CN104151479A - Preparation method of hyperbranched soap-free silicone acrylic emulsion - Google Patents
Preparation method of hyperbranched soap-free silicone acrylic emulsion Download PDFInfo
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- CN104151479A CN104151479A CN201410308702.6A CN201410308702A CN104151479A CN 104151479 A CN104151479 A CN 104151479A CN 201410308702 A CN201410308702 A CN 201410308702A CN 104151479 A CN104151479 A CN 104151479A
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Abstract
The invention provides a preparation method of a hyperbranched soap-free silicone acrylic emulsion, belonging to the technical field of chemical industry, and mainly used for the field of building coatings. The preparation method comprises the following step: by adopting tetramethyl tetravinyl cyclosiloxane and vinyl trimethoxy silane as organic silicon monomers, adopting methyl methacrylate, methacrylic acid and ethylene glycol mono-allyl ether as comonomers, and adopting K2S2O8-NaHSO3 as a redox initiator, performing polymerization without an emulsifying agent. The obtained silicone acrylic emulsion is small in particle size and narrow in distribution, has monodispersity, and is good in thermal stability; interior and exterior wall paints prepared by using the silicone acrylic emulsion as a film forming matter are fine and smooth in coating and good in decorative performance; the properties such as water resistance, alkali resistance, scrub resistance, freeze-thaw resistance, temperature change resistance and the like of the interior and exterior wall paints can reach or exceed the national standards; moreover, the silicone acrylic emulsion provided by the invention can be used for avoiding the environmental pollution caused by slow dissolution release of an emulsifying agent with the passage of time in a conventional silicone acrylic emulsion.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of preparation of organosilicon crylic acid latex, relate in particular to a kind of hyperbranched preparation method without soap organosilicon crylic acid latex, be mainly used in building coating field.
Background technology
Organosilicon-modified acrylate emulsion not only can make up cold short hot sticky deficiency after ACRYLIC EMULSION film forming, but also can obviously improve the performances such as weathering resistance, alkali resistance, water tolerance and the contamination resistance of paint film, the height that makes it simultaneously to possess silicone resin is weather-proof, stain resistance and acrylic resin high-decoration and be widely used.Conventionally organosilicon crylic acid latex organosilane monomer used is unsaturated organosilicon oxygen alkane, when with acrylic ester monomer copolymerization, can on main polymer chain, introduce siloxanes, when drying and forming-film, siloxanes is in the polycondensation that is hydrolyzed between polymer molecule and between polymkeric substance and base material, form cross-linked structure (Si-O-Si-), paint film adhesion and water tolerance are improved, but because polyacrylic ester and polysiloxane polarity differ greatly, activated silica alkanes or type siloxane are serious in polymerization and lay up period hydrolytic condensation tendency, system technology stability and package stability reduce, silicone content low (being conventionally less than 10%) in the organosilicon crylic acid latex multipolymer making, improve very limited to properties such as coating contamination resistances, therefore how to improve silicone content, reduce reactive silane hydrolytic crosslinking degree, obtain high uniformity organosilicon crylic acid latex and just become popular research topic.
Traditional solution is between polymerization period, to add a large amount of emulsifying agents the polymkeric substance that contains siloxanes is protected; stable with maintenance system; but emulsifying agent is trapped in resin and can causes again the performances such as gloss of film, sticking power, water tolerance, weathering resistance, scrub resistance significantly to reduce; affect usability and ornamental, the emulsifying agent in paint film also can slowly dissolve along with time lapse to discharge and cause environmental pollution simultaneously.
Summary of the invention
The object of the invention is for problems of the prior art, a kind of hyperbranched preparation method without soap organosilicon crylic acid latex is provided.
