CA3028455A1 - Preparation for acrylate resin coating and paint of flame-retardant, water-proof and water-based core-shell type - Google Patents
Preparation for acrylate resin coating and paint of flame-retardant, water-proof and water-based core-shell type Download PDFInfo
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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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
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- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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Abstract
A preparation for acrylate resin coating and paint of flame-retardant, water-proof and water-based core-shell type, which is prepared by adding the following weight ratio raw materials to a reaction vessel: 50-65 parts of water, 0.4-2.3 parts of emulsifier, methacrylic acid 0.6-3.0 parts and 0.3-0.7 parts of acrylic acid, heat up to 45°C, stir for 40min, add A monomer, emulsification time is 30-70min; heat up to 65°C to start reflux water, heat up to 77°C, keep warm, drop increase Agent A 0.3-0.7 parts by weight, the dropping time lasts for 1-3h, and the reaction is carried out for 2-4h after the addition, to obtain the core layer emulsion; the B monomer is added dropwise to the obtained core layer emulsion, 0.3-0.4 parts by weight Initiator A, the addition time lasts for 1-2h, after the addition is completed, the reaction is stirred at 75-85°C for 3h, then the flame retardant crosslinker is added to 0.6-1.1 parts by weight, the temperature is 75-95°C for 1-3h, and the temperature is lowered. Add 50 parts by weight of emulsifier to 50 ° C, the reaction time is 30 min, adjust the pH value to 7-8 with ammonia water, and obtain the flame retardant, water-repellent water-based core-shell acrylate resin coating and paint, and obtain the flame retardant water.
Core-shell acrylate resin coatings and paints have good flame retardancy.
Core-shell acrylate resin coatings and paints have good flame retardancy.
Description
Preparation for acrylate resin coating and paint of flame-retardant, water-proof and water-based core-shell type Technical field [01] The present invention relates to a method for preparing an aqueous core-shell type acrylate resin, particularly a flame-retardant aqueous core-shell type acrylate resin coating and a method for preparing a paint.
Background Arts
Background Arts
[02] Paint, the traditional name in China is paint.The so-called paint is a continuous film that is applied to the surface of the object to be protected or decorated and can form a firm adhesion with the object to be coated, usually based on resin, oil or emulsion, with or without adding pigments, fillers, and additions. A viscous liquid prepared with an organic solvent or water.
[03] In the 60 years since the founding of the People's Republic of China, along with the development of various industries in the national economy, the supporting coatings industry has gradually developed from an extremely unobtrusive small industry into an important industry in all areas of the national economy.After several generations of hard work and pioneering efforts, China has become the world's second largest paint producer and consumer, and has entered the mainstream of the world's coatings industry.
[04] Waterborne coatings and powder coatings have become a climate, especially architectural coatings based on waterborne paints, which account for about 38% of the total coatings in China.
Because the chemical properties of water-based paints and oil-based paints are fundamentally different, and the properties of water-based paints and oil-based paints are also very different, it is unscientific to define water-based paints as a major branch of the paint industry. .Water-based paints and oil (sex) paints should be listed as two different series in liquid paints.
Because the chemical properties of water-based paints and oil-based paints are fundamentally different, and the properties of water-based paints and oil-based paints are also very different, it is unscientific to define water-based paints as a major branch of the paint industry. .Water-based paints and oil (sex) paints should be listed as two different series in liquid paints.
[05] In the early stage of applying acrylic resin to leather finishing agent, people used the polymer synthesis technology such as bonding technology and cross-linking to introduce functional bases for their shortcomings such as water repellency, heat viscosity, cold brittleness and solvent resistance. Modification of styrene, acrylonitrile, etc., to meet the needs of the innate performance of leather finishing, and also established a foundation for the research of modern high-performance leather.
[06] The self-crosslinking acrylic resin finishing agent developed by Yang et al. can be obtained by introducing N-methylol acrylamide and acrylic acid in a butyl acrylate-acrylonitrile-methyl acrylate emulsion polymerization system. A leather finishing agent with better performance can improve the problem that the leather finishing agent is not resistant to organic solvents.
[07] Qi Shifang et al., after halogenating an acrylic monomer with phosphorus trichloride, reacted with polyethylene glycol to prepare a monoethylene glycol monoacrylate monomer containing a long polar side group, and then the single The acrylic resin emulsion is prepared by copolymerization of the body with other acrylates and vinyl compounds. The resin film has high tensile strength and elongation at break due to the presence of long, soft polar side groups;
Significantly improve the solvent and water resistance of the coating. Core-shell emulsion polymerization is a new technology developed in the 1980s. It is a new resin polymerization technology based on the principle of particle design. The core-shell type acrylic emulsion copolymer is heterogeneously coexisted in the latex particles by two or more kinds of polymers, that is, one polymer is a core, and the other is a core shell, and an outer layer is coated with an emulsion layer. The obtained emulsion has good anti-back tack, low film forming temperature, best film forming property, stability and superior mechanical properties, and the emulsion has the shell layer or the core layer of the latex particles by selecting different performance monomers respectively. Specific properties, the core-shell structure can solve the problems of resin properties such as soft and hard, heat and cold resistance. This technology has been widely used in the synthesis and modification of acrylic resins.
Significantly improve the solvent and water resistance of the coating. Core-shell emulsion polymerization is a new technology developed in the 1980s. It is a new resin polymerization technology based on the principle of particle design. The core-shell type acrylic emulsion copolymer is heterogeneously coexisted in the latex particles by two or more kinds of polymers, that is, one polymer is a core, and the other is a core shell, and an outer layer is coated with an emulsion layer. The obtained emulsion has good anti-back tack, low film forming temperature, best film forming property, stability and superior mechanical properties, and the emulsion has the shell layer or the core layer of the latex particles by selecting different performance monomers respectively. Specific properties, the core-shell structure can solve the problems of resin properties such as soft and hard, heat and cold resistance. This technology has been widely used in the synthesis and modification of acrylic resins.
[08] However, the currently used water-based acrylic resin coatings are also increasingly showing their insurmountable disadvantagesI71. For example, in the case of low temperature and high humidity, the drying is slow and difficult to form a film; the coating film is prone to mildew and is easily contaminated. It is not wear-resistant; the freeze-thaw stability and mechanical stability are not good; the dry and wet rubbing resistance of the finishing agent, the film formation compactness, the flatness and the glossiness are not good, and the further improvement of the performance of the finishing material is limited.
[09] In addition, there are defects in that the flame retardant performance is not high and the emulsifier is relatively cumbersome.
