CN117207625A - Antistatic polypropylene foamed floor and preparation method thereof - Google Patents
Antistatic polypropylene foamed floor and preparation method thereof Download PDFInfo
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- CN117207625A CN117207625A CN202311143902.6A CN202311143902A CN117207625A CN 117207625 A CN117207625 A CN 117207625A CN 202311143902 A CN202311143902 A CN 202311143902A CN 117207625 A CN117207625 A CN 117207625A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 92
- -1 polypropylene Polymers 0.000 title claims abstract description 92
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title abstract description 25
- 229920000642 polymer Polymers 0.000 claims abstract description 49
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 46
- 238000002156 mixing Methods 0.000 claims abstract description 40
- 239000010410 layer Substances 0.000 claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 238000005187 foaming Methods 0.000 claims abstract description 23
- 239000004088 foaming agent Substances 0.000 claims abstract description 15
- FZGFBJMPSHGTRQ-UHFFFAOYSA-M trimethyl(2-prop-2-enoyloxyethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CCOC(=O)C=C FZGFBJMPSHGTRQ-UHFFFAOYSA-M 0.000 claims abstract description 15
- FPCPOLLWTJARLO-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)acetic acid Chemical compound CC(=C)C(=O)OCC(O)=O FPCPOLLWTJARLO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000006260 foam Substances 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000002344 surface layer Substances 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 5
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 9
- 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 description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 8
- 238000004806 packaging method and process Methods 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 2
- 238000009408 flooring Methods 0.000 claims 5
- 230000000694 effects Effects 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000002216 antistatic agent Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 9
- 239000003292 glue Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XDZAFZVZTAGZHI-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;ethyl sulfate Chemical compound CCOS([O-])(=O)=O.CC[NH+]1CN(C)C=C1 XDZAFZVZTAGZHI-UHFFFAOYSA-N 0.000 description 2
- VEKIYFGCEAJDDT-UHFFFAOYSA-N 2-pyridin-3-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1 VEKIYFGCEAJDDT-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 238000005956 quaternization reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DXJLCRNXYNRGRA-UHFFFAOYSA-M tributyl(methyl)azanium;iodide Chemical compound [I-].CCCC[N+](C)(CCCC)CCCC DXJLCRNXYNRGRA-UHFFFAOYSA-M 0.000 description 2
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
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- 239000003999 initiator Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229920006126 semicrystalline polymer Polymers 0.000 description 1
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- 239000012855 volatile organic compound Substances 0.000 description 1
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- Laminated Bodies (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to the technical field of compositions of high molecular compounds, and particularly discloses an antistatic polypropylene foam floor and a preparation method thereof. The floor comprises a substrate layer and a decorative surface layer arranged on the substrate layer, wherein the substrate layer comprises the following raw materials in parts by weight: 20-80 parts of antistatic polypropylene, 1-5 parts of foaming agent, 1-2.5 parts of foaming auxiliary agent, 5-10 parts of maleic anhydride grafted polypropylene and 10-25 parts of reinforcing agent; the antistatic polypropylene is prepared by polymerizing 2,3' -bipyridine-5-vinyl, carboxymethyl methacrylate and acryloyloxyethyl trimethyl ammonium chloride to obtain a quaternary ammonium salt polymer, and then melt blending the quaternary ammonium salt polymer with polypropylene. Compared with the prior art, the foaming floor prepared by the invention has the advantages of good antistatic effect, high safety coefficient, good mechanical property and the like.
Description
Technical Field
The invention relates to the technical field of compositions of high molecular compounds, in particular to an antistatic polypropylene foam floor and a preparation method thereof.
Background
Static electricity is a static bound charge, which is seen everywhere in daily life. The material is usually electrically neutral, and the content of positive and negative charges in the material and on the surface is the same. Static charge is typically caused by mechanical action such as contact, friction, etc. of two objects (either the same or different substances). When contact and friction occur, the charge moves across the contact surface of the two objects and forms an electric double layer; when the two objects are separated by a certain mechanical action, static charges are generated on the surfaces of the two objects, the surface negative charges of one object are excessive, the surface positive charges of the other object are excessive, and the excessive charges cannot be dissipated or leaked as soon as possible, so that an electrostatic field is formed outside the material, and static electricity is generated.
