CN103709315A - Highlight acrylic ester emulsion for pigments and preparation method therefor - Google Patents
Highlight acrylic ester emulsion for pigments and preparation method therefor Download PDFInfo
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- CN103709315A CN103709315A CN201310648236.1A CN201310648236A CN103709315A CN 103709315 A CN103709315 A CN 103709315A CN 201310648236 A CN201310648236 A CN 201310648236A CN 103709315 A CN103709315 A CN 103709315A
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Abstract
Provided is a highlight acrylic ester emulsion for pigments. The emulsion is characterized by comprising the following ingredients: methyl methacrylate, butyl acrylate, acrylic acid, diacetone-acryloamide, dehydrated sorbitol oleate polyoxyethylene ether sulpho, disodium succinate and the like. The invention also discloses a preparation method for the emulsion. Compared with the prior art, the emulsion is advantageous in that the highlight performance is reflected effectively through addition of diacetone-acryloamide and dehydrated sorbitol oleate polyoxyethylene ether sulpho, disodium succinate in the emulsion system.
Description
Technical field
The present invention relates to a kind of pigment emulsion.The invention still further relates to the preparation method of this emulsion.
Background technology
The forties in 20th century, U.S. artist utilizes acrylic ester emulsion to have the advantage that fast light, sun-proof, water resistant wash away to carry out conditioned pigment and paint, and acrylic paints is born thus.The quality of acrylic paints quality can have a huge impact the performance of painting skill, is also one of prerequisite determining paint life-span length.Therefore, the performance of acrylic emulsion and be chosen in the over-all properties that has determined to a great extent acrylic paints.
In recent years, researcher has been carried out a lot of work in letex polymerization field, but relatively less with acrylic emulsion area research at drawing, to such an extent as to existing most polymer emulsion cannot be applied in the making of acrylic paints well.Based on this, the applicant discloses following patent documentation with regard to this field:
Application number is open this acrylic emulsion and preparation method thereof > > (application publication number is CN102399341A) for < < painting canvas dope of 201010278991.1 Chinese invention patent application, and the benzene emulsion in this application comprises polymerization single polymerization monomer, functional monomer, emulsifying agent, initiator water and the softening agent of vinylbenzene, acrylic monomer and acrylic ester monomer composition.
Application number is 201010278986.0 the open < < Self-thickening pure acrylic latex used in art paints of Chinese invention patent application and preparation method thereof > > (application publication number is CN102399344A), and pure the third latex in this application comprises that Acrylic Acid Monomer or alkyl acrylate are monomer, functional linking agent, emulsifying agent, initiator and water.
Although above-mentioned disclosed document provides some references, the good pigment of light effect lacks and does not also obtain R and D with acrylic ester emulsion.
Summary of the invention
Technical problem to be solved by this invention is to provide high light acrylic ester emulsion for a kind of pigment for the above-mentioned state of the art.
Another technical problem to be solved by this invention is to provide the preparation method of a kind of pigment with high light acrylic ester emulsion for the above-mentioned state of the art.
The present invention solves the problems of the technologies described above adopted technical scheme: high light acrylic ester emulsion for a kind of pigment, is characterized in that this emulsion comprises following component and weight proportion thereof:
As the best, this emulsion comprises following component and weight proportion thereof:
It is raw material that described T-80 disodium sulfosuccinate be take Tween80 or Tween20, first with the maleic anhydride condition that is catalyzer at sodium acetate, anhydrous under esterification, and then make with sodium sulphite anhydrous 99.3 generation sulfonation reaction.
As preferably, the mol ratio between described raw material and maleic anhydride, sodium sulphite anhydrous 99.3 and sodium acetate, anhydrous is 1:1～1.05:1～1.05:0.06～0.20.Optimum mole ratio is 1:1.025:1.025:1.3
A preparation method for high light acrylic ester emulsion for described pigment, is characterized in that comprising the steps:
1. first methyl methacrylate, butyl acrylate and vinylformic acid are mixed in advance, obtain monomer liquid;
2. by ammonium persulphate, diacetone-acryloamide(DAA) and part deionized water, mix to dissolving and obtain initiator dropping liquid;
3. fatty alcohol-polyoxyethylene ether sulfosuccinic acid monoesters disodium emulsifying agent, fatty alcohol (14) Soxylat A 25-7 (10) emulsifying agent, T-80 disodium sulfosuccinate and remaining deionized water are mixed, be heated to 50～55 ℃ of temperature, it is transparent that stirring is, name emulsifying agent water liquid;
4. get 1/3 of mix monomer liquid total amount, 1/3 and whole emulsifying agent water liquid of initiator dropping liquid total amount, drop in reactor, stirs, and intensification limit, limit pre-emulsification 0.5～1h, is pure white shape system;
5. continue heating and rise to 75～82 ℃, polyreaction causes, and system is rapidly heated to 90～105 ℃, treats that material temperature no longer rises, and 82～85 ℃ of constant temperature polyreaction 0.5～1h, are half micro emulsion state;
6. balance drips the initiator dropping liquid of remaining 2/3 mix monomer liquid and remaining 2/3,82～86 ℃ of reactions of material controlling temperature, dropwise reaction 3～5h respectively;
7. reaction is cooled to room temperature by system after finishing, and filters discharging.
