CN112266440A - Water-based acrylic resin with mildew-proof function - Google Patents
Water-based acrylic resin with mildew-proof function Download PDFInfo
- Publication number
- CN112266440A CN112266440A CN202011134672.3A CN202011134672A CN112266440A CN 112266440 A CN112266440 A CN 112266440A CN 202011134672 A CN202011134672 A CN 202011134672A CN 112266440 A CN112266440 A CN 112266440A
- Authority
- CN
- China
- Prior art keywords
- parts
- mildew
- stirring
- acrylic resin
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Plant Pathology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a water-based acrylic resin with a mildew-proof function, which comprises the following raw materials in parts by weight: 40-45 parts of butyl acrylate, 10-14 parts of methyl methacrylate, 10-14 parts of styrene, 11-15 parts of acrylic acid, 20-24 parts of beta-hydroxyethyl acrylate, 1.1-1.3 parts of glycidyl methacrylate, 2-4 parts of diacetone acrylamide, 0.1-0.3 part of dodecyl mercaptan, 1-3 parts of sodium bicarbonate, 10-12 parts of a mildew preventive and 0.6-1 part of an initiator; the addition agent is added in the process of preparing the mildew preventive, the addition agent is matched with the mildew preventive, the mildew preventive forms an environment which is not suitable for the existence of the mildew in the water-based acrylic resin, the presence of the addition agent improves the adhesive force of the water-based acrylic resin, simultaneously improves the compactness of a formed film of the water-based acrylic resin in the use process, and the formed relatively closed environment inhibits the growth of the mildew.
Description
Technical Field
The invention belongs to the technical field of acrylic resin, and particularly relates to water-based acrylic resin with a mildew-proof function.
Background
The aqueous acrylic resin comprises acrylic resin emulsion, acrylic resin aqueous dispersion and acrylic resin aqueous solution. Compared with the traditional solvent-based coating, the water-based coating has the advantages of low price, safe use, resource and energy conservation, environmental pollution and public nuisance reduction, and the like, thereby becoming the main direction for developing the coating industry at present. The water-based acrylic resin is pollution-free paint which is the fastest in development and the most in variety in water-based paint. Compared with the traditional solvent-based coating, the water-based coating has the advantages of low price, safe use, resource and energy conservation, environmental pollution and public nuisance reduction, and the like, thereby becoming the main direction for developing the coating industry at present.
The invention patent CN109776754A discloses a preparation method of a cationic waterborne UV polyurethane acrylate self-antibacterial resin. Firstly, mixing and heating polyisocyanate, a polyol compound and a catalyst to prepare an intermediate product containing 3-4 isocyanic acid radical (-NCO) groups; then adding amine compound and hydroxyl-terminated vinyl compound for end capping, adding organic acid and photoinitiator to obtain hydrophilic resin, adding water, stirring at high speed to form dispersion, and finally adding auxiliary agent to obtain the cationic water-based UV self-antibacterial coating. Aiming at the problems of poor storage stability, additional mildew preventive and weak antibacterial persistence of a common cationic water-based UV coating, the prepared coating has high stability, excellent mechanical property, tensile strength and thermal decomposition resistance of a coating film, and no toxicity and smell; the self-killing rate of the bacteria exceeds 99 percent.
Disclosure of Invention
In order to overcome the technical problems, the invention provides a water-based acrylic resin with a mildew-proof function.
The technical problems to be solved by the invention are as follows:
at present, materials for mildew resistance of coatings mainly comprise inorganic substances, such as nano titanium dioxide and inorganic copper salt; organic compounds such as imidazole compounds, quaternary ammonium compounds. However, the inorganic mildew inhibitor has poor effect persistence, needs to add a plurality of auxiliary agents, and has high processing cost; the organic mildew preventive can be aged and decomposed, so that the mildew preventive effect is reduced, and the film forming property of the coating is also influenced.
The purpose of the invention can be realized by the following technical scheme:
the water-based acrylic resin with the mildew-proof function comprises the following raw materials in parts by weight:
40-45 parts of butyl acrylate, 10-14 parts of methyl methacrylate, 10-14 parts of styrene, 11-15 parts of acrylic acid, 20-24 parts of beta-hydroxyethyl acrylate, 1.1-1.3 parts of glycidyl methacrylate, 2-4 parts of diacetone acrylamide, 0.1-0.3 part of dodecyl mercaptan, 1-3 parts of sodium bicarbonate, 10-12 parts of a mildew preventive and 0.6-1 part of an initiator;
the water-based acrylic resin with the mildew-proof function is prepared by the following steps:
firstly, uniformly mixing butyl acrylate, methyl methacrylate, styrene, acrylic acid, beta-hydroxyethyl acrylate, glycidyl methacrylate, diacetone acrylamide, dodecyl mercaptan and sodium bicarbonate, and then carrying out ultrasonic treatment for 30-40min at the frequency of 40-50kHz to obtain a monomer solution;
secondly, 1/4 monomer solution, butanol and mildew preventive are added into a three-neck flask, the temperature is set to be 70-80 ℃, the rotating speed is set to be 300-400r/min, stirring is carried out for 10-15min, then 1/3 initiator is added, stirring is carried out for 30min, then 1/3 initiator is added, and the residual monomer solution is added into the three-neck flask through a constant pressure dropping funnel;
and thirdly, after the monomer solution is dripped, keeping the temperature and the rotating speed unchanged, continuously stirring for 2-3h, then adding the rest initiator, raising the temperature to 90 ℃, continuously stirring for 2h, then reducing the temperature to 46-50 ℃, adjusting the pH value of the reaction solution to 7-8 by using triethylamine, then adding deionized water, diluting the volume of the reaction solution by 1 time, adding adipic dihydrazide at room temperature, and stirring for 50-60min to obtain the waterborne acrylic resin with the mildew-proof function.
