CN116731464B - High-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor and preparation method and application thereof - Google Patents
High-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor and preparation method and application thereof Download PDFInfo
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- CN116731464B CN116731464B CN202310917810.2A CN202310917810A CN116731464B CN 116731464 B CN116731464 B CN 116731464B CN 202310917810 A CN202310917810 A CN 202310917810A CN 116731464 B CN116731464 B CN 116731464B
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- polyvinyl chloride
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- coiled material
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- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 102
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 102
- 239000000463 material Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 10
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011737 fluorine Substances 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 12
- QOXQHDNHODRXMJ-UHFFFAOYSA-N 9-methyl-9h-fluorene-2,7-diol Chemical compound C1=C(O)C=C2C(C)C3=CC(O)=CC=C3C2=C1 QOXQHDNHODRXMJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000945 filler Substances 0.000 claims abstract description 9
- 239000004014 plasticizer Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005299 abrasion Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000007033 dehydrochlorination reaction Methods 0.000 claims description 10
- 238000009408 flooring Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical group C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000005485 electric heating Methods 0.000 claims description 3
- 238000004049 embossing Methods 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 239000008187 granular material Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 230000008646 thermal stress Effects 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- YYPAYCHEKJAQAK-UHFFFAOYSA-N C=CC.F Chemical group C=CC.F YYPAYCHEKJAQAK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 24
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 150000004291 polyenes Polymers 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 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 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- 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 a high-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor and a preparation method and application thereof. The high wear-resistant high-hardness polyvinyl chloride industrial coiled material floor comprises modified polyvinyl chloride, fluorine-containing high polymer, filler, plasticizer, modified whisker and auxiliary agent; the modified polyvinyl chloride is prepared by reacting PVC-g-MAH prepared by polyvinyl chloride and maleic anhydride with 2, 7-dihydroxy-9-methylfluorene; the modified whisker is prepared by modifying the surface of the potassium titanate whisker by a silane coupling agent. According to the polyvinyl chloride coiled material floor, the polyvinyl chloride is subjected to intramolecular modification and is grafted with the rigid fluorene ring structure, so that the mechanical strength and hardness of the material are remarkably improved, and the fluorine-containing high polymer and the modified whisker are added, so that the mechanical property of the material is further improved, and the wear resistance of the material is enhanced, and the polyvinyl chloride coiled material floor can be applied to industrial environments.
Description
Technical Field
The invention relates to the technical field of plates, in particular to a high-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor and a preparation method and application thereof.
Background
With the development of the economy in China, the public facilities are continuously sound and beautified, and the PVC pavement material is applied to pavement materials (especially PVC pavement materials) in public places such as airports, subways, hospitals, schools, kindergartens, salons, markets, office buildings and the like, and the demand of the PVC pavement materials is suddenly high.
PVC floor has the advantages of high tensile strength, good puncture resistance, aging resistance, ultraviolet radiation resistance and the like, has been widely used as a novel decorative material in factories, hospitals, schools, stadiums, vehicles, ships, airports and the like, and gradually becomes an important ground decorative material. The PVC floor classification method is various, and the PVC floor classification method can be divided into block floors and coiled material floors according to the appearance of the floor; the structure of the middle layer can be divided into a foaming floor and a compact floor; the floor processing method can be divided into a prolonged pressing floor, a coated floor, a composite floor, an extruded floor and the like; the floor overall structure can be divided into a multi-layer composite floor, a homogeneous permeable floor and a semi-homogeneous floor.
The coiled material floor in the PVC floor is one of the indispensable ground materials for modern living room decoration, is attractive in appearance and good in practical effect, and has the characteristics of sound insulation, moisture insulation, wear resistance, corrosion resistance and the like. The general coiled material floor is composed of a base material and a surface layer compounded on the surface of the base material, wherein the base material mainly comprises PVC, and then various functional auxiliary agents are added, and the base material is manufactured through processes of high-temperature mixing, extrusion and the like, wherein the surface layer can be manufactured into functional coatings with different color patterns according to actual use requirements of customers, and the thickness of the surface layer is thinner, so that the performance of the base material of the coiled material floor determines the actual use performance of the coiled material floor in actual use.
