CN116102819A - Antibacterial bamboo fiber reinforced polypropylene composite material and preparation method thereof - Google Patents
Antibacterial bamboo fiber reinforced polypropylene composite material and preparation method thereof Download PDFInfo
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- CN116102819A CN116102819A CN202211597015.1A CN202211597015A CN116102819A CN 116102819 A CN116102819 A CN 116102819A CN 202211597015 A CN202211597015 A CN 202211597015A CN 116102819 A CN116102819 A CN 116102819A
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- bamboo fiber
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- reinforced polypropylene
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- 235000017166 Bambusa arundinacea Nutrition 0.000 title claims abstract description 144
- 235000017491 Bambusa tulda Nutrition 0.000 title claims abstract description 144
- 241001330002 Bambuseae Species 0.000 title claims abstract description 144
- 235000015334 Phyllostachys viridis Nutrition 0.000 title claims abstract description 144
- 239000011425 bamboo Substances 0.000 title claims abstract description 144
- 239000000835 fiber Substances 0.000 title claims abstract description 142
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 52
- -1 polypropylene Polymers 0.000 title claims abstract description 49
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003513 alkali Substances 0.000 claims abstract description 11
- 230000003647 oxidation Effects 0.000 claims abstract description 11
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 32
- 239000003963 antioxidant agent Substances 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 12
- 238000009960 carding Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- ZXOATMQSUNJNNG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OCC2OC2)=CC=1C(=O)OCC1CO1 ZXOATMQSUNJNNG-UHFFFAOYSA-N 0.000 claims description 2
- KIKYOFDZBWIHTF-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-3-ene-1,2-dicarboxylate Chemical compound C1CC=CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KIKYOFDZBWIHTF-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 150000007970 thio esters Chemical class 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims 4
- 230000000845 anti-microbial effect Effects 0.000 claims 2
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000002262 Schiff base Substances 0.000 abstract description 3
- 150000004753 Schiff bases Chemical class 0.000 abstract description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000003746 surface roughness Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 9
- 238000011056 performance test Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 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 description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003733 fiber-reinforced composite Substances 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 241000228245 Aspergillus niger Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002494 Zein Polymers 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000008149 soap solution Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000005019 zein Substances 0.000 description 1
- 229940093612 zein Drugs 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/61—Polyamines polyimines
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2497/00—Characterised by the use of lignin-containing materials
- C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
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Abstract
The invention discloses an antibacterial bamboo fiber reinforced polypropylene composite material and a preparation method thereof, which belong to the field of polypropylene composite materials and are prepared from the following raw materials in parts by weight: 65-85 parts of polypropylene, 10-30 parts of modified bamboo fiber, 3-6 parts of compatilizer and 1-3 parts of auxiliary agent; wherein, the modified bamboo fiber is obtained by grafting PHMG antibacterial agent after alkali treatment and oxidation treatment of the bamboo fiber; compared with the prior art, the bamboo fiber reinforced polypropylene is adopted, and firstly, the bamboo fiber is subjected to alkali treatment and oxidation treatment, so that on one hand, the surface roughness of the fiber is increased, the mechanical locking between the fiber and a polymer matrix is improved, the hydroxyl on the surface of the fiber is promoted to be converted into carbonyl, the hydrophilicity of the bamboo fiber is greatly reduced, and the interface bonding between the bamboo fiber and the polypropylene matrix is facilitated; on the other hand, the treated bamboo fiber can graft PHMG with high-efficiency and durable antibacterial effect on the surface of the bamboo fiber through Schiff base reaction.
Description
Technical Field
The invention relates to the field of polypropylene composite materials, in particular to an antibacterial bamboo fiber reinforced polypropylene composite material and a preparation method thereof.
