CN103044818A - 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
- Publication number
- CN103044818A CN103044818A CN2012105720014A CN201210572001A CN103044818A CN 103044818 A CN103044818 A CN 103044818A CN 2012105720014 A CN2012105720014 A CN 2012105720014A CN 201210572001 A CN201210572001 A CN 201210572001A CN 103044818 A CN103044818 A CN 103044818A
- Authority
- CN
- China
- Prior art keywords
- pvc
- alloy material
- asa
- asa alloy
- material according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 111
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 110
- 239000000956 alloy Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 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
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 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 17
- 239000004902 Softening Agent Substances 0.000 claims description 14
- -1 pentaerythritol ester Chemical class 0.000 claims description 14
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 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
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- 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 6
- 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
- 235000006708 antioxidants Nutrition 0.000 claims 4
- 150000001875 compounds Chemical class 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000155 melt Substances 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
- 230000002596 correlated effect Effects 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- 239000000047 product 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
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 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
- OYUMYJKDVNCXAX-UHFFFAOYSA-N 2-(3,5-ditert-butyl-2-hydroxyphenyl)propanoic acid Chemical compound OC(=O)C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O OYUMYJKDVNCXAX-UHFFFAOYSA-N 0.000 description 1
- 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
- ZTOCZRQYNNKUDA-UHFFFAOYSA-N OCC(CO)(CO)CO.C(C)(C)(C)C=1C(=C(C=C(C1)C(C)(C)C)CCC(=O)O)O Chemical class OCC(CO)(CO)CO.C(C)(C)(C)C=1C(=C(C=C(C1)C(C)(C)C)CCC(=O)O)O ZTOCZRQYNNKUDA-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
- 239000012467 final product Substances 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
- 238000000465 moulding Methods 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
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 little yellow is translucent, and are glossy.Different with auxiliary dosage, be divided into soft, rigid polyvinyl chloride, soft goods is gentle and tough, and feel is sticking, 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 make its usage quantity occupy the second in general-purpose plastics, and chemical resistant properties is poor, the shortcoming such as crisp, easy decomposition of heatproof, matter and its use is restricted not but it also has, this just needs us with other resin and PVC blend that can remedy the PVC shortcoming, improves the performance of PVC itself.
The novel fire retardant material of PVC/ABS occurs at present, had very high cost performance, be applied in now every field, but because the PVC/ABS poor heat resistance, the heat-resistant deforming temperature is generally below 70 ℃, and this has limited its very many-sided application.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, a kind of high heat-resisting PVC/ASA alloy material is provided.
Another object of the present invention provides that a kind of technique is simple, and condition is easily controlled, the PVC/ASA alloy material preparation method that production cost is low.
In order to realize the foregoing invention purpose, 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 may further comprise the steps:
Take by weighing respectively each component according to above-mentioned PVC/ASA alloy material prescription;
Described each component that takes by weighing is carried out mixing treatment, obtain mixture;
Described mixture is melt extruded, and granulation obtains described PVC/ASA alloy material.
Above-mentioned PVC/ASA alloy material is take PVC, ASA as body material, melt extruding in the process in heat-resistant agent and other components and to act synergistically, give the resistance toheat of this PVC/ASA alloy material excellence, simultaneously also so that this PVC/ASA alloy material has good processing characteristics and excellent mechanical property.
Above-mentioned PVC/ASA alloy material preparation method only need mix each component to be incorporated in to melt extrude under the suitable temperature by prescription and can obtain product, and its preparation method technique is simple, and condition is easily controlled, and is with low cost, and characteristics low for equipment requirements are suitable for suitability for industrialized production.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is embodiment of the invention PVC/ASA alloy material preparation method's process flow diagram.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, 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, is not intended to limit the present invention.
The embodiment of the 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 number-average molecular weight and is preferably 56000～65000 polyvinyl chloride, and wherein, PVC can be PVC SG-6.Therefore, this PVC can be PVC of moulding of Ning Botai etc.
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 has kept 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 the PW-978B of strange U.S., the LI913 of Korea S LG etc.
Above-mentioned PVC and ASA are as the matrix component of PVC/ASA alloy material, and in melt extruding process, the components such as its molecule and other components such as heat-resistant agent act synergistically, thereby realize the modification to PVC.Above-mentioned preferred PVC and ASA can give embodiment of the invention PVC/ASA alloy material more excellent mechanical property.