The PVC base material in the prior art is limited to the performance of PVC materials, and can meet the requirements of environmental materials in daily life, but has higher requirements on the performance of floors in the environment of multiple objects and multiple transportation in the modern industry. In industrial annular, PVC coiled material floors in the prior art are easy to squeeze and deform under heavy objects, have higher requirements on hardness, are easy to wear under the condition that the heavy objects are transported frequently, have short service life, and have higher requirements on wear resistance of the coiled material floors.
Therefore, there is a need for a polyvinyl chloride industrial coiled material floor with high wear resistance and high hardness by modifying the PVC material and adding a modifying auxiliary agent.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the invention aims to provide a high-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor, and a preparation method and application thereof.
The technical scheme is as follows:
A high wear-resistant high-hardness PVC industrial coiled material floor comprises modified PVC, fluorine-containing high polymer, filler, plasticizer, modified whisker and auxiliary agent;
The modified polyvinyl chloride is prepared by reacting PVC-g-MAH prepared by polyvinyl chloride and maleic anhydride with 2, 7-dihydroxy-9-methylfluorene;
The modified whisker is prepared by modifying the surface of the potassium titanate whisker by a silane coupling agent.
Further, the fluorine-containing high polymer is selected from at least one of polyvinylidene fluoride propylene, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride or polytetrafluoroethylene; the filler is at least one of titanium dioxide, silicon dioxide, barium sulfate or calcium carbonate; the plasticizer is at least one selected from dioctyl phthalate or dibutyl phthalate; the auxiliary agent comprises an antioxidant, a stabilizer and a flame retardant.
According to the invention, the fluorine-containing high polymer is added, and the excellent wear resistance and chemical stability of the fluorine-containing high polymer can be compounded in the polyvinyl chloride material, so that the wear resistance and weather resistance of the coiled material floor can be obviously improved.
The antioxidant is selected from one of antioxidant 1010, antioxidant 168, antioxidant 1098 or antioxidant 1076;
the stabilizer is selected from one of Ca/Zn composite heat stabilizer or Ba/Zn composite heat stabilizer;
the flame retardant is selected from one of melamine cyanurate, aluminum tripolyphosphate or antimony trioxide.
Further, the modified polyvinyl chloride is prepared by the steps of:
(1) Adding polyvinyl chloride and sodium hydroxide solution into a reactor, heating to 80-90 ℃, stirring, refluxing, condensing, reacting for 1-2 hours, and carrying out suction filtration, washing and drying to obtain dehydrochlorination-treated polyvinyl chloride;
(2) Adding the dehydrochlorination polyvinyl chloride and acetone prepared in the step (1) into a reactor, sequentially adding maleic anhydride and an initiator, placing into a microwave oven with heating power of 500-700W, heating for 30-60 minutes, filtering, washing and drying to obtain PVC-g-MAH;
(3) Adding PVC-g-MAH and an organic solvent into a reactor, heating to 70-90 ℃, adding 2, 7-dihydroxy-9-methylfluorene, sodium bicarbonate and a water loss agent, reacting for 4-6 hours, separating out, filtering, washing and drying to obtain the modified polyvinyl chloride.
The mass fraction of the sodium hydroxide solution in the step (1) is 10-30%.
According to the invention, modified polyvinyl chloride is added, firstly, the polyvinyl chloride is subjected to dehydrochlorination treatment to form conjugated polyene chains, then maleic anhydride groups are grafted to prepare PVC-g-MAH, and finally, the PVC-g-MAH and 2, 7-dihydroxy-9-methylfluorene are subjected to esterification reaction, so that the polyvinyl chloride grafting has a rigid fluorene ring structure.
