CN103709315B - The pigment preparation method of high light acrylic ester emulsion - Google Patents
The pigment preparation method of high light acrylic ester emulsion Download PDFInfo
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- CN103709315B CN103709315B CN201310648236.1A CN201310648236A CN103709315B CN 103709315 B CN103709315 B CN 103709315B CN 201310648236 A CN201310648236 A CN 201310648236A CN 103709315 B CN103709315 B CN 103709315B
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Abstract
The high light acrylic ester emulsion of a kind of pigment, is characterized in that this emulsion comprises following component methyl methacrylate, butyl acrylate, vinylformic acid, diacetone-acryloamide(DAA), T-80 disodium sulfosuccinate etc.The invention also discloses the preparation method of this emulsion.Compared with prior art, the invention has the advantages that: added by diacetone-acryloamide(DAA) and T-80 disodium sulfosuccinate in emulsion system, high photosensitiveness is effectively embodied.
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 utilize acrylic ester emulsion to have advantage that fast light, sun-proof, water resistant wash away is carried out conditioned pigment and paints, 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, acrylic emulsion performance and select to determine to a great extent the over-all properties of acrylic paints.
In recent years, researcher has carried out a lot of work in letex polymerization field, but relatively less at drawing acrylic emulsion area research, 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 has disclosed following patent documentation with regard to this field:
Application number is open " painting canvas dope this acrylic emulsion and preparation method thereof " (application publication number is CN102399341A) of Chinese invention patent application of 201010278991.1, and the benzene emulsion in this application comprises polymerization single polymerization monomer, functional monomer, emulsifying agent, initiator water and the softening agent that vinylbenzene, acrylic monomer and acrylic ester monomer form.
Application number is open " Self-thickening pure acrylic latex used in art paints and preparation method thereof " (application publication number is CN102399344A) of Chinese invention patent application of 201010278986.0, and pure third latex in this application comprises Acrylic Acid Monomer or alkyl acrylate system monomer, functional cross-links agent, emulsifying agent, initiator and water.
Although above-mentioned disclosed document provides some references, the good pigment acrylic ester emulsion of light effect is scarce does not also obtain R and D.
Summary of the invention
Technical problem to be solved by this invention provides a kind of pigment high light acrylic ester emulsion for the above-mentioned state of the art.
Another technical problem to be solved by this invention provides a kind of pigment preparation method of 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: the high light acrylic ester emulsion of 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:
Described T-80 disodium sulfosuccinate is with Tween80 or Tween20 for raw material, and first is esterification under the condition of catalyzer at sodium acetate, anhydrous with maleic anhydride, and then obtains with sodium sulphite anhydrous 99.3 generation sulfonation reaction.
As preferably, 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.Optimum mole ratio is 1:1.025:1.025:1.3
A described pigment preparation method for high light acrylic ester emulsion, 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 DEG C of temperature, stir transparent, name emulsifying agent aqueous phase liquid;
4. get 1/3 of mix monomer liquid total amount, 1/3 and whole emulsifying agent aqueous phase liquid of initiator dropping liquid total amount, drop in reactor, stir, intensification limit, limit pre-emulsification 0.5 ~ 1h, in pure white shape system;
5. continue heating and rise to 75 ~ 82 DEG C, polyreaction causes, and system is rapidly heated to 90 ~ 105 DEG C, treats that material temperature no longer rises, and 82 ~ 85 DEG C of constant temperature polyreaction 0.5 ~ 1h, in half micro emulsion state;
6. balance drips the initiator dropping liquid of remaining 2/3 mix monomer liquid and remaining 2/3 respectively, material controlling temperature 82 ~ 86 DEG C reaction, dropwise reaction 3 ~ 5h;
7. system is cooled to room temperature after terminating by reaction, filters, discharging.