Above-mentioned toughner is preferably the terpolymer of methyl methacrylate (M), divinyl (B) and the vinylbenzene (S) of chlorinated polyvinyl chloride CPE-6000, MBS(nucleocapsid structure), the acrylic acid esters co-polymer of ACR(nucleocapsid structure) at least a, polyvinyl chloride CPE-6000 more preferably.This preferred chlorinated polyvinyl chloride CPE-6000 as toughner and other each components particularly PVC and ASA component good consistency is arranged, when can improve PVC/ASA alloy material toughness, the flame retardant resistance that can also give the PVC/ASA alloy material.
Above-mentioned heat-resistant agent is preferably heat-resistant agent SMA, and it is the random copolymers of vinylbenzene and maleic anhydride, is the SMA of SZ26120 such as the model of Dutch Polysope production import.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, and is little on other mechanical property 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 be selected other heat-resistant agents well known in the art.
Above-mentioned softening agent is preferably trioctyl trimellitate (TOTM), and this preferred softening agent can significantly promote the heat-drawn wire of above-described embodiment PVC/ASA alloy material.
The antioxidant property of PVC/ASA alloy material prolongs its work-ing life in the above-mentioned antioxidant component energy Effective Raise the various embodiments described above.In a preferred embodiment, the composite antioxidant that this oxidation inhibitor is made of primary antioxidant and auxiliary antioxidant, wherein, the weight of primary antioxidant and auxiliary antioxidant (or other unit) is than being 1:2～1:1, primary antioxidant is preferably four [3-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters or/and β-positive octadecanol ester of (3,5-di-tert-butyl-hydroxy phenyl) propionic acid, auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester).
Above-mentioned other auxiliary agents are at least a in processing aid, thermo-stabilizer, the lubricant.Wherein, processing aid can be selected epoxy soybean oil, organotin etc., and thermo-stabilizer can be selected calcium-zinc composite stabilizing agent, and lubricant can be selected Zinc Stearate, EBS(ethylene bis stearamide).
Above-mentioned PVC/ASA alloy material is take PVC, ASA as body material, melt extruding in the process in heat-resistant agent and other components and to act synergistically, give the resistance toheat of this PVC/ASA alloy material excellence, simultaneously also so that this PVC/ASA alloy material has good processing characteristics and excellent mechanical property.Wherein, the correlated performances such as the resistance toheat of this PVC/ASA alloy material and mechanical property see also hereinafter data in the table 1.Therefore, this PVC/ASA alloy material has effectively overcome the deficiency that existing PVC alloy material product exists.In addition, by to the content of each component and the adjustment of kind, improved further thermotolerance and the mechanical property of this PVC/ASA alloy material.
Correspondingly, the embodiment of the invention also 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. take by weighing recipe ingredient: the prescription according to above-mentioned PVC/ASA alloy material takes by weighing each component;
S02. prepare mixture: carry out mixing treatment with taking by weighing each component among the step S01, obtain mixture;
S03. melt extruding of mixture: the mixture among the step S02 is melt extruded, obtain described PVC/ASA alloy material.
Particularly, each component preferred content and kind in the prescription of the PVC/ASA alloy material among the above-mentioned steps S01 and the prescription are as indicated above, in order to save length, do not repeat them here.
Among the above-mentioned steps S02, each component is carried out the time of mixing treatment and can be adjusted flexibly according to actual production conditions, as long as each component premix fully, can be mixing machine etc. such as the equipment of mixing.
For so that each component is fully mixed, in a preferred embodiment, the mixing treatment of this step S02 is preferably mixed each component under 80 ℃ condition, until the PVC powder takes out after being loose shape, as mixes 10～15 minutes.
In further preferred embodiment, with the components such as ASA, heat-resistant agent 80 ℃ of dryings 2～4 hours in vacuum drying oven, fully remove moisture first.
Among the above-mentioned steps S03, mixture melt extrude the technique that can adopt this area routine.For so that each component in melt extruding better the synergy, give above-mentioned PVC/ASA alloy material more excellent thermotolerance and mechanical property, in a preferred embodiment, it is to adopt twin screw extruder to melt extrude that mixture melt extrudes, and the expressing technique condition is:
120～140 ℃ of one district's temperature, 150～170 ℃ of two district's temperature, 140～160 ℃ of three district's temperature, 140～160 ℃ of four district's temperature, 170～190 ℃ of heads, the residence time 2～3min, pressure are 12～18MPa.
Wherein, the twin screw rotating speed can be set to 130～150 rev/mins.
