CN112279968B - Preparation method of unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion - Google Patents
Preparation method of unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion Download PDFInfo
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- 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
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- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- 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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- 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
- C09D5/08—Anti-corrosive paints
Abstract
The invention relates to the technical field of acrylic emulsion, in particular to a preparation method of unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion, which comprises the following steps: a) mixing unsaturated fatty acid and epoxy chloropropane, and reacting under an alkaline condition to obtain unsaturated fatty acid glycidyl ester; b) preparing an acrylic resin solution; c) mixing the acrylic resin solution and unsaturated fatty acid glycidyl ester, and carrying out high-temperature condensation reaction under the action of a catalyst to obtain unsaturated fatty acid glycidyl ester modified acrylic resin; d) mixing unsaturated fatty acid glycidyl ester modified acrylic resin, ammonia water, (methyl) acrylate monomer and/or styrene and deionized water, and carrying out emulsion polymerization under the action of an initiator to obtain the unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion. The invention solves the problem that the VOC discharge capacity is increased because a film forming aid needs to be added in the preparation process of the existing acrylic emulsion.
Description
Technical Field
The invention relates to the technical field of acrylic emulsion, in particular to a preparation method of unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion.
Background
Emulsion paint is divided into two categories of polyvinyl acetate emulsion and acrylic emulsion according to different base materials, but no matter which paint contains more or less VOC, the VOC is volatile organic compound which has great influence on human health, when the VOC reaches a certain concentration, people can feel headache, nausea, vomit, hypodynamia and the like in a short time, and in severe cases, convulsion and coma can occur, respiratory diseases and leukemia are induced, the liver, kidney, brain and nervous system of people can be injured, and serious consequences such as hypomnesis can be caused.
At present, acrylic emulsion introduces small molecular organic compounds which are difficult to completely remove in the polymerization process, including unreacted monomers, organic impurities introduced by monomers, and organic substances generated by decomposition of surfactants or initiators. And because of the structural characteristics of the acrylic emulsion, the defects of sticky paint film and poor stain resistance of the paint film exist without adding a film forming aid, after the film forming aid is added, the film forming aid can promote the plastic flow and elastic deformation of a high molecular compound, the coalescence performance is improved, and a film can be formed in a wider construction temperature range. Thus, the film-forming aids used in the preparation of acrylic emulsions have become one of the major sources of VOC.
In order to realize the strategic goal of 'green development', the country and the place continuously set various environmental protection policies, and enterprises are guided to reduce the emission of VOC in the production process and when users use terminal products. Therefore, the development of an acrylic emulsion without using a film-forming aid in the preparation process tends to further improve the environmental protection level of the whole industry.
Disclosure of Invention
In view of the above, the invention provides a preparation method of unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion, and aims to solve the problem that the VOC (volatile organic compound) emission is increased due to the fact that a film-forming aid needs to be added in the preparation process of the existing acrylic emulsion.
In order to achieve the purpose, the invention is realized by the following technical scheme: a preparation method of unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion comprises the following steps:
a) mixing unsaturated fatty acid and epoxy chloropropane, heating, and reacting under an alkaline condition to obtain unsaturated fatty acid glycidyl ester;
b) heating ethanol, then dropwise adding a mixed solution of (methyl) acrylic acid, (methyl) acrylate monomer and/or styrene, azodiisobutyronitrile and mercaptan, and reacting to obtain an acrylic resin solution;
c) mixing the acrylic resin solution and unsaturated fatty acid glycidyl ester, and carrying out high-temperature condensation reaction under the action of a catalyst to obtain unsaturated fatty acid glycidyl ester modified acrylic resin;
d) mixing the unsaturated fatty acid glycidyl ester modified acrylic resin, ammonia water, (methyl) acrylate monomer and/or styrene and deionized water, and carrying out emulsion polymerization under the action of an initiator to obtain the unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion.
