CN108707414B - Epoxy resin modified polyurethane waterproof coating and preparation method thereof - Google Patents
Epoxy resin modified polyurethane waterproof coating and preparation method thereof Download PDFInfo
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- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/61—Polysiloxanes
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses an epoxy resin modified polyurethane waterproof coating and a preparation method thereof, wherein the epoxy resin modified polyurethane waterproof coating comprises the following components in parts by weight: 80-100 parts of polyether glycol, 20-40 parts of isophorone diisocyanate, 30-50 parts of epoxy resin, 2-6 parts of hydroxyl-terminated polydimethylsiloxane, 0.04-0.2 part of chloroplatinic acid, 0.6-1 part of silane coupling agent, 2-6 parts of dimethylolpropionic acid, 15-25 parts of acetone, 4-10 parts of triethylamine, 0.02-0.5 part of dibutyltin dilaurate, 5-10 parts of water and 30-60 parts of inorganic filler. The preparation method comprises the following steps: s1: modified epoxy resin; s2: carrying out nucleophilic addition reaction of polyether diol under the protection of nitrogen at 65-75 ℃; s3: copolymerizing the reaction product of S1 and S2 with dimethylolpropionic acid at 70 ℃; s4: neutralizing and homogenizing. The invention utilizes the mutual crosslinking modification of polydimethylsiloxane, epoxy resin and polyurethane, integrates the advantages of the polydimethylsiloxane, the epoxy resin and the polyurethane, improves the structural stability and the mechanical property of a coating film, and the produced polyurethane waterproof coating can be closely attached to a nonpolar base surface and has excellent waterproof and anti-permeability performance.
Description
Technical Field
The invention relates to the field of modified polyurethane waterproof coatings, and particularly relates to an epoxy resin modified polyurethane waterproof coating and a preparation method thereof.
Background
The water-proof polyurethane paint is prepared with isocyanate group-containing prepolymer prepared through addition polymerization of isocyanate, polyether, catalyst, anhydrous assistant, anhydrous stuffing, solvent, etc. and through mixing. The epoxy resin modified polyurethane is adopted to improve the physical strength and chemical stability of the polyurethane waterproof coating, but both the epoxy resin and the polyurethane contain a large amount of strong polar groups, the polarity of the polyurethane modified by the epoxy resin is stronger, the adhesion to non-polar substrates such as paraffin, polyethylene, polypropylene, polystyrene and the like is lower, the stripping is easy, and the application of the epoxy resin modified polyurethane waterproof coating is limited.
Both of the two patents with application numbers of CN201510826962.7 and CN201710408108.8 disclose modified polyurethane emulsion-containing waterborne wood coatings and preparation methods thereof, and hydrazide groups are introduced on a polyurethane main chain, and ketone carbonyl groups are introduced on an acrylic acid main chain, and the two patents are crosslinked into a compact film under the conditions of water evaporation or heating, so that the hardness and the resistance of the paint film are finally improved, but the hydrazide groups and the ketone carbonyl groups are strong polar bonds, so that the polarity of the modified polyurethane coating is further enhanced, the modified polyurethane coating is difficult to adhere to a non-polar base surface, and the application range of the modified polyurethane coating is limited.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an epoxy resin modified polyurethane waterproof coating and a preparation method thereof.
The technical scheme of the invention is summarized as follows:
an epoxy resin modified polyurethane waterproof coating comprises the following components in parts by weight:
preferably, the epoxy resin is a glycidyl ether type resin, and has an average molecular weight of 360-700, an average degree of polymerization of 0.4-1.6, and an epoxy value of 0.42-0.6.
Preferably, the epoxy resin monomer is one or more of bisphenol A diglycidyl ether, ethylene glycol monoglycidyl ether, and glycerol triglycidyl ether.
Preferably, the silane coupling agent comprises one or more of KH550, KH560, KH570, a 151.
Preferably, the inorganic filler comprises one or more of nano silica, mica powder and quartz powder.
