CN116714334B - Preparation method of high-stability sterile plastic with reduced thermal expansion, plastic and application of plastic - Google Patents
Preparation method of high-stability sterile plastic with reduced thermal expansion, plastic and application of plastic Download PDFInfo
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- CN116714334B CN116714334B CN202311004803.XA CN202311004803A CN116714334B CN 116714334 B CN116714334 B CN 116714334B CN 202311004803 A CN202311004803 A CN 202311004803A CN 116714334 B CN116714334 B CN 116714334B
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- China
- Prior art keywords
- composite material
- plastic
- hypocrellin
- section
- wood
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- 229920003023 plastic Polymers 0.000 title claims abstract description 77
- 239000004033 plastic Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- SBMXTMAIKRQSQE-UHFFFAOYSA-N Hypocrellin C Natural products O=C1C=C(OC)C2=C(C3=C45)C(OC)=CC(=O)C3=C(O)C(OC)=C4C(C(C)=O)=C(C)CC3=C5C2=C1C(O)=C3OC SBMXTMAIKRQSQE-UHFFFAOYSA-N 0.000 claims abstract description 193
- APTUSGMALOMQQL-UHFFFAOYSA-N Shiraiachrome C Natural products O=C1C(OC)=C2C(C(C)=O)=C(C)CC3=C(OC)C(=O)C4=C(O)C=C(OC)C5=C4C3=C2C2=C1C(O)=CC(OC)=C25 APTUSGMALOMQQL-UHFFFAOYSA-N 0.000 claims abstract description 110
- KGHNSNSWRMJVND-UHFFFAOYSA-N Hypocrellin Natural products COC1=CC(=O)C2=C3C4C(C(C(=O)C)C(C)(O)Cc5c(OC)c(O)c6C(=O)C=C(OC)C(=C13)c6c45)C(=C2O)OC KGHNSNSWRMJVND-UHFFFAOYSA-N 0.000 claims abstract description 103
- -1 amino hypocrellin B Chemical compound 0.000 claims abstract description 95
- 238000002156 mixing Methods 0.000 claims abstract description 89
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000004743 Polypropylene Substances 0.000 claims abstract description 83
- 229920001155 polypropylene Polymers 0.000 claims abstract description 83
- 239000000463 material Substances 0.000 claims abstract description 76
- 239000002131 composite material Substances 0.000 claims abstract description 73
- 229920001587 Wood-plastic composite Polymers 0.000 claims abstract description 57
- 239000011155 wood-plastic composite Substances 0.000 claims abstract description 57
- 229920001971 elastomer Polymers 0.000 claims abstract description 45
- 239000000806 elastomer Substances 0.000 claims abstract description 45
- 239000012792 core layer Substances 0.000 claims abstract description 43
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 39
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 36
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 33
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 33
- 238000007731 hot pressing Methods 0.000 claims abstract description 30
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims abstract description 27
- 239000002023 wood Substances 0.000 claims abstract description 18
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008117 stearic acid Substances 0.000 claims abstract description 12
- 238000005576 amination reaction Methods 0.000 claims description 78
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 78
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 63
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 51
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 51
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 46
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 34
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 29
- 238000001125 extrusion Methods 0.000 claims description 26
- 239000003112 inhibitor Substances 0.000 claims description 25
- 238000004132 cross linking Methods 0.000 claims description 24
- 239000003999 initiator Substances 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 23
- 239000010410 layer Substances 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 56
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 42
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 22
- 229960001701 chloroform Drugs 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 21
- 239000007795 chemical reaction product Substances 0.000 description 20
- 230000000844 anti-bacterial effect Effects 0.000 description 18
- 239000012043 crude product Substances 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 9
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 8
- 230000032683 aging Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002344 surface layer Substances 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 5
- 239000011162 core material Substances 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 235000013312 flour Nutrition 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241000209128 Bambusa Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 241000269435 Rana <genus> Species 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- VANSZAOQCMTTPB-SETSBSEESA-N hypocrellin Chemical compound C1[C@@](C)(O)[C@@H](C(C)=O)C2=C(OC)C(O)=C3C(=O)C=C(OC)C4=C3C2=C2C3=C4C(OC)=CC(=O)C3=C(O)C(OC)=C21 VANSZAOQCMTTPB-SETSBSEESA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- BQJKVFXDDMQLBE-UHFFFAOYSA-N shiraiachrome A Natural products COC1=C2C3=C(OC)C=C(O)C4=C3C3=C5C(CC(C)(O)C(C(C)=O)C3=C(OC)C4=O)=C(OC)C(=O)C(C(O)=C1)=C25 BQJKVFXDDMQLBE-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012932 thermodynamic analysis Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G19/00—Table service
- A47G19/02—Plates, dishes or the like
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G19/00—Table service
- A47G19/22—Drinking vessels or saucers used for table service
- A47G19/2205—Drinking glasses or vessels
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
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- B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
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- B32B2307/734—Dimensional stability
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
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Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the field of composite material processing, and discloses a preparation method of high-stability sterile plastic with reduced thermal expansion, the plastic and application thereof. Comprising the following steps: modified nano TiO 2 Mixing and hot-pressing the mesoporous nano silicon dioxide hollow sphere loaded amino hypocrellin B, wood powder, polypropylene, maleic anhydride grafted polyethylene and stearic acid to obtain a wood-plastic composite material; mixing and hot-pressing the modified polypropylene composite material, the modified propenyl elastomer and the modified calcium carbonate into a core layer composite material; the wood-plastic composite material and the core layer composite material are sequentially hot-pressed into the high-stability sterile plastic with reduced thermal expansion. The high-stability sterile plastic with reduced thermal expansion has wide application prospect in infant tableware.
Description
Technical Field
The invention relates to the field of composite material processing, in particular to a preparation method of high-stability sterile plastic for reducing thermal expansion, the plastic and application thereof.
Background
Tableware is a vessel and appliance for holding, dispensing or taking food, wherein the tableware for holding food comprises bowl, plate, dish, cup and the like. The infant's health is comparatively fragile, and does not have discernment consciousness to harmful article, very easily receives the piece that produces to the tableware after the striking to eat, and daily life gradually improves the requirement of thermal stability to the tableware simultaneously, consequently needs to promote plastic protection architecture's stability and mechanical properties, reduces its coefficient of thermal expansion simultaneously. After long-term use, bacteria are easy to grow in the overlapped gaps, so that the antibacterial performance of the plastic protection structure needs to be improved.
The prior art discloses a multilayer antibiotic stainless steel tableware like chinese patent CN218246672U, and its heat preservation protection architecture can be with basin inner wall and outer wall isolated, avoids basin outer wall too high temperature and scalds one's hand, does benefit to actual use more. However, the thermal insulation layer is made of a sheet material made of polyurethane foam materials, so that the mechanical property is not high, the antibacterial property is limited, and the application of the material in infant tableware is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of high-stability sterile plastic with reduced thermal expansion, which has excellent mechanical property and antibacterial property and wide application prospect in infant tableware.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a method for preparing a highly stable sterile plastic with reduced thermal expansion comprising the steps of:
step one, preparing a wood-plastic composite material and a core layer composite material; the preparation of the wood-plastic composite material comprises the following steps:
step (1) mixing hypocrellin B, N-dimethyl ethylenediamine and tetrahydrofuran, reacting, separating, purifying and drying after the reaction is finished to obtain aminated hypocrellin B;
Mixing the amination hypocrellin B with ethanol to prepare amination hypocrellin B solution, mixing mesoporous nano silicon dioxide hollow spheres with the amination hypocrellin B solution, reacting, centrifuging, washing and drying after the reaction is finished to obtain the mesoporous nano silicon dioxide hollow spheres loaded with the amination hypocrellin B;
step (3) modifying the nano TiO 2 Mixing the mesoporous nano silicon dioxide hollow sphere supported amino hypocrellin B, wood powder, polypropylene, maleic anhydride grafted polyethylene and stearic acid, adding into a double-screw extruder, melting and extruding, and hot-pressing to obtain the wood-plastic composite material; wherein, the preparation of the core layer composite material comprises the following steps:
step (1) mixing polypropylene, isoprene, styrene and di-tert-butyl peroxide, extruding, granulating to obtain a modified polypropylene composite material; mixing maleic anhydride solution and guanidine hydrochloride solution, reacting, and drying after the reaction is finished to obtain functionalized maleic anhydride; adding the propenyl elastomer, the functionalized maleic anhydride, the crosslinking inhibitor and the initiator into a double-screw extruder, and carrying out melt extrusion and granulation to obtain a modified propenyl elastomer; step (2) mixing the modified polypropylene composite material, the modified propenyl elastomer and the modified calcium carbonate, adding the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out hot pressing to form a core layer composite material;
And step two, superposing the wood-plastic composite material, the core layer composite material and the wood-plastic composite material in the sequence of one layer of wood-plastic composite material, one layer of core layer composite material and one layer of wood-plastic composite material, and hot-pressing to prepare the high-stability sterile plastic with reduced thermal expansion.
Preferably, in the preparation of the wood-plastic composite material, in the step (1): the mass ratio of hypocrellin B to N, N-dimethyl ethylenediamine to tetrahydrofuran is 1: (40-60): (440-500); the reaction conditions are as follows: reacting for 10-15h at 50-55 ℃ in the dark; the separation and purification comprises the following steps: carrying out suction filtration on the mixture obtained after the reaction is finished to obtain a reaction product; mixing the reaction product with chloroform, and adding an aqueous hydrochloric acid solution to make the pH value of the aqueous layer=7; concentrating the chloroform layer under reduced pressure to obtain an amination hypocrellin B crude product; and performing column chromatography to obtain the amino hypocrellin B.
