CN114874539B - Polypropylene composite material easy to clean and preparation method and application thereof - Google Patents
Polypropylene composite material easy to clean and preparation method and application thereof Download PDFInfo
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- CN114874539B CN114874539B CN202210333943.0A CN202210333943A CN114874539B CN 114874539 B CN114874539 B CN 114874539B CN 202210333943 A CN202210333943 A CN 202210333943A CN 114874539 B CN114874539 B CN 114874539B
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- -1 Polypropylene Polymers 0.000 title claims abstract description 86
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 74
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 230000003670 easy-to-clean Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 40
- 239000011737 fluorine Substances 0.000 claims abstract description 40
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 23
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000077 silane Inorganic materials 0.000 claims abstract description 23
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 20
- 229920006222 acrylic ester polymer Polymers 0.000 claims abstract description 10
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 15
- 230000003078 antioxidant effect Effects 0.000 claims description 14
- 239000000314 lubricant Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group 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
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical group COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 25
- 229920005989 resin Polymers 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 18
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 abstract description 16
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 abstract description 16
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 abstract description 16
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 15
- 239000003344 environmental pollutant Substances 0.000 abstract description 13
- 231100000719 pollutant Toxicity 0.000 abstract description 13
- 239000002861 polymer material Substances 0.000 abstract description 2
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000000844 anti-bacterial effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 239000000356 contaminant Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000001877 deodorizing effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 235000015113 tomato pastes and purées Nutrition 0.000 description 1
Classifications
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an easy-to-clean polypropylene composite material, a preparation method and application thereof, and belongs to the technical field of high polymer materials. The easy-to-clean polypropylene composite material comprises the following components in parts by weight: 75-95 parts of polypropylene resin; 2-6 parts of organic silicon-fluorine-containing acrylic ester copolymer; 1-3 parts of rosin resin; 1-3 parts of graphene; 1-2 parts of nano titanium dioxide; 0.5-1 part of processing aid; the organosilicon-fluorine-containing acrylic ester copolymer is obtained by copolymerizing silane, fluorine-containing acrylic acid and acrylic ester polymer; the mass ratio of silane, fluorine-containing acrylic acid and acrylic ester is (5-10): (10-20): (50-70). The easy-to-clean polypropylene composite material disclosed by the invention has very high compactness, can prevent pollutants from entering the inside of the polypropylene composite material, and is easy to wipe the material clean.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an easy-to-clean polypropylene composite material and a preparation method and application thereof.
Background
Polypropylene, PP for short, is a colorless, odorless, nontoxic, semitransparent solid substance. Polypropylene, as a general plastic, has the characteristics of high temperature resistance, corrosion resistance, no toxicity, no smell, easy processing and the like, and is widely applied to the fields of manufacturing lightweight vehicles, including automobile interior and exterior trim parts and the like.
The existing polypropylene composite material has poor antibacterial property and cleaning property, bacteria are easy to grow on the surface, especially after being stained with dirt at high temperature, the stain is easy to diffuse into the polypropylene composite material, and the surface of the polypropylene composite material is difficult to wipe clean.
The prior art discloses an easy-to-clean polypropylene material, which improves the hydrophobic effect of the material by adding three specific polypropylenes, can effectively prevent stains or dirt from being stained on the material, and ensures the cleanliness of the material. However, under the condition of high temperature, after the pollutant is attached on the surface of the material for a long time, the pollutant easily enters the inside of the polypropylene composite material, and the material is difficult to wipe clean.
Disclosure of Invention
The invention aims to overcome the defect and the defect that the existing polypropylene material is difficult to clean after being polluted by pollutants for a long time, and provides the easy-to-clean polypropylene composite material.
The invention also aims at providing a preparation method of the easy-to-clean polypropylene composite material.
Another object of the present invention is to provide an easy-to-clean polypropylene composite for use in the easy-to-clean field.
The above object of the present invention is achieved by the following technical scheme:
the easy-to-clean polypropylene composite material comprises the following components in parts by weight:
the organosilicon-fluorine-containing acrylic ester copolymer is obtained by copolymerizing silane, fluorine-containing acrylic acid and acrylic ester polymer;
the mass ratio of silane, fluorine-containing acrylic acid and acrylic ester is (5-10): (10-20): (50-70).
The following are to be described:
according to the easy-to-clean polypropylene composite material, the obtained easy-to-clean polypropylene composite material has high hydrophobicity, oleophobicity and compactness through the synergistic effect of the components such as the organosilicon-fluorine-containing acrylic ester copolymer rosin resin, the graphene, the nano titanium dioxide and the like, can prevent pollutants from entering the polypropylene composite material, and is easy to wipe the material clean.
