CN111154346B - Acrylate emulsion for building interior wall coating and preparation method and application thereof - Google Patents

Acrylate emulsion for building interior wall coating and preparation method and application thereof Download PDF

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CN111154346B
CN111154346B CN202010013071.0A CN202010013071A CN111154346B CN 111154346 B CN111154346 B CN 111154346B CN 202010013071 A CN202010013071 A CN 202010013071A CN 111154346 B CN111154346 B CN 111154346B
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emulsion
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acrylate
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acid
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CN111154346A (en
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王智英
侯雷刚
孙少文
马吉全
纪学顺
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
Wanhua Chemical Guangdong Co Ltd
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Wanhua Chemical Ningbo Co Ltd
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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
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/14—Copolymers of styrene with unsaturated esters
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/022—Emulsions, e.g. oil in water

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Abstract

The invention belongs to a buildingThe technical field of building coating, and provides an acrylate emulsion for building interior wall coating and a preparation method thereof, wherein the acrylate emulsion is prepared from a monovinyl aromatic monomer, alkyl (methyl) acrylate and alpha, beta-monoethylenically unsaturated C 3 ‑C 6 The single carboxylic acid or dicarboxylic acid, the reaction type film forming additive and the monomer with hydrolyzable Si-organic bond are prepared by free radical emulsion polymerization. The acrylate emulsion provided by the invention has excellent scrub resistance, good freeze-thaw stability and low-temperature film forming property, and is low in formula cost, simple in production process, beneficial to production and high in cost performance.

Description

Acrylate emulsion for building interior wall coating and preparation method and application thereof
Technical Field
The invention belongs to the technical field of building coatings, and relates to an acrylate emulsion for building interior wall coatings.
Background
Emulsion paints have environmental protection, safety and excellent properties, are gradually replacing traditional solvent-based coatings and are widely applied to the fields of architectural decoration and fitment, and increasingly show the advantages. The emulsion is used as a very important component in the latex paint and has a decisive effect on the performance of the latex paint. For example, scrub resistance is a concern in the design of high PVC (pigment volume concentration) interior wall latex paints because it tends to affect the adhesion, durability, water resistance, etc. properties of the interior wall latex paint coating. Since the main factor influencing the scrubbing resistance of latex paints is the adhesion of the coating film, and the latex paint mainly provides the film-forming substance, namely the emulsion, the scrubbing resistance of the emulsion needs to be improved.
The conventional method for improving the scrub resistance of emulsion is to increase the design Tg of the polymer to harden the surface of the polymer particles, thereby improving the scrub resistance. Because the hardness of the paint film is improved, the flexibility of the paint film is influenced and even becomes more brittle, and although the film-forming property or flexibility of the paint film can be improved by introducing a film-forming assistant into the paint formula in the later period, the additional or excessive film-forming assistant can generate more VOC (volatile organic compounds), so that the environmental pollution and the health problem are brought, and the formula cost of the latex paint is also increased; or functional monomers such as organic silicon and the like are selected to improve the scrub resistance, but the scrub resistance is improved to a limited extent, and meanwhile, the freeze-thaw stability of the latex paint is greatly influenced. The traditional method for improving the freeze-thaw stability is to add a nonionic surfactant with higher ethoxy number into the emulsion, but the scrub resistance of the emulsion is reduced; or more hydrophilic monomers are added to form a hydration layer to wrap the latex particles, but the amount of the hydrophilic monomers is increased, so that a latex paint film is very hydrophilic, the scrubbing resistance is inevitably reduced when a scrubbing resistance test is carried out, and the excellent freeze-thaw stability and the scrubbing resistance are hardly compatible.
In addition, in order to reduce the film forming temperature, a lower theoretical Tg needs to be designed, which also greatly reduces the scrub resistance and the freeze-thaw stability, so that great contradictions exist among the low-temperature film forming property, the high scrub resistance and the excellent freeze-thaw stability, and if the contradictions can be solved, great progress is certainly brought to the coating interface.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a novel acrylate emulsion for building interior walls, which can solve the technical problems.
In one aspect of the present invention, there is provided a method for preparing an acrylate emulsion, comprising:
1) preparation of pre-emulsion a: uniformly mixing 0.5-3.5 parts by mass of emulsifier with 65-100%, 0.1-1.0 part by mass of co-stabilizer with 25-55 parts by mass of water, sequentially adding component a, component b, component c with 25-50% and component d, and uniformly mixing; wherein, the components a, b, c and d are respectively:
a) from 40 to 70 parts by mass of at least one monovinylaromatic monomer, preferably from 45 to 60 parts by mass,
b)30 to 60 parts by mass of at least one alkyl (meth) acrylate, preferably 35 to 50 parts by mass,
c)0.5 to 5 parts by mass of at least one alpha, beta-monoethylenically unsaturated C 3 -C 6 Monocarboxylic or dicarboxylic acids, preferably 2.5 to 5.0 parts by mass, and
d)0.5 to 5.0 parts by mass of a reactive film-forming aid, preferably 0.5 to 2.0 parts by mass;
2) preparing kettle bottom liquid B: adding the rest of emulsifier, 0.1-1.0 mass part of buffering agent and 40-70 mass parts of water, mixing uniformly, and heating to 50-90 ℃;
3) preparation of initiator solution C: mixing 0.2-1.0 mass part of initiator with 3.5-20 mass parts of water uniformly;
4) adding 1-10% of pre-emulsion A and 10-60% of initiator solution C into kettle bottom solution B at 50-90 ℃, reacting for 10-30min under a stirring state, starting to synchronously dropwise add the rest pre-emulsion A and the initiator solution C after the seed emulsion is formed, stopping dropwise adding when the pre-emulsion A is 10-25%, adding the component e and the rest component C at one time, uniformly stirring, continuously and synchronously dropwise adding the rest pre-emulsion A and the initiator solution C, preferably, controlling the total time of dropwise adding the pre-emulsion A to be 180-fold for 300 min, ensuring that the initiator solution C is completely dropwise added 5-20 min later than the pre-emulsion A, and then preserving heat at 60-90 ℃ for 15-90 min; the component e is 1.0 to 5.0 parts by mass, preferably 1.5 to 3.5 parts by mass of a monomer having a hydrolyzable Si-organic bond;
5) and (3) dropwise adding 0.15-1.5 parts by mass of redox initiator into the system in the step 4) at 50-70 ℃, preferably, the dropwise adding completion time is 15-30 minutes, then, preserving the heat for 15-30 minutes, cooling to 15-45 ℃, optionally adding an antifoaming agent and a bactericide, adjusting the pH to 7.0-9.0 by using a pH regulator, and filtering to obtain a filtrate, namely the acrylate emulsion. The amount of defoamer and biocide is added as needed and is conventional in the art. "optionally" means "added or not added".
