CN117625031B - Preparation method of wear-resistant corrosion-resistant polyurethane self-leveling floor coating - Google Patents
Preparation method of wear-resistant corrosion-resistant polyurethane self-leveling floor coating Download PDFInfo
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 52
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 51
- 238000005260 corrosion Methods 0.000 title claims abstract description 23
- 230000007797 corrosion Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000576 coating method Methods 0.000 title claims description 28
- 239000011248 coating agent Substances 0.000 title claims description 27
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000005011 phenolic resin Substances 0.000 claims abstract description 51
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 51
- 239000003607 modifier Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 239000000945 filler Substances 0.000 claims abstract description 13
- 229920005862 polyol Polymers 0.000 claims abstract description 13
- 150000003077 polyols Chemical class 0.000 claims abstract description 13
- 239000013530 defoamer Substances 0.000 claims abstract description 11
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- 239000000049 pigment Substances 0.000 claims abstract description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 45
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 10
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 7
- FMDGXCSMDZMDHZ-UHFFFAOYSA-N 1-isocyanato-4-methoxybenzene Chemical compound COC1=CC=C(N=C=O)C=C1 FMDGXCSMDZMDHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- QPQDOIAJMPGRCZ-UHFFFAOYSA-N anisole;isocyanic acid Chemical compound N=C=O.COC1=CC=CC=C1 QPQDOIAJMPGRCZ-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- 230000003993 interaction Effects 0.000 abstract description 7
- 239000003973 paint Substances 0.000 abstract description 6
- 238000005187 foaming Methods 0.000 description 15
- 238000005336 cracking Methods 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 238000004132 cross linking Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 239000002313 adhesive film Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 5
- 239000011527 polyurethane coating Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920006264 polyurethane film Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- QRBHVARIMDDOOV-UHFFFAOYSA-N 1-(isocyanatomethyl)-4-methoxybenzene Chemical compound COC1=CC=C(CN=C=O)C=C1 QRBHVARIMDDOOV-UHFFFAOYSA-N 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010520 demethylation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000015784 hyperosmotic salinity response Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 229920003226 polyurethane urea Polymers 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
The invention relates to the technical field of paint, and discloses a preparation method of wear-resistant corrosion-resistant polyurethane self-leveling floor paint, which comprises the following components: 36-45 parts of polyol, 0.5-4 parts of organosilicon phenolic resin modifier, 0.4-0.8 part of defoamer, 0.3-0.6 part of flatting agent, 0.2-0.6 part of dispersing agent, 20-28 parts of filler and 3-6 parts of pigment. And the component B comprises the following components: 6-9 parts of isocyanate curing agent. Grafting the organic silicon phenolic resin into polyurethane molecular chains, wherein the urethane bond in the organic silicon phenolic resin can form hydrogen bond interaction with the urethane bond in polyurethane, so that the compatibility between the organic silicon phenolic resin and the polyurethane molecular chains is further improved; the corrosion resistance, the water resistance, the wear resistance, the impact resistance and the hardness of polyurethane are improved.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a preparation method of a wear-resistant corrosion-resistant polyurethane self-leveling floor coating.
Background
Polyurethane has good strength, elasticity and film forming property, and is widely applied to the aspects of floor coating, wood lacquer and the like; the existing polyurethane floor coating is mainly of an organic solvent type, a water solvent type and a solvent-free type; compared with the organic solvent type, the water solvent type and solvent-free type water-soluble organic solvent has the advantages of low VOC, environmental protection and the like. And the traditional polyurethane floor coating has the defects of poor wear resistance, corrosion resistance, poor water resistance and the like.
Phenolic resin has good mechanical strength, heat resistance, corrosion resistance, wear resistance and other properties, and has wide application in the field of paint, and patent publication No. CN109705718B discloses that phenolic resin, halogenated polyether polyol, isocyanate and the like are used as raw materials to prepare phenolic resin modified polyurethane/polyurea paint, so that the acid and alkali resistance, heat resistance and flame resistance of the paint are enhanced, but the wear resistance, impact resistance, hardness and other properties of the paint are not improved.
The organosilicon polymer has excellent flexibility, wear resistance, water resistance, acid and alkali resistance and other properties, and is a functional material; the organic silicon phenolic resin modifier prepared by the invention improves the performances of wear resistance, corrosion resistance and the like of the polyurethane self-leveling floor coating.
