CN114702765A - Modified nano-microsphere, PC/PET composite material and preparation method thereof - Google Patents
Modified nano-microsphere, PC/PET composite material and preparation method thereof Download PDFInfo
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- CN114702765A CN114702765A CN202210631819.2A CN202210631819A CN114702765A CN 114702765 A CN114702765 A CN 114702765A CN 202210631819 A CN202210631819 A CN 202210631819A CN 114702765 A CN114702765 A CN 114702765A
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- porous hollow
- polydopamine
- microspheres
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- polystyrene porous
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- 239000004005 microsphere Substances 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 92
- 239000004793 Polystyrene Substances 0.000 claims abstract description 89
- 229920002223 polystyrene Polymers 0.000 claims abstract description 89
- 229920001690 polydopamine Polymers 0.000 claims abstract description 80
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 11
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000003431 cross linking reagent Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 6
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical class OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000004108 freeze drying Methods 0.000 claims description 5
- -1 oxyethylene-oxypropylene Chemical group 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 4
- 238000009775 high-speed stirring Methods 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002077 nanosphere Substances 0.000 claims description 3
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 2
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 2
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims 1
- 235000021317 phosphate Nutrition 0.000 claims 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 11
- 239000003921 oil Substances 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 54
- 229920000139 polyethylene terephthalate Polymers 0.000 description 54
- 239000004417 polycarbonate Substances 0.000 description 47
- 239000000956 alloy Substances 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 230000006872 improvement Effects 0.000 description 7
- 238000009740 moulding (composite fabrication) Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000012994 photoredox catalyst Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 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 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- 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
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- 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
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- 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
-
- 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
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
- C08L2205/20—Hollow spheres
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a modified nano-microsphere, a PC/PET composite material and a preparation method thereof, belonging to the technical field of nano-materials and high polymer materials, and the modified nano-microsphere is prepared from the following raw materials in parts by weight: PC60-80 parts, PET12-32 parts, composite compatilizer 0.5-2 parts, transparent agent 0.1-0.3 part and antioxidant 0-0.5 part; the composite compatilizer comprises modified silicon dioxide/polydopamine/polystyrene porous hollow nano microspheres and maleic anhydride grafted polyethylene, and the mass ratio is (3-5): 7. the PC/PET composite material provided by the invention has high transparency, high mechanical property, better oil resistance, solvent resistance, heat resistance and the like, and has wide application prospect.
Description
Technical Field
The invention relates to the technical field of nano materials and high polymer materials, in particular to a PC/PET composite material containing modified nano microspheres and a preparation method thereof.
Background
PC (polycarbonate) has excellent transparency, mechanical strength and thermal stability, and is one of five general-purpose engineering plastics. However, PC has the disadvantages of high melt viscosity, difficult molding processing, no oil resistance, no solvent resistance and the like. PET (polyethylene terephthalate) is a crystalline material and has excellent oil resistance and solvent resistance, but when it is used alone, it has disadvantages such as poor heat resistance and low mechanical strength. And because the PET resin is a crystalline polymer and the PC resin is an amorphous polymer, the compatibility between the PET resin and the PC resin is poor, and the mechanical property of the composite material is reduced due to the mixing of the PET resin and the PC resin. In addition, because the PC resin contains terminal hydroxyl, the terminal hydroxyl can react with residual carboxyl and hydroxyl in the PET resin at high temperature in the presence of a titanium residual catalyst, the two-phase reaction can improve the compatibility of the terminal hydroxyl and the carboxyl, but has great uncertainty, and the reaction can cause rapid deterioration of the performance of the composite material in the later use process, so that the practicability of the PC/PET composite material is greatly reduced. In order to solve the technical problems, in the prior art, technicians use styrene-acrylonitrile-glycidyl methacrylate as a chain extender, so that the toughness and the stability of the obtained PC/PET composition are improved, but the addition of the chain extender can influence the fluidity and the glossiness of the composite material and limit the popularization and the application of the composite material.