[10] 201610506501.6 The present invention relates to a self-flame-retardant acrylic emulsion, characterized in that the self-flame-retardant modified styrene-acrylic emulsion is a reactive halogen-containing flame-retardant vinyl monomer which can be used with acrylic acid. The ester monomer undergoes emulsion copolymerization, and the flame retardant group is fixed on the molecular structure of the resin by chemical bonding, and does not resolve and fall off. The synthesized acrylic emulsion has self-flame retarding property, and no additional resistance is needed when preparing the coating. The flammable agent can provide long-lasting flame retardant properties; the present invention also provides a method for preparing a self-flame retardant acrylic emulsion. The self-defining flame-retardant acrylic emulsion prepared by the invention has good adhesion, water resistance and durability, and the prepared coating film has water resistance, alkali resistance, scrub resistance and long-lasting self-flame retarding property, and is widely used indoors. Flame retardant coating for exterior wood, steel structure and building, which plays a decorative role and protects 201610645798.4 The invention relates to the field of production and preparation of polymer products, in particular to an acrylic resin flame retardant coating, 12-18 parts amino resin, 3-6 parts ethyl acrylate, 3-5 parts of butyl acrylate, 2-10 parts melamine, 1-2 parts defoamer, 2-6 parts of pigment and filler, 2-3 parts of acrylic acid, 60 to 70 parts by weight of an anionic aqueous resin containing a carboxyl group, 5 to 10 parts by weight of a water-resistant pigment, 7 to 8 parts by weight of an auxiliary agent, 1 to 2 parts by weight of an interfacial adhesion promoter, 4-8 parts of charcoal agent, 10-20 parts by weight of deionized water; interface adhesion promoter is formed by reacting metal organic compounds, polyisocyanates and hydroxyl groups-containing oligomers. The acrylic resin coating of the present invention has excellent interfacial adhesion with the substrate and has a good flame retarding effect.
Summary of the invention
Summary of the invention
[11] The present invention relates to a flame-retardant aqueous core-shell type acrylate resin coating and a preparation method of a paint. The main synthetic route is to improve the water-based core-shell type acrylate resin coating and paint by flame retardant functionalization of the crosslinking agent. The flame retardancy, that is, the flame retardant modification from the viewpoint of the chemical materials required for the acrylate resin, and the stability of the acid-base salt is improved due to the anionic and nonionic combination required in the synthesis of the acrylate resin. The mechanical stirring stability, the two are combined into one, and a new type of emulsifier with both anionic and nonionic properties is prepared. The emulsifier has the advantages of convenient operation, stable acid-base salt stability and mechanical stirring stability.
Advantage.
Advantage.
[12] A method for preparing a flame-retardant aqueous core-shell acrylate resin coating and a paint, the preparation method thereof is:
(1) Adding the following weight ratio raw materials to the reaction vessel: 50 to 65 parts of water, 0.4 to 2.3 parts of emulsifier, 0.6 to 3.0 parts of methacrylic acid, and 0.3 to 0.7 parts of acrylic acid, and the temperature is raised to 45 C, and stirred for 40 minutes.
Adding A monomer, the emulsification time is 30-70min; the temperature is raised to 65 C and the reflux water is started.
After the temperature is raised to 77 C, the temperature is kept, and the initiator A0.3-0.7 parts by weight is added dropwise. The dropping time lasts for 1-3 hours. After the reaction, 2-4h, the core layer emulsion is obtained;
The monomer A is prepared by mixing 2-7 parts by weight of butyl acrylate, 2-5 parts by weight of methyl methacrylate, 3-3.5 parts by weight of ethyl acrylate, and 2-4 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 to 0.4 parts by weight of initiator A to the core layer emulsion obtained in the step (1), and the dropwise addition time lasts for 1 to 2 hours, and after the completion of the dropwise addition, the reaction is stirred at 75 to 85 C for 3 hours.
Then add 0.6-1.1 parts by weight of flame retardant cross-linking agent, heat-treat 75-95 C for l-3h, cool down to 50 C, add 0.3 parts by weight of emulsifier, react time for 30min, add ammonia to adjust pH to 7-8 , the flame retardant, water-repellent water-based core-shell acrylate resin coating and paint;
The B monomer is obtained by mixing 1 to 6 parts by weight of butyl acrylate, 3 to 7 parts by weight of methyl methacrylate, 3 to 5 parts by weight of ethyl acrylate, and 2 to 6 parts of hydroxyethyl acrylate.
(1) Adding the following weight ratio raw materials to the reaction vessel: 50 to 65 parts of water, 0.4 to 2.3 parts of emulsifier, 0.6 to 3.0 parts of methacrylic acid, and 0.3 to 0.7 parts of acrylic acid, and the temperature is raised to 45 C, and stirred for 40 minutes.
Adding A monomer, the emulsification time is 30-70min; the temperature is raised to 65 C and the reflux water is started.
After the temperature is raised to 77 C, the temperature is kept, and the initiator A0.3-0.7 parts by weight is added dropwise. The dropping time lasts for 1-3 hours. After the reaction, 2-4h, the core layer emulsion is obtained;
The monomer A is prepared by mixing 2-7 parts by weight of butyl acrylate, 2-5 parts by weight of methyl methacrylate, 3-3.5 parts by weight of ethyl acrylate, and 2-4 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 to 0.4 parts by weight of initiator A to the core layer emulsion obtained in the step (1), and the dropwise addition time lasts for 1 to 2 hours, and after the completion of the dropwise addition, the reaction is stirred at 75 to 85 C for 3 hours.
Then add 0.6-1.1 parts by weight of flame retardant cross-linking agent, heat-treat 75-95 C for l-3h, cool down to 50 C, add 0.3 parts by weight of emulsifier, react time for 30min, add ammonia to adjust pH to 7-8 , the flame retardant, water-repellent water-based core-shell acrylate resin coating and paint;
The B monomer is obtained by mixing 1 to 6 parts by weight of butyl acrylate, 3 to 7 parts by weight of methyl methacrylate, 3 to 5 parts by weight of ethyl acrylate, and 2 to 6 parts of hydroxyethyl acrylate.
