CN102898759B - Acrylonitrile-ethylene-styrene (AES) resin composition and preparation method thereof - Google Patents
Acrylonitrile-ethylene-styrene (AES) resin composition and preparation method thereof Download PDFInfo
- Publication number
- CN102898759B CN102898759B CN201210375634.6A CN201210375634A CN102898759B CN 102898759 B CN102898759 B CN 102898759B CN 201210375634 A CN201210375634 A CN 201210375634A CN 102898759 B CN102898759 B CN 102898759B
- Authority
- CN
- China
- Prior art keywords
- epdm
- weight
- parts
- ethylene
- compatilizer
- 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.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 229920001923 acrylonitrile-ethylene-styrene Polymers 0.000 title abstract 4
- 239000011342 resin composition Substances 0.000 title abstract 2
- 229920005989 resin Polymers 0.000 claims abstract description 77
- 239000011347 resin Substances 0.000 claims abstract description 77
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 45
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 229920000638 styrene acrylonitrile Polymers 0.000 claims abstract description 29
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000004971 Cross linker Substances 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011145 styrene acrylonitrile resin Substances 0.000 claims abstract 9
- 238000005453 pelletization Methods 0.000 claims description 30
- 239000003112 inhibitor Substances 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 21
- 238000007254 oxidation reaction Methods 0.000 claims description 21
- 238000007599 discharging Methods 0.000 claims description 15
- 229920000578 graft copolymer Polymers 0.000 claims description 13
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- PFNROQCAJVOSIR-UHFFFAOYSA-N oxiran-2-ylmethyl 2-methylprop-2-enoate;5-phenylpenta-2,4-dienenitrile Chemical compound CC(=C)C(=O)OCC1CO1.N#CC=CC=CC1=CC=CC=C1 PFNROQCAJVOSIR-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 4
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- 101000648997 Homo sapiens Tripartite motif-containing protein 44 Proteins 0.000 claims description 3
- 102100028017 Tripartite motif-containing protein 44 Human genes 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- AYBSOYWZTRUFMW-UHFFFAOYSA-N furan-2,5-dione;prop-2-enenitrile;styrene Chemical compound C=CC#N.O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 AYBSOYWZTRUFMW-UHFFFAOYSA-N 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 229920005608 sulfonated EPDM Polymers 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 abstract description 8
- 238000004891 communication Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 3
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000004566 building material Substances 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 4
- 238000010559 graft polymerization reaction Methods 0.000 description 4
- 230000035939 shock Effects 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- -1 wherein Polymers 0.000 description 2
- 238000013019 agitation Methods 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000000314 lubricant Substances 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
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- 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
- B29C48/92—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
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
- B29C2948/92885—Screw or gear
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an acrylonitrile-ethylene-styrene (AES) resin composition and a preparation method thereof. The composition comprises the following components in parts by weight: 10 to 50 parts of ethylene-propylene-diene monomer (EPDM) master batch, 50 to 90 parts of styrene-acrylonitrile (SAN) resin master batch, 0.02 to 0.2 part of initiator, 0.5 to 5 parts of co-crosslinker, and 0.3 to 1 part of antioxidant. The composition is prepared by adopting a reactive extrusion grafting method; and a compatilizer containing maleic anhydride (MAH) active functional groups, a compatilizer containing glycidyl methacrylate (GMA) active functional groups and modified EPDM and SAN resin are respectively prepared into the master batches, then other raw materials are added, the raw materials are stirred and mixed, and the mixture is extruded and granulated to form a sample. The reactive extrusion grafting method is environment-friendly, simple in equipment and convenient to operate; and the prepared composition has excellent weather resistance, low-temperature impact resistance, chemical corrosion resistance, size stability and processing performance, and can be applied to outdoor products such as building materials, sports equipment, communication equipment shells and automotive parts.
Description
Technical field
The present invention relates to resin combination and preparation method thereof, particularly relate to the preparation method of a kind of AES resin combination and its reactive extrusion.
