CN112409877B - Preparation method of flame-retardant water-based core-shell acrylic resin coating - Google Patents
Preparation method of flame-retardant water-based core-shell acrylic resin coating Download PDFInfo
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Abstract
The preparation method of the flame-retardant water-based core-shell acrylic resin coating and paint comprises the following steps: adding the following raw materials in parts by weight into a reaction vessel: heating water, an emulsifying agent, methacrylic acid and acrylic acid to 45 ℃, stirring for 40min, adding the monomer A, and emulsifying for 30-70 min; heating to 65 ℃ to start flowing back water, heating to 77 ℃, preserving heat, dropwise adding 0.3-0.7 part by weight of an initiator A for 1-3 hours, and reacting for 2-4 hours after dropwise adding to obtain a core layer emulsion; and simultaneously dropwise adding the B monomer and 0.3-0.4 part by weight of the initiator A into the obtained core-layer emulsion for 1-2 hours, preserving heat at 75-85 ℃ after dropwise adding, stirring and reacting for 3 hours, adding 0.6-1.1 part by weight of the flame-retardant cross-linking agent, preserving heat at 75-95 ℃ for 1-3 hours, cooling to 50 ℃, adding 0.3 part by weight of the emulsifying agent, reacting for 30 minutes, adding ammonia water and regulating the pH value to 7-8, thus obtaining the flame-retardant water-based core-shell acrylic resin paint and the flame-retardant water-based core-shell acrylic resin paint with good flame retardance.
Description
This application is a divisional application of the 2018107739807 patent application.
Technical Field
The invention relates to a preparation method of water-based core-shell acrylic resin, in particular to a preparation method of flame-retardant water-based core-shell acrylic resin paint and paint.
Background
The paint is a traditional name in China. The paint is a continuous film which is coated on the surface of the protected or decorated object and can form firm adhesion with the coated object, and is usually a viscous liquid prepared by using resin, oil or emulsion as main materials, adding or not adding pigment and filler, adding corresponding auxiliary agents and using organic solvent or water.
Water-based paint and powder paint are weather-developed, and especially building paint mainly comprising water-based paint accounts for about 38% of the total amount of paint in China. Because of the substantial difference in chemical properties between water-based paint and oil-based paint, the water-based paint and oil-based paint have very different product properties, and the water-based paint is regarded as a big branch of old understanding in the paint industry, which is not scientific. The water paint and the oil paint are parallel in two different series.
In the initial stage of applying the acrylic resin to the leather finishing agent, people aim at the defects of water drainage, hot adhesion, cold brittleness, solvent intolerance and the like, and utilize grafting, crosslinking and other polymer synthesis technologies, introduce functional groups such as styrene, acrylonitrile and the like for modification, thereby meeting the requirement of insufficient natural performance of leather finishing, and establishing a foundation for the research of modern high-performance leather.
The self-crosslinking acrylic resin coating agent developed by poplar more must and the like can be modified by introducing N-methylolacrylamide and acrylic acid in a butyl acrylate-acrylonitrile-methyl acrylate emulsion polymerization system to obtain the leather coating agent with better performance, and the problems of organic solvent intolerance and the like of the leather coating agent can be improved.
Luan Shifang et al, after halogenating acrylic acid monomer by phosphorus trichloride, react with polyethylene glycol to prepare an acrylic acid monopolyethylene glycol ester monomer containing long polar side group, then copolymerize this monomer with other acrylic acid ester, vinyl compound, prepare acrylic resin emulsion, because of existence of long, soft polar side group, this resin film has higher tensile strength, elongation at break; the solvent resistance and the water resistance of the coating can be obviously improved when the coating is used for leather finishing. Core-shell emulsion polymerization is a new technology developed in the 80 s, and is a brand new resin polymerization technology based on the particle design principle. The core-shell acrylic emulsion copolymer is formed by mixing more than two polymers in emulsion particles in a heterogeneous phase, namely, one polymer is a core, the other polymer is a core shell, and an emulsifying layer is coated outside the shell. The emulsion has good anti-back tack, low film forming temperature, good film forming property, good stability and better mechanical property, and the emulsion has specific properties by selecting different performance monomers as shell layers or core layers of emulsion particles respectively, and the core-shell structure can solve the problems of the traditional resin properties such as softness, hardness, heat resistance, cold resistance and the like one by one.