The modified polyvinyl chloride added by the invention has a rigid fluorene ring structure through grafting, so that the intramolecular structural strength of the modified polyvinyl chloride is enhanced, and the modified polyvinyl chloride has excellent hardness and mechanical strength and has excellent stability.
Further, the mass ratio of the polyvinyl chloride subjected to dehydrochlorination in the step (2) to the maleic anhydride is 4-6:1, a step of; the initiator is selected from one of potassium persulfate, sodium persulfate or ammonium persulfate.
Further, in the step (3), the mass ratio of the PVC-g-MAH to the 2, 7-dihydroxy-9-methylfluorene is 2-3:1, a step of; the water loss agent is selected from dicyclohexylcarbodiimide or N, N' -diisopropylcarbodiimide.
Further, the preparation of the modified whisker comprises the following steps: adding a silane coupling agent and an organic solvent into a reactor, uniformly stirring, regulating the pH to 1.5-2, heating to 40-50 ℃, adding potassium titanate whisker, keeping the temperature, stirring for 20-30 minutes, filtering, washing and drying to obtain the modified whisker.
According to the invention, the modified whisker is added, the surface of the potassium titanate whisker is modified by the silane coupling agent, so that the compatibility of the potassium titanate whisker and an organic material is improved, and the hardness and the wear resistance of the polyvinyl chloride coiled material floor can be remarkably improved based on excellent wear resistance, heat resistance and electric insulation capacity of the potassium titanate whisker.
Further, the silane coupling agent is selected from one of KH792 or KH 602; the mass ratio of the potassium titanate whisker to the silane coupling agent is 30-40:1.
The preparation method of the polyvinyl chloride industrial coiled material floor with high wear resistance and high hardness comprises the following steps:
(1) Adding modified polyvinyl chloride, fluorine-containing high polymer, filler, plasticizer, modified whisker and auxiliary agent into a high-speed mixer, heating to 70-80 ℃, stirring and mixing for 20-30 minutes, adding into a double-screw extruder for extrusion granulation, crushing, and sieving to obtain granules with particle size of 20-40 meshes;
(2) The granular particles in the step (1) are added into a vacuum drying oven to be dried for 3 to 6 hours at the temperature of 85 to 98 ℃, added into a calender to be extruded into coiled materials, added into an electric heating oven, and heated and plasticized at the temperature of 180 to 220 ℃;
(3) Adding the product obtained in the step (2) into a two-way calender, and extruding and forming at 140-160 ℃;
(4) And (3) heating the surface of the product obtained in the step (3) by infrared rays at 180-220 ℃, embossing, cooling, cutting edges, carrying out surface UV treatment, and cooling and rolling again after thermal stress is eliminated to obtain the high-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor.
The extrusion temperature of the twin-screw extruder in the step (1) is 160-180 ℃, and the screw rotating speed is 60-70r/min;
The surface UV treatment in the step (3) is to coat a layer of UV paint on the surface and cure the UV paint by ultraviolet equipment.
Further, the mass percentage of each component is as follows, based on 100% of the total mass:
The balance being filler.
The application of any of the high wear-resistant and high-hardness polyvinyl chloride industrial coiled material floors in industrial floors.
The beneficial effects are that:
(1) The modified polyvinyl chloride is added into the high-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor, the polyvinyl chloride is subjected to dehydrochlorination to form conjugated polyene chains, maleic anhydride groups are grafted to obtain PVC-g-MAH, and finally the PVC-g-MAH and 2, 7-dihydroxy-9-methylfluorene are subjected to esterification reaction to enable the polyvinyl chloride to be grafted to have a rigid fluorene ring structure.
(2) The modified polyvinyl chloride is added into the high-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor, and the rigid fluorene ring structure is grafted to strengthen the intramolecular structural strength of the modified polyvinyl chloride, so that the modified polyvinyl chloride has excellent hardness and mechanical strength and has excellent stability.