Further, the volume ratio of butanol to monomer solution in the second step is 1: 1.1-1.3; the dripping time of the residual monomer solution is controlled to be 1-3 drops/second; the initiator is one of dimethyl azodiisobutyrate and azodiisobutyl amidine hydrochloride; the mass ratio of adipic dihydrazide to diacetone acrylamide is 3: 5.
further, the mildewcide is prepared by the following steps:
step S11, stirring N-methyl pyrrolidone and bromoalkane at room temperature for 48-50h, washing the obtained reaction solution with diethyl ether for three times, removing the diethyl ether by using a rotary evaporator after washing is finished, and then drying in vacuum at 40 ℃ to constant weight to obtain a monomer a;
step S12, adding methyldiallylamine hydrochloride, an initiator and a chain transfer agent into a reaction kettle, setting the temperature at 60 ℃ and the rotation speed at 200-300r/min under the protection of nitrogen, reacting for 10-14h, adding acetone to separate out a precipitate after the reaction is finished, filtering, adding the obtained precipitate into a round-bottom flask under the condition of ice-water bath, then adding methanol and a sodium methoxide solution with the mass fraction of 30%, reacting for 4h, performing vacuum filtration after the reaction is finished, removing the methanol from the obtained filtrate by using a rotary evaporator, and drying at 40 ℃ under the vacuum condition to constant weight to obtain a polymer b;
step S13, mixing the obtained monomer a and polymer b according to the mass ratio of 10-12: 1, adding N, N-dimethylformamide, setting the temperature at 70-90 ℃ and the rotating speed at 300r/min, stirring for 25-27min, washing the obtained reaction solution with diethyl ether for three times after stirring is finished, removing the diethyl ether by using a rotary evaporator after washing is finished, and then drying in vacuum at 40 ℃ to constant weight to obtain a solid c;
and step S14, mixing the auxiliary agent and the deionized water, heating to 60 ℃, stirring for 10min, adding methyl orthosilicate, heating to 100 ℃, adding the solid c, reacting for 4h, cooling to 70 ℃, adding dibutylamine, stirring uniformly, and concentrating the obtained reaction solution under reduced pressure until the volume is not changed any more to obtain the mildew preventive.
Further, in the step S11, the alkyl bromide is one or two of N-butyl bromide and N-hexane bromide, and the molar ratio of N-methylpyrrolidone to alkyl bromide is 1: 1; in step S12, the initiator is azobisisobutyronitrile, the chain transfer agent is ethyl O-ethylxanthate propionate, and the amount ratio of the methyldiallylamine hydrochloride to the initiator to the chain transfer agent to the methanol to the sodium methoxide is 2 g: 0.1-0.3 g: 0.1 g: 10-20 mL: 6-10 mL.
Further, in step S13, the ratio of the amount of N, N-dimethylformamide to the sum of the mass of the monomer a and the mass of the polymer b is 10 to 15 mL: 1g of a compound; in the step S14, the dosage ratio of the auxiliary agent, the deionized water, the methyl orthosilicate, the solid c and the dibutylamine is 2-4 mL: 10-12 mL: 0.1-0.3 g: 1 g: 0.1-0.3 mL.
The monomer a contains hydrophilic cationic groups, the main chain of the polymer b is a hydrophobic carbon chain, the monomer a and the polymer b are prepared into the solid c, the hydrophilic cationic groups and the hydrophobic carbon chains in the solid c are alternately distributed, when the cationic hydrophilic groups and the hydrophobic parts are contacted with the surface of the mould, the hydrophobic parts are favorably inserted into phospholipid bilayers of cell membranes, and simultaneously the cationic hydrophilic groups are contacted with negative charges on the surface of the cell membranes, so that the cell membranes are broken to cause cell death, and the process can not cause strains to generate drug resistance, has broad-spectrum antibacterial property and has small influence on the environment. The addition agent is added in the process of preparing the mildew preventive, the addition agent is matched with the mildew preventive, the mildew preventive forms an environment which is not suitable for the existence of the mildew in the water-based acrylic resin, the presence of the addition agent improves the adhesive force of the water-based acrylic resin, simultaneously improves the compactness of a formed film of the water-based acrylic resin in the use process, and the formed relatively closed environment inhibits the growth of the mildew.
Further, the auxiliary agent is prepared by the following steps:
step S21, adding beta-cyclodextrin into deionized water, stirring for 20-24min at 80 ℃, then carrying out vacuum filtration, cooling the obtained filtrate to-10 ℃ to separate out crystals, and drying the obtained crystals to constant weight at 100 ℃ under vacuum when the crystal amount is not increased any more to obtain activated beta-cyclodextrin;
step S22, adding the activated beta-cyclodextrin, an emulsifier and deionized water into a four-neck flask, stirring for 20-30min at room temperature under the condition that the rotation speed is 200r/min, then heating to 50-60 ℃, adding methyl cyclotetrasiloxane, hydroxyl silicone oil and 20% of dodecafluoroheptyl methacrylate, stirring for 20min, then heating to 90 ℃, continuing to react for 2h, then adding an ammonium sulfate aqueous solution into the four-neck flask through a dropping funnel, simultaneously adding the remaining 80% of dodecafluoroheptyl methacrylate every 20min, continuing to react for 3h after the addition is finished, and obtaining the auxiliary agent after the reaction is finished. Hydroxyl silicone oil and methacrylic acid dodecafluoroheptyl ester are added in the process of preparing the auxiliary agent to modify beta-cyclodextrin, hydroxyl groups on the end group of the beta-cyclodextrin are replaced by fluorosilication, the prepared auxiliary agent introduces organosilicon and organic fluorine chain segments of a flexible segment while the molecular weight is increased, hydrophilic groups are increased, the intermolecular hydrogen bond acting force is enhanced, and the compactness of the surface of a film formed by later-stage acrylic resin curing is improved.