Chinese patent CN200710074569.2 reports a preparation method of a non-transparent PC/PET composite material; chinese patent CN200710019829.6 reports a preparation method of PC/PET composite material, which belongs to the field of material forming and processing, the processing process is complex, and PC/PET alloy sheets are prepared by procedures of pre-crystallization, drying, mixing plasticization, neck mold forming, cooling and calendaring and the like.
Disclosure of Invention
The invention aims to provide a modified nano microsphere, a PC/PET composite material containing the microsphere and a preparation method thereof, and the modified nano microsphere has high transparency, high mechanical property, better oil resistance, solvent resistance, heat resistance and other properties, and wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of modified silicon dioxide/polydopamine/polystyrene porous hollow nano microspheres, which is characterized by comprising the following steps:
s1, preparing polystyrene porous hollow nano microspheres: mixing and dissolving an initiator and a styrene monomer, adding a hydrophilic monomer methyl methacrylate and a pore-forming agent, stirring and mixing uniformly, adding an aqueous solution of PVA, performing ultrasonic dispersion uniformly to obtain a suspension, heating and polymerizing, performing high-speed stirring reaction for a first time period, then adding a cross-linking agent divinylbenzene, continuing stirring and reacting for a second time period, centrifuging, and performing freeze drying to obtain the polystyrene porous hollow nano-microsphere;
s2, preparing the polydopamine/polystyrene porous hollow nano-microspheres: dispersing the porous hollow nano-microspheres prepared in the step S1 into water, adding dopamine hydrochloride and a catalyst, heating, stirring, reacting, filtering, and washing with water to obtain the polydopamine/polystyrene porous hollow nano-microspheres;
s3, preparing the silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres: dispersing the polydopamine/polystyrene porous hollow nano-microspheres prepared in the step S2 into silica sol, heating for sol-gel reaction, centrifuging, and washing to obtain silica/polydopamine/polystyrene porous hollow nano-microspheres;
s4, preparing the modified silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres: and (4) adding the silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres prepared in the step (S3) into an ethanol solution containing a composite silane coupling agent, and heating for reaction to obtain the modified silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres.
As a further improvement of the present invention, in step S1, the initiator is selected from at least one of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate; the pore-foaming agent is selected from at least one of isooctane, cetyl trimethyl ammonium bromide, an oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and PEO106-PPO70-PEO 106; the PVA content in the PVA water solution is 3-5 wt%; the mass ratio of the initiator, the styrene monomer, the hydrophilic monomer methyl methacrylate, the pore-foaming agent, the PVA aqueous solution and the cross-linking agent divinylbenzene is (0.05-0.1): (1-2): (0.2-0.4): (0.02-0.07): (5-10): (0.1-0.3); the temperature is raised to 60-80 ℃, the high-speed stirring speed is 1500-.
As a further improvement of the invention, the catalyst in the step S2 is a Tris-HCl solution with the pH value of 5.5-6.6; the mass ratio of the polystyrene porous hollow nano-microspheres to the dopamine hydrochloride to the catalyst is 100: (25-35): (2-7); the heating temperature is 40-60 ℃, and the reaction time is 3-7 h.
As a further improvement of the invention, the preparation method of the silica sol in the step S3 comprises the following steps of mixing water, ethanol, 1-2mol/L hydrochloric acid and tetraethoxysilane according to the mass ratio of 1: (3-4): (0.1-0.4): (7-10) mixing, and uniformly stirring to obtain silicon dioxide sol; the heating temperature is 60-80 ℃, and the reaction lasts 18-24 h.
As a further improvement of the invention, in the step S4, the composite silane coupling agent is a compound mixture of KH560 and KH550, and the mass ratio is (3-5): 1.
as a further improvement of the present invention, in step S4, the mass ratio of the silica/polydopamine/polystyrene porous hollow nano-microspheres to the composite silane coupling agent is 30: (2-5); the heating temperature is 80-90 ℃ and the time is 3-5 h.
The invention further protects the modified silicon dioxide/polydopamine/polystyrene porous hollow nano-microsphere prepared by the preparation method.