(3) The fluorine-containing high polymer is added into the high-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor, and the excellent wear resistance and chemical stability of the fluorine-containing high polymer can obviously improve the wear resistance and weather resistance of the coiled material floor when the fluorine-containing high polymer is compounded into a polyvinyl chloride material.
(4) According to the invention, the modified whisker is added into the high-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor, the silane coupling agent is used for carrying out surface modification on the potassium titanate whisker, so that the compatibility of the potassium titanate whisker and an organic material is improved, and the excellent wear resistance, heat resistance and electric insulation capacity of the potassium titanate whisker are based, so that the hardness and wear resistance of the polyvinyl chloride coiled material floor can be remarkably improved.
Detailed Description
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
The commercial PVC coil flooring was FN4035 purchased from san color plastic flooring limited, everstate; polyvinyl chloride is P815909 purchased from Shanghai microphone Biochemical technologies Co., ltd; the potassium titanate whisker is a potassium hexatitanate whisker purchased from wuhank biomedical technologies limited; the Ca/Zn composite heat stabilizer is CZ-1059 purchased from Qingdao Sauno New Material Co., ltd; the rest reagents and equipment are conventional reagents and equipment in the technical field.
Preparation of modified polyvinyl chloride-1
The modified polyvinyl chloride-1 is prepared by the following steps:
(1) Adding 5g of polyvinyl chloride and 30mL of sodium hydroxide solution with mass fraction of 15% into a reactor, heating to 80 ℃, stirring, refluxing and condensing to react for 2 hours, and then carrying out suction filtration, washing and drying to obtain dehydrochlorination-treated polyvinyl chloride;
(2) Adding 40g of dehydrochlorination polyvinyl chloride and 80mL of acetone prepared in the step (1) into a single-port bottle, sequentially adding 10g of maleic anhydride and 1g of ammonium persulfate, placing into a microwave oven with the heating power of 600W, heating for 50 minutes, and carrying out suction filtration, washing and drying to obtain PVC-g-MAH;
(3) 20g of PVC-g-MAH and 50mL of tetrahydrofuran are added into a three-neck flask, after the mixture is heated to 80 ℃, 10g of 2, 7-dihydroxy-9-methylfluorene, 0.5g of sodium bicarbonate and 0.5g of dicyclohexylcarbodiimide are added, after the mixture reacts for 5 hours, the mixture is separated out, filtered by suction, washed and dried, and the modified polyvinyl chloride-1 is prepared.
Preparation of modified polyvinyl chloride-2
Substantially the same as modified polyvinyl chloride-1, except that 2, 7-dihydroxy-9-methylfluorene in step (3) was changed to an equivalent amount of n-butanol.
Preparation of modified whisker
The modified whisker is prepared by the following steps:
adding 0.5g of a silane coupling agent KH792 and 30mL of absolute ethyl alcohol into a reactor, uniformly stirring, regulating the pH to 2, heating to 50 ℃, adding 20g of potassium titanate whisker, carrying out heat preservation and stirring for 30 minutes, and then filtering, washing and drying to obtain the modified whisker.
Example 1
The high wear-resistant and high-hardness polyvinyl chloride industrial coiled material floor is prepared by the following steps:
(1) Adding modified polyvinyl chloride-1, polytetrafluoroethylene, silicon dioxide, dioctyl phthalate, modified whisker and an auxiliary agent into a high-speed mixer, heating to 80 ℃, stirring and mixing for 30 minutes, adding into a double-screw extruder, extruding and granulating, crushing, sieving the granule particle size to 35 meshes, wherein the extrusion temperature of the double-screw extruder is 180 ℃, and the screw rotating speed is 65r/min;
(2) The granular particles in the step (1) are added into a vacuum drying oven to be dried for 5 hours at the temperature of 95 ℃, added into a calender to be extruded into coiled materials, added into an electric heating oven, and heated and plasticized at the temperature of 200 ℃;
(3) Adding the product obtained in the step (2) into a two-way calender, and extruding and forming at 150 ℃;
(4) Heating the surface of the product obtained in the step (3) by infrared rays at 200 ℃, embossing, cooling, cutting edges, carrying out surface UV treatment, and cooling and rolling again after thermal stress is eliminated to obtain the high-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor;
The auxiliary agent comprises 20% of antioxidant 1010, 50% of Ca/Zn composite heat stabilizer and 30% of aluminum tripolyphosphate based on 100% of total mass.
