CN110041798B - Preparation method of PVC waterproof coating - Google Patents
Preparation method of PVC waterproof coating Download PDFInfo
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- CN110041798B CN110041798B CN201910266576.5A CN201910266576A CN110041798B CN 110041798 B CN110041798 B CN 110041798B CN 201910266576 A CN201910266576 A CN 201910266576A CN 110041798 B CN110041798 B CN 110041798B
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- 238000000576 coating method Methods 0.000 title claims abstract description 69
- 239000011248 coating agent Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 151
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 151
- 239000003822 epoxy resin Substances 0.000 claims abstract description 55
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 55
- 238000003756 stirring Methods 0.000 claims abstract description 45
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 16
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004014 plasticizer Substances 0.000 claims abstract description 9
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000003607 modifier Substances 0.000 claims description 36
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- RHQDFWAXVIIEBN-UHFFFAOYSA-N Trifluoroethanol Chemical compound OCC(F)(F)F RHQDFWAXVIIEBN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 9
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 abstract description 17
- 238000004132 cross linking Methods 0.000 abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 11
- 125000003277 amino group Chemical group 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 230000003712 anti-aging effect Effects 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- 125000003700 epoxy group Chemical group 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- -1 allyl hydrogen Chemical group 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 231100000206 health hazard Toxicity 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 125000001033 ether group Chemical group 0.000 description 3
- 231100000086 high toxicity Toxicity 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000009828 non-uniform distribution Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention discloses a preparation method of a PVC waterproof coating, which comprises the following specific preparation processes: adding the prepared branched polyvinyl chloride and absolute ethyl alcohol into a stirring kettle, simultaneously adding nano titanium dioxide, a plasticizer and a defoaming agent, stirring and mixing uniformly to obtain main slurry, adding the prepared fluorinated epoxy resin powder into the main slurry, and stirring and reacting at 40-45 ℃ for 30-40min to obtain viscous slurry, namely the PVC waterproof coating. According to the invention, alkoxy grafted polyvinyl chloride and fluorinated epoxy resin are directly subjected to curing and crosslinking, so that branched polyvinyl chloride and fluorinated epoxy resin are cured and crosslinked to form a net structure, nano titanium dioxide is wrapped in the net structure, and the nano titanium dioxide can be better fixed.
Description
Technical Field
The invention belongs to the field of paint preparation, and relates to a preparation method of a PVC waterproof paint.
Background
Polyvinyl chloride has excellent acid resistance, alkali resistance and corrosion resistance, higher hydrophobic property, high mechanical property and strong electrical insulation property, and is widely applied to protection of the surface of a plate, but polyvinyl chloride begins to decompose hydrogen chloride at 150 ℃ due to poor thermal stability and light resistance, and adverse reaction occurs along with the content of a plasticizer, so that a modifier is usually added in the processing and using process to improve the thermal stability and the ageing resistance of the polyvinyl chloride.
In the existing preparation process of polyvinyl chloride coating, polyvinyl chloride is usually subjected to polymerization modification and then is subjected to melt mixing with an anti-aging agent and a heat stabilizer to prepare the coating, interfacial tension exists between the polyvinyl chloride and the modifier, so that fusion and dispersion are uneven, further influences the improved performance, so that the thermal stability and the anti-aging performance of the modified polyvinyl chloride are still lower, meanwhile, as the polyvinyl chloride can only be dissolved in solvents with higher toxicity, such as cyclohexanone, dichloroethane, tetrahydrofuran, and the like, the direct addition of these solvents in the prepared coating can cause environmental pollution and health hazards, and the polyvinyl chloride has low adhesive property and adhesion, and the prior art usually coats a layer of adhesive on the bottom layer when coating the polyvinyl chloride coating to realize the adhesion of the polyvinyl chloride coating, and the coating process is complex, and the two layers are directly coated, and the compatibility between the two layers also influences the adhesive force of the polyvinyl chloride.