However, the aqueous emulsion type acrylic resin paint used at present also increasingly shows the insurmountable defects thereof [7] If the film is wet at low temperature, the drying is slow, and the film is difficult to form; the coating film is easy to mildew, easy to pollute and not wear-resistant; freeze thawing stability and mechanical stability are poor; the coating agent has poor dry and wet rubbing resistance, film forming compactness, flatness, glossiness and the like, so that the further improvement of the performance of the coating material is limited.
In addition, the flame retardant performance is not high and the emulsifier is more complicated to add.
201610506501.6 the invention relates to a self-flame-retardant acrylic emulsion, which is characterized in that: the self-flame-retardant modified styrene-acrylic emulsion is prepared by using a reactive halogen-containing flame-retardant vinyl monomer, and can perform emulsion copolymerization reaction with acrylic ester monomers, a flame-retardant group is fixed on a resin molecular structure in a chemical bond mode, and is not resolved and shed, the synthesized acrylic emulsion has self-flame-retardant performance, and the lasting flame-retardant performance can be achieved without adding other flame retardants when the coating is prepared; the invention also provides a preparation method of the self-flame-retardant acrylic emulsion. The prepared self-flame-retardant acrylic emulsion has good adhesive force, water resistance and durability, and the prepared coating film has water resistance, alkali resistance, scrubbing resistance and lasting self-flame-retardant property, and is widely used for flame-retardant coatings of indoor and outdoor woodware, steel structures and buildings, thereby playing a role in decoration and protection
201610645798.4 the invention relates to the field of production and preparation of high polymer products, in particular to an acrylic resin flame-retardant coating, which comprises 12-18 parts of amino resin, 3-6 parts of ethyl acrylate, 3-5 parts of butyl acrylate, 2-10 parts of melamine, 1-2 parts of defoamer, 2-6 parts of pigment, 2-3 parts of acrylic acid, 60-70 parts of anionic water-based resin containing carboxyl, 5-10 parts of water-resistant pigment, 7-8 parts of auxiliary agent, 1-2 parts of interfacial adhesion promoter, 4-8 parts of char former and 10-20 parts of deionized water; the interfacial adhesion promoter is formed by reacting a metal organic, a polyisocyanate, and an oligomer containing hydroxyl groups. The acrylic resin coating has excellent interfacial adhesion with a substrate and has good flame retardant effect.
Disclosure of Invention
The invention relates to a preparation method of flame-retardant water-based core-shell acrylic resin coating and paint, which mainly adopts a synthesis route that a cross-linking agent is subjected to flame-retardant functionalization to improve the flame retardance of the water-based core-shell acrylic resin coating and paint, namely flame-retardant modification is carried out from the angle of chemical materials required by acrylic resin, meanwhile, as the combination of anions and non-ions required by the synthesis of the acrylic resin at present improves the stability of acid-base salt and the stability of mechanical stirring, the two are combined into one, and a novel emulsifier with both the anions and the non-ions is self-made.
The preparation method of the flame-retardant water-based core-shell acrylic resin coating and paint comprises the following steps:
(1) Adding the following raw materials in parts by weight into a reaction vessel: 50-65 parts of water, 0.4-2.3 parts of emulsifying agent, 0.6-3.0 parts of methacrylic acid and 0.3-0.7 part of acrylic acid, heating to 45 ℃, stirring for 40min, adding the monomer A, and emulsifying for 30-70 min; heating to 65 ℃ to start flowing back water, heating to 77 ℃, preserving heat, dropwise adding 0.3-0.7 part by weight of an initiator A for 1-3 hours, and reacting for 2-4 hours after dropwise adding to obtain a core layer emulsion;
the A monomer is formed by: 2-7 parts of butyl acrylate, 2-5 parts of methyl methacrylate, 3-3.5 parts of ethyl acrylate and 2-4 parts of hydroxyethyl acrylate;
(2) Simultaneously dropwise adding a B monomer and 0.3-0.4 part by weight of an initiator A into the core-layer emulsion obtained in the step (1) for 1-2 hours, preserving heat at 75-85 ℃ after dropwise adding, stirring and reacting for 3 hours, adding 0.6-1.1 part by weight of a flame-retardant cross-linking agent, preserving heat at 75-95 ℃ for 1-3 hours, cooling to 50 ℃, adding 0.3 part by weight of an emulsifying agent, reacting for 30 minutes, and adding ammonia water to adjust the pH value to 7-8 to obtain the flame-retardant waterproof water-based core-shell acrylate resin coating and paint;
the monomer B is formed by: 1-6 parts of butyl acrylate, 3-7 parts of methyl methacrylate, 3-5 parts of ethyl acrylate and 2-6 parts of hydroxyethyl acrylate.
