CN110894321A - Preparation method of mildew-proof bamboo-plastic composite material - Google Patents
Preparation method of mildew-proof bamboo-plastic composite material Download PDFInfo
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- CN110894321A CN110894321A CN201911196096.2A CN201911196096A CN110894321A CN 110894321 A CN110894321 A CN 110894321A CN 201911196096 A CN201911196096 A CN 201911196096A CN 110894321 A CN110894321 A CN 110894321A
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 229920003023 plastic Polymers 0.000 title claims abstract description 32
- 239000004033 plastic Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 75
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims abstract description 51
- 235000017491 Bambusa tulda Nutrition 0.000 claims abstract description 51
- 241001330002 Bambuseae Species 0.000 claims abstract description 51
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims abstract description 51
- 239000011425 bamboo Substances 0.000 claims abstract description 51
- 239000003610 charcoal Substances 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 35
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 29
- -1 polypropylene Polymers 0.000 claims abstract description 29
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 27
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 26
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 20
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 19
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- HOJYCNSTMZLRCV-UHFFFAOYSA-N 5,5-dimethyl-3-prop-2-enylimidazolidine-2,4-dione Chemical compound CC1(C)NC(=O)N(CC=C)C1=O HOJYCNSTMZLRCV-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000004743 Polypropylene Substances 0.000 claims abstract description 16
- 229920001155 polypropylene Polymers 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- YJKHMSPWWGBKTN-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroheptyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F YJKHMSPWWGBKTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 14
- 229920001661 Chitosan Polymers 0.000 claims abstract description 12
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 10
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 229920002545 silicone oil Polymers 0.000 claims abstract description 10
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims abstract description 9
- 229920001971 elastomer Polymers 0.000 claims abstract description 9
- 239000000806 elastomer Substances 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000001746 injection moulding Methods 0.000 claims abstract description 9
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 8
- 229940057995 liquid paraffin Drugs 0.000 claims abstract description 8
- 239000000314 lubricant Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 15
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 8
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- 239000005457 ice water Substances 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 6
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000008117 stearic acid Substances 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 1
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000228153 Penicillium citrinum Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 241000223261 Trichoderma viride Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- 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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- 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
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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
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The invention discloses a preparation method of a mildew-proof bamboo-plastic composite material, which comprises the following steps: mixing methacrylic acid, 3-allyl-5, 5-dimethylhydantoin and water uniformly, dripping the mixture into a mixture of dodecafluoroheptyl methacrylate, liquid paraffin and span 80, introducing nitrogen, and adding azobisisobutyronitrile for reaction to obtain a material A; mixing 1, 3-di (4-aniline) adamantane, ferric nitrate and ethanol, adding bamboo charcoal after stirring, reacting in a high-pressure kettle, evaporating and drying to obtain a material B; mixing the material A and DMF, adding EDC, performing ultrasonic treatment, adding the material B, stirring, centrifuging, washing, drying, adding into sodium hypochlorite solution, stirring, filtering, washing, and drying to obtain modified bamboo charcoal; mixing polypropylene, bamboo powder, compatilizer, lubricant, antioxidant, modified bamboo charcoal, calcium carbonate, talcum powder, metallocene polyethylene elastomer, nano zinc oxide, chitosan and hydrogen-containing silicone oil, adding into an extruder, extruding, granulating, and injection molding.
Description
Technical Field
The invention relates to the technical field of bamboo-plastic materials, in particular to a preparation method of a mildew-proof bamboo-plastic composite material.
Background
The bamboo-plastic composite material is prepared by compounding thermoplastic plastics and bamboo powder (or bamboo fiber), has the advantages of good dimensional stability, no cracking, easy cutting, natural wood texture, environmental friendliness and the like, and is widely applied to the fields of automobile manufacturing, architectural decoration, indoor decoration, gardens, packaging and transportation and the like at present. Although the bamboo-plastic composite material has a plurality of advantages, the bamboo powder surface contains a large amount of polar groups, so that the bamboo-plastic composite material has strong hydrophilicity, and the product has high water absorption rate and is easy to go moldy and decay when used in a high-humidity environment, thereby reducing the performance of the material and limiting the application of the material.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a preparation method of the mildew-proof bamboo-plastic composite material, the process is simple and feasible, and the obtained composite material has excellent antibacterial and mildew-proof performance, low water absorption and long service life.