Disclosure of Invention
The invention aims to provide a preparation method of a PVC waterproof coating, which is characterized in that alkoxy grafted polyvinyl chloride and fluorinated epoxy resin are directly subjected to curing and crosslinking, so that branched polyvinyl chloride and fluorinated epoxy resin are cured and crosslinked to form a net structure, nano titanium dioxide is wrapped in the net structure, and the nano titanium dioxide can be better fixed.
According to the invention, alkoxy grafted polyvinyl chloride and fluorinated epoxy resin are directly subjected to curing and crosslinking, so that branched polyvinyl chloride and fluorinated epoxy resin are cured and crosslinked to form a net structure, and further epoxy resin and polyvinyl chloride are uniformly dispersed.
According to the invention, polyvinyl chloride is polymerized with the branched graft modifier, so that a large number of ether groups, amino groups, alkoxy groups and the like are introduced into a polyvinyl chloride chain, the flexibility of the polyvinyl chloride is increased, the symmetry of the polyvinyl chloride is destroyed, the solubility of the branched polyvinyl chloride is further improved, the prepared branched polyvinyl chloride can be directly dissolved in acetone and absolute ethyl alcohol, and the problems of environmental pollution and health hazard caused by the fact that the existing polyvinyl chloride is dissolved in solvents with high toxicity such as cyclohexanone, dichloroethane, tetrahydrofuran and the like are further solved.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a PVC waterproof coating comprises the following specific preparation processes:
the first step, preparing the branched graft modifier, the specific preparation process is as follows:
adding trimethylolpropane triglycidyl ether into a reaction kettle, cooling to 5-10 ℃, dropwise adding allylamine into the reaction kettle, stirring for reaction for 3-4h, and then heating to 30-35 ℃ for reaction for 1-1.5h to obtain a colorless and transparent solution;
adding r-aminopropyltriethoxysilane into the reaction kettle in the step I, heating to 80-90 ℃, stirring, refluxing and reacting for 9-10h, then reducing the temperature to room temperature, adding ethylenediamine into the reaction kettle, performing constant-temperature reflux reaction for 4-5h, performing reduced pressure distillation on the product to obtain a branched graft modifier, wherein the reaction structural formula is shown in figure 1, 1.01-1.02mol of allylamine is added into each mole of trimethylolpropane triglycidyl ether, 1-1.02mol of r-aminopropyltriethoxysilane is added, and 1.1-1.2mol of ethylenediamine is added; because the trimethylolpropane triglycidyl ether contains three epoxy groups, the three epoxy groups can perform ring opening reaction with amino in allylamine, so that allyl is introduced into the trimethylolpropane triglycidyl ether, the addition amount of the allylamine is controlled, only one epoxy group in the trimethylolpropane triglycidyl ether performs ring opening reaction, one of the other two epoxy groups reacts with r-aminopropyltriethoxysilane, so that alkoxy is introduced into a modifier, and finally, the added ethylenediamine reacts with the other epoxy group, so that the ethylenediamine is introduced into the modifier, and amino, alkoxy and allyl are introduced into the final modifier;
secondly, adding a certain amount of polyvinyl chloride into cyclohexanone, introducing nitrogen into a reaction container for 20-30min after stirring and dissolving, then adding benzoyl peroxide into the reaction container under the protection of nitrogen, adding the branched graft modifier prepared in the first step after uniformly stirring and mixing, heating to 120 ℃ after completely dripping, reacting for 8-10h at constant temperature, and then carrying out reduced pressure distillation to recover the solvent cyclohexanone in the branched polyvinyl chloride to obtain branched polyvinyl chloride; adding 1.83-1.86g of branched grafting modifier into each gram of polyvinyl chloride, adding 0.46-0.48g of benzoyl peroxide, abstracting tertiary hydrocarbon and allyl hydrogen on the polyvinyl chloride by free radicals generated by the benzoyl peroxide, abstracting hydrogen on olefin groups in the branched grafting modifier by the free radicals generated by the benzoyl peroxide, so that free radicals are generated on a polyvinyl chloride chain and the branched grafting modifier, grafting the branched grafting modifier on the polyvinyl