temperature 150 ~ 170 DEG C, three district's temperature 140 ~ 160 DEG C, four district's temperature 140 ~ 160 DEG C, head 170 ~ 190 DEG C, the residence time 2 ~ 3min, pressure is 12 ~ 18MPa.
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| CN103571103B (en) * | 2013-10-30 | 2016-03-09 | 芜湖海螺型材科技股份有限公司 | A kind of PVC Alloy And Preparation Method for ultra-thin co-extrusion |
| CN104804353A (en) * | 2015-03-20 | 2015-07-29 | 黄振祖 | ASA (acrylonitrile styrene acrylate)-modified material for co-extrusion coating with high weather resistance and preparation method of ASA-modified material |
| CN107459727B (en) * | 2016-06-03 | 2020-05-12 | 中国石油化工股份有限公司 | Antistatic PVC (polyvinyl chloride) plate composition |
| CN106519540A (en) * | 2016-10-21 | 2017-03-22 | 安徽江淮汽车集团股份有限公司 | Antistatic ASA-PVC composite and preparation method thereof |
| CN106589744A (en) * | 2016-12-15 | 2017-04-26 | 苏州纽东精密制造科技有限公司 | Environment-friendly plastic and preparation method thereof |
| CN107383748A (en) * | 2017-07-25 | 2017-11-24 | 安徽胜利精密制造科技有限公司 | A kind of notebook computer casing processing anti-impact modifier and preparation method thereof |
| CN110733209A (en) * | 2019-09-23 | 2020-01-31 | 江苏远祥新材料有限公司 | engineering plastic and alloy composite plastic template and preparation method thereof |
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