The initiator A is any one of ammonium persulfate, potassium persulfate and potassium hydrogen persulfate; the preparation method of the emulsifier comprises the steps of adding 15g of triethylene tetramine and 70g of water into a three-neck flask, heating to 30 ℃, slowly adding 40g of ethylene oxide and 1.2-2.4 g of substance A, reacting at 30 ℃ for 2 hours, cooling to 25 ℃ to obtain an intermediate product, adding 15g of dodecylphenol, 1.6g of m-pentadecyl phenol and 0.3g of substance B, heating to 100 ℃ and carrying out reflux reaction for 1 hour, and distilling the solvent under reduced pressure to obtain the emulsifier; the substance A is any one of ethyl 2-bromobutyrate, 9-fluorenylmethyl chloroformate and trimethyl cyclo-tribromoxane; the substance B is any one of ethoxyamine hydrochloride, methylethylamine and acetic anhydride; the preparation method of the flame-retardant cross-linking agent comprises the following steps: adding 2.1g of hydroxyethylidene diphosphonic acid, 2.5g of tetrakis (hydroxymethyl) phosphonium sulfate and 1.2g of substance C into 250ml of a three-neck flask, reacting for 1h at 70 ℃, adding 1.5g of formamide and 1.6g of 2, 3-pyridine dicarboxylic acid, and reacting for 1.5h at 65 ℃ to obtain the flame-retardant cross-linking agent; substance C is any one of 4,4' -bipyridine, aminoacetonitrile, iminodiacetonitrile.
The invention has the advantages that:
(1) The flame-retardant property of the water-based core-shell acrylic resin coating and paint is improved by the flame-retardant functionalization of the cross-linking agent, namely flame-retardant modification is performed from the angle of the chemical materials required by the acrylic resin, meanwhile, as the stability of acid-base salt and the stability of mechanical stirring are improved by the collocation of anions and non-ions required by the synthesis of the acrylic resin at present, the two are combined into one, and a novel emulsifier with both the properties of anions and non-ions is self-made.
(2) 2-bromobutyric acid ethyl ester, 9-fluorenylmethyl chloroformate and trimethyl cyclo-boroxine are used as an emulsifier synthesis catalyst, and ethoxyamine hydrochloride, methylethylamine and acetic anhydride are used for improving the synergists of dodecylphenol and m-pentadecylphenol; 4,4' -bipyridine, aminoacetonitrile, iminodiacetonitrile as catalyst of hydroxyethylidene diphosphonic acid and tetrakis (hydroxymethyl) phosphonium sulfate.
(3) The mechanism of the invention is that the crosslinking agent is adopted to lead the acrylic resin to form a compact film, and meanwhile, the surface of the acrylic resin is provided with flame retardant groups, thereby reducing the burning speed of flame and improving the flame retardance.
Detailed Description
Example 1
The preparation method of the flame-retardant water-based core-shell acrylic resin coating and paint comprises the following steps:
(1) Adding the following raw materials in parts by weight into a reaction vessel: 50 parts of water, 0.4 part of emulsifying agent, 0.6 part of methacrylic acid and 0.3 part of acrylic acid are added into a reaction vessel, the temperature is raised to 45 ℃, stirring is carried out for 40min, A monomer is added, and the emulsification time is 30min; heating to 65 ℃ to start flowing back water, heating to 77 ℃, preserving heat, dropwise adding 0.3 part by weight of ammonium persulfate (dissolved by 5g of water) for 1h, and reacting for 2h after dropwise adding to obtain nuclear layer emulsion;
the A monomer is formed by: 2 parts of butyl acrylate, 2 parts of methyl methacrylate, 3 parts of ethyl acrylate and 2 parts of hydroxyethyl acrylate;
(2) Simultaneously dropwise adding a B monomer and 0.3 part by weight of ammonium persulfate (dissolved by 5g of water) into the core-layer emulsion obtained in the step (1), wherein the dropwise adding time lasts for 1h, after dropwise adding, preserving heat at 75 ℃ and stirring for 3h, then adding 0.6 part by weight of flame-retardant cross-linking agent, preserving heat at 75 ℃ and reacting for 1h, cooling to 50 ℃, adding 0.3 part by weight of emulsifying agent, reacting for 30min, and adding ammonia water to adjust the pH value to 7-8 to obtain the flame-retardant water-based core-shell acrylic resin coating and paint;
the monomer B is formed by: 1 part by weight of butyl acrylate, 3 parts by weight of methyl methacrylate, 3 parts by weight of ethyl acrylate and 2 parts by weight of hydroxyethyl acrylate.