chloride through free radical polymerization, further introducing amino and alkoxy into monomers on the polyvinyl chloride chain, introducing a large amount of alkoxy into the polyvinyl chloride due to direct introduction of the alkoxy into the polyvinyl chloride monomer, further enabling the prepared branched polyvinyl chloride to have higher thermal stability, and simultaneously increasing the flexibility of the polyvinyl chloride due to introduction of a large amount of ether groups, amino groups, alkoxy and the like on the polyvinyl chloride chain, meanwhile, the symmetry of the polyvinyl chloride is destroyed, so that the solubility of the branched polyvinyl chloride is improved, the prepared branched polyvinyl chloride can be directly dissolved in acetone and absolute ethyl alcohol, and the problems of environmental pollution and health hazard caused by the fact that the existing polyvinyl chloride is dissolved in solvents with high toxicity, such as cyclohexanone, dichloroethane, tetrahydrofuran and the like, are solved;
thirdly, adding epoxy resin into acetone, stirring and dissolving, simultaneously adding trifluoroethanol, uniformly mixing, adding diisocyanate into the mixture at normal temperature, stirring and reacting for 5-6h, and then heating to 80-85 ℃ for evaporation to obtain fluorinated epoxy resin powder; wherein 0.032-0.035mol of trifluoroethanol is added into each gram of epoxy resin, wherein the ratio of the trifluoroethanol to the diisocyanate is 1: 1.1-1.2;
fourthly, adding the branched polyvinyl chloride and the absolute ethyl alcohol prepared in the second step into a stirring kettle, simultaneously adding the nano titanium dioxide, the plasticizer and the defoaming agent, stirring and mixing uniformly to obtain main slurry, adding the fluorinated epoxy resin powder prepared in the third step into the main slurry, and stirring and reacting at 40-45 ℃ for 30-40min to obtain viscous slurry, namely the PVC waterproof coating; when the coating is used, the main slurry and the fluorinated epoxy resin powder are prepared at the present time, the prepared PVC waterproof coating needs to be used within 8-9h at the temperature of 35 ℃, and otherwise, the PVC waterproof coating is easy to solidify and agglomerate; the branched polyvinyl chloride chain is introduced with amino groups, so that the branched polyvinyl chloride chain and epoxy groups at two ends of the fluorinated epoxy resin can perform ring-opening curing reaction, the branched polyvinyl chloride and the fluorinated epoxy resin are cured and crosslinked into a net structure, the nano titanium dioxide is wrapped in the net structure, and the nano titanium dioxide can be better fixed;
the PVC waterproof coating comprises the following raw materials in parts by weight:
57-62 parts of branched polyvinyl chloride, 63-67 parts of fluorinated epoxy resin powder, 2-3 parts of nano titanium dioxide, 3-5 parts of plasticizer, 3-5 parts of defoaming agent and 140 parts of anhydrous ethanol 130-;
and fifthly, directly coating the viscous slurry prepared in the fourth step on the surface of the plate, and curing for 20-30min at 60-65 ℃, wherein a layer of PVC waterproof film is compounded on the surface of the plate.
The invention has the beneficial effects that:
through directly carrying out solidification crosslinking effect with alkoxy grafting polyvinyl chloride and fluorinated epoxy resin, make branched polyvinyl chloride and fluorinated epoxy resin solidification crosslinking become network structure, make nanometer titanium dioxide wrap up wherein, and then can realize better fixed to nanometer titanium dioxide, evenly distributed has alkoxy and fluorine functional group on the network structure simultaneously, make the coating have even hydrophobicity, ageing resistance and heat stability, direct through the melt mixing method among the prior art has been solved, mix polyvinyl chloride and modifier, because there is interfacial tension between polyvinyl chloride and the modifier, cause to fuse dispersion inhomogeneous, and then influence the performance of improvement, make the thermal stability and the anti-aging performance of modified polyvinyl chloride still lower problem.
According to the invention, alkoxy grafted polyvinyl chloride and fluorinated epoxy resin are directly subjected to curing and crosslinking, so that branched polyvinyl chloride and fluorinated epoxy resin are cured and crosslinked to form a net structure, and further epoxy resin and polyvinyl chloride are uniformly dispersed.