The invention provides a preparation method of a mildew-proof bamboo-plastic composite material, which comprises the following steps:
s1, uniformly mixing methacrylic acid, 3-allyl-5, 5-dimethylhydantoin and water, dropwise adding the mixture into a mixture consisting of dodecafluoroheptyl methacrylate, liquid paraffin and span 80, introducing nitrogen, adding azobisisobutyronitrile, reacting for 3-5 hours at 65-75 ℃, and performing post-treatment after the reaction is finished to obtain a material A;
s2, mixing 1, 3-bis (4-aniline) adamantane, ferric nitrate and ethanol, stirring for 60-120min at 35-50 ℃, adding bamboo charcoal, stirring for 200min at 65-70 ℃, then transferring into an autoclave for reaction for 2-5h, wherein the reaction temperature in the autoclave is 100-120 ℃, the pressure is 1-1.45MPa, and evaporating and drying to obtain a material B;
s3, uniformly mixing the material A and DMF, adding EDC under the condition of ice water bath, adding the material B after ultrasonic treatment, stirring for 15-20h at 40-55 ℃, centrifuging, washing and drying to obtain an intermediate material, adding the intermediate material into a sodium hypochlorite solution, stirring for 3-5h at room temperature, filtering, washing and drying to obtain modified bamboo charcoal;
s4, mixing 40-55 parts of polypropylene, 50-60 parts of bamboo powder, 2-4.3 parts of a compatilizer, 1.5-2.5 parts of a lubricant, 0.16-0.28 part of an antioxidant, 4-15 parts of modified bamboo charcoal, 2-5 parts of calcium carbonate, 2-5 parts of talcum powder, 1-5 parts of metallocene polyethylene elastomer, 0.5-1.2 parts of nano zinc oxide, 1-3 parts of chitosan and 0.5-1.5 parts of hydrogen-containing silicone oil uniformly, adding the mixture into a double-screw extruder, extruding and granulating, and performing injection molding to obtain the mildew-proof bamboo-plastic composite material.
Preferably, in S1, the weight ratio of methacrylic acid, 3-allyl-5, 5-dimethylhydantoin, dodecafluoroheptyl methacrylate, azobisisobutyronitrile is 2-3.7: 0.3-0.5: 0.5-1.5: 0.08-0.17.
Preferably, in S2, the weight ratio of 1, 3-bis (4-aniline) adamantane, ferric nitrate and bamboo charcoal is 12-23: 2-8: 18-30.
Preferably, in S3, the weight ratio of material a to material B is 1: 6-10; the weight ratio of the intermediate material to the sodium hypochlorite is 1: 20-50.
Preferably, in S4, the bamboo powder has a particle size of 40-80 mesh.
Preferably, in S4, the compatibilizer is one or more of polyethylene grafted maleic anhydride, polypropylene grafted maleic anhydride, and polypropylene grafted glycidyl methacrylate.
Preferably, in S4, the lubricant is one or more of stearic acid, polyethylene wax, and ethylene bis stearamide.
Preferably, in S4, the antioxidant is a mixture of antioxidant 1076, antioxidant DLTP and antioxidant 168, and the weight ratio of antioxidant 1076, antioxidant DLTP and antioxidant 168 is 1: 1: 2-5.
Preferably, in S4, the temperature of the twin-screw extruder is 230-245 ℃ and the screw rotation speed is 85-100r/min during the extrusion granulation process.
Preferably, in S1, during the dropping, the method further comprises stirring the system.
Preferably, in S1, the 3-allyl-5, 5-dimethylhydantoin may be prepared according to the following process: uniformly mixing 5, 5-dimethylhydantoin, potassium hydroxide and water, adding a methanol solution of allyl bromide, stirring and reacting at 65-70 ℃ for 50-120min, adjusting the pH value to be neutral after the reaction is finished, extracting by dichloromethane, washing, performing rotary evaporation on the lower layer liquid, and drying to obtain the 3-allyl-5, 5-dimethylhydantoin.
Preferably, in S1, the post-processing includes the steps of: adding acetone into the reacted product, standing for layering, taking the lower layer liquid for rotary evaporation, washing with acetone, adding into DMF, centrifuging, and drying to obtain material A.
Preferably, in S2, the temperature of drying is 100 ℃.
Preferably, in S3, the temperature of the ice-water bath is 0-5 ℃.