Preferably, in the step (2), when preparing the wood-plastic composite material: the mass ratio of the mesoporous nano silicon dioxide hollow sphere to the amination hypocrellin B solution is 1: (105-110); the reaction conditions are as follows: the reaction is carried out for 16-24h at room temperature.
Further, the mass percentage of the amination hypocrellin B in the amination hypocrellin B solution is 0.02 percent.
Preferably, in the preparation of the wood-plastic composite material, in the step (3): modified nano TiO 2 The mass ratio of the mesoporous nano silicon dioxide hollow sphere loaded amino hypocrellin B to the wood powder to the polypropylene to the maleic anhydride grafted polyethylene to the stearic acid is (3-6): (3-6): (40-70): (45-50): (3-5): (2-5); the melt extrusion conditions were: the temperature of the first section is 70 ℃, the temperature of the second section is 145 ℃, the temperatures of the third section to the ninth section are 180-200 ℃, the temperature of the machine head is 215 ℃, and the rotating speed of the screw is 90-100r/min; the hot pressing conditions are as follows: prepressing for 15-20min at 150-180deg.C under 10Mpa, and pressurizing for 5-7min.
Preferably, when preparing the wood-plastic composite material, the modified nano TiO in the step (3) 2 The preparation method comprises the following steps: nano TiO 2 Mixing with deionized water in a mass ratio, stirring, and dispersing; adding a silane coupling agent, stirring for reaction, and separating and purifying after the reaction is finished to obtain modified nano TiO 2 。
Further, nano TiO 2 The mass ratio of the deionized water to the deionized water is 1:200, the mass of the silane coupling agent is nano TiO 2 0.5-2% of the weight; the reaction conditions are as follows: stirring and reacting for 1-2h at 60-80 ℃; the silane coupling agent comprises gamma-methacryloxypropyl trimethoxy silane; the separation and purification comprises the following steps: centrifuging the mixture obtained after the reaction is finished to obtain modified nano TiO 2 Crude product, modified nano TiO 2 Mixing the crude product with deionized water, performing ultrasonic dispersion and centrifugation; modified nano TiO 2 The mass ratio of the crude product to deionized water is 1: (200-300).
Preferably, in preparing the core composite, in step (1): the mass ratio of polypropylene, isoprene, styrene and di-tert-butyl peroxide is 100: (0.50-1): (0.50-1): (0.04-0.1); the extrusion conditions were: the first stage temperature is 70 ℃, the second stage temperature is 170 ℃, the temperatures of the third stage to the ninth stage are 200-205 ℃, the temperature of the machine head is 215 ℃, and the rotating speed of the screw is 60-120r/min.
Further, polypropylene is added from a first stage main feed port of the extruder, isoprene, styrene and di-tert-butyl peroxide are mixed uniformly at room temperature, and then injected from a third stage liquid feed port of the extruder, and mixed with polypropylene.
Preferably, the molar ratio of maleic anhydride in the maleic anhydride solution to guanidine hydrochloride in the guanidine hydrochloride solution is 2:1, a maleic anhydride solution comprises 27.3wt% of maleic anhydride solution, and is prepared from maleic anhydride and ethanol; the guanidine hydrochloride solution comprises 33.3wt% of guanidine hydrochloride solution and is prepared from guanidine hydrochloride and ethanol.
Preferably, in preparing the core composite, in step (1): the mass ratio of the propenyl elastomer, the initiator, the crosslinking inhibitor and the functionalized maleic anhydride is 1100:2:3:30; the conditions of melt extrusion were: the melt extrusion temperature is 170-200 ℃, the screw rotation speed is 250-500r/min, and the residence time is 30-60s.
Further, the manner of adding the propenyl elastomer, the functionalized maleic anhydride, the crosslinking inhibitor and the initiator into the twin-screw extruder comprises the following steps: the propylene-based elastomer, the functionalized maleic anhydride and the crosslinking inhibitor are put into a mixer to be mixed, then are added into a double-screw extruder through a main feed, and the initiator is added into the double-screw extruder through a side feed mode.
Preferably, in the preparation of the core composite, in step (2): the mass ratio of the modified polypropylene composite material to the modified propenyl elastomer to the modified calcium carbonate is (90-94): (5-9): 1, a step of; the conditions of melt extrusion were: the temperature of the first section is 70 ℃, the temperature of the second section is 145 ℃, the temperatures of the third section to the ninth section are 180-200 ℃, the temperature of the machine head is 215 ℃, and the rotating speed of the screw is 90-100r/min; the hot pressing conditions are as follows: prepressing for 15-20min at 180-200deg.C under 10Mpa, and pressurizing for 5-7min.
Further, the modified calcium carbonate is a silane coupling agent modified calcium carbonate, and the silane coupling agent comprises gamma-methacryloxypropyl trimethoxy silane.
Preferably, in the second step: the hot pressing conditions are as follows: prepressing for 15-20min at 150-180deg.C under 10Mpa, and pressurizing for 5-7min.
Preferably, the application of the high-stability sterile plastic with reduced thermal expansion prepared by adopting the preparation method of the high-stability sterile plastic with reduced thermal expansion in infant tableware is provided.
Compared with the prior art, the invention has the beneficial effects that: the high-stability sterile plastic with reduced thermal expansion is prepared through the sandwich structure of covering the upper surface and the lower surface of the light core layer with the two rigid wood-plastic surface layers, has higher impact strength and bending strength, improves the flexural modulus, reduces the thermal expansion coefficient and improves the dimensional stability; meanwhile, the weight of the high-stability sterile plastic with reduced thermal expansion is reduced due to the existence of the sandwich structure, so that the high-stability sterile plastic is lighter; the propylene-based elastomer added in the sandwich structure can disperse force, so that stress concentration of the material during damage is avoided, the material is not easy to crack, the impact strength of the sandwich material is improved, and the modified calcium carbonate is used as rigid particles to reduce the thermal expansion coefficient of the sandwich material; the wood plastic material with the surface layer structure is added with wood powder and modified nano TiO 2 The mesoporous nano silicon dioxide hollow sphere is used as a rigid particle, so that the mechanical property of the mesoporous nano silicon dioxide hollow sphere is greatly improved.
According to the invention, the hypocrellin B is subjected to amination modification, so that the photodynamic effect is improved and the dark toxicity is reduced on the basis of keeping the active structure of the forced hydroxyl of the parent hypocrellin B; meanwhile, as the amination hypocrellin B has amphiprotic property (fat solubility and water solubility), the mesoporous nano silicon dioxide hollow sphere with low toxicity, high stability, high surface permeability and high specific surface area is selected as a slow release carrier material of the amination hypocrellin B, and the amination hypocrellin B is adsorbed on the surface and the inner cavity of the mesoporous nano silicon dioxide hollow sphere by means of physical adsorption and intermolecular hydrogen bonding; because of the network structure of the mesoporous nano silicon dioxide hollow sphere, compared with the solid nano silicon dioxide sphere, the storage capacity and the diffusion resistance are improved, so that the time for the amination hypocrellin B to diffuse into the outside is prolonged, and the effects of adsorbing and slowly releasing the amination hypocrellin B active substances are achieved.
In the invention, through the surface layer junctionModified nano TiO (titanium dioxide) is added into structured wood-plastic material 2 And mesoporous silica hollow sphere loaded amino hypocrellin B, and nano TiO is used 2 And hypocrellin B, so as to achieve the purposes of inhibiting the aging of the polypropylene matrix and sterilizing; the polypropylene is modified by styrene and isoprene in the core layer structure, and the modified polypropylene is used as a matrix, so that the activity of methyl groups in the polypropylene is effectively inhibited, and the stability of the polypropylene material is improved; the functional maleic anhydride is prepared by carrying out antibacterial functional modification on maleic anhydride by guanidine hydrochloride, the macromolecular antibacterial agent cannot permeate into human skin, has low toxicity, has better antibacterial durability than a micromolecular antibacterial agent, and has good thermal stability; the functionalized maleic anhydride is grafted and connected with the propenyl elastomer, so that the prepared high-stability sterile plastic with reduced thermal expansion has ageing resistance and high stability, and meanwhile, the antibacterial function is more durable.
The high-stability sterile plastic with reduced thermal expansion has excellent mechanical property and antibacterial property, and has wide application prospect in infant tableware.