According to the invention, polyvinyl chloride is polymerized with the branched graft modifier, so that a large number of ether groups, amino groups, alkoxy groups and the like are introduced into a polyvinyl chloride chain, the flexibility of the polyvinyl chloride is increased, the symmetry of the polyvinyl chloride is destroyed, the solubility of the branched polyvinyl chloride is further improved, the prepared branched polyvinyl chloride can be directly dissolved in acetone and absolute ethyl alcohol, and the problems of environmental pollution and health hazard caused by the fact that the existing polyvinyl chloride is dissolved in solvents with high toxicity such as cyclohexanone, dichloroethane, tetrahydrofuran and the like are further solved.
Drawings
In order to facilitate understanding for those skilled in the art, the present invention will be further described with reference to the accompanying drawings.
FIG. 1 is a reaction formula of a branched graft modifier according to the present invention;
FIG. 2 is a reaction scheme of branched polyvinyl chloride of the present invention;
FIG. 3 is a structural formula of the curing reaction of the waterproof coating of the present invention;
FIG. 4 is a partial structural formula of FIG. 3;
FIG. 5 is a partial structural formula of FIG. 3.
Detailed Description
Referring to FIGS. 1-5, the following embodiments are illustrated in detail:
example 1:
the branched graft modifier is prepared by the following specific steps:
adding 3.02kg of trimethylolpropane triglycidyl ether into a reaction kettle, cooling to 5-10 ℃, dropwise adding 0.57kg of allylamine into the reaction kettle, stirring for reaction for 3-4h, heating to 30-35 ℃, and reacting for 1-1.5h to obtain a colorless and transparent solution;
adding 2.21 kgr-aminopropyltriethoxysilane into the reaction kettle in the step I, heating to 80-90 ℃, stirring, refluxing and reacting for 9-10h, then reducing the temperature to room temperature, adding 0.66kg ethylenediamine into the reaction kettle, refluxing and reacting for 4-5h at constant temperature, and distilling the product under reduced pressure to obtain the branched grafting modifier.
Example 2:
the branched graft modifier is prepared by the following specific steps:
adding 3.02kg of trimethylolpropane triglycidyl ether into a reaction kettle, cooling to 5-10 ℃, dropwise adding 0.57kg of allylamine into the reaction kettle, stirring for reaction for 3-4h, heating to 30-35 ℃, and reacting for 1-1.5h to obtain a colorless and transparent solution;
adding 1.77 kgr-aminopropyltriethoxysilane into the reaction kettle in the step I, heating to 80-90 ℃, stirring, refluxing and reacting for 9-10h, then reducing the temperature to room temperature, adding 0.78kg ethylenediamine into the reaction kettle, refluxing and reacting for 4-5h at constant temperature, and distilling the product under reduced pressure to obtain the branched grafting modifier.
Example 3:
the branched graft modifier is prepared by the following specific steps:
adding 3.02kg of trimethylolpropane triglycidyl ether into a reaction kettle, cooling to 5-10 ℃, dropwise adding 0.57kg of allylamine into the reaction kettle, stirring for reaction for 3-4h, heating to 30-35 ℃, and reacting for 1-1.5h to obtain a colorless and transparent solution;
adding 2.43 kgr-aminopropyltriethoxysilane into the reaction kettle in the step I, heating to 80-90 ℃, stirring, refluxing and reacting for 9-10h, then reducing the temperature to room temperature, adding 0.66kg ethylenediamine into the reaction kettle, refluxing and reacting for 4-5h at constant temperature, and distilling the product under reduced pressure to obtain the branched grafting modifier.