The weight percentage of each component is as follows, based on 100% of the total weight:
The balance being silicon dioxide.
Example 2
Substantially the same as in example 1, except that the total mass is 100%, the components and the mass percentages thereof are:
the balance being barium sulfate.
Example 3
Substantially the same as in example 1, except that the total mass is 100%, the components and the mass percentages thereof are:
the balance of titanium dioxide.
Comparative example 1
PVC coiled material floor is sold in the market.
Comparative example 2
Substantially the same as in example 1, except that the modified polyvinyl chloride-1 was changed to an equivalent amount of polyvinyl chloride.
Comparative example 3
Substantially the same as in example 1, except that the modified polyvinyl chloride-1 was changed to an equivalent amount of modified polyvinyl chloride-2.
Comparative example 4
Substantially the same as in example 1, except that polytetrafluoroethylene was changed to an equivalent amount of silica.
Comparative example 5
Substantially the same as in example 1, except that the modified whisker was changed to an equivalent amount of potassium titanate whisker.
Performance testing
Static bending strength detection: the static bending strength of the products of examples 1-3 and comparative examples 1-5 was measured according to GB/T17657-2013 method for testing physicochemical Properties of Artificial Board and veneered Artificial Board.
Bending strength detection: the flexural strength of the products of examples 1-3 and comparative examples 1-5 were tested according to GBT9341-2008 determination of flexural Properties of plastics.
The test results are shown in the following table:
| static bending strength MOR (MPa) | Flexural Strength (MPa) | |
| Example 1 | 22 | 27 |
| Example 2 | 22 | 26 |
| Example 3 | 21 | 26 |
| Comparative example 1 | 12 | 15 |
| Comparative example 2 | 17 | 21 |
| Comparative example 3 | 18 | 23 |
| Comparative example 4 | 20 | 25 |
| Comparative example 5 | 18 | 24 |
As can be seen from comparison of the detection results of examples 1-3 and comparative example 1, the high-wear-resistance and high-hardness polyvinyl chloride industrial coiled material floor provided by the invention has more excellent mechanical properties than the commercially available polyvinyl chloride coiled material floor.
According to comparison of the detection results of examples 1-3 and comparative examples 2 and 3, the modified polyvinyl chloride is used in the high-wear-resistance and high-hardness polyvinyl chloride industrial coiled material floor, and the structural strength of the modified polyvinyl chloride is enhanced by grafting a rigid fluorene ring structure in molecules, so that the product has excellent mechanical properties.
According to comparison of the detection results of examples 1-3 and comparative examples 4 and 5, the fluorine-containing high polymer and the modified whisker are added into the high-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor provided by the invention, so that the mechanical property of a product can be improved, and the silane coupling agent is used for carrying out surface modification on the potassium titanate whisker, so that the compatibility of the modified whisker and a material can be improved, and the mechanical property of the product can be further improved.
Hardness and wear resistance detection: after the Shore hardness of the products of examples 1-3 and comparative examples 1-5 was measured, the abrasion resistance of the materials was measured by using an abrasion tester under 5000N stress.