Preferably, in S3, the washing includes washing with water and ethanol during the preparation of the intermediate material; and adding the intermediate material into a sodium hypochlorite solution, stirring at room temperature for 3-5h, filtering, washing with water, and drying to obtain the modified bamboo charcoal.
In the invention, DMF is N, N-dimethylformamide; the EDC is ethyl [3- (dimethylamino) propyl ] carbodiimide hydrochloride.
The preparation method of the mildew-proof bamboo-plastic composite material comprises the following steps of firstly, taking methacrylic acid, 3-allyl-5, 5-dimethylhydantoin and dodecafluoroheptyl methacrylate as raw materials, and controlling reaction conditions to enable the raw materials to undergo polymerization reaction to obtain a material A; 1, 3-bis (4-aniline) adamantane, ferric nitrate and bamboo charcoal are used as raw materials, reaction conditions are controlled, so that the 1, 3-bis (4-aniline) adamantane and iron ions are firmly decorated on the surface and in gaps of the bamboo charcoal, the introduced iron ions have a hole expanding effect on the bamboo charcoal, the adsorption quantity of the 1, 3-bis (4-aniline) adamantane is increased, and a material B is obtained; then the material A and the material B are taken as raw materials, the reaction condition is controlled, carboxyl in the material A and amino in the material B are reacted, so that the material A and the material B are combined into a whole, sodium hypochlorite solution is added for chlorination reaction, modified bamboo charcoal is obtained, the modified bamboo charcoal is taken as the raw material of the composite material and is added into a system, the raw material is uniformly dispersed in the system, and the interface compatibility of the system is improved, on one hand, because an N-halamine structure is introduced and is matched with nano zinc oxide and chitosan, the synergy and complementary action of a high molecular antibacterial agent, an inorganic antibacterial agent and a natural antibacterial agent are exerted, the composite material has an antibacterial effect on various bacteria such as staphylococcus aureus, escherichia coli and the like, the killing rate reaches more than 98.9 percent, meanwhile, the adverse effects of aspergillus niger, trichoderma viride, penicillium citrinum and white rot fungi on the composite material can be inhibited, and, the composite material is endowed with excellent mildew resistance, on one hand, fluorine and an adamantane structure are introduced into a system, the composite material is endowed with certain hydrophobicity and is matched with hydrogen-containing silicone oil, so that the water absorption of the composite material is reduced, and on the other hand, the introduced adamantane structure is matched with calcium carbonate and talcum powder in a synergistic manner, so that the thermal stability of the composite material is improved.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of a mildew-proof bamboo-plastic composite material comprises the following steps:
s1, uniformly mixing methacrylic acid, 3-allyl-5, 5-dimethylhydantoin and water, dropwise adding the mixture into a mixture consisting of dodecafluoroheptyl methacrylate, liquid paraffin and span 80, introducing nitrogen, adding azobisisobutyronitrile, reacting for 3 hours at 75 ℃, and performing aftertreatment after the reaction is finished to obtain a material A;
s2, mixing 1, 3-bis (4-aniline) adamantane, ferric nitrate and ethanol, stirring for 120min at 35 ℃, adding bamboo charcoal, stirring for 200min at 65 ℃, transferring into an autoclave to react for 2h, wherein the reaction temperature in the autoclave is 120 ℃, the pressure is 1.45MPa, and evaporating and drying to obtain a material B;
s3, uniformly mixing the material A and DMF, adding EDC under the condition of ice water bath, adding the material B after ultrasonic treatment, stirring for 15h at 55 ℃, centrifuging, washing and drying to obtain an intermediate material, adding the intermediate material into a sodium hypochlorite solution, stirring for 3h at room temperature, filtering, washing and drying to obtain modified bamboo charcoal;
s4, mixing 55 parts of polypropylene, 55 parts of bamboo powder, 2 parts of a compatilizer, 2 parts of a lubricant, 0.16 part of an antioxidant, 12 parts of modified bamboo charcoal, 2 parts of calcium carbonate, 3 parts of talcum powder, 1 part of a metallocene polyethylene elastomer, 1.2 parts of nano zinc oxide, 1 part of chitosan and 1.5 parts of hydrogen-containing silicone oil uniformly according to parts by weight, adding the mixture into a double-screw extruder for extrusion granulation, and performing injection molding to obtain the mildew-proof bamboo-plastic composite material.