Polypropylene (PP) is a semi-crystalline polymer with excellent mechanical properties, heat resistance, chemical resistance and formability, and has been widely used in the industries of automobiles, home appliances, buildings and the like. PP has a strong electrical insulation property (surface resistivity up to 10 due to its small molecular polarity and poor water absorption 16 ～10 18 Ω) during production and use, static electricity is generated and accumulated on the surface of the product due to friction, peeling or induction processes, thereby generating static electricity hazards such as dust absorption, discharge, breakdown, and even burning or explosion. Thus, the polypropylene material is aimed atAntistatic modification of (a) has become one of the important directions in the field of plastic modification.
Antistatic modification to polypropylene is mainly melt blending modification, including antistatic agent blending and conductive filler blending. Antistatic blending is where, during melt blending, an antistatic agent is mixed into a material to uniformly disperse it throughout a polymer, and then drawn or shaped. After a period of time, the antistatic agent with hydrophilic groups continuously migrates to the surface of the material by virtue of the chain segment movement of the polymer, absorbs moisture in air, and forms a water film on the surface of the product so as to leak charges. When the antistatic agent on the surface of the material fails, the internal antistatic agent can continue to fill the interface of the material. The conductive filler method mainly comprises the steps of dispersing the conductive filler in a polypropylene matrix by a mixing method, so that the filler forms a conductive path or network inside the polypropylene to leak charges.
Chinese patent 202111426078.6 provides an antistatic agent, antistatic floor glue, preparation method and application of antistatic floor glue, antistatic floor and preparation method of antistatic floor, wherein the antistatic agent comprises tri-n-butyl methyl ammonium bis (trifluoromethanesulfonyl) imine and 1-ethyl-3-methylimidazole ethyl sulfate, and the weight ratio of tri-n-butyl methyl ammonium bis (trifluoromethanesulfonyl) imine to 1-ethyl-3-methylimidazole ethyl sulfate is (7-9): (1-3), the antistatic floor glue comprises a UV light curing acrylic resin coating, an initiator and an antistatic agent. After the antistatic agent is prepared into the antistatic floor glue, the antistatic floor glue is coated on the surface of a wood floor substrate, so that the wood floor coated with the antistatic floor glue has better and more stable antistatic performance, and toxic and harmful solvents such as formaldehyde and volatile organic compounds are not added into the antistatic floor glue material, so that the antistatic floor glue is environment-friendly.
Chinese patent 202210286051.X discloses a preparation method of antistatic high-strength PP material. The preparation method of the antistatic high-strength PP material comprises the following steps: (1) Taking N-methyldiethanolamine and gamma-chloropropyl trimethoxyl silane, putting the N-methyldiethanolamine and gamma-chloropropyl trimethoxyl silane into a reaction kettle, taking potassium iodide as a catalyst, taking isopropanol and methanol as polar organic solvents, heating to dissolve and uniformly mix the raw materials, transferring the raw materials into a microwave reaction device, cooling, standing and separating the liquid after the reaction is finished, and performing rotary evaporation to obtain the organosilicon quaternary ammonium salt; (2) The high molecular antistatic agent polyether ester and the obtained organosilicon quaternary ammonium salt are firstly subjected to drying treatment, then are uniformly mixed with PP, and are subjected to melt blending and extrusion molding in a double-screw extruder to prepare the antistatic high-strength polypropylene composite material. According to the method, the high-molecular antistatic agent and the small-molecular antistatic agent are added, so that the antistatic performance is improved from the two aspects of the bulk phase and the surface layer of the polypropylene, and the defect of insufficient antistatic performance of the polypropylene material is overcome.
Polypropylene has been widely used in the construction industry due to its excellent appearance in various aspects, but the defect that it is liable to cause electrostatic hazard when used as a floor is rarely noticed, and researches on such technologies are also being made in the prior art. At present, antistatic modification of polypropylene materials is mainly achieved by melt blending an antistatic agent with the antistatic agent, but partial antistatic agents such as quaternary ammonium salt and the like have relatively strong polarity so that the antistatic agent has poor compatibility with matrix resin, which affects the dispersion of the antistatic agent in the polymer, thereby directly affecting the antistatic effect, and therefore, the development of an antistatic agent for solving the problems and the application of the antistatic agent to the preparation of polypropylene floors has very important significance.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention is to solve the technical problem of an antistatic polypropylene foamed floor and a preparation method thereof.