[13] Initiator A is any one of ammonium persulfate, potassium persulfate, and potassium hydrogen persulfate; the emulsifier is prepared by adding 15 g of triethylenetetramine and 70 g of water to a three-necked flask, and heating to 30 C. 40 g of ethylene oxide and 1.2 to 2.4 g of substance A
were slowly added, and after reacting at 30 C for 2 h, cooled to 25 C to obtain an intermediate product, and then 15 g of dodecylphenol and 1.6 g of pentadecyl group were added. Phenol and substance B0.3g, and then increase the temperature to 100 C reflux reaction for lh, the solvent is distilled off under reduced pressure, which is an emulsifier; substance A is 2-bromobutyric acid ethyl ester, 9-fluorenyl methyl chloroformate, Any one of trimethylcyclotriborane; the substance B is any one of ethoxylated amine hydrochloride, methylethylamine and acetic anhydride; the flame retardant crosslinking agent is prepared by: 2.1 g of fork diphosphonic acid, 2.5 g of phosphorus tetramethylolsulfate and 1.2 g of the substance C1.2 were added to 250 ml of a three-necked flask, reacted at 70 C for 1 h, and 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were further added. The reaction is carried out at 65 C for 1.5 h to obtain the flame-retardant crosslinking agent; the substance C is any one of 4,41-bipyridine, aminoacetonitrile or iminodiacetonitrile.
were slowly added, and after reacting at 30 C for 2 h, cooled to 25 C to obtain an intermediate product, and then 15 g of dodecylphenol and 1.6 g of pentadecyl group were added. Phenol and substance B0.3g, and then increase the temperature to 100 C reflux reaction for lh, the solvent is distilled off under reduced pressure, which is an emulsifier; substance A is 2-bromobutyric acid ethyl ester, 9-fluorenyl methyl chloroformate, Any one of trimethylcyclotriborane; the substance B is any one of ethoxylated amine hydrochloride, methylethylamine and acetic anhydride; the flame retardant crosslinking agent is prepared by: 2.1 g of fork diphosphonic acid, 2.5 g of phosphorus tetramethylolsulfate and 1.2 g of the substance C1.2 were added to 250 ml of a three-necked flask, reacted at 70 C for 1 h, and 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were further added. The reaction is carried out at 65 C for 1.5 h to obtain the flame-retardant crosslinking agent; the substance C is any one of 4,41-bipyridine, aminoacetonitrile or iminodiacetonitrile.
[14] The advantages of the invention are:
(1) The flame retardant function of the cross-linking agent is improved to improve the flame retardancy of the aqueous core-shell type acrylate resin coating and the paint, that is, from the viewpoint of the chemical materials required for the acrylate resin, At the same time, due to the need of anionic and nonionic complexes in the synthesis of acrylate-based resins to improve the stability of acid-base salts and the stability of mechanical agitation, the two are combined into one, and a new type of anionic and nonionic properties is produced. An emulsifier which has the advantages of convenient operation, stability of acid-base salt and stability of mechanical stirring.
(1) The flame retardant function of the cross-linking agent is improved to improve the flame retardancy of the aqueous core-shell type acrylate resin coating and the paint, that is, from the viewpoint of the chemical materials required for the acrylate resin, At the same time, due to the need of anionic and nonionic complexes in the synthesis of acrylate-based resins to improve the stability of acid-base salts and the stability of mechanical agitation, the two are combined into one, and a new type of anionic and nonionic properties is produced. An emulsifier which has the advantages of convenient operation, stability of acid-base salt and stability of mechanical stirring.
[15] (2) 2-bromobutyric acid ethyl ester, 9-fluorenyl methyl chloroformate, trimethylcyclotriboroxane as an emulsifier synthesis catalyst, and ethoxylated amine hydrochloride, methyl Ethylamine and acetic acid propionic anhydride to enhance the synergist of dodecylphenol and m-pentadecylphenol; 4,4'-bipyridine, aminoacetonitrile, iminodiacetonitrile as hydroxyethylidene diphosphonic acid, tetrahydroxyl A catalyst for phosphorus methyl sulfate.
[16] (3) The mechanism of the present invention is to form a dense film by using a crosslinking agent, and a flame retardant group on the surface of the acrylate resin, thereby reducing the burning speed of the flame and improving the flame retardancy thereof. .
Embodiments
Embodiments
[17] Example 1 A method for preparing a flame-retardant aqueous core-shell acrylate resin coating and a paint, the preparation method thereof is:
(1) Adding the following weight ratio raw materials to the reaction vessel: 50 parts of water, 0.4 parts of emulsifier, 0.6 parts of methacrylic acid and 0.3 parts of acrylic acid were added to the reaction vessel, and the temperature was raised to 45 C, stirred for 40 minutes, and added to A.
Monomer, the emulsification time is 30min; the temperature is raised to 65 C, the reflux water is started, the temperature is raised to 77 C, the temperature is kept, 0.3 parts by weight of ammonium persulfate is added dropwise (dissolved with 5 g of water), the dropping time is continued for 1 h, and the reaction is completed after the dropwise addition.
2h, obtained a core layer emulsion;
The A monomer is prepared by mixing 2 parts by weight of butyl acrylate, 2 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate, and 2 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 parts by weight of ammonium persulfate (dissolved with 5 g of water) to the core layer emulsion obtained in the step (1), the dropwise addition time is continued for 1 hour, and after the completion of the dropwise addition, the reaction is stirred at 75 C for 3 hours. Then add 0.6 parts by weight of flame retardant cross-linking agent, keep the reaction time of 75 C for 1 h, reduce the temperature to 50 C, add 0.3 parts by weight of emulsifier, the reaction time is 30 min, add ammonia to adjust the pH value to 7-8, and obtain the resistance Water-based core-shell acrylate resin coatings and paints;
The B monomer is a mixture of 1 part by weight of butyl acrylate, 3 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate, and 2 parts of hydroxyethyl acrylate.
(1) Adding the following weight ratio raw materials to the reaction vessel: 50 parts of water, 0.4 parts of emulsifier, 0.6 parts of methacrylic acid and 0.3 parts of acrylic acid were added to the reaction vessel, and the temperature was raised to 45 C, stirred for 40 minutes, and added to A.
Monomer, the emulsification time is 30min; the temperature is raised to 65 C, the reflux water is started, the temperature is raised to 77 C, the temperature is kept, 0.3 parts by weight of ammonium persulfate is added dropwise (dissolved with 5 g of water), the dropping time is continued for 1 h, and the reaction is completed after the dropwise addition.
2h, obtained a core layer emulsion;
The A monomer is prepared by mixing 2 parts by weight of butyl acrylate, 2 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate, and 2 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 parts by weight of ammonium persulfate (dissolved with 5 g of water) to the core layer emulsion obtained in the step (1), the dropwise addition time is continued for 1 hour, and after the completion of the dropwise addition, the reaction is stirred at 75 C for 3 hours. Then add 0.6 parts by weight of flame retardant cross-linking agent, keep the reaction time of 75 C for 1 h, reduce the temperature to 50 C, add 0.3 parts by weight of emulsifier, the reaction time is 30 min, add ammonia to adjust the pH value to 7-8, and obtain the resistance Water-based core-shell acrylate resin coatings and paints;
The B monomer is a mixture of 1 part by weight of butyl acrylate, 3 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate, and 2 parts of hydroxyethyl acrylate.
