CN108795208B - Preparation method of flame-retardant water-based core-shell acrylate resin coating and paint - Google Patents

Preparation method of flame-retardant water-based core-shell acrylate resin coating and paint Download PDF

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CN108795208B
CN108795208B CN201810773980.7A CN201810773980A CN108795208B CN 108795208 B CN108795208 B CN 108795208B CN 201810773980 A CN201810773980 A CN 201810773980A CN 108795208 B CN108795208 B CN 108795208B
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CN108795208A (en
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段宝荣
赵玉真
冯练享
唐志海
张萌萌
王琦研
张田田
王全杰
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Shenyang Naisi Industrial Co ltd
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Yantai University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
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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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints

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Abstract

The preparation method of the flame-retardant water-based core-shell acrylate resin coating and paint comprises the following steps: adding the following raw materials in parts by weight into a reaction vessel: 50-65 parts of water, 0.4-2.3 parts of emulsifier, 0.6-3.0 parts of methacrylic acid and 0.3-0.7 part of acrylic acid, heating to 45 ℃, stirring for 40min, adding a monomer A, and emulsifying for 30-70 min; heating to 65 ℃, introducing reflux water, heating to 77 ℃, keeping the temperature, dropwise adding 0.3-0.7 weight part of initiator A, keeping the dropwise adding time for 1-3 hours, and reacting for 2-4 hours after dropwise adding to obtain a nuclear layer emulsion; and (2) simultaneously dropwise adding a monomer B and 0.3-0.4 part by weight of an initiator A into the obtained core-layer emulsion, wherein the dropwise adding time lasts for 1-2 hours, after the dropwise adding, keeping the temperature at 75-85 ℃, stirring and reacting for 3 hours, then adding 0.6-1.1 part by weight of a flame-retardant cross-linking agent, keeping the temperature at 75-95 ℃, reacting for 1-3 hours, cooling to 50 ℃, adding 0.3 part by weight of an emulsifier, reacting for 30 minutes, and adding ammonia water to adjust the pH value to 7-8 to obtain the flame-retardant and waterproof core-shell type acrylate resin coating and paint, and the obtained flame-retardant waterproof core-shell type acrylate resin coating and paint have good flame retardance.

Description

Preparation method of flame-retardant water-based core-shell acrylate resin coating and paint
Technical Field
The invention relates to a preparation method of water-based core-shell type acrylic resin, in particular to a preparation method of flame-retardant water-based core-shell type acrylic resin coating and paint.
Background
The coating is traditionally named as paint in China. The coating is a continuous film which is coated on the surface of an object to be protected or decorated and can form firm adhesion with the object to be coated, and is a viscous liquid which is prepared by taking resin, oil or emulsion as a main material, adding or not adding pigments and fillers, adding corresponding auxiliaries and using an organic solvent or water.
The new China is established for 60 years, and along with the development of various industries of national economy, the paint industry matched with the new China is gradually developed from a small industry which is not attractive, into an essential important industry in various fields of national economy. Through the obstinate fighting and development of several generations of people, China becomes the second largest world paint producing country and consuming country and enters the mainstream of the world paint industry development.
Water paint and powder paint become climate, especially the building paint mainly using water paint accounts for about 38% of the total amount of the paint in China. Since the chemical characteristics of the water-based paint and the oil-based paint are substantially different, and the properties of the water-based paint and the oil-based paint are also greatly different, it is not scientific to determine the water-based paint as a long-standing understanding of a large branch in the paint industry. The water paint and the oil paint are parallel to two different series of liquid paint.
In the initial stage of applying the acrylic resin to the leather finishing agent, people utilize macromolecular synthesis technologies such as grafting, crosslinking and the like to introduce styrene, acrylonitrile and the like with functional groups for modification aiming at the defects of water-releasing property, hot adhesion, cold brittleness, solvent intolerance and the like, so that the requirement of insufficient innate performance of leather finishing is met, and a foundation is established for the research of modern high-performance leather.
The self-crosslinking acrylic resin coating agent developed by Yankee et al can be modified by introducing N-methylolacrylamide and acrylic acid into a butyl acrylate-acrylonitrile-methyl acrylate emulsion polymerization system to obtain a leather coating agent with relatively good performance, and can improve the problems of organic solvent resistance of the leather coating agent and the like.