One, without the preparation of soap organosilicon crylic acid latex and paint film
1, the hyperbranched preparation without soap organosilicon crylic acid latex
The hyperbranched preparation method without soap organosilicon crylic acid latex of the present invention is that methyl methacrylate, methacrylic acid and allyl group hydroxyethyl ether are comonomer, K taking tetramethyl-four vinylcyclosiloxanes and vinyltrimethoxy silane as organosilane monomer
2s
2o
8-NaHSO
3for redox initiator, in deionized water, carry out emulsion polymerization, slaking, cooling, filter, obtain general have blue-opalescent without soap organosilicon crylic acid latex.Concrete preparation method is as follows:
Proportioning raw materials: in weight part:
15 ~ 25 parts of tetramethyl-four vinylcyclosiloxanes, 2 ~ 6 parts of vinyltrimethoxy silanes, 50 ~ 70 parts of methyl methacrylates, 5 ~ 12 parts of methacrylic acids, 5 ~ 15 parts of allyl group hydroxyethyl ethers, K
2s
2o
80.1 ~ 1 part, NaHSO
30.1 ~ 0.5 part, 80 ~ 120 parts of deionized waters.
Preparation method 1: tetramethyl-four vinylcyclosiloxanes, vinyltrimethoxy silane, methyl methacrylate, methacrylic acid, allyl group hydroxyethyl ether and partial oxidation reduction initiator are carried out to pre-emulsification by deionized water high speed dispersion and obtain pre-emulsion; Pre-emulsion and residue redox initiator are joined in reactor, adjust reactor system pH=3 ~ 6, in 80 ± 10 DEG C of polyreaction 2 ~ 10h; Slaking, cooling, adjusts pH=7.5 ± 0.5, filters, and obtains product, is designated as FE-SCE-A.
Preparation method 2: tetramethyl-four vinylcyclosiloxanes are disperseed in reactor high speed with deionized water, adjust system pH=3 ~ 4, carry out ring-opening reaction 2 ~ 3h at 80 ± 10 DEG C, obtain open loop silicon emulsion; Then open loop silicon emulsion and vinyltrimethoxy silane, methyl methacrylate, methacrylic acid alkene, propyl group hydroxyethyl ether and partial oxidation reduction initiator are carried out to pre-emulsification by deionized water high speed dispersion and obtain pre-emulsion; Pre-emulsion and residue redox initiator are joined in reactor, adjust reactor system pH=4 ~ 6, in 80 ± 10 DEG C of polyreaction 2 ~ 10h; Slaking, cooling, adjusts pH=7.5 ± 0.5, filters, and obtains product, is designated as FE-SCE-B.
In above-mentioned preparation method's pre-emulsification process, the add-on of redox initiator is 2/5 ~ 4/5 of initiator total amount.
2, the preparation of paint film
Wetting dispersing agent, defoamer, sanitas, thickening material are added to the water, and stirring and dissolving, adds Rutile type Titanium Dioxide R-930, after fully wetting, grinds, when fineness reaches below 10 m, add FE-SCE emulsion, stir evenly, filter, packaging, makes white interior wall coating, is called for short FE-SCEC.
Two, without the performance of soap organosilicon crylic acid latex and paint film
1, Infrared spectroscopy: get emulsion and be laid in watch-glass, drying and forming-film in 120 DEG C of baking ovens, takes out after constant weight, grinds, after washing, acetone extracting, oven dry, with the mixed compressing tablet grinding of KBr, by infrared spectrometer FT-IR sign (seeing Fig. 1 and Fig. 2).570 ~ 870cm in figure
-1for-Si (R)
2o-key skeleton stretches and rocking vibration absorption peak bands of a spectrum, 1174cm
-1for the vibration absorption peak of carbonyl C=O, 1406cm
-1for the symmetrical stretching vibration peak of acyloxy, 1473cm
-1for-CH
2-the characteristic peak of unsymmetrically formation vibration, 1575cm
-1for the antisymmetric stretching vibration peak of acyloxy, 1654cm
-1the stretching vibration peak of C-C, 1680-1750cm
-1for ester carbonyl group absorption band, 2895cm
-1for methylene radical stretching vibration peak, 2962cm
-1for methyl stretching vibration peak, 3466cm
-1for-OH vibration peak.At 1555 cm
-1place, without the ring body skeletal vibration peak of cyclosiloxane, illustrates the silica ring open loop in V4, at 1800 ~ 1860cm
-1without vinyl charateristic avsorption band, 3107cm
-1without the stretching vibration peak of the connected c h bond of C=C key, illustrate that in polymkeric substance, unparalleled key exists, show the full entry copolyreaction of all monomers, form silicon propylene copolymer.