[18] The emulsifier is prepared by adding 15 g of triethylenetetramine and 70 g of water to a three-necked flask. After heating to 30 C, 40 g of ethylene oxide and 1.2 g of ethyl 2-bromobutyrate are slowly added at 30 C. After 2 h of reaction, it was cooled to 25 C to b/14 obtain an intermediate product, then 15 g of dodecylphenol, 1.6 g of m-pentadecylphenol and 0.3 g of ethoxylated amine salt were added, and the temperature was raised to 100 C. The reaction was refluxed for 1 h, and the solvent was distilled off under reduced pressure to obtain an emulsifier;
The flame-retardant cross-linking agent is prepared by adding 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylolsulfate, and 1.2 g of 4,4'-bipyridine to 250 ml of a three-necked flask, and reacting at 70 C for 1 h. Further, 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were added, and the mixture was reacted at 65 C for 1.5 hours to obtain a flame-retardant crosslinking agent.
The flame-retardant cross-linking agent is prepared by adding 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylolsulfate, and 1.2 g of 4,4'-bipyridine to 250 ml of a three-necked flask, and reacting at 70 C for 1 h. Further, 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were added, and the mixture was reacted at 65 C for 1.5 hours to obtain a flame-retardant crosslinking agent.
[19] Example 2 A method for preparing a flame-retardant aqueous core-shell acrylate resin coating and a paint, the preparation method thereof is:
(1) The following weight ratio raw materials were added to the reaction vessel: 65 parts of water, 2.3 parts of emulsifier, 3.0 parts of methacrylic acid and 0.7 parts of acrylic acid, and the temperature was raised to 45 C, stirred for 40 minutes, and A monomer was added to emulsification time. 70min; heating to 65 C began to pass the reflux water, the temperature was raised to 77 C after the insulation, dropwise addition of 0.7 parts by weight of potassium persulfate (dissolved with 5g of water), the addition time lasted 3h, after the addition of reaction, 4h, the core layer Emulsion The A monomer is prepared by mixing 7 parts by weight of butyl acrylate, 5 parts by weight of methyl methacrylate, 3.5 parts by weight of ethyl acrylate, and 4 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.4 parts by weight of potassium persulfate (dissolved with 5 g of water) to the core layer emulsion obtained in the step (1), the dropwise addition time is continued for 2 hours, and after the completion of the dropwise addition, the mixture is stirred at 85 C for 3 hours. Then add 1.1 parts by weight of flame retardant cross-linking agent, keep the reaction time of 95 C for 3 h, reduce the temperature to 50 C, add 0.3 parts by weight of emulsifier, react time for 30 mm, add ammonia water to adjust the pH value to 7-8, and obtain the resistance Water-based core-shell acrylate resin coatings and paints;
The B monomer was prepared by mixing 6 parts by weight of butyl acrylate, 7 parts by weight of methyl methacrylate, 5 parts by weight of ethyl acrylate, and 6 parts of hydroxyethyl acrylate.
(1) The following weight ratio raw materials were added to the reaction vessel: 65 parts of water, 2.3 parts of emulsifier, 3.0 parts of methacrylic acid and 0.7 parts of acrylic acid, and the temperature was raised to 45 C, stirred for 40 minutes, and A monomer was added to emulsification time. 70min; heating to 65 C began to pass the reflux water, the temperature was raised to 77 C after the insulation, dropwise addition of 0.7 parts by weight of potassium persulfate (dissolved with 5g of water), the addition time lasted 3h, after the addition of reaction, 4h, the core layer Emulsion The A monomer is prepared by mixing 7 parts by weight of butyl acrylate, 5 parts by weight of methyl methacrylate, 3.5 parts by weight of ethyl acrylate, and 4 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.4 parts by weight of potassium persulfate (dissolved with 5 g of water) to the core layer emulsion obtained in the step (1), the dropwise addition time is continued for 2 hours, and after the completion of the dropwise addition, the mixture is stirred at 85 C for 3 hours. Then add 1.1 parts by weight of flame retardant cross-linking agent, keep the reaction time of 95 C for 3 h, reduce the temperature to 50 C, add 0.3 parts by weight of emulsifier, react time for 30 mm, add ammonia water to adjust the pH value to 7-8, and obtain the resistance Water-based core-shell acrylate resin coatings and paints;
The B monomer was prepared by mixing 6 parts by weight of butyl acrylate, 7 parts by weight of methyl methacrylate, 5 parts by weight of ethyl acrylate, and 6 parts of hydroxyethyl acrylate.
[20] The emulsifier is prepared by adding 15 g of triethylenetetramine and 70 g of water to a three-necked flask, and after heating to 30 C, 40 g of ethylene oxide and 2.4 g of 9-fluorenylmethyl chloroformate are slowly added. After reacting at 30 C for 2 h, it was cooled to 25 C to obtain an intermediate product, and then 15 g of dodecylphenol, 1.6 g of m-pentadecylphenol and methylethylamine 0.3 g were added, and the temperature was raised to 100 C to reflux. After reacting for 1 hour, the solvent is distilled off under reduced pressure to obtain an emulsifier; the flame-retardant cross-linking agent is prepared by adding 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylolsulfate, and 1.2 g of aminoacetonitrile to three. In a 250 ml flask, the reaction was carried out at 70 C for 1 h, and 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were further added, and the mixture was reacted at 65 C for 1.5 h to obtain a flame-retardant crosslinking agent.
[21] Example 3 A method for preparing a flame-retardant aqueous core-shell acrylate resin coating and a paint, the preparation method thereof is:
(1) The following weight-matching raw materials were added to the reaction vessel: 57 parts of water, 1.3 parts of emulsifier, 1.8 parts of methacrylic acid and 0.5 parts of acrylic acid, and the temperature was raised to 45 C, stirred for 40 minutes, and A monomer was added to emulsification time. 50min; heating to 65 C began to pass the reflux water, the temperature was raised to 77 C after the incubation, 0.5 parts by weight of potassium persulfate (dissolved with 5g of water), the addition time lasted 2h, after the addition of reaction, 3h, obtained nuclear Layer emulsion The A monomer is prepared by mixing 4.5 parts by weight of butyl acrylate, 3.5 parts by weight of methyl methacrylate, 3.3 parts by weight of ethyl acrylate, and 3 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 parts by weight of potassium persulfate (dissolved with 5 g of water) to the core layer emulsion obtained in the step (1), the dropping time is continued for 1.5 hours, and the mixture is kept at 80 C after the dropwise addition. 3h, adding 0.8 parts by weight of flame retardant cross-linking agent, keeping the reaction time of 85 C for 2 h, cooling to 50 C, adding 0.3 parts by weight of emulsifier, reaction time 30 min, adding ammonia to adjust pH to 7-8, Flame-retardant water-based core-shell acrylate resin coatings and paints;
The B monomer was prepared by mixing 3.5 parts by weight of butyl acrylate, 5 parts by weight of methyl methacrylate, 4 parts by weight of ethyl acrylate, and 4 parts of hydroxyethyl acrylate.