Above-mentioned PVC/ASA alloy material preparation method only need mix each component to be incorporated in to melt extrude under the suitable temperature by prescription and can obtain product, the temperature and time that only needs control to melt extrude in melt extruding process gets final product, therefore, its preparation method technique is simple, condition is easily controlled, characteristics with low cost, low for equipment requirements are suitable for suitability for industrialized production.
Now take the prescription of concrete PVC/ASA alloy material and preparation method as example, the present invention is further elaborated.
Embodiment 1
The weight percent recipe ingredient of the present embodiment PVC/ASA alloy material is referring to 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 that the model that Dutch Polysope produces is the SMA of SZ26120, softening agent is TOTM, oxidation inhibitor is that weight ratio is the primary antioxidant of 1:1 and the composite antioxidant that auxiliary antioxidant consists of, primary antioxidant is that four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester), select Ciba company to produce, trade names are respectively Irganox1010 and Irganox168; Weight ratio is organotin processing aid, Ca-Zn composite heat stabilizer and the Zinc Stearate lubricant of 1:1:1.
Its preparation method is as follows:
S11: take by weighing PVC 65.3%(weight percent according to 1 prescription of embodiment in the table 1 hereinafter, 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: with ASA, heat-resistant agent SMA 80 ℃ of dryings 2～4 hours in vacuum drying oven;
S13: with PVC, toughner, softening agent is put into high-speed mixer and was mixed 10～15 minutes, keeps mixing temperature at 80 ℃, treats that the PVC powder is loose shape and takes out;
S14: will carry out mixing treatment to mixing in other component mixing machines that take by weighing among step S12, step S13 and the step S11;
S15: place twin screw extruder to melt extrude the mixture among the step S14, granulation, wherein, screw rod is respectively distinguished the temperature setting and is respectively: 120～140 ℃ of district's temperature, 150～170 ℃ of two district's temperature, 140～160 ℃ of three district's temperature, 140～160 ℃ of four district's temperature, 170～190 ℃ of heads, the residence time 2～3min, pressure are 12～18MPa.Wherein, the twin screw rotating speed can be set to 130～150 rev/mins.
Embodiment 2
The weight percent recipe ingredient of the present embodiment PVC/ASA alloy material is referring to 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 that the model that Dutch Polysope produces is the SMA of SZ26120, softening agent is TOTM, oxidation inhibitor is that weight ratio is the primary antioxidant of 1:1 and the composite antioxidant that auxiliary antioxidant consists of, primary antioxidant is that four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester), select Ciba company to produce, trade names are respectively Irganox1010 and Irganox168; Weight ratio is organotin processing aid, Ca-Zn composite heat stabilizer and the Zinc Stearate lubricant of 1:1:1.
Its preparation method is as follows:
S21: take by weighing 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 2 prescriptions of embodiment in the table 1 hereinafter;
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: place twin screw extruder to melt extrude the mixture among the step S24, granulation, wherein, screw rod is respectively distinguished the temperature setting and is respectively: 120～140 ℃ of district's temperature, 150～170 ℃ of two district's temperature, 140～160 ℃ of three district's temperature, 140～160 ℃ of four district's temperature, 170～190 ℃ of heads, the residence time 2～3min, pressure are 12～18MPa.Wherein, the twin screw rotating speed can be set to 130～150 rev/mins.
Embodiment 3
The weight percent recipe ingredient of the present embodiment PVC/ASA alloy material is referring to 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 that the model that Dutch Polysope produces is the SMA of SZ26120, softening agent is TOTM, oxidation inhibitor is that weight ratio is the primary antioxidant of 1:1 and the composite antioxidant that auxiliary antioxidant consists of, primary antioxidant is that four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester), select Ciba company to produce, trade names are respectively Irganox1010 and Irganox168; Weight ratio is organotin processing aid, Ca-Zn composite heat stabilizer and the Zinc Stearate lubricant of 1:1:1.
Its preparation method is as follows:
S31: take by weighing 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 3 prescriptions of embodiment in the table 1 hereinafter;
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: place twin screw extruder to melt extrude the mixture among the step S34, granulation, wherein, screw rod is respectively distinguished the temperature setting and is respectively: 120～140 ℃ of district's temperature, 150～170 ℃ of two district's temperature, 140～160 ℃ of three district's temperature, 140～160 ℃ of four district's temperature, 170～190 ℃ of heads, the residence time 2～3min, pressure are 12～18MPa.Wherein, the twin screw rotating speed can be set to 130～150 rev/mins.