Drawings
FIG. 1 is a process flow diagram of the present invention for preparing a high stability sterile plastic with reduced thermal expansion;
FIG. 2 is a process flow diagram of the preparation of the wood-plastic composite of the present invention;
FIG. 3 is a process flow diagram of the preparation of a core composite material in accordance with the present invention;
FIG. 4 is a schematic illustration of a reaction for preparing an aminated hypocrellin B in accordance with the present invention;
FIG. 5 is a schematic illustration of the reaction of the present invention to produce functionalized maleic anhydride;
FIG. 6 is a plot of flexural strength against mechanical testing of high stability sterile plastics with reduced thermal expansion prepared in examples 1-4 and comparative examples 1-4 of the present invention;
FIG. 7 is a flexural modulus line graph of mechanical properties of high stability sterile plastics with reduced thermal expansion prepared in examples 1-4 and comparative examples 1-4 of the present invention;
FIG. 8 is a plot of impact strength versus mechanical properties of high stability sterile plastics with reduced thermal expansion prepared in examples 1-4 and comparative examples 1-4 of the present invention;
FIG. 9 is a graph of thermal expansion coefficients in mechanical property tests of high stability sterile plastics with reduced thermal expansion prepared in examples 1-4 and comparative examples 1-4 of the present invention.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
The embodiment discloses a preparation method of high-stability sterile plastic with reduced thermal expansion, which comprises the following steps:
(1) Nano TiO 2 Mixing with deionized water in a mass ratio of 1:200, stirring for 30min at the conditions of pH=4 and room temperature, and performing ultrasonic dispersion for 20min; adding a silane coupling agent, stirring at 80 ℃ for reaction for 1h, and centrifuging at 10000r/min for 20min after the reaction is finished to obtain modified nano TiO 2 Crude product; modified nano TiO 2 The crude product and deionized water are mixed according to the mass ratio of 1:300, dispersing for 8min by ultrasonic, centrifuging at 10000r/min for 20min, and drying the centrifugated precipitate at 100deg.C for 24 hr to obtain modified nanometer TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein the mass of the silane coupling agent is nano TiO 2 0.5% by mass; the silane coupling agent is gamma-methacryloxypropyl trimethoxy silane;
(2) Hypocrellin B, N-dimethyl ethylenediamine and tetrahydrofuran are mixed according to the mass ratio of 1:60:500, reacting for 10 hours at 55 ℃ in the dark, and filtering after the reaction is finished to obtain a reaction product; mixing the reaction product with chloroform in a mass ratio of 1:10 mixing, adding the reaction product and 1/2 of 10wt% hydrochloric acid aqueous solution in volume of chloroform at room temperature, and making pH of the aqueous layer=7; concentrating the chloroform layer under reduced pressure at a vacuum degree of 0.04MPa and a temperature of 65 ℃ to obtain an amination hypocrellin B crude product; performing column chromatography with a developing agent with the mass 25 times of that of the amination hypocrellin B crude product to obtain amination hypocrellin B; wherein the developing agent is acetone and ethyl acetate according to the mol ratio of 3:2, mixing to obtain the product; mixing mesoporous nano silicon dioxide hollow spheres with 0.02wt% of amination hypocrellin B solution according to the mass ratio of 1:110, reacting for 24 hours at room temperature; after the reaction is finished, centrifuging for 20min at the speed of 4000r/min, adding mesoporous nano-silica hollow spheres and amination hypocrellin B solution at room temperature, respectively washing three times by distilled water and ethanol with the mass of 10 times, and drying for 24h at 50 ℃ to obtain the mesoporous nano-silica hollow sphere loaded amination hypocrellin B; wherein, the 0.02wt% of the amination hypocrellin B solution is prepared by amination hypocrellin B and ethanol, and the mass percentage of the amination hypocrellin B is 0.02 percent;
(3) Modified nano TiO 2 The mesoporous nano silicon dioxide hollow sphere is loaded with amination hypocrellin B, 40-mesh wood powder, polypropylene, maleic anhydride grafted polyethylene and stearic acid in a ratio of 6:6:70:50:4:4, mixing for 5 hours at the speed of 3500r/min, adding the mixture into a double-screw extruder, melting and extruding at the temperature of 70 ℃ in the first section, 145 ℃ in the second section, 180 ℃ in the third section to the ninth section, 215 ℃ in the head, 100r/min in the screw rotating speed, prepressing for 20min at 180 ℃ and 10Mpa, pressurizing for 5min, and hot-pressing to obtain the wood-plastic composite material with the thickness of 1.5 mm;
(4) Adding polypropylene into an extruder from a first section main feed inlet, setting the feeding speed to be 0.1kg/min, setting the temperature of the first section to be 70 ℃, setting the temperature of the second section to be 170 ℃, setting the temperature of the third section to the ninth section to be 205 ℃, setting the temperature of a machine head to be 215 ℃, setting the rotating speed of a screw to be 120r/min, uniformly mixing isoprene, styrene and di-tert-butyl peroxide at room temperature, injecting the mixture into the extruder from a third section liquid feed inlet at the speed of 0.002kg/min, mixing the mixture with polypropylene, extruding and granulating to obtain a modified polypropylene composite material; wherein the mass ratio of the polypropylene to the isoprene to the styrene to the di-tert-butyl peroxide is 100:1:1:0.1; in the preparation process of the modified polypropylene composite material, under the condition that the vacuum degree is 0.01MPa, vacuum devolatilization is carried out in the eighth section of the extruder;
(5) 27.3wt% maleic anhydride solution and 33.3wt% guanidine hydrochloride solution were combined in a molar ratio of maleic anhydride to guanidine hydrochloride of 2:1, uniformly mixing, stirring and reacting for 7 hours at 75 ℃ in a nitrogen atmosphere, and drying for 24 hours at 60 ℃ under the vacuum degree of 0.2MPa after the reaction is finished to obtain the functionalized maleic anhydride; wherein, the 27.3wt% maleic anhydride solution is prepared by maleic anhydride and ethanol, and the mass percentage of the maleic anhydride is 27.3%; the 33.3wt% guanidine hydrochloride solution is prepared from guanidine hydrochloride and ethanol, and the mass percentage of the guanidine hydrochloride is 33.3%; mixing the allyl elastomer, the functionalized maleic anhydride and the crosslinking inhibitor in a mixer, adding the mixture into a double-screw extruder through a main feed, adding an initiator into the double-screw extruder through a side feed mode, and obtaining the modified allyl elastomer after extrusion granulation, wherein the melt extrusion temperature is 200 ℃, the screw speed is 250r/min and the residence time is 30 s; the mass ratio of the propenyl elastomer, the initiator, the crosslinking inhibitor and the functionalized maleic anhydride is 1100:2:3:30; the initiator is di-tert-butyl peroxide; the crosslinking inhibitor is stearic acid amide;
(6) The modified polypropylene composite material, the modified propenyl elastomer and the modified calcium carbonate are mixed according to the mass ratio of 90:9:1, mixing, adding into a double-screw extruder, melting and extruding under the conditions that the temperature of the first section is 70 ℃, the temperature of the second section is 145 ℃, the temperature of the third section to the ninth section is 200 ℃, the temperature of a machine head is 215 ℃, the rotating speed of a screw is 100r/min, prepressing for 20min under the conditions of 200 ℃, 10Mpa, pressurizing for 5min, and hot-pressing into a core layer composite material with the thickness of 1 mm; wherein the modified calcium carbonate is modified calcium carbonate of a silane coupling agent, and the silane coupling agent is gamma-methacryloxypropyl trimethoxy silane; the preparation method comprises the following steps: mixing gamma-methacryloxypropyl trimethoxy silane with cyclohexanone, adding calcium carbonate, reacting at 70 ℃ for 70min, filtering, washing with acetone, and drying at 80 ℃ to obtain modified calcium carbonate; the mass ratio of the gamma-methacryloxypropyl trimethoxy silane to the calcium carbonate to the cyclohexanone is 0.03:1:5, a step of;
(7) The wood-plastic composite material with the thickness of 1.5mm and the core layer composite material with the thickness of 1mm are arranged in the sequence of the wood-plastic composite material, the core layer composite material and the wood-plastic composite material, and the high-stability sterile plastic with the thermal expansion reduced is prepared by prepressing for 20min and pressurizing for 5min under the conditions of 180 ℃ and 10 Mpa.