(1) The following weight-matching raw materials were added to the reaction vessel: 57 parts of water, 1.3 parts of emulsifier, 1.8 parts of methacrylic acid and 0.5 parts of acrylic acid, and the temperature was raised to 45 C, stirred for 40 minutes, and A monomer was added to emulsification time. 50min; heating to 65 C began to pass the reflux water, the temperature was raised to 77 C after the incubation, 0.5 parts by weight of potassium persulfate (dissolved with 5g of water), the addition time lasted 2h, after the addition of reaction, 3h, obtained nuclear Layer emulsion The A monomer is prepared by mixing 4.5 parts by weight of butyl acrylate, 3.5 parts by weight of methyl methacrylate, 3.3 parts by weight of ethyl acrylate, and 3 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 parts by weight of potassium persulfate (dissolved with 5 g of water) to the core layer emulsion obtained in the step (1), the dropping time is continued for 1.5 hours, and the mixture is kept at 80 C after the dropwise addition. 3h, adding 0.8 parts by weight of flame retardant cross-linking agent, keeping the reaction time of 85 C for 2 h, cooling to 50 C, adding 0.3 parts by weight of emulsifier, reaction time 30 min, adding ammonia to adjust pH to 7-8, Flame-retardant water-based core-shell acrylate resin coatings and paints;
The B monomer was prepared by mixing 3.5 parts by weight of butyl acrylate, 5 parts by weight of methyl methacrylate, 4 parts by weight of ethyl acrylate, and 4 parts of hydroxyethyl acrylate.
[22] The emulsifier is prepared by adding 15 g of triethylenetetramine and 70 g of water to a three-necked flask, and after heating to 30 C, 40 g of ethylene oxide and 1.8 g of trimethylcyclotrioxane are slowly added, at 30 After reacting at C for 2 h, it was cooled to 25 C
to obtain an intermediate product, and then 15 g of dodecylphenol, 1.6 g of m-pentadecylphenol and acetic anhydride (0.3 g) were added, and the temperature was raised to 100 C to reflux for 1 h. The solvent is distilled off under reduced pressure, which is an emulsifier; the flame-retardant cross-linking agent is prepared by adding 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylolsulfate, and 1.2 g of iminodiacetonitrile to three. In a 250 ml flask, the reaction was carried out at 70 C for 1 h, and 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were further added, and the mixture was reacted at 65 C for 1.5 h to obtain a flame-retardant crosslinking agent.
to obtain an intermediate product, and then 15 g of dodecylphenol, 1.6 g of m-pentadecylphenol and acetic anhydride (0.3 g) were added, and the temperature was raised to 100 C to reflux for 1 h. The solvent is distilled off under reduced pressure, which is an emulsifier; the flame-retardant cross-linking agent is prepared by adding 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylolsulfate, and 1.2 g of iminodiacetonitrile to three. In a 250 ml flask, the reaction was carried out at 70 C for 1 h, and 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were further added, and the mixture was reacted at 65 C for 1.5 h to obtain a flame-retardant crosslinking agent.
[23] Example 4 A method for preparing a flame-retardant aqueous core-shell acrylate resin coating and a paint, the preparation method thereof is:
(1) The following weight ratio raw materials were added to the reaction vessel: 50 parts of water, 2.3 parts of emulsifier, 3.0 parts of methacrylic acid and 0.3 parts of acrylic acid, and the temperature was raised to 45 C, stirred for 40 minutes, and A monomer was added, and the emulsification time was 40min; warmed to 65 C began to pass the reflux water, the temperature was raised to 77 C after the insulation, dropwise addition of 0.4 parts by weight of ammonium persulfate (dissolved with 5g of water), the addition time lasted 1.5h, after the addition of reaction, 3h, the core layer Emulsion The A monomer is prepared by mixing 4 parts by weight of butyl acrylate, 3 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate, and 4 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 parts by weight of ammonium persulfate (dissolved with 5 g of water) to the core layer emulsion obtained in the step (1), the dropwise addition time is continued for 1 hour, and after the completion of the dropwise addition, the reaction is stirred at 75 C for 3 hours. Then add 0.7 parts by weight of the flame retardant cross-linking agent, keep the reaction time of 80 C for 2 h, cool down to 50 C, add 0.3 parts by weight of emulsifier, the reaction time is 30 min, add ammonia water to adjust the pH value to 7-8, and obtain the resistance Water-based core-shell type acrylate resin coating and paint; the B
monomer is composed of: 3 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, 4 parts by weight of ethyl acrylate, and 6 parts by weight of hydroxyethyl acrylate Mixed.
(1) The following weight ratio raw materials were added to the reaction vessel: 50 parts of water, 2.3 parts of emulsifier, 3.0 parts of methacrylic acid and 0.3 parts of acrylic acid, and the temperature was raised to 45 C, stirred for 40 minutes, and A monomer was added, and the emulsification time was 40min; warmed to 65 C began to pass the reflux water, the temperature was raised to 77 C after the insulation, dropwise addition of 0.4 parts by weight of ammonium persulfate (dissolved with 5g of water), the addition time lasted 1.5h, after the addition of reaction, 3h, the core layer Emulsion The A monomer is prepared by mixing 4 parts by weight of butyl acrylate, 3 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate, and 4 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 parts by weight of ammonium persulfate (dissolved with 5 g of water) to the core layer emulsion obtained in the step (1), the dropwise addition time is continued for 1 hour, and after the completion of the dropwise addition, the reaction is stirred at 75 C for 3 hours. Then add 0.7 parts by weight of the flame retardant cross-linking agent, keep the reaction time of 80 C for 2 h, cool down to 50 C, add 0.3 parts by weight of emulsifier, the reaction time is 30 min, add ammonia water to adjust the pH value to 7-8, and obtain the resistance Water-based core-shell type acrylate resin coating and paint; the B
monomer is composed of: 3 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, 4 parts by weight of ethyl acrylate, and 6 parts by weight of hydroxyethyl acrylate Mixed.
