WO2021227201A1 - Use of multi-element random copolymer in improving phase state structure and phase state stability of polyester/styrenic resin alloy - Google Patents
Use of multi-element random copolymer in improving phase state structure and phase state stability of polyester/styrenic resin alloy Download PDFInfo
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- WO2021227201A1 WO2021227201A1 PCT/CN2020/097305 CN2020097305W WO2021227201A1 WO 2021227201 A1 WO2021227201 A1 WO 2021227201A1 CN 2020097305 W CN2020097305 W CN 2020097305W WO 2021227201 A1 WO2021227201 A1 WO 2021227201A1
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- WIPO (PCT)
- Prior art keywords
- monomer
- polyester
- styrene resin
- acrylonitrile
- aromatic vinyl
- Prior art date
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- 239000000956 alloy Substances 0.000 title claims abstract description 50
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 48
- 229920005604 random copolymer Polymers 0.000 title claims abstract description 27
- 229920001890 Novodur Polymers 0.000 title description 4
- 229920001225 polyester resin Polymers 0.000 title 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 115
- 239000000178 monomer Substances 0.000 claims abstract description 61
- 229920000728 polyester Polymers 0.000 claims abstract description 61
- 229920005989 resin Polymers 0.000 claims abstract description 60
- 239000011347 resin Substances 0.000 claims abstract description 60
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 27
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims description 19
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 10
- -1 compatibilizer Substances 0.000 claims description 10
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 10
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 10
- 239000004417 polycarbonate Substances 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- 230000037396 body weight Effects 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000035945 sensitivity Effects 0.000 abstract description 3
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000000463 material Substances 0.000 description 16
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 229920007019 PC/ABS Polymers 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XHAFIUUYXQFJEW-UHFFFAOYSA-N 1-chloroethenylbenzene Chemical compound ClC(=C)C1=CC=CC=C1 XHAFIUUYXQFJEW-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920001587 Wood-plastic composite Polymers 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000013502 plastic waste Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011155 wood-plastic composite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
- C08F212/10—Styrene with nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/12—Copolymers of styrene with unsaturated nitriles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Definitions
- the invention relates to a special compatibilizer for improving the phase distribution and stability of a polyester/styrene resin alloy and its application.
- PC/ABS alloys because they have the comprehensive characteristics of both PC and ABS, they have improved fluidity compared to PC. It improves the processing performance and reduces the sensitivity of the product to stress. Compared with ABS, it has better thermal stability. Therefore, it can be used in many fields such as household appliances, office equipment, communication equipment, photographic equipment, medical equipment, construction and lighting appliances, aerospace, electronic computers, optical fiber and so on. In particular, it has been widely used in high-strength and high-heat-resistant parts such as automotive interiors, exteriors, and lights.
- PET polyethylene terephthalate
- R-PET PET recycled material
- ABS and PET can produce alloys with excellent performance, which has the advantages of both ABS and PET, which not only broadens the application field of recycled materials, but also overcomes some inherent performance defects of ABS and reduces the price. It is a very promising one. Such materials have been widely used in home appliances such as televisions, and OA products such as printers and copiers.
- polyester/styrene resin alloys are relatively high, and the solubility parameters of polyester and styrene resins are quite different, which is prone to phase separation.
- compatibility of PC/ABS is good, the ester group of PC is also easy to be degraded by the attack of active groups such as hydroxyl under the condition of long thermal history or strong shear, so it can be degraded during processing or recycling. It is easy to re-aggregate the dispersed phase; currently, to solve the compatibility problem of polyester/styrene resin is generally to add a compatibilizer.
- Common and reported in the literature are: isocyanate, oxazoline, epoxy and acid anhydride compatibilizers.
- the purpose of the present invention is and its preparation method. Compared with the prior art, the method has the advantages of simplicity and effectiveness, convenient use, low cost and the like.
- the polyester/styrene resin alloy with phase distribution structure and phase stability is prepared from polyester, styrene resin, compatibilizer, and auxiliary agent; the compatibilizer is a multi-element random copolymer.
- the preparation method of the above-mentioned polyester/styrene resin alloy with phase distribution structure and phase stability is to put the polyester, styrene resin, compatibilizer, and auxiliary agent into a high-mixer, and then discharge the material. , And then extrude and pelletize with a screw extruder to obtain a polyester/styrene resin alloy with phase distribution structure and phase stability.
- the processing temperature is 220-260°C
- the screw speed is 180-600 rpm
- the speed of the high mixer is 2000 rpm
- the aspect ratio of the twin-screw extruder is between 34-40.