Background technology
AES resin is that vinyl cyanide (AN) and vinylbenzene (ST) are grafted to the multipolymer that terpolymer EP rubber (EPDM) main chain is formed.AES resin basic physical properties compared with general ABS resin is similar, but because the terpolymer EP rubber rubber that have employed saturability instead of the polybutadiene rubber of nonsaturation, thus there is excellent weathering resistance, low-temperature impact property and chemicals-resistant corrosive nature, compensate for the performance deficiency of ABS resin, can be widely used in the outdoor products such as material of construction, sports equipment, communications equipment housings, automobile component, development space is huge, is a kind of up-and-coming engineering plastics.
The state difference that the graft copolymerization of AES resin participates in polyreaction with main polymer can be divided into aqueous suspension polymerization, emulsion polymerization, solution polymerization process, mass polymerization etc., the requirement of these methods to equipment is high, three-protection design amount is large, environmental pollution is serious, and percentage of grafting is on the low side.If publication number is the Chinese invention patent application of 102127192A, this invention relates to " a kind of method for preparing continuous bulk of AES resin, it comprises: EPDM (terpolymer EP rubber) is added in solvent the dissolving that heated up, with vinylbenzene, vinyl cyanide, initiator, chain-transfer agent, oxidation inhibitor, rubber solutions system is formed after mix lubricant, tower reactor successively through three series connection carries out graft polymerization reaction, aftertreatment adopts secondary vacuum devolatilization, by controlling rubber clone, rubber content, material feeding ratio is applicable to injection moulding with obtained, extrude the AES resin of processing.”
Also find in prior art retrieval, if publication number is the Chinese invention patent of CN101544727, this invention relates to " a kind of AES resin with high impact and preparation method thereof; the particle diameter that this resin is ethylene-propylene rubber(EPR), divinyl rubber and monoalkyl vinyl aromatic monomer and unsaturated nitrile monomer are formed is the graft copolymer of bimodal distribution, and described ethylene-propylene rubber(EPR) and the mass ratio of divinyl rubber are 1: 0.05 ~ 0.25.The preparation method of AES resin comprises batching, the material for preparing carries out graft polymerization reaction in the reactor and final reaction melt by devolatilization extruder granulation step, wherein, graft polymerization reaction refers at more than pressure 0.5MPa, under agitation condition, make starting material experience four-stage successively and obtain reaction melt, the temperature of four-stage is followed successively by 95 DEG C ~ 105 DEG C, 110 DEG C ~ 115 DEG C, 120 DEG C ~ 123 DEG C and 140 DEG C ~ 150 DEG C.”
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, a kind of AES resin combination and preparation method thereof is provided.The present invention adopts the method for reactive extrusion, by controlling material proportion, controlling the processing condition of reactive extrusion, obtains the AES resin of a kind of environmental friendliness, excellent performance.The present invention's more environmental protection, equipment are simpler, technological operation is more convenient, percentage of grafting improves, there is excellent weathering resistance, low-temperature impact property and chemicals-resistant corrosive nature, can be widely used in the outdoor products such as material of construction, sports equipment, communications equipment housings, automobile component.
The object of the invention is to be achieved through the following technical solutions:
The present invention relates to a kind of AES resin combination, comprise each component of following parts by weight:
EPDM master batch 10 ~ 50 parts,
SAN masterbatch resin 50 ~ 90 parts,
Initiator 0.02 ~ 0.2 part,
Additional crosslinker 0.5 ~ 5 part,
0.3 ~ 1 part, oxidation inhibitor.
Preferably, described EPDM master batch comprises each component of following parts by weight:
Modified epdm 80 ~ 90 parts,
Compatilizer A 10 ~ 20 parts,
0.3 ~ 1 part, oxidation inhibitor.
Preferably, described modified epdm is one or more in bromination EPDM, chlorination EPDM, sulfonated epdm, cis-butenedioic anhydride EPDM, maleation EPDM and propylene nitrilation EPDM; In described modified epdm, the weight percent content of EPDM is 88 ~ 98%.
Preferably, described compatilizer A to be the weight percent content of MAH be 1 ~ 10% ethylene-propylene acid resin and the graft copolymer of maleic anhydride MAH, the weight percent content of GMA active function groups be 1 ~ 10% ethylene-propylene acid resin and glycidyl methacrylate GMA active function groups graft copolymer in one or more.
Preferably, described compatilizer A is one or more in ethylene-methyl acrylate-maleic anhydride, Ethylene-butyl acrylate-maleic anhydride, ethylene-ethylacrylate-maleic anhydride, ethylene-methyl acrylate-glyceryl methacrylate ternary atactic copolymer, Ethylene-butyl acrylate-glycidyl methacrylate ternary atactic copolymer.