Compared with prior art, the invention has the advantages that: added by diacetone-acryloamide(DAA) and T-80 disodium sulfosuccinate in emulsion system, 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 while enhancing glossiness, water tolerance, solvent resistant, scrub resistances etc. significantly improve, the emulsion of preparation is used for acrylic paints, not easily crack, and drawing surface is glossy, can not come off for a long time.T-80 disodium sulfosuccinate is the New-type emulsifier of modification based on Tween-20 or Tween-80, relative to environmental protection more polyoxyethylene nonylphenol ether (OP-10) and derivative thereof, and emulsion intercalation method can be made to increase while raising emulsion glossiness, the stability particularly stored 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, the present invention is described in further detail.
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 poured into and be uniformly mixed for subsequent use in 50ml constant pressure funnel, 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.
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, about heating by electric cooker to temperature 50 C, stir transparent, speed is 300 revs/min, name emulsifying agent aqueous phase liquid c liquid.
Get 1/3 and whole emulsifying agent aqueous phase liquid c liquid of 1/3 of mix monomer a liquid total amount, initiator dropping liquid b liquid total amount, drop in 500ml glass reaction pot, start and stir, speed is 200 revs/min, and intensification limit, limit pre-emulsification 40min, in pure white shape system.Heating rises to material temperature 75 DEG C, and polyreaction causes, and system is rapidly heated to about 95 DEG C, and constant temperature 82 DEG C of polyreaction 30min after material temperature no longer rises, in half micro emulsion state.Balance drips mix monomer a liquid and initiator dropping liquid b liquid respectively, material controlling temperature 84 DEG C reaction, dropwise reaction 4h.After reaction terminates, 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 the more flat PHS-3C type PJ meter in Shanghai 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 measures; Infrared spectra adopts U.S. Perkin-Elmer company SpectrumOne type Fourier infrared spectrograph to measure, KBr compressing tablet; Size and distribution adopts Britain Malvern company AutosizeLoc-Fc-963 type laser light scattering particle size analyzer determination; The pattern of multipolymer is obtained by FEI Co. of U.S. TecnaiG20 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 emulsion is the highest, and its performance index are as following table:
As can be seen from the above table, emulsion solid content is higher, has good stability, and glossiness is high, reaches market like product performance index.Meanwhile, it is excellent that test obtains emulsion storage stability, stores and do not occur layering in six months under normal temperature.Glossiness measures the mensuration according to the GBT97541988 paint and varnish not colored paint paint film sum specular gloss of containing metal pigment.
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 represent that polyreaction is normally carried out, each monomer participates in polymerization, and extent of polymerization is higher.
Particle diameter test (PCS) of emulsion 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.
Transmission electron microscope (TEM) test of emulsion 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 size distribution is relatively homogeneous, and particle diameter is most between 60-95nm; In figure, microspherulite diameter records for particle diameter less relative to PCS, this is because copolymer microsphere is in solvent swelling state in aqueous, and the hydrophilic units maintenance extended configuration of stabilization is played at microsphere surface, 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.
Obtain the excellent high light acrylic ester emulsion of pigment of solid content about 48%, properties by seeded emulsion polymerization, adopt infrared spectra to show that each monomer participates in being polymerized to copolymer structure, and extent of polymerization is higher.With the size and 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.Have studied the microballoon pattern of polymkeric substance with TEM, can find out that polymkeric substance has regular globosity, and size distribution is relatively homogeneous, more regular, particle diameter is most between 60 ~ 95nm.
Comparative example: the disclosed technical scheme of open " Self-thickening pure acrylic latex used in art paints and preparation method thereof " (application publication number is CN102399344A) of Chinese invention patent application being 201010278986.0 according to document application number obtains following five comparative examples:
Existing glossiness can more than 52 as can be seen from the above table, the height that the emulsion glossiness obtained far below technical scheme disclosed in the present application is come.
It is raw material that T-80 disodium sulfosuccinate in the present embodiment can adopt with Tween-80, first is esterification under the condition of catalyzer at sodium acetate, anhydrous with maleic anhydride, and then obtains with sodium sulphite anhydrous 99.3 generation sulfonation reaction.Raw material and the mol ratio between maleic anhydride, sodium sulphite anhydrous 99.3 and sodium acetate, anhydrous (catalyzer) are 1:1 ~ 1.05:1 ~ 1.05:0.06 ~ 0.18, can certainly to adopt or Tween-20 is prepared by raw material, technique effect is comparatively close, but Tween-80 price is comparatively cheap, easily obtains.