Example 4:
a preparation method of a PVC waterproof coating comprises the following specific preparation processes:
adding 1kg of polyvinyl chloride into 15L of cyclohexanone, stirring for dissolving, introducing nitrogen into a reaction container for 20-30min, then adding 0.46kg of benzoyl peroxide into the reaction container under the protection of nitrogen, stirring and mixing uniformly, adding 1.83kg of the branched grafting modifier prepared in the example 1, heating to 120 ℃ after complete dropwise addition, reacting for 8-10h at constant temperature, and then carrying out reduced pressure distillation to recover the solvent cyclohexanone in the branched polyvinyl chloride to obtain the branched polyvinyl chloride;
secondly, adding 1kg of E44 type epoxy resin into 10L of acetone, stirring and dissolving, simultaneously adding 3.2kg of trifluoroethanol, uniformly mixing, adding 6.12kg of toluene diisocyanate into the mixture at normal temperature, stirring and reacting for 5-6h, and then heating to 80-85 ℃ for evaporation to obtain fluorinated epoxy resin powder;
adding 5.7kg of branched polyvinyl chloride prepared in the first step and 13kg of absolute ethyl alcohol into a stirring kettle, simultaneously adding 0.2kg of nano titanium dioxide, 0.3kg of plasticizer and 0.3kg of defoaming agent, uniformly stirring and mixing to obtain main slurry, adding 6.3kg of fluorinated epoxy resin powder prepared in the second step into the main slurry, and stirring and reacting at 40-45 ℃ for 30-40min to obtain viscous slurry, namely the PVC waterproof coating; when the coating is used, the main slurry and the fluorinated epoxy resin powder are prepared at the present time, the prepared PVC waterproof coating needs to be used within 8-9h at the temperature of 35 ℃, and otherwise, the PVC waterproof coating is easy to solidify and agglomerate;
and fourthly, directly coating the viscous slurry prepared in the third step on the surface of the plate, and curing for 20-30min at the temperature of 60-65 ℃, wherein a layer of PVC waterproof film is compounded on the surface of the plate.
Example 5:
a PVC waterproof coating was prepared in the same manner as in example 4 except that the branched graft modifier prepared in example 1 and added in the first step of example 4 was replaced with the branched graft modifier prepared in example 2.
Example 6:
a PVC waterproof coating was prepared in the same manner as in example 4 except that the branched graft modifier prepared in example 1 and added in the first step of example 4 was replaced with the branched graft modifier prepared in example 3.
Example 7:
a PVC waterproof coating was prepared in the same manner as in example 4 except that the branched graft modifier prepared in example 1 and added in the first step of example 4 was replaced with gamma- (methacryloyloxy) propyl trimethoxysilane.
Example 8:
a PVC waterproof coating was prepared in the same manner as in example 4 except that the amount of the fluorinated epoxy resin added in the third step in example 4 was changed to 5.2 kg.
Example 9:
a preparation method of a PVC waterproof coating comprises the following specific preparation processes:
adding 1kg of polyvinyl chloride into 15L of cyclohexanone, introducing nitrogen into a reaction container for 20-30min after stirring and dissolving, then adding 0.46kg of benzoyl peroxide into the reaction container under the protection of nitrogen, adding 1.83kg of gamma- (methacryloyloxy) propyl trimethoxy silane after uniformly stirring and mixing, heating to 120 ℃ after completely dropwise adding, reacting for 8-10h at constant temperature, and then carrying out reduced pressure distillation to recover the solvent cyclohexanone in the mixture to obtain branched polyvinyl chloride;
secondly, adding 5.7kg of branched polyvinyl chloride prepared in the first step and 13kg of absolute ethyl alcohol into a stirring kettle, simultaneously adding 0.2kg of nano titanium dioxide, 0.3kg of plasticizer and 0.3kg of defoaming agent, uniformly stirring and mixing to obtain main slurry, adding 6.3kg of epoxy resin and 18.2kg of trifluoroethanol into the main slurry, and stirring and reacting at 40-45 ℃ for 30-40min to obtain viscous slurry, namely the PVC waterproof coating; when the coating is used, the main slurry and the fluorinated epoxy resin powder are prepared at the present time, the prepared PVC waterproof coating needs to be used within 8-9h at the temperature of 35 ℃, and otherwise, the PVC waterproof coating is easy to solidify and agglomerate;
and step three, directly coating the viscous slurry prepared in the step two on the surface of the plate, and curing for 20-30min at the temperature of 60-65 ℃, wherein a layer of PVC waterproof membrane is compounded on the surface of the plate.