The invention is further improved in that the step a) is specifically as follows:
a1) ring opening esterification: mixing unsaturated fatty acid and epoxy chloropropane, heating to 50-55 ℃ under a stirring state to completely dissolve the unsaturated fatty acid and the epoxy chloropropane, adding 30% of sodium hydroxide solution into the mixture, and reacting at the temperature of 60-65 ℃ for 3-5 hours;
a2) dewatering and ring closing: after ring-opening esterification is finished, dropwise adding a 50% sodium hydroxide aqueous solution for 3-5 h; after the dropwise addition is finished, vacuumizing to 20-25kPa, heating to 65-75 ℃, and stirring for reaction for 2-3.5 h;
a3) removing epoxy chloropropane: after the dehydration and ring closure are finished, keeping the vacuum degree to be 20-25kPa, heating to 140-160 ℃, and stirring for reaction for 2-3.5 h;
a4) extraction and water washing: after the epoxy chloropropane is removed, cooling and maintaining the temperature to 70-85 ℃, adding methyl isobutyl ketone into the mixture for extraction, and standing for liquid separation; adding water into the grease layer, stirring, keeping the temperature to 70-85 ℃, stopping after 5-7 min, standing for liquid separation, and continuously and repeatedly washing for 3-4 times until the pH value of the water layer is 7-7.5;
a5) removing the solvent: and filtering the oil after water washing, heating to 140-160 ℃, and pumping the solvent out under the vacuum degree of 20-25kPa to obtain unsaturated fatty acid glycidyl ester.
The invention is further improved in that the dosage of each component in the step a) is as follows according to the parts by weight: 40-65 parts of unsaturated fatty acid, 30-40 parts of epoxy chloropropane, 0.5-1 part of 30% sodium hydroxide solution, 20-40 parts of 50% sodium hydroxide aqueous solution, 170-230 parts of methyl isobutyl ketone and 100-150 parts of water; the unsaturated fatty acid in the step a) comprises one or more of soya oil acid, linoleic acid, eleostearic acid and dehydrated ricinoleic acid.
The invention is further improved in that the step b) is specifically as follows: heating ethanol to 70-80 ℃, dropwise adding a mixed solution of (methyl) acrylic acid, (methyl) acrylate monomers and/or styrene, azodiisobutyronitrile and mercaptan for 2-5 h, and after dropwise adding, keeping the temperature at 70-80 ℃ for 2-4 h to obtain an acrylic resin solution.
The invention is further improved in that the dosage of each component in the step b) is as follows according to the parts by weight: 30-50 parts of ethanol, 15-30 parts of (methyl) acrylic acid, 50-70 parts of (methyl) acrylate monomer and/or styrene, 3-7 parts of azodiisobutyronitrile and 2-4 parts of mercaptan.
The invention is further improved in that the step c) is specifically as follows:
c1) mixing the acrylic resin solution and the glycidyl ester of unsaturated fatty acid, heating to 75-85 ℃ under a stirring state, and keeping the temperature;
c2) and (3) removing the solvent ethanol under reduced pressure, heating to 95-110 ℃, adding 0.2-0.5 part by weight of catalyst, heating to 115-130 ℃, and reacting for 3-6 hours to obtain the unsaturated fatty acid glycidyl ester modified acrylic resin.
The further improvement of the invention is that the acrylic resin solution, the glycidyl ester of unsaturated fatty acid and the catalyst in the step c) are used according to the following weight parts: 100-150 parts of acrylic resin solution, 10-40 parts of unsaturated fatty acid glycidyl ester and 0.2-0.5 part of catalyst; the catalyst is one or more of triethylamine, triethanolamine, tris (dimethylaminomethyl) phenol, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetrabutylammonium bromide, triphenylphosphine and triphenylphosphine chloride.
