CN112375188A - Preparation method of water-based acrylic acid self-defoaming microemulsion - Google Patents
Preparation method of water-based acrylic acid self-defoaming microemulsion Download PDFInfo
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- CN112375188A CN112375188A CN202011179741.2A CN202011179741A CN112375188A CN 112375188 A CN112375188 A CN 112375188A CN 202011179741 A CN202011179741 A CN 202011179741A CN 112375188 A CN112375188 A CN 112375188A
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- 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
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
Abstract
The invention provides a preparation method of a water-based acrylic acid self-defoaming microemulsion. The preparation method of the water-based acrylic acid self-defoaming microemulsion comprises the following steps: (1) preparing a seed monomer; (2) preparing a nuclear monomer; (3) preparing a seed emulsion; (4) preparing a nuclear emulsion; (5) preparing core-shell emulsion; (6) and preparing a shell edging layer. The invention adopts the production process of the microemulsion core-shell and the shell edging crosslinking layer, and has mild and stable polymerization and small particle size of the product. After the coating film is dried, the surface tension is low, the surface drying is slow, the drying is rapid, the dryness is good, the coating film is not sticky, and the adhesion to a base material is good.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a preparation method of a water-based acrylic acid self-defoaming microemulsion.
Background
The water-based coating is a trend of the coating industry, is an expression of improving environmental awareness, and is suitable for the requirement of social sustainable development. The application and development of the water-based acrylic emulsion play a great role in promoting the trend of changing oil into water in the coating industry. In the production and use process of the packaging material, the packaging material is accelerated to age and shorten the service life of the packaging material often due to external factors such as illumination, high temperature, humidity, bending, friction and the like. At present, environment-friendly waterborne polyurethane and waterborne acrylate coatings are mostly used in the market to treat the surface of a packaging material, so that the protection effect on a base material is achieved.
The water-based acrylic emulsion paint has the characteristics of low price, no toxicity, no odor, light and color retention, good weather resistance and the like, but has the defects of different degrees of redissolution, water resistance, adhesion resistance, poor adhesion to a substrate and the like, and the contradiction between redissolution and water resistance, the emulsion occasionally stops applying glue in the actual glue applying production process, the production equipment is in a semi-stop state, and at the moment, a material guide roller or a printing screen roller can show a drying and skinning phenomenon, if the water resistance of the emulsion is too good, the treatment of a drying layer on the screen roller is troublesome, the redissolution is too good, and the water resistance of a finished product can be greatly influenced.
CN101851447A discloses a microgel reaction type emulsion, which is prepared by polymerizing acrylic acid, butyl acrylate, styrene and azodiisobutyronitrile in a core-shell structure, the finished emulsion has good adhesive force, strong water resistance and quick drying, but the influence of the emulsion on redissolution is not mentioned or tested, and the production process does not relate to a core-shell production preparation method.
CN102199239A discloses a preparation method of self-crosslinking acrylic acid microemulsion with a core-shell structure, which comprises the following steps in sequence: pre-emulsifying a seed microemulsion monomer, preparing a seed microemulsion, preparing a core part microemulsion, pre-emulsifying a shell part microemulsion monomer, and preparing a self-crosslinking core-shell structure acrylic acid microemulsion. The preparation method of the acrylic acid microemulsion with the self-crosslinking core-shell structure adopts relatively common self-crosslinking monomers to replace expensive organosiloxane monomers and fluorine-containing vinyl monomers, utilizes a polymerization technology to improve the performance of the emulsion, and obtains the acrylic acid emulsion with similar and good adhesion resistance, water resistance, redissolution property and adhesion resistance, but the acrylic acid emulsion can not integrate the water resistance, the hydrophilicity, the redissolution property and the anti-retroadhesion property into a whole, and simultaneously adopts the traditional double-layer core-shell production process without relating to a shell edging crosslinking modification process.
CN103172786A discloses an acrylic emulsion with excellent performance and a method for producing the emulsion. The emulsion particles are fine, the average particle diameter is 70-100mm, the emulsion particles have a core-shell structure, different cross-linking methods are respectively adopted for the core and the shell, when the mass ratio of the core emulsion to the shell emulsion reaches a proper ratio, the emulsion has low-temperature film property, the emulsion performance is improved by using a polymerization technology, and the acrylic emulsion with similar and good anti-adhesion, waterproof, smooth and adhesive force is obtained, but the water resistance, the hydrophilicity, the redissolution and the anti-return property are not well integrated, and meanwhile, the traditional double-layer core-shell production process is adopted for both the emulsion particles, and the shell edging cross-linking modification process is not involved.
Combining with the existing patent reports, most of the existing microemulsion products pay attention to the water resistance, adhesion and drying speed, the traditional core-shell production process cannot be broken well, the problems of dry plate, net blocking and the like caused by too fast drying and too poor redissolution in the practical application of the products cannot be combined, and the technical difficulties are increasingly prominent at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of an aqueous acrylic acid self-defoaming microemulsion. The production process of the microemulsion core-shell and the shell edged crosslinking layer has mild and stable polymerization and small particle size of the product. After the coating film is dried, the surface tension is low, the surface drying is slow, the drying is rapid, the dryness is good, the coating film is not sticky, and the adhesion to a base material is good.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a preparation method of an aqueous acrylic acid self-defoaming microemulsion, comprising the following steps:
(1) preparation of seed monomers: mixing and dispersing acrylic acid alkyl ester, alkenyl carboxylic acid, an emulsifier and water to obtain a seed monomer;
(2) preparation of the core monomer: mixing and dispersing part of the seed monomers obtained in the step (1) and specific monomers to obtain nuclear monomers;
(3) preparing a seed emulsion: mixing and heating the residual seed monomer obtained in the step (1), an emulsifier, an initiator and water, adjusting the pH value, and diluting to obtain a seed emulsion;
(4) preparation of the core emulsion: mixing the seed emulsion obtained in the step (3), an initiator and the nuclear monomer obtained in the step (2) to obtain a nuclear emulsion;
(5) preparation of core-shell emulsion: mixing the core emulsion obtained in the step (4) with a shell monomer to obtain a core-shell emulsion;
(6) preparing a shell border layer: and (3) mixing the core-shell emulsion obtained in the step (5), acrylic acid alkyl ester and specific performance monomer to obtain the water-based acrylic acid self-defoaming microemulsion.