Disclosure of Invention
The technical problems to be solved are as follows: aiming at the defects of the prior art, the invention provides a solvent-free polyurethane self-leveling floor coating, which solves the problems of poor wear resistance, corrosion resistance and the like of the polyurethane floor coating.
The technical scheme is as follows: wear-resistant corrosion-resistant polyurethane self-leveling floor coating: the composite material consists of a component A and a component B;
the component A comprises the following components in parts by weight: 36-45 parts of polyalcohol, 0.5-4 parts of organosilicon phenolic resin modifier, 0.4-0.8 part of defoamer, 0.3-0.6 part of flatting agent, 0.2-0.6 part of dispersing agent, 20-28 parts of filler and 3-6 parts of pigment; the component B comprises 6-9 parts of isocyanate curing agent;
the organosilicon phenolic resin modifier is prepared from phenol, phenolic hydroxyl organosilicon monomers and formaldehyde through polymerization reaction; the structural formula of the phenolic hydroxyl organosilicon monomer is as follows:
；
the preparation method of the polyurethane self-leveling floor coating comprises the following steps: and uniformly mixing the polyol, the organosilicon phenolic resin modifier, the defoamer, the flatting agent, the dispersing agent, the filler and the pigment to obtain a component A, and uniformly mixing the component A and the component B to obtain the polyurethane self-leveling floor coating.
Wherein the filler is any one of barium sulfate, diatomite and wollastonite.
Wherein the isocyanate curing agent comprises diphenylmethane diisocyanate and aliphatic polyisocyanate.
The preparation process of the phenolic hydroxyl organosilicon monomer comprises the following steps: adding a reaction solvent, 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyl disiloxane and p-methoxy phenyl isocyanate into a reaction container containing a condensing reflux pipe, heating to 65-100 ℃, reacting for 6-18h, concentrating under reduced pressure, and washing with petroleum ether to obtain an intermediate; then adding pyridine hydrochloride into a new reaction container, heating to 155-160 ℃ for melting, adding an intermediate, stirring uniformly, heating to 200-210 ℃, reacting for 2-5h, cooling, adding water and dichloromethane, extracting and separating, and concentrating an organic phase under reduced pressure to obtain the phenolic hydroxyl organosilicon monomer. The reaction formula is as follows:
wherein the reaction solvent is any one of tetrahydrofuran, 1, 4-dioxane and toluene.
Wherein the mass of the p-methoxybenzene isocyanate is 115-140% of the mass of the 1, 3-di (3-hydroxypropyl) -1, 3-tetramethyl disiloxane.
The preparation process of the organosilicon phenolic resin modifier comprises the following steps: adding phenol, phenolic hydroxyl organic silicon monomer and sodium hydroxide into a reaction container containing a condensation reflux pipe, heating to 40-55 ℃, stirring for 20-40min, adding formaldehyde aqueous solution, heating to 85-95 ℃, carrying out polymerization for 15-30min, adding formaldehyde aqueous solution, continuing to react for 1-1.5h, cooling, washing with water, drying and crushing to obtain the organic silicon phenolic resin modifier.
Wherein the mass of the phenolic hydroxyl organosilicon monomer and the mass of the sodium hydroxide are respectively 12-40% and 3.5-4.8% of the mass of the phenol.
The technical effects are as follows: the invention utilizes 1, 3-di (3-hydroxypropyl) -1, 3-tetramethyl disiloxane and p-methoxy benzene isocyanate to carry out addition reaction and demethylation reaction to prepare phenolic hydroxyl organic silicon monomer, then carries out polymerization reaction with phenol and formaldehyde to obtain organic silicon phenolic resin modifier, then mixes with polyalcohol, auxiliary agents such as defoamer and the like and fillers such as wollastonite to obtain component A, and mixes with component B of isocyanate curing agent containing diphenylmethane diisocyanate and aliphatic polyisocyanate to obtain the solvent-free wear-resistant corrosion-resistant polyurethane self-leveling floor coating.