Background
In recent years, with the prominence of environmental protection and the increasing demand of ecological environment materials, the replacement of traditional synthetic fibers with renewable natural fibers rich in resources in composite materials has become an important direction of composite material research and development. Renewable natural fibers are classified into powder fibers, chopped fibers and long fibers by morphology. Of these, only chopped fibers and long fibers having a certain length have a remarkable reinforcing effect on the polymer resin. Under the condition of the same fineness, the longer the fiber length of the composite material is, the larger the length-diameter ratio of the composite material is, and the reinforcing effect of the natural fiber is more favorably exerted. Long fiber reinforced composites are an important trend in the future for the development of natural fiber composites. The bamboo resources in China are rich, and the bamboo fibers are high-performance natural fibers, so that bamboo fiber bundles with enough length are extracted in a certain mode, the bamboo fiber bundles are developed to serve as reinforcing materials to replace traditional synthetic fibers, and the bamboo fiber bundles are applied to multi-form composite materials and have positive significance in promoting the development of natural fiber composite materials and improving the industrial value of the bamboo materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an antibacterial bamboo fiber reinforced polypropylene composite material and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
an antibacterial bamboo fiber reinforced polypropylene composite material is prepared from the following raw materials in parts by weight: 65-85 parts of polypropylene, 10-30 parts of modified bamboo fiber, 3-6 parts of compatilizer and 1-3 parts of auxiliary agent;
wherein the modified bamboo fiber is obtained by grafting PHMG antibacterial agent after alkali treatment and oxidation treatment of the bamboo fiber.
Further, the preparation of the modified bamboo fiber comprises the following steps:
adding bamboo fibers into sodium hydroxide solution for dipping treatment; taking out and then adding the mixture into a potassium permanganate solution for dipping treatment; taking out, and then adding the mixture into an aqueous solution of PHMG for reaction; washing and drying the bamboo fiber after taking out to obtain modified bamboo fiber;
in the preparation of the modified bamboo fiber, firstly, alkali treatment is carried out on the bamboo fiber by adopting sodium hydroxide solution so as to remove hemicellulose, lignin, colloid, grease covering and other impurities on the surface of the bamboo fiber; then the potassium permanganate solution is adopted for oxidation treatment, and hydroxyl groups on the surface of the bamboo fiber are oxidized and converted into carbonyl groups, so that not only is the hydrophobicity of the bamboo fiber improved, but also a reaction group is provided for subsequent grafting; the oxidized bamboo fiber and PHMG react with Schiff base, so that the PHMG is grafted on the bamboo fiber, and the bamboo fiber has long-acting antibacterial effect.
Further, the temperature of the dipping treatment of the sodium hydroxide solution is 50-60 ℃, the dipping time is 15-30h, and the weight percentage concentration of the sodium hydroxide solution is 5-15%.
Further, the temperature of the potassium permanganate dipping treatment is 20-25 ℃, the dipping time is 1-5min, and the weight percentage concentration of the potassium permanganate solution is 0.01-0.1%.
Further, the concentration of the aqueous solution of PHMG is 0.1-0.5g/ml, and the reaction temperature of the bamboo fiber in the aqueous solution of PHMG is 20-25 ℃.
Further, the compatilizer is any one of PP-g-MAH, POE-g-MAH and SBS-g-MAH; the auxiliary agent comprises at least one of an antioxidant, an epoxy resin, a lubricant and a weather resistant agent; the antioxidant comprises at least two of amine antioxidants, hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants; the epoxy resin is liquid glycidyl ester epoxy resin; the lubricant is at least one of calcium stearate, ethylene bis-stearamide and stearate derivatives; the weather resistant agent is hindered amine weather resistant agent.
Further, the polypropylene is high impact copolymer polypropylene; the bamboo fiber is degummed bamboo fiber.
Further, the epoxy resin is diglycidyl isophthalate or diglycidyl tetrahydrophthalate.