2, FE-SCE emulsion thermostability: the organosilicon acrylic resin taking a morsel after drying and forming-film, carry out thermogravimetric analysis, its thermostability is shown in Fig. 2.As can be seen from Figure 2: the extension initial decomposition temperature of FE-SCE-A, FE-SCE-B is respectively 398 DEG C and 410 DEG C, extension final temperature is respectively 468 DEG C and 479 DEG C, and weightless peak is respectively 449 DEG C and 458 DEG C.Illustrate that the emulsion FE-SCE-B cross-linking density of copolymerization after first open loop and the emulsion FE-SCE-A that thermostability is carried out compared with ring opening copolymer are simultaneously good, approximately high 10 DEG C, this is that multipolymer heat resisting temperature is high because more containing siloxane bond (Si-O-).
3, particle size analysis: latex particle size is very large on the impact such as stability of emulsion and film-forming properties.Be conducive to improve pigment wetting dispersiveness, package stability, coating gloss, sticking power, water tolerance, weathering resistance and the over-all properties such as ornamental compared with small particle size.Fig. 3, Fig. 4 are the grain-size graph of two kinds of emulsions preparing of the present invention.Can find out from Fig. 3,4, FE-SCE-A median size is 158nm, and the median size of FE-SCE-B is 141nm.
4, latex Morphological Characterization: Fig. 5 is the hyperbranched transmission electron microscope TEM without soap organosilicon crylic acid latex of invention preparation, wherein a---FE-SCE-A, b---FE-SCE-B.As can be seen from Figure 5, FE-SCE-A and FE-SCE-B outward appearance are solid sphere, and interior outer density is more even, and edge line is clear, and median size 158 nm and 141nm illustrate that stability of emulsion is good.Fig. 6 is the hyperbranched without the scanning electron microscope sem after soap organosilicon crylic acid latex drying and forming-film of invention preparation.As can be seen from Figure 6, resin good film-forming property, surface uniform.
5, paint film Morphological Characterization: characterize with scanning electron microscope sem coating surface pattern.Fig. 6 be invent preparation hyperbranched be the scanning electron microscope (SEM) photograph of the latex film that forms after drying and forming-film without soap organosilicon crylic acid latex.Fig. 7 be with hyperbranched be that film forming matter is made the scanning electron microscope (SEM) photograph after white interior wall coating drying and forming-film without soap organosilicon crylic acid latex, can find out, paint film particle is little and even, average fineness is below 5um, structure is compacted, coating exquisiteness is ornamental good.
6, product performance test
6.1 FE-SCE performance test: FE-SCE are for building surface decorative painting, detect by GB/T20623-2006 " building coating emulsion " standard, FE-SCE(prepared by optimal processing parameter comprises FE-SCE-A and FE-SCE-B) indices all reaches GB, the results are shown in Table 1:
5.2 FE-SCEC performance test: FE-SCEC are composited by R-930 titanium dioxide and organosilicon crylic acid latex, there is the performances such as excellent weathering resistance, alkali resistance, scrub resistance, coating exquisiteness is smooth, for the application of inner wall of building high-decoration, coating is pressed GB/T3186 sampling, GB/T9271 making sheet, and test plate (panel) is placed under the humiture environment that GB/T9278 specifies and carries out film forming, detect by GB/T9756-2001 " resin latex dope " standard, the results are shown in Table 2:
In sum, the present invention is taking tetramethyl-four vinylcyclosiloxanes and vinyltrimethoxy silane as organosilane monomer, taking methyl methacrylate, methacrylic acid and allyl group hydroxyethyl ether as comonomer, with K
2s
2o
8-NaHSO
3for redox initiator, under emulsifier-free condition, carry out polymerization, the organosilicon crylic acid latex particle diameter obtaining is little, and narrowly distributing, is monodispersity; Emulsion Heat stability is good, below the about 5um of interior wall coating average fineness making, coating is moist, good decorative property, the performances such as water tolerance, alkali resistance, abrasion resistance, freeze-thaw resistance, temperature-change resistance meet or exceed GB, and have avoided emulsifying agent in traditional silicon acrylic emulsion can slowly dissolve along with time lapse release and cause environmental pollution.