- the multi-element random copolymer is used as a compatibilizer to prepare the polyester/styrene resin alloy; or used to improve the phase structure and phase stability of the polyester/styrene resin alloy.
- the multi-element random copolymer as a compatibilizer is made by the copolymerization of aromatic vinyl monomers, acrylonitrile-based monomers and methacrylate monomers; among the aromatic vinyl monomers and acrylonitrile-based monomers, aromatic The weight percentage of vinyl monomer is 50wt% ⁇ 90wt%, the balance is acrylonitrile monomer; the amount of methacrylate monomer is 0.1% ⁇ of the total weight of aromatic vinyl monomer and acrylonitrile monomer. 15%.
- the weight percentage of the aromatic vinyl monomer is 60 wt% to 80 wt%, and the balance is the acrylonitrile monomer; the amount of the methacrylate monomer It is 0.1% to 10% of the total weight of the aromatic vinyl monomer and acrylonitrile monomer, preferably 0.2% to 2%.
- the multi-element random copolymer of the present invention is added as a compatibilizer to the polyester/styrene resin alloy to improve the phase distribution and phase stability of the alloy.
- the weight percentage of the compatibilizer is 0.5-15% of the total weight of polyester, styrene resin, and compatibilizer.
- the special compatibilizer for polyester/styrene resin alloy of the present invention can be prepared by blending with other raw materials and extruding granulation during the preparation process to achieve simple, effective, convenient use, and low-cost preparation. In addition to its mechanical properties, it also has a polyester/styrene resin alloy with excellent phase distribution structure and phase stability.
- the auxiliary agent is a conventional choice.
- the auxiliary agent is an antioxidant and/or a lubricant.
- the auxiliary agent does not include a compatibilizer and a conductive agent.
- the amount of the auxiliary agent is added according to the actual situation, such as an antioxidant 0.1-1wt. %, the lubricant is 0.1-0.5wt%, based on the weight sum of polyester, styrene resin and compatibilizer.
- the weight percentage of the polyester is 30-90%
- the weight percentage of the compatibilizer is 0.5-15%
- the balance is styrene resin.
- the polyester may be one of polycarbonate, polyethylene terephthalate, and polybutylene terephthalate; the styrenic resin is ABS, SAN, ASA One or more of AES can be either the bulk method or the emulsion method.
- the weight average molecular weight of the multi-element random copolymer is 20000-100000, and the melt index at 235°C/2.16kg is 30-120g/10min.
- the aromatic vinyl monomer includes styrenic monomers, such as styrene monomer, ⁇ -methylstyrene monomer, ⁇ -chlorostyrene monomer or p-methylstyrene monomer
- the acrylonitrile monomer includes acrylonitrile monomer or ⁇ -methacrylonitrile monomer; the methacrylate may be one or more of methyl methacrylate and glycidyl methacrylate.
- a multi-element random copolymer is used as a compatibilizer, in which the GMA content is 0.1wt%-10wt%, preferably 0.2wt%-2wt%, which can maximize the mechanical properties of polyester/styrene resin materials , Improve the phase structure and phase stability of polyester/styrene resin.
- the present invention has the following beneficial effects.
- the compatibilizer of the present invention has good thermal stability in co-extrusion with polymer, does not cause problems such as precipitation or difficulty in migrating to the interface to reduce the reactivity, the content of reactive functional groups is appropriate, and it is easy to control the occurrence of black spots or gel phenomena; and Styrene resins are completely thermodynamically compatible, and there is no problem of phase separation. Moreover, it is convenient to use, does not require masterbatch, and there is no secondary pollution; the multi-element random copolymer of the present invention has high reactivity, high use efficiency, and the use cost is one-third to two-half lower than similar products on the market First, it has an excellent price/performance ratio. Wide range of uses: It also provides a suitable simple method for improving the phase structure and taking into account the mechanical properties of the recycled polyester/styrene resin.
- Figure 1 is a comparison of scanning electron micrographs of the alloys prepared in Examples 5-8.
- Fig. 2 is a comparison of multi-axis impact of Example 5 and Example 8.
- Figure 3 is a comparison of the phase stability (TEM) between the near gate and the far gate of the injection molded parts of Example 5 and Example 6.
- Figure 4 is a comparison of the impact performance of the injection molded parts of Example 5 and Example 6 between the near gate and the far gate.
- Figure 5 is a comparison of the phase stability of Example 5 and Example 3 after multiple extrusions.
- Fig. 6 is a comparison diagram of the microscopic appearance diagrams of Examples 9-13.
- the invention discloses a multi-element random copolymer as a compatibilizer by copolymerization of aromatic vinyl monomers, acrylonitrile monomers and methacrylate monomers; the specific preparation method can be selected according to the prior art, as follows.