Goldenrain, et al, react acrylic monomer with polyethylene glycol after phosphorus trichloride acyl halide to prepare a mono-polyethylene glycol acrylate monomer containing long polar side groups, and then copolymerize the monomer with other acrylates and vinyl compounds to prepare acrylic resin emulsion, wherein the resin film has high tensile strength and elongation at break due to the existence of long, soft polar side groups; when the paint is used for leather finishing, the solvent resistance and the water resistance of the coating can be obviously improved. Core-shell emulsion polymerization was a new technology developed in the 80 s, a completely new resin polymerization technology based on the principle of particle design. The core-shell acrylic emulsion copolymer is formed by two or more polymers which are in heterogeneous coexistence in emulsion particles, namely, one polymer is used as a core, the other polymer is used as a core shell, and an emulsion layer is wrapped outside the shell. The obtained emulsion has good anti-tack property, low film-forming temperature, best film-forming property, stability and more excellent mechanical property, and the emulsion has specific property by selecting different performance monomers as the shell layer or the core layer of the emulsion particle respectively, and the core-shell structure can solve the problems of the prior resin property such as soft and hard, heat resistance and cold resistance one by one, and the technology is widely applied to the synthesis and modification research of acrylic resin.
However, the currently used water-emulsion acrylic resin coatings increasingly show their insurmountable disadvantages[7]For example, in the case of low temperature and high humidity, the drying is slow and the film is difficult to form; the coating is easy to mildew, easy to pollute and not wear-resistant; the freeze-thaw stability and the mechanical stability are poor; the coating agent is inferior in dry and wet rub resistance, film-forming denseness, flatness and gloss, and further improvement of coating material performance is limited.
In addition, the defects of low flame retardant property and more complicated addition of the emulsifier exist.
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 utilizes a reactive halogen-containing flame-retardant vinyl monomer, can generate emulsion copolymerization with an acrylate monomer, fixes a flame-retardant group on a resin molecular structure in a chemical bond mode, cannot be resolved and fall off, has self-flame-retardant performance, and can play a role in lasting flame-retardant performance without adding other flame retardants when preparing the coating; the invention also provides a preparation method of the self-flame-retardant acrylic emulsion. The self-flame-retardant acrylic emulsion prepared by the invention has good adhesive force, water resistance and durability, and the prepared coating has water resistance, alkali resistance, scrub resistance and lasting self-flame-retardant property, is widely used for flame-retardant coatings of indoor and outdoor woodware, steel structures and buildings, plays a role in decoration and protection
201610645798.4 the invention relates to the production preparation field of macromolecule products, in particular to an acrylic resin flame retardant coating, 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 defoaming agent, 2-6 parts of pigment and filler, 2-3 parts of acrylic acid, 60-70 parts of carboxyl-containing anionic water-based resin, 5-10 parts of water-resistant pigment, 7-8 parts of auxiliary agent, 1-2 parts of interface adhesion promoter, 4-8 parts of char forming agent and 10-20 parts of deionized water; the interface adhesion promoter is prepared by the reaction of metal organic matter, polyisocyanate and oligomer containing hydroxyl. The acrylic resin coating disclosed by the invention has excellent interface adhesion with a base material and has a good flame retardant effect.
Disclosure of Invention
The invention relates to a preparation method of flame-retardant water-based core-shell acrylate resin coating and paint, which mainly adopts a synthetic route that a cross-linking agent is subjected to flame-retardant functionalization to improve the flame retardance of the water-based core-shell acrylate resin coating and paint, namely, the flame-retardant modification is carried out from the perspective of chemical materials required by the acrylate resin, and meanwhile, because anions and non-ions required in the synthesis of the existing acrylate resin are matched to improve the stability of acid-base salt and the stability of mechanical stirring, the two are combined into one, and a novel emulsifier with both anion and non-ion performances is prepared.