The preparation method of the emulsifier comprises the steps of adding 15g of triethylene tetramine and 70g of water into a three-neck flask, heating to 30 ℃, slowly adding 40g of ethylene oxide and 1.2g of ethyl 2-bromobutyrate, reacting at 30 ℃ for 2 hours, cooling to 25 ℃ to obtain an intermediate product, adding 0.3g of dodecylphenol, 1.6g of m-pentadecyl phenol and ethoxyamine hydrochloride, heating to 100 ℃ for reflux reaction for 1 hour, and distilling the solvent under reduced pressure to obtain the emulsifier;
the preparation method of the flame-retardant cross-linking agent comprises the following steps: 2.1g of hydroxyethylidene diphosphonic acid, 2.5g of tetrakis (hydroxymethyl) phosphonium sulfate and 1.2g of 4,4' -bipyridine are added into 250ml of a three-neck flask to react for 1h at 70 ℃, and then 1.5g of formamide and 1.6g of 2, 3-pyridine dicarboxylic acid are added to react for 1.5h at 65 ℃ to obtain the flame-retardant cross-linking agent.
Example 2
The preparation method of the flame-retardant water-based core-shell acrylic resin coating and paint comprises the following steps:
(1) Adding the following raw materials in parts by weight into a reaction vessel: 65 parts of water, 2.3 parts of emulsifying agent, 3.0 parts of methacrylic acid and 0.7 part of acrylic acid are heated to 45 ℃, stirred for 40min, added with A monomer and emulsified for 70min; heating to 65deg.C, introducing reflux water, heating to 77 deg.C, maintaining the temperature, dropwise adding potassium persulfate 0.7 weight parts (dissolved in 5g water) for 3 hr, and reacting for 4 hr to obtain core-layer emulsion;
the A monomer is formed by: 7 parts of butyl acrylate, 5 parts of methyl methacrylate, 3.5 parts of ethyl acrylate and 4 parts of hydroxyethyl acrylate;
(2) Simultaneously dropwise adding B monomer and 0.4 part by weight of potassium persulfate (dissolved by 5g of water) into the core-layer emulsion obtained in the step (1) for 2 hours, preserving heat at 85 ℃ after dropwise adding, stirring and reacting for 3 hours, adding 1.1 part by weight of flame-retardant cross-linking agent, preserving heat at 95 ℃ for 3 hours, cooling to 50 ℃, adding 0.3 part by weight of emulsifying agent, reacting for 30 minutes, and adding ammonia water to adjust the pH value to 7-8 to obtain the flame-retardant water-based core-shell acrylic resin coating and paint;
the monomer B is formed by: 6 parts of butyl acrylate, 7 parts of methyl methacrylate, 5 parts of ethyl acrylate and 6 parts of hydroxyethyl acrylate.
The preparation method of the emulsifier comprises the steps of adding 15g of triethylene tetramine and 70g of water into a three-neck flask, heating to 30 ℃, slowly adding 40g of ethylene oxide and 2.4g of 9-fluorenylmethylchloroformate, reacting at 30 ℃ for 2 hours, cooling to 25 ℃ to obtain an intermediate product, adding 15g of dodecylphenol, 1.6g of m-pentadecylphenol and 0.3g of methylethylamine, heating to 100 ℃ and carrying out reflux reaction for 1 hour, and distilling the solvent under reduced pressure to obtain the emulsifier;
the preparation method of the flame-retardant cross-linking agent comprises the following steps: 2.1g of hydroxyethylidene diphosphonic acid, 2.5g of tetrakis (hydroxymethyl) phosphonium sulfate and 1.2g of aminoacetonitrile are added into 250ml of a three-neck flask to react for 1h at 70 ℃, and then 1.5g of formamide and 1.6g of 2, 3-pyridine dicarboxylic acid are added to react for 1.5h at 65 ℃ to obtain the flame-retardant cross-linking agent.