Example 2
The embodiment discloses a preparation method of high-stability sterile plastic with reduced thermal expansion, which comprises the following steps:
(1) Modified nano TiO 2 Is prepared as in example 1;
(2) Hypocrellin B, N-dimethyl ethylenediamine and tetrahydrofuran are mixed according to the mass ratio of 1:40:440, reacting for 15 hours at 50 ℃ in the dark, and filtering after the reaction is finished to obtain a reaction product; mixing the reaction product with chloroform in a mass ratio of 1:5 mixing, adding the reaction product and 1/10 of 10wt% hydrochloric acid aqueous solution in volume of chloroform at room temperature, so that the pH of the aqueous layer is=7; concentrating the chloroform layer under reduced pressure at a vacuum degree of 0.03MPa and a temperature of 55 ℃ to obtain an amination hypocrellin B crude product; performing column chromatography with a developing agent with the mass of 20 times of the mass of the amination hypocrellin B crude product to obtain amination hypocrellin B; wherein the developing agent is acetone and ethyl acetate according to the mol ratio of 3:2, mixing to obtain the product; mixing mesoporous nano silicon dioxide hollow spheres with 0.02wt% of amination hypocrellin B solution according to the mass ratio of 1:105, and reacting for 16h at room temperature; after the reaction is finished, centrifuging for 30min at the speed of 3000r/min, adding mesoporous nano-silica hollow spheres and amination hypocrellin B solution at room temperature, respectively washing three times by 8 times of distilled water and ethanol, and drying for 12h at the temperature of 60 ℃ to obtain mesoporous nano-silica hollow spheres loaded with amination hypocrellin B; wherein, the 0.02wt% of the amination hypocrellin B solution is prepared by amination hypocrellin B and ethanol, and the mass percentage of the amination hypocrellin B is 0.02 percent;
(3) Modified nano TiO 2 Mesoporous nano silica hollow sphere supported amination hypocrellin B, 40 mesh wood powder, polypropylene, maleic anhydride grafted polyethylene and stearic acidAnd 5:5:60:49:3:3, mixing for 0.5h at 4000r/min, adding into a double-screw extruder after mixing, melting and extruding under the conditions that the temperature of the first section is 70 ℃, the temperature of the second section is 145 ℃, the temperature of the third section to the ninth section is 200 ℃, the temperature of a machine head is 215 ℃, the rotating speed of a screw is 90r/min, prepressing for 15min at 150 ℃ and 10Mpa, pressurizing for 7min, and hot-pressing to obtain the wood-plastic composite material with the thickness of 1.5 mm;
(4) Adding polypropylene into an extruder from a first section main feed inlet, setting the feeding speed to be 0.1kg/min, setting the temperature of the first section to be 70 ℃, setting the temperature of the second section to be 170 ℃, setting the temperature of the third section to the ninth section to be 200 ℃, setting the temperature of a machine head to be 215 ℃, setting the rotating speed of a screw to be 60r/min, uniformly mixing isoprene, styrene and di-tert-butyl peroxide at room temperature, injecting the mixture into the extruder from a third section liquid feed inlet at the speed of 0.002kg/min, mixing the mixture with polypropylene, extruding and granulating to obtain a modified polypropylene composite material; wherein the mass ratio of the polypropylene to the isoprene to the styrene to the di-tert-butyl peroxide is 100:0.9:0.9:0.08; in the preparation process of the modified polypropylene composite material, under the condition that the vacuum degree is 0.08MPa, vacuum devolatilization is carried out in the eighth section of the extruder;
(5) 27.3wt% maleic anhydride solution and 33.3wt% guanidine hydrochloride solution were combined in a molar ratio of maleic anhydride to guanidine hydrochloride of 2:1, uniformly mixing, stirring and reacting for 10 hours at 65 ℃ in a nitrogen atmosphere, and drying for 18 hours at 60 ℃ under the vacuum degree of 0.2MPa after the reaction is finished to obtain the functionalized maleic anhydride; wherein, the 27.3wt% maleic anhydride solution is prepared by maleic anhydride and ethanol, and the mass percentage of the maleic anhydride is 27.3%; the 33.3wt% guanidine hydrochloride solution is prepared from guanidine hydrochloride and ethanol, and the mass percentage of the guanidine hydrochloride is 33.3%; mixing the allyl elastomer, the functionalized maleic anhydride and the crosslinking inhibitor in a mixer, adding the mixture into a double-screw extruder through a main feed, adding an initiator into the double-screw extruder through a side feed mode, and obtaining the modified allyl elastomer after extrusion granulation, wherein the melt extrusion temperature is 170 ℃, the screw speed is 500r/min and the residence time is 60 s; the mass ratio of the propenyl elastomer, the initiator, the crosslinking inhibitor and the functionalized maleic anhydride is 1075:1:4:25, a step of selecting a specific type of material; the initiator is di-tert-butyl peroxide; the crosslinking inhibitor is stearic acid amide;
(6) Modified polypropylene composite material, modified propenyl elastomer and modified calcium carbonate are mixed according to the mass ratio of 91:8:1, mixing, adding into a double-screw extruder, melting and extruding under the conditions that the temperature of the first section is 70 ℃, the temperature of the second section is 145 ℃, the temperature of the third section to the ninth section is 180 ℃, the temperature of a machine head is 215 ℃, the rotating speed of a screw is 90r/min, prepressing for 15min under the conditions of 180 ℃ and 10Mpa, pressurizing for 7min, and hot-pressing into a core layer composite material with the thickness of 1 mm; wherein the modified calcium carbonate is the same as the modified calcium carbonate prepared in example 1;
(7) The wood-plastic composite material with the thickness of 1.5mm and the core layer composite material with the thickness of 1mm are arranged in the sequence of the wood-plastic composite material, the core layer composite material and the wood-plastic composite material, and the high-stability sterile plastic with the thermal expansion reduced is prepared by prepressing for 15min and pressurizing for 7min under the condition of 150 ℃ and 10 Mpa.
Example 3
The embodiment discloses a preparation method of high-stability sterile plastic with reduced thermal expansion, which comprises the following steps:
(1) Modified nano TiO 2 Is prepared as in example 1;
(2) Hypocrellin B, N-dimethyl ethylenediamine and tetrahydrofuran are mixed according to the mass ratio of 1:50:480, reacting for 12 hours at 53 ℃ in the dark, and filtering after the reaction is finished to obtain a reaction product; mixing the reaction product with chloroform in a mass ratio of 1:8, adding the reaction product and a 1/5 10wt% hydrochloric acid aqueous solution in volume of chloroform at room temperature, so that the pH value of the aqueous layer is=7; concentrating the chloroform layer under reduced pressure at 60 deg.C and vacuum degree of 0.03MPa to obtain amination hypocrellin B crude product; performing column chromatography with a developing agent with 23 times of the mass of the amination hypocrellin B crude product to obtain amination hypocrellin B; wherein the developing agent is acetone and ethyl acetate according to the mol ratio of 3:2, mixing to obtain the product; mixing mesoporous nano silicon dioxide hollow spheres with 0.02wt% of amination hypocrellin B solution according to the mass ratio of 1:108, mixing and reacting for 18h at room temperature; after the reaction is finished, centrifuging for 25min at the speed of 3500r/min, adding mesoporous nano-silica hollow spheres and amination hypocrellin B solution at room temperature, respectively washing three times by 9 times of distilled water and ethanol, and drying for 18h at the temperature of 55 ℃ to obtain mesoporous nano-silica hollow spheres loaded with amination hypocrellin B; wherein, the 0.02wt% of the amination hypocrellin B solution is prepared by amination hypocrellin B and ethanol, and the mass percentage of the amination hypocrellin B is 0.02 percent;
(3) Modified nano TiO 2 The mesoporous nano silicon dioxide hollow sphere is loaded with amination hypocrellin B, 40-mesh wood powder, polypropylene, maleic anhydride grafted polyethylene and stearic acid according to the following weight ratio of 4:4:50:45:4:4, mixing for 2 hours at the speed of 3800r/min, adding the mixture into a double-screw extruder, melting and extruding at the temperature of the first section of 70 ℃, the temperature of the second section of 145 ℃, the temperature of the third section to the ninth section of 190 ℃, the temperature of a machine head of 215 ℃, the rotating speed of the screw rod of 95r/min, prepressing for 15min at 160 ℃ and 10Mpa, pressurizing for 7min, and hot-pressing to obtain the wood-plastic composite material with the thickness of 1.5 mm;
(4) Adding polypropylene into an extruder from a first section main feed inlet, setting the feeding speed to be 0.1kg/min, setting the temperature of the first section to be 70 ℃, setting the temperature of the second section to be 170 ℃, setting the temperature of the third section to the ninth section to be 200 ℃, setting the temperature of a machine head to be 215 ℃, setting the rotating speed of a screw to be 80r/min, uniformly mixing isoprene, styrene and di-tert-butyl peroxide at room temperature, injecting the mixture into the extruder from a third section liquid feed inlet at the speed of 0.002kg/min, mixing the mixture with polypropylene, extruding and granulating to obtain a modified polypropylene composite material; wherein the mass ratio of the polypropylene to the isoprene to the styrene to the di-tert-butyl peroxide is 100:0.7:0.7:0.06; in the preparation process of the modified polypropylene composite material, under the condition that the vacuum degree is 0.04MPa, vacuum devolatilization is carried out in the eighth section of the extruder;
(5) 27.3wt% maleic anhydride solution and 33.3wt% guanidine hydrochloride solution were combined in a molar ratio of maleic anhydride to guanidine hydrochloride of 2:1, uniformly mixing, stirring and reacting for 8 hours at 70 ℃ in a nitrogen atmosphere, and drying for 20 hours at 60 ℃ under the vacuum degree of 0.2MPa after the reaction is finished to obtain functionalized maleic anhydride; wherein, the 27.3wt% maleic anhydride solution is prepared by maleic anhydride and ethanol, and the mass percentage of the maleic anhydride is 27.3%; the 33.3wt% guanidine hydrochloride solution is prepared from guanidine hydrochloride and ethanol, and the mass percentage of the guanidine hydrochloride is 33.3%; mixing the allyl elastomer, the functionalized maleic anhydride and the crosslinking inhibitor in a mixer, adding the mixture into a double-screw extruder through a main feed, adding an initiator into the double-screw extruder through a side feed mode, and obtaining the modified allyl elastomer after extrusion granulation, wherein the melt extrusion temperature is 180 ℃, the screw speed is 350r/min and the residence time is 50 s; the mass ratio of the propenyl elastomer, the initiator, the crosslinking inhibitor and the functionalized maleic anhydride is 1050:3:1:20, a step of; the initiator is di-tert-butyl peroxide; the crosslinking inhibitor is stearic acid amide;
(6) The modified polypropylene composite material, the modified propenyl elastomer and the modified calcium carbonate are mixed according to the mass ratio of 93:6:1, mixing, adding into a double-screw extruder, melting and extruding under the conditions that the temperature of the first section is 70 ℃, the temperature of the second section is 145 ℃, the temperature of the third section to the ninth section is 180 ℃, the temperature of a machine head is 215 ℃, the rotating speed of a screw is 90r/min, prepressing for 15min under the conditions of 180 ℃ and 10Mpa, pressurizing for 7min, and hot-pressing into a core layer composite material with the thickness of 1 mm; wherein the modified calcium carbonate is the same as the modified calcium carbonate prepared in example 1;
(7) The wood-plastic composite material with the thickness of 1.5mm and the core layer composite material with the thickness of 1mm are arranged in the sequence of the wood-plastic composite material, the core layer composite material and the wood-plastic composite material, and the high-stability sterile plastic with the thermal expansion reduced is prepared by prepressing for 15min and pressurizing for 7min under the condition of 150 ℃ and 10 Mpa.