The preparation method of the flame-retardant water-based core-shell acrylate 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 emulsifier, 0.6-3.0 parts of methacrylic acid and 0.3-0.7 part of acrylic acid, heating to 45 ℃, stirring for 40min, adding a monomer A, and emulsifying for 30-70 min; heating to 65 ℃, introducing reflux water, heating to 77 ℃, keeping the temperature, dropwise adding 0.3-0.7 weight part of initiator A, keeping the dropwise adding time for 1-3 hours, and reacting for 2-4 hours after dropwise adding to obtain a nuclear layer emulsion;
the monomer A is prepared from: 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 dripping a monomer B and 0.3-0.4 part by weight of an initiator A into the core layer emulsion obtained in the step (1), keeping the dripping time for 1-2 h, keeping the temperature at 75-85 ℃ after the dripping is finished, stirring and reacting for 3h, adding 0.6-1.1 part by weight of a flame-retardant cross-linking agent, keeping the temperature at 75-95 ℃ for reacting for 1-3 h, cooling to 50 ℃, adding 0.3 part by weight of an emulsifier, reacting for 30min, and adding ammonia water to adjust the pH value to 7-8 to obtain the flame-retardant and waterproof water-based core-shell acrylate resin coating and paint;
the B monomer is prepared from: 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 a substance A, 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 a substance B, heating to 100 ℃, 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 2-bromobutyric acid ethyl ester, 9-fluorenylmethyl chloroformate and trimethylcyclotriboroxane; the substance B is any one of ethoxyamine hydrochloride, methyl ethylamine and acetic propionic 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 a substance into 250ml of a three-neck flask, reacting for 1h at 70 ℃, adding 1.5g of formamide and 1.6g of 2, 3-pyridinedicarboxylic acid, and reacting for 1.5h at 65 ℃ to obtain the flame-retardant cross-linking agent; the substance C is any one of 4,4' -bipyridine, aminoacetonitrile and iminodiacetonitrile.
The invention has the advantages that:
(1) the 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 perspective of chemical materials required by acrylic resin, and meanwhile, because anions and non-ions required in the synthesis of the existing acrylic resin are matched to improve the stability of acid-base salt and the stability of mechanical stirring, the anions and the non-ions are combined into a whole, so that a novel emulsifier with both anion and non-ion performances is prepared.
(2) 2-ethyl bromobutyrate, 9-fluorenylmethyl chloroformate and trimethylcyclotriboroxane are used as an emulsifier synthesis catalyst, and ethoxyamine hydrochloride, methylethylamine and acetic propionic anhydride are adopted to improve the synergist of the dodecylphenol and the m-pentadecylphenol; 4,4' -bipyridine, aminoacetonitrile and iminodiacetonitrile are used as catalysts of hydroxyethylidene diphosphonic acid and tetrakis hydroxymethyl phosphonium sulfate.
(3) The mechanism of the invention is that the acrylic resin forms a compact film by adopting the cross-linking agent, and the surface of the acrylic resin is provided with the flame-retardant group, 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 acrylate resin coating and paint comprises the following steps:
(1) adding the following raw materials in parts by weight into a reaction vessel: adding 50 parts of water, 0.4 part of emulsifier, 0.6 part of methacrylic acid and 0.3 part of acrylic acid into a reaction container, heating to 45 ℃, stirring for 40min, adding a monomer A, and emulsifying for 30 min; heating to 65 ℃, introducing reflux water, heating to 77 ℃, keeping the temperature, dropwise adding 0.3 weight part of ammonium persulfate (dissolved by 5g of water), continuing for 1h, and reacting for 2h after dropwise adding to obtain a nuclear layer emulsion;
the monomer A is prepared from: 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 monomer B and 0.3 part by weight of ammonium persulfate (dissolved by 5g of water) into the core-layer emulsion obtained in the step (1), keeping the dropwise adding time for 1h, keeping the temperature at 75 ℃ after dropwise adding, stirring for reaction for 3h, then adding 0.6 part by weight of flame-retardant cross-linking agent, keeping the temperature at 75 ℃ for reaction for 1h, cooling to 50 ℃, adding 0.3 part by weight of emulsifier, reacting for 30min, and adding ammonia to adjust the pH value to 7-8 to obtain the flame-retardant water-based core-shell acrylate resin coating and paint;
the B monomer is prepared from: butyl acrylate 1 weight portion, methyl methacrylate 3 weight portions, ethyl acrylate 3 weight portions, hydroxyethyl acrylate 2 weight portions.
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 15g of dodecylphenol, 1.6g of m-pentadecylphenol and 0.3g of ethoxyamine hydrochloride, heating to 100 ℃, 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 4,4' -bipyridine are added into 250ml of a three-neck flask and reacted for 1h at 70 ℃, 1.5g of formamide and 1.6g of 2, 3-pyridinedicarboxylic acid are added and reacted for 1.5h at 65 ℃, and the flame-retardant cross-linking agent is obtained.