Example 2
A preparation method of a mildew-proof bamboo-plastic composite material comprises the following steps:
s1, uniformly mixing methacrylic acid, 3-allyl-5, 5-dimethylhydantoin and water, dropwise adding the mixture into a mixture consisting of dodecafluoroheptyl methacrylate, liquid paraffin and span 80, introducing nitrogen, adding azobisisobutyronitrile, reacting for 5 hours at 65 ℃, and performing aftertreatment after the reaction is finished to obtain a material A; wherein the weight ratio of methacrylic acid, 3-allyl-5, 5-dimethylhydantoin, dodecafluoroheptyl methacrylate to azobisisobutyronitrile is 3.7: 0.3: 1.5: 0.08;
s2, mixing 1, 3-bis (4-aniline) adamantane, ferric nitrate and ethanol, stirring at 40 ℃ for 100min, and adding bamboo charcoal, wherein the weight ratio of the 1, 3-bis (4-aniline) adamantane to the ferric nitrate to the bamboo charcoal is 12: 8: 18, stirring for 150min at 70 ℃, then transferring into an autoclave for reaction for 5h, wherein the reaction temperature in the autoclave is 100 ℃, the pressure is 1MPa, and evaporating and drying to obtain a material B;
s3, uniformly mixing the material A and DMF, adding EDC under the condition of ice water bath, adding the material B after ultrasonic treatment, stirring for 20h at 40 ℃, centrifuging, washing and drying to obtain an intermediate material, adding the intermediate material into a sodium hypochlorite solution, stirring for 5h at room temperature, filtering, washing and drying to obtain modified bamboo charcoal; wherein the weight ratio of the material A to the material B is 1: 6; the weight ratio of the intermediate material to the sodium hypochlorite in the sodium hypochlorite solution is 1: 20;
s4, uniformly mixing 40 parts by weight of polypropylene, 60 parts by weight of bamboo powder, 4.3 parts by weight of compatilizer, 2.5 parts by weight of lubricant, 0.28 part by weight of antioxidant, 15 parts by weight of modified bamboo charcoal, 5 parts by weight of calcium carbonate, 5 parts by weight of talcum powder, 5 parts by weight of metallocene polyethylene elastomer, 0.8 part by weight of nano zinc oxide, 3 parts by weight of chitosan and 1 part by weight of hydrogen-containing silicone oil, adding the mixture into a double-screw extruder for extrusion granulation, and performing injection molding to obtain the mildew-proof bamboo-plastic composite material; wherein the particle size of the bamboo powder is 80 meshes; the compatilizer is polyethylene grafted maleic anhydride; the lubricant is stearic acid; the antioxidant is a mixture of antioxidant 1076, antioxidant DLTP and antioxidant 168, and the weight ratio of the antioxidant 1076, the antioxidant DLTP and the antioxidant 168 is 1: 1: 2; in the extrusion granulation process, the temperature of the double-screw extruder is 230 ℃, and the screw rotating speed is 100 r/min.
Example 3
A preparation method of a mildew-proof bamboo-plastic composite material comprises the following steps:
s1, mixing methacrylic acid, 3-allyl-5, 5-dimethylhydantoin and water uniformly, dripping the mixture into a mixture consisting of dodecafluoroheptyl methacrylate, liquid paraffin and span 80, introducing nitrogen, and adding azobisisobutyronitrile, wherein the weight ratio of the methacrylic acid to the 3-allyl-5, 5-dimethylhydantoin to the dodecafluoroheptyl methacrylate to the azobisisobutyronitrile is 2: 0.5: 0.5: 0.15, reacting for 4 hours at 68 ℃, and obtaining a material A after the reaction is finished and post-treatment;
s2, mixing 1, 3-bis (4-aniline) adamantane, ferric nitrate and ethanol, stirring at 50 ℃ for 60min, and adding bamboo charcoal, wherein the weight ratio of the 1, 3-bis (4-aniline) adamantane to the ferric nitrate to the bamboo charcoal is 23: 2: 30, stirring for 180min at 68 ℃, then transferring into a high-pressure kettle for reaction for 3h, wherein the reaction temperature in the high-pressure kettle is 110 ℃, the pressure is 1.3MPa, and evaporating and drying to obtain a material B;