The invention is further improved in that the step d) is specifically as follows:
d1) adding ammonia water into unsaturated fatty acid glycidyl ester modified acrylic resin, uniformly stirring, adjusting the pH to 7-8, adding deionized water, heating to 75-85 ℃ under a stirring state, and then preserving heat to obtain a mixed solution A;
d2) uniformly mixing a (methyl) acrylate monomer and/or styrene with an initiator to obtain a mixed solution B;
d3) and dropwise adding the mixed solution B into the mixed solution A under the stirring and heat preservation conditions, wherein the dropwise adding time is 2-4 h, and after the dropwise adding is finished, preserving the heat for 2h at the temperature of 75-85 ℃ to obtain the unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion.
The invention is further improved in that the dosage of each component in the step d) is as follows according to parts by weight: 8-16 parts of unsaturated fatty acid glycidyl ester modified acrylic resin, 1-7 parts of ammonia water, 0.2-1.0 part of initiator, 50-80 parts of (methyl) acrylate monomer and/or styrene and 100-150 parts of deionized water.
In a further improvement of the invention, the (meth) acrylate monomer comprises one or more of methyl methacrylate, butyl acrylate and octyl acrylate; the initiator comprises potassium persulfate, ammonium persulfate and sodium persulfate.
In the invention, 50-70 parts of (methyl) acrylate monomer and/or styrene refers to that 50-70 parts of a mixture of the (methyl) acrylate monomer and styrene can be added, or only 50-70 parts of (methyl) acrylate monomer can be added. In the present invention, the term "(meth) acrylate" refers to both acrylate and methacrylate; "(meth) acrylic acid" refers to both acrylic acid and methacrylic acid.
Due to the adoption of the technical scheme, the invention has the technical progress that:
1. according to the invention, epoxy chloropropane is used for modifying unsaturated fatty acid, and the prepared unsaturated fatty acid containing epoxy groups can perform high-temperature ring-opening esterification reaction with an acrylic resin solution to generate unsaturated fatty acid glycidyl ester modified acrylic resin. In the unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion prepared from the unsaturated fatty acid glycidyl ester modified acrylic resin, the modified unsaturated fatty acid plays roles in improving the glossiness and enhancing the water resistance.
2. The test results according to HG/T4758-2014 show that the antirust paint prepared from the unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion has stable performance, excellent initial water resistance, good adhesive force, good gloss and good hardness, does not need to be added with a film-forming assistant, thereby reducing the discharge of VOC.
3. The unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion prepared from the unsaturated fatty acid glycidyl ester modified acrylic resin integrates the advantages of unsaturated fatty acid and acrylic emulsion, and a paint film can be subjected to oxidative crosslinking in air, so that the paint film of the product paint has the characteristics of good film forming property, high glossiness and good aging resistance.
Drawings
FIG. 1 is a graph showing the effects of tests on rust inhibitive paints prepared using the emulsions synthesized in examples 1 and 2 and comparative examples, respectively (from left to right: A is a graph showing the effects of tests on rust inhibitive paints prepared using the emulsions synthesized in example 1, B is a graph showing the effects of tests on rust inhibitive paints prepared using the emulsions synthesized in example 2, and C is a graph showing the effects of tests on rust inhibitive paints prepared using the emulsions synthesized in comparative examples).
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Unless otherwise specified, the following amounts are in parts by weight.
A preparation method of unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion comprises the following steps:
a) mixing unsaturated fatty acid and epoxy chloropropane, heating, and reacting under an alkaline condition to obtain unsaturated fatty acid glycidyl ester, wherein the reaction process is as follows:
b) heating ethanol, then dropwise adding a mixed solution of (methyl) acrylic acid, (methyl) acrylate monomer and/or styrene, azodiisobutyronitrile and mercaptan, and reacting to obtain an acrylic resin solution;
c) mixing the acrylic resin solution in the step b) with the unsaturated fatty acid glycidyl ester in the step a), and carrying out high-temperature condensation reaction under the action of a catalyst to obtain unsaturated fatty acid glycidyl ester modified acrylic resin;
d) mixing the unsaturated fatty acid glycidyl ester modified acrylic resin in the step c) with ammonia water, (methyl) acrylate monomer and/or styrene and deionized water, and carrying out emulsion polymerization under the action of an initiator to obtain the unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion.