[24] The emulsifier is prepared by adding 15 g of triethylenetetramine and 70 g of water to a three-necked flask, and heating to 30 C, and slowly adding 40 g of ethylene oxide and 1.6 g of ethyl 2-bromobutyrate at 30 C. After 2 h of reaction, it was cooled to 25 C to obtain an intermediate product, then 15 g of dodecylphenol, 1.6 g of m-pentadecylphenol and 0.3 g of ethoxylated amine salt were added, and the temperature was raised to 100 C.
The reaction was refluxed for 1 h, and the solvent was distilled off under reduced pressure to obtain an emulsifier.
The flame-retardant cross-linking agent was prepared by adding 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylolsulfate, and 1.2 g of aminoacetonitrile. In 250 ml of a three-necked flask, the reaction was carried out at 70 C for 1 h, and 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were further added, and the mixture was reacted at 65 C for 1.5 h to obtain a flame-retardant crosslinking agent.
The reaction was refluxed for 1 h, and the solvent was distilled off under reduced pressure to obtain an emulsifier.
The flame-retardant cross-linking agent was prepared by adding 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylolsulfate, and 1.2 g of aminoacetonitrile. In 250 ml of a three-necked flask, the reaction was carried out at 70 C for 1 h, and 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were further added, and the mixture was reacted at 65 C for 1.5 h to obtain a flame-retardant crosslinking agent.
[25] Example 5 A method for preparing a flame-retardant aqueous core-shell acrylate resin coating and a paint, the preparation method thereof is:
(1) The following weight ratio raw materials were added to the reaction vessel: 65 parts of water, 2.3 parts of emulsifier, 3.0 parts of methacrylic acid and 0.7 parts of acrylic acid, and the temperature was raised to 45 C, stirred for 40 minutes, and A monomer was added to emulsification time. 70min; warming to 65 C began to pass the reflux water, warmed to 77 C
after the insulation, dropwise addition of 0.7 parts by weight of potassium persulfate (dissolved with 5g of water), the addition time lasted for lh, after the completion of the addition of reaction for 2h, the nuclear layer Emulsion The monomer A is prepared by mixing 7 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate, and 2 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 parts by weight of potassium persulfate (dissolved with 5 g of water) to the core layer emulsion obtained in the step (1), the dropwise addition time is continued for 1 hour, and after the completion of the dropwise addition, the reaction is stirred at 75 C for 3 hours. Then add 0.6 parts by weight of flame retardant cross-linking agent, keep the reaction time of 75 C for 1 h, reduce the temperature to 50 C, add 0.3 parts by weight of emulsifier, the reaction time is 30 min, add ammonia to adjust the pH value to 7-8, and obtain the resistance Water-based core-shell type acrylate resin coating and paint; the B
monomer is composed of: 6 parts by weight of butyl acrylate, 7 parts by weight of methyl methacrylate, 5 parts by weight of ethyl acrylate, and 6 parts by weight of hydroxyethyl acrylate Mixed.
(1) The following weight ratio raw materials were added to the reaction vessel: 65 parts of water, 2.3 parts of emulsifier, 3.0 parts of methacrylic acid and 0.7 parts of acrylic acid, and the temperature was raised to 45 C, stirred for 40 minutes, and A monomer was added to emulsification time. 70min; warming to 65 C began to pass the reflux water, warmed to 77 C
after the insulation, dropwise addition of 0.7 parts by weight of potassium persulfate (dissolved with 5g of water), the addition time lasted for lh, after the completion of the addition of reaction for 2h, the nuclear layer Emulsion The monomer A is prepared by mixing 7 parts by weight of butyl acrylate, 4 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate, and 2 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 parts by weight of potassium persulfate (dissolved with 5 g of water) to the core layer emulsion obtained in the step (1), the dropwise addition time is continued for 1 hour, and after the completion of the dropwise addition, the reaction is stirred at 75 C for 3 hours. Then add 0.6 parts by weight of flame retardant cross-linking agent, keep the reaction time of 75 C for 1 h, reduce the temperature to 50 C, add 0.3 parts by weight of emulsifier, the reaction time is 30 min, add ammonia to adjust the pH value to 7-8, and obtain the resistance Water-based core-shell type acrylate resin coating and paint; the B
monomer is composed of: 6 parts by weight of butyl acrylate, 7 parts by weight of methyl methacrylate, 5 parts by weight of ethyl acrylate, and 6 parts by weight of hydroxyethyl acrylate Mixed.
[26] The preparation method of the emulsifier is to add 15 g of triethylenetetramine and 70 g of water to a three-necked flask, and after heating to 30 C, 40 g of ethylene oxide and 1.6 g of 9-fluorenylmethyl chloroformate are slowly added. After reacting at 30 C for 2 h, it was cooled to 25 C to obtain an intermediate product, and then 15 g of dodecylphenol, 1.6 g of m-pentadecylphenol and methylethylamine 0.3 g were added, and the temperature was raised to 100 C to reflux. After reacting for 1 h, the solvent was distilled off under reduced pressure to obtain an emulsifier; the preparation method of the flame-retardant cross-linking agent was as follows; 2.1 g of hydroxyethylidene diphosphonic acid, 2.5 g of tetramethylolsulfate and 1.2 g of iminodiacetonitrile were added. The mixture was reacted at 250 C for 1 hour in 250 ml of a three-necked flask, and 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were further added thereto, and the mixture was reacted at 65 C for 1.5 hours to obtain a flame-retardant crosslinking agent.
[27] Flame retardancy is measured by oxygen index and flaming time.
[28] Table 1 Test performance Example Example 2 Example 3 Example 4 Example 5 Oxygen Index/% 29.4 29.6 30.4 29.8 29.8 Flaming burning 1.1 1.6 0.8 1.2 2.1 time / s It can be seen from Table 1 that the oxygen index of the flame-retardant aqueous core-shell type acrylate resin coating and paint is greatly increased, while the flaming burning time is greatly reduced, and the oxygen index and the flaming burning time of Example 1 of 201610506501.6 and 201610645798.4 are compared. They are 22.6, 26.5s and 24.1 and 36.5s respectively.
[29] Table 2 Test performance (no flame retardant crosslinker added) Example 1 Example 2 Example 3 Example 4 Example 5 Oxygen 21.6 22.7 20.4 21.2 21.7 Index/%
Flaming burning time31.2 32.7 29.4 22.1 25.7 /s It can be seen from Table 2 that the oxygen index of the flame-retardant water-based core-shell type acrylate resin coating and the paint without the flame-retardant cross-linking agent is greatly reduced, and the flaming burning time is greatly improved.
Flaming burning time31.2 32.7 29.4 22.1 25.7 /s It can be seen from Table 2 that the oxygen index of the flame-retardant water-based core-shell type acrylate resin coating and the paint without the flame-retardant cross-linking agent is greatly reduced, and the flaming burning time is greatly improved.