The organosilicon phenolic resin modifier can carry out crosslinking curing reaction with polyalcohol and isocyanate curing agent in the component B, thereby grafting the organosilicon phenolic resin into polyurethane molecular chains, enhancing the interfacial force between the organosilicon phenolic resin and polyurethane, and improving the urethane bond in the organosilicon phenolic resin) Can form hydrogen bond interaction with urethane bond in polyurethane, so that the urethane bond and the urethane bond form chemical bond crosslinking and hydrogen bond interaction, and the compatibility between the urethane bond and the hydrogen bond is further improved; the phenolic resin has good water resistance, and simultaneously, the functional organic silicon structure is introduced into the phenolic resin to graft and modify polyurethane, so that the salt water resistance and alkali resistance of the polyurethane coating adhesive film are improved, and the polyurethane coating adhesive film has good corrosion resistance and water resistance. Meanwhile, the organosiloxane structure has the characteristics of high wear resistance and good flexibility; the phenolic resin has the advantages of high wear resistance, high strength and the like, and meanwhile, the organosilicon phenolic resin modifier and the polyurethane have chemical bond crosslinking and hydrogen bond interaction to form an interpenetrating double crosslinking network, so that the organosilicon phenolic resin modifier remarkably improves the wear resistance, impact resistance and hardness of the polyurethane.
Detailed Description
The main raw materials of the invention are as follows:
polyol: polyether polyol, brand PM200.
Defoaming agent: brand STA-6800A
Leveling agent: brand BYK346.
Dispersing agent: brand BYK-2155.
1, 3-Bis (3-hydroxypropyl) -1, 3-tetramethyldisiloxane: CAS number 18001-97-3.
P-methoxybenzyl isocyanate: CAS number 5416-93-3.
Diphenylmethane diisocyanate: CAS number 101-68-8.
Aliphatic polyisocyanates: brand HT-100.
Example 1
(1) 10ML of toluene solvent, 0.4g of 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyl disiloxane and 0.56g of p-methoxy phenyl isocyanate are added into a reaction vessel containing a condensing reflux pipe, and the mixture is heated to 100 ℃ for reaction for 6 hours, concentrated under reduced pressure and washed by petroleum ether to obtain an intermediate; then adding 3.5g of pyridine hydrochloride into a new reaction vessel, heating to 160 ℃ for melting, adding the intermediate, stirring uniformly, heating to 200 ℃, reacting for 5 hours, cooling, adding water and dichloromethane, extracting and separating, and concentrating an organic phase under reduced pressure to obtain the phenolic hydroxyl organosilicon monomer.
(2) Adding 2g of phenol, 0.24g of phenolic hydroxyl organic silicon monomer and 70mg of sodium hydroxide into a reaction vessel containing a condensation reflux pipe, heating to 50 ℃, stirring for 40min, then adding 0.8mL of 37% formaldehyde aqueous solution by mass fraction, heating to 95 ℃, carrying out polymerization for 15min, adding 1.4mL of formaldehyde aqueous solution, continuing to react for 1h, cooling, washing, drying and crushing to obtain the organic silicon phenolic resin modifier.
(3) Uniformly mixing 36g of polyol, 0.5g of organosilicon phenolic resin modifier, 0.6g of defoamer, 0.5g of flatting agent, 0.2g of dispersing agent, 20g of filler barium sulfate and 6g of pigment titanium dioxide to obtain a component A; 0.8g of diphenylmethane diisocyanate and 7.5g of aliphatic polyisocyanate were uniformly mixed to obtain a component B. And uniformly mixing the component A and the component B to obtain the solvent-free wear-resistant corrosion-resistant polyurethane self-leveling floor coating.
Example 2
(1) 10ML of 1, 4-dioxane solvent, 0.4g of 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyl disiloxane and 0.46g of p-methoxy-phenyl isocyanate are added into a reaction vessel containing a condensing reflux pipe, the mixture is heated to 100 ℃ to react for 18 hours, and the mixture is concentrated under reduced pressure and washed by petroleum ether to obtain an intermediate; then adding 5g of pyridine hydrochloride into a new reaction vessel, heating to 160 ℃ for melting, adding the intermediate, stirring uniformly, heating to 210 ℃, reacting for 2 hours, cooling, adding water and dichloromethane, extracting and separating, and concentrating an organic phase under reduced pressure to obtain the phenolic hydroxyl organosilicon monomer.