Example 1
a) Preparation of unsaturated fatty acid glycidyl ester:
a1) ring opening esterification: mixing 60 parts of soya-bean oil acid and 36 parts of epoxy chloropropane, heating to 50-55 ℃ under a stirring state to completely dissolve the soya-bean oil acid and the epoxy chloropropane, adding 0.7 part of 30% sodium hydroxide solution into the mixture, and reacting for 4 hours at the temperature of 60-65 ℃;
a2) dewatering and ring closing: after ring opening esterification is finished, 30 parts of 50% sodium hydroxide aqueous solution is dripped into the mixture for 4 hours; after the dropwise addition is finished, vacuumizing to 20-25kPa, heating to 70 ℃, and stirring for reaction for 3 hours;
a3) removing epoxy chloropropane: after dehydration and ring closure are finished, keeping the vacuum degree to 20-25kPa, heating to 150 ℃, and stirring for reaction for 3 hours;
a4) extraction and water washing: after the epoxy chloropropane is removed, cooling and maintaining the temperature to 70-85 ℃, adding 200 parts of methyl isobutyl ketone into the mixture for extraction, and standing and separating the liquid; adding 130 parts of water into the grease layer, stirring, keeping the temperature to 70-85 ℃, stopping after 5-7 min, standing for liquid separation, and continuously and repeatedly washing for 3 times until the pH value of the water layer is 7-7.5;
a5) removing the solvent: and filtering the water-washed grease, heating to 140-160 ℃, vacuumizing to 20-25kPa to remove methyl isobutyl ketone to obtain unsaturated fatty acid glycidyl ester, and cooling for later use.
b) Preparation of acrylic resin solution: adding 40 parts of ethanol into a reaction kettle, heating to 75 ℃, dropwise adding a mixed solution of 20 parts of acrylic acid, 30 parts of styrene, 30 parts of butyl acrylate, 4 parts of Azobisisobutyronitrile (AIBN) and 3 parts of tert-dodecyl mercaptan for 3 hours, keeping the temperature for 3 hours at 75 ℃ after dropwise adding is finished to obtain an acrylic resin solution, and cooling and taking out of the kettle for later use.
c) Preparation of unsaturated fatty acid glycidyl ester modified acrylic resin:
c1) adding 120 parts of the acrylic resin solution in the step b) and 20 parts of the glycidyl ester of the soya-bean oil acid in the step a) into a reaction kettle, mixing, heating to 80 ℃ under a stirring state, and keeping the temperature;
c2) and (3) removing the solvent ethanol under reduced pressure, heating to 100 ℃, adding 0.3 part of triphenylphosphine, heating to 120-125 ℃, reacting for 5 hours to obtain unsaturated fatty acid glycidyl ester modified acrylic resin, and cooling and taking out of the pot for later use.
d) Preparation of unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion:
d1) weighing 15 parts of unsaturated fatty acid glycidyl ester modified acrylic resin obtained in the step c), adding 1.5 parts of ammonia water, uniformly stirring, adjusting the pH to 7-8, dissolving in 100 parts of deionized water, putting into a reaction kettle, heating to 80 ℃ under a stirring state, and keeping the temperature to obtain a mixed solution A;
d2) uniformly mixing 26 parts of styrene, 24 parts of methyl methacrylate, 20 parts of butyl acrylate and 0.5 part of potassium persulfate (dissolved in 5g of deionized water) to obtain a mixed solution B;
d3) and (3) dropwise adding the mixed solution B into the mixed solution A under the stirring and heat preservation conditions, wherein the dropwise adding time is 3-3.5 h, preserving the heat for 2h at 80-84 ℃ after the dropwise adding is finished, obtaining unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion, cooling to 35-40 ℃, filtering and packaging.
The oleic acid modified soap-free acrylic emulsion synthesized in example 1 above, as measured by a malvern laser particle sizer, had an average particle size of 104.3nm and a particle size distribution Pdi of 0.018, indicating that the soap-free acrylic emulsion synthesized in example 1 had a smaller particle size and a concentrated particle size distribution, which contributed to the stability of the later coating.