Further, in the step S21, the dosage ratio of the beta-cyclodextrin to the deionized water is 1: 10-15 mL; in the step S22, the emulsifier is sodium dodecyl sulfate and nonylphenol polyvinyl fluoride according to the mass ratio of 3: 1, and the dosage ratio of the activated beta-cyclodextrin, the emulsifier, the deionized water, the methylcyclotetrasiloxane, the hydroxyl silicone oil and the dodecafluoroheptyl methacrylate is 1 g: 0.1-0.3 g: 12mL of: 1-3 mL: 2mL of: 10 mL; the mass fraction of the ammonium sulfate aqueous solution is 8-10%; the remaining 80% of the methacrylic acid was added in eight equal amounts.
The invention has the beneficial effects that:
hydroxyl silicone oil and dodecafluoroheptyl methacrylate are added in the process of preparing an auxiliary agent to modify beta-cyclodextrin, hydroxyl groups on the end group of the beta-cyclodextrin are replaced by fluorosilication, the prepared auxiliary agent introduces organic silicon and organic fluorine chain segments of a flexible segment while the molecular weight is increased, hydrophilic groups are increased, the acting force of hydrogen bonds among molecules is enhanced, and the compactness of the surface of a film formed by curing and film forming of the acrylic resin at the later stage is improved.
The monomer a contains hydrophilic cationic groups, the main chain of the polymer b is a hydrophobic carbon chain, the monomer a and the polymer b are prepared into the solid c, the hydrophilic cationic groups and the hydrophobic carbon chains in the solid c are alternately distributed, when the cationic hydrophilic groups and the hydrophobic parts are contacted with the surface of the mould, the hydrophobic parts are favorably inserted into phospholipid bilayers of cell membranes, and simultaneously the cationic hydrophilic groups are contacted with negative charges on the surface of the cell membranes, so that the cell membranes are broken to cause cell death, and the process can not cause strains to generate drug resistance, has broad-spectrum antibacterial property and has small influence on the environment. The addition agent is added in the process of preparing the mildew preventive, the addition agent is matched with the mildew preventive, the mildew preventive forms an environment which is not suitable for the existence of the mildew in the water-based acrylic resin, the presence of the addition agent improves the adhesive force of the water-based acrylic resin, simultaneously improves the compactness of a formed film of the water-based acrylic resin in the use process, and the formed relatively closed environment inhibits the growth of the mildew.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The water-based acrylic resin with the mildew-proof function comprises the following raw materials in parts by weight: 40 parts of butyl acrylate, 10 parts of methyl methacrylate, 10 parts of styrene, 11 parts of acrylic acid, 20 parts of beta-hydroxyethyl acrylate, 1.1 parts of glycidyl methacrylate, 2 parts of diacetone acrylamide, 0.1 part of dodecyl mercaptan, 1 part of sodium bicarbonate, 10 parts of a mildew inhibitor and 0.6 part of an initiator;
the water-based acrylic resin with the mildew-proof function is prepared by the following steps:
firstly, uniformly mixing butyl acrylate, methyl methacrylate, styrene, acrylic acid, beta-hydroxyethyl acrylate, glycidyl methacrylate, diacetone acrylamide, dodecyl mercaptan and sodium bicarbonate, and then carrying out ultrasonic treatment for 30min at the frequency of 40kHz to obtain a monomer solution;
secondly, 1/4 monomer solution, butanol and a mildew preventive are added into a three-neck flask, the temperature is set to be 70 ℃, the rotating speed is set to be 300r/min, stirring is carried out for 10min, then 1/3 initiator is added, stirring is carried out for 30min, then 1/3 initiator is added, and the residual monomer solution is added into the three-neck flask through a constant pressure dropping funnel;
and thirdly, after the monomer solution is dripped, keeping the temperature and the rotating speed unchanged, continuously stirring for 2h, then adding the rest initiator, raising the temperature to 90 ℃, continuously stirring for 2h, then reducing the temperature to 46 ℃, adjusting the pH value of the reaction solution to 7 by triethylamine, then adding deionized water, diluting the volume of the reaction solution by 1 time, adding adipic dihydrazide at room temperature, and stirring for 50min to obtain the waterborne acrylic resin with the mildew-proof function.
Wherein, the volume ratio of the butanol to the monomer solution in the second step is 1: 1.1; the dripping time of the residual monomer solution is controlled to be 1 drop/second; the initiator is dimethyl azodiisobutyrate.
The mildew preventive is prepared by the following steps:
step S11, stirring N-methyl pyrrolidone and bromoalkane at room temperature for 48 hours, washing the obtained reaction solution with diethyl ether for three times, removing the diethyl ether by using a rotary evaporator after washing is finished, and then drying in vacuum at 40 ℃ to constant weight to obtain a monomer a;
step S12, adding methyldiallylamine hydrochloride, an initiator and a chain transfer agent into a reaction kettle, setting the temperature at 60 ℃ and the rotating speed at 200r/min under the protection of nitrogen, reacting for 10 hours, adding acetone to separate out a precipitate after the reaction is finished, filtering, adding the obtained precipitate into a round-bottom flask under the condition of ice-water bath, then adding methanol and a sodium methoxide solution with the mass fraction of 30%, reacting for 4 hours, carrying out vacuum filtration after the reaction is finished, removing the methanol from the obtained filtrate by using a rotary evaporator, and drying the filtrate to constant weight under the vacuum condition at 40 ℃ to obtain a polymer b;
step S13, mixing the obtained monomer a and polymer b according to the mass ratio of 10: 1, adding N, N-dimethylformamide, setting the temperature at 70 ℃ and the rotating speed at 300r/min, stirring for 25min, washing the obtained reaction solution with diethyl ether for three times after stirring is finished, removing the diethyl ether by using a rotary evaporator after washing is finished, and then drying in vacuum at 40 ℃ to constant weight to obtain a solid c;
and step S14, mixing the auxiliary agent and the deionized water, heating to 60 ℃, stirring for 10min, adding methyl orthosilicate, heating to 100 ℃, adding the solid c, reacting for 4h, cooling to 70 ℃, adding dibutylamine, stirring uniformly, and concentrating the obtained reaction solution under reduced pressure until the volume is not changed any more to obtain the mildew preventive.