The test results are shown in the following table:
| Hardness (Shore A) | Abrasion value (g/100 r) | |
| Example 1 | 62 | 0.05 |
| Example 2 | 62 | 0.06 |
| Example 3 | 61 | 0.06 |
| Comparative example 1 | 35 | 0.19 |
| Comparative example 2 | 53 | 0.07 |
| Comparative example 3 | 55 | 0.07 |
| Comparative example 4 | 59 | 0.11 |
| Comparative example 5 | 57 | 0.12 |
As can be seen from comparison of the test results of examples 1-3 and comparative example 1, the high abrasion-resistant and high hardness PVC industrial coiled material floor provided by the invention has stronger hardness and more excellent abrasion resistance than the PVC industrial coiled material floor sold in the market, and is more suitable for industrial environment.
According to the comparison of the detection results of examples 1-3 and comparative examples 2 and 3, the modified polyvinyl chloride is used in the high-wear-resistance and high-hardness polyvinyl chloride industrial coiled material floor, and the structural strength of the modified polyvinyl chloride is enhanced by grafting a rigid fluorene ring structure in a molecule, so that the hardness of the material can be improved.
According to comparison of the detection results of examples 1-3 and comparative examples 4 and 5, the fluorine-containing high polymer and the modified whisker are added into the high-wear-resistance and high-hardness polyvinyl chloride industrial coiled material floor, the fluorine-containing high polymer can effectively improve the wear resistance of materials, and the silane coupling agent is used for carrying out surface modification on the potassium titanate whisker, so that the compatibility of the modified whisker and the materials can be improved, and the wear resistance of the materials is further improved.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement it, but not limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. The coiled material floor for the polyvinyl chloride industry with high wear resistance and high hardness is characterized by comprising modified polyvinyl chloride, fluorine-containing high polymer, filler, plasticizer, modified whisker and auxiliary agent;
The modified polyvinyl chloride is prepared by reacting PVC-g-MAH prepared by polyvinyl chloride and maleic anhydride with 2, 7-dihydroxy-9-methylfluorene;
The modified whisker is prepared by modifying the surface of the potassium titanate whisker by a silane coupling agent.
2. The high abrasion resistant, high hardness polyvinyl chloride industrial coil flooring according to claim 1, wherein the fluorine-containing high polymer is selected from at least one of the group consisting of polyvinylidene fluoride propylene, ethylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, and polytetrafluoroethylene; the filler is at least one of titanium dioxide, silicon dioxide, barium sulfate or calcium carbonate; the plasticizer is at least one selected from dioctyl phthalate or dibutyl phthalate; the auxiliary agent comprises an antioxidant, a stabilizer and a flame retardant.
3. The high abrasion resistant high hardness polyvinyl chloride industrial coil flooring according to claim 1, wherein the modified polyvinyl chloride is prepared by:
(1) Adding polyvinyl chloride and sodium hydroxide solution into a reactor, heating to 80-90 ℃, stirring, refluxing, condensing, reacting for 1-2 hours, and carrying out suction filtration, washing and drying to obtain dehydrochlorination-treated polyvinyl chloride;
(2) Adding the dehydrochlorination polyvinyl chloride and acetone prepared in the step (1) into a reactor, sequentially adding maleic anhydride and an initiator, placing into a microwave oven with heating power of 500-700W, heating for 30-60 minutes, filtering, washing and drying to obtain PVC-g-MAH;
(3) Adding PVC-g-MAH and an organic solvent into a reactor, heating to 70-90 ℃, adding 2, 7-dihydroxy-9-methylfluorene, sodium bicarbonate and a water loss agent, reacting for 4-6 hours, separating out, filtering, washing and drying to obtain the modified polyvinyl chloride.
4. The high abrasion-resistant, high hardness polyvinyl chloride industrial coil flooring according to claim 3, wherein the mass ratio of the dehydrochlorination-treated polyvinyl chloride to the maleic anhydride in the step (2) is 4 to 6:1, a step of; the initiator is selected from one of potassium persulfate, sodium persulfate or ammonium persulfate.