Example 2
a) Preparation of unsaturated fatty acid glycidyl ester:
a1) ring opening esterification: mixing 55 parts of eleostearic acid and 36 parts of epoxy chloropropane, heating to 50-55 ℃ under a stirring state to completely dissolve the eleostearic acid and the epoxy chloropropane, adding 0.7 part of 30% sodium hydroxide solution into the mixture, and reacting for 4 hours at the temperature of 60-65 ℃;
a2) dewatering and ring closing: after ring opening esterification is finished, 30 parts of 50% sodium hydroxide aqueous solution is dripped into the mixture for 4 hours; after the dropwise addition is finished, vacuumizing to 20-25kPa, adding alkali, heating to 70 ℃, and stirring for reaction for 3 hours;
a3) removing epoxy chloropropane: after dehydration and ring closure are finished, keeping the vacuum degree to 20-25kPa, heating to 150 ℃, and stirring for reaction for 3 hours;
a4) extraction and water washing: after the epoxy chloropropane is removed, cooling and maintaining the temperature to 70-85 ℃, adding 200 parts of methyl isobutyl ketone into the mixture for extraction, and standing for liquid separation; adding 130 parts of water into the grease layer, stirring, keeping the temperature to 70-85 ℃, stopping after 5-7 min, standing for liquid separation, and continuously and repeatedly washing for 3 times until the pH value of the water layer is 7-7.5;
a5) removing the solvent: and filtering the water-washed grease, heating to 140-160 ℃, vacuumizing to 20-25kPa to remove methyl isobutyl ketone to obtain unsaturated fatty acid glycidyl ester, and cooling for later use.
b) Preparation of acrylic resin solution: adding 40 parts of ethanol into a reaction kettle, heating to 75 ℃, dropwise adding a mixed solution of 20 parts of acrylic acid, 30 parts of styrene, 30 parts of butyl acrylate, 4 parts of Azobisisobutyronitrile (AIBN) and 3 parts of tert-dodecyl mercaptan for 3 hours, keeping the temperature for 3 hours at 75 ℃ after dropwise adding is finished to obtain an acrylic resin solution, and cooling and taking out of the kettle for later use.
c) Preparation of unsaturated fatty acid glycidyl ester modified acrylic resin:
c1) adding 120 parts of the acrylic resin solution in the step b) and 20 parts of the glycidyl eleostearate in the step a) into a reaction kettle for mixing, heating to 80 ℃ under a stirring state, and preserving heat;
c2) and (3) removing the solvent ethanol under reduced pressure, heating to 100 ℃, adding 0.3 part of triphenylphosphine, heating to 120-125 ℃, reacting for 5 hours to obtain unsaturated fatty acid glycidyl ester modified acrylic resin, and cooling and taking out of the pot for later use.
d) Preparation of unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion:
d1) weighing 15 parts of unsaturated fatty acid glycidyl ester modified acrylic resin obtained in the step c), adding 1.5 parts of ammonia water into the unsaturated fatty acid glycidyl ester modified acrylic resin, uniformly stirring, adjusting the pH to 7-8, dissolving the mixture in 100 parts of deionized water, putting the mixture into a reaction kettle, heating the mixture to 80 ℃ under a stirring state, and keeping the temperature to obtain a mixed solution A;
d2) uniformly mixing 26 parts of styrene, 24 parts of methyl methacrylate, 20 parts of butyl acrylate and 0.5 part of potassium persulfate (dissolved in 5g of deionized water) to obtain a mixed solution B;
d3) and (3) dropwise adding the mixed solution B into the mixed solution A under the stirring and heat preservation conditions, wherein the dropwise adding time is 3-3.5 h, preserving the heat for 2h at 80-84 ℃ after the dropwise adding is finished, obtaining unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion, cooling to 35-40 ℃, filtering and packaging.