The high molecular quaternary ammonium salt antistatic agent is a polymer containing quaternary ammonium salt groups on a main chain or a branched chain. The structure of the antistatic agent contains stable ammonium cations so that the charge density of the polymer is increased, and meanwhile, the polarity of the polymer is enhanced by introducing quaternary ammonium salt components, the transfer of charges is promoted, and the antistatic effect is quite obvious. In addition, the quaternization of the molecular chains also enhances the hydrophilicity of the polymer, so that the polymer can absorb moisture in the air better. However, the polarity difference makes the quaternary ammonium salt antistatic agent and the matrix resin not fully compatible, so that it is critical to reduce the agglomeration phenomenon and make the antistatic agent uniformly dispersed in the matrix resin.
According to the invention, the quaternary ammonium salt polymer is obtained by introducing 2,3' -bipyridine-5-vinyl, carboxymethyl methacrylate and acryloyloxyethyl trimethyl ammonium chloride with lower polarity and mixing the quaternary ammonium salt polymer with polypropylene in a melt blending way, so that the antistatic polypropylene is obtained, and the prepared quaternary ammonium salt polymer has good compatibility with polypropylene, so that the dispersibility is good. In addition, the bipyridyl introduced into the quaternary ammonium salt polymer structure can form a passage more suitable for ion conduction, so that the resistivity is reduced, meanwhile, the carboxyl on the structure can form a hydrogen bond network with the pyridyl, the conduction passage is further enlarged, and the water absorption of the polymer can be enhanced by adding the carboxyl, the dissociation of quaternary ammonium cations is promoted, and the antistatic effect is enhanced. The hydroxy oxygen of the carboxyl group on the carboxymethyl methacrylate is sp 3 The hybridization can form coordination effect with N atoms in the acryloyloxyethyl trimethyl ammonium chloride, so that quaternary ammonium cations can be dissociated more effectively, and the ionic conductivity can be further improved. The antistatic polypropylene is applied to the polypropylene floor, so that the antistatic and dustproof floor material can be obtained, has good mechanical properties and high safety coefficient, and has wide application prospect.
In order to achieve the above purpose, the invention provides an antistatic polypropylene foam floor, which comprises a substrate layer and a decorative surface layer arranged on the substrate layer, wherein the substrate layer comprises the following raw materials in parts by weight: 20-80 parts of antistatic polypropylene, 1-5 parts of foaming agent, 1-2.5 parts of foaming auxiliary agent, 5-10 parts of maleic anhydride grafted polypropylene and 10-25 parts of reinforcing agent; the antistatic polypropylene is prepared by polymerizing 2,3' -bipyridine-5-vinyl, carboxymethyl methacrylate and acryloyloxyethyl trimethyl ammonium chloride to obtain a quaternary ammonium salt polymer, and then melt blending the quaternary ammonium salt polymer with polypropylene.
The preparation method of the antistatic polypropylene comprises the following steps:
s1, adding 1-3 parts by weight of 2,3' -bipyridine-5-vinyl, 6-15 parts by weight of carboxymethyl methacrylate and 15-25 parts by weight of acryloyloxyethyl trimethyl ammonium chloride into 100-500 parts by weight of absolute ethyl alcohol, stirring and mixing uniformly under a nitrogen atmosphere, adding 0.1-1 part by weight of azodiisobutyronitrile, heating to 70-85 ℃, stirring for 4-8 hours, cooling to room temperature, concentrating under reduced pressure to 1/4 of the original volume, adding into toluene, precipitating, filtering, and drying residues to obtain a quaternary ammonium salt polymer;
s2, uniformly mixing 15-25 parts by weight of quaternary ammonium salt polymer and 75-85 parts by weight of polypropylene, extruding, granulating and drying at 190-220 ℃ to obtain the antistatic polypropylene.