Further, the preparation of the bamboo fiber comprises the following steps:
pretreatment: steaming and softening bamboo chips in an alkali solution, taking out, neutralizing with an acid solution to remove residual alkali on the surface, washing with deionized water for several times until the bamboo chips are neutral, then placing the bamboo chips in an ultrasonic cleaning machine for ultrasonic treatment, taking out the bamboo chips after the ultrasonic treatment, and draining at normal temperature;
wherein the alkali solution is sodium hydroxide, sodium carbonate, sodium silicate or soap solution, the concentration is 1% -10%, the cooking temperature is 60-100deg.C, and the cooking time is 3-5min;
the acid solution is nitric acid, hydrofluoric acid, hydrochloric acid or sulfuric acid solution, the concentration is 1% -10%, and the treatment time is 0.5-2min;
the ultrasonic treatment conditions are as follows: the ultrasonic power is 200W, the ultrasonic frequency is 50KHz, the ultrasonic time is 20-60min, and the ultrasonic temperature is 60-90 ℃.
And (3) rolling: rolling the pretreated bamboo chips in a roll squeezer for 3-4 times, and rolling the bamboo chips into a net shape or a coarse bundle shape;
one carding, namely fastening one end of the rolled bamboo chip, carding for several times along the axial direction of the bamboo chip by using a steel comb, fastening the other end of the rolled bamboo chip, carding for several times along the axial direction of the bamboo chip in the same way, and obtaining a neat filiform long bamboo fiber bundle, wherein no obvious hard strip and drawing phenomenon are observed by naked eyes;
and (3) secondary carding, namely after primary carding, carrying out secondary carding on the long bamboo fiber bundles by using a soft dense comb, wherein the carding mode is the same as that of a steel comb, and the secondary carding is carried out to remove the forked fibers, the secondary short fibers, the residual parts on the surfaces of the bamboo fibers and the like, so that the separated bamboo fibers are further thinned and homogenized.
The long bamboo fibers are sewn to form bamboo fiber mats, and the bamboo fiber mats are placed in a zein solution for modification and are reserved for standby;
preparing a polypropylene film, laminating the polypropylene film and a long bamboo fiber mat to form a blank, and performing hot press molding by a hot press to obtain the composite material.
The invention also discloses a preparation method of the antibacterial bamboo fiber reinforced polypropylene composite material, which comprises the following steps:
weighing the raw materials according to a proportion, mixing polypropylene, a compatilizer and an auxiliary agent, and adding the mixture into a main feeding hopper of a double-screw extruder; adding the modified bamboo fibers into a side feeding hopper of a double-screw extruder; melting, extruding and drying to obtain the antibacterial bamboo fiber reinforced polypropylene composite material;
wherein the extrusion temperature of the double-screw extruder is 150-200 ℃, and the screw combination of the double-screw extruder is weak shearing and strong dispersion.
The invention has the beneficial effects that:
according to the invention, the bamboo fiber reinforced polypropylene is adopted, and firstly, the bamboo fiber is subjected to alkali treatment and oxidation treatment, so that on one hand, the surface roughness of the fiber is increased, the mechanical locking between the fiber and a polymer matrix is improved, the hydroxyl on the surface of the fiber is promoted to be converted into carbonyl, the hydrophilicity of the bamboo fiber is greatly reduced, and the interface bonding between the bamboo fiber and the polypropylene matrix is facilitated; on the other hand, the treated bamboo fiber can be grafted on the surface of the bamboo fiber through Schiff base reaction, the PHMG is a common cationic bactericide, has good water solubility, is colorless and odorless, has the effects of killing various microorganisms in a high-efficiency broad spectrum, and can not achieve ideal antibacterial effect when being directly added into the material, and the grafted bamboo fiber has long-acting antibacterial effect. In the extrusion process, the combination of the weak shearing and strong dispersing screws is adopted, and the modified bamboo fibers are added from a side feeding hopper of a double-screw extruder, so that the length of the bamboo fibers is reserved as much as possible, and the excellent mechanical property of the composite material is ensured; the prepared composite material has excellent mechanical property and high-efficiency antibacterial property.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
Preparing modified bamboo fibers: adding bamboo fibers into 10% sodium hydroxide solution, wherein the feed liquid ratio g/mL is 1:10, soaking for 24 hours at 50 ℃, and then transferring to a potassium permanganate solution with the concentration of 0.04% for oxidation treatment, wherein the feed liquid ratio g/mL is 1:10, treating for 2min at room temperature, and then adding the oxidized bamboo fiber into 0.1g/mL PHMG water solution, wherein the feed liquid ratio g/mL is 1:10, fully stirring, reacting for 6 hours at normal temperature, cleaning, and finally obtaining the PHMG grafted and modified bamboo fiber, and fully drying in an oven for later use.