Preferably, described EPDM master batch prepares by the following method and obtains:
(1) by 80 ~ 90 part by weight modified EPDM, 10 ~ 20 parts by weight of compatible agent A, 0.3 ~ 1 weight part oxidation inhibitor, puts into homogenizer and stirs discharging after 5 ~ 30 minutes and obtain mixture;
(2) added by the main charging opening of described mixture from twin screw extruder, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 150 ~ 220 DEG C, and screw speed is 100 ~ 400rpm, and extruding pelletization obtains described EPDM master batch.
Preferably, described SAN masterbatch resin comprises each component of following parts by weight:
SAN resin 80 ~ 90 parts,
Compatilizer B 10 ~ 20 parts,
0.3 ~ 1 part, oxidation inhibitor.
Preferably, described SAN resin is weight-average molecular weight is 100,000 ~ 250, the vinyl cyanide of 000 and cinnamic graft copolymer; In described vinyl cyanide and cinnamic graft copolymer, the weight percent content of vinyl cyanide is 28 ~ 38%.
Preferably, described compatilizer B is one or more in the graft copolymer of the graft copolymer of styrene-acrylonitrile SAN resin and maleic anhydride MAH, glycidyl methacrylate GMA active function groups; Described glycidyl methacrylate GMA active function groups can with the glycidyl methacrylate GMA active function groups generation chemical reaction in compatilizer A.
Preferably, described compatilizer B is one or both in styrene-acrylonitrile-maleic anhydride, styrene-acrylonitrile-glycidyl methacrylate ternary atactic copolymer; In described ternary atactic copolymer, the weight percent content of glycidyl methacrylate is 1 ~ 10%.
Preferably, described SAN masterbatch resin prepares by the following method and obtains:
(1) by 80 ~ 90 weight part SAN resins, 10 ~ 20 parts by weight of compatible agent B, 0.3 ~ 1 weight part oxidation inhibitor is put into homogenizer and is stirred discharging after 5 ~ 30 minutes and obtain mixture;
(2) added by the main charging opening of mixture from twin screw extruder, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 180 ~ 230 DEG C, and screw speed is 200 ~ 600rpm, and extruding pelletization obtains described SAN masterbatch resin.
Preferably, described initiator is dicumyl peroxide DCP, two (tert-butyl peroxide) diisopropylbenzene(DIPB) BIPB or two two or five ［ 2,5-diethyl-2,5-bis-(tert-butyl peroxide) hexanes ］.
Preferably, described additional crosslinker to be fusing point the be iso-cyanuric acid triallyl ester TAIC of 20 ~ 40 DEG C.
The invention still further relates to a kind of preparation method of aforesaid AES resin combination, comprise the steps:
(1) 10 ~ 50 weight part EPDM master batches, 50 ~ 90 weight part SAN masterbatch resins, 0.02 ~ 0.2 weight part initiator, 0.5 ~ 5 weight part additional crosslinker and 0.3 ~ 1 weight part oxidation inhibitor are put into homogenizer stir 5-30min after discharging obtain mixture;
(2) added by the main charging opening of described mixture from twin screw extruder, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 150 ~ 220 DEG C, and screw speed is 100 ~ 400rpm, and extruding pelletization obtains sample.
The present invention solves that prior art equipment requirements is high, three-protection design amount is large, and environmental pollution is serious, the shortcoming that percentage of grafting is on the low side.Compared with prior art, the present invention has following beneficial effect:
(1) adopt the method for reactive extrusion to carry out alternative existing graft polymerization procedure, equipment is simple, and technology controlling and process is convenient, and industrialization cost is low, and environment is very friendly, avoids the three wastes that discharge is a large amount of;
(2) select the compatilizer A of band MAH and GMA active function groups and modified epdm to make master batch, one end is compatible with matrix EPDM, and the other end active function groups and compatilizer B react.Select and chemical reaction can occur with compatilizer A, there is the compatilizer B of different activities functional group, one end can with SAN resin compatible, the other end and compatilizer A react, thus improve the consistency of SAN resin and modified epdm;
(3) select and can produce free radical at short notice containing two effective peroxy group DCP or PIBP as initiator, make modified epdm and the reaction of SAN resin generation cross-linked graft, and adding of additional crosslinker iso-cyanuric acid triallyl ester (TAIC) can promote that cross-linked graft reacts, raise the efficiency.