Example 3
The preparation method of the flame-retardant water-based core-shell acrylic resin coating and paint comprises the following steps:
(1) Adding the following raw materials in parts by weight into a reaction vessel: 57 parts of water, 1.3 parts of emulsifying agent, 1.8 parts of methacrylic acid and 0.5 part of acrylic acid are heated to 45 ℃, stirred for 40min, added with the A monomer and emulsified for 50min; heating to 65deg.C, introducing reflux water, heating to 77 deg.C, maintaining the temperature, dropwise adding potassium hydrogen persulfate 0.5 weight parts (dissolved in 5g water) for 2 hr, and reacting for 3 hr to obtain core emulsion;
the A monomer is formed by: 4.5 parts of butyl acrylate, 3.5 parts of methyl methacrylate, 3.3 parts of ethyl acrylate and 3 parts of hydroxyethyl acrylate;
(2) Simultaneously dropwise adding B monomer and 0.3 part by weight of potassium hydrogen persulfate (dissolved by 5g of water) into the core-layer emulsion obtained in the step (1), wherein the dropwise adding time lasts for 1.5 hours, preserving heat at 80 ℃ after dropwise adding, stirring and reacting for 3 hours, adding 0.8 part by weight of flame-retardant cross-linking agent, preserving heat at 85 ℃ for 2 hours, cooling to 50 ℃, adding 0.3 part by weight of emulsifying agent, reacting for 30 minutes, and adding ammonia water to adjust the pH value to 7-8 to obtain the flame-retardant water-based core-shell acrylic resin paint and the paint;
the monomer B is formed by: 3.5 parts of butyl acrylate, 5 parts of methyl methacrylate, 4 parts of ethyl acrylate and 4 parts of hydroxyethyl acrylate.
The preparation method of the emulsifier comprises the steps of adding 15g of triethylene tetramine and 70g of water into a three-neck flask, heating to 30 ℃, slowly adding 40g of ethylene oxide and 1.8g of trimethyl-cyclotron-boroxine, reacting at 30 ℃ for 2 hours, cooling to 25 ℃ to obtain an intermediate product, adding 15g of dodecylphenol, 1.6g of m-pentadecyl phenol and 0.3g of acetic anhydride, heating to 100 ℃ and reflux-reacting for 1 hour, and distilling the solvent under reduced pressure to obtain the emulsifier;
the preparation method of the flame-retardant cross-linking agent comprises the following steps: 2.1g of hydroxyethylidene diphosphonic acid, 2.5g of tetrakis (hydroxymethyl) phosphonium sulfate and 1.2g of iminodiacetonitrile are added into 250ml of a three-neck flask to react for 1h at 70 ℃, and then 1.5g of formamide and 1.6g of 2, 3-pyridine dicarboxylic acid are added to react for 1.5h at 65 ℃ to obtain the flame-retardant cross-linking agent.
Example 4
The preparation method of the flame-retardant water-based core-shell acrylic resin coating and paint comprises the following steps:
(1) Adding the following raw materials in parts by weight into a reaction vessel: 50 parts of water, 2.3 parts of emulsifying agent, 3.0 parts of methacrylic acid and 0.3 part of acrylic acid, heating to 45 ℃, stirring for 40min, adding the A monomer, and emulsifying for 40min; heating to 65 ℃ to start flowing back water, heating to 77 ℃, preserving heat, dropwise adding 0.4 part by weight of ammonium persulfate (dissolved by 5g of water), keeping the dropwise adding time for 1.5 hours, and reacting for 3 hours after the dropwise adding is finished to obtain a nuclear layer emulsion;
the A monomer is formed by: 4 parts of butyl acrylate, 3 parts of methyl methacrylate, 3 parts of ethyl acrylate and 4 parts of hydroxyethyl acrylate;
(2) Simultaneously dropwise adding a B monomer and 0.3 part by weight of ammonium persulfate (dissolved by 5g of water) into the core-layer emulsion obtained in the step (1), wherein the dropwise adding time lasts for 1h, after dropwise adding, preserving heat at 75 ℃ and stirring for 3h, adding 0.7 part by weight of flame-retardant cross-linking agent, preserving heat at 80 ℃ and reacting for 2h, cooling to 50 ℃, adding 0.3 part by weight of emulsifying agent, reacting for 30min, and adding ammonia water to adjust the pH value to 7-8 to obtain the flame-retardant water-based core-shell acrylic resin coating and paint;
the monomer B is formed by: 3 parts of butyl acrylate, 4 parts of methyl methacrylate, 4 parts of ethyl acrylate and 6 parts of hydroxyethyl acrylate.