Example 10:
a preparation method of a PVC waterproof coating comprises the following specific preparation processes:
adding 1kg of polyvinyl chloride into 15L of cyclohexanone, introducing nitrogen into a reaction container for 20-30min after stirring and dissolving, then adding 0.46kg of benzoyl peroxide into the reaction container under the protection of nitrogen, adding 1.83kg of gamma- (methacryloyloxy) propyl trimethoxy silane after uniformly stirring and mixing, heating to 120 ℃ after completely dropwise adding, reacting for 8-10h at constant temperature, and then carrying out reduced pressure distillation to recover the solvent cyclohexanone in the mixture to obtain branched polyvinyl chloride;
secondly, adding 5.7kg of branched polyvinyl chloride prepared in the first step and 13kg of absolute ethyl alcohol into a stirring kettle, simultaneously adding 0.2kg of nano titanium dioxide, 0.3kg of plasticizer and 0.3kg of defoamer into the stirring kettle, stirring and mixing uniformly to obtain main slurry, adding 18.2kg of trifluoroethanol into the main slurry, and stirring and reacting for 30-40min at 40-45 ℃ to obtain the waterproof coating;
and step three, directly coating the viscous slurry prepared in the step three on the surface of the plate, and curing for 20-22h at the temperature of 60-65 ℃, wherein a layer of PVC waterproof membrane is compounded on the surface of the plate.
Example 11:
the plates of examples 4 to 10, on which a layer of PVC waterproof film was laminated on the surface, were simultaneously irradiated under the same ultraviolet light for 100h, 150h, 200h, and 250h, and then the change of the waterproof film surface was observed, with the results shown in table 1:
TABLE 1 degree of chalking of PVC waterproof film surface under different UV irradiation in examples 4-10
As can be seen from Table 1, the PVC waterproof films prepared in examples 4 and 5 have high aging resistance, and no chalking occurs after the ultraviolet light irradiation for 300 h; in example 6, the branched graft modifier used in the preparation process of the branched polyvinyl chloride contains a large amount of r-aminopropyltriethoxysilane, which causes a decrease in the content of amino groups grafted on trimethylolpropane triglycidyl ether, and further causes a decrease in the content of amino groups on branched polyvinyl chloride chains, and when the branched polyvinyl chloride and the fluorinated epoxy resin are crosslinked and cured, the fluorinated epoxy resin crosslinked between the branched polyvinyl chloride chains is decreased, and further causes the unfluorinated epoxy resin to be dispersed between the coatings, so that the fluorinated epoxy resin in the prepared coating is not uniformly dispersed, and further causes a non-uniform distribution of fluorine elements in the coating, and the anti-aging capability of the coating is reduced; meanwhile, in the embodiment 7, the branched polyvinyl chloride is directly polymerized with the gamma- (methacryloyloxy) propyl trimethoxy silane, so that no amino group exists on the chain of the prepared branched polyethylene, and the prepared branched polyethylene cannot be crosslinked and fixed with the fluorinated epoxy resin, so that the fluorinated epoxy resin and the branched polyethylene cannot be uniformly dispersed, fluorine is not uniformly dispersed, and the anti-aging capability of the branched polyvinyl chloride is reduced; the content of fluorine in the coating is reduced and the anti-aging capability of the coating is reduced due to the fact that the adding amount of the fluorinated epoxy resin is reduced in the embodiment 8, meanwhile, trifluoroethanol is directly added into the coating in the preparation process of the coating in the embodiments 9 and 10, and due to the fact that the trifluoroethanol is poor in compatibility with branched polyvinyl chloride and epoxy resin, the trifluoroethanol cannot be uniformly dispersed in the coating, and the anti-aging performance of the coating is greatly reduced.