Example 2
The preparation method of the flame-retardant water-based core-shell acrylate resin coating and paint comprises the following steps:
(1) adding the following raw materials in parts by weight into a reaction vessel: heating 65 parts of water, 2.3 parts of emulsifier, 3.0 parts of methacrylic acid and 0.7 part of acrylic acid to 45 ℃, stirring for 40min, adding monomer A, and emulsifying for 70 min; heating to 65 ℃, introducing reflux water, heating to 77 ℃, keeping the temperature, dropwise adding 0.7 weight part of potassium persulfate (dissolved by 5g of water), continuing for 3 hours, and reacting for 4 hours after dropwise adding to obtain a nuclear layer emulsion;
the monomer A is prepared from: 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 a monomer B and 0.4 part by weight of potassium persulfate (dissolved in 5g of water) into the core layer emulsion obtained in the step (1), keeping the dropwise adding time for 2 hours, keeping the temperature at 85 ℃ after the dropwise adding, stirring and reacting for 3 hours, then adding 1.1 part by weight of flame-retardant cross-linking agent, keeping the temperature at 95 ℃ for reacting for 3 hours, cooling to 50 ℃, adding 0.3 part by weight of emulsifier, reacting for 30 minutes, and adding ammonia to adjust the pH value to 7-8 to obtain the flame-retardant water-based core-shell acrylate resin coating and paint;
the B monomer is prepared from: 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-fluorenylmethyl chloroformate, 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 ℃, 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 and reacted for 1h at 70 ℃, 1.5g of formamide and 1.6g of 2, 3-pyridinedicarboxylic acid are added and reacted for 1.5h at 65 ℃, and the flame-retardant cross-linking agent is obtained.
Example 3
The preparation method of the flame-retardant water-based core-shell acrylate resin coating and paint comprises the following steps:
(1) adding the following raw materials in parts by weight into a reaction vessel: heating 57 parts of water, 1.3 parts of emulsifier, 1.8 parts of methacrylic acid and 0.5 part of acrylic acid to 45 ℃, stirring for 40min, adding the monomer A, and emulsifying for 50 min; heating to 65 ℃, introducing reflux water, heating to 77 ℃, keeping the temperature, dropwise adding 0.5 weight part of potassium hydrogen persulfate (dissolved by 5g of water), keeping the dropwise adding time for 2 hours, and reacting for 3 hours after the dropwise adding is finished to obtain a nuclear layer emulsion;
the monomer A is prepared from: 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 a monomer B and 0.3 part by weight of potassium hydrogen persulfate (dissolved in 5g of water) into the core layer emulsion obtained in the step (1), keeping the dropwise adding time for 1.5h, keeping the temperature of 80 ℃ after dropwise adding, stirring and reacting for 3h, then adding 0.8 part by weight of flame-retardant cross-linking agent, keeping the temperature of 85 ℃ for reacting for 2h, cooling to 50 ℃, adding 0.3 part by weight of emulsifier, reacting for 30min, and adding ammonia to adjust the pH value to 7-8, thus obtaining the flame-retardant water-based core-shell acrylate resin coating and paint;
the B monomer is prepared from: 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 trimethylcyclotriboroxane, 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 acetic propionic anhydride, heating to 100 ℃, 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 and reacted for 1h at 70 ℃, 1.5g of formamide and 1.6g of 2, 3-pyridinedicarboxylic acid are added and reacted for 1.5h at 65 ℃, and the flame-retardant cross-linking agent is obtained.
Example 4
The preparation method of the flame-retardant water-based core-shell acrylate 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 emulsifier, 3.0 parts of methacrylic acid and 0.3 part of acrylic acid, heating to 45 ℃, stirring for 40min, adding the monomer A, and emulsifying for 40 min; heating to 65 ℃, introducing reflux water, heating to 77 ℃, keeping the temperature, dropwise adding 0.4 weight part of ammonium persulfate (dissolved by 5g of water), continuing for 1.5h, and reacting for 3h after dropwise adding to obtain a nuclear layer emulsion;
the monomer A is prepared from: 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 monomer B and 0.3 part by weight of ammonium persulfate (dissolved by 5g of water) into the core-layer emulsion obtained in the step (1), keeping the dropwise adding time for 1h, keeping the temperature at 75 ℃ after dropwise adding, stirring for reaction for 3h, then adding 0.7 part by weight of flame-retardant cross-linking agent, keeping the temperature at 80 ℃ for reaction for 2h, cooling to 50 ℃, adding 0.3 part by weight of emulsifier, reacting for 30min, and adding ammonia to adjust the pH value to 7-8 to obtain the flame-retardant water-based core-shell acrylate resin coating and paint;
the B monomer is prepared from: 3 parts of butyl acrylate, 4 parts of methyl methacrylate, 4 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 ethyl 2-bromobutyrate, 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 ethoxyamine hydrochloride, heating to 100 ℃, 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 and reacted for 1h at 70 ℃, 1.5g of formamide and 1.6g of 2, 3-pyridinedicarboxylic acid are added and reacted for 1.5h at 65 ℃, and the flame-retardant cross-linking agent is obtained.