The emulsifier is preferably fatty alcohol polyoxyethylene ether sulfate, and the polymerization degree (EO number) of polyoxyethylene is 2-20.
The co-stabilizer is preferably at least one of sodium vinyl sulfonate, sodium vinyl benzene sulfonate and sodium 3-allyloxy-1-hydroxy-propane sulfonate, and more preferably sodium vinyl benzene sulfonate.
The buffer is preferably at least one of sodium carbonate, sodium bicarbonate, sodium phosphate, and sodium dihydrogen phosphate, and more preferably sodium carbonate.
The initiator is preferably a water-soluble initiator, including but not limited to at least one of ammonium persulfate, sodium persulfate, and potassium persulfate, more preferably ammonium persulfate;
the redox initiator includes but is not limited to at least one of tert-butyl hydroperoxide (T-BHP), tert-amyl hydroperoxide (T-AHP), sodium bisulfite, sodium dithionite and isoascorbic acid, etc., preferably tert-butyl hydroperoxide and/or isoascorbic acid, more preferably tert-butyl hydroperoxide to isoascorbic acid in a mass ratio of 2: 1;
the pH regulator is preferably NaOH aqueous solution, and can be 6% NaOH aqueous solution.
In a preferred embodiment, the reactive coalescent of component d) has the following structural formula:
Figure BDA0002357846950000031
wherein R is 1 、R 2 Independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, hexyl, isohexyl, sec-hexyl, heptyl, isoheptyl, sec-heptyl, octyl, isooctyl, sec-octyl, nonyl, isononyl, sec-nonyl, decyl, isodecyl, vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl; phenyl, tolyl, xylyl, cumyl; one of cyclopentyl, cyclohexyl, cycloheptyl, methyl cyclopentyl and methyl cyclohexyl。
The R is 1 、R 2 More preferably one selected from methyl, ethyl, propyl, isopropyl, butyl and isobutyl.
Preferably, the reactive coalescent may be 2,2, 4-trimethyl-3-en-pentanol isobutyrate and/or 2,2, 4-triethyl-3-en-pentanol isobutyrate, both available from alatin.
In a preferred embodiment, the monomers of component e having hydrolyzable Si-organic bonds include one or more of vinylsilane, methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyltripropoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxysilane), and vinyltriisopropoxysilane, preferably one or more of vinylsilane, methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane.
In a preferred embodiment, the α, β -monoethylenically unsaturated C of component C 3 -C 6 The monocarboxylic or dicarboxylic acid is preferably selected from acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, allylacetic acid, crotonic acid, vinylacetic acid, fumaric acid, maleic acid, 2-methylmaleic acid and any combination thereof, and acrylic acid, methacrylic acid, itaconic acid and any combination thereof are particularly preferred. In a preferred embodiment, the monovinylaromatic monomer of component a is styrene, 2-methylstyrene, 4-methylstyrene, 2- (n-butyl) styrene, 4- (n-butyl) styrene and/or 4- (n-decyl) styrene, preferably styrene.
In a preferred embodiment, the alkyl (meth) acrylate of component b is selected from the group consisting of n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isooctyl acrylate and any combination thereof, preferably n-butyl acrylate and/or isooctyl acrylate.
In a second aspect, the present invention provides acrylate emulsions prepared by free radical emulsion polymerization of components a to e.
In a preferred embodiment, the acrylate emulsion is prepared by the process of the present invention.
In a third aspect, the present invention provides the use of an acrylate emulsion as described above or an acrylate emulsion prepared by a process as described above for the preparation of a latex paint, preferably for the preparation of an interior wall latex paint.
In a fourth aspect, the present invention provides a latex paint comprising the acrylate emulsion of the present invention or an acrylate emulsion prepared by the method of the present invention; preferably, the latex paint is an interior wall latex paint.
The amounts of the components are referred to in the present invention, and all expressed in parts represent parts by mass.
According to the method for preparing the acrylate latex, the reactive film-forming assistant is introduced in the polymerization process, so that the final scrubbing resistance of the latex paint is greatly improved while the low-temperature film-forming property is maintained, the addition amount of the film-forming assistant in the latex paint can be reduced, and the content of organic volatile matters in the latex paint is reduced because: firstly, the addition of the reactive film-forming assistant can effectively reduce the film-forming temperature; secondly, the latex particles are added in the polymerization process, so that the latex particles can participate in polymerization to form a part of a polymer and can fully swell, the effective utilization rate of the latex particles is improved, and the amount of a film forming auxiliary agent in the final latex paint formula is reduced; and thirdly, after the emulsion becomes a part of the polymer, the emulsion can not only reach the original coating film hardness, but also be even higher, thereby improving the final scrubbing resistance of the emulsion paint, and the emulsion paint does not form VOC in the formula.
In the later stage of polymerization, the method adopts a process of adding functional monomers, so that mono-alkene carboxylic acid and hydrolysable reaction type organosilicon monomers are enriched on the surface layer at the same time, the freeze-thaw stability is ensured, the crosslinking density of a coating film and the interaction of components in the coating can be greatly improved, and the scrub resistance is obviously improved. The carboxyl group of the carboxylic acid monomer added later is distributed on the surface of the latex particle after polymerization, and subsequent alkali neutralization ionizes the carboxyl group, so that the freeze-thaw stability of the carboxylic acid monomer is effectively ensured; meanwhile, the organic silicon added later is crosslinked on the surface of the latex particles, so that the crosslinking density of the coating is greatly improved, and the organic silicon and the latex particles have synergistic effect, so that the freeze-thaw stability of the emulsion is ensured, and the scrubbing resistance can be obviously improved.
In the preparation process, the invention adopts a continuous dropwise addition polymerization process, so that emulsion with smaller particle size and wider distribution is easily obtained, the smaller particle size is beneficial to mutual permeation of chain ends on the surface of particles, the deformation and film formation of the particles are promoted, the film formation temperature is reduced, and a more compact film is formed; wider distribution is favorable for improving the viscoelasticity of the emulsion and the adhesive force to a base material, and the viscoelasticity and the adhesive force have synergistic effect, so that the film forming temperature of the emulsion can be reduced, and the scrubbing resistance of a coating film can be improved.
According to the method for preparing the acrylate emulsion, the reactive film-forming aid is introduced in the polymerization process, the functional monomer is added in the later polymerization stage, the monoethylenically carboxylic acid and the hydrolyzable reactive organosilicon monomer are simultaneously enriched on the surface layer, and the emulsion is obtained by copolymerization of the free radical emulsion polymerization and the acrylate monomer. The acrylate emulsion provided by the invention has excellent scrub resistance, good freeze-thaw stability and low-temperature film-forming property, and is low in formula cost, simple in production process, beneficial to production and high in cost performance.