Embodiment 4
The weight percent recipe ingredient of the present embodiment PVC/ASA alloy material is referring to 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 that the model that Dutch Polysope produces is the SMA of SZ26120, softening agent is TOTM, oxidation inhibitor is that weight ratio is the primary antioxidant of 1:1 and the composite antioxidant that auxiliary antioxidant consists of, primary antioxidant is that four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester), select Ciba company to produce, trade names are respectively Irganox1010 and Irganox168; Weight ratio is epoxy soybean oil processing aid, Ca-Zn composite heat stabilizer and the EBS lubricant of 1:1:1.
Its preparation method is as follows:
S41: take by weighing PVC 55.3%(weight percent according to 4 prescriptions of embodiment in the table 1 hereinafter, 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: place twin screw extruder to melt extrude the mixture among the step S44, granulation, wherein, screw rod is respectively distinguished the temperature setting and is respectively: 120～140 ℃ of district's temperature, 150～170 ℃ of two district's temperature, 140～160 ℃ of three district's temperature, 140～160 ℃ of four district's temperature, 170～190 ℃ of heads, the residence time 2～3min, pressure are 12～18MPa.Wherein, the twin screw rotating speed can be set to 130～150 rev/mins.
Performance test:
The PVC/ASA alloy material of above-described embodiment 1 to embodiment 4 preparation is carried out the correlated performance test.Wherein, each correlated performance testing method is as follows:
With the particle of finishing granulation in above-described embodiment 1～4 in 80～100 ℃ convection oven dry 4～6 hours respectively, again with particle injection moulding sample preparation on the 80T injection moulding machine of drying, keep the mould temperature in the sample making course between 50～70 ℃.
Tensile strength: test by GB/T 1040 standards.Specimen types is the I type, and batten size (mm): 170(is long) * (20 ± 0.2) (end 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), rate of bending are 20mm/min;
Notched Izod impact strength: test by GB/T 1043 standards.Specimen types is the I type, specimen size (mm): (80 ± 2) * (10 ± 0.2) * (4 ± 0.2); The breach type is category-A, and the breach residual thickness is 3.2mm;
Heat-drawn wire: test by ASTM D648 standard, batten size (mm) is 1.85MPa for the load of (128 ± 2) * (13 ± 0.2) * (6.4 ± 0.2).
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
| Form (% 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 (℃) | 67 | 69 | 73 | 72 |
By finding out in the 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 in 2%～3% part of scope, and the heat-drawn wire test result of high heat-resistant PVC/ASA alloy is best, increase with heat-resisting SMA content, high heat-resistant PVC/ASA alloy can be lost its flame retardant resistance, but stretches all more than 45MPa, impacts more than 100MPa.The consideration of comprehensive cost and performance, the optimum addition of ASA are 15～20%.The present invention adds heat-resistant agent in 15～20% scopes by selecting suitable heat-resistant agent can obtain the splendid high heat-resistant PVC of mechanical property/ASA alloy, and can satisfy the materials hot deformation test condition is under the 1.85MPa, the requirement of heat-drawn wire up to 73 ℃.And existing PVC/ABS and PVC/ASA all can't reach this performance.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. PVC/ASA alloy material comprises the recipe ingredient of following weight percent:
2. PVC/ASA alloy material according to claim 1, it is characterized in that: described heat-resistant agent is heat-resistant agent SMA.
3. PVC/ASA alloy material according to claim 1, it is characterized in that: the relative density of described ASA is 1.05～1.07.
4. arbitrary described PVC/ASA alloy material according to claim 1～3, it is characterized in that: described PVC is the polyvinyl chloride of number-average molecular weight 56000～65000.
5. arbitrary described PVC/ASA alloy material according to claim 1～3 is characterized in that: described toughner is at least a among chlorinated polyvinyl chloride CPE-6000, MBS, the ACR.
6. arbitrary described PVC/ASA alloy material according to claim 1～3, it is characterized in that: described softening agent is trioctyl trimellitate.
7. arbitrary described PVC/ASA alloy material according to claim 1～3, it is characterized in that: described oxidation inhibitor is that mass ratio is the primary antioxidant of 1:1～2 and the compound of auxiliary anti-oxidant, described primary antioxidant is that four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester is or/and β-(3, the 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, described auxiliary antioxidant is tricresyl phosphite (2,4-di-t-butyl phenyl ester).
8. arbitrary described PVC/ASA alloy material according to claim 1～3 is characterized in that: described other auxiliary agents are at least a in processing aid, thermo-stabilizer, the lubricant.