Example 5
The preparation method of the flame-retardant water-based core-shell acrylate resin coating and paint comprises the following steps:
(1) adding the following raw materials in parts by weight into a reaction vessel: heating 65 parts of water, 2.3 parts of emulsifier, 3.0 parts of methacrylic acid and 0.7 part of acrylic acid to 45 ℃, stirring for 40min, adding monomer A, and emulsifying for 70 min; heating to 65 ℃, introducing reflux water, heating to 77 ℃, keeping the temperature, dropwise adding 0.7 weight part of potassium persulfate (dissolved by 5g of water), keeping the dropwise adding time for 1 hour, and reacting for 2 hours after the dropwise adding is finished to obtain a nuclear layer emulsion;
the monomer A is prepared from: 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 a monomer B and 0.3 part by weight of potassium persulfate (dissolved in 5g of water) into the core layer emulsion obtained in the step (1), keeping the dropwise adding time for 1h, keeping the temperature at 75 ℃ after dropwise adding, stirring and reacting for 3h, then adding 0.6 part by weight of flame-retardant cross-linking agent, keeping the temperature at 75 ℃ for reaction for 1h, cooling to 50 ℃, adding 0.3 part by weight of emulsifier, reacting for 30min, and adding ammonia water to adjust the pH value to 7-8 to obtain the flame-retardant water-based core-shell acrylate resin coating and paint;
the B monomer is prepared from: 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-fluorenylmethyl chloroformate, 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 ℃, 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 and reacted for 1h at 70 ℃, 1.5g of formamide and 1.6g of 2, 3-pyridinedicarboxylic acid are added and reacted for 1.5h at 65 ℃, and the flame-retardant cross-linking agent is obtained.
Flame retardancy is measured by the oxygen index, the flaming combustion time.
TABLE 1 test Properties
Example 1 Example 2 Example 3 Example 4 Example 5
Oxygen index/% 29.4 29.6 30.4 29.8 29.8
Flame combustion 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 aqueous core-shell type acrylic resin coating and paint was greatly increased and the flaming combustion time was greatly decreased, whereas the oxygen index and the flaming combustion time of example 1 of comparative examples 201610506501.6 and 201610645798.4 were 22.6, 26.5s and 24.1 and 36.5s, respectively.
TABLE 2 Performance test (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 combustion 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 waterborne core-shell acrylic resin coating and paint without adding the flame-retardant cross-linking agent is greatly reduced, and the flaming combustion time is greatly improved.
TABLE 3 test of the Properties (with flame-retardant crosslinker, without substance C)
Example 1 Example 2 Example 3 Example 4 Example 5
Oxygen index/% 25.2 24.7 26.4 25.3 27.2
Flame combustion 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 waterborne core-shell acrylate resin coating and the paint with the flame-retardant crosslinking agent added and without the substance C is greatly increased, and the flaming combustion time is greatly reduced compared with the coating and the paint without the flame-retardant crosslinking agent added.
TABLE 4 testing of the properties (addition of flame-retardant crosslinking agent, addition of substance C, absence of 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 combustion 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 waterborne core-shell acrylate resin coating and the paint added with the flame-retardant crosslinking agent and the substance C without the 2, 3-pyridinedicarboxylic acid is greatly increased compared with that of the flame-retardant crosslinking agent, and the flaming combustion time is greatly reduced.
And (3) chemical reagent resistance stability, namely respectively mixing the emulsion with a 5% sodium chloride solution according to the volume ratio of 1: 4, sealing and standing for 48h, and observing the precipitation amount of the mixture.
Gel fraction: the weight of the gel in the acrylic resin synthesis was measured as a percentage of the weight of the theoretically obtained emulsion.