The invention further provides a PC/PET composite material which is prepared from the following raw materials in parts by weight: 60-80 parts of PC, 12-32 parts of PET, 0.5-2 parts of composite compatilizer, 0.1-0.3 part of transparent agent and 0-0.5 part of antioxidant; the composite compatilizer comprises the modified silica/polydopamine/polystyrene porous hollow nano-microsphere and maleic anhydride grafted polyethylene, and the mass ratio is (3-5): 7.
as a further improvement of the invention, the clearing agent is selected from at least one of aryl phosphate and sorbitol compounds; the antioxidant is selected from at least one of phenolic antioxidant and phosphite antioxidant.
The invention further provides a preparation method of the PC/PET composite material, which comprises the following steps: weighing the components according to the formula ratio, putting the components into a mixer for uniformly mixing to obtain a premix, adding the premix into a double-screw extruder for melting and mixing, and extruding and granulating to obtain a PC/PET composite material; the length-diameter ratio of the screws of the double-screw extruder is (35-40): 1; the temperature of the screw cylinder is 260-270 ℃, and the rotating speed of the screw is 450-550 r/min.
The invention has the following beneficial effects:
the invention has prepared a kind of modified silicon dioxide/poly dopamine/polystyrene porous hollow nanometer microballoon, the monomer that is added in the initial stage includes styrene and hydrophilic monomer methyl methacrylate, does not contain cross-linking agent, after the initial polymerization is a period of time, because contain hydrophilic monomer but not contain cross-linking agent in the system, the polymer molecular chain has stronger ability of moving to the surface of suspending the little liquid drop, wrap the pore-forming agent in the centre of little liquid drop, form the initial shell, add cross-linking agent further, the cross-linking agent only takes place the cross-linking reaction on the surface of liquid drop, finally cross-link the polymer into the shell, stir constantly in this process, the pore-forming agent of the inner layer is transferred to some shell positions, and then form the porous hollow structure pore-forming, the remover, can get the polystyrene porous hollow nanometer microballoon;
further forming a polydopamine layer on the surface through reaction, wherein the polyamino structure of the polydopamine is positively charged, and the silica sol is negatively charged, so that the silica sol can interact with the polydopamine and be adsorbed to the surface of the polydopamine, the silica sol can be slowly adsorbed to the whole polydopamine layer under an acidic condition, and the surface of gel reaction is uniformly carried out to obtain the silica/polydopamine/polystyrene porous hollow nano-microspheres;
then adding a silane coupling agent KH550 with amino groups and a silane coupling agent KH560 with epoxy groups for surface modification to obtain modified silica/polydopamine/polystyrene porous hollow nano-microspheres;
the composite compatilizer comprises modified silicon dioxide/polydopamine/polystyrene porous hollow nano microspheres and maleic anhydride grafted polyethylene, wherein, the surface of the modified silica/polydopamine/polystyrene porous hollow nano microsphere is provided with abundant amino (from a silane coupling agent KH 550), hydroxyl (from polydopamine) and epoxy (from a silane coupling agent KH 560), after the three groups are added into a PET/PC matrix, can react with the terminal hydroxyl and the segment carboxyl of PET, the generated graft copolymer reduces the interfacial tension, greatly improves the compatibility among components, limits the degree of phase separation, refines the dispersed phase particles, can absorb more impact energy when being subjected to external force, is beneficial to improving the toughness and the strength of the material, and simultaneously, the reaction between the two components can greatly reduce the interfacial tension and improve the compatibility of the PC and PET components; on the other hand, the modified silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres can also play a role of nucleating agent to promote PET crystallization, so that the mechanical property of the alloy is improved; moreover, the porous structure of the modified silica/polydopamine/polystyrene porous hollow nano-microsphere prepared by the invention enables macromolecular chains of PET and PC to pass through the microsphere from macropores, thereby avoiding the influence of rigid particles on the mechanical property of the alloy due to the blockage of the molecular chains, further improving the strength, toughness and compatibility of the PC/PET alloy, and having the synergistic effect due to the addition of the composite silane coupling agent;
in addition, the added maleic anhydride grafted polyethylene serving as another compatilizer is a flexible molecule, so that the collision probability of PC rigid particles and PET chains is reduced, the POE is a flexible particle and can play a role of an accelerant, the two functions cooperate to enable crystallization of PET to be easy, and the toughness of the material is further improved;
the invention improves the visible light transmittance of the composite material by reducing the PET crystal region crystal nucleus through the transparent agent and the composite compatilizer, and the provided PC/PET composite material has high transparency, high mechanical property, better oil resistance, solvent resistance, heat resistance and other properties, and has wide application prospect in the preparation of medical multilayer copolymer film materials and other fields.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an SEM image of modified silica/polydopamine/polystyrene porous hollow nanospheres prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The present example provides a PC/PET composite:
the raw materials comprise the following components in parts by weight: 60 parts of PC, 12 parts of PET, 0.5 part of composite compatilizer and 0.1 part of sorbitol serving as a transparent agent. The composite compatilizer comprises modified silicon dioxide/polydopamine/polystyrene porous hollow nano microspheres and maleic anhydride grafted polyethylene, and the mass ratio is 3: 7.