15g of triethylene tetramine and 70g of water are added into a three-neck flask, 40g of ethylene oxide and 1.6g of ethyl 2-bromobutyrate are slowly added after the temperature is raised to 30 ℃, the mixture is reacted for 2 hours at the temperature of 30 ℃, then the mixture is cooled to 25 ℃ to obtain an intermediate product, then 15g of dodecylphenol, 1.6g of m-pentadecyl phenol and 0.3g of ethoxyamine hydrochloride are added, the mixture is heated to 100 ℃ to reflux and react for 1 hour, and the solvent is distilled off under reduced pressure to obtain the emulsifier;
the preparation method of the flame-retardant cross-linking agent comprises the following steps: 2.1g of hydroxyethylidene diphosphonic acid, 2.5g of tetrakis (hydroxymethyl) phosphonium sulfate and 1.2g of aminoacetonitrile are added into 250ml of a three-neck flask to react for 1h at 70 ℃, and then 1.5g of formamide and 1.6g of 2, 3-pyridine dicarboxylic acid are added to react for 1.5h at 65 ℃ to obtain the flame-retardant cross-linking agent.
Example 5
The preparation method of the flame-retardant water-based core-shell acrylic resin coating and paint comprises the following steps:
(1) Adding the following raw materials in parts by weight into a reaction vessel: 65 parts of water, 2.3 parts of emulsifying agent, 3.0 parts of methacrylic acid and 0.7 part of acrylic acid are heated to 45 ℃, stirred for 40min, added with A monomer and emulsified for 70min; heating to 65deg.C, introducing reflux water, heating to 77 deg.C, maintaining the temperature, dropwise adding potassium persulfate 0.7 weight parts (dissolved in 5g water) for 1 hr, and reacting for 2 hr to obtain core-layer emulsion;
the A monomer is formed by: 7 parts of butyl acrylate, 4 parts of methyl methacrylate, 3 parts of ethyl acrylate and 2 parts of hydroxyethyl acrylate;
(2) Simultaneously dropwise adding B monomer and 0.3 part by weight of potassium persulfate (dissolved by 5g of water) into the core-layer emulsion obtained in the step (1) for 1h, keeping the temperature at 75 ℃ after dropwise adding, stirring and reacting for 3h, adding 0.6 part by weight of flame-retardant cross-linking agent, keeping the temperature at 75 ℃ for 1h, cooling to 50 ℃, adding 0.3 part by weight of emulsifying agent, reacting for 30min, and adding ammonia water to adjust the pH value to 7-8 to obtain the flame-retardant water-based core-shell acrylic resin coating and paint;
the monomer B is formed by: 6 parts of butyl acrylate, 7 parts of methyl methacrylate, 5 parts of ethyl acrylate and 6 parts of hydroxyethyl acrylate.
The preparation method of the emulsifier comprises the steps of adding 15g of triethylene tetramine and 70g of water into a three-neck flask, heating to 30 ℃, slowly adding 40g of ethylene oxide and 1.6g of 9-fluorenylmethylchloroformate, reacting at 30 ℃ for 2 hours, cooling to 25 ℃ to obtain an intermediate product, adding 15g of dodecylphenol, 1.6g of m-pentadecylphenol and 0.3g of methylethylamine, heating to 100 ℃ and carrying out reflux reaction for 1 hour, and distilling the solvent under reduced pressure to obtain the emulsifier;
the preparation method of the flame-retardant cross-linking agent comprises the following steps: 2.1g of hydroxyethylidene diphosphonic acid, 2.5g of tetrakis (hydroxymethyl) phosphonium sulfate and 1.2g of iminodiacetonitrile are added into 250ml of a three-neck flask to react for 1h at 70 ℃, and then 1.5g of formamide and 1.6g of 2, 3-pyridine dicarboxylic acid are added to react for 1.5h at 65 ℃ to obtain the flame-retardant cross-linking agent.