[30] Table 3 test performance (add flame retardant crosslinker, no added material C) Example 1 Example 2 Example 3 Example 4 Example 5 Oxygen 25.2 24.7 26.4 25.3 27.2 Index/%
Flaming burning time 11.2 22.7 25.4 16.1 18.2 /s It can be seen from Table 3 that the flame retardant aqueous core-shell acrylate resin coating and the paint have a substantially higher oxygen index than the flame retardant cross-linking agent when the flame retardant cross-linking agent is added with no substance C. The flame burning time has dropped dramatically.
Flaming burning time 11.2 22.7 25.4 16.1 18.2 /s It can be seen from Table 3 that the flame retardant aqueous core-shell acrylate resin coating and the paint have a substantially higher oxygen index than the flame retardant cross-linking agent when the flame retardant cross-linking agent is added with no substance C. The flame burning time has dropped dramatically.
[31] Table 4 test performance (add flame retardant crosslinker, addition of substance C, without addition of 2,3-pyridinedicarboxylic acid) Example 1 Example 2 Example 3 Example 4 Example 5 Oxygen 26.3 25.8 27.1 26.1 27.3 Index/%
Flaming burning time 10.3 14.2 18.3 12.0 12.4 It can be seen from Table 4 that the flame retardant aqueous core-shell acrylate resin coating and the paint have no oxygen index when the flame retardant crosslinking agent and the additive C are added without adding 2,3-pyridinedicarboxylic acid. The addition of the flame retardant cross-linking agent is greatly increased, while the flaming burning time is greatly reduced.
Flaming burning time 10.3 14.2 18.3 12.0 12.4 It can be seen from Table 4 that the flame retardant aqueous core-shell acrylate resin coating and the paint have no oxygen index when the flame retardant crosslinking agent and the additive C are added without adding 2,3-pyridinedicarboxylic acid. The addition of the flame retardant cross-linking agent is greatly increased, while the flaming burning time is greatly reduced.
[32] Chemical resistance stability: The emulsion was mixed with a 5% sodium chloride solution at a volume ratio of 1:4, sealed and allowed to stand for 48 hours, and the amount of precipitation was observed.
[33] Gel fraction: The percentage of the weight of the gel in the synthesis of the acrylic resin to the weight of the theoretically obtained emulsion was measured.
[34] Table 5 Emulsion stability data Example 1 Example 2 Example 3 Example 4 Example 5 Stable Stable Stable Stable Stable Chemical without without without without without resistance stratification stratification stratification stratification stratification Gel filter /% 1.6 2.1 1.7 1.1 0.8 It can be seen from Table 5 that the chemical resistance and gel filtration of the present invention are relatively good.The gel filtration of Example 1 of the comparative samples of 201610506501.6 and 201610645798.4 was 9.7% and 8.3%, respectively.
[35] Table 6 Emulsion stability data (without substance A) Example 1 Example 2 Example 3 Example 4 Example 5 Stable Stable Chemical without Layering without Layering Layering resistance stratification stratification Gel filter /% 7.6 5.8 6.2 4.8 6.6 From Table 6, it can be seen that the chemical resistance and gel filtration of the present invention without the substance A are remarkably lowered.
[36] Table 7 Emulsion stability data (addition A, no addition B) Example 1 Example 2 Example 3 Example 4 Example 5 Chemical Layering Layering Layering Layering Layering resistance Gel filter /% 7.7 10.3 12.7 8.6 14.3 It can be seen from Table 7 that the gel and chemical resistance of the unsubstance B of the present invention are remarkably lowered.
Claims (6)
1. A preparation for acrylate resin coating and paint of flame-retardant, water-proof and water-based core-shell type thereof is:
(1) adding the following weight ratio raw materials to the reaction vessel:
mixing 50 to 65 parts of water, 0.4 to 2.3 parts of emulsifier, 0.6 to 3.0 parts of methacrylic acid, and 0.3 to 0.7 parts of acrylic acid, and heating to 45 ° C. Stir for 40min, add A monomer, emulsification time is 30-70min; start to reflux water after heating to 65°C, heat up to 77°C, keep warm, add initiator A0.3-0.7wt, drop time lasts for 1-3h After the completion of the dropwise addition, the reaction is carried out for 2 to 4 hours to obtain a core layer emulsion;
The monomer A is prepared by mixing 2-7 parts by weight of butyl acrylate, 2-5 parts by weight of methyl methacrylate, 3-3.5 parts by weight of ethyl acrylate, and 2-4 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 to 0.4 parts by weight of initiator A to the core layer emulsion obtained in the step (1), and the dropwise addition time lasts for 1 to 2 hours, and after the completion of the dropwise addition, the reaction is stirred at 75 to 85 ° C for 3 hours.
Then add 0.6-1.1 parts by weight of flame retardant cross-linking agent, heat-treat 75-95°C for 1-3h, cool down to 50°C, add 0.3 parts by weight of emulsifier, react time for 30min, add ammonia to adjust pH to 7-8 , the flame retardant, water-repellent water-based core-shell acrylate resin coating and paint;
The B monomer is obtained by mixing 1 to 6 parts by weight of butyl acrylate, 3 to 7 parts by weight of methyl methacrylate, 3 to 5 parts by weight of ethyl acrylate, and 2 to 6 parts of hydroxyethyl acrylate.
(1) adding the following weight ratio raw materials to the reaction vessel:
mixing 50 to 65 parts of water, 0.4 to 2.3 parts of emulsifier, 0.6 to 3.0 parts of methacrylic acid, and 0.3 to 0.7 parts of acrylic acid, and heating to 45 ° C. Stir for 40min, add A monomer, emulsification time is 30-70min; start to reflux water after heating to 65°C, heat up to 77°C, keep warm, add initiator A0.3-0.7wt, drop time lasts for 1-3h After the completion of the dropwise addition, the reaction is carried out for 2 to 4 hours to obtain a core layer emulsion;
The monomer A is prepared by mixing 2-7 parts by weight of butyl acrylate, 2-5 parts by weight of methyl methacrylate, 3-3.5 parts by weight of ethyl acrylate, and 2-4 parts of hydroxyethyl acrylate;
(2) simultaneously adding B monomer and 0.3 to 0.4 parts by weight of initiator A to the core layer emulsion obtained in the step (1), and the dropwise addition time lasts for 1 to 2 hours, and after the completion of the dropwise addition, the reaction is stirred at 75 to 85 ° C for 3 hours.