The preparation of the antibacterial bamboo fiber reinforced polypropylene composite material is as follows: weighing 75 parts of PP with the model number of K9017H, 4 parts of compatilizer CA100, 0.5 part of antioxidant (antioxidant 1010:0.2 part, antioxidant 168:0.3 part), 0.5 part of PE wax and 1 part of HALS944 according to the weight, adding the mixture into a medium-low speed mixer, mixing for 4min, and then adding the mixture into a main feeding hopper; adding 20 parts of the prepared modified bamboo fibers into a side feeding hopper of a double-screw extruder; melt extrusion, extrusion temperature is zone 1: 120 ℃,2-5 regions: 200 ℃,6-9 regions: 150 ℃, the machine head: 180 ℃; host rotational speed: 400RPM, selecting a screw combination as weak shearing and strong dispersion; and extruding according to the set technological parameters to obtain the final product. And (5) placing the prepared product into a constant temperature oven, drying the water, and sampling for performance test.
Example 2
The modified bamboo fiber was prepared as in example 1.
The antibacterial bamboo fiber reinforced polypropylene composite material was prepared, differing from example 1 only in that the addition amount of the modified bamboo fiber was 10 parts.
Example 3
The modified bamboo fiber was prepared as in example 1.
The antibacterial bamboo fiber reinforced polypropylene composite material was prepared, differing from example 1 only in that the addition amount of the modified bamboo fiber was 30 parts.
Example 4
Preparing modified bamboo fibers: adding bamboo fibers into 5% sodium hydroxide solution, wherein the feed liquid ratio g/mL is 1:10, immersing for 30h at 60 ℃, then transferring to a potassium permanganate solution with the concentration of 0.01% for oxidation treatment, wherein the feed liquid ratio g/mL is 1:10, treating for 5min at room temperature, and then adding the oxidized bamboo fiber into a PHMG aqueous solution with the ratio g/mL of 0.3g/mL, wherein the ratio g/mL of the feed liquid is 1:10, fully stirring, reacting for 6 hours at normal temperature, cleaning, and finally obtaining the PHMG grafted and modified bamboo fiber, and fully drying in an oven for later use.
The preparation of the antibacterial bamboo fiber reinforced polypropylene composite material is as follows: weighing 85 parts of PP with the model number of K9017H, 3 parts of compatilizer CA100, 0.5 part of antioxidant (antioxidant 1010:0.2 part, antioxidant 168:0.3 part), 0.5 part of PE wax and 1 part of HALS944 according to weight, adding the mixture into a medium-low speed mixer, mixing for 4min, and then adding the mixture into a main feeding hopper; adding 10 parts of the prepared modified bamboo fibers into a side feeding hopper of a double-screw extruder; extrusion temperature was zone 1: 120 ℃,2-5 regions: 200 ℃,6-9 regions: 150 ℃, the machine head: 180 ℃; host rotational speed: 400RPM, selecting a screw combination as weak shearing and strong dispersion; and extruding according to the set technological parameters to obtain the final product. And (5) placing the prepared product into a constant temperature oven, drying the water, and sampling for performance test.