Compared with prior art, the invention has the advantages that: in emulsion system, by diacetone-acryloamide(DAA) and T-80 disodium sulfosuccinate, add, high photosensitiveness is effectively embodied, diacetone-acryloamide(DAA) is a kind of novel vinyl function monomer simultaneously, belong to multi-functional group monomer, its interpolation makes emulsion sticking power when strengthening glossiness, water tolerance, resistance to solvent, scrub resistances etc. obviously improve, the emulsion of preparation is for acrylic paints, be difficult for cracking, and drawing surface is glossy, can not come off for a long time.T-80 disodium sulfosuccinate is to take the New-type emulsifier that Tween-20 or Tween-80 be basic modification, environmental protection more with respect to polyoxyethylene nonylphenol ether (OP-10) and derivative thereof, and when improving emulsion glossiness, can make the stability of emulsion increase, the stability particularly storing summer.
Accompanying drawing explanation
Fig. 1 is polymer emulsion infrared spectra (FTIR) spectrogram in embodiment 1.
Fig. 2 is polymer emulsion size distribution (PCS) spectrogram in embodiment 1.
Fig. 3 is polymer emulsion scanning electronic microscope (SEM) spectrogram (0.5um) in embodiment 1.
Fig. 4 is polymer emulsion scanning electronic microscope (SEM) spectrogram (0.2um) in embodiment 1.
Fig. 5 is polymer emulsion scanning electronic microscope (SEM) spectrogram (100nm) in embodiment 1.
Fig. 6 is polymer emulsion scanning electronic microscope (SEM) spectrogram (50nm) in embodiment 1.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
Methyl methacrylate, vinylformic acid, butyl ester vinylformic acid, ammonium persulphate, diacetone-acryloamide(DAA), fatty alcohol (14) Soxylat A 25-7 (10) and fatty alcohol-polyoxyethylene ether sulfosuccinic acid monoesters disodium are technical grade; T-80 disodium sulfosuccinate.
The preparation of emulsion:
Methyl methacrylate, butyl acrylate, vinylformic acid, mix in advance, mixed solution gradation is poured into and in 50ml constant pressure funnel, is uniformly mixed standbyly, speed is 300 revs/min, called after monomer a liquid.
Ammonium persulphate, diacetone-acryloamide(DAA), water, mixes to dissolving (diacetone-acryloamide(DAA) is more difficult entirely molten), pours in 50ml constant pressure funnel name initiator dropping liquid b liquid into.
Water, fatty alcohol-polyoxyethylene ether sulfosuccinic acid monoesters disodium emulsifying agent, fatty alcohol (14) Soxylat A 25-7 (10) emulsifying agent, T-80 disodium sulfosuccinate, heating by electric cooker is to temperature 50 C left and right, it is transparent that stirring is, and speed is 300 revs/min, name emulsifying agent water liquid c liquid.
Get 1/3 of mix monomer a liquid total amount, 1/3 and whole emulsifying agent water liquid c liquid of initiator dropping liquid b liquid total amount, drop in 500ml glass reaction pot, starts and stir, and speed is 200 revs/min, and intensification limit, limit pre-emulsification 40min, is pure white shape system.Heating rises to 75 ℃ of material temperatures, and polyreaction causes, and system is rapidly heated to 95 ℃ of left and right, and after material temperature no longer rises, 82 ℃ of polyreaction 30min of constant temperature, are half micro emulsion state.Balance drips mix monomer a liquid and initiator dropping liquid b liquid, 84 ℃ of reactions of material controlling temperature, dropwise reaction 4h respectively.After reaction finishes, system is cooled to room temperature, filters discharging.
Instrument and characterization test:
Viscosity adopts upper Nereid's sunshine NDJ-79 type rotational viscosimeter to measure; PH value adopts Shanghai more flat PHS-3C type PJ to count to measure glossiness; Density adopts Shanghai more flat JA2003 type electron density balance to test; Glossiness adopts Tianjin Yong Lida JWG-60 type vancometer to measure; Stability of emulsion adopts, flying pigeon board TDL-80-2B desk centrifuge is measured; Infrared spectra adopts the U.S. Spectrum One of Perkin-Elmer company type Fourier infrared spectrograph to measure, KBr compressing tablet; Particle diameter and the employing Britain Autosize Loc-Fc-963 of the Malvern company type laser light scattering particle size analyzer determination that distributes; The pattern of multipolymer is obtained by the Tecnai G20 of U.S. FEI Co. type transmission electron microscope observation.
Table 1 and table 2 are embodiment 1～embodiment 8, specific as follows:
Table 1
Table 2
The glossiness of embodiment 5 gained emulsions is the highest, and its performance index are as following table:
As can be seen from the above table, emulsion solid content is higher, have good stability, and glossiness is high, reaches market like product performance index.Meanwhile, it is good that test obtains emulsion storage stability, stores and within six months, do not occur layering under normal temperature.Glossiness is measured according to the GBT97541988 paint and varnish mensuration of the colored paint paint film sum specular gloss of containing metal pigment not.
The Infrared Characterization of emulsion polymer structure in embodiment 5:
In Fig. 1 2957,2874cm
-1place is CH in multipolymer
2, CH stretching vibration absorption peak, 1735cm
-1place is the stretching vibration absorption peak of C=O, and expression polyreaction is normally carried out, and each monomer participates in polymerization, and extent of polymerization is higher.
The particle diameter of emulsion test (PCS) in embodiment 5
By PCS analyser test copolymer emulsion particle size distribution, the median size D of emulsion
hfor 128nm, molecular weight distributing index PDI is only 0.083, and result as shown in Figure 2.
The transmission electron microscope of emulsion (TEM) test in embodiment 5
By tem observation, the morphological structure of copolymer emulsion particle, as shown in Fig. 3～Fig. 6, can find out that multipolymer has regular globosity, and the relative homogeneous of size distribution, and the particle diameter overwhelming majority is between 60-95nm; In figure, microspherulite diameter is less for PCS records particle diameter, this is because copolymer microsphere is in solvent swelling state in the aqueous solution, and the hydrophilic units that plays stabilization at microsphere surface keeps extended configuration, make microspherulite diameter larger, and when TEM sample preparation along with solvent evaporation of water microspheres shrink is subsided, the hydrophilic segment shrinkage crimping of extended configuration, and then particle diameter diminishes.
By seeded emulsion polymerization, obtained solid content 48% left and right, the good high light acrylic ester emulsion for pigment of properties, adopt infrared spectra to show that to copolymer structure each monomer participates in polymerization, and extent of polymerization has been higher.With particle diameter and the distribution of PCS Study Polymer Melts, the median size D of emulsion
hfor 128nm, molecular weight distributing index PDI is only 0.083, emulsion particle diameter narrow distribution.With TEM, studied the microballoon pattern of polymkeric substance, can find out that polymkeric substance has regular globosity, and the relative homogeneous of size distribution, more regular, the particle diameter overwhelming majority is between 60～95nm.
Comparative example: open < < Self-thickening pure acrylic latex used in art paints of the Chinese invention patent application that is 201010278986.0 according to document application number and preparation method thereof disclosed technical scheme of > > (application publication number is CN102399344A) makes
Following five comparative examples:
Existing glossiness does not have to surpass 52 as can be seen from the above table, the height that the emulsion glossiness obtaining far below the disclosed technical scheme of the application is come.
T-80 disodium sulfosuccinate in the present embodiment can adopt take Tween-80 as raw material, esterification under the condition that elder generation and maleic anhydride are catalyzer at sodium acetate, anhydrous, and then make with sodium sulphite anhydrous 99.3 generation sulfonation reaction.Mol ratio between raw material and maleic anhydride, sodium sulphite anhydrous 99.3 and sodium acetate, anhydrous (catalyzer) is 1:1～1.05:1～1.05:0.06～0.18, can certainly adopt or Tween-20 is prepared by raw material, technique effect is comparatively approaching, but Tween-80 price is comparatively cheap, easily obtain.
Concrete minute esterification and sulfonation reaction two steps are as follows:
Take a certain amount of Tween-80(or Tween-20), join in reactor, thermal dehydration under the protection of nitrogen, according to mol ratio n (Tween-80): n (maleic anhydride)=1:1, add the maleic anhydride of metering again, in 0.5～1h, divide and add for 2 times, the sodium acetate, anhydrous that adds again a certain amount of mol ratio, 90～105 ℃ of constant temperature 3～5h; At the mixing solutions of esterification gained, add the sodium sulphite anhydrous 99.3 of a certain amount of mol ratio, 80～95 ℃ of constant temperature 3～4h, obtain light yellow transparence liquid, i.e. required synthetic emulsifying agent.Specifically can be with reference to < < Guangdong chemical industry > > the 1st phase in 2010, total the 201st phase of the 37th volume, " preparation of anion-nonionic rosin emulsifying agent and the application " that Zhang Jianyu etc. show.
Claims (5)
1. a high light acrylic ester emulsion for pigment, is characterized in that this emulsion comprises following component and weight proportion thereof:
2. high light acrylic ester emulsion for pigment according to claim 1, is characterized in that this emulsion comprises following component and weight proportion thereof:
3. high light acrylic ester emulsion for pigment according to claim 1, it is characterized in that it is raw material that described T-80 disodium sulfosuccinate be take Tween80 or Tween20, esterification under the condition that elder generation and maleic anhydride are catalyzer at sodium acetate, anhydrous, and then make with sodium sulphite anhydrous 99.3 generation sulfonation reaction.
4. high light acrylic ester emulsion for pigment according to claim 1, is characterized in that described raw material and the mol ratio between maleic anhydride, sodium sulphite anhydrous 99.3 and sodium acetate, anhydrous are 1:1～1.05:1～1.05:0.06～0.20.
5. the preparation method of high light acrylic ester emulsion for any described pigment in claim 1～4, is characterized in that comprising the steps:
1. first methyl methacrylate, butyl acrylate and vinylformic acid are mixed in advance, obtain monomer liquid;
2. by ammonium persulphate, diacetone-acryloamide(DAA) and part deionized water, mix to dissolving and obtain initiator dropping liquid;
3. fatty alcohol-polyoxyethylene ether sulfosuccinic acid monoesters disodium emulsifying agent, fatty alcohol (14) Soxylat A 25-7 (10) emulsifying agent, T-80 disodium sulfosuccinate and remaining deionized water are mixed, be heated to 50～55 ℃ of temperature, it is transparent that stirring is, name emulsifying agent water liquid;
4. get 1/3 of mix monomer liquid total amount, 1/3 and whole emulsifying agent water liquid of initiator dropping liquid total amount, drop in reactor, stirs, and intensification limit, limit pre-emulsification 0.5～1h, is pure white shape system;
5. continue heating and rise to 75～82 ℃, polyreaction causes, and system is rapidly heated to 90～105 ℃, treats that material temperature no longer rises, and 82～85 ℃ of constant temperature polyreaction 0.5～1h, are half micro emulsion state;
6. balance drips the initiator dropping liquid of remaining 2/3 mix monomer liquid and remaining 2/3,82～86 ℃ of reactions of material controlling temperature, dropwise reaction 3～5h respectively;
7. reaction is cooled to room temperature by system after finishing, and filters discharging.
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| CN104151903A (en) * | 2014-08-21 | 2014-11-19 | 宁波高新区康大美术新材料有限公司 | Graphene-containing high-luster propylene pigment and preparation method thereof |
| CN104774287A (en) * | 2015-03-12 | 2015-07-15 | 杭州海维特化工科技有限公司 | Polyacrylate emulsion microgel and preparation method thereof |
| CN109438612A (en) * | 2018-10-17 | 2019-03-08 | 广州锋凌新材料科技有限公司 | High glaze acrylic paints lotion containing modified graphene oxide and preparation method thereof |
| CN109485781A (en) * | 2018-10-17 | 2019-03-19 | 广州锋凌新材料科技有限公司 | High glaze acrylic paints lotion containing modified graphene and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104151903A (en) * | 2014-08-21 | 2014-11-19 | 宁波高新区康大美术新材料有限公司 | Graphene-containing high-luster propylene pigment and preparation method thereof |
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| CN109438612A (en) * | 2018-10-17 | 2019-03-08 | 广州锋凌新材料科技有限公司 | High glaze acrylic paints lotion containing modified graphene oxide and preparation method thereof |
| CN109485781A (en) * | 2018-10-17 | 2019-03-19 | 广州锋凌新材料科技有限公司 | High glaze acrylic paints lotion containing modified graphene and preparation method thereof |
| CN109438612B (en) * | 2018-10-17 | 2021-03-19 | 广州锋凌新材料科技有限公司 | Emulsion containing modified graphene oxide for high-gloss propylene pigment and preparation method thereof |
| CN109485781B (en) * | 2018-10-17 | 2021-03-23 | 广州锋凌新材料科技有限公司 | Emulsion containing modified graphene and used for high-gloss propylene pigment and preparation method thereof |
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