(2) Adding 2g of phenol, 0.56g of phenolic hydroxyl organic silicon monomer and 85mg of sodium hydroxide into a reaction vessel containing a condensation reflux pipe, heating to 40 ℃, stirring for 40min, then adding 0.8mL of 37% formaldehyde aqueous solution by mass fraction, heating to 90 ℃, carrying out polymerization for 30min, adding 1.6mL of formaldehyde aqueous solution, continuing to react for 1.5h, cooling, washing, drying and crushing to obtain the organic silicon phenolic resin modifier.
(3) Uniformly mixing 40g of polyol, 2g of organosilicon phenolic resin modifier, 0.8g of defoamer, 0.3g of flatting agent, 0.4g of dispersing agent, 25g of filler diatomite and 4g of pigment titanium dioxide to obtain a component A; 1g of diphenylmethane diisocyanate and 6.5g of aliphatic polyisocyanate were uniformly mixed to obtain a component B. And uniformly mixing the component A and the component B to obtain the solvent-free wear-resistant corrosion-resistant polyurethane self-leveling floor coating.
Example 3
(1) Adding 5mL of tetrahydrofuran solvent, 0.4g of 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyl disiloxane and 0.46g of p-methoxy phenyl isocyanate into a reaction vessel containing a condensing reflux pipe, heating to 65 ℃, reacting for 18h, concentrating under reduced pressure, and washing with petroleum ether to obtain an intermediate; then adding 5g of pyridine hydrochloride into a new reaction vessel, heating to 155 ℃ for melting, adding the intermediate, stirring uniformly, heating to 210 ℃, reacting for 3 hours, cooling, adding water and dichloromethane, extracting and separating, and concentrating an organic phase under reduced pressure to obtain the phenolic hydroxyl organosilicon monomer.
(2) Adding 2g of phenol, 0.8g of phenolic hydroxyl organic silicon monomer and 96mg of sodium hydroxide into a reaction vessel containing a condensation reflux pipe, heating to 55 ℃, stirring for 20min, then adding 0.8mL of 37% formaldehyde aqueous solution with mass fraction, heating to 85 ℃, carrying out polymerization for 30min, adding 1.9mL of formaldehyde aqueous solution, continuing to react for 1.5h, cooling, washing, drying and crushing to obtain the organic silicon phenolic resin modifier.
(3) Uniformly mixing 45g of polyol, 4g of organosilicon phenolic resin modifier, 0.4g of defoamer, 0.6g of flatting agent, 0.2g of dispersing agent, 28g of filler wollastonite and 3g of pigment titanium dioxide to obtain a component A; 1.5g of diphenylmethane diisocyanate and 7.5g of aliphatic polyisocyanate were uniformly mixed to obtain a component B. And uniformly mixing the component A and the component B to obtain the solvent-free wear-resistant corrosion-resistant polyurethane self-leveling floor coating.
Comparative example 1
The difference from example 1 is that the A-component is free of the addition of a silicone phenolic resin modifier.
Uniformly mixing 36g of polyol, 0.6g of defoamer, 0.5g of flatting agent, 0.2g of dispersing agent, 20g of filler barium sulfate and 6g of pigment titanium dioxide to obtain a component A; 0.8g of diphenylmethane diisocyanate and 7.5g of aliphatic polyisocyanate were uniformly mixed to obtain a component B. And uniformly mixing the component A and the component B to obtain the solvent-free polyurethane self-leveling floor coating.
Comparative example 2
The difference from example 1 is that no phenolic hydroxyl silicone monomer was added in the preparation of the silicone phenolic resin modifier.
(1) Adding 2g of phenol and 70mg of sodium hydroxide into a reaction vessel containing a condensing reflux pipe, heating to 50 ℃, stirring for 40min, then adding 0.8mL of 37% formaldehyde aqueous solution by mass fraction, heating to 95 ℃, carrying out polymerization for 15min, adding 1.4mL of formaldehyde aqueous solution, continuing to react for 1h, cooling, washing with water, drying and crushing to obtain the phenolic resin.
(2) Uniformly mixing 36g of polyol, 0.5g of phenolic resin, 0.6g of defoamer, 0.5g of flatting agent, 0.2g of dispersing agent, 20g of filler barium sulfate and 6g of pigment titanium dioxide to obtain a component A; 0.8g of diphenylmethane diisocyanate and 7.5g of aliphatic polyisocyanate were uniformly mixed to obtain a component B. And uniformly mixing the component A and the component B to obtain the solvent-free polyurethane self-leveling floor coating.