Detailed Description
Some of the specific steps involved in the experimental procedures used in the examples described below were, unless otherwise specified, routine procedures.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The present invention will be further described with reference to the following examples. It should be understood that the following examples are illustrative only and are not intended to limit the scope of the present invention.
The "%" referred to in the following examples means mass% unless otherwise specified.
2,2, 4-trimethyl-3-en-pentanol isobutyrate (reactive film-forming aid) is a product of the company Aladdin;
2,2, 4-triethyl-3-en-pentanol isobutyrate (reactive film-forming aid) is a product of the company Aladdin;
texanol (a common film-forming aid) is a product of Iseman corporation;
the anionic emulsifier CM-50(EO number 4) is a product of Sorvey;
the anionic emulsifier BES-20(EO number 20) is a product of BASF corporation;
the co-stabilizer sodium vinylbenzene sulfonate is a product of Shandong Xingxi company;
the buffering agent sodium bicarbonate is a product of Chinese medicine reagent company;
the organosilicon monomer vinyltrimethoxysilane (namely A-171) is a product of Mayer company;
the organosilicon monomer methacryloxypropyltrimethoxysilane (namely A-174) is a product of Michigan company;
the antifoaming agent B-943 is a product of ADEKA company;
the bactericides LX-150 and KORDEK are products of Dow chemical company.
Example 1
Weighing the following raw materials by mass: 40g of styrene (a), 30g of n-butyl acrylate (b), 0.1g of sodium vinylbenzenesulfonate (co-stabilizer), 0.5g of 2,2, 4-trimethyl-3-en-pentanol isobutyrate (d), 0.125g of methacrylic acid (c), 0.375g of acrylic acid (c), A-1712.5g of (e), A-1742.5 g of (e), CM-500.5 g of emulsifier, 0.4g of sodium bicarbonate (buffer), 0.2g of ammonium persulfate (initiator), 0.1g of tert-butyl hydroperoxide (redox initiator), 0.05g of erythorbic acid (redox initiator), and appropriate amounts of 6% aqueous NaOH solution (pH regulator) and deionized water.
1) Preparation of pre-emulsion a: adding 0.5g of CM-50, 0.1g of sodium vinyl benzene sulfonate and 35g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer at normal temperature and normal pressure, fully stirring and dissolving, sequentially adding 40g of styrene, 30g of n-butyl acrylate and 0.125g of methacrylic acid 0.5g of 2,2, 4-trimethyl-3-ene-pentanol isobutyrate, and fully stirring for 20-30 minutes for later use;
2) preparing kettle bottom liquid B: adding 0.4g of sodium bicarbonate and 50g of deionized water into a polymerization kettle with a stirrer, a condenser, a constant flow pump feeding device and a constant flow dropwise adding metering device, fully stirring and dissolving, and heating until the temperature in the polymerization kettle reaches 80 ℃;
3) preparation of initiator solution C: at normal temperature and normal pressure, 0.2g of ammonium persulfate and 3.5g of deionized water are added into an initiator tank with a stirrer and a constant-current dropping device, and stirred until the ammonium persulfate and the deionized water are completely dissolved for later use;
4) when the temperature in the polymerization kettle reaches 80 ℃, adding 10 percent of the total amount of the pre-emulsion A and 10 percent of the total amount of the initiator solution C into the kettle, reacting for 10 minutes under a stirring state, after the seed emulsion is formed, beginning to synchronously dropwise add the rest of the pre-emulsion A and the initiator solution C into the polymerization kettle through a constant flow pump feeding device and a constant flow dropwise adding metering device, stopping dropwise adding when the pre-emulsion A is 17 percent remained, adding 0.375g of acrylic acid, 2.5g A-171 and 2.5g A-174 into the pre-emulsion at one time, continuously and synchronously dropwise adding the rest of the pre-emulsion A and the initiator solution C after uniformly stirring, controlling the total time for dropwise adding the pre-emulsion A to be 180 minutes, and ensuring that the initiator solution C is completely dropwise added 5 minutes later than the pre-emulsion A;
5) controlling the temperature in the polymerization kettle at 80 ℃, keeping the temperature for 15 minutes, cooling to 65 ℃, synchronously dropwise adding an aqueous solution containing 0.1g of tert-butyl hydroperoxide and an aqueous solution containing 0.05g of isoascorbic acid in a double manner, keeping the temperature for 20 minutes, continuously cooling to 45 ℃, adding 0.03g of defoamer B-943 and 0.4g of bactericide KORDEK, adjusting the pH to 9 by using a 6% NaOH aqueous solution, stirring, filtering by using a 100-mesh filter screen, and discharging to obtain the acrylate emulsion.
Example 2
Weighing the following raw materials by mass: styrene 51g (a), n-butyl acrylate 20g (b), isooctyl acrylate 20g (b), sodium vinylbenzenesulfonate 0.5g (co-stabilizer), 2, 4-triethyl-3-ene-pentanol isobutyrate 1.5g (d), acrylic acid 3.5g (c), A-1712.5g (e), CM-502.5 g (emulsifier), sodium bicarbonate 0.7g (buffer), ammonium persulfate 0.5g (initiator), tert-butyl hydroperoxide 0.5g (redox initiator), isoascorbic acid (redox initiator) 0.25g, and appropriate amount of 6% aqueous NaOH solution (pH regulator) and deionized water.
1) Preparation of pre-emulsion a: adding 2.0g of CM-50, 0.5g of sodium vinyl benzene sulfonate and 35g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer at normal temperature and normal pressure, fully stirring and dissolving, sequentially adding 51g of styrene, 20g of n-butyl acrylate, 20g of isooctyl acrylate, 1.05g of acrylic acid and 1.5g of 2,2, 4-triethyl-3-ene-pentanol isobutyrate, and fully stirring for 20-30 minutes for later use;
2) preparing kettle bottom liquid B: adding 0.7g of sodium bicarbonate, 0.5g of CM-50 and 60g of deionized water into a polymerization kettle with a stirrer, a condenser, a constant flow pump feeding device and a constant flow dropwise adding dosage device, fully stirring and dissolving, and heating until the temperature in the polymerization kettle reaches 70 ℃;
3) preparation of initiator solution C: at normal temperature and normal pressure, 0.5g of ammonium persulfate and 7.5g of deionized water are added into an initiator tank with a stirrer and a constant-current dropping device, and stirred until the ammonium persulfate and the deionized water are completely dissolved for later use;
4) when the temperature in the polymerization kettle reaches 70 ℃, adding 1 percent of the total amount of the pre-emulsion A and 40 percent of the total amount of the initiator solution C into the kettle, reacting for 20 minutes under a stirring state, after the seed emulsion is formed, beginning to synchronously dropwise add the residual pre-emulsion A and the initiator solution C into the polymerization kettle through a constant flow pump feeding device and a constant flow dropwise adding metering device, stopping dropwise adding when the residual pre-emulsion A is 10 percent, adding 2.45g of acrylic acid and 2.5g A-171 into the pre-emulsion at one time, stirring uniformly, continuing to synchronously dropwise add the residual pre-emulsion A and the initiator solution C again, controlling the total time of dropwise adding the pre-emulsion A to be 210 minutes, and ensuring that the initiator solution C is completely dropwise added 10 minutes later than the pre-emulsion A;
5) controlling the temperature in the polymerization kettle to be 85 ℃, keeping the temperature for 45 minutes, cooling to 60 ℃, synchronously dropwise adding an aqueous solution containing 0.5g of tert-butyl hydroperoxide and an aqueous solution containing 0.25g of isoascorbic acid for 20 minutes, keeping the temperature for 25 minutes, continuously cooling to 15 ℃, adding 0.04g of defoamer B-943 and 0.5g of bactericide KORDEK, adjusting the pH to 7 by using a 6% NaOH aqueous solution, stirring, filtering by using a 100-mesh filter screen, and discharging to obtain the acrylate emulsion.