Example 12:
the plate with the surface compounded with the PVC waterproof film in examples 4-10 was placed in a constant temperature and humidity cabinet at 25 ℃ and humidity of 75% for one week, and according to the standard of GB4893.4-85, an adhesion test was performed with a multi-purpose dry film tester for paint film adhesion, the peeling condition of the paint film was observed under a microscope, the number of the peeling grids of the paint film at the intersection of the cutting marks was counted, and the peeling rate of the paint film was calculated as the number of the peeling grids of the paint film/the number of all the cutting grids, and the results are shown in table 2:
TABLE 2 adhesion measurement results of PVC composite films prepared on the surfaces of the sheets in examples 4 to 10
As can be seen from table 2, the PVC composite films prepared in examples 4 and 5 have strong adhesion and are difficult to peel off, the fluorinated epoxy resin and the branched polyvinyl chloride are cross-cured to form a network structure, the epoxy resin is uniformly dispersed in the coating, and the epoxy resin has high adhesion, so that the prepared PVC film has uniform adhesion and strong adhesion on the plate and is not easy to peel off; however, in the preparation process of the branched graft modifier used in the preparation process of the branched polyvinyl chloride in example 6, the content of the added r-aminopropyltriethoxysilane is high, so that the content of the amino group grafted on the trimethylolpropane triglycidyl ether is reduced, the content of the amino group on the branched polyvinyl chloride chain is reduced, the crosslinking curing amount of the branched polyvinyl chloride and the fluorinated epoxy resin is reduced, and the network structure formed after crosslinking is not compact, so that the adhesion strength is reduced; meanwhile, in the embodiment 7 and the embodiment 9, since the branched polyvinyl chloride and the epoxy resin cannot be directly cured and crosslinked, and are directly dispersed in the coating, the adhesion property of the branched polyvinyl chloride is poor, and the adhesion capability of the epoxy resin is strong, so that the adhesion force is not uniform, and thus the local part of the coating is easy to peel off, meanwhile, in the embodiment 8, since the content of the epoxy resin is reduced, the adhesion force of the coating is reduced, and when the epoxy resin is not added, the adhesion force of the branched polyvinyl chloride is low, and the peeling is easy to occur.
Example 13:
the PVC coated plates and the PVC uncoated plates of examples 4 to 10 were weighed to have masses of M0 and N0, respectively, and then both plates were immersed in water for 5 days at the same time, after which the surfaces of both plates were wiped dry and then weighed to have masses of M1 and N1, respectively, and then the water absorption rates of the PVC composite films [ (M1-N1) - (M0-NO) ]/(M0-NO)%, the measurement results were as shown in table 3:
table 3 water absorption test results of PVC composite films prepared in examples 4 to 10
As can be seen from table 3, the PVC composite films prepared in examples 4, 8 and 10 have a low water absorption, and since the fluorinated epoxy resin and the branched polyvinyl chloride in example 4 are cross-cured to form a network structure, the branched polyvinyl chloride has a high hydrophobic property, and meanwhile, a large number of alkoxy groups are grafted on the branched polyvinyl chloride, and the branched polyvinyl chloride has a hydrophobic property, and the fluorine element grafted on the epoxy resin also has a certain hydrophobic property, the prepared coating has a high hydrophobic property, and the network dense hydrophobic structure formed by the branched polyvinyl chloride and the fluorinated epoxy resin makes the water absorption of the coating low; in the embodiment 5, the content of the introduced r-aminopropyltriethoxysilane is low, so that the content of alkoxy in the coating is reduced, and the hydrophobic property of the coating is reduced; meanwhile, in the embodiment 7 and the embodiment 9, the polyvinyl chloride is directly grafted with the gamma- (methacryloyloxy) propyl trimethoxy silane, so that the polyvinyl chloride grafted on the child and the epoxy resin are not crosslinked, a network structure is not formed in the coating, and the branched polyvinyl chloride and the fluorinated epoxy resin are not uniformly distributed, so that the hydrophobic property of the part of the coating is reduced.