the preparation method comprises the following steps:
(1) the preparation method of the modified silicon dioxide/polydopamine/polystyrene porous hollow nano-microsphere comprises the following steps:
s1, preparing polystyrene porous hollow nano microspheres: mixing and dissolving 0.05g of benzoyl peroxide and 1g of styrene monomer, adding 0.2g of hydrophilic monomer methyl methacrylate and 0.02g of hexadecyl trimethyl ammonium bromide, stirring and mixing uniformly, adding 5g of aqueous solution containing 3wt% of PVA, performing ultrasonic dispersion for 20min at 1000W to obtain suspension, heating to 60 ℃, stirring and reacting for 2h at the rotating speed of 1500r/min, then adding 0.1g of cross-linking agent divinylbenzene, continuing to stir and react for 1h, centrifuging, and performing freeze drying to obtain the polystyrene porous hollow nano-microsphere;
s2, preparing the polydopamine/polystyrene porous hollow nano-microspheres: dispersing 100g of the porous hollow polystyrene nano-microspheres prepared in the step S1 into 200mL of water, adding 25g of dopamine hydrochloride and 2g of Tris-HCl solution with the pH value of 5.5, heating to 40 ℃, stirring for reaction for 3h, filtering, and washing with water to obtain the porous hollow polydopamine/polystyrene nano-microspheres;
s3, preparation of the silica sol: water, ethanol, 1mol/L hydrochloric acid and tetraethoxysilane are mixed according to the mass ratio of 1: 3: 0.1: 7, mixing and uniformly stirring to obtain silicon dioxide sol;
s4, preparing the silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres: dispersing 20g of the polydopamine/polystyrene porous hollow nano-microspheres prepared in the step S2 into 50g of the silicon dioxide sol prepared in the step S3, heating to 60 ℃, reacting for 18 hours, centrifuging, and washing to obtain silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres;
s5, preparing the modified silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres: adding 30g of the silica/polydopamine/polystyrene porous hollow nano-microspheres prepared in the step S4 into 2g of 100mL of ethanol solution containing a composite silane coupling agent, heating to 80 ℃, and reacting for 3h to obtain modified silica/polydopamine/polystyrene porous hollow nano-microspheres; the composite silane coupling agent is a compound mixture of KH560 and KH550, and the mass ratio is 3: 1; the SEM image of the obtained microsphere is shown in FIG. 1, and it can be seen that a large number of macropores with a diameter of between 300 and 400nm are formed on the surface of the microsphere.
(2) Weighing the components according to the formula, putting the components into a mixer for uniformly mixing to obtain a premix, adding the premix into a double-screw extruder for melt mixing and extrusion granulation, wherein the ratio of the long diameter of a screw of the double-screw extruder to the diameter of the screw is 35: 1; the temperature of the screw cylinder is 260 ℃, the rotating speed of the screw is 450r/min, and the PC/PET composite material is obtained.