To sum up, method more environmental protection, the equipment of reactive extrusion of the present invention are simpler, technological operation AES resin combination that is more convenient, gained has excellent weathering resistance, low-temperature impact property and chemicals-resistant corrosive nature, can be widely used in the outdoor products such as material of construction, sports equipment, communications equipment housings, automobile component.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.It should be pointed out that to those skilled in the art, without departing from the inventive concept of the premise, some distortion and improvement can also be made.These all belong to protection scope of the present invention.
embodiment 1
The AES resin combination of the present embodiment, comprises each component as shown in table 1 and parts by weight thereof.Its preparation method is specific as follows:
One, EPDM master batch is prepared
By 90Kg modified epdm (maleation EPDM, wherein, EPDM content is 95wt%), 10Kg compatilizer A ethylene-methyl acrylate-maleic anhydride (wherein, MAH content is 1wt%) and 0.5Kg oxidation inhibitor joins in high-speed mixer and stirs discharging after 15 minutes, obtains mixture A.Added from the main charging opening of twin screw extruder by mixture A, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 150 ~ 180 DEG C, and screw speed is 100 ~ 200rpm, and extruding pelletization obtains EPDM master batch.
Two, SAN masterbatch resin is prepared
(weight-average molecular weight is 100 to 90KgSAN resin, 000 ~ 150,000, wherein, the content of vinyl cyanide is 33wt%), 10Kg compatilizer B styrene-acrylonitrile-glycidyl methacrylate (wherein, GMA content is 5wt%), 0.5Kg oxidation inhibitor is put into homogenizer and is stirred discharging after 20 minutes and obtain mixture B.Added from the main charging opening of twin screw extruder by mixture B, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 180 ~ 200 DEG C, and screw speed is 200 ~ 350rpm, and extruding pelletization obtains SAN masterbatch resin.
Three, AES resin combination is prepared
10KgEPDM master batch, 90KgSAN masterbatch resin, 0.05Kg initiator dicumyl peroxide, 2Kg additional crosslinker iso-cyanuric acid triallyl ester (fusing point is 20 ~ 40 DEG C) and 0.5Kg oxidation inhibitor are put into homogenizer stir 20min after discharging obtain mixture C.Added by the main charging opening of mixture C from twin screw extruder, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 150 ~ 200 DEG C, and screw speed is 100 ~ 250rpm, and extruding pelletization obtains sample.
embodiment 2 ~ 4
In order to embody the feature of above-mentioned AES resin combination preferably, present invention uses embodiment 2 ~ 4, compare different EPDM master batch consumption, different SAN masterbatch resin consumption, different additional crosslinker consumption to the impact of product performance, concrete component formula refers to table 1, and step is with embodiment 1.
embodiment 5
The AES resin combination of the present embodiment, comprises each component as shown in table 1 and parts by weight thereof.Its preparation method is specific as follows:
One, EPDM master batch is prepared
By 80Kg modified epdm, (mass ratio is the bromination EPDM of 1:1:1, sulfonated epdm and chlorination EPDM, wherein EPDM content is 88wt% ~ 92wt%), 20Kg compatilizer A(compatilizer A is: the Ethylene-butyl acrylate-glycidyl methacrylate of MAH content to be the Ethylene-butyl acrylate-maleic anhydride of 10wt% and GMA content be 1wt%, the two mass ratio can be any ratio, be preferably 1:2 in the present embodiment) and 1Kg oxidation inhibitor to join in high-speed mixer stirring discharging after 5 minutes, obtain mixture A.Added from the main charging opening of twin screw extruder by mixture A, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 180 ~ 200 DEG C, and screw speed is 200 ~ 300rpm, and extruding pelletization obtains EPDM master batch.
Two, SAN masterbatch resin is prepared
(weight-average molecular weight is 150 to 80KgSAN resin, 000 ~ 200,000, wherein, acrylonitrile content is 38wt%), 20Kg compatilizer B styrene-acrylonitrile-glycidyl methacrylate (wherein, GMA content is 10wt%), 1Kg oxidation inhibitor is put into homogenizer and is stirred discharging after 30 minutes and obtain mixture B.Added from the main charging opening of twin screw extruder by mixture B, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 200 ~ 230 DEG C, and screw speed is 350 ~ 500rpm, and extruding pelletization obtains SAN masterbatch resin.
Three, AES resin combination is prepared
50KgEPDM master batch, 50KgSAN masterbatch resin, 0.2Kg initiator two (tert-butyl peroxide) diisopropylbenzene(DIPB), 0.5Kg additional crosslinker iso-cyanuric acid triallyl ester (fusing point is 20 ~ 40 DEG C) and 0.3Kg oxidation inhibitor are put into homogenizer stir 5min after discharging obtain mixture C.Added by the main charging opening of mixture C from twin screw extruder, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 200 ~ 220 DEG C, and screw speed is 250 ~ 400rpm, and extruding pelletization obtains sample.
embodiment 6
The AES resin combination of the present embodiment, comprises each component as shown in table 1 and parts by weight thereof.Its preparation method is specific as follows:
One, EPDM master batch is prepared
By 85Kg modified epdm (propylene nitrilation EPDM, wherein, EPDM content is 98wt%), 15Kg compatilizer A ethylene-methyl acrylate-glyceryl methacrylate (wherein, the content of GMA active function groups is 10wt%) and 0.3Kg oxidation inhibitor join in high-speed mixer and stir discharging after 30 minutes, obtain mixture A.Added from the main charging opening of twin screw extruder by mixture A, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 200 ~ 220 DEG C, and screw speed is 300 ~ 400rpm, and extruding pelletization obtains EPDM master batch.
Two, SAN masterbatch resin is prepared
(weight-average molecular weight is 200 to 85KgSAN resin, 000 ~ 250,000, wherein, acrylonitrile content is 28wt%), 15Kg compatilizer B(compatilizer B is: GMA content is styrene-acrylonitrile-glycidyl methacrylate and the styrene-acrylonitrile-maleic anhydride of 1wt%, and the two mass ratio can be any ratio, be 2:3 in the present embodiment), 0.3Kg oxidation inhibitor is put into homogenizer and is stirred discharging after 5 minutes and obtain mixture B.Added from the main charging opening of twin screw extruder by mixture B, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 200 ~ 210 DEG C, and screw speed is 500 ~ 600rpm, and extruding pelletization obtains SAN masterbatch resin.
Three, AES resin combination is prepared
By 40KgEPDM master batch, 60KgSAN masterbatch resin, 0.02Kg initiator two 25 ［ 2,5-diethyl-2,5-bis-(tert-butyl peroxide) hexane ］, 0.5Kg additional crosslinker iso-cyanuric acid triallyl ester (fusing point is 20 ~ 40 DEG C) and 1Kg oxidation inhibitor put into homogenizer stir 30min after discharging obtain mixture C.Added by the main charging opening of mixture C from twin screw extruder, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 180 ~ 200 DEG C, and screw speed is 200 ~ 300rpm, and extruding pelletization obtains sample.
comparative example 1 ~ 3
In order to embody the feature of AES resin combination of the present invention preferably, comparative example 1 ~ 3 also use single stage method and add formula that the formula of compatilizer, single stage method do not add compatilizer, the formula that employs emulsion method AES resin contrasts, concrete major ingredient formula refers to table 1.
The formula table of table 1 embodiment 1 ~ 6 and comparative example 1 ~ 3
embodiment 7, performance test
For the above AES resin combination prepared according to embodiment 1 ~ 4 and comparative example 1 ~ 3, prepare test bars according to identical injecting condition, concrete physicals test item is as follows:
Tensile strength: measure tensile strength according to ASTM D 638 standard.
Normal temperature notched Izod impact strength: measure normal temperature notched Izod impact strength according to ASTM D256 standard (1/8 " breach, 23 DEG C).
Melt flow rate (MFR): measure melt flow rate (MFR) according to ASTM D 1238 standard (temperature 220 DEG C, load 10Kg).
The performance comparison of table 2 embodiment 1 ~ 4 and comparative example 1 ~ 3
By the Performance comparision of table 2, can find out, the AES resin that reactive extrusion obtains comparatively with AES resin prepared by emulsion method, has higher shock strength and better flowing property; Along with the raising of EPDM master batch consumption, the shock strength of material significantly improves, and the mobility of material reduces, and tensile strength declines; The raising of additional crosslinker consumption can cause being cross-linked, and shock strength is reduced, and mobility reduces; Add compatilizer but when use single stage method, two kinds of compatilizers are not distributed in EPDM and SAN resin respectively, but direct instead given birth to chemical reaction, do not play the effect improving consistency, show shock strength, tensile strength and mobility all on the low side; The performance that employing single stage method does not add compatilizer is then poorer.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (10)
1. an AES resin combination, is characterized in that, comprises each component of following parts by weight:
Described EPDM master batch comprises each component of following parts by weight:
Modified epdm 80 ~ 90 parts,
Compatilizer A 10 ~ 20 parts,
0.3 ~ 1 part, oxidation inhibitor,
Described compatilizer A to be the weight percent content of MAH be 1 ~ 10% ethylene-propylene acid resin and the graft copolymer of MAH, the weight percent content of GMA active function groups be 1 ~ 10% ethylene-propylene acid resin and GMA active function groups graft copolymer in one or more;
Described SAN masterbatch resin comprises each component of following parts by weight:
SAN resin 80 ~ 90 parts,
Compatilizer B 10 ~ 20 parts,
0.3 ~ 1 part, oxidation inhibitor,
Described compatilizer B is one or more in the graft copolymer of the graft copolymer of styrene-acrylonitrile resin and MAH, GMA active function groups; Can chemical reaction be there is in described compatilizer A and compatilizer B.
2. AES resin combination according to claim 1, is characterized in that, described modified epdm is one or more in bromination EPDM, chlorination EPDM, sulfonated epdm, cis-butenedioic anhydride EPDM, maleation EPDM and propylene nitrilation EPDM; In described modified epdm, the weight percent content of EPDM is 88 ~ 98%.
3. AES resin combination according to claim 1, it is characterized in that, described compatilizer A is one or more in ethylene-methyl acrylate-maleic anhydride, Ethylene-butyl acrylate-maleic anhydride, ethylene-ethylacrylate-maleic anhydride, ethylene-methyl acrylate-glyceryl methacrylate ternary atactic copolymer, Ethylene-butyl acrylate-glycidyl methacrylate ternary atactic copolymer.
4. AES resin combination according to claim 1, is characterized in that, described EPDM master batch prepares by the following method and obtains:
(1) by 80 ~ 90 part by weight modified EPDM, 10 ~ 20 parts by weight of compatible agent A, 0.3 ~ 1 weight part oxidation inhibitor, puts into homogenizer and stirs discharging after 5 ~ 30 minutes and obtain mixture;
(2) added by the main charging opening of described mixture from twin screw extruder, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 150 ~ 220 DEG C, and screw speed is 100 ~ 400rpm, and extruding pelletization obtains described EPDM master batch.
5. AES resin combination according to claim 1, is characterized in that, described SAN resin is weight-average molecular weight is 100,000 ~ 250, the vinyl cyanide of 000 and cinnamic graft copolymer; In described vinyl cyanide and cinnamic graft copolymer, the weight percent content of vinyl cyanide is 28 ~ 38%.
6. AES resin combination according to claim 1, is characterized in that, described compatilizer B is one or both in styrene-acrylonitrile-maleic anhydride, styrene-acrylonitrile-glycidyl methacrylate ternary atactic copolymer; In described ternary atactic copolymer, the weight percent content of glycidyl methacrylate is 1 ~ 10%.
7. AES resin combination according to claim 1, is characterized in that, described SAN masterbatch resin prepares by the following method and obtains:
(1) by 80 ~ 90 weight part SAN resins, 10 ~ 20 parts by weight of compatible agent B, 0.3 ~ 1 weight part oxidation inhibitor is put into homogenizer and is stirred discharging after 5 ~ 30 minutes and obtain mixture;
(2) added by the main charging opening of mixture from twin screw extruder, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 180 ~ 230 DEG C, and screw speed is 200 ~ 600rpm, and extruding pelletization obtains described SAN masterbatch resin.
8. the AES resin combination according to any one of claim 1 ~ 7, is characterized in that, described initiator is dicumyl peroxide, two (tert-butyl peroxide) diisopropylbenzene(DIPB).
9. the AES resin combination according to any one of claim 1 ~ 7, is characterized in that, described additional crosslinker to be fusing point the be iso-cyanuric acid triallyl ester of 20 ~ 40 DEG C.
10. a preparation method for AES resin combination as claimed in claim 1, is characterized in that, comprise the steps:
(1) after 10 ~ 50 weight part EPDM master batches, 50 ~ 90 weight part SAN masterbatch resins, 0.02 ~ 0.2 weight part initiator, 0.5 ~ 5 weight part additional crosslinker and 0.3 ~ 1 weight part oxidation inhibitor being put into homogenizer stirring 5 ~ 30min, discharging obtains mixture;
(2) added by the main charging opening of described mixture from twin screw extruder, through twin screw extruder extruding pelletization, the barrel zone temperature controlling forcing machine is 150 ~ 220 DEG C, and screw speed is 100 ~ 400rpm, and extruding pelletization obtains sample.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210375634.6A CN102898759B (en) | 2012-09-27 | 2012-09-27 | Acrylonitrile-ethylene-styrene (AES) resin composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210375634.6A CN102898759B (en) | 2012-09-27 | 2012-09-27 | Acrylonitrile-ethylene-styrene (AES) resin composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102898759A CN102898759A (en) | 2013-01-30 |
| CN102898759B true CN102898759B (en) | 2015-05-13 |
Family
ID=47571264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210375634.6A Expired - Fee Related CN102898759B (en) | 2012-09-27 | 2012-09-27 | Acrylonitrile-ethylene-styrene (AES) resin composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102898759B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104452096A (en) * | 2014-12-06 | 2015-03-25 | 常熟江南玻璃纤维有限公司 | Production process of glass fiber composite |
| CN104452094A (en) * | 2014-12-06 | 2015-03-25 | 常熟江南玻璃纤维有限公司 | Production process of glass fiber composite |
| CN104480629A (en) * | 2014-12-06 | 2015-04-01 | 常熟江南玻璃纤维有限公司 | Preparation method of glass fiber composite material |
| CN104480632A (en) * | 2014-12-06 | 2015-04-01 | 常熟江南玻璃纤维有限公司 | Method for preparing glass fiber composite material |
| CN104480633A (en) * | 2014-12-06 | 2015-04-01 | 常熟江南玻璃纤维有限公司 | Process for preparing glass fiber composite material |
| CN104480630A (en) * | 2014-12-06 | 2015-04-01 | 常熟江南玻璃纤维有限公司 | Preparation process of glass fiber composite material |
| CN104480631A (en) * | 2014-12-06 | 2015-04-01 | 常熟江南玻璃纤维有限公司 | Method used for producing glass fiber composite material |
| CN104945581A (en) * | 2015-07-06 | 2015-09-30 | 常州大学 | Preparation for SAN/EPDM compatibilizer with high grafting ratio |
| CN104927279A (en) * | 2015-07-06 | 2015-09-23 | 常州大学 | Blending method for preparing high performance SAN/EPDM blend |
| CN105367927A (en) * | 2015-12-04 | 2016-03-02 | 安徽瑞鑫自动化仪表有限公司 | Corrosion-resistant rubber material used for SF6 density relays, and preparation method thereof |
| CN105369471A (en) * | 2015-12-15 | 2016-03-02 | 常熟江南玻璃纤维有限公司 | Technology for producing glass fiber composite |
| CN107446296B (en) * | 2016-05-31 | 2019-11-19 | 金发科技股份有限公司 | A kind of refrigeration equipment environmental protection and energy saving structure sheaf and its application |
| CN107722486A (en) * | 2017-09-19 | 2018-02-23 | 广东圆融新材料有限公司 | A kind of weather-proof antibacterial and mouldproof AES materials and preparation method thereof |
| CN110527027B (en) * | 2019-08-15 | 2022-02-22 | 杭州华聚复合材料有限公司 | Graft of acid modified styrene polymer, composite material and application thereof |
| CN111499813B (en) * | 2020-04-09 | 2022-12-06 | 北方华锦化学工业股份有限公司 | Method for preparing high-flow AES resin by adopting continuous bulk method |
| CN115505235A (en) * | 2022-11-02 | 2022-12-23 | 北方华锦化学工业股份有限公司 | High-fluidity, high-impact-resistance and weather-resistant ABS resin material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050257A (en) * | 2007-04-28 | 2007-10-10 | 华南理工大学 | Method for preparing EPDM g-SAN toughening agent containing high quantity EPDM |
| CN101696279A (en) * | 2009-10-22 | 2010-04-21 | 金发科技股份有限公司 | Method for preparing thermoplastic elastomer through dynamic vulcanization |
| CN102153830A (en) * | 2011-04-20 | 2011-08-17 | 上海锦湖日丽塑料有限公司 | ACS (acrylonitrile-chlorinated polyethylene-styrene) resin composition and method for preparing same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10259500A1 (en) * | 2002-12-19 | 2004-07-01 | Bayer Ag | Graft polymers based on ethylene-α-olefin rubbers and process for their preparation |
-
2012
- 2012-09-27 CN CN201210375634.6A patent/CN102898759B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050257A (en) * | 2007-04-28 | 2007-10-10 | 华南理工大学 | Method for preparing EPDM g-SAN toughening agent containing high quantity EPDM |
| CN101696279A (en) * | 2009-10-22 | 2010-04-21 | 金发科技股份有限公司 | Method for preparing thermoplastic elastomer through dynamic vulcanization |
| CN102153830A (en) * | 2011-04-20 | 2011-08-17 | 上海锦湖日丽塑料有限公司 | ACS (acrylonitrile-chlorinated polyethylene-styrene) resin composition and method for preparing same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102898759A (en) | 2013-01-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102898759B (en) | Acrylonitrile-ethylene-styrene (AES) resin composition and preparation method thereof | |
| CN101747600B (en) | Method for preparing polyethylene terephthalate (PET) blend | |
| CN110804135B (en) | High-melt-strength polypropylene and preparation method thereof | |
| CN102391431B (en) | Nylon toughener and preparation method and application thereof | |
| CN102153830B (en) | ACS (acrylonitrile-chlorinated polyethylene-styrene) resin composition and method for preparing same | |
| CN103436012B (en) | Ultrahigh-molecular weight polyethylene modified nylon 66 and preparation method thereof | |
| CN111499813A (en) | Method for preparing high-flow AES resin by adopting continuous bulk method | |
| CN106633686A (en) | Core-shell particle toughened PBT/PC alloy and preparation method | |
| CN105037951A (en) | Inorganic rigid particle three-element blend toughened system RRP (polypropylene random) tube and preparation method thereof | |
| CN103059534A (en) | Polycarbonate blending material with high toughness and preparation method thereof | |
| CN102558697A (en) | Preparation method of ultrahigh-toughness polystyrene resin | |
| CN100590138C (en) | Process of grafting maleic anhydride with vinyl methacrylate | |
| CN109517119A (en) | A kind of enhancing PC/ABS alloy ductility and the compound material of ingredient compatibility and preparation method thereof | |
| CN106032398A (en) | A preparing method of long-chain branched polypropylene | |
| CN102295797B (en) | Zero-halogen flame-retardant polyolefin material and preparation method as well as application thereof | |
| CN110240778A (en) | A kind of preparation method of ontology ABS resin | |
| CN102321217A (en) | Multipolymer of a kind of melt polypropylene grafted maleic anhydride and preparation method thereof | |
| KR101540542B1 (en) | Methylmethacrylate-butadiene-styrene impact modifier and polycarbonate resin composition comprising the same | |
| CN108659367B (en) | Composition for transparent washing machine cover and preparation method | |
| CN115703904A (en) | High-heat-resistance polyethylene pipe composition and preparation method thereof | |
| CN105462149A (en) | Macromolecular compatilizer for ABS (acrylonitrile-butadiene-styrene)-HIPS (high impact polystyrene) alloys and preparation method of macromolecular compatilizer | |
| CN106832863B (en) | A kind of the regeneration PC alloy material and its production method of anti-stress cracking | |
| CN111484721A (en) | Low-temperature impact resistant PC/ABS composite material and preparation method thereof | |
| CN110591100A (en) | Ultralow temperature resistant nylon toughening agent and preparation method and application thereof | |
| CN104693723A (en) | Core-shell-particle toughened modified PC/PET alloy material |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150513 |