Performance test of polyurethane self-leveling floor coating: and uniformly mixing the component A and the component B, pouring into a die, scraping the surface of the mixed material with a scraper, and curing for 12 hours at 60 ℃ to obtain the polyurethane adhesive film.
The salt water resistance and alkali resistance of the polyurethane adhesive film are tested according to the method of GB/T9274-1988.
The water resistance of the polyurethane film was tested according to the method of GB/T1733-1993.
TABLE 1 polyurethane film Performance test
| Salt tolerance (3% NaCl solution, 360 h) | Alkali resistance (20% NaOH solution, 120 h) | Water resistance (360 h) | |
| Example 1 | No foaming, no cracking and no falling off | No foaming, no cracking and no falling off | No foaming, no cracking and no falling off |
| Example 2 | No foaming, no cracking and no falling off | No foaming, no cracking and no falling off | No foaming, no cracking and no falling off |
| Example 3 | No foaming, no cracking and no falling off | No foaming, no cracking and no falling off | No foaming, no cracking and no falling off |
| Comparative example 1 | Foaming, cracking, no falling off | Foaming, cracking, obvious falling off | Foaming, cracking, no falling off |
| Comparative example 2 | Foaming, cracking, no falling off | Foaming, cracking, no falling off | Foaming, no crack and no falling off |
Examples 1 to 3 add a silicone phenolic resin modifier containing hydroxyl groups which can undergo a crosslinking curing reaction with a polyol and an isocyanate curing agent in the B component, thereby grafting the silicone phenolic resin into the polyurethane molecular chain, enhancing the interfacial force between the silicone phenolic resin and the polyurethane, and urethane bonds in the silicone phenolic resin) Can form hydrogen bond interaction with urethane bond in polyurethane, and has chemical bond crosslinking and hydrogen bond interaction, so that the compatibility between the two is further improved; the phenolic resin has good water resistance, and simultaneously, the functional organic silicon structure is introduced into the phenolic resin to graft and modify polyurethane, so that the salt water resistance and alkali resistance of the polyurethane coating adhesive film are improved, and the polyurethane coating adhesive film has good corrosion resistance and water resistance.
Comparative example 1 was not added with phenolic resin, and the polyurethane was inferior in corrosion resistance and water resistance.
The phenolic resin was added in comparative example 2, and the corrosion resistance and water resistance of polyurethane were improved to some extent, but the phenolic resin did not contain a functional silicone structure, and the improvement effect was inferior to examples 1 to 3.
The abrasion resistance of the polyurethane was tested according to the method of GB T1768-2006. The load is 1000, the rotating speed is 70r/min, and the abrasion times are 1000 times.
The impact resistance of the polyurethanes was tested according to the method of GB/T1732-2020.
Table 2 mechanical property test of polyurethane film
| Wearing capacity (mg) | Impact resistance (cm) | Hardness of pencil | |
| Example 1 | 12.4 | 40 | 5H |
| Example 2 | 8.8 | 50 | 5H |
| Example 3 | 6.3 | 50 | 4H |
| Comparative example 1 | 135.4 | 20 | H |
| Comparative example 2 | 39.2 | 30 | 2H |
In the embodiments 1 to 3, the organosilicon phenolic resin modifier is added to carry out crosslinking curing reaction with the polyol and the isocyanate curing agent in the component B, so that the organosilicon phenolic resin is grafted into polyurethane molecular chains, and the organosilicon structure has the characteristics of high wear resistance and good flexibility; the phenolic resin has the advantages of high wear resistance, high strength and the like, and meanwhile, the organosilicon phenolic resin modifier and the polyurethane have chemical bond crosslinking and hydrogen bond interaction to form an interpenetrating double crosslinking network, so that the wear resistance, impact resistance and hardness of the polyurethane are improved under the synergistic effect.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A preparation method of wear-resistant corrosion-resistant polyurethane self-leveling floor coating is characterized by comprising the following steps of: the polyurethane self-leveling floor coating consists of a component A and a component B;
The A component comprises the following components in parts by weight: 36-45 parts of polyalcohol, 0.5-4 parts of organosilicon phenolic resin modifier, 0.4-0.8 part of defoamer, 0.3-0.6 part of flatting agent, 0.2-0.6 part of dispersing agent, 20-28 parts of filler and 3-6 parts of pigment;