Example 5
Preparing modified bamboo fibers: adding bamboo fibers into 15% sodium hydroxide solution, wherein the feed liquid ratio g/mL is 1:10, immersing for 15h at 50 ℃, then transferring to a potassium permanganate solution with the concentration of 0.1% for oxidation treatment, wherein the feed liquid ratio g/mL is 1:10, treating for 1min at room temperature, and then adding the oxidized bamboo fiber into a PHMG aqueous solution with the concentration of 0.5g/mL, wherein the feed liquid ratio g/mL is 1:10, fully stirring, reacting for 8 hours at normal temperature, cleaning to finally obtain the PHMG grafted and modified bamboo fiber, and fully drying in an oven for later use.
The preparation of the antibacterial bamboo fiber reinforced polypropylene composite material is as follows: 65 parts of PP with the model number of K9017H, 6 parts of compatilizer CA100, 0.5 part of antioxidant (antioxidant 1010:0.2 part, antioxidant 168:0.3 part), 0.5 part of PE wax and 1 part of HALS944 are weighed according to the weight, added into a medium-low speed mixer for mixing for 4min, and then added into a main feeding hopper; adding 30 parts of modified bamboo fibers into a side feeding hopper of a double-screw extruder; extrusion temperature was zone 1: 120 ℃,2-5 regions: 200 ℃,6-9 regions: 150 ℃, the machine head: 180 ℃; host rotational speed: 400RPM, selecting a screw combination as weak shearing and strong dispersion; and extruding according to the set technological parameters to obtain the final product. And (5) placing the prepared product into a constant temperature oven, drying the water, and sampling for performance test.
Comparative example 1
The modified bamboo fiber treatment process comprises the following steps: adding bamboo fibers into 10% sodium hydroxide solution, wherein the feed liquid ratio g/mL is 1:10, soaking for 24 hours at 50 ℃, and then transferring to a potassium permanganate solution with the concentration of 0.04% for oxidation treatment, wherein the feed liquid ratio g/mL is 1:10, treating for 2min at room temperature, cleaning, and fully drying in an oven for standby.
The preparation of the bamboo fiber reinforced polypropylene composite material is as follows: weighing 75 parts of PP with the model number of K9017H, 4 parts of compatilizer CA100, 0.5 part of antioxidant (antioxidant 1010:0.2 part, antioxidant 168:0.3 part), 0.5 part of PE wax and 1 part of HALS944 according to the weight, adding the mixture into a medium-low speed mixer, mixing for 4min, and then adding the mixture into a main feeding hopper; adding 20 parts of modified bamboo fibers into a side feeding hopper of a double-screw extruder; melt extrusion, extrusion temperature is zone 1: 120 ℃,2-5 regions: 200 ℃,6-9 regions: 150 ℃, the machine head: 180 ℃; host rotational speed: 400RPM, selecting a screw combination as weak shearing and strong dispersion; and extruding according to the set technological parameters to obtain the final product. And (5) placing the prepared product into a constant temperature oven, drying the water, and sampling for performance test.
Comparative example 2
The modified bamboo fiber treatment process comprises the following steps: adding bamboo fibers into 10% sodium hydroxide solution, wherein the feed liquid ratio g/mL is 1:10, soaking for 24 hours at 50 ℃, and then transferring to a potassium permanganate solution with the concentration of 0.04% for oxidation treatment, wherein the feed liquid ratio g/mL is 1:10, treating for 2min at room temperature, cleaning, and fully drying in an oven for standby.
The preparation of the bamboo fiber reinforced polypropylene composite material is as follows: the preparation of the antibacterial bamboo fiber reinforced polypropylene composite material is as follows: weighing 75 parts of PP with the model number of K9017H, 4 parts of compatilizer CA100, 0.5 part of antioxidant (antioxidant 1010:0.2 part, antioxidant 168:0.3 part), 0.5 part of PE wax and 1 part of HALS944 according to the weight, adding the mixture into a medium-low speed mixer, mixing for 4min, and then adding the mixture into a main feeding hopper; adding 20 parts of modified bamboo fibers and 2 parts of PHMG into a side feeding hopper of a double-screw extruder; melt extrusion, extrusion temperature is zone 1: 120 ℃,2-5 regions: 200 ℃,6-9 regions: 150 ℃, the machine head: 180 ℃; host rotational speed: 400RPM, selecting a screw combination as weak shearing and strong dispersion; and extruding according to the set technological parameters to obtain the final product. And (5) placing the prepared product into a constant temperature oven, drying the water, and sampling for performance test.