The oleic acid modified soap-free acrylic emulsion synthesized in the above example 2 was measured by a malvern laser particle sizer, and found that the average particle size was 109.8nm and the particle size distribution Pdi was 0.021, indicating that the soap-free acrylic emulsion synthesized in example 2 had a small particle size and a concentrated particle size distribution, contributing to the stability of the coating at the later stage.
Comparative example
a) Sequentially adding 3.75g of emulsifier (SR-10) and 200g of deionized water into a 1000ml four-neck flask provided with a stirring device, a thermometer and nitrogen protection, stirring, heating to 75 ℃, and stopping heating;
b) dissolving 4.5g of emulsifier (SR-10) in 150g of deionized water in an emulsifying kettle, then sequentially adding 98g of methyl methacrylate, 100g of styrene, 122g of butyl acrylate, 5.6g of methacrylic acid and 0.8g of tert-dodecyl mercaptan into an emulsifier aqueous solution in a high-speed dispersion state, and stirring for 30-40 min to prepare a monomer pre-emulsion;
c) adding 5% of monomer pre-emulsion into a reaction kettle, adding 0.6g of sodium persulfate (dissolved in 5g of deionized water) aqueous solution, and keeping the temperature for 15 minutes;
d) when the temperature of the reaction kettle reaches 80 ℃, dropwise adding the residual emulsion and 1.2g of sodium persulfate (dissolved in 30g of deionized water) aqueous solution, and completing dropwise adding within 3-3.5 hours; after the dropwise addition is finished, preserving the heat for 1-1.5 hours at the temperature of 80-84 ℃;
e) the temperature of the reaction kettle is reduced to 35-40 ℃; and sequentially adding 4.8g of ammonia water into the reaction kettle, stirring for 30-40 minutes, filtering and packaging.
The above SR-10 is an allyloxy aliphatic alcohol ethoxylate ammonium sulfate product produced by Ediko, Japan, and the remainder are commercially available products.
The emulsion synthesized in the above comparative example was measured by malvern laser particle sizer, and found that the average particle diameter was 129.8nm and the particle diameter distribution Pdi was 0.056.
After comparative experiments were performed by preparing rust inhibitive paints using the emulsions synthesized in example 1, example 2, and comparative example, respectively, experimental data and analysis were as follows:
preparation of a rust inhibitive paint using the emulsion synthesized in example 1: 160g of the emulsion synthesized in example 1 is added into a dispersion tank, 1g of a pH regulator AMP-95 is added under stirring, the pH is adjusted to 8-9, 34 parts of iron oxide red paste is added, 0.8g of a defoaming agent BYK-093, 0.4g of an anti-flash embroidery agent raybo60, 0.8g of a thickening agent PU337 are added, 1500r/min are dispersed for 15 minutes, 1.2g of a BYK349 base material wetting agent and 0.2g of BYK-028 are added, the viscosity is adjusted by water, and 1000r/min is dispersed for 15 minutes.
Preparation of a rust inhibitive paint using the emulsion synthesized in example 2: 160g of the emulsion synthesized in the example 2 is added into a dispersion tank, 1g of a pH value regulator AMP-95 is added under stirring, the pH value is adjusted to 8-9, 34 parts of iron oxide red paste is added, 0.8g of a defoaming agent BYK-093, 0.4g of an anti-flash embroidery agent raybo60, 0.8g of a thickening agent PU337 is added, 1500r/min is dispersed for 15 minutes, 4g of diethylene glycol butyl ether and 4g of dipropylene glycol butyl ether are added, 1000r/min is dispersed for 10 minutes, 1.2g of a BYK349 substrate wetting agent and 0.2g of K-028 are added, the viscosity is adjusted by water, and 1000r/min is dispersed for 15 minutes.