The action mechanism of each component of the easy-to-clean polypropylene composite material is as follows:
the organosilicon-fluorine-containing acrylic ester copolymer has the function of improving the hydrophobicity and oleophobicity of the composite material, and as the silicon atoms, methyl and fluorine-containing side chains in the acrylic ester polymer extend outwards to enable the acrylic ester polymer to occupy the interface between the polymer and air, the surface energy of the material is greatly reduced, and the excellent hydrophobicity and oleophobicity are realized, so that pollutants can be prevented from entering the polypropylene composite material, and the easy cleaning property of the polypropylene composite material is realized.
The hydrophobic and oleophobic properties of the composite material can be obviously reduced due to excessive usage of the organosilicon-fluorine-containing acrylic copolymer.
The rosin resin has the effects of improving the surface activity of the composite material, penetrating the surface of the composite material in the processing process, improving the combination of the organosilicon-fluorine-containing acrylic ester copolymer and the matrix in the amorphous area of the polypropylene, and simultaneously improving the combination efficiency of graphene and nano titanium dioxide, so that the antibacterial property of the polypropylene composite material can be improved, and the antibacterial effect of the polypropylene composite material can be realized.
The rosin resin is excessively used, so that the rosin resin can be concentrated on the surface of the material and can cover other components, and therefore, the easy-to-clean performance of the composite material can be obviously reduced.
The graphene has the effects of improving the contact efficiency of the nano titanium dioxide of the composite material, increasing more contact surfaces through the activity of rosin, and facilitating the penetration of the nano titanium dioxide into the deep layer of the graphene material, so that the continuous antibacterial property of the polypropylene composite material is facilitated. Moreover, the graphene can also improve the surface activity of the system and enable other components to achieve better dispersing effect.
The use amount of the graphene is too much, so that the antibacterial performance of the composite material can be obviously reduced.
The nanometer titanium dioxide can generate photocatalysis reaction similar to photosynthesis under the irradiation of light, generates free hydroxyl and active oxygen with extremely strong oxidizing capability, has extremely strong photooxidation-reduction function, can oxidatively decompose various organic compounds and partial inorganic matters, can destroy bacterial membranes and solidify proteins of viruses, can kill bacteria and decompose organic pollutants, and can decompose the organic pollutants into pollution-free water (H 2 O) and carbon dioxide (CO) 2 ) Therefore, the multifunctional sterilizing and deodorizing and mildew-proof air-purifying agent has extremely strong sterilizing, deodorizing, mildew-proof, antifouling and self-cleaning functions.
The nanometer titanium dioxide can utilize oxygen molecules and water molecules in the air to convert the contacted organic matters into substances which are unchanged but can promote chemical reaction, so that the nanometer titanium dioxide has very long theoretical effective period and low maintenance cost.
The addition amount of the nano titanium dioxide is too large, so that the antibacterial property of the material can be improved, but the agglomeration of the nano titanium dioxide can be increased, the easy-cleaning property of the material can be reduced, and meanwhile, the impact resistance of the material can be obviously reduced.
According to the invention, through the synergistic effect of the organosilicon-fluorine-containing acrylic ester, the rosin resin, the graphene and the nano titanium dioxide, the obtained easy-to-clean polypropylene composite material has high hydrophobicity and oleophobicity, can prevent pollutants from entering the interior of the polypropylene composite material, and is easy to wipe the material clean.
Preferably, in order to further improve the easy-cleaning effect of the easy-to-clean polypropylene composite, the mass ratio of silane, fluorine-containing acrylic acid and acrylic ester is preferably (7 to 8): (13-16): (55-65).
Still more preferably, the mass ratio of silane, fluorine-containing acrylic acid and acrylic ester is 8:15:60.
preferably, in order to further enhance the easy cleaning effect of the easy-to-clean polypropylene composite, the acrylate polymer is preferably polymerized from methyl methacrylate and/or butyl methacrylate.
Preferably, in order to further improve the easy-cleaning effect of the easy-cleaning polypropylene composite material, the purity of the graphene is more than or equal to 95%.
Preferably, the processing aid is a lubricant and/or an antioxidant.
Preferably, the lubricant is a stearate type lubricant.