Wherein, the alkane bromide in the step S11 is n-butane bromide; in the step S12, the initiator is azobisisobutyronitrile, and the chain transfer agent is ethyl O-ethylxanthate propionate; the dosage ratio of the methyldiallylamine hydrochloride, the initiator, the chain transfer agent, the methanol and the sodium methoxide is 2 g: 0.1 g: 0.1 g: 10mL of: 6 mL.
Wherein, in the step S13, the dosage ratio of the N, N-dimethylformamide to the sum of the mass of the monomer a and the mass of the polymer b is 10 mL: 1g of a compound; in the step S14, the dosage ratio of the auxiliary agent, the deionized water, the methyl orthosilicate, the solid c and the dibutylamine is 2 mL: 10mL of: 0.1 g: 1 g: 0.1 mL.
The auxiliary agent is prepared by the following steps:
step S21, adding beta-cyclodextrin into deionized water, stirring for 20min at 80 ℃, then carrying out vacuum filtration, cooling the obtained filtrate to-10 ℃ to separate out crystals, and drying the obtained crystals to constant weight at 100 ℃ under vacuum condition when the crystal amount is not increased any more to obtain activated beta-cyclodextrin;
step S22, adding the activated beta-cyclodextrin, an emulsifier and deionized water into a four-neck flask, stirring for 20min at room temperature and at a rotation speed of 200r/min, then heating to 50 ℃, adding methylcyclotetrasiloxane, hydroxy silicone oil and 20% of dodecafluoroheptyl methacrylate, stirring for 20min, heating to 90 ℃, continuing to react for 2h, then adding an ammonium sulfate aqueous solution into the four-neck flask through a dropping funnel, simultaneously adding the remaining 80% of dodecafluoroheptyl methacrylate every 20min, continuing to react for 3h after the addition is finished, and obtaining the auxiliary agent after the reaction is finished.
Wherein the dosage ratio of the beta-cyclodextrin to the deionized water in the step S21 is 1: 10 mL; in the step S22, the emulsifier is sodium dodecyl sulfate and nonylphenol polyvinyl fluoride according to the mass ratio of 3: 1, and the dosage ratio of the activated beta-cyclodextrin, the emulsifier, the deionized water, the methylcyclotetrasiloxane, the hydroxyl silicone oil and the dodecafluoroheptyl methacrylate is 1 g: 0.1 g: 12mL of: 1mL of: 2mL of: 10 mL; the mass fraction of the ammonium sulfate aqueous solution is 8%.
Example 2
The water-based acrylic resin with the mildew-proof function comprises the following raw materials in parts by weight: 42 parts of butyl acrylate, 12 parts of methyl methacrylate, 12 parts of styrene, 13 parts of acrylic acid, 22 parts of beta-hydroxyethyl acrylate, 1.2 parts of glycidyl methacrylate, 3 parts of diacetone acrylamide, 0.2 part of dodecyl mercaptan, 2 parts of sodium bicarbonate, 11 parts of a mildew inhibitor and 0.8 part of an initiator;
the water-based acrylic resin with the mildew-proof function is prepared by the following steps:
firstly, uniformly mixing butyl acrylate, methyl methacrylate, styrene, acrylic acid, beta-hydroxyethyl acrylate, glycidyl methacrylate, diacetone acrylamide, dodecyl mercaptan and sodium bicarbonate, and then carrying out ultrasonic treatment for 35min at the frequency of 45kHz to obtain a monomer solution;
secondly, 1/4 monomer solution, butanol and a mildew preventive are added into a three-neck flask, the temperature is set to be 75 ℃, the rotating speed is 350r/min, stirring is carried out for 12min, then 1/3 initiator is added, stirring is carried out for 30min, then 1/3 initiator is added, and the residual monomer solution is added into the three-neck flask through a constant pressure dropping funnel;
and thirdly, after the monomer solution is dripped, keeping the temperature and the rotating speed unchanged, continuously stirring for 2.5 hours, then adding the rest initiator, raising the temperature to 90 ℃, continuously stirring for 2 hours, then reducing the temperature to 48 ℃, adjusting the pH value of the reaction solution to 7 by using triethylamine, then adding deionized water, diluting the volume of the reaction solution by 1 time, adding adipic dihydrazide at room temperature, and stirring for 55 minutes to obtain the waterborne acrylic resin with the mildew-proof function.
Wherein, the volume ratio of the butanol to the monomer solution in the second step is 1: 1.2; the dripping time of the residual monomer solution is controlled to be 2 drops/second; the initiator is dimethyl azodiisobutyrate.