Example 3
Weighing the following raw materials by mass: styrene 70g (a), n-butyl acrylate 60g (b), sodium vinylbenzenesulfonate 1.0g (co-stabilizer), 2, 4-trimethyl-3-ene-pentanol isobutyrate 5.0g (d), acrylic acid 5.0g (c), A-1711.0 g (e), BES-203.5 g (emulsifier), sodium bicarbonate 1.0g (buffer), ammonium persulfate 1.0g (initiator), t-butyl hydroperoxide 1.0g (redox initiator), isoascorbic acid 0.5g (redox initiator), and appropriate amount of 6% aqueous NaOH solution (pH regulator) and deionized water.
1) Preparation of pre-emulsion a: adding 3.0g of BES-20, 1.0g of sodium vinyl benzene sulfonate and 55g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer at normal temperature and normal pressure, fully stirring and dissolving, sequentially adding 70g of styrene, 60g of n-butyl acrylate, 2.5g of acrylic acid and 5.0g of 2,2, 4-trimethyl-3-ene-pentanol isobutyrate, and fully stirring for 20-30 minutes for later use;
2) preparing kettle bottom liquid B: adding 1.0g of sodium bicarbonate, 0.5g of BES-20 and 70g of deionized water into a polymerization kettle with a stirrer, a condenser, a constant flow pump feeding device and a constant flow dropwise adding metering device, fully stirring and dissolving, and heating until the temperature in the polymerization kettle reaches 90 ℃;
3) preparation of initiator solution C: adding 1.0g of ammonium persulfate and 20g of deionized water into an initiator tank with a stirrer and a constant-current dropping device at normal temperature and normal pressure, and stirring until the ammonium persulfate and the deionized water are completely dissolved for later use;
4) when the temperature in the polymerization kettle reaches 90 ℃, adding 2 percent of the total amount of the pre-emulsion A and 30 percent of the total amount of the initiator solution C into the kettle, reacting for 15 minutes under a stirring state, after the seed emulsion is formed, beginning to synchronously dropwise add the residual pre-emulsion A and the initiator solution C into the polymerization kettle through a constant flow pump feeding device and a constant flow dropwise adding metering device, stopping dropwise adding when the residual pre-emulsion A is 25 percent, adding 2.5g of acrylic acid and 1.0g A-171 into the pre-emulsion at one time, stirring uniformly, continuing to synchronously dropwise add the residual pre-emulsion A and the initiator solution C again, controlling the total time for dropwise adding the pre-emulsion A to be 240 minutes, and ensuring that the initiator solution C is completely dropwise added 15 minutes later than the pre-emulsion A;
5) controlling the temperature in the polymerization kettle at 90 ℃, keeping the temperature for 75 minutes, cooling to 70 ℃, synchronously dropwise adding an aqueous solution containing 1.0g of tert-butyl hydroperoxide and an aqueous solution containing 0.5g of isoascorbic acid in a double manner, wherein the dropwise adding time is 25 minutes, keeping the temperature for 30 minutes, continuously cooling to 30 ℃, adding 0.06g of defoamer B-943 and 0.78g of bactericide KORDEK, adjusting the pH to 8 by using 6% NaOH aqueous solution, stirring, filtering and discharging by using a 100-mesh filter screen to obtain the acrylate emulsion.
Example 4
Weighing the following raw materials by mass: 45g of styrene (a), 35g of isooctyl acrylate (b), 0.4g of sodium vinylbenzenesulfonate (co-stabilizer), 1.0g of 2,2, 4-trimethyl-3-en-pentanol isobutyrate (d), 2.5g of acrylic acid (c), A-1741.5 g (e), CM-501.0 g (emulsifier), 0.55g of sodium bicarbonate (buffer), 0.5g of ammonium persulfate (initiator), 0.3g of tert-butyl hydroperoxide (redox initiator), 0.15g of isoascorbic acid (redox initiator) and appropriate amounts of 6% aqueous NaOH solution and deionized water.
1) Preparation of pre-emulsion a: at normal temperature and normal pressure, adding 0.75g of CM-50, 0.4g of sodium vinyl benzene sulfonate and 40g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer, fully stirring and dissolving, sequentially adding 45g of styrene, 35g of isooctyl acrylate, 0.875g of acrylic acid and 1.0g of 2,2, 4-trimethyl-3-ene-pentanol isobutyrate, and fully stirring for 20-30 minutes for later use;
2) preparing kettle bottom liquid B: adding 0.55g of sodium bicarbonate, 0.25g of CM-50 and 55g of deionized water into a polymerization kettle with a stirrer, a condenser, a constant flow pump feeding device and a constant flow dropwise adding metering device, fully stirring and dissolving, and heating until the temperature in the polymerization kettle reaches 75 ℃;
3) preparation of initiator solution C: at normal temperature and normal pressure, 0.5g of ammonium persulfate and 7g of deionized water are added into an initiator tank with a stirrer and a constant-current dropping device, and stirred until the ammonium persulfate and the deionized water are completely dissolved for later use;
4) when the temperature in the polymerization kettle reaches 75 ℃, adding 5 percent of the total amount of the pre-emulsion A and 60 percent of the total amount of the initiator solution C into the kettle, reacting for 30 minutes under a stirring state, after the seed emulsion is formed, beginning to synchronously dropwise add the rest of the pre-emulsion A and the initiator solution C into the polymerization kettle through a constant flow pump feeding device and a constant flow dropwise adding metering device, stopping dropwise adding when the pre-emulsion A is 15 percent remained, adding 1.625g of acrylic acid and 1.5g A-174 into the pre-emulsion at one time, stirring uniformly, continuing to synchronously dropwise add the rest of the pre-emulsion A and the initiator solution C again, controlling the total time of dropwise adding the pre-emulsion A at 270 minutes, and ensuring that the initiator solution C is completely dropwise added 20 minutes later than the pre-emulsion A;
5) controlling the temperature in the polymerization kettle at 60 ℃, keeping the temperature for 90 minutes, cooling to 50 ℃, synchronously dropwise adding an aqueous solution containing 0.3g of tert-butyl hydroperoxide and an aqueous solution containing 0.15g of isoascorbic acid for 30 minutes, keeping the temperature for 15 minutes, continuously cooling to 40 ℃, adding 0.04g of defoamer B-943 and 0.46g of bactericide KORDEK, adjusting the pH to 8.5 by using a 6% NaOH aqueous solution, stirring, filtering by using a 100-mesh filter screen, and discharging to obtain the acrylate emulsion.