Flame retardancy is measured by oxygen index, flame burn time.
Table 1 test performance
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Oxygen index/% | 29.4 | 29.6 | 30.4 | 29.8 | 29.8 |
| Flame burn time/s | 1.1 | 1.6 | 0.8 | 1.2 | 2.1 |
As can be seen from Table 1, the oxygen index of the flame retardant waterborne core-shell acrylate resin coating and paint was greatly increased and the flame burn time was greatly reduced, whereas the oxygen index and flame burn time of example 1, comparative 201610506501.6 and 201610645798.4 were 22.6, 26.5s and 24.1 and 36.5s, respectively.
TABLE 2 testing Properties (without flame retardant crosslinker)
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Oxygen index/% | 21.6 | 22.7 | 20.4 | 21.2 | 21.7 |
| Flame burn time/s | 31.2 | 32.7 | 29.4 | 22.1 | 25.7 |
As can be seen from Table 2, the oxygen index of the flame retardant aqueous core-shell acrylic resin coating and paint without flame retardant cross-linking agent is greatly reduced, and the flame burning time is greatly improved.
TABLE 3 testing Properties (flame retardant crosslinker added, no material C added)
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Oxygen index/% | 25.2 | 24.7 | 26.4 | 25.3 | 27.2 |
| Flame burn time/s | 11.2 | 22.7 | 25.4 | 16.1 | 18.2 |
As can be seen from Table 3, the oxygen index of the flame retardant aqueous core-shell acrylate resin coating and paint with the flame retardant cross-linking agent without the substance C is greatly increased compared with that of the flame retardant cross-linking agent without the substance C, and the flame burning time is greatly reduced.
TABLE 4 testing Properties (flame retardant crosslinker, substance C, no 2, 3-pyridinedicarboxylic acid)
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Oxygen index/% | 26.3 | 25.8 | 27.1 | 26.1 | 27.3 |
| Flame burn time/s | 10.3 | 14.2 | 18.3 | 12.0 | 12.4 |
As can be seen from Table 4, the oxygen index of the flame retardant aqueous core-shell type acrylate resin coating and paint without the addition of 2, 3-pyridinedicarboxylic acid, with the addition of the flame retardant crosslinking agent and the addition of the substance C, was greatly increased and the flame burning time was greatly reduced as compared with that without the addition of the flame retardant crosslinking agent.
Chemical reagent resistance stability, namely respectively mixing the emulsion with 5% sodium chloride solution according to the volume ratio of 1:4, sealing and standing for 48 hours, and observing the precipitation amount.
Gel fraction: the percentage of the weight of gel in the acrylic resin synthesis to the weight of the theoretically obtained emulsion was measured.
TABLE 5 emulsion stability data
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Chemical resistance | Stable and non-layered | Stable and non-layered | Stable and non-layered | Stable and non-layered | Stable and non-layered |
| Gel filtration/% | 1.6 | 2.1 | 1.7 | 1.1 | 0.8 |
As can be seen from Table 5, the chemical resistance and gel filtration of the present invention are both good. Gel filtration of example 1 for the control 201610506501.6 and 201610645798.4 was 9.7% and 8.3%, respectively.
TABLE 6 emulsion stability data (without adding substance A)
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Chemical resistance | Stable and non-layered | Layering | Stable and non-layered | Layering | Layering |
| Gel filtration/% | 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 substance A were significantly reduced.
TABLE 7 emulsion stability data (with addition of substance A, without addition of substance B)
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Chemical resistance | Layering | Layering | Layering | Layering | Layering |
| Gel filtration/% | 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 present invention to which substance B was not added were significantly reduced.
Claims (2)
1. The preparation method of the used emulsifier of the flame-retardant water-based core-shell acrylic resin coating is characterized by comprising the following steps:
15g of triethylene tetramine and 70g of water are added into a three-neck flask, 40g of ethylene oxide and 1.2g of ethyl 2-bromobutyrate are slowly added after the temperature is raised to 30 ℃, the mixture is reacted for 2 hours at 30 ℃, then the mixture is cooled to 25 ℃ to obtain an intermediate product, then 15g of dodecylphenol, 1.6g of m-pentadecylphenol and 0.3g of ethoxyamine hydrochloride are added, the temperature is raised to 100 ℃ for reflux reaction for 1 hour, and the solvent is distilled out under reduced pressure, thus obtaining the emulsifier.