9. the preparation method of a PVC/ASA alloy material may further comprise the steps:
Take by weighing respectively each component according to the described PVC/ASA alloy material of claim 1～8 prescription;
Described each component that takes by weighing is carried out mixing treatment, obtain mixture;
Described mixture is melt extruded, and granulation obtains described PVC/ASA alloy material.
10. PVC/ASA alloy material according to claim 9 is characterized in that: described to melt extrude be to adopt twin-screw extrusion, and its expressing technique condition is:
120～140 ℃ of one district's temperature, 150～170 ℃ of two district's temperature, 140～160 ℃ of three district's temperature, 140～160 ℃ of four district's temperature, 170～190 ℃ of heads, the residence time 2～3min, pressure are 12～18MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210572001.4A CN103044818B (en) | 2012-12-26 | 2012-12-26 | PVC/ASA (polyvinyl chloride/ acrylic-styrene-acrylonitrile copolymer) alloy material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210572001.4A CN103044818B (en) | 2012-12-26 | 2012-12-26 | PVC/ASA (polyvinyl chloride/ acrylic-styrene-acrylonitrile copolymer) alloy material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103044818A true CN103044818A (en) | 2013-04-17 |
| CN103044818B CN103044818B (en) | 2015-04-29 |
Family
ID=48057691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210572001.4A Expired - Fee Related CN103044818B (en) | 2012-12-26 | 2012-12-26 | PVC/ASA (polyvinyl chloride/ acrylic-styrene-acrylonitrile copolymer) alloy material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103044818B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571103A (en) * | 2013-10-30 | 2014-02-12 | 芜湖海螺型材科技股份有限公司 | PVC (polyvinyl chloride) alloy for ultrathin coextrusion and preparation method of PVC alloy |
| 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 |
| 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 |
| CN107459727A (en) * | 2016-06-03 | 2017-12-12 | 中国石油化工股份有限公司 | A kind of antistatic PVC board composition |
| 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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111876A (en) * | 1976-03-30 | 1978-09-05 | Union Carbide Corporation | Impact modifiers for polyvinyl chloride |
| US4391948A (en) * | 1982-06-25 | 1983-07-05 | Borg-Warner Chemicals, Inc. | Emulsion/suspension ASA graft copolymers as flow modifiers for PVC |
| EP0894827A1 (en) * | 1997-07-31 | 1999-02-03 | Granulat 2000 Kunstoff Compound GmbH & Co KG | Moulding composition based on polyvinyl chloride |
| CN101531797A (en) * | 2009-04-27 | 2009-09-16 | 国家复合改性聚合物材料工程技术研究中心 | A polyvinyl chloride/ASA alloy |
| CN101875748A (en) * | 2010-03-31 | 2010-11-03 | 深圳市科聚新材料有限公司 | Heat-resistance ABS/PVC alloy and preparation method thereof |
| CN102627816A (en) * | 2012-04-26 | 2012-08-08 | 安徽雄峰实业有限公司 | Spraying-free unleaded fridge door vertical column and production method thereof |
-
2012
- 2012-12-26 CN CN201210572001.4A patent/CN103044818B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4111876A (en) * | 1976-03-30 | 1978-09-05 | Union Carbide Corporation | Impact modifiers for polyvinyl chloride |
| US4391948A (en) * | 1982-06-25 | 1983-07-05 | Borg-Warner Chemicals, Inc. | Emulsion/suspension ASA graft copolymers as flow modifiers for PVC |
| EP0894827A1 (en) * | 1997-07-31 | 1999-02-03 | Granulat 2000 Kunstoff Compound GmbH & Co KG | Moulding composition based on polyvinyl chloride |
| CN101531797A (en) * | 2009-04-27 | 2009-09-16 | 国家复合改性聚合物材料工程技术研究中心 | A polyvinyl chloride/ASA alloy |
| CN101875748A (en) * | 2010-03-31 | 2010-11-03 | 深圳市科聚新材料有限公司 | Heat-resistance ABS/PVC alloy and preparation method thereof |
| CN102627816A (en) * | 2012-04-26 | 2012-08-08 | 安徽雄峰实业有限公司 | Spraying-free unleaded fridge door vertical column and production method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103571103A (en) * | 2013-10-30 | 2014-02-12 | 芜湖海螺型材科技股份有限公司 | PVC (polyvinyl chloride) alloy for ultrathin coextrusion and preparation method of PVC alloy |
| 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 |
| CN107459727A (en) * | 2016-06-03 | 2017-12-12 | 中国石油化工股份有限公司 | A kind of antistatic PVC board 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103044818B (en) | 2015-04-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103044818B (en) | PVC/ASA (polyvinyl chloride/ acrylic-styrene-acrylonitrile copolymer) alloy material and preparation method thereof | |