Brief description of the drawings
Fig. 1 is the hyperbranched infrared spectrogram without soap organosilicon crylic acid latex FE-SCE-A prepared by the present invention.
Fig. 2 is the hyperbranched infrared spectrogram without soap organosilicon crylic acid latex FE-SCE-B prepared by the present invention.
Fig. 3 is the hyperbranched thermogravimetric curve without soap organosilicon crylic acid latex prepared by the present invention.
Fig. 4 is that the present invention is the hyperbranched particle size analysis figure without soap organosilicon crylic acid latex FE-SCE-A prepared by the present invention.
Fig. 5 is that the present invention is the hyperbranched particle size analysis figure without soap organosilicon crylic acid latex FE-SCE-B prepared by the present invention.
Fig. 6 is the hyperbranched transmission electron microscope TEM without soap organosilicon crylic acid latex of invention preparation.
Fig. 7 is the hyperbranched without the scanning electron microscope sem after soap organosilicon crylic acid latex drying and forming-film of invention preparation.
Fig. 8 be invent preparation hyperbranched be the scanning electron microscope sem of the paint film prepared of film forming matter without soap organosilicon crylic acid latex.
Embodiment
Below by specific embodiment, the present invention is described further without preparation and the performance of soap organosilicon crylic acid latex.
Embodiment 1, without the preparation of soap organosilicon crylic acid latex FE-SCE-A
Proportioning raw materials: in weight part: 20 parts of tetramethyl-four vinylcyclosiloxanes, 6 parts of vinyltrimethoxy silanes, 60 parts of methyl methacrylates, 10 parts of methacrylic acids, 8 parts of allyl group hydroxyethyl ethers, K
2s
2o
80.4 part, NaHSO
30.2 part, 100 parts of deionized waters.
Preparation method: add part deionized water, 0.06 part of K in the four-hole bottle that variable speed stirrer, reflux condensing tube, dropping funnel, thermometer are housed
2s
2o
8, 0.04 part of NaHSO
3, stirring and dissolving; By whole monomers and 0.24 part of K
2s
2o
8, 0.16 part of NaHSO
3obtain pre-emulsion by pre-emulsification under a small amount of deionized water high-speed stirring, be placed in dropping funnel; When system temperature in four-hole bottle rises to 80 ± 2 DEG C, slowly drip pre-emulsion, adjust system pH=5.0 ± 0.1 with dilute hydrochloric acid simultaneously, approximately use 3 ~ 4h to drip off, keep 2h, finally add remaining initiator, continue to be cooled to below 50 DEG C after slaking 2h, adjust pH=7.5 ± 0.1 with ammoniacal liquor, cross 100 mesh sieves, obtain general have blue-opalescent without soap organosilicon crylic acid latex.Property indices is in table 1.
Embodiment 2, without the preparation of soap organosilicon crylic acid latex FE-SCE-A
Proportioning raw materials: in weight part:
25 parts of tetramethyl-four vinylcyclosiloxanes, 4 parts of vinyltrimethoxy silanes, 70 parts of methyl methacrylates, 12 parts of methacrylic acids, 15 parts of allyl group hydroxyethyl ethers, K
2s
2o
81 part, NaHSO
30.5 part, 120 parts of deionized waters.
Preparation method: add part deionized water, 0.2 part of K in the four-hole bottle that variable speed stirrer, reflux condensing tube, dropping funnel, thermometer are housed
2s
2o
8, 0.1 part of NaHSO
3stirring and dissolving; By whole monomers and 0.6 part of K
2s
2o
8, 0.3 part of NaHSO
3obtain pre-emulsion by pre-emulsification under a small amount of deionized water high-speed stirring, be placed in dropping funnel; When system temperature in four-hole bottle rises to 75 ± 2 DEG C, slowly drip pre-emulsion, adjust system pH=4.0 ± 0.1 with dilute hydrochloric acid simultaneously, approximately use 3 ~ 4h to drip off, keep 2h, finally add remaining initiator, continue to be cooled to below 50 DEG C after slaking 2h, adjust pH=7.5 ± 0.1 with ammoniacal liquor, cross 100 mesh sieves, obtain general have blue-opalescent without soap organosilicon crylic acid latex.Property indices is in table 1.
Embodiment 3, without the preparation of soap organosilicon crylic acid latex FE-SCE-A
Proportioning raw materials: in weight part:
15 parts of tetramethyl-four vinylcyclosiloxanes, 2 parts of vinyltrimethoxy silanes, 50 parts of methyl methacrylates, 5 parts of methacrylic acids, 5 parts of allyl group hydroxyethyl ethers, K
2s
2o
80.1 part, NaHSO
30.1 part, 80 parts of deionized waters.
Preparation method: add part deionized water, 0.02 part of K in the four-hole bottle that variable speed stirrer, reflux condensing tube, dropping funnel, thermometer are housed
2s
2o
8, 0.02 part of NaHSO
3stirring and dissolving; By whole monomers and 0.04 part of K
2s
2o
8, 0.04 part of NaHSO
3obtain pre-emulsion by pre-emulsification under a small amount of deionized water high-speed stirring, be placed in dropping funnel; When system temperature in four-hole bottle rises to 80 ± 2 DEG C, slowly drip pre-emulsion, adjust system pH=3.5 ± 0.1 with dilute hydrochloric acid simultaneously, approximately use 3 ~ 4h to drip off, keep 2h, finally add remaining initiator, continue to be cooled to below 50 DEG C after slaking 2h, adjust pH=7.5 ± 0.1 with ammoniacal liquor, cross 100 mesh sieves, obtain general have blue-opalescent without soap organosilicon crylic acid latex.Property indices is in table 1.
Embodiment 4, without the preparation of soap organosilicon crylic acid latex FE-SCE-B
Proportioning raw materials: in weight part: 20 parts of tetramethyl-four vinylcyclosiloxanes, 6 parts of vinyltrimethoxy silanes, 60 parts of methyl methacrylates, 10 parts of methacrylic acids, 8 parts of allyl group hydroxyethyl ethers, K
2s
2o
80.4 part, NaHSO
30.2 part, 100 parts of deionized waters.
Preparation method: add a small amount of deionized water, tetramethyl-four vinylcyclosiloxanes in four-hole bottle, disperse 0.5h, regulate pH=3.5 ± 0.1 with dilute hydrochloric acid, heat up 80 ± 10 DEG C, ring-opening polymerization 3 ~ 4h, obtains open loop silicon emulsion; Then by other monomer and 0.24 part of K
2s
2o
8, 0.16 part of NaHSO
3join in four-hole bottle, high speed dispersion is carried out pre-emulsification and is obtained pre-emulsion.Pre-emulsion is slowly joined in reactor and (in reactor, added in advance residue deionized water and 0.06 part of K with dropping funnel
2s
2o
8, 0.04 part of NaHSO
3), in polymerization process, adjust reactor system pH=5.5 ± 0.1 in 80 ± 2 DEG C of polyreaction 3 ~ 5h(); Reaction finish after, add residue redox initiator carry out slaking, cooling, adjust pH=7.5 ± 0.1, filter, obtain general have blue-opalescent without soap organosilicon crylic acid latex product, be called for short FE-SCE-B.Performance index are in table 1.
Embodiment 5, without the preparation of soap organosilicon crylic acid latex FE-SCE-B
Proportioning raw materials: in weight part: 25 parts of tetramethyl-four vinylcyclosiloxanes, 4 parts of vinyltrimethoxy silanes, 70 parts of methyl methacrylates, 12 parts of methacrylic acids, 15 parts of allyl group hydroxyethyl ethers, K
2s
2o
81 part, NaHSO
30.5 part, 120 parts of deionized waters.
Preparation method: add a small amount of deionized water, tetramethyl-four vinylcyclosiloxanes to disperse 0.5h in four-hole bottle, regulate pH=4.0 ± 0.1 with dilute hydrochloric acid, heat up 80 ± 2 DEG C, ring-opening polymerization 3 ~ 4h, obtains open loop silicon emulsion; Then by other monomer and 0.6 part of K
2s
2o
8, 0.3 part of NaHSO
3join in four-hole bottle, high speed dispersion is carried out pre-emulsification and is obtained pre-emulsion.Pre-emulsion is slowly joined in reactor and (in reactor, added in advance residue deionized water and 0.2 part of K with dropping funnel
2s
2o
8, 0.1 part of NaHSO
3), in polymerization process, adjust reactor system pH=5.0 ± 0.1 in 80 ± 2 DEG C of polyreaction 3 ~ 5h(); Reaction finish after, add residue redox initiator carry out slaking, cooling, adjust pH=7.5 ± 0.1, filter, obtain general have blue-opalescent without soap organosilicon crylic acid latex product, be called for short FE-SCE-B.Property indices is in table 1.
Embodiment 6, without the preparation of soap organosilicon crylic acid latex FE-SCE-B
Proportioning raw materials: in weight part:
15 parts of tetramethyl-four vinylcyclosiloxanes, 2 parts of vinyltrimethoxy silanes, 50 parts of methyl methacrylates, 5 parts of methacrylic acids, 5 parts of allyl group hydroxyethyl ethers, K
2s
2o
80.1 part, NaHSO
30.1 part, 80 parts of deionized waters.
Preparation method: add a small amount of deionized water, tetramethyl-four vinylcyclosiloxanes in four-hole bottle, disperse 0.5h, regulate pH=3.5 ± 0.1 with dilute hydrochloric acid, heat up 75 ± 2 DEG C, ring-opening polymerization 3 ~ 4h, obtains open loop silicon emulsion; Then by other monomer and 0.04 part of K
2s
2o
8, 0.04 part of NaHSO
3join in four-hole bottle, high speed dispersion is carried out pre-emulsification and is obtained pre-emulsion.Pre-emulsion is slowly joined in reactor and (in reactor, added in advance residue deionized water and 0.02 part of K with dropping funnel
2s
2o
8, 0.02 part of NaHSO
3), in polymerization process, adjust reactor system pH=5.5 ± 0.1 in 80 ± 2 DEG C of polyreaction 3 ~ 5h(); Reaction finish after, add residue redox initiator carry out slaking, cooling, adjust pH=7.5 ± 0.1, filter, obtain general have blue-opalescent without soap organosilicon crylic acid latex product, be called for short FE-SCE-B.Performance index are in table 1.
Claims (4)
1. the hyperbranched preparation method without soap organosilicon crylic acid latex is that methyl methacrylate, methacrylic acid and allyl group hydroxyethyl ether are comonomer, K taking tetramethyl-four vinylcyclosiloxanes and vinyltrimethoxy silane as organosilane monomer
2s
2o
8-NaHSO
3for redox initiator, in deionized water, carry out emulsion polymerization, slaking, cooling, filter, obtain general have blue-opalescent without soap organosilicon crylic acid latex; Described each raw material carries out proportioning by following weight part:
15 ~ 25 parts of tetramethyl-four vinylcyclosiloxanes, 2 ~ 6 parts of vinyltrimethoxy silanes, 50 ~ 70 parts of methyl methacrylates, 5 ~ 12 parts of methacrylic acids, 5 ~ 15 parts of allyl group hydroxyethyl ethers, K
2s
2o
80.1 ~ 1 part, NaHSO
30.1 ~ 0.5 part, 80 ~ 120 parts of deionized waters.
2. the hyperbranched preparation method without soap organosilicon crylic acid latex as claimed in claim 1, is characterized in that: tetramethyl-four vinylcyclosiloxanes, vinyltrimethoxy silane, methyl methacrylate, methacrylic acid, allyl group hydroxyethyl ether and partial oxidation reduction initiator deionized water high speed dispersion are carried out to pre-emulsification and obtain pre-emulsion; Pre-emulsion and residue redox initiator are joined in reactor, adjust reactor system pH=3 ~ 6, in 80 ± 10 DEG C of polyreaction 2 ~ 10h; Slaking, cooling, adjusts pH=7.5 ± 0.5, filters, and obtains product.
3. the hyperbranched preparation method without soap organosilicon crylic acid latex as claimed in claim 1, is characterized in that: tetramethyl-four vinylcyclosiloxanes deionized water is disperseed, adjust system pH=3 ~ 4, carry out ring-opening reaction 2 ~ 3h at 80 ± 10 DEG C, obtain open loop silicon emulsion; Then by open loop silicon emulsion and vinyltrimethoxy silane, methyl methacrylate,, methacrylic acid, allyl group hydroxyethyl ether and partial oxidation reduction initiator carry out pre-emulsification by deionized water high speed dispersion and obtain pre-emulsion; Pre-emulsion and residue redox initiator are joined in reactor, adjust reactor system pH=4 ~ 6, in 80 ± 10 DEG C of polyreaction 2 ~ 10h; Slaking, cooling, adjusts pH=7.5 ± 0.5, filters, and obtains product.
4. the hyperbranched preparation method without soap organosilicon crylic acid latex as described in claim 2,3, is characterized in that: in described pre-emulsification process, the add-on of redox initiator is 2/5 ~ 4/5 of initiator total amount.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116285549A (en) * | 2023-04-14 | 2023-06-23 | 广东绿树环保涂料科技有限公司 | Anti-aging exterior wall paint and preparation method thereof |
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| CN1629202A (en) * | 2004-10-22 | 2005-06-22 | 同济大学 | High-silicon content shell-core structured silicon/acrylic emulsion and method for preparing same |
| CN101550217A (en) * | 2009-05-12 | 2009-10-07 | 天津城市建设学院 | Method for preparing soap-free silicone-acrylic emulsion with core-shell structure |
| CN101781390A (en) * | 2009-05-12 | 2010-07-21 | 天津城市建设学院 | Preparation method of nuclear shell structure high-silicon silicone acrylic emulsion used for building exterior wall |
| CN103382236A (en) * | 2013-05-12 | 2013-11-06 | 北京化工大学 | Silicone-acrylate emulsion with high organosilicon content and preparation method thereof |
-
2014
- 2014-07-01 CN CN201410308702.6A patent/CN104151479B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1629202A (en) * | 2004-10-22 | 2005-06-22 | 同济大学 | High-silicon content shell-core structured silicon/acrylic emulsion and method for preparing same |
| CN101550217A (en) * | 2009-05-12 | 2009-10-07 | 天津城市建设学院 | Method for preparing soap-free silicone-acrylic emulsion with core-shell structure |
| CN101781390A (en) * | 2009-05-12 | 2010-07-21 | 天津城市建设学院 | Preparation method of nuclear shell structure high-silicon silicone acrylic emulsion used for building exterior wall |
| CN103382236A (en) * | 2013-05-12 | 2013-11-06 | 北京化工大学 | Silicone-acrylate emulsion with high organosilicon content and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116285549A (en) * | 2023-04-14 | 2023-06-23 | 广东绿树环保涂料科技有限公司 | Anti-aging exterior wall paint and preparation method thereof |
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