Example 4
The embodiment discloses a preparation method of high-stability sterile plastic with reduced thermal expansion, which comprises the following steps:
(1) Modified nano TiO 2 Is prepared as in example 1;
(2) Hypocrellin B, N-dimethyl ethylenediamine and tetrahydrofuran are mixed according to the mass ratio of 1:50:480, reacting for 15 hours at 50 ℃ in the dark, and filtering after the reaction is finished to obtain a reaction product; mixing the reaction product with chloroform in a mass ratio of 1:8, adding the reaction product and a 1/5 10wt% hydrochloric acid aqueous solution in volume of chloroform at room temperature, so that the pH value of the aqueous layer is=7; concentrating the chloroform layer under reduced pressure at a vacuum degree of 0.04MPa and a temperature of 65 ℃ to obtain an amination hypocrellin B crude product; performing column chromatography with a developing agent with the mass of 20 times of the mass of the amination hypocrellin B crude product to obtain amination hypocrellin B; wherein the developing agent is acetone and ethyl acetate according to the mol ratio of 3:2, mixing to obtain the product; mixing mesoporous nano silicon dioxide hollow spheres with 0.02wt% of amination hypocrellin B solution according to the mass ratio of 1:110, reacting for 24 hours at room temperature; after the reaction is finished, centrifuging for 25min at the speed of 3500r/min, adding mesoporous nano-silica hollow spheres and amination hypocrellin B solution at room temperature, respectively washing three times by distilled water and ethanol with the mass of 10 times, and drying for 24h at 50 ℃ to obtain the mesoporous nano-silica hollow sphere loaded amination hypocrellin B; wherein, the 0.02wt% of the amination hypocrellin B solution is prepared by amination hypocrellin B and ethanol, and the mass percentage of the amination hypocrellin B is 0.02 percent;
(3) Modified nano TiO 2 The mesoporous nano silicon dioxide hollow sphere is loaded with amination hypocrellin B, 40-mesh wood powder, polypropylene, maleic anhydride grafted polyethylene and stearic acid in a ratio of 3:3:40:45:4:5, mixing for 0.5h at 4000r/min, adding into a double-screw extruder after mixing, melting and extruding under the conditions that the temperature of the first section is 70 ℃, the temperature of the second section is 145 ℃, the temperature of the third section to the ninth section is 190 ℃, the temperature of a machine head is 215 ℃, the rotating speed of a screw is 95r/min, prepressing for 20min at 160 ℃ and 10Mpa, pressurizing for 5min, and hot-pressing into a wood-plastic composite material with the thickness of 1.5 mm;
(4) Adding polypropylene into an extruder from a first section main feed inlet, setting the feeding speed to be 0.1kg/min, setting the temperature of the first section to be 70 ℃, setting the temperature of the second section to be 170 ℃, setting the temperature of the third section to the ninth section to be 205 ℃, setting the temperature of a machine head to be 215 ℃, setting the rotating speed of a screw to be 120r/min, uniformly mixing isoprene, styrene and di-tert-butyl peroxide at room temperature, injecting the mixture into the extruder from a third section liquid feed inlet at the speed of 0.002kg/min, mixing the mixture with polypropylene, extruding and granulating to obtain a modified polypropylene composite material; wherein the mass ratio of the polypropylene to the isoprene to the styrene to the di-tert-butyl peroxide is 100:0.5:0.5:0.04; in the preparation process of the modified polypropylene composite material, under the condition that the vacuum degree is 0.04MPa, vacuum devolatilization is carried out in the eighth section of the extruder;
(5) 27.3wt% maleic anhydride solution and 33.3wt% guanidine hydrochloride solution were combined in a molar ratio of maleic anhydride to guanidine hydrochloride of 2:1, uniformly mixing, stirring and reacting for 8 hours at 70 ℃ in a nitrogen atmosphere, and drying for 24 hours at 60 ℃ under the vacuum degree of 0.2MPa after the reaction is finished to obtain the functionalized maleic anhydride; wherein, the 27.3wt% maleic anhydride solution is prepared by maleic anhydride and ethanol, and the mass percentage of the maleic anhydride is 27.3%; the 33.3wt% guanidine hydrochloride solution is prepared from guanidine hydrochloride and ethanol, and the mass percentage of the guanidine hydrochloride is 33.3%; mixing the allyl elastomer, the functionalized maleic anhydride and the crosslinking inhibitor in a mixer, adding the mixture into a double-screw extruder through a main feed, adding an initiator into the double-screw extruder through a side feed mode, and obtaining the modified allyl elastomer after extrusion granulation, wherein the melt extrusion temperature is 180 ℃, the screw speed is 350r/min and the residence time is 50 s; the mass ratio of the propenyl elastomer, the initiator, the crosslinking inhibitor and the functionalized maleic anhydride is 1000:0.5:5:15; the initiator is di-tert-butyl peroxide; the crosslinking inhibitor is stearic acid amide;
(6) The modified polypropylene composite material, the modified propenyl elastomer and the modified calcium carbonate are mixed according to the mass ratio of 94:5:1, mixing, adding into a double-screw extruder, melting and extruding under the conditions that the temperature of the first section is 70 ℃, the temperature of the second section is 145 ℃, the temperature of the third section to the ninth section is 180 ℃, the temperature of a machine head is 215 ℃, the rotating speed of a screw is 90r/min, prepressing for 20min under the conditions of 180 ℃ and 10Mpa, pressurizing for 5min, and hot-pressing into a core layer composite material with the thickness of 1 mm; wherein the modified calcium carbonate is the same as the modified calcium carbonate prepared in example 1;
(7) The wood-plastic composite material with the thickness of 1.5mm and the core layer composite material with the thickness of 1mm are arranged in the sequence of the wood-plastic composite material, the core layer composite material and the wood-plastic composite material, and the high-stability sterile plastic with the thermal expansion reduced is prepared by prepressing for 20min and pressurizing for 5min under the condition of 150 ℃ and 10 Mpa.
Comparative example 1
This comparative example discloses a process for the preparation of a highly stable sterile plastic with reduced thermal expansion comprising the steps of:
(1) Wood flour of 40 mesh, polypropylene, maleic anhydride grafted polyethylene, stearic acid at 70:50:4:4, mixing for 5 hours at the speed of 3500r/min, adding the mixture into a double-screw extruder, melting and extruding at the temperature of 70 ℃ in the first section, 145 ℃ in the second section, 180 ℃ in the third section to the ninth section, 215 ℃ in the head, 100r/min in the screw rotating speed, prepressing for 20min at 180 ℃ and 10Mpa, pressurizing for 5min, and hot-pressing to obtain the wood-plastic composite material with the thickness of 1.5 mm;
(2) Adding polypropylene into an extruder from a first section main feed inlet, setting the feeding speed to be 0.1kg/min, setting the temperature of the first section to be 70 ℃, setting the temperature of the second section to be 170 ℃, setting the temperature of the third section to the ninth section to be 205 ℃, setting the temperature of a machine head to be 215 ℃, setting the rotating speed of a screw to be 120r/min, uniformly mixing isoprene, styrene and di-tert-butyl peroxide at room temperature, injecting the mixture into the extruder from a third section liquid feed inlet at the speed of 0.002kg/min, mixing the mixture with polypropylene, extruding and granulating to obtain a modified polypropylene composite material; wherein the mass ratio of the polypropylene to the isoprene to the styrene to the di-tert-butyl peroxide is 100:1:1:0.1; in the preparation process of the modified polypropylene composite material, under the condition that the vacuum degree is 0.01MPa, vacuum devolatilization is carried out in the eighth section of the extruder;
(3) 27.3wt% maleic anhydride solution and 33.3wt% guanidine hydrochloride solution were combined in a molar ratio of maleic anhydride to guanidine hydrochloride of 2:1, uniformly mixing, stirring and reacting for 7 hours at 75 ℃ in a nitrogen atmosphere, and drying for 24 hours at 60 ℃ under the vacuum degree of 0.2MPa after the reaction is finished to obtain the functionalized maleic anhydride; wherein, the 27.3wt% maleic anhydride solution is prepared by maleic anhydride and ethanol, and the mass percentage of the maleic anhydride is 27.3%; the 33.3wt% guanidine hydrochloride solution is prepared from guanidine hydrochloride and ethanol, and the mass percentage of the guanidine hydrochloride is 33.3%; mixing the allyl elastomer, the functionalized maleic anhydride and the crosslinking inhibitor in a mixer, adding the mixture into a double-screw extruder through a main feed, adding an initiator into the double-screw extruder through a side feed mode, and obtaining the modified allyl elastomer after extrusion granulation, wherein the melt extrusion temperature is 200 ℃, the screw speed is 250r/min and the residence time is 30 s; the mass ratio of the propenyl elastomer, the initiator, the crosslinking inhibitor and the functionalized maleic anhydride is 1100:2:3:30; the initiator is di-tert-butyl peroxide; the crosslinking inhibitor is stearic acid amide;
(4) The modified polypropylene composite material, the modified propenyl elastomer and the modified calcium carbonate are mixed according to the mass ratio of 90:9:1, mixing, adding into a double-screw extruder, melting and extruding under the conditions that the temperature of the first section is 70 ℃, the temperature of the second section is 145 ℃, the temperature of the third section to the ninth section is 200 ℃, the temperature of a machine head is 215 ℃, the rotating speed of a screw is 100r/min, prepressing for 20min under the conditions of 200 ℃, 10Mpa, pressurizing for 5min, and hot-pressing into a core layer composite material with the thickness of 1 mm; wherein the modified calcium carbonate is the same as the modified calcium carbonate prepared in example 1;
(5) The wood-plastic composite material with the thickness of 1.5mm and the core layer composite material with the thickness of 1mm are arranged in the sequence of the wood-plastic composite material, the core layer composite material and the wood-plastic composite material, and the high-stability sterile plastic with the thermal expansion reduced is prepared by prepressing for 20min and pressurizing for 5min under the conditions of 180 ℃ and 10 Mpa.