Further, the foaming agent is selected from one or a mixture of two of an AC foaming agent and an NC foaming agent.
Further, the foaming auxiliary agent is zinc oxide.
Further, the reinforcing agent is light calcium carbonate.
The preparation method of the antistatic polypropylene foaming floor comprises the following steps:
stirring and mixing the raw materials in the substrate layer uniformly, carrying out hot mixing at 110-140 ℃, carrying out cold mixing and cooling, extruding to obtain a micro-foaming substrate, extruding and shaping to obtain the substrate layer, hot-pressing the substrate layer and the decorative surface layer, and then carrying out slitting, slotting and packaging to obtain the micro-foaming substrate.
The invention has the beneficial effects that:
compared with the prior art, the quaternary ammonium salt polymer obtained by the invention has good compatibility with polypropylene, good dispersibility, good absorbability and good ion conduction efficiency, so that the quaternary ammonium salt polymer has good antistatic effect, and the floor prepared by melt blending the quaternary ammonium salt polymer and polypropylene can be antistatic and dustproof, has higher safety coefficient and has wide application prospect.
Detailed Description
2,3 '-bipyridyl-5-vinyl, 2,3' -Bipyridine,5-ethenyl-, CAS number: 78210-81-8.
Carboxymethyl methacrylate, carboxymethyl methacrylate, CAS No.: 6852-90-0.
Acryloyloxyethyl trimethyl ammonium chloride, CAS number: 44992-01-0.
Polypropylene, model: t300, shanghai petrochemical industry.
PVC transparent layer, goods number: FGT-praise, jiangsu feichi new material.
Maleic anhydride grafted polypropylene, model: ZJ-900P, zhongjie chemical industry.
Comparative example 1
The preparation method of the antistatic polypropylene foaming floor comprises the following steps:
7.5kg of antistatic polypropylene, 125g of AC foaming agent, 185g of zinc oxide, 0.8kg of maleic anhydride grafted polypropylene and 2kg of light calcium carbonate are stirred and mixed uniformly, hot mixed at 120 ℃, cooled by cold mixing, extruded to obtain a micro-foaming substrate, extruded and shaped to obtain a substrate layer, and the substrate layer and a PVC transparent layer are subjected to hot pressing, slitting, slotting and packaging to obtain the PVC transparent composite material.
The preparation method of the antistatic polypropylene comprises the following steps:
150g of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate and 850g of polypropylene are uniformly mixed, extruded, granulated and dried at 210 ℃ to obtain the antistatic polypropylene.
Example 1
The preparation method of the antistatic polypropylene foaming floor comprises the following steps:
7.5kg of antistatic polypropylene, 125g of AC foaming agent, 185g of zinc oxide, 0.8kg of maleic anhydride grafted polypropylene and 2kg of light calcium carbonate are stirred and mixed uniformly, hot mixed at 120 ℃, cooled by cold mixing, extruded to obtain a micro-foaming substrate, extruded and shaped to obtain a substrate layer, and the substrate layer and a PVC transparent layer are subjected to hot pressing, slitting, slotting and packaging to obtain the PVC transparent composite material.
The preparation method of the antistatic polypropylene comprises the following steps:
s1, adding 180g of 2,3' -bipyridine-5-vinyl, 1.3kg of carboxymethyl methacrylate and 1.9kg of acryloyloxyethyl trimethyl ammonium chloride into 30L of absolute ethyl alcohol, uniformly stirring and mixing under a nitrogen atmosphere, adding 50g of azodiisobutyronitrile, heating to 75 ℃, stirring for 8 hours, cooling to room temperature, concentrating under reduced pressure, adding into toluene after concentrating the volume to 1/4 of the original volume, precipitating, filtering, and drying the residue at 85 ℃ for 8 hours to obtain a quaternary ammonium salt polymer;
s2, uniformly mixing 1.5kg of quaternary ammonium salt polymer and 8.5kg of polypropylene, extruding, granulating and drying at 210 ℃ to obtain the antistatic polypropylene.