Example 2
The present example provides a PC/PET composite:
the raw materials comprise the following components in parts by weight: 80 parts of PC, 32 parts of PET, 2 parts of composite compatilizer, 0.3 part of transparent triaryl phosphate and 0.5 part of antioxidant triphenyl phosphite. The composite compatilizer comprises modified silicon dioxide/polydopamine/polystyrene porous hollow nano microspheres and maleic anhydride grafted polyethylene, and the mass ratio is 5: 7.
the preparation method comprises the following steps:
(1) the preparation method of the modified silicon dioxide/polydopamine/polystyrene porous hollow nano-microsphere comprises the following steps:
s1, preparing polystyrene porous hollow nano microspheres: mixing and dissolving 0.1g of dicumyl peroxide and 2g of styrene monomer, adding 0.4g of hydrophilic monomer methyl methacrylate and 0.07g of isooctane, stirring and mixing uniformly, adding 10g of aqueous solution containing 5wt% of PVA, performing ultrasonic dispersion for 20min at 1000W to obtain suspension, heating to 80 ℃, stirring and reacting for 4h at the rotating speed of 2000r/min, then adding 0.3g of cross-linking agent divinylbenzene, continuing to stir and react for 2h, centrifuging, and freeze-drying to obtain the polystyrene porous hollow nano-microsphere;
s2, preparing the polydopamine/polystyrene porous hollow nano-microspheres: dispersing 100g of the porous hollow polystyrene nano-microspheres prepared in the step S1 into 200mL of water, adding 35g of dopamine hydrochloride and 7g of Tris-HCl solution with the pH value of 6.6, heating to 60 ℃, stirring for reaction for 7h, filtering, and washing with water to obtain the porous hollow polydopamine/polystyrene nano-microspheres;
s3, preparation of the silica sol: water, ethanol, 2mol/L hydrochloric acid and tetraethoxysilane are mixed according to the mass ratio of 1: 4: 0.4: 10, mixing and uniformly stirring to obtain silicon dioxide sol;
s4, preparing the silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres: dispersing 20g of the polydopamine/polystyrene porous hollow nano-microspheres prepared in the step S2 into 50g of the silicon dioxide sol prepared in the step S3, heating to 80 ℃, reacting for 24 hours, centrifuging, and washing to obtain silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres;
s5, preparing the modified silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres: adding 30g of the silica/polydopamine/polystyrene porous hollow nano-microspheres prepared in the step S4 into 5g of 100mL of ethanol solution containing a composite silane coupling agent, heating to 90 ℃, and reacting for 5h to obtain modified silica/polydopamine/polystyrene porous hollow nano-microspheres; the composite silane coupling agent is a compound mixture of KH560 and KH550, and the mass ratio is 5: 1;
(2) weighing the components according to the formula ratio, putting the components into a mixer for uniformly mixing to obtain a premix, adding the premix into a double-screw extruder for melt mixing and extrusion granulation, wherein the ratio of the length to the diameter of a screw of the double-screw extruder is 40: 1; the temperature of the screw cylinder is 270 ℃, the rotating speed of the screw is 550r/min, and the PC/PET composite material is obtained.
Example 3
The present example provides a PC/PET composite:
the raw materials comprise the following components in parts by weight: 70 parts of PC, 18 parts of PET, 1 part of composite compatilizer, 0.2 part of sorbitol serving as a transparent agent and 0.2 part of 2, 6-di-tert-butyl-4-cresol serving as an antioxidant. The composite compatilizer comprises modified silicon dioxide/polydopamine/polystyrene porous hollow nano microspheres and maleic anhydride grafted polyethylene, and the mass ratio of the modified silicon dioxide/polydopamine/polystyrene porous hollow nano microspheres to the maleic anhydride grafted polyethylene is 4: 7.
the preparation method comprises the following steps:
(1) the preparation method of the modified silicon dioxide/polydopamine/polystyrene porous hollow nano-microsphere comprises the following steps:
s1, preparing polystyrene porous hollow nano microspheres: mixing and dissolving 0.07g of tert-butyl peroxypivalate and 1.5g of styrene monomer, adding 0.3g of hydrophilic monomer methyl methacrylate and 0.05g of PEO20-PPO70-PEO20, stirring and mixing uniformly, adding 7g of aqueous solution containing 4wt% of PVA, performing ultrasonic dispersion for 20min at 1000W to obtain suspension, heating to 70 ℃, stirring and reacting for 3h at the rotating speed of 1700r/min, then adding 0.2g of cross-linking agent divinylbenzene, continuing stirring and reacting for 1.5h, centrifuging, and freeze-drying to obtain the polystyrene porous hollow nano-microspheres;
s2, preparing the polydopamine/polystyrene porous hollow nano-microspheres: dispersing 100g of the porous hollow polystyrene nano-microspheres prepared in the step S1 into 200mL of water, adding 30g of dopamine hydrochloride and 5g of Tris-HCl solution with the pH value of 6, heating to 50 ℃, stirring for reaction for 5 hours, filtering, and washing with water to obtain the porous hollow polydopamine/polystyrene nano-microspheres;
s3, preparation of the silica sol: water, ethanol, 1.5mol/L hydrochloric acid and ethyl orthosilicate according to the mass ratio of 1: 3.5: 0.25: 8, mixing and uniformly stirring to obtain silicon dioxide sol;
s4, preparing the silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres: dispersing 20g of the polydopamine/polystyrene porous hollow nano-microspheres prepared in the step S2 into 50g of the silicon dioxide sol prepared in the step S3, heating to 70 ℃, reacting for 21 hours, centrifuging, and washing to obtain silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres;
s5, preparing the modified silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres: adding 30g of the silica/polydopamine/polystyrene porous hollow nano-microspheres prepared in the step S4 into 3.5g of 100mL of ethanol solution containing a composite silane coupling agent, heating to 85 ℃ and reacting for 4h to obtain modified silica/polydopamine/polystyrene porous hollow nano-microspheres; the composite silane coupling agent is a compound mixture of KH560 and KH550, and the mass ratio is 4: 1;
(2) weighing the components according to the formula, putting the components into a mixer for uniformly mixing to obtain a premix, adding the premix into a double-screw extruder for melt mixing and extrusion granulation, wherein the ratio of the long diameter of a screw of the double-screw extruder to the diameter of the screw is 37: 1; the temperature of the screw barrel is 265 ℃, the rotating speed of the screw is 500r/min, and the PC/PET composite material is obtained.
Example 4
Compared with example 3, the complex silane coupling agent is completely replaced by KH560, and other conditions are not changed.
Example 5
Compared with example 3, the compound silane coupling agent is completely replaced by the compound mixture of KH550, and other conditions are not changed.
Comparative example 1
Compared with the embodiment 3, the composite compatilizer is completely replaced by the modified silicon dioxide/polydopamine/polystyrene porous hollow nano microspheres, and other conditions are not changed.
Comparative example 2
Compared with example 3, the composite compatilizer is completely replaced by maleic anhydride grafted polyethylene, and other conditions are not changed.
Comparative example 3
Compared with the example 3, the composite compatilizer is not added, and other conditions are not changed.
The raw materials comprise the following components in parts by weight: 70 parts of PC, 18 parts of PET, 0.2 part of sorbitol serving as a transparent agent and 0.2 part of 2, 6-di-tert-butyl-4-cresol serving as an antioxidant.
Comparative example 4
Compared with example 3, no clearing agent was added, and other conditions were not changed.
The raw materials comprise the following components in parts by weight: 70 parts of PC, 18 parts of PET, 1 part of composite compatilizer and 0.2 part of antioxidant 2, 6-di-tert-butyl-4-cresol.
Test example 1 mechanical Property test
The PC/PET composite materials obtained in examples 1 to 5 of the present invention and comparative examples 1 to 4 were subjected to performance tests, and the results are shown in Table 1.
Tensile properties were tested according to ISO527-2-2012, type 1A specimen, tensile rate 50 mm/min.
The bending properties were measured according to ISO178-2010 at a test rate of 2 mm/min.
Notched Izod impact strength was measured according to ISO180-2000, type 180/A, and the impact energy was 2.75J.
The hardness was measured according to astm d 785.
TABLE 1
As can be seen from the table, the PC/PET composite material prepared by the invention has good mechanical properties.
Test example 2
The PC/PET composite materials obtained in examples 1 to 5 of the present invention and comparative examples 1 to 4 were subjected to comprehensive property tests, and the results are shown in Table 2.
Notched impact strength retention: soaking the notched impact test sample in solvent for 5min, drying at 70 deg.c for 2 hr, regulating at room temperature for 24 hr, and testing notched impact strength as compared with notched impact strength tested with the test sample without soaked solvent.
Coating solvent cracking time: fixing the tensile sample on a Belgen elliptical fixture, coating a solvent on the surface, and observing the time of crack occurrence.
TABLE 2
Note: □ shows no cracks appearing after continuous observation for 30 d.
Compared with the example 3, the compound silane coupling agent of the examples 4 and 5 is completely replaced by KH560 or KH550, the mechanical property is reduced, the surface of the modified silica/polydopamine/polystyrene porous hollow nano microsphere is provided with rich amino (from a silane coupling agent KH 550), hydroxyl (from polydopamine) and epoxy (from a silane coupling agent KH 560), after the three groups are added into a PET/PC matrix, can react with terminal hydroxyl and segment carboxyl of PET, the generated graft copolymer reduces the interfacial tension, greatly improves the compatibility among components, limits the degree of phase separation, and refines dispersed phase particles, can absorb more impact energy when being subjected to external force, is beneficial to improving the toughness and the strength of the material, and simultaneously, the reaction between the two components can greatly reduce the interfacial tension and improve the compatibility of the PC and PET components; on the other hand, the modified silica/polydopamine/polystyrene porous hollow nano-microspheres can also play a role of nucleating agent to promote PET crystallization, so that the mechanical property of the alloy is improved; in addition, the porous structure of the modified silica/polydopamine/polystyrene porous hollow nano-microsphere prepared by the invention enables macromolecular chains of PET and PC to pass through the microsphere from macropores, thereby avoiding the influence of rigid particles on the mechanical property of the alloy due to the blockage of the molecular chains, further improving the strength, toughness and compatibility of the PC/PET alloy, and having the synergistic effect due to the addition of the composite silane coupling agent.
Compared with the embodiment 3, the composite compatilizer is completely replaced by the modified silica/polydopamine/polystyrene porous hollow nano-microspheres or the maleic anhydride grafted polyethylene, the mechanical property of the composite compatilizer is obviously reduced in the comparative example 2, the notched impact strength retention rate of the modified silica/polydopamine/polystyrene porous hollow nano-microspheres is reduced, the solvent resistance of the composite compatilizer is reduced, the mechanical property and the solvent resistance of the composite compatilizer are obviously reduced in the comparative example 3 compared with the embodiment 3 without adding the composite compatilizer, the strength, the toughness and the compatibility of the PC/PET alloy are improved by the modified silica/polydopamine/polystyrene porous hollow nano-microspheres, the maleic anhydride grafted polyethylene serving as another compatilizer is a flexible molecule, the collision probability of rigid PC particles and PET chains is reduced, the POE serving as a flexible particle can play a role of an accelerant, and the two roles cooperate to enable the crystallization of PET to be easy, the toughness of the material is further improved, and the addition of the modified silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres and the maleic anhydride grafted polyethylene has a synergistic effect.
Compared with the embodiment 3, the transmittance of the PC/PET composite material is obviously reduced without adding the transparent agent, the visible light transmittance of the composite material is improved by reducing the crystal nucleus of the PET crystal region through the transparent agent and the composite compatilizer in the embodiment of the invention, and the provided PC/PET composite material has high transparency.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of modified silica/polydopamine/polystyrene porous hollow nano-microspheres is characterized by comprising the following steps:
s1, preparing polystyrene porous hollow nano microspheres: mixing and dissolving an initiator and a styrene monomer, adding a hydrophilic monomer methyl methacrylate and a pore-forming agent, stirring and mixing uniformly, adding an aqueous solution of PVA, performing ultrasonic dispersion uniformly to obtain a suspension, heating and polymerizing, performing high-speed stirring reaction for a first time period, then adding a cross-linking agent divinylbenzene, continuing stirring and reacting for a second time period, centrifuging, and performing freeze drying to obtain the polystyrene porous hollow nano-microsphere;
s2, preparing the polydopamine/polystyrene porous hollow nano-microspheres: dispersing the porous hollow nano-microspheres prepared in the step S1 into water, adding dopamine hydrochloride and a catalyst, heating, stirring, reacting, filtering, and washing with water to obtain the polydopamine/polystyrene porous hollow nano-microspheres;
s3, preparing the silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres: dispersing the polydopamine/polystyrene porous hollow nano-microspheres prepared in the step S2 into silica sol, heating for sol-gel reaction, centrifuging, and washing to obtain silica/polydopamine/polystyrene porous hollow nano-microspheres;
s4, preparing the modified silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres: and (4) adding the silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres prepared in the step (S3) into an ethanol solution containing a composite silane coupling agent, and heating for reaction to obtain the modified silicon dioxide/polydopamine/polystyrene porous hollow nano-microspheres.