Comparative example 2
This comparative example discloses a process for the preparation of a highly stable sterile plastic with reduced thermal expansion comprising the steps of:
(1) Modified nano TiO 2 Is prepared as in example 1;
(2) Hypocrellin B, N-dimethyl ethylenediamine and tetrahydrofuran are mixed according to the mass ratio of 1:60:500, reacting for 10 hours at 55 ℃ in the dark, and filtering after the reaction is finished to obtain a reaction product; mixing the reaction product with chloroform in a mass ratio of 1:10 mixing, adding the reaction product and 1/2 of 10wt% hydrochloric acid aqueous solution in volume of chloroform at room temperature, and making pH of the aqueous layer=7; concentrating the chloroform layer under reduced pressure at a vacuum degree of 0.04MPa and a temperature of 65 ℃ to obtain an amination hypocrellin B crude product; performing column chromatography with a developing agent with the mass 25 times of that of the amination hypocrellin B crude product to obtain amination hypocrellin B; wherein the developing agent is acetone and ethyl acetate according to the mol ratio of 3:2, mixing to obtain the product; mixing mesoporous nano silicon dioxide hollow spheres with 0.02wt% of amination hypocrellin B solution according to the mass ratio of 1:110, reacting for 24 hours at room temperature; after the reaction is finished, centrifuging for 20min at the speed of 4000r/min, adding mesoporous nano-silica hollow spheres and amination hypocrellin B solution at room temperature, respectively washing three times by distilled water and ethanol with the mass of 10 times, and drying for 24h at 50 ℃ to obtain the mesoporous nano-silica hollow sphere loaded amination hypocrellin B; wherein, the 0.02wt% of the amination hypocrellin B solution is prepared by amination hypocrellin B and ethanol, and the mass percentage of the amination hypocrellin B is 0.02 percent;
(3) Modified nano TiO 2 The mesoporous nano silicon dioxide hollow sphere is loaded with amination hypocrellin B, 40-mesh wood powder, polypropylene, maleic anhydride grafted polyethylene and stearic acid according to the proportion of 5:5:60:49:3:3, mixing for 5 hours at the speed of 3500r/min, adding the mixture into a double-screw extruder, melting and extruding at the temperature of 70 ℃ in the first section, 145 ℃ in the second section, 180 ℃ in the third section to the ninth section, 215 ℃ in the head, 100r/min in the screw rotating speed, prepressing for 20min at 180 ℃ and 10Mpa, pressurizing for 5min, and hot-pressing to obtain the wood-plastic composite material with the thickness of 1.5 mm;
(4) Adding polypropylene into an extruder from a first section main feed inlet, setting the feeding speed to be 0.1kg/min, setting the temperature of the first section to be 70 ℃, setting the temperature of the second section to be 170 ℃, setting the temperature of the third section to the ninth section to be 205 ℃, setting the temperature of a machine head to be 215 ℃, setting the rotating speed of a screw to be 120r/min, uniformly mixing isoprene, styrene and di-tert-butyl peroxide at room temperature, injecting the mixture into the extruder from a third section liquid feed inlet at the speed of 0.002kg/min, mixing and extruding the mixture with polypropylene, prepressing the mixture for 20min at the temperature of 200 ℃ and 10Mpa, pressurizing the mixture for 5min, and hot-pressing the mixture into a core layer composite material with the thickness of 1 mm; wherein the mass ratio of the polypropylene to the isoprene to the styrene to the di-tert-butyl peroxide is 100:0.9:0.9:0.08; in the preparation process of the core layer composite material, under the condition that the vacuum degree is 0.01MPa, performing vacuum devolatilization in an eighth section of an extruder;
(5) The wood-plastic composite material with the thickness of 1.5mm and the core layer composite material with the thickness of 1mm are arranged in the sequence of the wood-plastic composite material, the core layer composite material and the wood-plastic composite material, and the high-stability sterile plastic with the thermal expansion reduced is prepared by prepressing for 20min and pressurizing for 5min under the conditions of 180 ℃ and 10 Mpa.
Comparative example 3
This comparative example discloses a process for the preparation of a highly stable sterile plastic with reduced thermal expansion comprising the steps of:
(1) Modified nano TiO 2 Is prepared as in example 1;
(2) Hypocrellin B, N-dimethyl ethylenediamine and tetrahydrofuran are mixed according to the mass ratio of 1:60:500, reacting for 10 hours at 55 ℃ in the dark, and filtering after the reaction is finished to obtain a reaction product; mixing the reaction product with chloroform in a mass ratio of 1:10 mixing, adding the reaction product and 1/2 of 10wt% hydrochloric acid aqueous solution in volume of chloroform at room temperature, and making pH of the aqueous layer=7; concentrating the chloroform layer under reduced pressure at a vacuum degree of 0.04MPa and a temperature of 65 ℃ to obtain an amination hypocrellin B crude product; performing column chromatography with a developing agent with the mass 25 times of that of the amination hypocrellin B crude product to obtain amination hypocrellin B; wherein the developing agent is acetone and ethyl acetate according to the mol ratio of 3:2, mixing to obtain the product; mixing mesoporous nano silicon dioxide hollow spheres with 0.02wt% of amination hypocrellin B solution according to the mass ratio of 1:110, reacting for 24 hours at room temperature; after the reaction is finished, centrifuging for 20min at the speed of 4000r/min, adding mesoporous nano-silica hollow spheres and amination hypocrellin B solution at room temperature, respectively washing three times by distilled water and ethanol with the mass of 10 times, and drying for 24h at 50 ℃ to obtain the mesoporous nano-silica hollow sphere loaded amination hypocrellin B; wherein, the 0.02wt% of the amination hypocrellin B solution is prepared by amination hypocrellin B and ethanol, and the mass percentage of the amination hypocrellin B is 0.02 percent;
(3) Modified nano TiO 2 The mesoporous nano silicon dioxide hollow sphere is loaded with amino hypocrellin B, polypropylene, maleic anhydride grafted polyethylene and stearic acid in a ratio of 3:3:50:3:2 in a mass ratio of 3500r/minMixing at a speed for 5h, adding the mixed materials into a double-screw extruder, melting and extruding at a first stage temperature of 70 ℃, a second stage temperature of 145 ℃, third to ninth stage temperatures of 180 ℃, a machine head temperature of 215 ℃ and a screw speed of 100r/min, prepressing for 20min at 180 ℃ and 10Mpa, pressurizing for 5min, and hot-pressing to obtain a wood-plastic composite material with a thickness of 1.5 mm;
(4) Adding polypropylene into an extruder from a first section main feed inlet, setting the feeding speed to be 0.1kg/min, setting the temperature of the first section to be 70 ℃, setting the temperature of the second section to be 170 ℃, setting the temperature of the third section to the ninth section to be 205 ℃, setting the temperature of a machine head to be 215 ℃, setting the rotating speed of a screw to be 120r/min, uniformly mixing isoprene, styrene and di-tert-butyl peroxide at room temperature, injecting the mixture into the extruder from a third section liquid feed inlet at the speed of 0.002kg/min, mixing the mixture with polypropylene, extruding and granulating to obtain a modified polypropylene composite material; wherein the mass ratio of the polypropylene to the isoprene to the styrene to the di-tert-butyl peroxide is 100:0.7:0.7:0.06; in the preparation process of the modified polypropylene composite material, under the condition that the vacuum degree is 0.01MPa, vacuum devolatilization is carried out in the eighth section of the extruder;
(5) 27.3wt% maleic anhydride solution and 33.3wt% guanidine hydrochloride solution were combined in a molar ratio of maleic anhydride to guanidine hydrochloride of 2:1, uniformly mixing, stirring and reacting for 7 hours at 75 ℃ in a nitrogen atmosphere, and drying for 24 hours at 60 ℃ under the vacuum degree of 0.2MPa after the reaction is finished to obtain the functionalized maleic anhydride; wherein, the 27.3wt% maleic anhydride solution is prepared by maleic anhydride and ethanol, and the mass percentage of the maleic anhydride is 27.3%; the 33.3wt% guanidine hydrochloride solution is prepared from guanidine hydrochloride and ethanol, and the mass percentage of the guanidine hydrochloride is 33.3%; mixing the allyl elastomer, the functionalized maleic anhydride and the crosslinking inhibitor in a mixer, adding the mixture into a double-screw extruder through a main feed, adding an initiator into the double-screw extruder through a side feed mode, and obtaining the modified allyl elastomer after extrusion granulation, wherein the melt extrusion temperature is 200 ℃, the screw speed is 250r/min and the residence time is 30 s; the mass ratio of the propenyl elastomer, the initiator, the crosslinking inhibitor and the functionalized maleic anhydride is 1050:3:1:20, a step of; the initiator is di-tert-butyl peroxide; the crosslinking inhibitor is stearic acid amide;
(6) The modified polypropylene composite material and the modified propenyl elastomer are mixed according to the mass ratio of 94:6, mixing, adding into a double-screw extruder, melting and extruding under the conditions that the temperature of the first section is 70 ℃, the temperature of the second section is 145 ℃, the temperature of the third section to the ninth section is 200 ℃, the temperature of a machine head is 215 ℃, the rotating speed of a screw is 100r/min, prepressing for 20min under the conditions of 200 ℃, 10Mpa, pressurizing for 5min, and hot-pressing into a core layer composite material with the thickness of 1 mm;
(7) The wood-plastic composite material with the thickness of 1.5mm and the core layer composite material with the thickness of 1mm are arranged in the sequence of the wood-plastic composite material, the core layer composite material and the wood-plastic composite material, and the high-stability sterile plastic with the thermal expansion reduced is prepared by prepressing for 20min and pressurizing for 5min under the conditions of 180 ℃ and 10 Mpa.