s3, uniformly mixing the material A with DMF (dimethyl formamide), adding EDC under the condition of ice-water bath, and adding the material B after ultrasonic treatment, wherein the weight ratio of the material A to the material B is 1: stirring for 17 hours at 45 ℃, centrifuging, washing and drying to obtain an intermediate material, and adding the intermediate material into a sodium hypochlorite solution, wherein the weight ratio of the intermediate material to sodium hypochlorite in the sodium hypochlorite solution is 1: 50, stirring for 4 hours at room temperature, filtering, washing and drying to obtain modified bamboo charcoal;
s4, mixing 48 parts by weight of polypropylene, 50 parts by weight of bamboo powder with the particle size of 40 meshes, 2 parts by weight of polypropylene grafted maleic anhydride, 1 part by weight of polypropylene grafted glycidyl methacrylate, 1.5 parts by weight of polyethylene wax, 10760.03 parts by weight of antioxidant, 0.03 part by weight of antioxidant DLTP, 1680.15 parts by weight of antioxidant, 4 parts by weight of modified bamboo charcoal, 3.5 parts by weight of calcium carbonate, 2 parts by weight of talcum powder, 4 parts by weight of metallocene polyethylene elastomer, 0.5 part by weight of nano zinc oxide, 2 parts by weight of chitosan and 0.5 part by weight of hydrogen-containing silicone oil uniformly, adding the mixture into a double-screw extruder, extruding and granulating, wherein the temperature of the double-screw extruder is 245 ℃, the rotating speed of a screw is 85r/min, and performing injection molding.
Example 4
A preparation method of a mildew-proof bamboo-plastic composite material comprises the following steps:
s1, mixing methacrylic acid, 3-allyl-5, 5-dimethylhydantoin and water uniformly, dripping the mixture into a mixture consisting of dodecafluoroheptyl methacrylate, liquid paraffin and span 80, introducing nitrogen, and adding azobisisobutyronitrile, wherein the weight ratio of the methacrylic acid to the 3-allyl-5, 5-dimethylhydantoin to the dodecafluoroheptyl methacrylate to the azobisisobutyronitrile is 3: 0.4: 1: 0.17, reacting for 4.5h at 70 ℃, and performing post-treatment after the reaction to obtain a material A;
s2, mixing 1, 3-bis (4-aniline) adamantane, ferric nitrate and ethanol, stirring for 90min at 37 ℃, and adding bamboo charcoal, wherein the weight ratio of the 1, 3-bis (4-aniline) adamantane to the ferric nitrate to the bamboo charcoal is 17: 5: 20, stirring for 160min at 68 ℃, then transferring into a high-pressure kettle for reaction for 3.5h, wherein the reaction temperature in the high-pressure kettle is 105 ℃, the pressure is 1.2MPa, and evaporating and drying to obtain a material B;
s3, uniformly mixing the material A with DMF (dimethyl formamide), adding EDC under the condition of ice-water bath, and adding the material B after ultrasonic treatment, wherein the weight ratio of the material A to the material B is 1: 8, stirring for 17h at 48 ℃, centrifuging, washing and drying to obtain an intermediate material, and adding the intermediate material into a sodium hypochlorite solution, wherein the weight ratio of sodium hypochlorite in the intermediate material and the sodium hypochlorite solution is 1: 35, stirring for 3.8 hours at room temperature, filtering, washing and drying to obtain modified bamboo charcoal;
s4, mixing 48 parts by weight of polypropylene, 52 parts by weight of bamboo powder with the particle size of 60 meshes, 3 parts by weight of polypropylene grafted glycidyl methacrylate, 0.5 part by weight of stearic acid, 1.5 parts by weight of ethylene bis stearamide, 10760.04 parts by weight of antioxidant, 0.04 part by weight of antioxidant DLTP, 1680.12 parts by weight of antioxidant, 11 parts by weight of modified bamboo charcoal, 4.3 parts by weight of calcium carbonate, 3.6 parts by weight of talcum powder, 3.7 parts by weight of metallocene polyethylene elastomer, 0.9 part by weight of nano zinc oxide, 2.6 parts by weight of chitosan and 1 part by weight of hydrogen-containing silicone oil uniformly, adding the mixture into a double-screw extruder for extrusion and granulation, wherein in the extrusion and granulation processes, the temperature of the double-screw extruder is 240 ℃, the rotating speed of a screw is 90r/min, and performing injection molding.