Preferably, the antioxidant is hindered phenol antioxidant and/or phosphite antioxidant
The invention also provides a preparation method of the easy-to-clean polypropylene composite material, which specifically comprises the following steps:
and uniformly mixing the components, performing melt extrusion and granulation at 200-230 ℃ by a double-screw extruder, and drying to obtain the easy-to-clean polypropylene composite material.
The easy-to-clean polypropylene composite material prepared by the method has good easy-to-clean performance, can be widely applied to the preparation of plastic products, and particularly protects the application of the easy-to-clean polypropylene composite material in the easy-to-clean field.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses an easy-to-clean polypropylene composite material, which is prepared by the synergistic effect of components such as polypropylene resin, organosilicon-fluorine-containing acrylic ester copolymer, rosin resin, graphene, nano titanium dioxide and the like, has very high hydrophobicity, oleophobicity and compactness, can prevent pollutants from entering the interior of the polypropylene composite material, and is easy to wipe the material clean.
Drawings
FIG. 1 is a schematic illustration of a contaminant drip point in an easy-to-clean performance.
Fig. 2 is an initial state diagram of a template in the description of the easy-to-clean evaluation level.
Fig. 3 shows that the color change of the sample plate is 1 in the description of the easy-to-clean evaluation level.
Fig. 4 shows that the color change of the sample plate is 2 in the description of the easy-to-clean evaluation level.
Fig. 5 shows that the color change of the sample plate is 3 in the description of the easy-to-clean evaluation level.
Fig. 6 shows that the color change of the sample plate is 4 in the description of the easy-to-clean evaluation level.
Fig. 7 shows that the color change of the sample plate is 5 in the description of the easy-to-clean evaluation level.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
The raw materials used in the invention are as follows:
the polypropylene resin is M2600R, manufacturer: petrochemical Shanghai;
methyl methacrylate, manufacturer: jilin petrochemical industry;
fluorine-containing acrylic acid, manufacturer: shandong Gao Ming;
silane WD-72, manufacturer: star science and technology;
rosin resin is Foral105, manufacturer: pi Nuowa;
the graphene is graphene MG-GO-01, the purity is 95%, and the manufacturer has Shanghai mao fruits;
nanometer titanium dioxide with the brand MZT-A01, and the manufacturer receives new materials very little;
the antioxidants are hindered phenols and phosphites, the weight ratio of hindered phenols to phosphites is 1:1, commercially available and all examples and comparative examples are the same;
lubricants, stearates, are commercially available and are the same for all examples and comparative examples; examples 1 to 5
The easy-to-clean polypropylene composite material comprises the following components in parts by weight:
a polypropylene resin; organosilicon-fluoroacrylate copolymers; rosin resin; a graphene; nano titanium dioxide; an antioxidant; a lubricant;
wherein the organosilicon-fluorine-containing acrylic ester copolymer is obtained by copolymerizing silane, fluorine-containing acrylic acid and acrylic ester polymer;
the mass ratio of silane, fluorine-containing acrylic acid and acrylic ester is 8:15:60.
the preparation method of the organosilicon-fluorine-containing acrylic ester copolymer comprises the following steps:
s1, adding methyl methacrylate and azodiisobutyl cyanide accounting for 1.2% of the total mass of monomers into a xylene solution, heating to 65-80 ℃ and reacting for 1h;
s2, dropwise adding the silane and the xylene solution containing the fluorine-containing methacrylic acid into the S1, after 30 minutes of titration, maintaining the temperature at 65-80 ℃, then reacting for 1h, and cooling to obtain the organosilicon-fluorine-containing acrylic ester copolymer.
Wherein the specific content of each component is shown in the following table 1;
| 1 | 2 | 3 | 4 | 5 | |
| polypropylene resin | 91.3 | 86.5 | 79.3 | 86.3 | 81.3 |
| Organosilicon-fluoroacrylate copolymers | 2 | 3 | 4 | 5 | 6 |
| Rosin resin | 1 | 2 | 3 | 1 | 2 |
| Graphene | 1 | 2 | 3 | 1 | 2 |
| Nanometer titanium dioxide | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Antioxidant | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Calcium stearate | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
The preparation method of the easy-to-clean polypropylene composite material of each example in table 1 is specifically as follows:
s1: the preparation method comprises the steps of (1) putting polypropylene resin, organosilicon-fluorine-containing acrylic ester copolymer, graphene, calcium stearate, nano titanium dioxide and rosin resin into a ball mill for grinding, wherein the ground powder is required to pass through a 200-mesh screen for screening;
s2: grinding into powder, and stirring the powder at a speed of 1200r/min for 30min to obtain a mixture A;
s3: introducing the mixture A into a screw extruder for extrusion molding to obtain the easy-to-clean polypropylene composite material;
wherein the working temperature of the screw extruder is 230 ℃ and the pressure is 25MPa,
the drying mode is air cooling, and the air speed is controlled to be 12m/s.