Then add 0.6-1.1 parts by weight of flame retardant cross-linking agent, heat-treat 75-95°C for 1-3h, cool down to 50°C, add 0.3 parts by weight of emulsifier, react time for 30min, add ammonia to adjust pH to 7-8 , the flame retardant, water-repellent water-based core-shell acrylate resin coating and paint;
The B monomer is obtained by mixing 1 to 6 parts by weight of butyl acrylate, 3 to 7 parts by weight of methyl methacrylate, 3 to 5 parts by weight of ethyl acrylate, and 2 to 6 parts of hydroxyethyl acrylate.
2. A preparation for acrylate resin coating and paint of flame-retardant, water-proof and water-based core-shell type according to claim 1, wherein the initiator A is any one of ammonium persulfate, potassium persulfate, and potassium hydrogenpersulfate.
3. The Preparation for acrylate resin coating and paint of flame-retardant, water-proof and water-based core-shell type according to claim 1, wherein the emulsifier is prepared by adding 15 g of triethylenetetramine and 70 g of water to a three-necked flask to raise the temperature. After 30 ° C, 40 g of ethylene oxide and 1.2 to 2.4 g of material A were slowly added, and after reacting at 30 ° C for 2 h, cooled to 25 ° C to obtain an intermediate product, and then 15 g of 1/2.
dodecylphenol and 1.6 g were added. The pentadecyl phenol and the substance B
0.3 g were further refluxed at 100 ° C for 1 h, and the solvent was distilled off under reduced pressure to obtain an emulsifier.
dodecylphenol and 1.6 g were added. The pentadecyl phenol and the substance B
0.3 g were further refluxed at 100 ° C for 1 h, and the solvent was distilled off under reduced pressure to obtain an emulsifier.
4. a Preparation for acrylate resin coating and paint of flame-retardant, water-proof and water-based core-shell type according to claim 3, wherein the substance A
is ethyl 2-bromobutyrate, 9-fluorenyl methyl chloroformate, or a trimethyl ring. Any one of triborane.
is ethyl 2-bromobutyrate, 9-fluorenyl methyl chloroformate, or a trimethyl ring. Any one of triborane.
The Preparation for acrylate resin coating and paint of flame-retardant, water-proof and water-based core-shell type according to claim 3, wherein the substance B
is any one of ethoxylated amine hydrochloride, methylethylamine and acetic acid propionic anhydride.
is any one of ethoxylated amine hydrochloride, methylethylamine and acetic acid propionic anhydride.
6. The Preparation for acrylate resin coating and paint of flame-retardant, water-proof and water-based core-shell type according to claim 1, wherein the flame-retardant crosslinking agent is prepared by: 2.1 g of hydroxyethylidene diphosphonic acid, tetrahydroxyl 2.5 g of methyl sulphate and 1.2 g of the substance C were added to 250 ml of a three-necked flask, and reacted at 70 ° C
for 1 h, and then 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were added, and the reaction was carried out at 65 ° C for 1.5 h. The flame retardant crosslinking agent.
The flame-retardant aqueous core-shell type acrylate resin coating material and the method for producing a paint according to claim 6, wherein the substance C is any one of 4,4'-bipyridine, aminoacetonitrile or iminodiacetonitrile.
for 1 h, and then 1.5 g of formamide and 1.6 g of 2,3-pyridinedicarboxylic acid were added, and the reaction was carried out at 65 ° C for 1.5 h. The flame retardant crosslinking agent.
The flame-retardant aqueous core-shell type acrylate resin coating material and the method for producing a paint according to claim 6, wherein the substance C is any one of 4,4'-bipyridine, aminoacetonitrile or iminodiacetonitrile.
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| CN201810773980.7A CN108795208B (en) | 2018-07-15 | 2018-07-15 | Preparation method of flame-retardant water-based core-shell acrylate resin coating and paint |
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| CN117024663A (en) * | 2023-08-08 | 2023-11-10 | 南京科工煤炭科学技术研究有限公司 | Acrylate emulsion for core-shell polymer cement and preparation method thereof |
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| CN112646269B (en) * | 2020-12-17 | 2023-04-28 | 安徽强旭塑业科技有限公司 | Environment-friendly high-flame-retardance battery shell and preparation method thereof |
| CN112625173B (en) * | 2020-12-17 | 2021-12-24 | 常熟国和新材料有限公司 | Water-based acrylic resin with good viscosity stability and preparation method thereof |
| CN118139901A (en) * | 2021-10-26 | 2024-06-04 | 3M创新有限公司 | Flame-retardant pressure-sensitive adhesive and preparation method thereof |
| CN115160480A (en) * | 2022-02-14 | 2022-10-11 | 上海金狮化工有限公司 | Waterborne acrylic resin for coloring woodware and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0794584B2 (en) * | 1987-01-07 | 1995-10-11 | 日本ペイント株式会社 | Method for producing aqueous dispersion of anionic gel particles |
| CN1010589B (en) * | 1988-06-04 | 1990-11-28 | 薛志纯 | Modified acrylic ester resin emulsion and preparation thereof |
| CN102875723B (en) * | 2012-10-26 | 2014-04-16 | 烟台大学 | Preparation method of flame-retardant core-shell-type acrylic resin |
| CN105111876B (en) * | 2014-07-27 | 2017-06-13 | 河北晨阳工贸集团有限公司 | Building, the preparation method of the core-shell type aqueous acrylic resin coating of furniture |
| CN108459136A (en) * | 2018-05-29 | 2018-08-28 | 上海福乐医药科技有限公司 | A kind of method of three boroxane content of titration measuring front three basic ring |
| CN112409877B (en) * | 2018-07-15 | 2023-08-01 | 广东省漆色彩新型材料有限公司 | Preparation method of flame-retardant water-based core-shell acrylic resin coating |
-
2018
- 2018-07-15 CN CN202011369854.9A patent/CN112409877B/en active Active
- 2018-07-15 CN CN201810773980.7A patent/CN108795208B/en active Active
- 2018-12-13 WO PCT/CN2018/120939 patent/WO2020015289A1/en active Application Filing
- 2018-12-27 CA CA3028455A patent/CA3028455A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117024663A (en) * | 2023-08-08 | 2023-11-10 | 南京科工煤炭科学技术研究有限公司 | Acrylate emulsion for core-shell polymer cement and preparation method thereof |
| CN117024663B (en) * | 2023-08-08 | 2024-05-10 | 南京科工煤炭科学技术研究有限公司 | Acrylate emulsion for core-shell polymer cement and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108795208B (en) | 2020-12-18 |
| CN112409877B (en) | 2023-08-01 |
| CN112409877A (en) | 2021-02-26 |
| CN108795208A (en) | 2018-11-13 |
| WO2020015289A1 (en) | 2020-01-23 |
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