Example 14:
the plates compounded with the PVC composite films of examples 4 to 10 were respectively placed in ovens of 85 ℃, 90 ℃, 100 ℃ and 120 ℃ and baked for 5min, and then the morphology of the PVC composite film was observed, and the results are shown in table 4:
TABLE 4 examples 4-10 changes in morphology of PVC composite films on sheet surfaces after baking in ovens at 85 deg.C, 90 deg.C, 100 deg.C and 120 deg.C for 5min
As can be seen from table 4, the coating films prepared in examples 4 and 6 are not changed at 120 ℃ and are slightly softened at 160 ℃, while in example 5, the content of r-aminopropyltriethoxysilane introduced into the graft modifier is low, so that the content of alkoxy groups in the coating material is reduced, so that the thermal stability of branched polyvinyl chloride is reduced, and the surface of the coating film is slightly softened at 90 ℃, and meanwhile, in examples 7, 9 and 10, the branched polyvinyl chloride is not crosslinked with epoxy resin, so that the branched polyvinyl chloride cannot be uniformly dispersed in the coating material, so that the dispersion of siloxane in the coating material is not uniform, and the thermal stability is reduced.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (1)
1. The preparation method of the PVC waterproof coating is characterized in that the PVC waterproof coating comprises the following raw materials in parts by weight: 57-62 parts of branched polyvinyl chloride, 63-67 parts of fluorinated epoxy resin powder, 2-3 parts of nano titanium dioxide, 3-5 parts of plasticizer, 3-5 parts of defoaming agent and 140 parts of anhydrous ethanol 130-;
the preparation process comprises the following steps:
firstly, adding a certain amount of polyvinyl chloride into cyclohexanone, introducing nitrogen into a reaction container for 20-30min after stirring and dissolving, then adding benzoyl peroxide into the reaction container under the protection of nitrogen, adding a branched grafting modifier into the mixture after stirring and mixing uniformly, heating to 120 ℃ after completely dripping, reacting for 8-10h at constant temperature, and then carrying out reduced pressure distillation to recover the solvent cyclohexanone in the mixture to obtain branched polyvinyl chloride; in the first step, 1.83 to 1.86g of branched grafting modifier and 0.46 to 0.48g of benzoyl peroxide are added into each gram of polyvinyl chloride;
secondly, adding epoxy resin into acetone, stirring and dissolving, adding trifluoroethanol, uniformly mixing, adding diisocyanate into the mixture at normal temperature, stirring and reacting for 5-6h, and then heating to 80-85 ℃ for evaporation to obtain fluorinated epoxy resin powder; in the second step, 0.032-0.035mol of trifluoroethanol is added into each gram of epoxy resin, wherein the ratio of the trifluoroethanol to the diisocyanate is 1: 1.1-1.2;
thirdly, adding the branched polyvinyl chloride and the absolute ethyl alcohol prepared in the first step into a stirring kettle, simultaneously adding the nano titanium dioxide, the plasticizer and the defoaming agent, stirring and mixing uniformly to obtain main slurry, adding the fluorinated epoxy resin powder prepared in the second step into the main slurry, and stirring and reacting for 30-40min at 40-45 ℃ to obtain viscous slurry, namely the PVC waterproof coating;
step four, directly coating the viscous slurry prepared in the step three on the surface of the plate, and curing for 20-30min at the temperature of 60-65 ℃, wherein a layer of PVC waterproof film is compounded on the surface of the plate;
the branched graft modifier is prepared by the following specific steps:
adding trimethylolpropane triglycidyl ether into a reaction kettle, cooling to 5-10 ℃, dropwise adding allylamine into the reaction kettle, stirring for reaction for 3-4h, and then heating to 30-35 ℃ for reaction for 1-1.5h to obtain a colorless and transparent solution;
adding r-aminopropyltriethoxysilane into the reaction kettle in the step I, heating to 80-90 ℃, stirring, refluxing and reacting for 9-10h, then reducing the temperature to room temperature, adding ethylenediamine into the reaction kettle, refluxing and reacting for 4-5h at constant temperature, and distilling the product under reduced pressure to obtain a branched grafting modifier;
1.01-1.02mol of allylamine, 1-1.02mol of r-aminopropyltriethoxysilane and 1.1-1.2mol of ethylenediamine are added into each mol of trimethylolpropane triglycidyl ether.
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