Example 6
The easy-to-clean polypropylene composite material comprises the following components in parts by weight:
a polypropylene resin; organosilicon-fluoroacrylate copolymers; rosin resin; a graphene; nano titanium dioxide; an antioxidant; a lubricant;
wherein the organosilicon-fluorine-containing acrylic ester copolymer is obtained by copolymerizing silane, fluorine-containing acrylic acid and acrylic ester polymer;
the mass ratio of silane, fluorine-containing acrylic acid and acrylic ester is 5:20:70.
the remainder is the same as in example 1 and will not be described again here.
Example 7
The easy-to-clean polypropylene composite material comprises the following components in parts by weight:
a polypropylene resin; organosilicon-fluoroacrylate copolymers; rosin resin; a graphene; nano titanium dioxide; an antioxidant; a lubricant;
wherein the organosilicon-fluorine-containing acrylic ester copolymer is obtained by copolymerizing silane, fluorine-containing acrylic acid and acrylic ester polymer;
the mass ratio of silane, fluorine-containing acrylic acid and acrylic ester is 10:10:70.
the remainder is the same as in example 1 and will not be described again here.
Comparative examples 1 to 7
The polypropylene composite material comprises the following components in parts by weight, wherein the specific contents of the components are shown in the following table 2.
Table 2 Polypropylene composite compositions (in parts by weight) of the respective comparative examples
The preparation method of the easy-to-clean polypropylene composite material is the same as that of example 1, and is not repeated here.
Comparative example 8
The polypropylene composite material comprises the following components in parts by weight:
a polypropylene resin; organosilicon-fluoroacrylate copolymers; rosin resin; a graphene; nano titanium dioxide; an antioxidant; a lubricant;
wherein the organosilicon-fluorine-containing acrylic ester copolymer is obtained by copolymerizing silane, fluorine-containing acrylic acid and acrylic ester polymer;
the mass ratio of silane, fluorine-containing acrylic acid and acrylic ester is 8:5:70.
the remainder is the same as in example 1 and will not be described again here.
Comparative example 9
The polypropylene composite material comprises the following components in parts by weight:
a polypropylene resin; organosilicon-fluoroacrylate copolymers; rosin resin; a graphene; nano titanium dioxide; an antioxidant; a lubricant;
wherein the organosilicon-fluorine-containing acrylic ester copolymer is obtained by copolymerizing silane, fluorine-containing acrylic acid and acrylic ester polymer;
the mass ratio of silane, fluorine-containing acrylic acid and acrylic ester is 2:11:70.
the remainder is the same as in example 1 and will not be described again here.
Result detection
The polypropylene composites of the above examples and comparative examples were tested by the following performance test methods:
(1) Antibacterial test the antibacterial properties were tested according to the GB/T31402-2015 method.
(2) The easy-to-clean performance was evaluated as follows:
the method comprises the steps of selecting common coffee for liquid pollutants, transferring the coffee to the surface of a test board with the height of 10cm multiplied by 10cm from the surface of the test board by using a dropper, wherein 2 drops are respectively dropped at each of 3 positions including the position 1, the position 2 and the position 3 as shown in figure 1, two templates are required to be tested, one of the templates is placed in a baking oven at 70 ℃ for 24 hours, then the sample is taken out and cooled to room temperature, and then the cleaning easiness is evaluated, and the other sample is placed at the room temperature for 24 hours.
Tomato paste is selected as the pasty pollutant, and 0.1g of the paste is uniformly smeared on the positions 1, 2 and 3 shown in the upper graph by using a plastic spoon, wherein the diameter of each position is about 1cm. Two templates were treated, one of which was kept in an oven at 70℃for 24 hours, taken out and cooled to room temperature, and then the cleanability was evaluated, and the other was left at room temperature for 24 hours.
The cleaning method comprises the following steps: dry and water wipes.
Spot on test panels, respectively:
wiping the cloth with clean fine cotton cloth back and forth for X times with moderate force (grade record is A-X), wherein X is less than or equal to 10;
wiping the cloth with clean fine cotton cloth in water for X times with moderate force (grade record is B-X), wherein X is less than or equal to 10;
and after the sample is treated in a corresponding cleaning mode, comparing the uncontaminated positions (No. 4 positions) of the test sample, and evaluating the pollutant erasure and sample color change conditions of each position of the sample.