Comparative example 4
This comparative example discloses a process for the preparation of a highly stable sterile plastic with reduced thermal expansion comprising the steps of:
(1) Modified nano TiO 2 Is prepared as in example 1;
(2) Modified nano TiO 2 Mesoporous nano silica hollow sphere, 40 mesh wood powder, polypropylene, maleic anhydride grafted polyethylene and stearic acid in a ratio of 3:3:40:45:4:5, mixing for 5 hours at the speed of 3500r/min, adding the mixture into a double-screw extruder, melting and extruding at the temperature of 70 ℃ in the first section, 145 ℃ in the second section, 180 ℃ in the third section to the ninth section, 215 ℃ in the head, 100r/min in the screw rotating speed, prepressing for 20min at 180 ℃ and 10Mpa, pressurizing for 5min, and hot-pressing to obtain the wood-plastic composite material with the thickness of 1.5 mm;
(3) Adding polypropylene into an extruder from a first section main feed inlet, setting the feeding speed to be 0.1kg/min, setting the temperature of the first section to be 70 ℃, setting the temperature of the second section to be 170 ℃, setting the temperature of the third section to the ninth section to be 205 ℃, setting the temperature of a machine head to be 215 ℃, setting the rotating speed of a screw to be 120r/min, uniformly mixing isoprene, styrene and di-tert-butyl peroxide at room temperature, injecting the mixture into the extruder from a third section liquid feed inlet at the speed of 0.002kg/min, mixing the mixture with polypropylene, extruding and granulating to obtain a modified polypropylene composite material; wherein the mass ratio of the polypropylene to the isoprene to the styrene to the di-tert-butyl peroxide is 100:0.5:0.5:0.04; in the preparation process of the modified polypropylene composite material, under the condition that the vacuum degree is 0.01MPa, vacuum devolatilization is carried out in the eighth section of the extruder;
(4) The modified polypropylene composite material, the propenyl elastomer and the modified calcium carbonate are mixed according to the mass ratio of 94:5:1, mixing, adding into a double-screw extruder, melting and extruding under the conditions that the temperature of the first section is 70 ℃, the temperature of the second section is 145 ℃, the temperature of the third section to the ninth section is 200 ℃, the temperature of a machine head is 215 ℃, the rotating speed of a screw is 100r/min, prepressing for 20min under the conditions of 200 ℃, 10Mpa, pressurizing for 5min, and hot-pressing into a core layer composite material with the thickness of 1 mm; wherein the modified calcium carbonate is the same as the modified calcium carbonate prepared in example 1;
(5) The wood-plastic composite material with the thickness of 1.5mm and the core layer composite material with the thickness of 1mm are arranged in the sequence of the wood-plastic composite material, the core layer composite material and the wood-plastic composite material, and the high-stability sterile plastic with the thermal expansion reduced is prepared by prepressing for 20min and pressurizing for 5min under the conditions of 180 ℃ and 10 Mpa.
Examples 1 to 4 and comparative examples 1 to 4, nano TiO 2 Product number T832270, CAS number from Shanghai microphone Biochemical technologies Co., ltd: 13463-67-7; gamma-methacryloxypropyl trimethoxysilane was obtained from Nanjing disilicide Co., ltd., CAS number: 2530-85-0; the mesoporous nano silica hollow sphere is from Beijing Kokoku science and technology Co., ltd, has a particle size of 200nm, and is brand-name Koku; cetyl trimethylammonium chloride is available from Guangdong Weng Jiang chemical agent Co., ltd., CAS number: 112-02-7; anhydrous sodium carbonate comes from the company of chemical industry, inc. In the century of atanan, CAS No.: 497-19-8; ethanol is from Shanghai Poisson chemical Co., ltd., CAS number: 64-17-5; hypocrellin was obtained from Chengdu Biotechnology Co., ltd., CAS number: 123940-54-5; n, N-dimethylethylenediamine was from Sigma, product number D157805, CAS number: 110-70-3; tetrahydrofuran was from guangzhou prefecture, inc, CAS number: 109-99-9; trichloromethane is from AlfaAesar corporation, CAS No.: 67-66-3; acetone is available from Shandong Shaoshan chemical Co., ltd., CAS number :67-64-1; ethyl acetate from Jiangsu Pu Le Si biotechnology Co., ltd., CAS number: 141-78-6; wood flour is from the company Asahi building materials, hebei, inc., product number KX-M1; polypropylene was from the Dongguan sodium baichuan plasticization limited, product number PPH603, brand Braskem, CAS number: 9003-07-0; maleic anhydride grafted polyethylene was from Dongguan mountain one plasticization strength supplier, brand rana bamboos, CAS number: 9006-26-2; stearic acid from guangdong Weng Jiang chemical company, CAS No.: 57-11-4; isoprene is from Adamas-beta company under the trade designation C63-83523c, cas designation: 78-79-5; styrene comes from the company Jinan century, chemical industry Co., ltd, brand Li Huayi, CAS number: 100-42-5; di-t-butyl peroxide is available from Shaanxi, inc., pharmaceutical and chemical Co., ltd., CAS number: 110-05-4; maleic anhydride comes from the company Jinan century to chemical industry Co., ltd., CAS number: 108-31-6; guanidine hydrochloride is from Shanghai sushi chemical Co., ltd., CAS number: 50-01-1; the propylene-based elastomer is from the company ExxonMobil, under the brand vistamaxx6102; stearamide is from the biological sciences of the Ji Yibang, wuhan, CAS number: 124-26-5; the calcium carbonate comes from the fine stone powder factory of the Chengshi city, the fineness is 400 meshes, and the CAS number is: 471-34-1.
Test examples
(1) Mechanical property test
Mechanical property tests were performed on the high stability sterile plastics with reduced thermal expansion prepared in examples 1-4 and comparative examples 1-4. The specific test results are shown in Table 1:
the detection of each index in table 1 is based on the following criteria: flexural strength, flexural modulus are determined by ASTM D790-03 Standard test method for the flexural Properties of unreinforced and reinforced plastics and electric insulation; impact strength was determined by ASTM D4812 test method for impact strength of plastic unnotched cantilever beam; the coefficient of thermal expansion is determined by ISO 11359-2014, thermodynamic analysis of plastics; the ageing resistance is obtained by GB/T16422.2-2014 part 2 of the light source exposure test method of plastics laboratory: xenon arc lamp.
As can be seen from the test results in Table 1, the high-stability sterile plastic with reduced thermal expansion prepared by the invention has excellent mechanical properties.
The high-stability sterile plastic with reduced thermal expansion is prepared through the sandwich structure of covering the upper surface and the lower surface of the light core layer with the two rigid wood-plastic surface layers, has higher impact strength and bending strength, improves the flexural modulus, reduces the thermal expansion coefficient and improves the dimensional stability; meanwhile, the weight of the high-stability sterile plastic with reduced thermal expansion is reduced due to the existence of the sandwich structure, so that the high-stability sterile plastic is lighter; the propylene-based elastomer added in the sandwich structure can disperse force, so that stress concentration of the material during damage is avoided, the material is not easy to crack, the impact strength of the sandwich material is improved, and the modified calcium carbonate is used as rigid particles to reduce the thermal expansion coefficient of the sandwich material; the wood plastic material with the surface layer structure is added with wood powder and modified nano TiO 2 The mesoporous nano silicon dioxide hollow sphere is used as a rigid particle, so that the mechanical property of the mesoporous nano silicon dioxide hollow sphere is greatly improved; in the invention, modified nano TiO is added to the wood-plastic material with a surface layer structure 2 And mesoporous nano silicon dioxide hollow sphere loaded amino hypocrellin B, and nano TiO is used 2 And hypocrellin B, so as to achieve the aim of inhibiting the aging of the polypropylene matrix; the polypropylene is modified by styrene and isoprene in the core layer structure, and the modified polypropylene is used as a matrix, so that the activity of methyl groups in the polypropylene is effectively inhibited, the stability of the polypropylene material is improved, and the prepared high-stability sterile plastic with reduced thermal expansion has ageing resistance and high stability.
Comparative example 1 no mesoporous nanosilica hollow sphere loaded with aminated hypocrellin B and modified nano TiO 2 As the photosensitive aging inhibitor, although the core layer structure still has the modified polypropylene modified by styrene and isoprene, the wood-plastic material of the surface layer structure does not have good aging resistance, so the aging resistance is inferior to examples 1 to 4 and comparative examples 2 to 4; meanwhile, due to the lack of mesoporous nano silicon dioxide hollow spheres and modified nano Rice TiO 2 As rigid particles, the mechanical properties are slightly lower than those of example 1, and the thermal expansion coefficient is higher than that of example 1; comparative example 2, in which no modified acryl-based elastomer was added as a core material, had lower impact strength than example 2; since no modified acryl-based elastomer having a higher thermal expansion coefficient and a lower flexural strength was added to the core layer structure, the thermal expansion coefficient and flexural strength thereof were lower than those of example 2; comparative example 3 in which wood flour and modified calcium carbonate were not added as rigid particles even with mesoporous nanosilica hollow spheres and modified nano-TiO 2 As rigid particles, but due to insufficient addition, the mechanical properties are far lower than those of example 3, and the thermal expansion coefficient is far higher than that of example 3;
(2) Antibacterial property test
Antibacterial property tests were conducted on the high-stability sterile plastics with reduced thermal expansion prepared in examples 1 to 4 and comparative examples 1 to 4. The specific test results are shown in Table 2:
table 2 the detection of the various indicators is based on the following criteria: the antibacterial rate and the mold growth grade were measured by QB/T2591 test method for antibacterial Plastic-antibacterial Property and antibacterial Effect.
As can be seen from the test results of Table 2, the high-stability sterile plastic with reduced thermal expansion prepared by the present invention has excellent antibacterial properties.