Example 2
The preparation method of the antistatic polypropylene foaming floor comprises the following steps:
7.5kg of antistatic polypropylene, 125g of AC foaming agent, 185g of zinc oxide, 0.8kg of maleic anhydride grafted polypropylene and 2kg of light calcium carbonate are stirred and mixed uniformly, hot mixed at 120 ℃, cooled by cold mixing, extruded to obtain a micro-foaming substrate, extruded and shaped to obtain a substrate layer, and the substrate layer and a PVC transparent layer are subjected to hot pressing, slitting, slotting and packaging to obtain the PVC transparent composite material.
The preparation method of the antistatic polypropylene comprises the following steps:
s1, 180g of styrene, 1.3kg of carboxymethyl methacrylate and 1.9kg of acryloyloxyethyl trimethyl ammonium chloride are added into 30L of absolute ethyl alcohol, 50g of azodiisobutyronitrile is added after stirring and mixing uniformly under nitrogen atmosphere, the mixture is heated to 75 ℃ and stirred for 8 hours, the mixture is cooled to room temperature, the mixture is concentrated under reduced pressure to 1/4 of the original volume and then added into toluene, precipitation is carried out, and the mixture is filtered, and the residue is dried for 8 hours at 85 ℃ to obtain a quaternary ammonium salt polymer;
s2, uniformly mixing 1.5kg of quaternary ammonium salt polymer and 8.5kg of polypropylene, extruding, granulating and drying at 210 ℃ to obtain the antistatic polypropylene.
Example 3
The preparation method of the antistatic polypropylene foaming floor comprises the following steps:
7.5kg of antistatic polypropylene, 125g of AC foaming agent, 185g of zinc oxide, 0.8kg of maleic anhydride grafted polypropylene and 2kg of light calcium carbonate are stirred and mixed uniformly, hot mixed at 120 ℃, cooled by cold mixing, extruded to obtain a micro-foaming substrate, extruded and shaped to obtain a substrate layer, and the substrate layer and a PVC transparent layer are subjected to hot pressing, slitting, slotting and packaging to obtain the PVC transparent composite material.
The preparation method of the antistatic polypropylene comprises the following steps:
s1, adding 180g of 2,3' -bipyridine-5-vinyl, 1.3kg of hydroxyethyl methacrylate and 1.9kg of acryloyloxyethyl trimethyl ammonium chloride into 30L of absolute ethyl alcohol, uniformly stirring and mixing under a nitrogen atmosphere, adding 50g of azobisisobutyronitrile, heating to 75 ℃, stirring for 8 hours, cooling to room temperature, concentrating under reduced pressure, adding into toluene after concentrating the volume to 1/4 of the original volume, precipitating, filtering, and drying residues at 85 ℃ for 8 hours to obtain a quaternary ammonium salt polymer;
s2, uniformly mixing 1.5kg of quaternary ammonium salt polymer and 8.5kg of polypropylene, extruding, granulating and drying at 210 ℃ to obtain the antistatic polypropylene.
Example 4
The preparation method of the antistatic polypropylene foaming floor comprises the following steps:
7.5kg of antistatic polypropylene, 125g of AC foaming agent, 185g of zinc oxide, 0.8kg of maleic anhydride grafted polypropylene and 2kg of light calcium carbonate are stirred and mixed uniformly, hot mixed at 120 ℃, cooled by cold mixing, extruded to obtain a micro-foaming substrate, extruded and shaped to obtain a substrate layer, and the substrate layer and a PVC transparent layer are subjected to hot pressing, slitting, slotting and packaging to obtain the PVC transparent composite material.
The preparation method of the antistatic polypropylene comprises the following steps:
s1, adding 180g of 2,3' -bipyridine-5-vinyl, 1.3kg of carboxymethyl methacrylate and 1.9kg of acryloyloxyethyl trimethyl ammonium chloride into 30L of absolute ethyl alcohol, uniformly stirring and mixing under a nitrogen atmosphere, adding 50g of azodiisobutyronitrile, heating to 75 ℃, stirring for 8 hours, cooling to room temperature, concentrating under reduced pressure, adding into toluene after concentrating the volume to 1/4 of the original volume, precipitating, filtering, and drying the residue at 85 ℃ for 8 hours to obtain a quaternary ammonium salt polymer;
s2, uniformly mixing 1.8kg of quaternary ammonium salt polymer and 8.5kg of polypropylene, extruding, granulating and drying at 210 ℃ to obtain the antistatic polypropylene.