Stage 1: the contaminants tested were hardly removed;
2 stages: the contaminants tested were removed by small amounts, most of the contaminants still present;
3 stages: the tested pollutants are removed by more than 50%, and the pollution part is moderately discolored;
4 stages: most of the pollutants tested are cleaned, and the pollution part is slightly discolored;
5 stages: the contaminants tested were completely removed.
If the level reaches 5, the subsequent cleaning is not needed and the wiping times are recorded; each template is tested for three positions to calculate an average value and the result is recorded, wherein point No. 4 is a test comparison point.
(3) Water and oil contact angle test method: the contact angle measuring instrument is used for testing, equipment is Shanghai Zhongqu, model CSDC-2000S, and water contact angle testing liquid is as follows: purified water, the oil contact angle test liquid is paraffin oil. The specific operation method comprises the following steps: the contact angle tester is opened, the liquid drop amount is controlled to be within 1-5 microliter as much as possible, and the sample is placed on the sample table. The brightness of the light source is adjusted according to the actual operation condition, automatic liquid dripping is carried out after software is opened, and finally the contact angle is read out through equipment. The larger water contact angle indicates better hydrophobic effect, and the larger oil contact angle indicates better oleophobic effect.
The specific test results for each example are set forth in Table 3 below:
the specific test results of each comparative example are shown in table 4 below.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The easy-to-clean polypropylene composite material is characterized by comprising the following components in parts by weight:
the organosilicon-fluorine-containing acrylic ester copolymer is obtained by copolymerizing silane, fluorine-containing acrylic acid and acrylic ester polymer;
the mass ratio of silane, fluorine-containing acrylic acid and acrylic ester is (5-10): (10-20): (50-70);
the silane is vinyltris (beta-methoxyethoxy) silane.
2. The easy-to-clean polypropylene composite material according to claim 1, wherein the mass ratio of silane, fluorine-containing acrylic acid and acrylic ester is (7 to 8): (13-16): (55-65).
3. The easy-to-clean polypropylene composite material according to claim 2, wherein the mass ratio of silane, fluorine-containing acrylic acid and acrylic ester is 8:15:60.
4. the easy-to-clean polypropylene composite according to claim 1, wherein the acrylate polymer is polymerized from methyl methacrylate and/or butyl methacrylate.
5. The easy-to-clean polypropylene composite material according to claim 1, wherein the purity of the graphene is not less than 95%.
6. The easy-to-clean polypropylene composite according to claim 1, wherein the processing aid is a lubricant and/or an antioxidant.
7. The easy-to-clean polypropylene composite according to claim 6, wherein the lubricant is a stearate type lubricant.
8. The easy-to-clean polypropylene composite material according to claim 6, wherein the antioxidant is a hindered phenol antioxidant and/or a phosphite antioxidant.
9. The method for preparing the easy-to-clean polypropylene composite material according to any one of claims 1 to 8, which is characterized by comprising the following steps:
and uniformly mixing the components, performing melt extrusion and granulation at 200-230 ℃ by a double-screw extruder, and drying to obtain the easy-to-clean polypropylene composite material.
10. Use of the easy-to-clean polypropylene composite material according to any one of claims 1 to 8 in the easy-to-clean field.
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| CN111440501A (en) * | 2020-05-14 | 2020-07-24 | 郑州知淘信息科技有限责任公司 | Organic silicon-fluorine modified acrylic resin powder coating and preparation method thereof |
| CN112778642A (en) * | 2020-12-31 | 2021-05-11 | 浙江佳华精化股份有限公司 | Easy-to-clean master batch and preparation method thereof |
| CN114213746A (en) * | 2021-12-20 | 2022-03-22 | 江苏尚艾新材料科技有限公司 | Oil-stain-resistant polypropylene material and preparation method thereof |
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| CN111440501A (en) * | 2020-05-14 | 2020-07-24 | 郑州知淘信息科技有限责任公司 | Organic silicon-fluorine modified acrylic resin powder coating and preparation method thereof |
| CN112778642A (en) * | 2020-12-31 | 2021-05-11 | 浙江佳华精化股份有限公司 | Easy-to-clean master batch and preparation method thereof |
| CN114213746A (en) * | 2021-12-20 | 2022-03-22 | 江苏尚艾新材料科技有限公司 | Oil-stain-resistant polypropylene material and preparation method thereof |
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