The products prepared in the above examples and comparative examples were subjected to performance tests, and the test standards and conditions were as follows:
(1) Density testing: according to method A (immersion method) in GB/T1033.1, the test conditions are: absolute ethyl alcohol, detecting environment temperature and humidity: 23 ℃/50% rh, number of samples tested: 3pcs, test instrument: a densitometer.
(2) Tensile strength test: test according to GB/T1040.2 rule method, test speed: 5mm/min, sample number was measured using dumbbell type 1A test bars: 5pcs, test instrument: a universal testing machine.
(3) Bending strength test: test according to GB/T9341 rule method, test speed: 2mm/min, spline size: 80 mm. Times.10 mm. Times.4 mm, number of samples tested: 5pcs, test instrument: a universal testing machine.
(4) Cantilever notched impact test criteria: pendulum energy tested according to GB/T1843 specification method: 2.75J, spline size: 80 mm. Times.10 mm. Times.4 mm, number of samples tested: 10pcs, test instrument: impact testing machine.
(5) Antibacterial test: the test was performed as per astm g 21-96: growing mould is observed after 28 days of culture, and bacteria for detection are used: aspergillus niger; the judgment grade is as follows:
level 0: no growth marks, i.e. no growth marks were observed under a microscope (magnification 50);
stage 1: growth marks, i.e. macroscopic growth, but growth coverage less than 10%;
2 stages: growing in a small amount, wherein the growth coverage area is 10% -30%;
3 stages: medium growth, the growth coverage area is 30% -60%;
4 stages: growing in large quantity, wherein the production coverage area is 60% -100%;
the test results are shown in Table 1.
Table 1 performance test data for polypropylene composites prepared in examples and comparative examples
From the data of examples 1 to 3 in Table 1, it can be seen that as the addition ratio of the modified bamboo fibers is increased, the tensile strength and the bending strength of the composite material are gradually increased, the impact performance is attenuated, the tensile strength of the 30% modified bamboo fiber reinforced polypropylene composite material reaches 30.2MPa, the bending strength reaches 43.5MPa, the impact performance is 6.7MPa, and the comprehensive mechanical property is excellent.
As the antibacterial agent in the composite material is not easy to be added too much, or the mechanical property of the material is affected, the PHMG which is directly added to the system of the comparative example 2 by 2 parts or less is suitable through experimental exploration, and the comprehensive mechanical property and the antibacterial property are good. By comparing the data of examples 1-3 and comparative examples 1-2, it can be seen that the antibacterial properties of the bamboo fiber reinforced composite material grafted with PHMG are significantly improved compared with that of the composite material not grafted with PHMG, and the PHMG is directly added into the system for blending without grafting, so that the antibacterial effect is much poorer, because the PHMG is directly added into the bamboo fiber component which is not uniformly dispersed and does not cover the bamboo fiber component with poorer complete antibacterial properties;
by comparing the examples 1 and 4-5, it can be seen that the product obtained by adjusting the process range in the invention has excellent comprehensive mechanical properties and antibacterial properties.
The antibacterial bamboo fiber reinforced polypropylene material with excellent output mechanical properties is prepared by modifying the bamboo fibers and improving the extrusion process, and the application requirements of materials in the fields of automobiles, packaging, tableware, home decoration and the like are met.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (10)
1. The antibacterial bamboo fiber reinforced polypropylene composite material is characterized by being prepared from the following raw materials in parts by weight: 65-85 parts of polypropylene, 10-30 parts of modified bamboo fiber, 3-6 parts of compatilizer and 1-3 parts of auxiliary agent;
wherein the modified bamboo fiber is obtained by grafting PHMG antibacterial agent after alkali treatment and oxidation treatment.