Concrete point esterification and sulfonation reaction two step are as follows:
Take a certain amount of Tween-80 (or Tween-20), join in reactor, thermal dehydration under the protection of nitrogen, the maleic anhydride of metering is added again according to mol ratio n (Tween-80): n (maleic anhydride)=1:1, divide in 0.5 ~ 1h and add for 2 times, add the sodium acetate, anhydrous of a certain amount of mol ratio again, 90 ~ 105 DEG C 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 DEG C of constant temperature 3 ~ 4h, obtain light yellow clear shape liquid, be i.e. the emulsifying agent of required synthesis.Specifically can with reference to " Guangdong chemical industry " the 1st phase in 2010, the 37th volume total 201st phase, " Synthesis and applications of anion-nonionic rosin emulsifying agent " that Zhang Jianyu etc. show.
Claims (4)
1. a pigment preparation method for high light acrylic ester emulsion, is characterized in that this emulsion comprises following component and weight proportion thereof:
This preparation method comprises 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 portions of de-ionized water, mix to dissolving and obtain initiator dropping liquid;
3. fatty alcohol-polyoxyethylene ether sulfosuccinic acid monoesters disodium emulsifying agent, fatty alcohol-polyoxyethylene ether emulsifying agent, T-80 disodium sulfosuccinate and remaining deionized water are mixed, be heated to 50 ~ 55 DEG C of temperature, stir transparent, name emulsifying agent aqueous phase liquid;
4. get 1/3 of monomer liquid total amount, 1/3 and whole emulsifying agent aqueous phase liquid of initiator dropping liquid total amount, drop in reactor, stir, intensification limit, limit pre-emulsification 0.5 ~ 1h, in pure white shape system;
5. continue heating and rise to 75 ~ 82 DEG C, polyreaction causes, and system is rapidly heated to 90 ~ 105 DEG C, treats that material temperature no longer rises, and 82 ~ 85 DEG C of constant temperature polyreaction 0.5 ~ 1h, in half micro emulsion state;
6. balance drips the initiator dropping liquid of remaining 2/3 monomer liquid and remaining 2/3 respectively, material controlling temperature 82 ~ 86 DEG C reaction, dropwise reaction 3 ~ 5h;
7. system is cooled to room temperature after terminating by reaction, filters, discharging.
2. preparation method according to claim 1, is characterized in that this emulsion comprises following component and weight proportion thereof:
3. preparation method according to claim 1, it is characterized in that described T-80 disodium sulfosuccinate with Tween80 or Tween20 for raw material, first is esterification under the condition of catalyzer at sodium acetate, anhydrous with maleic anhydride, and then obtains with sodium sulphite anhydrous 99.3 generation sulfonation reaction.
4. preparation method according to claim 3, 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.
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| CN104151903B (en) * | 2014-08-21 | 2016-03-23 | 宁波高新区康大美术新材料有限公司 | High gloss acrylic paints of a kind of graphene-containing and preparation method thereof |
| CN104774287B (en) * | 2015-03-12 | 2017-04-26 | 杭州海维特化工科技有限公司 | Polyacrylate emulsion microgel 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 |
| 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 |
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| 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 |
| WO2011121568A2 (en) * | 2010-04-01 | 2011-10-06 | Vinavil S.P.A. | Process for acrylic resin application for the treatment, with or without durable shape -memory, of ready-made cotton and mixed cotton garments |
| CN102399344A (en) * | 2010-09-09 | 2012-04-04 | 宁波康大美术用品有限公司 | Self-thickening pure acrylic latex used in art paints, and preparation method thereof |
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| 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 |
| WO2011121568A2 (en) * | 2010-04-01 | 2011-10-06 | Vinavil S.P.A. | Process for acrylic resin application for the treatment, with or without durable shape -memory, of ready-made cotton and mixed cotton garments |
| CN102399344A (en) * | 2010-09-09 | 2012-04-04 | 宁波康大美术用品有限公司 | Self-thickening pure acrylic latex used in art paints, and preparation method thereof |
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