Example 5
The preparation method of the antistatic polypropylene foaming floor comprises the following steps:
7.5kg of antistatic polypropylene, 125g of AC foaming agent, 185g of zinc oxide, 0.8kg of maleic anhydride grafted polypropylene and 2kg of light calcium carbonate are stirred and mixed uniformly, hot mixed at 120 ℃, cooled by cold mixing, extruded to obtain a micro-foaming substrate, extruded and shaped to obtain a substrate layer, and the substrate layer and a PVC transparent layer are subjected to hot pressing, slitting, slotting and packaging to obtain the PVC transparent composite material.
The preparation method of the antistatic polypropylene comprises the following steps:
s1, adding 180g of 2,3' -bipyridine-5-vinyl, 1.3kg of carboxymethyl methacrylate and 1.9kg of acryloyloxyethyl trimethyl ammonium chloride into 30L of absolute ethyl alcohol, uniformly stirring and mixing under a nitrogen atmosphere, adding 50g of azodiisobutyronitrile, heating to 75 ℃, stirring for 8 hours, cooling to room temperature, concentrating under reduced pressure, adding into toluene after concentrating the volume to 1/4 of the original volume, precipitating, filtering, and drying the residue at 85 ℃ for 8 hours to obtain a quaternary ammonium salt polymer;
s2, uniformly mixing 2kg of quaternary ammonium salt polymer and 8.5kg of polypropylene, extruding, granulating and drying at 210 ℃ to obtain the antistatic polypropylene.
Test example 1
Dielectric and resistive Properties of solid insulation according to GB/T31838.3-2019 section 3: resistance characteristics (DC method) surface electrical Specification the method in the specification measures the surface resistivity of a polypropylene foamed floor in a specific environment (23 ℃ C., relative humidity 50%) and sets the test voltage to 500V. The samples were left for 24 hours at 23℃and 50% relative humidity before testing.
TABLE 1 surface resistivity of Polypropylene foam floor
| Experimental protocol | Surface resistivity/Ω |
| Comparative example 1 | 6.2×10 11 |
| Example 1 | 4.5×10 9 |
| Example 2 | 3.5×10 10 |
| Example 3 | 4.1×10 10 |
| Example 4 | 4.3×10 9 |
| Example 5 | 4.1×10 9 |
The antistatic agent used in the preparation of antistatic polypropylene in comparative example 1 is octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, the small molecular antistatic agent is usually coated on the surface of a high polymer because of poor compatibility with the high polymer, the antistatic effect is achieved by adsorbing moisture in air, the surface resistivity in comparative example 1 is high because of poor compatibility with polypropylene matrix resin, and the quaternary ammonium salt polymer prepared in examples contains stable ammonium cations so that the charge density of the polymer is increased, and meanwhile, the polarity of the polymer is enhanced by introducing quaternary ammonium salt components so that the transfer of charges is promoted, and the antistatic effect is quite obvious. In addition, the quaternization of the molecular chains also enhances the hydrophilicity of the polymer, so that the polymer can absorb moisture in air better, and therefore, the surface resistivity is lower. In contrast, example 1 and examples 2 to 3 have a bipyridine structure, and thus are advantageous in reducing the resistivity because they can form a more ion-conductive pathway. In addition, in example 1, compared with example 2, the carboxyl groups on the quaternary ammonium salt polymer structure can form a hydrogen bond network with the pyridyl group, so that the conduction path is further enlarged, and the addition of the carboxyl groups can also enhance the water absorption of the polymer and promote the dissociation of the quaternary ammonium cation, so that the antistatic effect is enhanced. Carboxymethyl methacrylateThe hydroxy oxygen of the carboxyl group being sp 3 The hybridization can form coordination effect with N atoms in the acryloyloxyethyl trimethyl ammonium chloride, so that quaternary ammonium cations can be dissociated more effectively, and the ionic conductivity can be further improved. However, in examples 4 to 5, the surface conductivity was continuously decreased due to the increase in the amount of the quaternary ammonium salt polymer, but the addition of the quaternary ammonium salt polymer was too much, which resulted in the internal non-uniformity of polypropylene, and the mechanical properties were decreased due to the formation of defects, so that it was the best solution to achieve the balance between antistatic properties and mechanical properties.