Example 5
A preparation method of a mildew-proof bamboo-plastic composite material comprises the following steps:
s1, uniformly mixing 3g of methacrylic acid, 0.4g of 3-allyl-5, 5-dimethylhydantoin and 50ml of water, dropwise adding the mixture into a mixture consisting of 1g of dodecafluoroheptyl methacrylate, 60ml of liquid paraffin and 3ml of span 80, stirring the system in the dropwise adding process, introducing nitrogen for 30min, adding 0.15g of azobisisobutyronitrile, reacting for 4h at 70 ℃, adding acetone after the reaction is finished, standing for layering, taking the lower layer of liquid for rotary evaporation, adding the lower layer of liquid into DMF after washing with acetone, centrifuging and drying to obtain a material A;
s2, mixing 19g of 1, 3-bis (4-aniline) adamantane, 6g of ferric nitrate and 100ml of ethanol, stirring for 120min at 36 ℃, adding 22g of bamboo charcoal, stirring for 150min at 66 ℃, transferring into an autoclave to react for 4.5h, wherein the reaction temperature in the autoclave is 105 ℃, the pressure is 1.3MPa, evaporating the ethanol at 80 ℃, and drying in an oven at 100 ℃ to obtain a material B;
s3, uniformly mixing 1g of the material A with 500ml of DMF (dimethyl formamide), adding 0.3g of EDC under the condition of ice-water bath, carrying out ultrasonic treatment for 30min, adding 7g of the material B, stirring for 17h at 48 ℃, centrifuging, washing with water and ethanol in sequence, carrying out freeze drying to obtain an intermediate material, adding 1g of the intermediate material into a sodium hypochlorite solution containing 45g of sodium hypochlorite, stirring for 4h at room temperature, filtering, washing a filter cake with water, and carrying out freeze drying to obtain modified bamboo charcoal;
s4, mixing 52kg of polypropylene, 58kg of bamboo powder with the particle size of 60 meshes, 2.7kg of polyethylene grafted maleic anhydride, 1kg of stearic acid, 1kg of polyethylene wax, 10760.05 kg of antioxidant, 0.05kg of antioxidant DLTP, 1680.175 kg of antioxidant, 12kg of modified bamboo charcoal, 3.7kg of calcium carbonate, 4.1kg of talcum powder, 2.9kg of metallocene polyethylene elastomer, 0.9kg of nano zinc oxide, 2.3kg of chitosan and 1.2kg of hydrogen-containing silicone oil uniformly, adding the mixture into a double-screw extruder, extruding and granulating, wherein in the extruding and granulating process, the temperature of the double-screw extruder is 235 ℃, the rotating speed of a screw is 90r/min, and obtaining the mildew-proof bamboo-plastic composite material after injection molding.
Comparative example 1
A preparation method of a bamboo-plastic composite material comprises the following steps: 52kg of polypropylene, 58kg of bamboo powder with the particle size of 60 meshes, 2.7kg of polyethylene grafted maleic anhydride, 1kg of stearic acid, 1kg of polyethylene wax, 10760.05 kg of antioxidant, 0.05kg of antioxidant DLTP, 1680.175 kg of antioxidant, 12kg of bamboo charcoal, 3.7kg of calcium carbonate, 4.1kg of talcum powder, 2.9kg of metallocene polyethylene elastomer, 0.9kg of nano zinc oxide, 2.3kg of chitosan and 1.2kg of hydrogen-containing silicone oil are uniformly mixed, and then the mixture is added into a double-screw extruder to be extruded and granulated, wherein in the extrusion and granulation process, the temperature of the double-screw extruder is 235 ℃, the rotating speed of a screw is 90r/min, and injection molding is carried out.
Comparative example 2
The only difference from example 5 is that: in S4, nano zinc oxide 0.9kg was not contained.
Comparative example 3
The only difference from example 5 is that: in S4, 2.3kg of chitosan was not contained.
Comparative example 4
The only difference from example 5 is that: in S4, 0.9kg of nano zinc oxide and 2.3kg of chitosan are not contained.