The invention also provides a preparation method of the epoxy resin modified polyurethane waterproof coating, which comprises the following steps:
s1: heating hydroxyl-terminated polydimethylsiloxane, chloroplatinic acid and a silane coupling agent to 40-60 ℃, then dropwise adding epoxy resin, continuously stirring, carrying out condensation reaction until the quantity of-0H in a reaction system is reduced by 30-60%, and stopping reaction to obtain polydimethylsiloxane modified epoxy resin;
s2: heating polyether glycol to 100-120 ℃ in a vacuum environment, dehydrating for 1h, cooling to 65-75 ℃, adding isophorone diisocyanate and dibutyltin dilaurate under the protection of 80-120KPa nitrogen gas, and carrying out nucleophilic addition reaction to obtain a polyurethane prepolymer;
s3: blending the polyurethane prepolymer, the polydimethylsiloxane modified epoxy resin and the dimethylolpropionic acid, keeping the temperature and stirring at 70 ℃ for reacting for 1-3h, continuously dripping acetone during the reaction period, reducing the viscosity, and reacting until the-NCO content is lower than 3% to obtain the epoxy resin modified polyurethane composite emulsion;
s4: and (2) dropwise adding triethylamine into the epoxy resin modified polyurethane composite emulsion at 40 ℃ to perform neutralization reaction, then adding inorganic filler and water, and homogenizing to obtain the acrylate modified polyurethane waterproof coating.
The invention has the beneficial effects that:
(1) in order to weaken the polarity of the waterproof coating, polydimethylsiloxane is adopted to pretreat epoxy resin, polar functional groups such as-OH, C ═ O and the like in the epoxy resin are removed by utilizing the condensation reaction between the epoxy resin and the polydimethylsiloxane, and nonpolar structures such as Si-O-Si, C-Si-C and the like are inserted into the main chain of the epoxy resin, so that the polarity of the epoxy resin is weakened to the maximum extent, the modified epoxy resin is further crosslinked with polyurethane prepolymer, and the nonpolar structures are introduced into an epoxy resin/polyurethane crosslinking network, so that the epoxy resin/polyurethane crosslinking network has stronger nonpolar, the hydrophobic and anti-permeability functions of the coating are strengthened, the coating can be closely attached to a nonpolar base surface, and the peeling strength of a coating film is improved.
(2) The invention utilizes the mutual crosslinking modification of polydimethylsiloxane, epoxy resin and polyurethane, improves the chemical crosslinking density of the coating, integrates the advantages of the polydimethylsiloxane, the epoxy resin and the polyurethane, and improves the structural stability and the mechanical property of the coating.
(3) The silane coupling agent is used for reducing the interfacial tension between an organic phase and an inorganic phase, and the modified polyurethane emulsion and the inorganic filler are further coupled to be condensed into a three-dimensional cross-linked network structure with interpenetrating Si-O-Si and C-Si-C, O-Si-C, so that the problem of poor compatibility of the two is fundamentally solved, the cross-linking density of the waterproof coating is improved, the waterproof coating is uniform and stable, has excellent physical strength, and the service life of the coating is remarkably prolonged.
Detailed Description
The present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
Example 1
An epoxy resin modified polyurethane waterproof coating comprises the following components in parts by weight:
the invention also provides a preparation method of the epoxy resin modified polyurethane waterproof coating, which comprises the following steps:
s1: heating hydroxyl-terminated polydimethylsiloxane, chloroplatinic acid and a silane coupling agent to 40 ℃, then dropwise adding epoxy resin, continuously stirring the epoxy resin which is glycidyl ether type resin polymerized by bisphenol A diglycidyl ether monomer and having the average molecular weight of 360, the average polymerization degree of 0.4 and the epoxy value of 0.42, carrying out condensation reaction until the number of-0H in a reaction system is reduced by 30%, and stopping the reaction to obtain polydimethylsiloxane modified epoxy resin;
s2: heating polyether glycol to 100 ℃ in a vacuum environment, dehydrating for 1h, cooling to 65 ℃, adding isophorone diisocyanate and dibutyltin dilaurate under the protection of 80KPa nitrogen gas, and carrying out nucleophilic addition reaction to obtain a polyurethane prepolymer;
s3: blending the polyurethane prepolymer, the polydimethylsiloxane modified epoxy resin and the dimethylolpropionic acid, keeping the temperature and stirring at 70 ℃ for reacting for 1h, continuously dripping acetone during the reaction period, reducing the viscosity, and reacting until the-NCO content is lower than 3% to obtain the epoxy resin modified polyurethane composite emulsion;
s4: and (2) dropwise adding triethylamine into the epoxy resin modified polyurethane composite emulsion at 40 ℃ to perform neutralization reaction, then adding nano silicon dioxide and water, and homogenizing to obtain the acrylate modified polyurethane waterproof coating.
Example 2
An epoxy resin modified polyurethane waterproof coating comprises the following components in parts by weight:
the preparation method of the waterproof coating is the same as that of the embodiment 1, and the differences are that:
s1: the condensation reaction temperature is 50 ℃, the reaction degree is 45 percent less than-0H, and the used epoxy resin is glycidyl ether resin which is polymerized by ethylene glycol-glycidyl ether monomer and has the average molecular weight of 530, the average polymerization degree of 1 and the epoxy value of 0.51;
s2: the dehydration temperature is 110 ℃, the nucleophilic addition reaction conditions are 70 ℃ and 100KPa nitrogen;
s3: keeping the temperature and stirring for reaction for 2 hours;
example 3
An epoxy resin modified polyurethane waterproof coating comprises the following components in parts by weight:
the preparation method of the waterproof coating is the same as that of the embodiment 1, and the differences are that:
s1: the condensation reaction temperature is 60 ℃, the reaction degree is 60 percent of the reduction of-0H, and the used epoxy resin is glycidyl ether resin which is polymerized by glycerol triglycidyl ether monomer and has the average molecular weight of 700, the average polymerization degree of 1.6 and the epoxy value of 0.6;
s2: the dehydration temperature is 120 ℃, the nucleophilic addition reaction conditions are 75 ℃ and 120KPa nitrogen;
s3: the reaction time is 3h under the condition of heat preservation and stirring.
The common epoxy resin modified polyurethane waterproof paint is used as a comparative example, the examples 1 to 3 and the comparative example are respectively coated on the surfaces of polyethylene, polypropylene and polystyrene materials, the coating thickness is 3cm, the peel strength of the examples 1 to 3 and the comparative example is tested, and the results are shown in the following table:
| example 1 | Example 2 | Example 3 | Comparative example | |
| Polyethylene | 92.7N/cm | 94.1N/cm | 95.3N/cm | 58.4N/cm |
| Polypropylene | 91.5N/cm | 93.4N/cm | 93.8N/cm | 56.7N/cm |
| Polystyrene | 89.2N/cm | 92.0N/cm | 92.5N/cm | 55.8N/cm |
As can be seen from the above table, the invention obviously improves the adhesion and peel strength of the epoxy resin modified polyurethane waterproof coating to the nonpolar substrate, and expands the application range of the waterproof coating.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (6)
1. The epoxy resin modified polyurethane waterproof coating is characterized by comprising the following components in parts by weight:
the preparation method of the epoxy resin modified polyurethane waterproof coating comprises the following steps:
s1: heating hydroxyl-terminated polydimethylsiloxane, chloroplatinic acid and a silane coupling agent to 40-60 ℃, then dropwise adding epoxy resin, continuously stirring, carrying out condensation reaction until the quantity of-0H in a reaction system is reduced by 30-60%, and stopping reaction to obtain polydimethylsiloxane modified epoxy resin;
s2: heating polyether glycol to 100-120 ℃ in a vacuum environment, dehydrating for 1h, cooling to 65-75 ℃, adding isophorone diisocyanate and dibutyltin dilaurate under the protection of 80-120KPa nitrogen gas, and carrying out nucleophilic addition reaction to obtain a polyurethane prepolymer;
s3: blending the polyurethane prepolymer, the polydimethylsiloxane modified epoxy resin and the dimethylolpropionic acid, keeping the temperature and stirring at 70 ℃ for reacting for 1-3h, continuously dripping acetone during the reaction period, reducing the viscosity, and reacting until the-NCO content is lower than 3% to obtain the epoxy resin modified polyurethane composite emulsion;
s4: and (2) dropwise adding triethylamine into the epoxy resin modified polyurethane composite emulsion at 40 ℃ to perform neutralization reaction, then adding inorganic filler and water, and homogenizing to obtain the epoxy resin modified polyurethane waterproof coating.
2. The epoxy resin-modified polyurethane waterproof coating material as claimed in claim 1, wherein the epoxy resin is a glycidyl ether type resin, and has an average molecular weight of 360-700, an average degree of polymerization of 0.4-1.6, and an epoxy value of 0.42-0.6.
3. The epoxy resin modified polyurethane waterproof coating as claimed in any one of claims 1 or 2, wherein the epoxy resin monomer is one or more of bisphenol a diglycidyl ether, ethylene glycol monoglycidyl ether, and glycerol triglycidyl ether.
4. The epoxy resin modified polyurethane waterproof coating material as claimed in claim 1, wherein the silane coupling agent comprises one or more of KH550, KH560, KH570 and A151.
5. The epoxy resin modified polyurethane waterproof paint as claimed in claim 1, wherein the inorganic filler comprises one or more of nano silica, mica powder and quartz powder.
6. The preparation method of the epoxy resin modified polyurethane waterproof coating as claimed in any one of claims 1 to 5, characterized by comprising the following steps:
s1: heating hydroxyl-terminated polydimethylsiloxane, chloroplatinic acid and a silane coupling agent to 40-60 ℃, then dropwise adding epoxy resin, continuously stirring, carrying out condensation reaction until the quantity of-0H in a reaction system is reduced by 30-60%, and stopping reaction to obtain polydimethylsiloxane modified epoxy resin;
s2: heating polyether glycol to 100-120 ℃ in a vacuum environment, dehydrating for 1h, cooling to 65-75 ℃, adding isophorone diisocyanate and dibutyltin dilaurate under the protection of 80-120KPa nitrogen gas, and carrying out nucleophilic addition reaction to obtain a polyurethane prepolymer;
s3: blending the polyurethane prepolymer, the polydimethylsiloxane modified epoxy resin and the dimethylolpropionic acid, keeping the temperature and stirring at 70 ℃ for reacting for 1-3h, continuously dripping acetone during the reaction period, reducing the viscosity, and reacting until the-NCO content is lower than 3% to obtain the epoxy resin modified polyurethane composite emulsion;
s4: and (2) dropwise adding triethylamine into the epoxy resin modified polyurethane composite emulsion at 40 ℃ to perform neutralization reaction, then adding inorganic filler and water, and homogenizing to obtain the epoxy resin modified polyurethane waterproof coating.
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| CN201810479900.7A CN108707414B (en) | 2018-05-18 | 2018-05-18 | Epoxy resin modified polyurethane waterproof coating and preparation method thereof |
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| CN109575697B (en) * | 2018-11-19 | 2020-12-18 | 西华大学 | Starch-based water-based paint composition and preparation method thereof |
| CN110379541A (en) * | 2019-07-24 | 2019-10-25 | 杭州新业能电力科技有限公司 | A kind of manufacturing process of fusing type cable connector |
| CN110467711B (en) * | 2019-09-10 | 2021-09-28 | 武汉海威船舶与海洋工程科技有限公司 | Epoxy resin/polysiloxane/polyurethane polymer material and preparation method thereof |
| CN110791196B (en) * | 2019-11-15 | 2021-03-09 | 江南大学 | Preparation method of photo-thermal dual-curing high-weather-resistance organic silicon modified epoxy resin |
| CN111635499A (en) * | 2020-06-05 | 2020-09-08 | 西安增材制造国家研究院有限公司 | Epoxy modified polyurethane resin, system, preparation method and application thereof |
| CN112745756B (en) * | 2021-01-15 | 2022-04-22 | 上海典跃建材科技有限公司 | Preparation method of epoxy resin modified polyurethane waterproof coating |
| CN113637409B (en) * | 2021-10-14 | 2022-02-18 | 科顺防水科技股份有限公司 | Single-component polyurethane waterproof coating composition and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504524A (en) * | 2012-01-06 | 2012-06-20 | 常州大学 | Polysiloxane modified polyurethane-epoxy resin polymer material, preparation method thereof and use thereof |
| CN106243311A (en) * | 2016-08-03 | 2016-12-21 | 广东科德环保科技股份有限公司 | A kind of aqueous epoxy resin emulsion and preparation method thereof, cathode electrophoresis dope |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102504524A (en) * | 2012-01-06 | 2012-06-20 | 常州大学 | Polysiloxane modified polyurethane-epoxy resin polymer material, preparation method thereof and use thereof |
| CN106243311A (en) * | 2016-08-03 | 2016-12-21 | 广东科德环保科技股份有限公司 | A kind of aqueous epoxy resin emulsion and preparation method thereof, cathode electrophoresis dope |
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