| CN102443256B (en) | High-heat-resistance polycarbonate (PC)/acrylonitrile styrene acrylate copolymer (ASA) alloy material and preparation method thereof | |
| CN101759942B (en) | PMMA/PVC polymeric material and preparing method thereof | |
| CN103601976B (en) | Fiber glass reinforced polypropylene material of a kind of ladder of swimming pool pedal and preparation method thereof | |
| CN102617929A (en) | High-gloss modified polypropylene resin and preparation method for same | |
| CN103059412A (en) | Polypropylene composite material with low after-shrinkage and high gloss and preparation method thereof | |
| CN1580126A (en) | Preparation of PC/ABS alloy | |
| CN102731921A (en) | Weatherproof polymer alloy used for replacing ABS | |
| CN104017323A (en) | ABS/PVC blend alloy and preparation method thereof | |
| CN106751654A (en) | A kind of wear-resisting regeneration PC/POK alloy materials and its preparation method and application | |
| CN101993586B (en) | Flame-resistant polycarbonate/ABS (Acrylonitrile Butadiene Styrene) material | |
| CN102942736B (en) | High-glass fiber content reinforced polypropylene material and preparation method thereof | |
| KR101056931B1 (en) | Acrylic copolymer for processing aid of vinyl chloride-based resin composition, method for preparing the same, and vinyl chloride-based resin composition comprising the same | |
| KR101884972B1 (en) | Thermoplastic resin composition having gloss and reduced gloss and molded article made from same | |
| CN104109367B (en) | A kind of fire retardation PC/PBT composite and preparation method thereof | |
| KR102276848B1 (en) | Polymer resin composition and molded product of the same | |
| CN107501771A (en) | A kind of low-shrinkage modified polypropylene material and preparation method thereof | |
| CN103965599B (en) | PLA (polylactic acid)/ABS (acrylonitrile-butadiene-styrene copolymers) alloy material and preparation method thereof | |
| CN1563186B (en) | Low warped and high surfaceness PBT composite material enhanced by fiberglass | |
| KR100828620B1 (en) | Styrenic thermoplastic resin compositions having thermal resistance and high fluidity | |
| CN104497463A (en) | HIPS (high impact polystyrene) composite material and preparation method thereof | |
| CN112724578B (en) | Polypropylene compound and application and preparation method thereof | |
| CN103937094A (en) | Screwing burst resisting enhanced polypropylene material as well as preparation method and application thereof | |
| CN112552586B (en) | Glass fiber reinforced polypropylene composition and preparation method thereof | |
| CN103102633A (en) | Highly weather-proof environment-friendly high-molecular weight bromine flame-retardant ASA material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: PVC/ASA alloy material and preparation method thereof Effective date of registration: 20150817 Granted publication date: 20150429 Pledgee: China Everbright Bank Shenzhen branch Pledgor: Polymer Science (Anhui) New Material Co., Ltd. Registration number: 2015990000681 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20161202 Granted publication date: 20150429 Pledgee: China Everbright Bank Shenzhen branch Pledgor: Polymer Science (Anhui) New Material Co., Ltd. Registration number: 2015990000681 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: PVC/ASA alloy material and preparation method thereof Effective date of registration: 20170106 Granted publication date: 20150429 Pledgee: Bank of Shizuishan Limited by Share Ltd Yinchuan branch Pledgor: Anhui science and Technology Co., Ltd.|Shenzhen branch poly new materials Co., Ltd.|Xu Dong Registration number: 2016990001133 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20180904 Granted publication date: 20150429 Pledgee: Bank of Shizuishan Limited by Share Ltd Yinchuan branch Pledgor: Polymer Science (Anhui) New Material Co., Ltd.|Shenzhen Keju New Material Co., Ltd.|Xu Dong Registration number: 2016990001133 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: PVC/ASA alloy material and preparation method thereof Effective date of registration: 20180912 Granted publication date: 20150429 Pledgee: Bank of Shizuishan Limited by Share Ltd Yinchuan branch Pledgor: Polymer Science (Anhui) New Material Co., Ltd.|Shenzhen Keju New Material Co., Ltd. Registration number: 2018440020055 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150429 Termination date: 20181226 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |