CN105693938A - Preparation method of imidized SMA modified cationic styrene-acrylic emulsion - Google Patents
Preparation method of imidized SMA modified cationic styrene-acrylic emulsion Download PDFInfo
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Abstract
The invention relates to a preparation method of an imidized SMA modified cationic styrene-acrylic emulsion. The product is mainly prepared by cationic emulsion polymerization of imidized SMA quaternary ammonium salt, styrene, acrylic monomer containing carboxy group, acrylic monomer containing hydroxyl group and acrylic monomer obtained by free radical polymerization. According to the prepared imidized SMA modified cationic styrene-acrylic emulsion, due to the introduction of imidized SMA functional resin, temperature resistance, alkali resistance, wear resistance, compatibility, water resistance and excellent adhesive force of a film can be effectively raised, and particle size of the emulsion reaches nanoscale (being less than or equal to 280 nm). Thus, the cationic styrene-acrylic emulsion is a nano-microemulsion, has very strong permeability, and can react with an alkaline substance. A film formed has high compactness and strong sealing performance, and alkali burnout resistance and salting-out resistance of the film can be effectively raised. The product is widely used in seal primers for interior and exterior walls, water-based paints, water-borne wood sealing primers, water-based ink, sizing agents, adhesives and the like.
Description
Technical field
The preparation method that the present invention relates to a kind of modifying cinepazid emulsion, refers more particularly to a kind of imidizate SMA modified cation styrene-acrylic emulsion。
Background technology
Styrene-acrylic emulsion is a kind of economical and practical water paint film forming matter, it is the product being jointly polymerized by styrene, acrylicacidandesters class monomer, its technique is simply with low cost, can be widely applied to the fields such as coating for internal and external wall, water color ink, binding agent and sizing agent；But the alkali resistance of this emulsion, resistance to water, closure, temperature tolerance, weatherability etc. are all not ideal enough, and thickness during styrene-acrylic emulsion high temperature, become fragile during low temperature, limit its application。
Common seal coat is typically all the modulation of anionic emulsion and forms, and current domestic widely used acrylic copolymer emulsions is as film forming matter, because methacrylic acid is as the monomer strengthening adhesive force, but there is the shortcoming that poor adhesive force, alkali resistance are weak；The particle diameter relatively much bigger (general emulsion particle diameter is 0.1～10 μm) of the anionic emulsion that the anionic and nonionic emulsifying agent used produces, surface tension is very big, generally it is difficult to penetrate in the tiny pore within ground, so the density of surface of bottom material film can only be relied on to realize the effect of back cover；Additionally the breathability of emulsion paint also becomes the factor of film defects such as the accumulation of salt in the surface soil occurring, saltout, and after water drenches, water penetration, inside paint film, dissolves soluble-salt therein, has also dissolved water soluble alkali simultaneously, is partly dissolved thing along with water translocation to surface of bottom material and CO2Reaction generates salt, and along with the continuous evaporation of moisture in the process migrated, the continuous crystallization of solute, if crystallization is easy for causing coming off of paint film between paint film and ground, if crystallization is formed for the accumulation of salt in the surface soil at coating surface and saltouts。
The seal coat that cation emulsion produces is adopted to have less surface tension, the permeability of ground is extremely strong, alkaline matter and temperature all can promote the cross-linking reaction of cation emulsion, so alkaline new metope meeting is so as to there is better film-formation result, play better sealing process, improve the alkali resistance of film and resistance to saltouing property。
Current cation emulsion seal coat is mostly cation silicone acrylic emulsion, cation acrylic emulsion system, and it is less to do seal coat report by cationic styrene-acrylic emulsion, because existing cationic styrene-acrylic emulsion exists particle diameter greatly, alkali resistance is poor, is extremely difficult to the anti-accumulation of salt in the surface soil of seal coat and performance of saltouing；Therefore, existing cationic styrene-acrylic emulsion is mostly used for paper surface sizing agent。