Test example 2
Determination of tensile Properties of plastics according to the standard GB/T1040.1-2018 section 1: general rule, determination of impact Property of Plastic simple Beam section 1 of GB/T1043.1-2008: the mechanical properties of the prepared polypropylene foam floor were tested by the testing method in the non-instrumented impact test, and specific testing results are shown in Table 2.
Table 2 mechanical property test of polypropylene foamed floor
| Experimental protocol | Tensile Strength/MPa | Impact strength/kJ/m 2 |
| Comparative example 1 | 21.4 | 4.2 |
| Example 1 | 27.5 | 7.5 |
| Example 2 | 26.3 | 6.8 |
| Example 3 | 26.5 | 7.0 |
| Example 4 | 22.0 | 5.1 |
| Example 5 | 18.6 | 3.4 |
From the results of the mechanical property test, the compatibility of the quaternary ammonium salt and the polypropylene directly affects the final mechanical test results, while from the comparison of examples 1 to 5, it can be found that when the addition amount of the quaternary ammonium salt polymer is increased, the mechanical property is correspondingly reduced, which is probably due to the defect that the quaternary ammonium salt polymer is agglomerated inside the polypropylene, and the void is easily generated under the action of external force, so that the tensile strength and the impact strength are obviously reduced.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (7)
1. An antistatic polypropylene foam floor is characterized by comprising a base material layer and a decorative surface layer arranged on the base material layer; the substrate layer comprises the following raw materials in parts by weight: 20-80 parts of antistatic polypropylene, 1-5 parts of foaming agent, 1-2.5 parts of foaming auxiliary agent, 5-10 parts of maleic anhydride grafted polypropylene and 10-25 parts of reinforcing agent; the antistatic polypropylene is prepared by polymerizing 2,3' -bipyridine-5-vinyl, carboxymethyl methacrylate and acryloyloxyethyl trimethyl ammonium chloride to obtain a quaternary ammonium salt polymer, and then melt blending the quaternary ammonium salt polymer with polypropylene.
2. The polypropylene foam flooring of claim 1, wherein: the antistatic polypropylene is prepared by the following steps:
s1, adding 1-3 parts by weight of 2,3' -bipyridine-5-vinyl, 6-15 parts by weight of carboxymethyl methacrylate and 15-25 parts by weight of acryloyloxyethyl trimethyl ammonium chloride into 100-500 parts by weight of absolute ethyl alcohol, stirring and mixing uniformly under a nitrogen atmosphere, adding 0.1-1 part by weight of azodiisobutyronitrile, heating to 70-85 ℃, stirring for 4-8 hours, cooling to room temperature, concentrating under reduced pressure to 1/4 of the original volume, adding into toluene, precipitating, filtering, and drying residues to obtain a quaternary ammonium salt polymer;
s2, uniformly mixing 15-25 parts by weight of quaternary ammonium salt polymer and 75-85 parts by weight of polypropylene, extruding, granulating and drying at 190-220 ℃ to obtain the antistatic polypropylene.
3. The polypropylene foam flooring of claim 1, wherein: the decorative surface layer is a PVC transparent layer.
4. The polypropylene foam flooring of claim 1, wherein: the foaming agent is one or a mixture of two of an AC foaming agent and an NC foaming agent.
5. The polypropylene foam flooring of claim 1, wherein: the foaming auxiliary agent is zinc oxide.
6. The polypropylene foam flooring of claim 1, wherein: the reinforcing agent is light calcium carbonate.
7. A method for preparing a polypropylene foamed floor according to any one of claims 1 to 6, comprising the steps of:
stirring and mixing the raw materials in the substrate layer uniformly, carrying out hot mixing at 110-140 ℃, carrying out cold mixing and cooling, extruding to obtain a micro-foaming substrate, extruding and shaping to obtain the substrate layer, hot-pressing the substrate layer and the decorative surface layer, and then carrying out slitting, slotting and packaging to obtain the micro-foaming substrate.
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