The properties of the composite materials prepared in examples 4 to 5 of the present invention and comparative examples 1 to 4 were measured, wherein the evaluation criteria of the mold resistance rating were ASTM G21-09: level 0-no mildew, level 1-mildew area less than 10%, level 2-mildew growth coverage of 10-30%, level 3-mildew growth coverage of 30-60%, level 4-mildew growth coverage of more than 60%; the water absorption is tested according to GB/T1034-2008 'determination of Plastic Water absorption'; the results are shown in the following table:
| detecting items | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Mildew resistance rating | 0 | 0 | 2 | 1 | 1 | 1 |
| Water absorption/%) | 0.64 | 0.58 | 1.39 | 0.86 | 0.77 | 0.95 |
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. The preparation method of the mildew-proof bamboo-plastic composite material is characterized by comprising the following steps of:
s1, uniformly mixing methacrylic acid, 3-allyl-5, 5-dimethylhydantoin and water, dropwise adding the mixture into a mixture consisting of dodecafluoroheptyl methacrylate, liquid paraffin and span 80, introducing nitrogen, adding azobisisobutyronitrile, reacting for 3-5 hours at 65-75 ℃, and performing post-treatment after the reaction is finished to obtain a material A;
s2, mixing 1, 3-bis (4-aniline) adamantane, ferric nitrate and ethanol, stirring for 60-120min at 35-50 ℃, adding bamboo charcoal, stirring for 200min at 65-70 ℃, then transferring into an autoclave for reaction for 2-5h, wherein the reaction temperature in the autoclave is 100-120 ℃, the pressure is 1-1.45MPa, and evaporating and drying to obtain a material B;
s3, uniformly mixing the material A and DMF, adding EDC under the condition of ice water bath, adding the material B after ultrasonic treatment, stirring for 15-20h at 40-55 ℃, centrifuging, washing and drying to obtain an intermediate material, adding the intermediate material into a sodium hypochlorite solution, stirring for 3-5h at room temperature, filtering, washing and drying to obtain modified bamboo charcoal;
s4, mixing 40-55 parts of polypropylene, 50-60 parts of bamboo powder, 2-4.3 parts of a compatilizer, 1.5-2.5 parts of a lubricant, 0.16-0.28 part of an antioxidant, 4-15 parts of modified bamboo charcoal, 2-5 parts of calcium carbonate, 2-5 parts of talcum powder, 1-5 parts of metallocene polyethylene elastomer, 0.5-1.2 parts of nano zinc oxide, 1-3 parts of chitosan and 0.5-1.5 parts of hydrogen-containing silicone oil uniformly, adding the mixture into a double-screw extruder, extruding and granulating, and performing injection molding to obtain the mildew-proof bamboo-plastic composite material.
2. The method for preparing the mildewproof bamboo-plastic composite material according to claim 1, wherein in S1, the weight ratio of the methacrylic acid to the 3-allyl-5, 5-dimethylhydantoin to the dodecafluoroheptyl methacrylate to the azobisisobutyronitrile is 2-3.7: 0.3-0.5: 0.5-1.5: 0.08-0.17.
3. The preparation method of the mildewproof bamboo-plastic composite material according to claim 1, wherein in S2, the weight ratio of 1, 3-bis (4-phenylamine) adamantane, ferric nitrate and bamboo charcoal is 12-23: 2-8: 18-30.
4. The preparation method of the mildewproof bamboo-plastic composite material according to claim 1, wherein in S3, the weight ratio of the material A to the material B is 1: 6-10; the weight ratio of the intermediate material to the sodium hypochlorite is 1: 20-50.
5. The method for preparing the mildewproof bamboo-plastic composite material according to claim 1, wherein in S4, the grain size of the bamboo powder is 40-80 meshes.
6. The method for preparing the mildewproof bamboo-plastic composite material according to claim 1, wherein in S4, the compatilizer is one or a mixture of polyethylene grafted maleic anhydride, polypropylene grafted maleic anhydride and polypropylene grafted glycidyl methacrylate.
7. The method for preparing the mildewproof bamboo-plastic composite material according to claim 1, wherein in S4, the lubricant is one or a mixture of stearic acid, polyethylene wax and ethylene bis stearamide.
8. The preparation method of the mildewproof bamboo-plastic composite material according to claim 1, wherein in S4, the antioxidant is a mixture of an antioxidant 1076, an antioxidant DLTP and an antioxidant 168, and the weight ratio of the antioxidant 1076, the antioxidant DLTP and the antioxidant 168 is 1: 1: 2-5.
9. The method for preparing the mildewproof bamboo-plastic composite material according to any one of claims 1 to 8, wherein in the S4, the temperature of a double-screw extruder is 230-245 ℃ and the screw rotating speed is 85-100r/min in the extrusion granulation process.
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