Table 5 emulsion stability data
Example 1 Example 2 Example 3 Example 4 Example 5
Chemical resistance stability Stable and non-laminated Stable and non-laminated Stable and non-laminated Stable and non-laminated Stable and non-laminated
Gel filtration/% 1.6 2.1 1.7 1.1 0.8
From Table 5, it can be seen that the chemical resistance and gel filtration of the present invention are both good. The gel filtration of example 1 of comparative 201610506501.6 and 201610645798.4 was 9.7% and 8.3%, respectively.
TABLE 6 emulsion stability data (without addition of substance A)
Example 1 Example 2 Example 3 Example 4 Example 5
Chemical resistance stability Stable and non-laminated Layering Stable and non-laminated 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 addition of substance a are significantly reduced.
TABLE 7 emulsion stability data (with substance A, without substance B)
Example 1 Example 2 Example 3 Example 4 Example 5
Chemical resistance stability Layering Layering Layering Layering Layering
Gel filtration/% 7.7 10.3 12.7 8.6 14.3
From table 7 it can be seen that the gel and chemical resistance of the invention without addition of substance B is significantly reduced.

Claims (3)

1. The preparation method of the flame-retardant water-based core-shell acrylate 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 emulsifier and methyl propyl
Mixing and stirring 0.6-3.0 parts of olefine acid and 0.3-0.7 part of acrylic acid, heating to 45 ℃, stirring for 40min, adding a monomer A, and emulsifying for 30-70 min; heating to 65 ℃, introducing reflux water, heating to 77 ℃, keeping the temperature, dropwise adding 0.3-0.7 weight part of initiator A, keeping the dropwise adding time for 1-3 hours, and reacting for 2-4 hours after dropwise adding to obtain a nuclear layer emulsion;
the monomer A is prepared from: 2-7 parts of butyl acrylate, 2-5 parts of methyl methacrylate and 3-3.5 parts of ethyl acrylate
Mixing the components by weight part and 2-4 parts of hydroxyethyl acrylate;
(2) simultaneously dripping a monomer B and 0.3-0.4 part by weight of an initiator A into the core layer emulsion obtained in the step (1), keeping the dripping time for 1-2 h, keeping the temperature at 75-85 ℃ after the dripping is finished, stirring and reacting for 3h, adding 0.6-1.1 part by weight of a flame-retardant cross-linking agent, keeping the temperature at 75-95 ℃ for reacting for 1-3 h, cooling to 50 ℃, adding 0.3 part by weight of an emulsifier, reacting for 30min, and adding ammonia water to adjust the pH value to 7-8 to obtain the flame-retardant water-based core-shell acrylate resin coating and paint; 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 a substance into 250ml of a three-neck flask, reacting for 1h at 70 ℃, adding 1.5g of formamide and 1.6g of 2, 3-pyridinedicarboxylic acid, and reacting for 1.5h at 65 ℃ to obtain the flame-retardant cross-linking agent; the substance C is any one of 4,4' -bipyridyl, aminoacetonitrile and iminodiacetonitrile;
the B monomer is prepared from: 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.
2. The method for preparing the flame-retardant aqueous core-shell type acrylic resin coating and paint according to claim 1, wherein the primer is a flame retardant
The hair agent A is any one of ammonium persulfate, potassium persulfate and potassium hydrogen persulfate.
3. The method for preparing the flame-retardant aqueous core-shell type acrylic resin coating and paint according to claim 1, wherein the emulsion is
The preparation method of the catalyst comprises the steps of adding 15g of triethylene tetramine and 70g of water into a three-neck flask, heating to 30 ℃, and slowly adding a ring
40g of ethylene oxide and 1.2-2.4 g of a substance A react at 30 ℃ for 2 hours, 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 a substance B are added, the temperature is raised to 100 ℃ for reflux reaction for 1 hour, the solvent is distilled under reduced pressure to obtain an emulsifier, and the substance A is any one of 2-ethyl bromobutyrate, 9-fluorenylmethylchloroformate and trimethylcyclotriboroxane; the substance B is any one of ethoxyamine hydrochloride, methyl ethylamine and acetic propionic anhydride.
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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
WO2023073470A1 (en) * 2021-10-26 2023-05-04 3M Innovative Properties Company Flame retardant pressure-sensitive adhesive and method of making
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
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