Preparing a rust inhibitive paint using the emulsion synthesized in the comparative example: 160g of the emulsion synthesized in the comparative example is added into a dispersion tank, 1g of AMP-95 as a pH regulator is added under stirring, the pH value is adjusted to 8-9, 34 parts of iron oxide red paste is added, 0.8g of defoaming agent BYK-093, 0.4g of anti-flash embroidery agent raybo60 and 0.8g of thickening agent PU337 are added, 1500r/min is added for dispersion for 15 minutes, 8g of diethylene glycol butyl ether and 8g of dipropylene glycol butyl ether are added, 1000r/min is dispersed for 10 minutes, 1.2g of BYK349 substrate wetting agent and 0.2g of BYK-028 are added, the viscosity is adjusted by water, and 500r/min is dispersed for 15 minutes.
The iron oxide red color paste used for preparing the anti-rust paint is purchased from the world-name technology (60% solid content). As shown in FIG. 1, the results of various performance tests in industry of anti-rust paints prepared in example 1, example 2 and comparative example according to the HG/T4758-2014 standard are shown in Table 1:
as can be seen from Table 1, the antirust paint prepared from the unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion has the advantages of level and smooth surface of a paint film, stable performance, excellent initial water resistance, good adhesive force, luster and hardness without adding a film-forming assistant.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A preparation method of unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion is characterized by comprising the following steps:
a) mixing unsaturated fatty acid and epoxy chloropropane, heating, and reacting under an alkaline condition to obtain unsaturated fatty acid glycidyl ester;
b) heating ethanol, then dropwise adding a mixed solution of (methyl) acrylic acid, (methyl) acrylate monomer and/or styrene, azodiisobutyronitrile and mercaptan, and reacting to obtain an acrylic resin solution;
c) mixing the acrylic resin solution and unsaturated fatty acid glycidyl ester, and carrying out high-temperature condensation reaction under the action of a catalyst to obtain unsaturated fatty acid glycidyl ester modified acrylic resin;
d) mixing the unsaturated fatty acid glycidyl ester modified acrylic resin, ammonia water, (methyl) acrylate monomer and/or styrene and deionized water, and carrying out emulsion polymerization under the action of an initiator to obtain unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion;
the step a) is specifically as follows:
a1) ring opening esterification: mixing unsaturated fatty acid and epoxy chloropropane, heating to 50-55 ℃ under a stirring state to completely dissolve the unsaturated fatty acid and the epoxy chloropropane, adding 30% of sodium hydroxide solution into the mixture, and reacting at the temperature of 60-65 ℃ for 3-5 hours;
a2) dewatering and ring closing: after ring-opening esterification is finished, dropwise adding a 50% sodium hydroxide aqueous solution for 3-5 h; after the dropwise addition is finished, vacuumizing to 20-25kPa, heating to 65-75 ℃, and stirring for reaction for 2-3.5 h;
a3) removing epoxy chloropropane: after the dehydration and ring closure are finished, keeping the vacuum degree to be 20-25kPa, heating to 140-160 ℃, and stirring for reaction for 2-3.5 h;
a4) extraction and water washing: after the epoxy chloropropane is removed, cooling and maintaining the temperature to 70-85 ℃, adding methyl isobutyl ketone into the mixture for extraction, and standing for liquid separation; adding water into the grease layer, stirring, keeping the temperature to 70-85 ℃, stopping after 5-7 min, standing for liquid separation, and continuously and repeatedly washing for 3-4 times until the pH value of the water layer is 7-7.5;
a5) removing the solvent: and filtering the oil after water washing, heating to 140-160 ℃, and pumping the solvent out under the vacuum degree of 20-25kPa to obtain unsaturated fatty acid glycidyl ester.
2. The method for preparing unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion according to claim 1, wherein the components in step a) are used in parts by weight as follows: 40-65 parts of unsaturated fatty acid, 30-40 parts of epoxy chloropropane, 0.5-1 part of 30% sodium hydroxide solution, 20-40 parts of 50% sodium hydroxide aqueous solution, 170-230 parts of methyl isobutyl ketone and 100-150 parts of water; the unsaturated fatty acid in the step a) comprises one or more of soya oil acid, linoleic acid, eleostearic acid and dehydrated ricinoleic acid.