The component B comprises 6-9 parts of isocyanate curing agent;
the organosilicon phenolic resin modifier is prepared by the polymerization reaction of phenol, phenolic hydroxyl organosilicon monomers and formaldehyde; the structural formula of the phenolic hydroxyl organosilicon monomer is as follows:
；
The preparation process of the phenolic hydroxyl organosilicon monomer comprises the following steps: adding a reaction solvent, 1, 3-bis (3-hydroxypropyl) -1, 3-tetramethyl disiloxane and p-methoxy phenyl isocyanate into a reaction container containing a condensing reflux pipe, heating to 65-100 ℃, reacting for 6-18h, concentrating under reduced pressure, and washing with petroleum ether to obtain an intermediate; then adding pyridine hydrochloride into a new reaction container, heating to 155-160 ℃ for melting, adding an intermediate, stirring uniformly, heating to 200-210 ℃, reacting for 2-5h, cooling, adding water and dichloromethane, extracting and separating, and concentrating an organic phase under reduced pressure to obtain a phenolic hydroxyl organosilicon monomer;
The preparation process of the organosilicon phenolic resin modifier comprises the following steps: adding phenol, phenolic hydroxyl organic silicon monomer and sodium hydroxide into a reaction container containing a condensation return pipe, wherein the mass of the phenolic hydroxyl organic silicon monomer and the mass of the sodium hydroxide are respectively 12-40% and 3.5-4.8% of the mass of the phenol; heating to 40-55 ℃, stirring for 20-40min, adding formaldehyde aqueous solution, heating to 85-95 ℃, performing polymerization reaction for 15-30min, adding formaldehyde aqueous solution, continuing to react for 1-1.5h, cooling, washing with water, drying, and crushing to obtain the organosilicon phenolic resin modifier;
The preparation method of the polyurethane self-leveling floor coating comprises the following steps: and uniformly mixing the polyol, the organosilicon phenolic resin modifier, the defoamer, the flatting agent, the dispersing agent, the filler and the pigment to obtain a component A, and uniformly mixing the component A and the component B to obtain the polyurethane self-leveling floor coating.
2. The method for preparing the wear-resistant corrosion-resistant polyurethane self-leveling floor coating according to claim 1, which is characterized by comprising the following steps: the filler is any one of barium sulfate, diatomite and wollastonite.
3. The method for preparing the wear-resistant corrosion-resistant polyurethane self-leveling floor coating according to claim 1, which is characterized by comprising the following steps: the isocyanate curing agent comprises diphenylmethane diisocyanate and aliphatic polyisocyanate.
4. The method for preparing the wear-resistant corrosion-resistant polyurethane self-leveling floor coating according to claim 1, which is characterized by comprising the following steps: the reaction solvent is any one of tetrahydrofuran, 1, 4-dioxane and toluene.
5. The method for preparing the wear-resistant corrosion-resistant polyurethane self-leveling floor coating according to claim 1, which is characterized by comprising the following steps: the mass of the p-methoxybenzene isocyanate is 115-140% of the mass of the 1, 3-di (3-hydroxypropyl) -1, 3-tetramethyl disiloxane.
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| US4631322A (en) * | 1984-04-09 | 1986-12-23 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Curable composition of phenolic resin and polyether containing silicone containing reactive group |
| CN102863609A (en) * | 2012-09-06 | 2013-01-09 | 中科院广州化学有限公司 | Organic silicon curing agent for epoxy floor paint and preparation method and application thereof |
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| CN109554104A (en) * | 2018-08-27 | 2019-04-02 | 成都虹润制漆有限公司 | A kind of aqueous thick-slurry type aliphatic polyurethane floor coatings and preparation method thereof |
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- 2024-01-23 CN CN202410090919.8A patent/CN117625031B/en active Active
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| US4631322A (en) * | 1984-04-09 | 1986-12-23 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Curable composition of phenolic resin and polyether containing silicone containing reactive group |
| CN102863609A (en) * | 2012-09-06 | 2013-01-09 | 中科院广州化学有限公司 | Organic silicon curing agent for epoxy floor paint and preparation method and application thereof |
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| CN109554104A (en) * | 2018-08-27 | 2019-04-02 | 成都虹润制漆有限公司 | A kind of aqueous thick-slurry type aliphatic polyurethane floor coatings and preparation method thereof |
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