- the preparation of the compatibilizer in the following examples can be carried out according to this, and the addition of raw materials can be adjusted in proportion.
- the polyester/styrene resin alloy with phase distribution structure and phase stability is prepared from polyester, styrene resin, compatibilizer, and auxiliary agent; the compatibilizer is a multi-element random copolymer.
- the auxiliary agent is a conventional choice, for example, the auxiliary agent is an antioxidant and/or a lubricant.
- Example 1-4 According to the raw material composition ratio in Table 1, a special compatibilizer for improving the phase distribution and stability of polyester/styrene resin alloy was prepared. Examples 1-4, 14 and Comparative Example 1 -2 (The preparation method is the same as the embodiment, and the addition is adjusted regularly). And these compatibilizers are used to prepare polyester/styrene resin alloys to study the improvement of the phase state and phase stability of such alloys.
- Example 5-9 PC resin is selected from Teijin Corporation’s PCI250WP (relative number average molecular weight is 22000g/mol, glass transition temperature is 140°C); ABS resin is selected from Korea’s Kumho Petrochemical’s P/D190 (relative weight average molecular weight is 120,000 g/mol, wherein the butadiene weight percentage content is 50%, the acrylonitrile weight percentage content is 15%, and the styrene weight percentage content is 35%.
- the processing temperature is 220 ⁇ 260°C, and the screw speed is 300 rpm; high-mixer
- the speed of the twin-screw extruder is 2000rpm, and the aspect ratio of the twin-screw extruder is 36.
- Example 2 and Comparative Examples 1 and 2 are relatively blank samples without compatibilizer can improve the phase structure, but in comparison, in the case of the same composition, the PC/ABS with Example 2 as the compatibilizer has A finer dispersed phase structure. Combined with the mechanical properties data in Table 3, a better phase structure also means better mechanical properties, especially impact strength. Although the components of Examples 7 and 8 have higher rubber components, the results show that Example 5 The impact performance is better, which is mainly due to the optimization of the phase structure.
- Example 3 was used to replace Example 2 in Example 5, and the rest remained unchanged.
- the resulting sheet material (Example 15) had a cantilever beam impact strength of 748J/m;
- Example 1 was used to replace Example 2 in Example 5.
- the rest remains unchanged, and the obtained sheet cantilever beam impact strength is 808J/m, which has decreased.
- the optimization of the phase state of the present invention in addition to showing advantages in conventional mechanical properties, can also have special effects in some special applications.
- Figure 2 The results of multi-axis impact show the destructiveness of impact, which is more specific. The conventional impact performance is high, but the multi-axis impact performance is not necessarily good. It can be seen that the performance advantages of the present invention are obvious.
- ASTM In D1709 due to the change of the phase structure, there is an essential difference.
- the sample of Example 5 using Example 2 as a compatibilizer shows better passability, while Examples 6-8 respectively show A certain degree of failure occurs.
- Example 8 the total energy of Example 8 is 52.2J, all brittleness, the total energy of Example 7 is 55.3J, 50% toughness, the total energy of Example 6 is 54.8J, 70% toughness, and the total energy of Example 5 is 56.4 J. 100% toughness; this difference allows PC/ABS alloy to be used in higher-level safety protection materials.
- Example 5 and 6 are different. Combined with the scanning electron microscope of Figure 3, the injection molded parts of Example 5 and Example 6 were sampled at the near gate position and the far gate position, respectively, and then subjected to transmission electron microscopy analysis after slicing. Phase structure to observe its phase stability. In order to illustrate the influence of the compatibilizer of the present invention on the stability of the alloy phase distribution, conventional injection molding with a large mold was used to prepare injection molded parts with a length of 30 cm and a width of the standard width of the notched impact spline.
- the special compatibilizer for improving the phase distribution and stability of the polyester/styrene resin alloy disclosed in the present invention has a more efficient performance.
- the phase stability is compared with repeated extrusion and granulation. That is, after the first extruding and granulating with the screw extruder, the particles are put into the extruder again, and the granulation is continued, which is a secondary extrusion. Such a cycle. The particles obtained from different extrusion times are injected according to the same conventional method as mentioned above. The transmission electron microscope TEM of the alloy sheet can be seen from the figure.
- Example 3 After multiple extrusion processing, due to multiple heat-shearing history, the phase state of Example 3 has a certain degree of disperse phase aggregation, while that of Example 5 It still maintains a better phase structure, and therefore performs better in terms of mechanical properties. See Table 4, which is the sheet test after the particles are conventionally injected. The test method is as above.
- Embodiment 9 ⁇ 12 PET resin selected commercial embodiment Bottle regrind (intrinsic viscosity 0.65); ABS resin selected Korea Kumho Petrochemical P / D190 (a relative weight average molecular weight of 120000g / mol, wherein the percentage by weight of butadiene 50%, 15% by weight of acrylonitrile and 35% by weight of styrene) and Taiwan Chemical’s SAN resin NF2200 (relative weight average molecular weight is about 120,000g/mol, of which 24% by weight of acrylonitrile, benzene The ethylene weight percentage content is 76%).
- the processing temperature is 220 ⁇ 260°C, and the screw speed is 500 rpm; high-mixer
- the speed of the twin-screw extruder is 2000rpm, and the aspect ratio of the twin-screw extruder is 36.
- the particles prepared according to Examples 9 to 13 were conventionally injection molded into sheets and then subjected to microscopic morphology observation and mechanical property testing.
- the cross-sectional SEM morphology is shown in Figure 6. It can be seen from Figure 6 that the phase state of Examples 9-11 is better than that of Examples 12 and 13, which is related to the structure of the selected compatibilizer, and compares the two of Example 2 and Comparative Example 1 in the PC/ABS system. The results of a compatibilizer are similar.
- Example 13 is the worst.
- the uniformity of the phase state of Example 12 is acceptable, but the particle size of the dispersed phase is too large, and the compatibilizer used also has GMA functional groups. This result may be related to the MMA in the structure.
- the existence of MMA affects GMA The reaction activity, which leads to the difference in phase state.
- Table 6 shows the mechanical performance test data, and the test method is as above.
- the obtained sheet notched impact strength (1/8 inch) is 178J/m; replace Example 2 in Example 10 of the present invention with the compatibilizer prepared in Example 4 of the existing CN105462149A, and the rest remain unchanged, the resulting sheet notched impact strength (1/8 inch) is 141J/m; replacing Example 2 in Example 10 of the present invention with the existing ADR-4370 compatibilizer, and the rest remain unchanged, the obtained sheet notched impact strength (1/8 inch) is 152J/m.
- the method of the present invention is simple and easy to implement.
- a multi-element random copolymer of the present invention as a compatibilizer, adding a suitable ratio and selecting a suitable functional group content, the polyester/styrene resin can be effectively improved.
- the mechanical properties of the material increase the phase structure of the polyester/styrene resin and the phase stability during processing. This is because the multi-element random copolymer of the present invention makes the dispersed phase particle size finer, smaller shape change, and more evenly distributed through chemical reaction, so that the alloy material can absorb more energy when subjected to external force, showing In order to increase the impact strength, the sensitivity to the notch decreases and other performance advantages.
- Multi-element random copolymers can be directly mixed with polyester and styrene resins without masterbatch, easy to use, and low addition. It is a method to obtain high-performance polyester/styrene resin alloys.
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims (10)
- 多元无规共聚物在制备聚酯/苯乙烯类树脂合金中的应用或者多元无规共聚物在改善聚酯/苯乙烯类树脂合金的相态结构及相态稳定性中的应用,其特征在于,所述多元无规共聚物由芳香族乙烯基单体、丙烯腈系单体和甲基丙烯酸酯单体共聚而成。The application of multiple random copolymers in the preparation of polyester/styrene resin alloys or the application of multiple random copolymers in improving the phase structure and phase stability of polyester/styrene resin alloys is characterized by The multi-element random copolymer is formed by copolymerization of aromatic vinyl monomers, acrylonitrile monomers and methacrylate monomers.
- 根据权利要求1所述的应用,其特征在于,聚酯/苯乙烯类树脂合金由聚酯、苯乙烯类树脂、相容剂、助剂制备。The application according to claim 1, wherein the polyester/styrene resin alloy is prepared from polyester, styrene resin, compatibilizer, and auxiliary agent.
- 根据权利要求1所述的应用,其特征在于,所述芳香族乙烯基单体包括苯乙烯系单体;所述丙烯腈系单体包括丙烯腈单体或α-甲基丙烯腈单体;所述甲基丙烯酸酯为甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯的一种或者几种。The application according to claim 1, wherein the aromatic vinyl monomer comprises a styrenic monomer; the acrylonitrile monomer comprises an acrylonitrile monomer or an α-methacrylonitrile monomer; The methacrylate is one or more of methyl methacrylate and glycidyl methacrylate.
- 根据权利要求1所述的应用,其特征在于,芳香族乙烯基单体、丙烯腈系单体中,芳香族乙烯基单体的重量百分数为50wt%~90wt%,余量为丙烯腈系单体;甲基丙烯酸酯单体的用量为芳香族乙烯基单体、丙烯腈系单体重量和的0.1%~15%。The application according to claim 1, wherein in the aromatic vinyl monomers and acrylonitrile-based monomers, the weight percentage of the aromatic vinyl monomer is 50wt% to 90wt%, and the balance is the acrylonitrile-based monomer. The amount of methacrylate monomer is 0.1%-15% of the total weight of aromatic vinyl monomer and acrylonitrile monomer.
- 根据权利要求1所述的应用,其特征在于,所述聚酯为聚碳酸酯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯中的一种;所述苯乙烯类树脂为ABS、SAN、ASA、AES中的一种或几种。The application according to claim 1, wherein the polyester is one of polycarbonate, polyethylene terephthalate, and polybutylene terephthalate; the styrene The similar resin is one or more of ABS, SAN, ASA, and AES.
- 具有相态分布结构及相态稳定性的聚酯/苯乙烯类树脂合金,由聚酯、苯乙烯类树脂、相容剂、助剂制备;所述相容剂为多元无规共聚物,其特征在于,所述多元无规共聚物由芳香族乙烯基单体、丙烯腈系单体和甲基丙烯酸酯单体共聚而成。The polyester/styrene resin alloy with phase distribution structure and phase stability is prepared from polyester, styrene resin, compatibilizer, and auxiliary agent; the compatibilizer is a multi-element random copolymer, which It is characterized in that the multi-element random copolymer is formed by copolymerization of aromatic vinyl monomers, acrylonitrile-based monomers and methacrylate monomers.
- 根据权利要求6所述具有相态分布结构及相态稳定性的聚酯/苯乙烯类树脂合金,其特征在于,芳香族乙烯基单体、丙烯腈系单体中,芳香族乙烯基单体的重量百分数为50wt%~90wt%,余量为丙烯腈系单体;甲基丙烯酸酯单体的用量为芳香族乙烯基单体、丙烯腈系单体重量和的0.1%~15%。The polyester/styrene resin alloy having a phase distribution structure and phase stability according to claim 6, wherein among the aromatic vinyl monomers and acrylonitrile-based monomers, the aromatic vinyl monomers The weight percentage of is 50wt% to 90wt%, and the balance is acrylonitrile monomer; the amount of methacrylate monomer is 0.1% to 15% of the total weight of aromatic vinyl monomer and acrylonitrile monomer.
- 根据权利要求6所述具有相态分布结构及相态稳定性的聚酯/苯乙烯类树脂合金,其特征在于,聚酯、苯乙烯类树脂、相容剂中,聚酯的重量百分数为30~90%,相容剂的重量百分数为0.5~15%,余量为苯乙烯类树脂。The polyester/styrene resin alloy with phase distribution structure and phase stability according to claim 6, wherein the weight percentage of polyester in the polyester, styrene resin, and compatibilizer is 30 ~90%, the weight percentage of the compatibilizer is 0.5-15%, and the balance is styrene resin.
- 多元无规共聚物,其特征在于,所述多元无规共聚物由芳香族乙烯基单体、丙烯腈系单体和甲基丙烯酸酯单体共聚而成;芳香族乙烯基单体、丙烯腈系单体中,芳香族乙烯基单体的重量百分数为50wt%~90wt%,余量为丙烯腈系单体;甲基丙烯酸酯单体的用量为芳香族乙烯基单体、丙烯腈系单体重量和的0.1%~15%。The multi-element random copolymer is characterized in that the multi-element random copolymer is copolymerized by an aromatic vinyl monomer, an acrylonitrile-based monomer, and a methacrylate monomer; the aromatic vinyl monomer, acrylonitrile Among the monomers, the weight percentage of the aromatic vinyl monomer is 50% to 90% by weight, and the balance is the acrylonitrile monomer; the amount of the methacrylate monomer is the aromatic vinyl monomer and the acrylonitrile monomer. 0.1% to 15% of the total body weight.
- 根据权利要求9所述多元无规共聚物,其特征在于,所述芳香族乙烯基单体包括苯乙烯系单体;所述丙烯腈系单体包括丙烯腈单体或α-甲基丙烯腈单体;所述甲基丙烯酸酯为甲基丙烯酸甲酯、甲基丙烯酸缩水甘油酯的一种或者几种。The multi-element random copolymer according to claim 9, wherein the aromatic vinyl monomer comprises a styrenic monomer; the acrylonitrile monomer comprises an acrylonitrile monomer or α-methacrylonitrile Monomer; The methacrylate is one or more of methyl methacrylate and glycidyl methacrylate.
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