The mildew preventive is prepared by the following steps:
step S11, stirring N-methyl pyrrolidone and bromoalkane at room temperature for 49 hours, washing the obtained reaction solution with diethyl ether for three times, removing the diethyl ether by using a rotary evaporator after washing is finished, and then drying in vacuum at 40 ℃ to constant weight to obtain a monomer a;
step S12, adding methyldiallylamine hydrochloride, an initiator and a chain transfer agent into a reaction kettle, setting the temperature at 60 ℃ and the rotating speed at 250r/min under the protection of nitrogen, reacting for 12 hours, adding acetone to separate out a precipitate after the reaction is finished, filtering, adding the obtained precipitate into a round-bottom flask under the condition of ice-water bath, then adding methanol and a sodium methoxide solution with the mass fraction of 30%, reacting for 4 hours, carrying out vacuum filtration after the reaction is finished, removing the methanol from the obtained filtrate by using a rotary evaporator, and drying the filtrate to constant weight under the vacuum condition at 40 ℃ to obtain a polymer b;
step S13, mixing the obtained monomer a and polymer b according to the mass ratio of 11: 1, adding N, N-dimethylformamide, setting the temperature at 80 ℃ and the rotating speed at 300r/min, stirring for 26min, washing the obtained reaction solution with diethyl ether for three times after stirring is finished, removing the diethyl ether by using a rotary evaporator after washing is finished, and then drying in vacuum at 40 ℃ to constant weight to obtain a solid c;
and step S14, mixing the auxiliary agent and the deionized water, heating to 60 ℃, stirring for 10min, adding methyl orthosilicate, heating to 100 ℃, adding the solid c, reacting for 4h, cooling to 70 ℃, adding dibutylamine, stirring uniformly, and concentrating the obtained reaction solution under reduced pressure until the volume is not changed any more to obtain the mildew preventive.
Wherein, in the step S11, the brominated alkanes are n-butyl bromide and n-hexane bromide according to the mass ratio of 1: 1, mixing; in the step S12, the initiator is azobisisobutyronitrile, and the chain transfer agent is ethyl O-ethylxanthate propionate; the dosage ratio of the methyldiallylamine hydrochloride, the initiator, the chain transfer agent, the methanol and the sodium methoxide is 2 g: 0.2 g: 0.1 g: 15mL of: 8 mL.
Wherein the dosage ratio of the N, N-dimethylformamide to the sum of the mass of the monomer a and the mass of the polymer b in the step S13 is 12 mL: 1g of a compound; in the step S14, the dosage ratio of the auxiliary agent, the deionized water, the methyl orthosilicate, the solid c and the dibutylamine is 3 mL: 11mL of: 0.2 g: 1 g: 0.2 mL.
The auxiliary agent is prepared by the following steps:
step S21, adding beta-cyclodextrin into deionized water, stirring for 22min at 80 ℃, then carrying out vacuum filtration, cooling the obtained filtrate to-10 ℃ to separate out crystals, and drying the obtained crystals to constant weight at 100 ℃ under vacuum when the crystal amount is not increased any more to obtain activated beta-cyclodextrin;
step S22, adding the activated beta-cyclodextrin, an emulsifier and deionized water into a four-neck flask, stirring for 20-30min at room temperature under the condition that the rotation speed is 200r/min, then heating to 55 ℃, adding methylcyclotetrasiloxane, hydroxy silicone oil and 20% of dodecafluoroheptyl methacrylate, stirring for 20min, heating to 90 ℃, continuing to react for 2h, then adding an ammonium sulfate aqueous solution into the four-neck flask through a dropping funnel, simultaneously adding the remaining 80% of dodecafluoroheptyl methacrylate every 20min, continuing to react for 3h after the addition is finished, and obtaining the assistant after the reaction is finished.
Wherein the dosage ratio of the beta-cyclodextrin to the deionized water in the step S21 is 1: 12 mL; in the step S22, the emulsifier is sodium dodecyl sulfate and nonylphenol polyvinyl fluoride according to the mass ratio of 3: 1, and the dosage ratio of the activated beta-cyclodextrin, the emulsifier, the deionized water, the methylcyclotetrasiloxane, the hydroxyl silicone oil and the dodecafluoroheptyl methacrylate is 1 g: 0.2 g: 12mL of: 2mL of: 2mL of: 10 mL; the mass fraction of the ammonium sulfate aqueous solution is 9%.
Example 3
The water-based acrylic resin with the mildew-proof function comprises the following raw materials in parts by weight: 45 parts of butyl acrylate, 14 parts of methyl methacrylate, 14 parts of styrene, 15 parts of acrylic acid, 24 parts of beta-hydroxyethyl acrylate, 1.3 parts of glycidyl methacrylate, 4 parts of diacetone acrylamide, 0.3 part of dodecyl mercaptan, 3 parts of sodium bicarbonate, 12 parts of a mildew preventive and 1 part of an initiator;
the water-based acrylic resin with the mildew-proof function is prepared by the following steps:
firstly, uniformly mixing butyl acrylate, methyl methacrylate, styrene, acrylic acid, beta-hydroxyethyl acrylate, glycidyl methacrylate, diacetone acrylamide, dodecyl mercaptan and sodium bicarbonate, and then carrying out ultrasonic treatment for 40min at the frequency of 50kHz to obtain a monomer solution;
secondly, 1/4 monomer solution, butanol and a mildew preventive are added into a three-neck flask, the temperature is set to be 80 ℃, the rotating speed is set to be 400r/min, stirring is carried out for 15min, then 1/3 initiator is added, stirring is carried out for 30min, then 1/3 initiator is added, and the residual monomer solution is added into the three-neck flask through a constant pressure dropping funnel;
and thirdly, after the monomer solution is dripped, keeping the temperature and the rotating speed unchanged, continuously stirring for 2-3h, then adding the rest initiator, raising the temperature to 90 ℃, continuously stirring for 2h, then reducing the temperature to 46-50 ℃, adjusting the pH value of the reaction solution to 8 by using triethylamine, then adding deionized water, diluting the volume of the reaction solution by 1 time, adding adipic dihydrazide at room temperature, and stirring for 60min to obtain the waterborne acrylic resin with the mildew-proof function.