2. The preparation method of the used emulsifier of the flame-retardant water-based core-shell acrylic resin coating is characterized by comprising the following steps:
15g of triethylene tetramine and 70g of water are added into a three-neck flask, 40g of ethylene oxide and 1.6g of ethyl 2-bromobutyrate are slowly added after the temperature is raised to 30 ℃, the mixture is reacted for 2 hours at the temperature of 30 ℃, then the mixture is cooled to 25 ℃ to obtain an intermediate product, then 15g of dodecylphenol, 1.6g of m-pentadecylphenol and 0.3g of ethoxyamine hydrochloride are added, the temperature is raised to 100 ℃ for reflux reaction for 1 hour, and the solvent is distilled off under reduced pressure, thus obtaining the emulsifier.
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| CN202011369854.9A CN112409877B (en) | 2018-07-15 | 2018-07-15 | Preparation method of flame-retardant water-based core-shell acrylic resin coating |
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|---|---|---|---|
| CN202011369854.9A CN112409877B (en) | 2018-07-15 | 2018-07-15 | Preparation method of flame-retardant water-based core-shell acrylic resin coating |
| CN201810773980.7A CN108795208B (en) | 2018-07-15 | 2018-07-15 | Preparation method of flame retardant water-based core-shell acrylic resin coating and paint |
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| CN202011369854.9A Active CN112409877B (en) | 2018-07-15 | 2018-07-15 | Preparation method of flame-retardant water-based core-shell acrylic resin coating |
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| CN108795208B (en) * | 2018-07-15 | 2020-12-18 | 烟台大学 | Preparation method of flame retardant water-based core-shell acrylic resin coating and paint |
| CN109468006A (en) * | 2018-11-15 | 2019-03-15 | 段瑶瑶 | A kind of preparation method of the core-shell type aqueous acrylic resin coating of antifriction |
| CN109181458A (en) * | 2018-11-21 | 2019-01-11 | 段瑶瑶 | A kind of preparation method of waterproofness core-shell type aqueous acrylic resin coating and finishing agent |
| CN109705681A (en) * | 2018-12-25 | 2019-05-03 | 杨记周 | A kind of new-energy automobile environment-friendly water-based paint and preparation method thereof |
| CN112322132B (en) * | 2019-07-17 | 2023-04-07 | 烟台大学 | Preparation method of flame-retardant core-shell environment-friendly water-based resin coating |
| CN110642982B (en) * | 2019-09-17 | 2022-02-01 | 湖北工业大学 | Preparation method of high-tensile-strength amide benzene ring emulsion polymer with core-shell structure |
| CN111794012B (en) * | 2020-06-24 | 2022-04-29 | 杭州华旺新材料科技股份有限公司 | High-strength water-resistant flame-retardant plain colored paper and preparation method thereof |
| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63170443A (en) * | 1987-01-07 | 1988-07-14 | Nippon Paint Co Ltd | Production of aqueous dispersion of anionic gel fine particles |
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| CN1010589B (en) * | 1988-06-04 | 1990-11-28 | 薛志纯 | Modified acrylate 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 |
| CN104086698B (en) * | 2014-07-27 | 2016-05-18 | 朱蕾 | The preparation method of the core-shell type aqueous acrylic resin coating of a kind of anti-flammability |
| 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 |
| CN108795208B (en) * | 2018-07-15 | 2020-12-18 | 烟台大学 | Preparation method of flame retardant water-based core-shell acrylic resin coating and paint |
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- 2018-07-15 CN CN202011369854.9A patent/CN112409877B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63170443A (en) * | 1987-01-07 | 1988-07-14 | Nippon Paint Co Ltd | Production of aqueous dispersion of anionic gel fine particles |
Non-Patent Citations (1)
| Title |
|---|
| 高产率制备甲基硼酸;李恒光,刘志煜,陈淑华;化学试剂;19(03);第185页 * |
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| CA3028455A1 (en) | 2020-01-15 |
| CN108795208B (en) | 2020-12-18 |
| CN112409877A (en) | 2021-02-26 |
| CN108795208A (en) | 2018-11-13 |
| WO2020015289A1 (en) | 2020-01-23 |
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