Example 5
Weighing the following raw materials by mass: 60g of styrene (a), 50g of n-butyl acrylate (b), 0.8g of sodium vinylbenzenesulfonate (co-stabilizer), 2.0g of 2,2, 4-trimethyl-3-en-pentanol isobutyrate (d), 2.0g of acrylic acid (c), 3.0g of methacrylic acid (c), A-1713.5 g (e), CM-503.0 g (emulsifier), 0.85g of sodium bicarbonate (buffer), 0.8g of ammonium persulfate (initiator), 0.7g of tert-butyl hydroperoxide (redox initiator), 0.35g of isoascorbic acid (redox initiator) and appropriate amounts of 6% aqueous NaOH solution and deionized water.
1) Preparation of pre-emulsion a: adding 2.0g of CM-50, 0.8g of sodium vinyl benzene sulfonate and 50g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer at normal temperature and normal pressure, fully stirring and dissolving, sequentially adding 60g of styrene, 50g of n-butyl acrylate, 2.0g of acrylic acid and 2.0g of 2,2, 4-trimethyl-3-ene-pentanol isobutyrate, and fully stirring for 20-30 minutes for later use;
2) preparing kettle bottom liquid B: adding 0.85g of sodium bicarbonate, 1.0g of CM-50 and 65g of deionized water into a polymerization kettle with a stirrer, a condenser, a constant flow pump feeding device and a constant flow dropwise adding metering device, fully stirring and dissolving, and heating until the temperature in the polymerization kettle reaches 85 ℃;
3) preparation of initiator solution C: at normal temperature and normal pressure, 0.8g of ammonium persulfate and 12g of deionized water are added into an initiator tank with a stirrer and a constant-current dropping device, and stirred until the ammonium persulfate and the deionized water are completely dissolved for later use;
4) when the temperature in the polymerization kettle reaches 85 ℃, adding 8 percent of the total amount of the pre-emulsion A and 50 percent of the total amount of the initiator solution C into the kettle, reacting for 25 minutes under a stirring state, after the seed emulsion is formed, beginning to synchronously dropwise add the rest of the pre-emulsion A and the initiator solution C into the polymerization kettle through a constant flow pump feeding device and a constant flow dropwise adding metering device, stopping dropwise adding when the pre-emulsion A is 20 percent remained, adding 3.0g of methacrylic acid and 3.5g of 3.5g A-171 into the pre-emulsion at one time, stirring uniformly, continuing to synchronously dropwise add the rest of the pre-emulsion A and the initiator solution C, controlling the total time of dropwise adding the pre-emulsion A to be 300 minutes, and ensuring that the initiator solution C is completely dropwise added 15 minutes later than the pre-emulsion A;
5) controlling the temperature in the polymerization kettle at 70 ℃, keeping the temperature for 60 minutes, cooling to 55 ℃, synchronously dropwise adding an aqueous solution containing 0.7g of tert-butyl hydroperoxide and an aqueous solution containing 0.35g of isoascorbic acid in a double manner, keeping the temperature for 20 minutes, continuously cooling to 20 ℃, adding 0.05g of defoamer B-943 and 0.61g of bactericide KORDEK, adjusting the pH to 7.5 by using a 6% NaOH aqueous solution, stirring, filtering by using a 100-mesh filter screen, and discharging to obtain the acrylate emulsion.
Comparative example 1
Weighing the following raw materials by mass: 70g of styrene, 60g of n-butyl acrylate, 1.0g of sodium vinylbenzene sulfonate, 5.0g of Texanol (a common film-forming aid), 5.0g of acrylic acid, A-1711.0 g, BES-203.5 g, 1.0g of sodium bicarbonate, 1.0g of ammonium persulfate, 1.0g of tert-butyl hydroperoxide, 0.5g of isoascorbic acid and appropriate amounts of 6% NaOH aqueous solution and deionized water.
1) Preparation of pre-emulsion a: at normal temperature and normal pressure, adding 3.0g of BES-20, 1.0g of sodium vinyl benzene sulfonate and 55g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer, fully stirring for dissolving, sequentially adding 70g of styrene, 60g of n-butyl acrylate, 2.5g of acrylic acid and 5.0g of Texanol, and fully stirring for 20-30 minutes for later use;
2) preparing kettle bottom liquid B: adding 1.0g of sodium bicarbonate, 0.5g of BES-20 and 70g of deionized water into a polymerization kettle with a stirrer, a condenser, a constant flow pump feeding device and a constant flow dropwise adding metering device, fully stirring and dissolving, and heating until the temperature in the polymerization kettle reaches 90 ℃;
3) preparation of initiator solution C: adding 1.0g of ammonium persulfate and 20g of deionized water into an initiator tank with a stirrer and a constant-current dropping device at normal temperature and normal pressure, and stirring until the ammonium persulfate and the deionized water are completely dissolved for later use;
4) when the temperature in the polymerization kettle reaches 90 ℃, adding 2 percent of the total amount of the pre-emulsion A and 30 percent of the total amount of the initiator solution C into the kettle, reacting for 15 minutes, after the seed emulsion is formed, beginning to synchronously dropwise add the rest of the pre-emulsion A and the initiator solution C into the polymerization kettle through a constant flow pump feeding device and a constant flow dropwise adding metering device, stopping dropwise adding when the pre-emulsion A is 25 percent remained, adding 2.5g of acrylic acid and 1.0g A-171 into the pre-emulsion at one time, stirring uniformly, then continuing to synchronously dropwise add the rest of the pre-emulsion A and the initiator solution C, controlling the total time for dropwise adding the pre-emulsion A to be 240 minutes, and ensuring that the initiator solution C is completely dropwise added 15 minutes later than the pre-emulsion A;
5) controlling the temperature in the polymerization kettle at 90 ℃, keeping the temperature for 75 minutes, cooling to 70 ℃, synchronously dropwise adding an aqueous solution containing 1.0g of tert-butyl hydroperoxide and an aqueous solution containing 0.5g of isoascorbic acid in a double manner, keeping the temperature for 30 minutes, continuously cooling to 15-45 ℃, adding 0.06g of defoamer B-943 and 0.78g of bactericide KORDEK, adjusting the pH to 7-9 by using a 6% NaOH aqueous solution, stirring, filtering by using a 100-mesh filter screen, and discharging to obtain the acrylate emulsion.
Comparative example 2
Weighing the following raw materials by mass: 70g of styrene, 60g of n-butyl acrylate, 1.0g of sodium vinyl benzene sulfonate, 5.0g of acrylic acid, A-1711.0 g, BES-203.5 g, 1.0g of sodium bicarbonate, 1.0g of ammonium persulfate, 1.0g of tert-butyl hydroperoxide, 0.5g of isoascorbic acid and proper amounts of 6 percent NaOH aqueous solution and deionized water.
1) Preparation of pre-emulsion a: adding 3.0g of BES-20, 1.0g of sodium vinyl benzene sulfonate and 55g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer at normal temperature and normal pressure, fully stirring and dissolving, sequentially adding 70g of styrene, 60g of n-butyl acrylate and 2.5g of acrylic acid, and fully stirring for 20-30 minutes for later use;
2) preparing kettle bottom liquid B: adding 1.0g of sodium bicarbonate, 0.5g of BES-20 and 70g of deionized water into a polymerization kettle with a stirrer, a condenser, a constant flow pump feeding device and a constant flow dropwise adding metering device, fully stirring and dissolving, and heating until the temperature in the polymerization kettle reaches 90 ℃;
3) preparation of initiator solution C: adding 1.0g of ammonium persulfate and 20g of deionized water into an initiator tank with a stirrer and a constant-current dropping device at normal temperature and normal pressure, and stirring until the ammonium persulfate and the deionized water are completely dissolved for later use;
4) when the temperature in the polymerization kettle reaches 90 ℃, adding 2 percent of the total amount of the pre-emulsion A and 30 percent of the total amount of the initiator solution C into the kettle, reacting for 15 minutes, after the seed emulsion is formed, beginning to synchronously dropwise add the rest of the pre-emulsion A and the initiator solution C into the polymerization kettle through a constant flow pump feeding device and a constant flow dropwise adding metering device, stopping dropwise adding when the pre-emulsion A is 25 percent remained, adding 2.5g of acrylic acid and 1.0g A-171 into the pre-emulsion at one time, stirring uniformly, then continuing to synchronously dropwise add the rest of the pre-emulsion A and the initiator solution C, controlling the total time for dropwise adding the pre-emulsion A to be 240 minutes, and ensuring that the initiator solution C is completely dropwise added 15 minutes later than the pre-emulsion A;
5) controlling the temperature in the polymerization kettle at 90 ℃, keeping the temperature for 75 minutes, cooling to 70 ℃, synchronously dropwise adding an aqueous solution containing 1.0g of tert-butyl hydroperoxide and an aqueous solution containing 0.5g of isoascorbic acid in a double manner, keeping the temperature for 30 minutes, continuously cooling to 15-45 ℃, adding 0.06g of defoamer B-943 and 0.78g of bactericide KORDEK, adjusting the pH to 7-9 by using a 6% NaOH aqueous solution, stirring, filtering by using a 100-mesh filter screen, and discharging to obtain the acrylate emulsion.
Comparative example 3
Weighing the following raw materials by mass: 70g of styrene, 60g of n-butyl acrylate, 1.0g of sodium vinylbenzenesulfonate, 5.0g of 2,2, 4-trimethyl-3-en-pentanoylisobutyrate, 5.0g of acrylic acid, A-1711.0 g, BES-203.5 g, 1.0g of sodium bicarbonate, 1.0g of ammonium persulfate, 1.0g of tert-butyl hydroperoxide, 0.5g of isoascorbic acid and appropriate amounts of 6% aqueous NaOH solution and deionized water.
1) Preparation of pre-emulsion a: adding 3.0g of BES-20, 1.0g of sodium vinyl benzene sulfonate and 55g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer at normal temperature and normal pressure, fully stirring and dissolving, sequentially adding 70g of styrene, 60g of n-butyl acrylate, 5.0g of acrylic acid, 5.0g of dodecene and 1.0g A-171, and fully stirring for 20-30 minutes for later use;
2) preparing kettle bottom liquid B: adding 1.0g of sodium bicarbonate, 0.5g of BES-20 and 70g of deionized water into a polymerization kettle with a stirrer, a condenser, a constant flow pump feeding device and a constant flow dropwise adding metering device, fully stirring and dissolving, and heating until the temperature in the polymerization kettle reaches 90 ℃;
3) preparation of initiator solution C: adding 1.0g of ammonium persulfate and 20g of deionized water into an initiator tank with a stirrer and a constant-current dropping device at normal temperature and normal pressure, and stirring until the ammonium persulfate and the deionized water are completely dissolved for later use;
4) when the temperature in the polymerization kettle reaches 90 ℃, adding 2 percent of the total amount of the pre-emulsion A and 30 percent of the total amount of the initiator solution C into the kettle, reacting for 15 minutes, after the seed emulsion is formed, beginning to synchronously dropwise add the rest pre-emulsion A and the initiator solution C into the polymerization kettle through a constant flow pump feeding device and a constant current dropwise adding metering device, controlling the total time for dropwise adding the pre-emulsion A to be 240 minutes, and ensuring that the initiator solution C is completely dropwise added 15 minutes later than the pre-emulsion A;
5) controlling the temperature in the polymerization kettle at 90 ℃, keeping the temperature for 75 minutes, cooling to 70 ℃, synchronously dropwise adding an aqueous solution containing 1.0g of tert-butyl hydroperoxide and an aqueous solution containing 0.5g of isoascorbic acid in a double manner, keeping the temperature for 30 minutes, continuously cooling to 15-45 ℃, adding 0.06g of defoamer B-943 and 0.78g of bactericide KORDEK, adjusting the pH to 7-9 by using a 6% NaOH aqueous solution, stirring, filtering by using a 100-mesh filter screen, and discharging to obtain the acrylate emulsion.
Comparative example 4
Weighing the following raw materials by mass: 70g of styrene, 60g of n-butyl acrylate, 1.0g of sodium vinyl benzene sulfonate, 5.0g of acrylic acid, A-1711.0 g, BES-203.5 g, 1.0g of sodium bicarbonate, 1.0g of ammonium persulfate, 1.0g of tert-butyl hydroperoxide, 0.5g of isoascorbic acid and proper amounts of 6 percent NaOH aqueous solution and deionized water.
1) Preparation of pre-emulsion a: adding 3.0g of BES-20, 1.0g of sodium vinyl benzene sulfonate and 55g of deionized water into a pre-emulsification tank with a monomer metering tank and a stirrer at normal temperature and normal pressure, fully stirring and dissolving, sequentially adding 70g of styrene, 60g of n-butyl acrylate, 5.0g of acrylic acid and 1.0g A-171, and fully stirring for 20-30 minutes for later use;
2) preparing kettle bottom liquid B: adding 1.0g of sodium bicarbonate, 0.5g of BES-20 and 70g of deionized water into a polymerization kettle with a stirrer, a condenser and a constant flow pump feeding device, fully stirring and dissolving, and heating until the temperature in the polymerization kettle reaches 90 ℃;
3) preparation of initiator solution C: adding 1.0g of ammonium persulfate and 20g of deionized water into an initiator tank with a stirrer and a constant-current dropping device at normal temperature and normal pressure, and stirring until the ammonium persulfate and the deionized water are completely dissolved for later use;
4) when the temperature in the polymerization kettle reaches 90 ℃, adding 2 percent of the total amount of the pre-emulsion A and 30 percent of the total amount of the initiator solution C into the kettle, reacting for 15 minutes, after the seed emulsion is formed, beginning to synchronously dropwise add the rest pre-emulsion A and the initiator solution C into the polymerization kettle through a constant flow pump feeding device and a constant current dropwise adding metering device, controlling the total time for dropwise adding the pre-emulsion A to be 240 minutes, and ensuring that the initiator solution C is completely dropwise added 15 minutes later than the pre-emulsion A;
5) controlling the temperature in the polymerization kettle at 90 ℃, keeping the temperature for 75 minutes, cooling to 70 ℃, synchronously dropwise adding an aqueous solution containing 1.0g of tert-butyl hydroperoxide and an aqueous solution containing 0.5g of isoascorbic acid in a double manner, keeping the temperature for 30 minutes, continuously cooling to 15-45 ℃, adding 0.06g of defoamer B-943 and 0.78g of bactericide KORDEK, adjusting the pH to 7-9 by using a 6% NaOH aqueous solution, stirring, filtering by using a 100-mesh filter screen, and discharging to obtain the acrylate emulsion.
Experimental example 1:
the emulsions obtained in examples 1 to 5 and comparative examples 1 to 4 were tested under the following conditions:
the solids content, particle size and pH were measured by conventional methods.
Emulsion MFFT: namely, the lowest film forming temperature is carried out according to GB/T9267, and a QMB type lowest film forming temperature tester is adopted, and the measurement range is (-5 to +50) DEG C.
Emulsion freeze-thaw stability: 50g of the emulsion was charged into a cylindrical plastic or glass container of about 100ml, taking care not to mix in air bubbles, and sealed with a cap. Placing into a low temperature box at (-5 + -2) ° C, taking out after 18h, and standing at (23 + -2) ° C for 6 h. After repeating this procedure for 3 times, the vessel was opened, and the sample was stirred with a glass rod to observe whether or not abnormal phenomena such as hard lumps and aggregation were present in the sample. If not, the result is considered to be passed. The presence of flocs can be observed after the sample is coated on a glass plate in a uniform thin layer by means of a glass rod.
The test results are shown in table 1.
Table 1: basic properties and test results of the emulsions obtained in examples and comparative examples
Solids content/% p H value Particle size/nm MFFT/℃ Freeze thaw stability
Example 1 48.8％ 9.0 135.5 24 By passing
Example 2 48.6％ 7.0 140.2 24.5 By passing
Example 3 48.3％ 8.0 137.8 25 By passing
Example 4 48.6％ 8.5 138.3 24 By passing
Example 5 48.5％ 7.5 141.2 24.5 By passing
Comparative example 1 48.3％ 7.9 133.3 28 By passing
Comparative example 2 48.5％ 8.2 135.4 34 By passing
Comparative example 3 48.6％ 8.6 136.8 24 Do not pass through
Comparative example 4 48.2％ 7.2 134.7 33 Do not pass through
From table 1, it can be seen that the emulsions prepared by the present invention combine a lower MFFT with excellent freeze-thaw stability, whereas emulsions prepared by conventional methods do not provide a good compromise between the two.
Experimental example 2: emulsion paint preparation and Performance analysis
The emulsions obtained in examples 1 to 5 and comparative examples 1 to 4 were used for architectural interior wall coatings, and emulsion paints were prepared according to the following formulation:
table 2: paint test formulation
Name of raw materials Amount of addition Remarks for note
Water (W) 350
250HBR 5.5 Cellulose, process for producing the same, and process for producing cellulose
BD-405 1.0 Wetting agent
SN-5040 3.5 Dispersing agent
NXZ 1.0 Defoaming agent
Propylene glycol 8.0 Antifreezing agent
AMP-95 1.0 PH regulator
R996 25 Titanium white powder
DB-80 60 Calcined kaolin
Washing kaolin 75 Washing kaolin
CC700 350 Heavy calcium carbonate
Emulsion 90 Emulsion and method of making
Texanol 9 Film forming aid
NXZ 1.0 Defoaming agent
LX-150 1.0 Bactericide
Water (W) 19
Total of 1000
The detection method is carried out according to the following standards:
scrub resistance: performing according to GB/T9266-2009, adopting a JTX-II architectural coating scrub-resistant instrument, wherein a scrubbing medium is a washing powder solution with the mass fraction of 0.5%, the p H value is 9.5-11.0, a substrate is a non-asbestos fiber cement board, a 120-micrometer wire bar is used for maintaining for 6 hours, a 80-micrometer second line is used for maintaining at (23 +/-2) DEG C and at (50 +/-5)% humidity for 7 days, and two templates are used for performing parallel tests; before testing, 2ml of brushing medium is dripped into a sample plate test area in advance, and the brushing times of whether the coating is damaged to expose the substrate or not or the coating is just damaged to expose the substrate are recorded.
The VOC content of the latex paint is as follows: is executed according to GB/18582-.
Freeze-thaw stability of latex paint: the method is executed according to the method A in GB/T9268-2008.
The test results are shown in Table 3.
Table 3: coating test results
Emulsion and method of making Number of scrub resistance Freeze thaw stability VOC content g/L
Example 1 1183 By passing 1.2
Example 2 1220 By passing 1.1
Example 3 1320 By passing 1.3
Example 4 1200 By passing 1.1
Example 5 1250 By passing 1.05
Comparative example 1 880 By passing 3.2
Comparative example 2 452 By passing 1.2
Comparative example 3 760 Do not pass through 1.3
Comparative example 4 330 Do not pass through 1.1
As can be seen from Table 3, the coatings prepared using the emulsions of the present invention have both excellent scrub resistance and freeze-thaw stability. In addition, the VOC content of the resulting coating is also lower due to the lower MFFT of the emulsion.

Claims (19)

1. A method of preparing an acrylate emulsion comprising:
1) preparation of pre-emulsion a: mixing 0.5-3.5 parts by mass of emulsifier, 0.1-1.0 part by mass of co-stabilizer and 25-55 parts by mass of water, sequentially adding the component a, the component b, the component c and the component d in an amount of 25-50%, and mixing uniformly; wherein, the components a, b, c and d are respectively:
a)40 to 70 parts by mass of at least one monovinylaromatic monomer,
b)30 to 60 parts by mass of at least one alkyl (meth) acrylate,
c)0.5 to 5 parts by mass of at least one alpha, beta-monoethylenically unsaturated C 3 -C 6 A monocarboxylic or dicarboxylic acid, and
d)0.5-5.0 parts by mass of a reactive film-forming aid;
2) preparing kettle bottom liquid B: adding the rest of emulsifier, 0.1-1.0 mass part of buffering agent and 40-70 mass parts of water, mixing uniformly, and heating to 50-90 ℃;
3) preparation of initiator solution C: mixing 0.2-1.0 mass part of initiator with 3.5-20 mass parts of water uniformly;
4) adding 1-10% of pre-emulsion A and 10-60% of initiator solution C into the kettle bottom solution B at 50-90 ℃, reacting for 10-30min under a stirring state, starting to synchronously dropwise add the rest pre-emulsion A and the initiator solution C after the seed emulsion is formed, stopping dropwise adding when the pre-emulsion A is 10-25% remained, adding the component e and the rest component C at one time, and continuously and synchronously dropwise adding the rest pre-emulsion A and the initiator solution C after uniform stirring; the component e is 1.0 to 5.0 parts by mass of a monomer having a hydrolyzable Si-organic bond,
wherein the hydrolyzable Si-organic bond-bearing monomer of component e is selected from one or more of methacryloxypropyltrimethoxysilane, methacryloxypropyltriethoxysilane, methacryloxypropyltripropoxysilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane and vinyltriisopropoxysilane;
5) dripping 0.15-1.5 parts by mass of redox initiator into the system in the step 4) at 50-70 ℃, optionally adding defoaming agent and bactericide, adjusting the pH to 7.0-9.0 by using pH regulator, and filtering to obtain filtrate;
wherein, the reactive film-forming assistant of the component d) has the following structural formula:
Figure FDA0003723493320000021
wherein R is 1 、R 2 Independently selected from the group consisting of methyl, ethyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, sec-pentyl, isohexyl, sec-hexyl, isoheptyl, sec-heptyl, isooctyl, sec-octyl, isononyl, sec-nonyl, isodecyl, vinyl, allyl, isopropenyl, isobutenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl; phenyl, tolyl, xylyl, cumyl; one of cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl and methylcyclohexyl.
2. The production method according to claim 1, wherein component a) is 45 to 60 parts by mass.
3. The production method according to claim 1, wherein component b) is 35 to 50 parts by mass.
4. The production method according to claim 1, wherein component c) is 2.5 to 5.0 parts by mass.
5. The production method according to claim 1, wherein component d) is 0.5 to 2.0 parts by mass.
6. The preparation method according to claim 1, wherein in the step 4), the total time for dropping the pre-emulsion A is controlled to be 180-300 minutes, and the initiator solution C is ensured to be dropped 5-20 minutes later than the pre-emulsion A, and then the temperature is maintained at 60-90 ℃ for 15-90 minutes.
7. The production method according to claim 1, wherein the component e is 1.5 to 3.5 parts by mass.
8. The preparation method according to claim 1, wherein the completion time of dropping the redox initiator in the step 5) is 15-30 minutes, and then the temperature is maintained for 15-30 minutes and is reduced to 15-45 ℃.
9. The production method according to claim 1, wherein the reactive film-forming assistant is 2,2, 4-trimethyl-3-en-pentanol isobutyrate and/or 2,2, 4-triethyl-3-en-pentanol isobutyrate.
10. The production method according to any one of claims 1 to 9,
the alpha, beta-monoethylenically unsaturated C of the component C 3 -C 6 The monocarboxylic or dicarboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, itaconic acid, allylacetic acid, crotonic acid, vinylacetic acid, fumaric acid, maleic acid, 2-methylmaleic acid, and any combination thereof; and/or
The monovinyl aromatic monomer of the component a is styrene, 2-methylstyrene, 4-methylstyrene, 2-n-butylstyrene, 4-n-butylstyrene and/or 4-n-decylstyrene and any combination thereof; and/or
The alkyl (meth) acrylate of component b is selected from the group consisting of n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, isooctyl acrylate and any combination thereof.
11. The production method according to any one of claims 1 to 9,
the emulsifier is fatty alcohol polyoxyethylene ether sulfate, wherein the polymerization degree of polyoxyethylene is 2-20; and/or
The co-stabilizer is at least one of sodium vinyl sulfonate, sodium vinyl benzene sulfonate and sodium 3-allyloxy-1-hydroxy-propane sulfonate; and/or
The buffer is selected from at least one of sodium carbonate, sodium bicarbonate, sodium phosphate and sodium dihydrogen phosphate; and/or
The initiator is a water-soluble initiator, and the water-soluble initiator is selected from at least one of ammonium persulfate, sodium persulfate and potassium persulfate; and/or
The oxidant in the redox initiator is selected from tert-butyl hydroperoxide and/or tert-amyl hydroperoxide; the reducing agent in the redox initiator is at least one selected from sodium bisulfite, sodium hydrosulfite and isoascorbic acid; and/or
The pH regulator is NaOH aqueous solution.
12. The method according to claim 11, wherein the oxidizing agent in the redox initiator is selected from t-butyl hydroperoxide, and the reducing agent in the redox initiator is selected from erythorbic acid.
13. The production method according to claim 12, wherein the mass ratio of the tert-butyl hydroperoxide to the erythorbic acid is 2: 1.
14. The method of claim 11, wherein the pH adjusting agent is 6% NaOH aqueous solution.
15. An acrylate emulsion obtained by the production method according to any one of claims 1 to 14.
16. Use of the acrylate emulsion according to claim 15 or the acrylate emulsion obtained by the preparation method according to any one of claims 1 to 14 for the preparation of latex paints.
17. Use of the acrylate emulsion according to claim 15 or the acrylate emulsion obtained by the preparation method according to any one of claims 1 to 14 for preparing interior wall latex paints.
18. A latex paint comprising the acrylate emulsion according to claim 15 or the acrylate emulsion obtained by the preparation method according to any one of claims 1 to 14.
19. The latex paint of claim 18 which is an interior wall latex paint.
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