3. The method for preparing unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion according to claim 1, wherein the step b) is specifically: heating ethanol to 70-80 ℃, dropwise adding a mixed solution of (methyl) acrylic acid, (methyl) acrylate monomers and/or styrene, azodiisobutyronitrile and mercaptan for 2-5 h, and after dropwise adding, keeping the temperature at 70-80 ℃ for 2-4 h to obtain an acrylic resin solution.
4. The method for preparing unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion according to claim 1, wherein the components in step b) are used in parts by weight as follows: 30-50 parts of ethanol, 15-30 parts of (methyl) acrylic acid, 50-70 parts of (methyl) acrylate monomer and/or styrene, 3-7 parts of azodiisobutyronitrile and 2-4 parts of mercaptan.
5. The method for preparing unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion according to claim 1, wherein the step c) is specifically as follows:
c1) mixing the acrylic resin solution and the glycidyl ester of unsaturated fatty acid, heating to 75-85 ℃ under a stirring state, and keeping the temperature;
c2) and (3) removing the solvent ethanol under reduced pressure, heating to 95-110 ℃, adding 0.2-0.5 part by weight of catalyst, heating to 115-130 ℃, and reacting for 3-6 hours to obtain the unsaturated fatty acid glycidyl ester modified acrylic resin.
6. The method for preparing unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion according to claim 1, wherein the acrylic resin solution, the unsaturated fatty acid glycidyl ester and the catalyst in the step c) are used in the following weight parts: 100-150 parts of acrylic resin solution, 10-40 parts of unsaturated fatty acid glycidyl ester and 0.2-0.5 part of catalyst; the catalyst is one or more of triethylamine, triethanolamine, tris (dimethylaminomethyl) phenol, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, tetrabutylammonium bromide, triphenylphosphine and triphenylphosphine chloride.
7. The method for preparing unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion according to claim 1, wherein the step d) is specifically as follows:
d1) adding ammonia water into unsaturated fatty acid glycidyl ester modified acrylic resin, uniformly stirring, adjusting the pH to 7-8, adding deionized water, heating to 75-85 ℃ under a stirring state, and then preserving heat to obtain a mixed solution A;
d2) uniformly mixing a (methyl) acrylate monomer and/or styrene with an initiator to obtain a mixed solution B;
d3) and dropwise adding the mixed solution B into the mixed solution A under the stirring and heat preservation conditions, wherein the dropwise adding time is 2-4 h, and after the dropwise adding is finished, preserving the heat for 2h at the temperature of 75-85 ℃ to obtain the unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion.
8. The method for preparing unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion according to claim 1, wherein the components in step d) are used in the following weight parts: 8-16 parts of unsaturated fatty acid glycidyl ester modified acrylic resin, 1-7 parts of ammonia water, 0.2-1.0 part of initiator, 50-80 parts of (methyl) acrylate monomer and/or styrene and 100-150 parts of deionized water.
9. The method for preparing the unsaturated fatty acid glycidyl ester modified soap-free acrylic emulsion according to any one of claims 1 to 8, wherein the (meth) acrylate monomer comprises one or more of methyl methacrylate, butyl acrylate and octyl acrylate; the initiator comprises potassium persulfate, ammonium persulfate and sodium persulfate.
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| CN111662415A (en) * | 2020-06-18 | 2020-09-15 | 恒昌涂料（惠阳）有限公司 | Soap-free self-crosslinking nano acrylic emulsion and preparation method and application thereof |
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| CN111662415A (en) * | 2020-06-18 | 2020-09-15 | 恒昌涂料（惠阳）有限公司 | Soap-free self-crosslinking nano acrylic emulsion and preparation method and application thereof |
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Denomination of invention: Preparation method of soap free acrylic lotion modified by Unsaturated fat fatty acid Glycidol ester Effective date of registration: 20230713 Granted publication date: 20220701 Pledgee: Renmin sub branch of Hengshui Bank Co.,Ltd. Pledgor: HENGSHUI XINGUANG NEW MATERIAL TECHNOLOGY CO.,LTD. Registration number: Y2023980048488 |
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