In the invention, modified nano TiO is added 2 And mesoporous nano silicon dioxide hollow sphere loaded amino hypocrellin B, and nano TiO is used 2 And hypocrellin B, so as to achieve the aim of sterilization, thereby making the prepared high-stability sterile plastic with reduced thermal expansion have antibacterial property; the functional maleic anhydride is prepared by carrying out antibacterial functional modification on maleic anhydride by guanidine hydrochloride, the macromolecular antibacterial agent cannot permeate into human skin, has low toxicity, has better antibacterial durability than a micromolecular antibacterial agent, and has good thermal stability; will functionThe maleic anhydride is grafted and connected with the propenyl elastomer, so that the prepared high-stability sterile plastic with reduced thermal expansion has longer antibacterial function.
Comparative example 4 was free of functionalized maleic anhydride and aminated hypocrellin B as antibacterial agents, even with modified nano TiO 2 Sterilization can be performed using photocatalytic activity, but since there is no synergistic effect of the aminated hypocrellin b, the antibacterial performance is inferior to examples 1 to 4 and comparative examples 1 to 3.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A method for preparing a highly stable sterile plastic with reduced thermal expansion, comprising the steps of:
step one, preparing a wood-plastic composite material and a core layer composite material; the preparation of the wood-plastic composite material comprises the following steps:
step (1) mixing hypocrellin B, N-dimethyl ethylenediamine and tetrahydrofuran, reacting, separating, purifying and drying after the reaction is finished to obtain aminated hypocrellin B;
mixing the amination hypocrellin B with ethanol to prepare amination hypocrellin B solution, mixing mesoporous nano silicon dioxide hollow spheres with the amination hypocrellin B solution, reacting, centrifuging, washing and drying after the reaction is finished to obtain the mesoporous nano silicon dioxide hollow spheres loaded with the amination hypocrellin B;
step (3) modifying the nano TiO 2 Mixing the mesoporous nano silicon dioxide hollow sphere supported amino hypocrellin B, wood powder, polypropylene, maleic anhydride grafted polyethylene and stearic acid, adding into a double-screw extruder, melting and extruding, and hot-pressing to obtain the wood-plastic composite material; wherein, the preparation of the core layer composite material comprises the following steps:
step (1) mixing polypropylene, isoprene, styrene and di-tert-butyl peroxide, extruding, granulating to obtain a modified polypropylene composite material; mixing maleic anhydride solution and guanidine hydrochloride solution, reacting, and drying after the reaction is finished to obtain functionalized maleic anhydride; adding the propenyl elastomer, the functionalized maleic anhydride, the crosslinking inhibitor and the initiator into a double-screw extruder, and carrying out melt extrusion and granulation to obtain a modified propenyl elastomer;
Step (2) mixing the modified polypropylene composite material, the modified propenyl elastomer and the modified calcium carbonate, adding the mixture into a double-screw extruder, carrying out melt extrusion, and carrying out hot pressing to form a core layer composite material;
and step two, superposing the wood-plastic composite material, the core layer composite material and the wood-plastic composite material in the sequence of one layer of wood-plastic composite material, one layer of core layer composite material and one layer of wood-plastic composite material, and hot-pressing to prepare the high-stability sterile plastic with reduced thermal expansion.
2. The method for producing a highly stable sterile plastic with reduced thermal expansion according to claim 1, wherein in the step (1) of producing a wood-plastic composite material: the mass ratio of hypocrellin B to N, N-dimethyl ethylenediamine to tetrahydrofuran is 1: (40-60): (440-500); the reaction conditions are as follows: reacting for 10-15h at 50-55deg.C in dark condition.
3. The method for producing a highly stable sterile plastic with reduced thermal expansion according to claim 1, wherein in the step (2) of producing a wood-plastic composite material: the mass ratio of the mesoporous nano silicon dioxide hollow sphere to the amination hypocrellin B solution is 1: (105-110); the reaction conditions are as follows: the reaction is carried out for 16-24h at room temperature.
4. The method for producing a highly stable sterile plastic with reduced thermal expansion according to claim 1, wherein in the step (3) of producing a wood-plastic composite material: modified nano TiO 2 Mesoporous nano silicon dioxide hollow sphere loaded amino hypocrellin B, wood powder, polypropylene, maleic anhydride grafted polyethylene and stearylThe mass ratio of the acid is (3-6): (3-6): (40-70): (45-50): (3-5): (2-5); the melt extrusion conditions were: the temperature of the first section is 70 ℃, the temperature of the second section is 145 ℃, the temperatures of the third section to the ninth section are 180-200 ℃, the temperature of the machine head is 215 ℃, and the rotating speed of the screw is 90-100r/min; the hot pressing conditions are as follows: prepressing for 15-20min at 150-180deg.C under 10Mpa, and pressurizing for 5-7min.
5. The method for preparing high-stability sterile plastic with reduced thermal expansion according to claim 1, wherein the modified nano-TiO in step (3) is used for preparing a wood-plastic composite material 2 The preparation method comprises the following steps: nano TiO 2 Mixing with deionized water, stirring, and dispersing; adding a silane coupling agent, stirring for reaction, and separating and purifying after the reaction is finished to obtain modified nano TiO 2 。
6. The method of producing a highly stable sterile plastic with reduced thermal expansion according to claim 1, wherein, in the step (1), when producing the core composite material: the mass ratio of polypropylene, isoprene, styrene and di-tert-butyl peroxide is 100: (0.50-1): (0.50-1): (0.04-0.1); the extrusion conditions were: the temperature of the first section is 70 ℃, the temperature of the second section is 170 ℃, the temperatures of the third section to the ninth section are 200-205 ℃, the temperature of the machine head is 215 ℃, and the rotating speed of the screw is 60-120r/min; the molar ratio of maleic anhydride in the maleic anhydride solution to guanidine hydrochloride in the guanidine hydrochloride solution is 2:1, a maleic anhydride solution comprises 27.3wt% of maleic anhydride solution, and is prepared from maleic anhydride and ethanol; the guanidine hydrochloride solution comprises 33.3wt% of guanidine hydrochloride solution and is prepared from guanidine hydrochloride and ethanol; the mass ratio of the propenyl elastomer, the initiator, the crosslinking inhibitor and the functionalized maleic anhydride is 1100:2:3:30; the conditions of melt extrusion were: the melt extrusion temperature is 170-200 ℃, the screw rotation speed is 250-500r/min, and the residence time is 30-60s.
7. The method of producing a highly stable sterile plastic with reduced thermal expansion according to claim 1, wherein, in the step (2), when producing the core composite material: the mass ratio of the modified polypropylene composite material to the modified propenyl elastomer to the modified calcium carbonate is (90-94): (5-9): 1, a step of; the conditions of melt extrusion were: the temperature of the first section is 70 ℃, the temperature of the second section is 145 ℃, the temperatures of the third section to the ninth section are 180-200 ℃, the temperature of the machine head is 215 ℃, and the rotating speed of the screw is 90-100r/min; the hot pressing conditions are as follows: prepressing for 15-20min at 180-200deg.C under 10Mpa, and pressurizing for 5-7min.
8. The method for preparing a highly stable sterile plastic with reduced thermal expansion according to claim 1, wherein in the second step: the hot pressing conditions are as follows: prepressing for 15-20min at 150-180deg.C under 10Mpa, and pressurizing for 5-7min.
9. A high-stability sterile plastic with reduced thermal expansion prepared by the method for preparing a high-stability sterile plastic with reduced thermal expansion according to any one of claims 1 to 8.
10. Use of a highly stable sterile plastic with reduced thermal expansion according to claim 9 in infant cutlery.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898591A (en) * | 2012-11-05 | 2013-01-30 | 华东理工大学 | Method for preparing styrene/isoprene in-situ toughened polypropylene |
| CN105566547A (en) * | 2015-12-01 | 2016-05-11 | 陕西一品达石化有限公司 | Preparation method of guanidine-containing polymeric antibacterial agent |
| KR20170090022A (en) * | 2016-01-27 | 2017-08-07 | 충북대학교 산학협력단 | Thermocolor tableware comprising wood plastic composite and preperation method thereof |
| CN109096601A (en) * | 2018-07-03 | 2018-12-28 | 广东康百文创科技有限公司 | A kind of preparation method of acidproof flame-proof antibiotic crystalline p p sheet |
| CN109294264A (en) * | 2018-09-29 | 2019-02-01 | 陈炳奎 | A kind of high impact copolymer Wood-plastic material and preparation method thereof |
| CN111484698A (en) * | 2020-04-27 | 2020-08-04 | 上海应用技术大学 | Preparation method of guanidine hydrochloride antibacterial agent modified maleic anhydride graft copolymerization polypropylene composite material |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898591A (en) * | 2012-11-05 | 2013-01-30 | 华东理工大学 | Method for preparing styrene/isoprene in-situ toughened polypropylene |
| CN105566547A (en) * | 2015-12-01 | 2016-05-11 | 陕西一品达石化有限公司 | Preparation method of guanidine-containing polymeric antibacterial agent |
| KR20170090022A (en) * | 2016-01-27 | 2017-08-07 | 충북대학교 산학협력단 | Thermocolor tableware comprising wood plastic composite and preperation method thereof |
| CN109096601A (en) * | 2018-07-03 | 2018-12-28 | 广东康百文创科技有限公司 | A kind of preparation method of acidproof flame-proof antibiotic crystalline p p sheet |
| CN109294264A (en) * | 2018-09-29 | 2019-02-01 | 陈炳奎 | A kind of high impact copolymer Wood-plastic material and preparation method thereof |
| CN111484698A (en) * | 2020-04-27 | 2020-08-04 | 上海应用技术大学 | Preparation method of guanidine hydrochloride antibacterial agent modified maleic anhydride graft copolymerization polypropylene composite material |
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