Wherein, the volume ratio of the butanol to the monomer solution in the second step is 1: 1.3; the dripping time of the residual monomer solution is controlled to be 3 drops/second; the initiator is azobisisobutylamidine hydrochloride.
The mildew preventive is prepared by the following steps:
step S11, stirring N-methyl pyrrolidone and bromoalkane for 50 hours at room temperature, washing the obtained reaction solution for three times by using ether, removing the ether by using a rotary evaporator after washing is finished, and then drying in vacuum at 40 ℃ to constant weight to obtain a monomer a;
step S12, adding methyldiallylamine hydrochloride, an initiator and a chain transfer agent into a reaction kettle, setting the temperature at 60 ℃ and the rotating speed at 300r/min under the protection of nitrogen, reacting for 14 hours, adding acetone to separate out a precipitate after the reaction is finished, filtering, adding the obtained precipitate into a round-bottom flask under the condition of ice-water bath, then adding methanol and a sodium methoxide solution with the mass fraction of 30%, reacting for 4 hours, carrying out vacuum filtration after the reaction is finished, removing the methanol from the obtained filtrate by using a rotary evaporator, and drying the filtrate to constant weight under the vacuum condition at 40 ℃ to obtain a polymer b;
step S13, mixing the obtained monomer a and polymer b according to the mass ratio of 12: 1, adding N, N-dimethylformamide, setting the temperature at 90 ℃ and the rotating speed at 300r/min, stirring for 27min, washing the obtained reaction solution with diethyl ether for three times after stirring is finished, removing the diethyl ether by using a rotary evaporator after washing is finished, and then drying in vacuum at 40 ℃ to constant weight to obtain a solid c;
and step S14, mixing the auxiliary agent and the deionized water, heating to 60 ℃, stirring for 10min, adding methyl orthosilicate, heating to 100 ℃, adding the solid c, reacting for 4h, cooling to 70 ℃, adding dibutylamine, stirring uniformly, and concentrating the obtained reaction solution under reduced pressure until the volume is not changed any more to obtain the mildew preventive.
Wherein, the alkane bromide in the step S11 is n-hexane bromide; in the step S12, the initiator is azobisisobutyronitrile, and the chain transfer agent is ethyl O-ethylxanthate propionate; the dosage ratio of the methyldiallylamine hydrochloride, the initiator, the chain transfer agent, the methanol and the sodium methoxide is 2 g: 0.3 g: 0.1 g: 20mL of: 10 mL.
Wherein the dosage ratio of the N, N-dimethylformamide to the sum of the mass of the monomer a and the mass of the polymer b in the step S13 is 15 mL: 1g of a compound; in the step S14, the dosage ratio of the auxiliary agent, the deionized water, the methyl orthosilicate, the solid c and the dibutylamine is 4 mL: 12mL of: 0.3 g: 1 g: 0.3 mL.
The auxiliary agent is prepared by the following steps:
step S21, adding beta-cyclodextrin into deionized water, stirring for 20-24min at 80 ℃, then carrying out vacuum filtration, cooling the obtained filtrate to-10 ℃ to separate out crystals, and drying the obtained crystals to constant weight at 100 ℃ under vacuum when the crystal amount is not increased any more to obtain activated beta-cyclodextrin;
step S22, adding the activated beta-cyclodextrin, an emulsifier and deionized water into a four-neck flask, stirring for 30min at room temperature and at a rotation speed of 200r/min, then heating to 60 ℃, adding methylcyclotetrasiloxane, hydroxy silicone oil and 20% of dodecafluoroheptyl methacrylate, stirring for 20min, heating to 90 ℃, continuing to react for 2h, then adding an ammonium sulfate aqueous solution into the four-neck flask through a dropping funnel, simultaneously adding the remaining 80% of dodecafluoroheptyl methacrylate every 20min, continuing to react for 3h after the addition is finished, and obtaining the auxiliary agent after the reaction is finished.
Wherein the dosage ratio of the beta-cyclodextrin to the deionized water in the step S21 is 1: 15 mL; in the step S22, the emulsifier is sodium dodecyl sulfate and nonylphenol polyvinyl fluoride according to the mass ratio of 3: 1, and the dosage ratio of the activated beta-cyclodextrin, the emulsifier, the deionized water, the methylcyclotetrasiloxane, the hydroxyl silicone oil and the dodecafluoroheptyl methacrylate is 1 g: 0.3 g: 12mL of: 3mL of: 2mL of: 10 mL; the mass fraction of the ammonium sulfate aqueous solution is 10%.
Comparative example 1
The auxiliaries from example 1 were not added, and the remaining starting materials and preparation were kept unchanged.
Comparative example 2
The fungicide of example 1 was not added, and the rest of the raw materials and the preparation process remained unchanged.
Comparative example 3
The comparative example is a common water-based acrylic resin with a mildew-proof function in the market.
The performance test of the aqueous acrylic resin prepared in examples 1 to 3 and comparative examples 1 to 3 was carried out, mold was inoculated into the aqueous acrylic resin, and then the degree of mold development after infestation was tested under the same environmental conditions; according to GB/T1728 test drying time, the water-based acrylic resin prepared in the examples 1-3 and the comparative examples 1-3 is smeared on a tin plate, the thickness is 1mm, the surface film forming time is the surface drying time, and the solid film forming time is the actual drying time; the water resistance was determined according to GB/T1733, and the dried paint was immersed in water for 100 hours and the state was recorded. The test results are shown in table 1 below:
TABLE 1
As can be seen from the above Table 1, the presence of the mildew preventive in the waterborne acrylic resin with the mildew preventive function provided by the invention forms an environment which is not suitable for the existence of the mildew; hydroxyl silicone oil and methacrylic acid dodecafluoroheptyl ester are added in the process of preparing the auxiliary agent to modify beta-cyclodextrin, hydroxyl groups on the end group of the beta-cyclodextrin are replaced by fluorosilication, the prepared auxiliary agent introduces organosilicon and organic fluorine chain segments of a flexible segment while the molecular weight is increased, hydrophilic groups are increased, the intermolecular hydrogen bond acting force is enhanced, and the compactness of the surface of a film formed by later-stage acrylic resin curing is improved.
The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.
Claims (7)
1. The water-based acrylic resin with the mildew-proof function is characterized by comprising the following raw materials in parts by weight: 40-45 parts of butyl acrylate, 10-14 parts of methyl methacrylate, 10-14 parts of styrene, 11-15 parts of acrylic acid, 20-24 parts of beta-hydroxyethyl acrylate, 1.1-1.3 parts of glycidyl methacrylate, 2-4 parts of diacetone acrylamide, 0.1-0.3 part of dodecyl mercaptan, 1-3 parts of sodium bicarbonate, 10-12 parts of a mildew preventive and 0.6-1 part of an initiator;
the water-based acrylic resin with the mildew-proof function is prepared by the following steps:
firstly, uniformly mixing butyl acrylate, methyl methacrylate, styrene, acrylic acid, beta-hydroxyethyl acrylate, glycidyl methacrylate, diacetone acrylamide, dodecyl mercaptan and sodium bicarbonate, and then carrying out ultrasonic treatment for 30-40min at the frequency of 40-50kHz to obtain a monomer solution;
secondly, 1/4 monomer solution, butanol and mildew preventive are added into a three-neck flask, the temperature is set to be 70-80 ℃, the rotating speed is set to be 300-400r/min, stirring is carried out for 10-15min, then 1/3 initiator is added, stirring is carried out for 30min, then 1/3 initiator is added, and the residual monomer solution is added into the three-neck flask through a constant pressure dropping funnel;
and thirdly, after the monomer solution is dripped, keeping the temperature and the rotating speed unchanged, continuously stirring for 2-3h, then adding the rest initiator, raising the temperature to 90 ℃, continuously stirring for 2h, then reducing the temperature to 46-50 ℃, adjusting the pH value of the reaction solution to 7-8 by using triethylamine, then adding deionized water, diluting the volume of the reaction solution by 1 time, adding adipic dihydrazide at room temperature, and stirring for 50-60min to obtain the waterborne acrylic resin with the mildew-proof function.
2. The aqueous acrylic resin having a mold-proofing function according to claim 1, wherein the volume ratio of the butanol to the monomer solution in the second step is 1: 1.1-1.3; the dripping time of the residual monomer solution is controlled to be 1-3 drops/second; the initiator is one of dimethyl azodiisobutyrate and azodiisobutyl amidine hydrochloride; the mass ratio of adipic dihydrazide to diacetone acrylamide is 3: 5.
3. the water-based acrylic resin with the mildew-proof function as claimed in claim 1, wherein the mildew-proof agent is prepared by the following steps:
step S11, stirring N-methyl pyrrolidone and bromoalkane at room temperature for 48-50h, washing the obtained reaction solution with diethyl ether for three times, removing the diethyl ether by using a rotary evaporator after washing is finished, and then drying in vacuum at 40 ℃ to constant weight to obtain a monomer a;
step S12, adding methyldiallylamine hydrochloride, an initiator and a chain transfer agent into a reaction kettle, setting the temperature at 60 ℃ and the rotation speed at 200-300r/min under the protection of nitrogen, reacting for 10-14h, adding acetone to separate out a precipitate after the reaction is finished, filtering, adding the obtained precipitate into a round-bottom flask under the condition of ice-water bath, then adding methanol and a sodium methoxide solution with the mass fraction of 30%, reacting for 4h, performing vacuum filtration after the reaction is finished, removing the methanol from the obtained filtrate by using a rotary evaporator, and drying at 40 ℃ under the vacuum condition to constant weight to obtain a polymer b;
step S13, mixing the obtained monomer a and polymer b according to the mass ratio of 10-12: 1, adding N, N-dimethylformamide, setting the temperature at 70-90 ℃ and the rotating speed at 300r/min, stirring for 25-27min, washing the obtained reaction solution with diethyl ether for three times after stirring is finished, removing the diethyl ether by using a rotary evaporator after washing is finished, and then drying in vacuum at 40 ℃ to constant weight to obtain a solid c;
and step S14, mixing the auxiliary agent and the deionized water, heating to 60 ℃, stirring for 10min, adding methyl orthosilicate, heating to 100 ℃, adding the solid c, reacting for 4h, cooling to 70 ℃, adding dibutylamine, stirring uniformly, and concentrating the obtained reaction solution under reduced pressure until the volume is not changed any more to obtain the mildew preventive.
4. The waterborne acrylic resin with the mildew-proof function of claim 3, wherein in the step S11, the alkyl bromide is one or two of N-butyl bromide and N-hexane bromide, and the molar ratio of the N-methylpyrrolidone to the alkyl bromide is 1: 1; in the step S12, the initiator is azobisisobutyronitrile, and the chain transfer agent is ethyl O-ethylxanthate propionate; the dosage ratio of the methyldiallylamine hydrochloride, the initiator, the chain transfer agent, the methanol and the sodium methoxide is 2 g: 0.1-0.3 g: 0.1 g: 10-20 mL: 6-10 mL.
5. The waterborne acrylic resin with the mildew-proof function of claim 3, wherein the dosage ratio of the N, N-dimethylformamide to the sum of the mass of the monomer a and the mass of the polymer b in the step S13 is 10-15 mL: 1g of a compound; in the step S14, the dosage ratio of the auxiliary agent, the deionized water, the methyl orthosilicate, the solid c and the dibutylamine is 2-4 mL: 10-12 mL: 0.1-0.3 g: 1 g: 0.1-0.3 mL.
6. The water-based acrylic resin with the mildew-proof function as claimed in claim 3, wherein the auxiliary agent is prepared by the following steps:
step S21, adding beta-cyclodextrin into deionized water, stirring for 20-24min at 80 ℃, then carrying out vacuum filtration, cooling the obtained filtrate to-10 ℃ to separate out crystals, and drying the obtained crystals to constant weight at 100 ℃ under vacuum when the crystal amount is not increased any more to obtain activated beta-cyclodextrin;
step S22, adding the activated beta-cyclodextrin, an emulsifier and deionized water into a four-neck flask, stirring for 20-30min at room temperature under the condition that the rotation speed is 200r/min, then heating to 50-60 ℃, adding methyl cyclotetrasiloxane, hydroxyl silicone oil and 20% of dodecafluoroheptyl methacrylate, stirring for 20min, then heating to 90 ℃, continuing to react for 2h, then adding an ammonium sulfate aqueous solution into the four-neck flask through a dropping funnel, simultaneously adding the remaining 80% of dodecafluoroheptyl methacrylate every 20min, continuing to react for 3h after the addition is finished, and obtaining the auxiliary agent after the reaction is finished.
7. The waterborne acrylic resin with the mildew-proof function of claim 6, wherein the amount ratio of the beta-cyclodextrin to the deionized water in the step S21 is 1: 10-15 mL; in the step S22, the emulsifier is sodium dodecyl sulfate and nonylphenol polyvinyl fluoride according to the mass ratio of 3: 1, and the dosage ratio of the activated beta-cyclodextrin, the emulsifier, the deionized water, the methylcyclotetrasiloxane, the hydroxyl silicone oil and the dodecafluoroheptyl methacrylate is 1 g: 0.1-0.3 g: 12mL of: 1-3 mL: 2mL of: 10 mL; the mass fraction of the ammonium sulfate aqueous solution is 8-10%; the remaining 80% of the methacrylic acid was added in eight equal amounts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011134672.3A CN112266440A (en) | 2020-10-21 | 2020-10-21 | Water-based acrylic resin with mildew-proof function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011134672.3A CN112266440A (en) | 2020-10-21 | 2020-10-21 | Water-based acrylic resin with mildew-proof function |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112266440A true CN112266440A (en) | 2021-01-26 |
Family
ID=74341375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011134672.3A Withdrawn CN112266440A (en) | 2020-10-21 | 2020-10-21 | Water-based acrylic resin with mildew-proof function |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112266440A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114834113A (en) * | 2022-04-28 | 2022-08-02 | 江阴市沪澄绝缘材料有限公司 | Aramid cloth phenolic resin laminated board for ship shockproof machinery |
-
2020
- 2020-10-21 CN CN202011134672.3A patent/CN112266440A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114834113A (en) * | 2022-04-28 | 2022-08-02 | 江阴市沪澄绝缘材料有限公司 | Aramid cloth phenolic resin laminated board for ship shockproof machinery |
| CN114834113B (en) * | 2022-04-28 | 2023-11-14 | 江阴市沪澄绝缘材料有限公司 | Aramid fiber cloth phenolic resin laminated board for ship vibration-proof machinery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2604508B2 (en) | Cationic microgels and their use in electrodeposition | |
| DE3807571C2 (en) | ||
| CN107488244B (en) | POSS (polyhedral oligomeric silsesquioxane) modified styrene-acrylic emulsion copolymer, and preparation method and application thereof | |
| CN1438257A (en) | Acrylic polyurethane copolymer emulsion, its preparation method and use | |
| JPH11509563A (en) | Aqueous powder coating dispersion | |
| CN103012689A (en) | Organic silicon acrylic acid modified waterborne epoxy emulsion and preparation method thereof | |
| CN113956422B (en) | Silane modified acrylate polymer, preparation method and application thereof, acrylate polymer coating and application thereof | |
| CN112266440A (en) | Water-based acrylic resin with mildew-proof function | |
| CN112143320B (en) | Ultraviolet-curing acrylic resin water-based paint and preparation method thereof | |
| CN109627959A (en) | Plentiful high thoroughly clear priming paint of a kind of aqueous UV high and its preparation method and application | |
| CN111944369A (en) | Antibacterial anticorrosive paint for building exterior wall and preparation method thereof | |
| CN106906462A (en) | A kind of metal surface pretreating reagent and preparation method thereof, application | |
| WO1994002425A2 (en) | Silicon or silica substrate with a modified surface, process for producing the same, new orthoesters and process for producing the same | |
| CN114133819A (en) | Antibacterial water-based acrylic resin coating and preparation method thereof | |
| CN102031055A (en) | Volatile organic solvent-free UV spraying finish coat | |
| CN110396175B (en) | Self-emulsifying antibacterial water-based epoxy resin and application thereof in wood and bamboo protection | |
| CN116463091B (en) | Double-component weather-resistant epoxy adhesive and preparation method thereof | |
| CN112175510A (en) | Environment-friendly water-based epoxy resin paint and processing method thereof | |
| CN113930117B (en) | Simple construction artistic coating and preparation method thereof | |
| JPH061928A (en) | Cationic micro-emulsion composition and its production | |
| CN111393985B (en) | Modified polyurethane water-based paint and preparation method thereof | |
| CN111019082B (en) | Nonionic photo-curing polyurethane aqueous dispersion resin composition with excellent compatibility and preparation method and application thereof | |
| CN113321958A (en) | Preservative composition and application thereof in anticorrosive high-temperature-resistant coating | |
| CN106590188A (en) | High-chlorinated polyethylene composite anti-corrosion coating being excellent in fireproofing performance and preparation method thereof | |
| CN106279545B (en) | Polystyrene foam plastics modified acrylic acid emulsion and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210126 |