2. The antibacterial bamboo fiber reinforced polypropylene composite material according to claim 1, wherein the preparation of the modified bamboo fiber comprises the following steps:
adding bamboo fibers into sodium hydroxide solution for dipping treatment; taking out and then adding the mixture into a potassium permanganate solution for dipping treatment; taking out, and then adding the mixture into an aqueous solution of PHMG for reaction; and (5) washing and drying the bamboo fiber after taking out to obtain the modified bamboo fiber.
3. The antibacterial bamboo fiber reinforced polypropylene composite material according to claim 2, wherein the temperature of the sodium hydroxide solution impregnation treatment is 50-60 ℃, the impregnation time is 15-30h, and the concentration of the sodium hydroxide solution is 5-15% by weight.
4. The antibacterial bamboo fiber reinforced polypropylene composite material according to claim 2, wherein the temperature of the potassium permanganate impregnation treatment is 20-25 ℃, the impregnation time is 1-5min, and the weight percentage concentration of the potassium permanganate solution is 0.01-0.1%.
5. The antibacterial bamboo fiber reinforced polypropylene composite according to claim 2, wherein the concentration of the aqueous solution of PHMG is 0.1-0.5g/ml, and the reaction temperature of the bamboo fiber in the aqueous solution of PHMG is 20-25 ℃.
6. The antibacterial bamboo fiber reinforced polypropylene composite material according to claim 1, wherein the compatilizer is any one of PP-g-MAH, POE-g-MAH, SBS-g-MAH; the auxiliary agent comprises at least one of an antioxidant, an epoxy resin, a lubricant and a weather resistant agent; the antioxidant comprises at least two of amine antioxidants, hindered phenol antioxidants, phosphite antioxidants and thioester antioxidants; the epoxy resin is liquid glycidyl ester epoxy resin; the lubricant is at least one of calcium stearate, ethylene bis-stearamide and stearate derivatives; the weather resistant agent is hindered amine weather resistant agent.
7. The antimicrobial bamboo fiber reinforced polypropylene composite of claim 1, wherein the polypropylene is a high impact co-polypropylene; the bamboo fiber is degummed bamboo fiber.
8. The antibacterial bamboo fiber reinforced polypropylene composite according to claim 1, wherein the epoxy resin is diglycidyl isophthalate or diglycidyl tetrahydrophthalate.
9. The antimicrobial bamboo fiber reinforced polypropylene composite of claim 1, wherein the preparation of the bamboo fiber comprises the steps of:
steaming and softening bamboo chips in an alkali solution, taking out, neutralizing with an acid solution to remove residual alkali on the surface, washing with deionized water for several times until the bamboo chips are neutral, then placing the bamboo chips in an ultrasonic cleaning machine for ultrasonic treatment, taking out the bamboo chips after the ultrasonic treatment, and draining at normal temperature; rolling the drained bamboo chips into a net shape or a coarse bundle shape;
fastening one end of the rolled bamboo chip, and carding positively along the axial direction of the bamboo chip by using a steel comb; after forward carding, fastening the other end of the bamboo chip, and carding reversely along the axial direction of the bamboo chip in the same way until the bamboo fibers are separated to obtain a filiform long bamboo fiber bundle; the long bamboo fiber bundles are combed for the second time through the soft dense comb, and the combing mode of the soft dense comb is the same as that of the steel comb.
10. A method for preparing the antibacterial bamboo fiber reinforced polypropylene composite material according to any one of claims 1 to 9, comprising the following steps:
weighing the raw materials according to a proportion, mixing polypropylene, a compatilizer and an auxiliary agent, and adding the mixture into a main feeding hopper of a double-screw extruder; adding the modified bamboo fibers into a side feeding hopper of a double-screw extruder; melting, extruding and drying to obtain the antibacterial bamboo fiber reinforced polypropylene composite material;
wherein the extrusion temperature of the double-screw extruder is 150-200 ℃, and the screw combination of the double-screw extruder is weak shearing and strong dispersion.
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