5. The high abrasion-resistant and high hardness polyvinyl chloride industrial coiled material floor according to claim 3, wherein the mass ratio of the PVC-g-MAH to the 2, 7-dihydroxy-9-methylfluorene in the step (3) is 2-3:1, a step of; the water loss agent is selected from dicyclohexylcarbodiimide or N, N' -diisopropylcarbodiimide.
6. The high abrasion resistant, high hardness polyvinyl chloride industrial coil flooring according to claim 1, wherein the modified whiskers are prepared by the steps of: adding a silane coupling agent and an organic solvent into a reactor, uniformly stirring, regulating the pH to 1.5-2, heating to 40-50 ℃, adding potassium titanate whisker, keeping the temperature, stirring for 20-30 minutes, filtering, washing and drying to obtain the modified whisker.
7. The high abrasion resistant, high hardness polyvinyl chloride industrial coil flooring according to claim 6, wherein the silane coupling agent is selected from one of KH792 or KH 602; the mass ratio of the potassium titanate whisker to the silane coupling agent is 30-40:1.
8. The method for preparing the high wear-resistant and high-hardness polyvinyl chloride industrial coiled material floor as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps:
(1) Adding modified polyvinyl chloride, fluorine-containing high polymer, filler, plasticizer, modified whisker and auxiliary agent into a high-speed mixer, heating to 70-80 ℃, stirring and mixing for 20-30 minutes, adding into a double-screw extruder for extrusion granulation, crushing, and sieving to obtain granules with particle size of 20-40 meshes;
(2) The granular particles in the step (1) are added into a vacuum drying oven to be dried for 3 to 6 hours at the temperature of 85 to 98 ℃, added into a calender to be extruded into coiled materials, added into an electric heating oven, and heated and plasticized at the temperature of 180 to 220 ℃;
(3) Adding the product obtained in the step (2) into a two-way calender, and extruding and forming at 140-160 ℃;
(4) And (3) heating the surface of the product obtained in the step (3) by infrared rays at 180-220 ℃, embossing, cooling, cutting edges, carrying out surface UV treatment, and cooling and rolling again after thermal stress is eliminated to obtain the high-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor.
9. The method for preparing the high-wear-resistance high-hardness polyvinyl chloride industrial coiled material floor according to claim 8, wherein the mass percentage of each component is as follows, based on 100% of the total mass:
40-50% of modified polyvinyl chloride
5-10% Of fluorine-containing high polymer
5-10% Of plasticizer
3-5% Of modified whisker
1 To 5 percent of auxiliary agent
The balance being filler.
10. Use of a high wear resistant, high hardness polyvinyl chloride industrial coil flooring according to any one of claims 1-9 in industrial flooring.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105086323A (en) * | 2015-09-07 | 2015-11-25 | 安徽雄亚塑胶科技有限公司 | High-strength halogen-free and flame-retardant TPE (thermoplastic elastomer) cable material and preparation method thereof |
| CN108864635A (en) * | 2018-07-03 | 2018-11-23 | 合肥华盖光伏科技有限公司 | A kind of preparation method on PVC roll material floor |
| WO2020233028A1 (en) * | 2019-05-22 | 2020-11-26 | 宁波先锋新材料股份有限公司 | Flame-retardant and smoke-suppressing soft polyvinyl chloride composite material having good mechanical performance and preparation method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105086323A (en) * | 2015-09-07 | 2015-11-25 | 安徽雄亚塑胶科技有限公司 | High-strength halogen-free and flame-retardant TPE (thermoplastic elastomer) cable material and preparation method thereof |
| CN108864635A (en) * | 2018-07-03 | 2018-11-23 | 合肥华盖光伏科技有限公司 | A kind of preparation method on PVC roll material floor |
| WO2020233028A1 (en) * | 2019-05-22 | 2020-11-26 | 宁波先锋新材料股份有限公司 | Flame-retardant and smoke-suppressing soft polyvinyl chloride composite material having good mechanical performance and preparation method therefor |
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