CN103194933A discloses a kind of cation styrene-acrylic microemulsion paper surface-sizing agent and preparation method thereof, microemulsion is formed compound emulsifying agent by fellatio, nonionic emulsifier, comonomer is formed by cationic monomer, styrene, acrylic monomer and fluorine-containing or silicon-containing monomer, introduce cross-linking agent, cause preparing nanometer micro-emulsion with water-soluble cationic initiator；This cation styrene-acrylic microemulsion can be used for the fields such as paper making additive, has good stability, and resistance to water is strong, and adhesive force is strong, solid content high。
The preparation method that CN102230301B discloses a kind of cationic styrene acrylic surface sizing agent, adopt macromolecule emulsifier a or b, add quaternizing agent, emulsion polymerization is carried out again with water soluble starter, polymerization single polymerization monomer is the mixture that forms of methacrylate of the styrene by 30～70% and 30～70%, and this mixture has extremely low foaming characteristic and fabulous water-resistance as Cypres。Wherein styrene acrylic emulsifying agent a is by styrene, methacrylate, tertiary amines methacrylate, adopts polymerisation in solution, prepared polymer to add glacial acetic acid and neutralizes, be subsequently adding deionized water and form under the existence of oil-soluble initiator；Cation aqueous polyurethane class emulsifying agent b is first carried out prepolymerization reaction by polyhydric alcohol and isocyanates under catalyst, adds tertiary amine chain extender chain extension, adds glacial acetic acid neutralization and deionized water forms。
CN101831027A discloses a kind of cation soap-free styrene-acrylate surface sizing agent and preparation method thereof, by with polyvinyl alcohol 1799 for dispersant, with Ammonium persulfate. for initiator, with styrene, methyl methacrylate, butyl acrylate, propenyl and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride are that mix monomer carries out emulsifier-free emulsion polymerization reaction and prepares cation soap-free styrene-acrylate surface sizing agent, the cation soap-free styrene-acrylate surface sizing agent of gained has with fiber in conjunction with excellent, alleviate hair and powder dropping, improve degree of sizing, improve surface strength and adapt to the features such as high speed printing。
CN101824116B disclosure of the invention cationic core-shell copolymerized styrene-acrylic surface sizing agent and preparation method thereof, with polyvinyl alcohol 1788 for dispersant, with Ammonium persulfate. for initiator, carry out core-shell emulsion polymerization reaction with styrene, methyl methacrylate, propenyl and MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride for mix monomer and prepare cationic core-shell copolymerized styrene-acrylic surface sizing agent；This Cypres has the structure of stone and soft shell, when under tension, pulling force can be transferred on emulsion particle by hydrogen bond action by fiber, when being under pressure, the stone being arranged in network of fibers will bear pressure, it is possible to increase the ring crush intensity of fluting medium, deflection and water repelling property。
Wu Wen etc. adopt semicontinuous pre-emulsification polymerization technique, with cation quaternary ammonium salt emulsifying agent J, OP-10 for composite emulsifier, with water-soluble free radical type initiator initiator system, carry out emulsion polymerization with styrene, acrylic monomers, functional monomer, prepare a kind of cationic styrene-acrylic emulsion for woodenware priming paint, solid content up to 42%。
Summary of the invention
Imidizate SMA quaternary amine is kind of a polymerizable cationic polymeric surfactant, has good reactivity with activated monomer such as styrene, acrylic monomer；Adopt sun/non-ionic polymeric, import imidizate SMA functional resin, modified cationic styrene-acrylic emulsion can be effectively improved the adhesive force of the temperature tolerance of paint film, alkali resistance, wearability, the compatibility, resistance to water and excellence, and the particle diameter of emulsion reaches nanoscale (≤280nm), therefore imidizate SMA cationic styrene-acrylic emulsion is a kind of nanometer micro-emulsion, there is very strong permeability, can react with alkaline matter, the film compactness formed is high, closure is strong, can be effectively improved the alkali burnout resistance of film and resistance to saltouing property。
In order to solve techniques as described above problem, the present invention takes techniques below scheme: the present invention relates to a kind of imidizate SMA modified cation styrene-acrylic emulsion, it consists of: imidizate SMA quaternary amine 8～20%, styrene 10～25 parts, carboxylic acrylic monomers 2～8%, the acrylic monomers 2～8% of hydroxyl, the acrylic monomers 10～30% of radical polymerization, OP-10 emulsifying agent 1～4%, cationic initiator 0.2～0.5%, deionized water 50～65 parts。
Wherein, described carboxylic acrylic monomers is the one of acrylic or methacrylic acid；The acrylic monomers of described hydroxyl is at least one of acrylic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, acrylic acid-2-hydroxy butyl ester, 2-hydroxyethyl methacry-late, Hydroxypropyl methacrylate or methacrylic acid-2-hydroxy butyl ester；The acrylic monomers of described radical polymerization is the monomer of more than at least two of methyl methacrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile, acrylamide。
Described cationic initiator is the one in azo-bis-isobutyrate hydrochloride (AIBA) and azo two isobutyl imidazoline hydrochloride (AIBI)。
The preparation method that the present invention proposes a kind of imidizate SMA modified cation styrene-acrylic emulsion, its preparation method, comprise the steps:
A, in the reaction vessel being furnished with speed-adjustable stir device, return duct, Dropping funnel and thermometer, by formula ratio add imidizate SMA quaternary amine, 25～30% mix monomer, OP-10 emulsifying agent and 60～80% deionized water, it is heated to 60 DEG C to all dissolving, carry out emulsifying under high velocity agitation, obtain pre-emulsion；
B, it is filled with N2, it is warmed up at 80 DEG C, under the stirring of certain speed, the cationic initiator aqueous solution (3% mass ratio) of dropping 20%, reacts 0.5～1h；
C, maintain the temperature at 81～83 DEG C, at the uniform velocity drip the mix monomer of upper remaining 70～75% and remaining 80% ionic initiator aqueous solution, after dripping off in 1.5～2hr, it is warmed up to 90 DEG C, insulation reaction 0.5hr, cools to 60 DEG C, adds remaining water, be cooled to 40 DEG C filter and package, obtain solid content be 40 ± 2%, particle diameter≤280nm, pH value be 4～6 the cation-modified styrene-acrylic emulsion of imidizate SMA。
The imidizate SMA modified cation styrene-acrylic emulsion that the present invention prepares, owing to importing imidizate SMA functional resin, the adhesive force of the temperature tolerance of paint film, alkali resistance, wearability, the compatibility, resistance to water and excellence can be effectively improved, and the particle diameter of emulsion reaches nanoscale (≤280nm), therefore cationic styrene-acrylic emulsion is a kind of nanometer micro-emulsion, there is very strong permeability, can react with alkaline matter, the film compactness formed is high, closure is strong, can be effectively improved the alkali burnout resistance of film and resistance to saltouing property；It is widely used in inner-outer wall seal coat, water paint, aqueous wooden ware seal coat, water color ink, sizing agent, binding agent etc.。
Detailed description of the invention
Embodiment prepares material according to the component formula of table 1。
1: three embodiment component formula (mass parts) of table
| Material name | Example 1 | Example 2 | Example 3 |
| Styrene | 12 | 12 | 12 |
| Imidizate SMA quaternary amine | 12 | 14 | 12 |
| Butyl acrylate | 5.6 | 5.2 | 6.0 |
| Methyl methacrylate | 4.0 | 3.6 | 5.0 |
| Acrylic acid | - | 2.4 | - |
| Acrylic acid-2-hydroxyl ethyl ester | 2.6 | - | - |
| Acrylic acid-2-hydroxy butyl ester | - | 2.8 | - |
| Methacrylic acid | 3.0 | - | 2.6 |
| Acrylonitrile | - | - | 2.4 |
| Emulsifier op-10 | 2.0 | 2.0 | 2.5 |
| AIBA | 0.30 | 0.3 | - |
| AIBI | - | - | 0.3 |
| Deionized water | 58.5 | 57.7 | 57.2 |
Embodiment 1:
The preparation method that the present invention proposes a kind of imidizate SMA modified cation styrene-acrylic emulsion, its preparation method, comprise the steps:
A, in the reaction vessel being furnished with speed-adjustable stir device, return duct, Dropping funnel and thermometer, add 12 parts of imidizate SMA quaternary amines, the mix monomer of 30%, 2 parts of OP-10 emulsifying agents and 70% deionized water, it is heated to 60 DEG C to all dissolving, carry out emulsifying under high velocity agitation, obtain pre-emulsion；
B, it is filled with N2, it is warmed up at 80 DEG C, under the stirring of certain speed, drips the AIBA aqueous solution (3% mass ratio) of 2 parts, react 0.5～1h；
C, maintain the temperature at 81～83 DEG C, at the uniform velocity drip the mix monomer of upper remaining 70% and remaining 8 parts of AIBA aqueous solutions, after dripping off in 1.5～2hr, it is warmed up to 90 DEG C, insulation reaction 0.5hr, cools to 60 DEG C, adds remaining water, be cooled to 40 DEG C filter and package, obtain solid content be 40.6%, particle diameter≤168nm, pH value be 5.2 cation-modified styrene-acrylic emulsion。
Embodiment 2, embodiment 3 preparation carry out with reference to the step in embodiment 1。
The key property of the imidizate SMA modified cation styrene-acrylic emulsion that the present invention is prepared, detects according to relevant national standard, and test result is as shown in table 2。
Table 2: imidizate SMA modified cation styrene-acrylic emulsion performance
The imidizate SMA modified cation styrene-acrylic emulsion that three embodiments are prepared makes film with cationic styrene-acrylic emulsion (comparative example) on the market, detect according to relevant national standard, film performance is carried out contrast test, and test result is as shown in table 3。
Table 3: sun styrene-acrylic emulsion film performance
Although the present invention has been explained in detail and has quoted as proof embodiment, but for those of ordinary skill in the art, it is clear that can various schemes, amendment and change that make as specified above, should be construed as being included within scope of the claims。
Claims (4)
1. an imidizate SMA modified cation styrene-acrylic emulsion, it is characterised in that: it consists of: imidizate SMA quaternary amine 8～20%, styrene 10～25 parts, carboxylic acrylic monomers 2～8%, the acrylic monomers 2～8% of hydroxyl, the acrylic monomers 10～30% of radical polymerization, OP-10 emulsifying agent 1～4%, cationic initiator 0.2～0.5%, deionized water 50～65 parts。
2. a kind of imidizate SMA modified cation styrene-acrylic emulsion as claimed in claim 1, it is characterised in that: described carboxylic acrylic monomers is the one of acrylic or methacrylic acid；The acrylic monomers of described hydroxyl is at least one of acrylic acid-2-hydroxyl ethyl ester, 2-hydroxypropyl acrylate, acrylic acid-2-hydroxy butyl ester, 2-hydroxyethyl methacry-late, Hydroxypropyl methacrylate or methacrylic acid-2-hydroxy butyl ester；The acrylic monomers of described radical polymerization is the monomer of more than at least two of methyl methacrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile, acrylamide。
3. a kind of imidizate SMA modified cation styrene-acrylic emulsion as claimed in claim 1, it is characterised in that: described cationic initiator is the one in azo-bis-isobutyrate hydrochloride (AIBA) and azo two isobutyl imidazoline hydrochloride (AIBI)。
4. the preparation method of a kind of imidizate SMA modified cation styrene-acrylic emulsion as described in claim 1,2,3, it is characterised in that: described preparation method, comprise the steps:
A, in the reaction vessel being furnished with speed-adjustable stir device, return duct, Dropping funnel and thermometer, by formula ratio add imidizate SMA quaternary amine, 25～30% mix monomer, OP-10 emulsifying agent and 60～80% deionized water, it is heated to 60 DEG C to all dissolving, carry out emulsifying under high velocity agitation, obtain pre-emulsion；
B, it is filled with N2, it is warmed up at 80 DEG C, under the stirring of certain speed, the cationic initiator aqueous solution (3% mass ratio) of dropping 20%, reacts 0.5～1h；
C, maintain the temperature at 81～83 DEG C, at the uniform velocity drip the mix monomer of upper remaining 70～75% and remaining 80% ionic initiator aqueous solution, after dripping off in 1.5～2hr, it is warmed up to 90 DEG C, insulation reaction 0.5hr, cools to 60 DEG C, adds remaining water, be cooled to 40 DEG C filter and package, obtain solid content be 40 ± 2%, particle diameter≤280nm, pH value be 4～6 the cation-modified styrene-acrylic emulsion of imidizate SMA。
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Cited By (3)
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| CN106634316A (en) * | 2016-12-31 | 2017-05-10 | 上海巴德富实业有限公司 | High-penetration tear-resistant enclosed type primer and preparation method thereof |
| CN110054937A (en) * | 2018-01-19 | 2019-07-26 | 上海宝银电子材料有限公司 | A kind of stretch-proof water-soluble conducting ink and preparation method thereof |
| CN111087512A (en) * | 2019-10-18 | 2020-05-01 | 江苏富琪森新材料有限公司 | Acrylic emulsion for PET film coating material and preparation method thereof |
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| CN106634316A (en) * | 2016-12-31 | 2017-05-10 | 上海巴德富实业有限公司 | High-penetration tear-resistant enclosed type primer and preparation method thereof |
| CN110054937A (en) * | 2018-01-19 | 2019-07-26 | 上海宝银电子材料有限公司 | A kind of stretch-proof water-soluble conducting ink and preparation method thereof |
| CN111087512A (en) * | 2019-10-18 | 2020-05-01 | 江苏富琪森新材料有限公司 | Acrylic emulsion for PET film coating material and preparation method thereof |
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