In the present invention, the aqueous acrylic self-defoaming microemulsion comprises the following operation steps: pre-emulsifying a microemulsion seed monomer, preparing and adjusting a microemulsion seed, pre-emulsifying a microemulsion core monomer, preparing a microemulsion core part, preparing an emulsion shell part, and embedding a self-crosslinking shell edging layer. The preparation method of the environment-friendly water-based acrylic acid self-defoaming microemulsion adopts common self-crosslinking monomers on the market, and the microemulsion prepared by the core-shell edging layer structure synthesis technology can keep the low cost advantage of the water-based acrylic acid microemulsion and improve the performance of the microemulsion, and meanwhile, the microemulsion polymerization process is stable, the requirement on production equipment is low, the average particle size of the product is distributed between 5nm and 10nm, the adhesion to a substrate is strong, the water release performance in the coating film drying process is good, and the good hydrophobic effect is achieved after drying, so that the good anti-reverse adhesion effect of a coating is kept, and the coating has good transparency and high gloss.
Preferably, the acrylic acid alkyl esters in step (1) and step (6) are each independently selected from any one of methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, n-octyl methacrylate, lauryl acrylate or n-propyl methacrylate or a combination of at least two thereof.
Preferably, the emulsifier in step (1) and step (3) is independently selected from any one of citric acid fatty acid glyceride, lactic acid fatty acid glyceride, isomeric fatty alcohol polyoxyethylene ether, alkyl alcohol ether succinic acid monoester disodium, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester or environmental hormone reaction type emulsifier or a combination of at least two thereof.
Preferably, the alkenyl carboxylic acid in step (1) is selected from any one of methacrylic acid, acrylic acid, maleic acid, fumaric acid or itaconic acid or a combination of at least two thereof.
Preferably, the specific monomers in step (2) and step (6) are each independently selected from any one of isobornyl methacrylate, beta-hydroxyethyl acrylate, beta-hydroxypropyl methacrylate, N-hydroxyethyl acrylamide, glycidyl methacrylate, vinyl acetate, monobutyl itaconate, adipic acid dihydrazide or diacetone acrylamide or a combination of at least two thereof.
Preferably, the initiator in the step (3) and the initiator in the step (4) are selected from any one or a combination of at least two of ammonium persulfate, potassium persulfate and sodium persulfate.
Preferably, the raw materials for preparing the seed monomer in the step (1) comprise the following components in parts by weight: 10-80 parts of acrylic alkyl ester, 0.5-8 parts of alkenyl carboxylic acid, 1-3 parts of emulsifier and 25-100 parts of water.
In the step (1), the amount of the acrylic alkyl ester to be added is 10 to 80 parts, and may be, for example, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, or the like.
In the step (1), the alkenyl carboxylic acid may be added in an amount of 0.5 to 8 parts, for example, 0.5 part, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, etc.
In step (1), the amount of the emulsifier added is 1 to 3 parts, and may be, for example, 1 part, 1.2 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, or the like.
In step (1), the amount of water added is 25 to 100 parts, and may be, for example, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, or the like.
Preferably, the mixing and dispersing in the step (1) comprises the following specific steps: placing water in an emulsification cylinder and dispersing at the speed of 300-400rpm (for example, 300rpm, 320rpm, 340rpm, 360rpm, 380rpm, 400rpm and the like), adding an emulsifier and continuing to disperse at the speed of 300-400rpm (for example, 300rpm, 320rpm, 340rpm, 360rpm, 380rpm, 400rpm and the like) for 5-15min (for example, 5min, 6min, 8min, 10min, 12min, 14min, 15min and the like), finally adding an acrylic alkyl ester and alkenyl carboxylic acid, dispersing at the speed of 600-1000rpm (for example, 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm and the like) for 10-15min (for example, 10min, 12min, 14min, 15min and the like) to obtain a seed monomer.
Preferably, the part of seed monomers in step (2) accounts for 60-90% of the total mass of the seed monomers obtained in step (1), and may be, for example, 60%, 65%, 70%, 75%, 80%, 85%, 90%, etc.
Preferably, the amount of the specific monomer added in step (2) is 0.1 to 5 parts, and may be, for example, 0.1 part, 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, or the like.
Preferably, the specific steps of mixing and dispersing in the step (2) are as follows: after mixing a part of seed monomers and specific monomers, firstly dispersing at a speed of 600-1000rpm (for example, 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm, etc.) for 10-15min (for example, 10min, 12min, 14min, 15min, etc.), stopping dispersing for 5-15min (for example, 5min, 6min, 8min, 10min, 12min, 14min, 15min, etc.), and then dispersing at a speed of 1200-1500rpm (for example, 1200rpm, 1300rpm, 1400rpm, 1500rpm, etc.) for 10-15min (for example, 10min, 12min, 14min, 15min, etc.), thereby obtaining the core monomers.
Preferably, the raw materials for preparing the seed emulsion in the step (3) comprise the following components in parts by weight: 0.03-2 parts of emulsifier, 0.1-3 parts of initiator and 6-35 parts of water.
In the step (3), the amount of the emulsifier added is 0.03 to 2 parts, and may be, for example, 0.03 part, 0.05 part, 0.08 part, 0.1 part, 0.5 part, 0.8 part, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, or the like.
In the step (3), the amount of the initiator to be added is 0.1 to 3 parts, and may be, for example, 0.1 part, 0.5 part, 0.8 part, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 3 parts, or the like.
Preferably, the specific steps of mixing in step (3) are: mixing water and emulsifier, heating to 60-95 deg.C (such as 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, 95 deg.C, etc.), adding initiator, and dripping the rest seed monomers obtained in step (1) at constant speed for 20-60min (such as 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, etc.).
Preferably, the specific steps of the dilution after the pH adjustment in the step (3) are as follows: and cooling the seed emulsion, mixing with a buffer solution, adjusting the pH, and adding water for dilution.
Preferably, the cooling temperature is 35-45 deg.C, such as 35 deg.C, 36 deg.C, 38 deg.C, 40 deg.C, 42 deg.C, 44 deg.C, 45 deg.C, etc
Preferably, the buffer is selected from an aqueous ammonia solution and/or a soda solution.
Preferably, the pH is adjusted to 6.8-7.2, which may be, for example, 6.8, 6.9, 7.0, 7.1, 7.2, and the like.
Preferably, the water is added in an amount of 25 to 100 parts, and may be, for example, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, etc.
Preferably, the initiator is added in step (4) in an amount of 0.1 to 3 parts, and may be, for example, 0.1 part, 0.5 part, 0.8 part, 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.5 parts, 3 parts, etc.
Preferably, the specific steps of mixing in step (4) are: adding an initiator into the seed emulsion obtained in the step (3), keeping the temperature at 60-90 ℃ (for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ and the like), dripping the nuclear monomer obtained in the step (2) into the seed emulsion at a constant speed within 80-150min (for example, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min and the like), and finally keeping the temperature for 20-60min (for example, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min and the like) to obtain the nuclear emulsion.
Preferably, the shell monomer in step (5) is a mixture of 0.5-5 parts (e.g., may be 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, etc.) of alkenyl carboxylic acid, 10-90 parts (e.g., may be 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, etc.) of acrylic alkyl ester.
In the present invention, in the shell monomer in the step (5), the alkenyl carboxylic acid is selected from any one of methacrylic acid, acrylic acid, maleic acid, fumaric acid or itaconic acid or a combination of at least two thereof.
In the present invention, in the shell monomer in the step (5), the acrylic acid alkyl ester is selected from any one or a combination of at least two of methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, n-octyl methacrylate, lauryl acrylate or n-propyl methacrylate.
Preferably, the specific steps of mixing in step (5) are: dripping shell monomer into the core emulsion obtained in step (4) at a constant speed within 80-150min (such as 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, etc.) at 60-90 deg.C (such as 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, etc.), and keeping the temperature for 20-60min (such as 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, 60min, etc.), to obtain the core emulsion.
Preferably, the acrylic alkyl ester is added in the step (6) in an amount of 1 to 10 parts (for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, etc.), and the specific performance monomer is added in an amount of 0.1 to 5 parts (for example, 0.1 part, 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 4.5 parts, 5 parts, etc.).
Preferably, the specific steps of mixing in step (6) are: dropping acrylic acid alkyl ester and specific performance monomer into the core-shell emulsion obtained in the step (5) at a constant speed within 20-40min (such as 20min, 25min, 30min, 35min, 40 min) at 60-90 deg.C (such as 60 deg.C, 65 deg.C, 70 deg.C, 75 deg.C, 80 deg.C, 85 deg.C, 90 deg.C, etc.) to obtain the water-based acrylic acid self-defoaming microemulsion.
Preferably, the preparation method of the aqueous acrylic acid self-defoaming microemulsion comprises the following steps:
(1) preparation of seed monomers: placing 25-100 parts of water in an emulsification cylinder and dispersing at the speed of 300-400rpm, adding 1-3 parts of emulsifier and continuing to disperse at the speed of 300-400rpm for 5-15min, finally adding 10-80 parts of acrylic alkyl ester and 0.5-8 parts of alkenyl carboxylic acid, and dispersing at the speed of 600-1000rpm for 10-15min to obtain a seed monomer;
(2) preparation of the core monomer: mixing the seed monomer accounting for 60-90% of the total mass of the seed monomer obtained in the step (1) with 0.1-5 parts of specific monomer, dispersing at the speed of 600-1500 rpm for 10-15min, stopping dispersing for 5-15min, and then dispersing at the speed of 1200-1500rpm for 10-15min to obtain a nuclear monomer;
(3) preparing a seed emulsion: mixing 6-35 parts of water and 0.03-2 parts of emulsifier, heating to 60-95 ℃, adding 0.1-3 parts of initiator, finally dripping the residual seed monomer obtained in the step (1) at a constant speed within 20-60min, cooling to 35-45 ℃, mixing with buffer solution, adjusting the pH value to 6.8-7.2, adding 25-100 parts of water for dilution, and obtaining seed emulsion;
(4) preparation of the core emulsion: adding 0.1-3 parts of initiator into the seed emulsion obtained in the step (3), keeping the temperature at 60-90 ℃, completing the uniform dripping of the nuclear monomer obtained in the step (2) within 80-150min, and finally keeping the temperature for 20-60min to obtain nuclear emulsion;
(5) preparation of core-shell emulsion: dripping a mixture of 0.5-5 parts of alkenyl carboxylic acid and 10-90 parts of acrylic acid alkyl ester into the nuclear emulsion obtained in the step (4) at a constant speed within 80-150min at 60-90 ℃, and finally preserving heat for 20-60min to obtain the nuclear emulsion;
(6) preparing a shell border layer: and (3) at the temperature of 60-90 ℃, dripping 1-10 parts of acrylic acid alkyl ester and 0.1-5 parts of specific performance monomer into the core-shell emulsion obtained in the step (5) at a constant speed within 20-40min to obtain the water-based acrylic acid self-defoaming microemulsion.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts the production process of the microemulsion core shell and the shell edge cross-linking layer, the polymerization is mild and stable, the raw materials are easy to obtain, and the production cost of the product is low;
(2) the product particles prepared by the preparation method of the water-based acrylic acid self-defoaming microemulsion have low surface tension, slow surface drying, quick drying, good dryness, no back adhesion and good adhesion to a base material after a coating film is dried;
(3) the aqueous acrylic acid self-defoaming microemulsion disclosed by the invention contains halogen, is non-toxic and non-flammable, is environment-friendly, has certain hydrophilicity, and is good in water resistance after drying.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides an aqueous acrylic acid self-defoaming microemulsion, and the preparation method of the aqueous acrylic acid self-defoaming microemulsion comprises the following steps:
(1) preparation of seed monomers: putting 50 parts of deionized water into an emulsifying cylinder and dispersing at the speed of 400rpm, adding 1.35 parts of citric acid fatty glyceride and continuing to disperse at the speed of 400rpm for 10min, finally adding 30 parts of methyl methacrylate, 20 parts of isooctyl acrylate and 5 parts of methacrylic acid, and dispersing at the speed of 800rpm for 12min to obtain a seed monomer;
(2) preparation of the core monomer: mixing seed monomers accounting for 80% of the total mass of the seed monomers obtained in the step (1) with 2 parts of isobornyl methacrylate, dispersing at the speed of 800rpm for 12min, stopping dispersing for 10min, and then dispersing at the speed of 1300rpm for 12min to obtain nuclear monomers;
(3) preparing a seed emulsion: mixing 20 parts of deionized water and 1 part of citric acid fatty glyceride, heating to 80 ℃, adding 1 part of ammonium persulfate, finally completing uniform dripping of the residual seed monomer obtained in the step (1) within 40min, cooling to 40 ℃, mixing with ammonia water, adjusting the pH to 7.0, adding 50 parts of deionized water for dilution, and obtaining a seed emulsion;
(4) preparation of the core emulsion: adding 1 part of ammonium persulfate into the seed emulsion obtained in the step (3), keeping the temperature at 80 ℃, completing the uniform dripping of the nuclear monomer obtained in the step (2) within 120min, and finally keeping the temperature for 40min to obtain nuclear emulsion;
(5) preparation of core-shell emulsion: dripping a mixture of 2 parts of methacrylic acid, 30 parts of methyl methacrylate and 20 parts of isooctyl acrylate into the nuclear emulsion obtained in the step (4) within 120min at the temperature of 80 ℃, and finally preserving heat for 40min to obtain the nuclear emulsion;
(6) preparing a shell border layer: and (3) dripping 5 parts of methyl methacrylate and 2 parts of isobornyl methacrylate into the core-shell emulsion obtained in the step (5) at a constant speed within 30min at 80 ℃ to obtain the water-based acrylic acid self-defoaming microemulsion.
Example 2
The embodiment provides an aqueous acrylic acid self-defoaming microemulsion, and the preparation method of the aqueous acrylic acid self-defoaming microemulsion comprises the following steps:
(1) preparation of seed monomers: putting 60 parts of deionized water into an emulsifying cylinder, dispersing at the speed of 300rpm, adding 1.35 parts of lactic acid fatty glyceride, continuously dispersing at the speed of 300rpm for 10min, finally adding 30 parts of methyl methacrylate, 30 parts of isooctyl acrylate and 5 parts of maleic acid, and dispersing at the speed of 800rpm for 12min to obtain a seed monomer;
(2) preparation of the core monomer: mixing the seed monomer accounting for 75% of the total mass of the seed monomer obtained in the step (1) with 2 parts of methacrylic acid-beta-hydroxyethyl ester, dispersing at the speed of 800rpm for 12min, stopping dispersing for 10min, and then dispersing at the speed of 1300rpm for 12min to obtain a nuclear monomer;
(3) preparing a seed emulsion: mixing 20 parts of deionized water and 1 part of lactic acid fatty glyceride, heating to 80 ℃, adding 1 part of ammonium persulfate, finally completing uniform dripping of the residual seed monomer obtained in the step (1) within 40min, cooling to 40 ℃, mixing with ammonia water to adjust the pH value to 7.0, and adding 50 parts of deionized water for dilution to obtain a seed emulsion;
(4) preparation of the core emulsion: adding 1 part of ammonium persulfate into the seed emulsion obtained in the step (3), keeping the temperature at 80 ℃, completing the uniform dripping of the nuclear monomer obtained in the step (2) within 120min, and finally keeping the temperature for 40min to obtain nuclear emulsion;
(5) preparation of core-shell emulsion: dripping a mixture of 2 parts of maleic acid, 30 parts of methyl methacrylate and 30 parts of isooctyl acrylate into the nuclear emulsion obtained in the step (4) at a constant speed within 120min at 80 ℃, and finally preserving heat for 40min to obtain the nuclear emulsion;
(6) preparing a shell border layer: and (3) dripping 5 parts of methyl methacrylate and 2 parts of methacrylic acid-beta-hydroxyethyl into the core-shell emulsion obtained in the step (5) at a constant speed within 30min at 80 ℃ to obtain the water-based acrylic acid self-defoaming microemulsion.
Example 3
The embodiment provides an aqueous acrylic acid self-defoaming microemulsion, and the preparation method of the aqueous acrylic acid self-defoaming microemulsion comprises the following steps:
(1) preparation of seed monomers: putting 70 parts of deionized water into an emulsifying cylinder, dispersing at the speed of 300rpm, adding 1.5 parts of lactic acid fatty glyceride, continuously dispersing at the speed of 300rpm for 10min, finally adding 30 parts of methyl acrylate, 40 parts of lauryl acrylate and 5 parts of itaconic acid, and dispersing at the speed of 800rpm for 12min to obtain a seed monomer;
(2) preparation of the core monomer: mixing the seed monomer accounting for 70% of the total mass of the seed monomer obtained in the step (1) with 2 parts of N-hydroxyethyl acrylamide, dispersing at the speed of 800rpm for 12min, stopping dispersing for 10min, and then dispersing at the speed of 1300rpm for 12min to obtain a nuclear monomer;
(3) preparing a seed emulsion: mixing 20 parts of deionized water and 1 part of lactic acid fatty glyceride, heating to 80 ℃, adding 1 part of potassium persulfate, finally completing uniform dripping of the residual seed monomer obtained in the step (1) within 40min, cooling to 40 ℃, mixing with ammonia water, adjusting the pH value to 7.0, adding 50 parts of deionized water for dilution, and obtaining a seed emulsion;
(4) preparation of the core emulsion: adding 1 part of ammonium persulfate into the seed emulsion obtained in the step (3), keeping the temperature at 80 ℃, completing the uniform dripping of the nuclear monomer obtained in the step (2) within 120min, and finally keeping the temperature for 40min to obtain nuclear emulsion;
(5) preparation of core-shell emulsion: dripping a mixture of 2 parts of itaconic acid, 30 parts of methyl acrylate and 40 parts of lauryl acrylate into the nuclear emulsion obtained in the step (4) at a constant speed within 120min at 80 ℃, and finally preserving heat for 40min to obtain the nuclear emulsion;
(6) preparing a shell border layer: and (3) dripping 5 parts of methyl acrylate and 2 parts of N-hydroxyethyl acrylamide into the core-shell emulsion obtained in the step (5) at a constant speed within 30min at 80 ℃ to obtain the water-based acrylic acid self-defoaming microemulsion.
Example 4
This example provides an aqueous acrylic self-defoaming microemulsion, differing from example 1 only in that, in step (2), 50% by mass of seed monomer based on the total mass of seed monomers obtained in step (1) is mixed with 2 parts of isobornyl methacrylate.
Example 5
This example provides an aqueous acrylic self-defoaming microemulsion, differing from example 1 only in that, in step (2), a seed monomer accounting for 95% of the total mass of the seed monomers obtained in step (1) and 2 parts of isobornyl methacrylate are mixed.
Example 6
This example provides an aqueous acrylic self-defoaming microemulsion, which differs from example 1 only in that step (2) is: mixing the seed monomer accounting for 80% of the total mass of the seed monomer obtained in the step (1) with 2 parts of isobornyl methacrylate, and dispersing at the speed of 800rpm for 20min to obtain the core monomer.
Example 7
This example provides an aqueous acrylic self-defoaming microemulsion, which differs from example 1 only in that step (2) is: and (2) mixing the seed monomer accounting for 80% of the total mass of the seed monomer obtained in the step (1) with 2 parts of isobornyl methacrylate, and dispersing at 1300rpm for 20min to obtain the core monomer.
Example 8
This example provides an aqueous acrylic self-defoaming microemulsion, which differs from example 1 only in that in step (3), it is mixed with aqueous ammonia and adjusted to pH 6.0.
Example 9
This example provides an aqueous acrylic self-defoaming microemulsion, which differs from example 1 only in that in step (3), it is mixed with aqueous ammonia and adjusted to pH 8.0.
Example 10
This example provides an aqueous acrylic self-defoaming microemulsion, which differs from example 1 only in that, in step (3), 120 parts of deionized water is added to dilute the microemulsion to obtain a seed emulsion.
Example 11
This example provides an aqueous acrylic self-defoaming microemulsion, which differs from example 1 only in that 20 parts of deionized water are added to dilute in step (3) to obtain a seed emulsion.
Example 12
This example provides an aqueous acrylic self-defoaming microemulsion, which is different from example 1 only in that in step (3), the residual seed monomer obtained in step (1) is not dropped at a constant speed, but directly poured in.
Example 13
This example provides an aqueous acrylic self-defoaming microemulsion, which differs from example 1 only in that in step (4), the core monomer obtained in step (2) is not dropped at a constant speed, but the core monomer obtained in step (2) is poured directly.
Example 14
This example provides an aqueous acrylic self-defoaming microemulsion, which differs from example 1 only in that in step (5), the core emulsion obtained in step (4) is not dropped at a constant speed, but the core emulsion obtained in step (4) is poured directly.
Example 15
This example provides an aqueous acrylic self-defoaming microemulsion, differing from example 1 only in that no more methacrylic acid was added in step (5) and the amount of methyl methacrylate added was increased to 32 parts.
Comparative example 1
The comparative example provides a water-based acrylic acid self-defoaming microemulsion, and the preparation method of the water-based acrylic acid self-defoaming microemulsion comprises the following steps:
(1) preparation of seed monomers: putting 50 parts of deionized water into an emulsifying cylinder and dispersing at the speed of 400rpm, adding 1.35 parts of citric acid fatty glyceride and continuing to disperse at the speed of 400rpm for 10min, finally adding 30 parts of methyl methacrylate, 20 parts of isooctyl acrylate and 5 parts of methacrylic acid, and dispersing at the speed of 800rpm for 12min to obtain a seed monomer;
(2) preparation of the core monomer: mixing seed monomers accounting for 80% of the total mass of the seed monomers obtained in the step (1) with 2 parts of isobornyl methacrylate, dispersing at the speed of 800rpm for 12min, stopping dispersing for 10min, and then dispersing at the speed of 1300rpm for 12min to obtain nuclear monomers;
(3) preparing a seed emulsion: mixing 20 parts of deionized water and 1 part of citric acid fatty glyceride, heating to 80 ℃, adding 1 part of ammonium persulfate, finally completing uniform dripping of the residual seed monomer obtained in the step (1) within 40min, cooling to 40 ℃, mixing with ammonia water, adjusting the pH to 7.0, adding 50 parts of deionized water for dilution, and obtaining a seed emulsion;
(4) preparation of the core emulsion: adding 1 part of ammonium persulfate into the seed emulsion obtained in the step (3), keeping the temperature at 80 ℃, finishing dripping the nuclear monomer obtained in the step (2) at a constant speed within 120min, and finally keeping the temperature for 40min to obtain nuclear emulsion;
(5) preparation of core-shell emulsion: and (3) dripping a mixture of 2 parts of methacrylic acid, 30 parts of methyl methacrylate and 20 parts of isooctyl acrylate into the nuclear emulsion obtained in the step (4) at a constant speed within 120min at the temperature of 80 ℃, and finally preserving the temperature for 40min to obtain the water-based acrylic acid self-defoaming microemulsion.
Performance testing
The performance of the aqueous acrylic self-defoaming microemulsion provided in examples 1-15 and comparative example 1 above was tested, and the test methods and test standards are as follows:
(1) glass transition temperature: the transition temperature of amorphous polymer (including amorphous part in crystalline polymer) from glassy state to high elastic state or from the latter to the former is the lowest temperature of free movement of macromolecular chain segment of amorphous polymer, and the patent uses the theoretical calculation temperature of glass transition temperature as reference, and the design of glass transition temperature is usually represented by the formula of FOX:
wherein the mass fraction of the ith monomer is the glass transition temperature of the corresponding homopolymer of the ith monomer, and the unit is K.
(2) Viscosity: the flowing-out time of a certain amount of liquid sample from a specified caliber of an observation cup at a specified temperature is expressed by the number of the observation cup per second: wiping the viscosity cup, horizontally supporting the viscosity cup, plugging a nozzle leaking hole by a finger, pouring a sample with the temperature adjusted to 30 +/-1 ℃ into the viscosity cup until the sample is flush with the edge of the cup, scraping bubbles by a glass rod, and testing the flowing-out time of the liquid. The test standard is referred to liquid ink viscosity test method GB-T13217.4-2008, and the used equipment is a Carne 2# cup.
(3) pH: a certain amount of liquid to be tested is transferred into a beaker, the temperature is reduced to 30 ℃ by ice water, and the pH value is tested by a well-established pH meter, which is referred to in the test Standard test method for the pH value of aqueous polymer and copolymer dispersions GB 8325-.
(4) Fineness: and (3) testing the fineness of the emulsion by using a scraper blade fineness meter, pouring a sufficient amount of sample into the deep end of the groove, and uniformly scraping the whole surface of the fineness plate to the end with zero groove depth within 1-2 s by using a scraper. The test standard refers to the determination of grinding fineness of paint varnish and printing ink GB/T6753.1-2007, and the devices are a scratch board fineness meter QXD 0-25 and QXD 0-50. As a result: the fineness is preferably 0-15 μm; fine fineness is 15-30 μm; the difference is more than 30 μm in fineness range.
(5) Leveling: the sample was uniformly spread onto the plastic film using a spatula and the coating was observed for dry flatness using a japanese OSP screw spatula. As a result: the surface of the coating is smooth; the coating surface is slightly indented; the difference is that the coating surface is deposited with obvious dents or pinholes.
(6) Attachment: dyeing a sample by using self-made color paste, uniformly spreading the sample on a plastic film material by using a sample scraping rod, air-drying, covering the film material by using a 3M adhesive tape, compacting, then uncovering, comparing the fading degree, and referring to the test standard GB _ T13217.7-2009 (liquid ink adhesion fastness test method). As a result: preferably, the film layer is not damaged, and the adhesive tape does not change color; good is 'the film layer is not bad, the adhesive tape changes color' or 'the film layer is slightly damaged, the adhesive tape does not change color'; the difference is more than one of 'serious damage of the film layer' and 'obvious color loss'.
(7) Water resistance: dyeing the sample by self-made color paste, uniformly spreading the sample on a plastic film material by a sample scraping rod, air-drying, and wiping the film layer back and forth by a wet tissue. As a result: preferably, the film layer is not damaged, and the paper does not change color; good is 'the film layer is not bad, the paper changes color' or 'the film layer is slightly damaged, the paper does not change color'; the difference is more than one of 'serious damage of the film layer' and 'obvious color loss'.
(8) Re-dissolubility: dyeing a sample by using a self-made color paste, uniformly spreading the sample on a plastic film material by using a sample scraping rod, adding 1 drop of deionized water on a coating when the self-drying rate of the sample is detected to be 85-90% by using an analytical balance under the same room temperature environment, gently kneading for 10 seconds by using fingers, and if the self-drying rate is redissolved within the kneading range, obtaining excellent redissolution; if the kneading range is not completely dissolved and the fineness is 25-35 mu m, the product is good; if the fineness of the kneading range is more than 35 μm, the kneading range is poor even if the kneading range is insoluble.
(9) Blocking resistance: dyeing a sample by using self-made color paste, uniformly spreading the sample on a plastic film material by using a sample scraping rod, air-drying for 48 hours, folding the film layer and the film layer in half, placing the film layer and the film layer at 50 ℃ under the condition that the relative humidity is 80 percent, and using 0.5Kg/cm2The film layer is vertically extruded under the pressure of (1), the temperature is kept for 10min, and the adhesion condition is observed. The test standard is referred to paint film tack-back determination GB 1762-1980, and the equipment used is a constant temperature and humidity test chamber TH-80 CH. As a result: the folded film layer is excellent in that the film layer is not easy to uncover and is noiseless; sound but no obvious change of flower and dark of the film layer is good; after uncovering the filmDelamination, discoloration, and even tearing without tearing are poor.
(10) Defoaming property: adding 45g of emulsion and 5g of deionized water into a clean 500mL mineral water bottle, fixing the bottle on a quick-hand mixer, shaking for 1min, taking off the bottle, timing, and observing the disappearance duration of foam. The used equipment is a quick-hand mixer QL-TG-Q. As a result: preferably the length of time for defoaming is less than 0.5h (including 0.5 h); the grain size is 0.5-1 h (including 1 h); the difference is greater than 1 h.
The specific test results are as follows:
TABLE 1
As can be seen from the test data in Table 1, the glass transition temperature of the aqueous acrylic acid self-defoaming microemulsion prepared by the invention is 9.1-31.7 ℃, the viscosity is 15-40s, the pH is 6.1-8.2, and the fineness is 5-42 μm, and the product particles prepared by the preparation method of the aqueous acrylic acid self-defoaming microemulsion have the advantages of low surface tension after coating film drying, slow surface drying, quick drying, good drying and refreshing property, no back adhesion and good substrate adhesion.
As can be seen from the comparison between example 1 and examples 4 and 5, the amount of the seed monomer in the core monomer is too small, and when too many seed monomers are dropped into the prepared seed emulsion, the seed emulsion preferentially contacts with the large micelle, so that the size distribution of the micelle is too wide, and the prepared microemulsion has poor fineness, leveling property, adhesion, water resistance, re-solubility and defoaming property. And the seed monomers in the nuclear monomers are too many, and because the formed seed emulsion micelles are few, when the nuclear monomers are dripped, the micelles relatively grow too fast, and even side reactions can occur, the prepared microemulsion has poor fineness, water resistance and re-solubility.
It is clear from the comparison between example 1 and examples 6 and 7 that the dispersion is carried out only at a low speed, but not stopped in the middle, and the dispersion of the functional monomer is not uniform, so that the local reaction in the reaction process is too violent, and the fineness, leveling, adhesion, redissolution and defoaming property of the prepared microemulsion are poor. And the dispersion is carried out at a high speed without stopping the dispersion in the middle, and the high-speed dispersion is not beneficial to the functional monomer to enter the micelle of the pre-emulsion, so that the functional monomer is aggregated and layered in the storage standby process, and the prepared fineness, leveling property, adhesion, water resistance, re-solubility and defoaming property are poor.
As can be seen from the comparison between the embodiment 1 and the embodiments 8 and 9, the pH adjusting range is too acid, the seed micelle swells and spreads, which is not beneficial to the reaction of the nuclear emulsion, and the reaction is relatively violent under the condition of too acid, so the fineness and leveling property of the prepared microemulsion are poor; when the pH adjusting range is over alkaline, the electron cloud density of acrylic acid on carboxyl in a water phase is reduced, so that the addition reaction activity of acrylic acid monomers is influenced, and the fineness, the leveling property, the adhesion property, the water resistance and the re-solubility of the prepared microemulsion are poor.
As can be seen from the comparison between the embodiment 1 and the embodiments 10 and 11, the seed emulsion is too thin, and the collision probability between the seed micelle and the added nuclear monomer at the early stage is low, so that the molecular weight distribution of the emulsion is broadened, and the water resistance and the defoaming property of the prepared microemulsion are poor; and the seed emulsion is excessively concentrated, because the collision probability of the seed micelle and the nuclear monomer is high, the micelle preferentially reacts with the monomer with high reactivity ratio, the non-target structure of the monomer with reactivity ratio after being delayed is rapidly increased, and the fineness, the leveling property and the defoaming property of the prepared microemulsion are poor.
It can be known from the comparison between example 1 and comparative example 1 that, the shell edging layer of the last step is not carried out, the crosslinkable functional group density of the outermost layer of the emulsion molecule is extremely low, the surface tension of the emulsion molecule is influenced, the crosslinking effect of the emulsion during drying is influenced, the glass transition temperature of the prepared waterborne acrylic acid self-defoaming microemulsion is reduced, and the adhesive force and the defoaming property are poor.
The applicant states that the present invention is illustrated by the above examples to the preparation method of the aqueous acrylic self-defoaming microemulsion, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must rely on the above examples to be carried out. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The preparation method of the water-based acrylic acid self-defoaming microemulsion is characterized by comprising the following steps:
(1) preparation of seed monomers: mixing and dispersing acrylic acid alkyl ester, alkenyl carboxylic acid, an emulsifier and water to obtain a seed monomer;
(2) preparation of the core monomer: mixing and dispersing part of the seed monomers obtained in the step (1) and specific monomers to obtain nuclear monomers;
(3) preparing a seed emulsion: mixing and heating the residual seed monomer obtained in the step (1), an emulsifier, an initiator and water, adjusting the pH value, and diluting to obtain a seed emulsion;
(4) preparation of the core emulsion: mixing the seed emulsion obtained in the step (3), an initiator and the nuclear monomer obtained in the step (2) to obtain a nuclear emulsion;
(5) preparation of core-shell emulsion: mixing the core emulsion obtained in the step (4) with a shell monomer to obtain a core-shell emulsion;
(6) preparing a shell border layer: and (3) mixing the core-shell emulsion obtained in the step (5), acrylic acid alkyl ester and specific performance monomer to obtain the water-based acrylic acid self-defoaming microemulsion.
2. The method for preparing the aqueous acrylic self-defoaming microemulsion according to the claim 1, wherein the alkyl acrylates in the steps (1) and (6) are independently selected from any one or a combination of at least two of methyl acrylate, methyl methacrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, n-octyl methacrylate, isooctyl acrylate, isooctyl methacrylate, n-octyl methacrylate, lauryl acrylate or n-propyl methacrylate;
preferably, the emulsifiers in step (1) and step (3) are each independently selected from any one of or a combination of at least two of citric acid fatty acid glyceride, lactic acid fatty acid glyceride, isomeric fatty alcohol polyoxyethylene ether, alkyl alcohol ether succinic acid monoester disodium, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, or an environmental hormone-reactive emulsifier;
preferably, the alkenyl carboxylic acid in step (1) is selected from any one or a combination of at least two of methacrylic acid, acrylic acid, maleic acid, fumaric acid or itaconic acid;
preferably, the specific monomers in step (2) and step (6) are each independently selected from any one of isobornyl methacrylate, beta-hydroxyethyl acrylate, beta-hydroxypropyl methacrylate, N-hydroxyethyl acrylamide, glycidyl methacrylate, vinyl acetate, monobutyl itaconate, adipic acid dihydrazide or diacetone acrylamide or a combination of at least two thereof;
preferably, the initiator in the step (3) and the initiator in the step (4) are selected from any one or a combination of at least two of ammonium persulfate, potassium persulfate and sodium persulfate.
3. The preparation method of the aqueous acrylic self-defoaming microemulsion according to claim 1 or 2, wherein the raw materials for preparing the seed monomer in the step (1) comprise the following components in parts by weight: 10-80 parts of acrylic alkyl ester, 0.5-8 parts of alkenyl carboxylic acid, 1-3 parts of emulsifier and 25-100 parts of water;
preferably, the mixing and dispersing in the step (1) comprises the following specific steps: placing water in an emulsification cylinder and dispersing at the speed of 300-400rpm, adding an emulsifier and continuing to disperse at the speed of 300-400rpm for 5-15min, and finally adding acrylic alkyl ester and alkenyl carboxylic acid and dispersing at the speed of 600-1000rpm for 10-15min to obtain the seed monomer.
4. The method for preparing the aqueous acrylic self-defoaming microemulsion according to any one of claims 1 to 3, wherein the partial seed monomers in the step (2) account for 60 to 90 percent of the total mass of the seed monomers obtained in the step (1);
preferably, the addition amount of the specific monomer in the step (2) is 0.1-5 parts;
preferably, the specific steps of mixing and dispersing in the step (2) are as follows: after mixing part of seed monomers and specific monomers, firstly dispersing at the speed of 600-1000rpm for 10-15min, stopping dispersing for 5-15min, and then dispersing at the speed of 1200-1500rpm for 10-15min to obtain the nuclear monomers.
5. The method for preparing the aqueous acrylic self-defoaming microemulsion according to any one of claims 1 to 4, wherein the raw materials for preparing the seed emulsion in the step (3) comprise the following components in parts by weight: 0.03-2 parts of emulsifier, 0.1-3 parts of initiator and 6-35 parts of water;
preferably, the specific steps of mixing in step (3) are: mixing water and an emulsifier, heating to 60-95 ℃, adding an initiator, and finally dripping the residual seed monomer obtained in the step (1) within 20-60 min.
6. The method for preparing the aqueous acrylic acid self-defoaming microemulsion according to any one of claims 1 to 5, wherein the specific steps of dilution after pH adjustment in step (3) are as follows: cooling the seed emulsion, mixing with a buffer solution, adjusting the pH value, and adding water for dilution;
preferably, the cooling temperature is 35-45 ℃;
preferably, the buffer is selected from an aqueous ammonia solution and/or a soda solution;
preferably, the pH is adjusted to 6.8-7.2;
preferably, the water is added in an amount of 25 to 100 parts.
7. The method for preparing the aqueous acrylic self-defoaming microemulsion according to any one of claims 1 to 6, wherein the addition amount of the initiator in the step (4) is 0.1 to 3 parts;
preferably, the specific steps of mixing in step (4) are: and (3) adding an initiator into the seed emulsion obtained in the step (3), keeping the temperature at 60-90 ℃, completely dripping the nuclear monomer obtained in the step (2) within 80-150min, and finally keeping the temperature for 20-60min to obtain the nuclear emulsion.
8. The method for preparing the aqueous acrylic self-defoaming microemulsion according to any one of claims 1 to 7, wherein the shell monomer in the step (5) is a mixture of 0.5 to 5 parts of alkenyl carboxylic acid, 10 to 90 parts of alkyl acrylate;
preferably, the specific steps of mixing in step (5) are: and (3) dripping the shell monomer into the core emulsion obtained in the step (4) at a constant speed within 80-150min at the temperature of 60-90 ℃, and finally preserving the heat for 20-60min to obtain the core emulsion.
9. The method for preparing the aqueous acrylic self-defoaming microemulsion according to any one of claims 1 to 8, wherein the addition amount of the acrylic alkyl ester in the step (6) is 1 to 10 parts, and the addition amount of the specific performance monomer is 0.1 to 5 parts;
preferably, the specific steps of mixing in step (6) are: and (3) dropping acrylic acid alkyl ester and specific performance monomers into the core-shell emulsion obtained in the step (5) at a constant speed within 20-40min at the temperature of 60-90 ℃ to obtain the water-based acrylic acid self-defoaming microemulsion.
10. The method for preparing an aqueous acrylic self-defoaming microemulsion according to any one of claims 1 to 9, characterized in that it comprises the following steps:
(1) preparation of seed monomers: placing 25-100 parts of water in an emulsification cylinder and dispersing at the speed of 300-400rpm, adding 1-3 parts of emulsifier and continuing to disperse at the speed of 300-400rpm for 5-15min, finally adding 10-80 parts of acrylic alkyl ester and 0.5-8 parts of alkenyl carboxylic acid, and dispersing at the speed of 600-1000rpm for 10-15min to obtain a seed monomer;
(2) preparation of the core monomer: mixing the seed monomer accounting for 60-90% of the total mass of the seed monomer obtained in the step (1) with 0.1-5 parts of specific monomer, dispersing at the speed of 600-1500 rpm for 10-15min, stopping dispersing for 5-15min, and then dispersing at the speed of 1200-1500rpm for 10-15min to obtain a nuclear monomer;
(3) preparing a seed emulsion: mixing 6-35 parts of water and 0.03-2 parts of emulsifier, heating to 60-95 ℃, adding 0.1-3 parts of initiator, finally dripping the residual seed monomer obtained in the step (1) at a constant speed within 20-60min, cooling to 35-45 ℃, mixing with buffer solution, adjusting the pH value to 6.8-7.2, adding 25-100 parts of water for dilution, and obtaining seed emulsion;
(4) preparation of the core emulsion: adding 0.1-3 parts of initiator into the seed emulsion obtained in the step (3), keeping the temperature at 60-90 ℃, completing the uniform dripping of the nuclear monomer obtained in the step (2) within 80-150min, and finally keeping the temperature for 20-60min to obtain nuclear emulsion;
(5) preparation of core-shell emulsion: dripping a mixture of 0.5-5 parts of alkenyl carboxylic acid and 10-90 parts of acrylic acid alkyl ester into the nuclear emulsion obtained in the step (4) at a constant speed within 80-150min at 60-90 ℃, and finally preserving heat for 20-60min to obtain the nuclear emulsion;
(6) preparing a shell border layer: and (3) at the temperature of 60-90 ℃, dripping 1-10 parts of acrylic acid alkyl ester and 0.1-5 parts of specific performance monomer into the core-shell emulsion obtained in the step (5) at a constant speed within 20-40min to obtain the water-based acrylic acid self-defoaming microemulsion.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438253A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylate micro-emulsion with high solid content, its preparation method and use |
| CN101481437A (en) * | 2009-01-23 | 2009-07-15 | 华南理工大学 | Preparation of high closeness polyacrylacid ester dispersion |
| CN101787098A (en) * | 2010-02-26 | 2010-07-28 | 华南理工大学 | Preparation method and application of acrylate heterozygotic emulsion |
| CN102199239A (en) * | 2010-03-24 | 2011-09-28 | 东莞大宝化工制品有限公司 | Preparation method for acrylic acid microemulsion with self-crosslinking core-shell structure |
| CN106832090A (en) * | 2016-12-23 | 2017-06-13 | 湖北工程学院 | Acrylic acid ester emulsion of flexible PVC water-based ink and preparation method thereof |
| CN107266626A (en) * | 2017-06-08 | 2017-10-20 | 北京化工大学 | A kind of multiple self-crosslinking core-shell type emulsion of room temperature and its preparation method and application |
| CN107353363A (en) * | 2017-06-22 | 2017-11-17 | 佛山市四喜环保材料有限公司 | A kind of high performance thin film printing emulsion, preparation method and applications |
| CN110407987A (en) * | 2019-07-08 | 2019-11-05 | 联泓(江苏)新材料研究院有限公司 | A kind of acrylic emulsion and its preparation method and application |
-
2020
- 2020-10-29 CN CN202011179741.2A patent/CN112375188B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438253A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylate micro-emulsion with high solid content, its preparation method and use |
| CN101481437A (en) * | 2009-01-23 | 2009-07-15 | 华南理工大学 | Preparation of high closeness polyacrylacid ester dispersion |
| CN101787098A (en) * | 2010-02-26 | 2010-07-28 | 华南理工大学 | Preparation method and application of acrylate heterozygotic emulsion |
| CN102199239A (en) * | 2010-03-24 | 2011-09-28 | 东莞大宝化工制品有限公司 | Preparation method for acrylic acid microemulsion with self-crosslinking core-shell structure |
| CN106832090A (en) * | 2016-12-23 | 2017-06-13 | 湖北工程学院 | Acrylic acid ester emulsion of flexible PVC water-based ink and preparation method thereof |
| CN107266626A (en) * | 2017-06-08 | 2017-10-20 | 北京化工大学 | A kind of multiple self-crosslinking core-shell type emulsion of room temperature and its preparation method and application |
| CN107353363A (en) * | 2017-06-22 | 2017-11-17 | 佛山市四喜环保材料有限公司 | A kind of high performance thin film printing emulsion, preparation method and applications |
| CN110407987A (en) * | 2019-07-08 | 2019-11-05 | 联泓(江苏)新材料研究院有限公司 | A kind of acrylic emulsion and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 王海侨等: "适于塑料薄膜印刷用的水性油墨丙烯酸树脂连接料的制备研究", 《化工新型材料》 * |
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