2. The method according to claim 1, wherein the initiator in step S1 is at least one selected from the group consisting of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate; the pore-foaming agent is selected from at least one of isooctane, cetyl trimethyl ammonium bromide, an oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and PEO106-PPO70-PEO 106; the PVA content in the aqueous solution of the PVA is 3-5 wt%; the mass ratio of the initiator, the styrene monomer, the hydrophilic monomer methyl methacrylate, the pore-foaming agent, the PVA aqueous solution and the cross-linking agent divinylbenzene is (0.05-0.1): (1-2): (0.2-0.4): (0.02-0.07): (5-10): (0.1-0.3); the temperature is raised to 60-80 ℃, the high-speed stirring speed is 1500-.
3. The method according to claim 1, wherein the catalyst in step S2 is a Tris-HCl solution having a pH of 5.5 to 6.6; the mass ratio of the polystyrene porous hollow nano-microspheres to the dopamine hydrochloride to the catalyst is 100: (25-35): (2-7); the heating temperature is 40-60 ℃, and the reaction time is 3-7 h.
4. The method according to claim 1, wherein the silica sol is prepared in step S3 by mixing water, ethanol, 1-2mol/L hydrochloric acid, and tetraethoxysilane in a mass ratio of 1: (3-4): (0.1-0.4): (7-10) mixing, and uniformly stirring to obtain silicon dioxide sol; the heating temperature is 60-80 ℃, and the reaction is carried out for 18-24 h.
5. The preparation method according to claim 1, wherein the composite silane coupling agent in step S4 is a compounded mixture of KH560 and KH550, and the mass ratio is (3-5): 1.
6. the preparation method according to claim 1, wherein the mass ratio of the silica/polydopamine/polystyrene porous hollow nanospheres to the composite silane coupling agent in step S4 is 30: (2-5); the heating temperature is 80-90 ℃ and the time is 3-5 h.
7. A modified silica/polydopamine/polystyrene porous hollow nanosphere prepared according to the preparation method of any one of claims 1-6.
8. The PC/PET composite material is characterized by being prepared from the following raw materials in parts by weight: 60-80 parts of PC, 12-32 parts of PET, 0.5-2 parts of composite compatilizer, 0.1-0.3 part of transparent agent and 0-0.5 part of antioxidant; the composite compatilizer comprises the modified silica/polydopamine/polystyrene porous hollow nano microsphere and maleic anhydride grafted polyethylene according to claim 7, and the mass ratio of the modified silica/polydopamine/polystyrene porous hollow nano microsphere to the maleic anhydride grafted polyethylene is (3-5): 7.
9. the PC/PET composite material according to claim 8, wherein the transparent agent is at least one selected from aryl phosphates, sorbitol compounds; the antioxidant is at least one selected from phenolic antioxidants and phosphite antioxidants.
10. A method for preparing a PC/PET composite material according to claim 8 or 9, comprising the steps of: weighing the components according to the formula ratio, putting the components into a mixer for uniformly mixing to obtain a premix, adding the premix into a double-screw extruder for melting and mixing, and extruding and granulating to obtain a PC/PET composite material; the length-diameter ratio of the screws of the double-screw extruder is (35-40): 1; the temperature of the screw cylinder is 260-270 ℃, and the rotating speed of the screw is 450-550 r/min.
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