CN102382236B - Cationic organosilicon-acrylate aqueous dispersion and preparation method thereof - Google Patents
Cationic organosilicon-acrylate aqueous dispersion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses cationic organosilicon-acrylate aqueous dispersion and a preparation method thereof. The preparation method of the cationic organosilicon-acrylate aqueous dispersion comprises the following steps of mixing 5 to 13 parts by weight of one or more organosilicon monomers, 5 to 13 parts by weight of styrene, 56 to 74 parts by weight of one or more acrylate monomers, 1 to 2 parts by weight of an initiator and 0 to 1 part by weight of a chain transferring agent to obtain a composition A, dissolving 0.2 to 0.5 parts by weight of the initiator in 2 to 5 parts by weight of one or more solvents to obtain a composition B, adding 30 to 50 parts by weight of the one or more solvents in a polymerization reactor, heating to a temperature of 80 to 100 DEG C, adding 10 to 20 parts by weight of the composition A into the reactor, then dropwisely adding the rest of the composition A into the reactor, dropwisely adding 8 to 20 parts by weight of methacryloxyethyltrimethyl ammonium chloride into the reactor, then adding the composition B into the reactor, adding 13.5 to 27.0 parts by weight of an amine substance into the reactor, and carrying out product dispersion. The cationic organosilicon-acrylate aqueous dispersion obtained by the preparation method is even and transparent, and has good waterproofness, strong stickiness and excellent storage stability.
Description
Technical field
The present invention relates to macromolecule material preparation area, specifically is a kind of cation type organic silicon-acrylate water dispersion and preparation method thereof.
Background technology
The cationic acrylate polymkeric substance refers to the polymkeric substance or the multipolymer that adopt cationic surfactant or cationic acrylate class monomer to make, and its essential characteristic is that polymer surfaces or polymkeric substance itself are positively charged.Cationic acrylic resin is because surface or himself is positively charged, therefore aspect a lot of, have negatively charged ion or the incomparable function of non-ionic type ACRYLIC EMULSION, not only be conducive to neutralization, the absorption and bonding on electronegative surface, but also have sterilization, dustproof and antistatic property.When being used for woodenware priming paint as cationic acrylic resin, natural lines and the true qualities of timber are shown especially; Simultaneously, functional groups such as the ester group in cationic acrylic resin and the timber, hydroxyl produce and interact, and play certain oil sealing effect.Therefore, the preparation and application of acrylic cationic resin research is one of focus of present acrylic resin research.
Though cationic acrylic resin exists many advantages, because acrylic resin is generally the chain linear structure, belong to thermoplastic material, very responsive to temperature, show as " hot sticky cold crisp ".In addition, the film water tolerance that acrylic resin forms is relatively poor, and under the organic solvent effect swelling phenomenon can take place, and causes coating shedding, and these have all limited the further application in its some field.
Main chain Si-O-Si key is inorganic structure in the organosilicon structure, and side chain is-CH
3Deng organic group, thereby it is typical half inorganic half organic polymer.Si-O bond energy height in the organosilicon, the internal rotation energy barrier is low, and the molecule molecular volume is big, surface energy is low, and these constitutional featuress make organosilicon have the hydrophobicity of excellent resistant of high or low temperature, height, weathering resistance etc.By organosilicon acrylate is carried out comprehensively both advantages of modification, improve acrylate " hot sticky cold crisp ", performance such as water-fast.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of cation type organic silicon-acrylate water dispersion and preparation method thereof is provided.The cation type organic silicon that the inventive method makes-acrylate water dispersion homogeneous, transparent has strong water-repellancy, strong adhesive power and good excellent properties such as storage stability.
For achieving the above object, the present invention adopts following technical scheme:
The preparation method of a kind of cation type organic silicon-acrylate water dispersion comprises the steps:
(1) in parts by weight, with 5.0～13.0 parts of organosilane monomers, 5.0～13.0 parts of vinylbenzene, 56.0～74.0 parts of acrylic ester monomers, 1.0～2.0 parts of initiators, 0～1.0 part of mixing of chain-transfer agent, stir, be mixed with combination A;
(2) 0.2～0.5 part of initiator is dissolved in 2.0～5.0 parts of solvents, is mixed with combination B;
(4) 30.0～50.0 parts of solvents are added in the polymerization reaction kettle, be warming up to 80～100 ℃, add 10.0～20.0 parts of combination A earlier, behind reaction 20～40min, drip remaining combination A again, 2.5 after～3.5h drips off continuously, then drip 8.0～20.0 parts of methylacryoyloxyethyl trimethyl ammonium chlorides, 0.5～1.5h drips off continuously, insulation 1～2h, add combination B again, after continuing to be incubated 1～2h, be cooled to again below 40 ℃;
(4) in polymerization reaction kettle, add 13.5～31.1 parts of amine substances and neutralize, and the reaction product water is disperseed, can make required cationic type organic silicon-acrylate water dispersion.
Described organosilane monomer be in vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane and the gamma-methyl allyl acyloxypropyl trimethoxysilane any one or more than.
Described acrylic ester monomer be in methyl methacrylate, vinylformic acid, butyl acrylate, methacrylic acid, Hydroxyethyl acrylate and the Propylene glycol monoacrylate any one or more than.
Described initiator is dibenzoyl peroxide or azo-bis-isobutyl cyanide.
Described chain-transfer agent is Dodecyl Mercaptan or mercaptoethanol.
Described solvent be in n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, dioxane, espeleton and the mibk any one or more than.
Described amine substance is ammoniacal liquor or triethylamine.
Compared with prior art, the present invention has following advantage and beneficial effect:
1) good emulsion stability.Owing to adopted amphipathic quaternary ammonium salt cationic monomer, the hydrophilic end oleophylic of organosilicon modified crylic acid resin segment one end that copolymerization is made has the self-emulsifying function, can improve stability in storage and the dilution stability of emulsion.
2) water-repellancy is strong.Because the special construction that organosilane monomer itself has makes the cation type organic silicon modified acrylic resin of gained have the better waterproof energy.
3) bounding force is strong.The cation type organic silicon modified acrylic resin of the present invention's preparation itself has positive charge, and natural fiber class base materials such as timber, paper are electronegative, can improve bounding force certainly with this resin.
4) the simple and safety and environmental protection of technology.Atmospheric pressure environment and temperature are lower, and be workable, and facility investment is little, is beneficial to suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment the present invention is done further concrete detailed description the in detail, but embodiments of the present invention are not limited thereto, the processing parameter for not indicating especially can carry out with reference to routine techniques.
Embodiment 1
Vinyltrimethoxy silane 8.0g, vinylbenzene 12.0g, vinylformic acid 24.0g, methyl methacrylate 24.0g, butyl acrylate 24.0g, benzoyl peroxide 1.5g, Dodecyl Mercaptan 1.0g are mixed, stir, be mixed with combination A; Then benzoyl peroxide 0.3g is dissolved in the 3.0g propyl carbinol, is mixed with combination B; The 30.0g propyl carbinol is added in the polymerization reaction kettle, be warming up to 90 ℃, add 10.0g combination A, behind the reaction 30min, drip remaining combination A, after 3.5h drips off continuously, then drip methylacryoyloxyethyl trimethyl ammonium chloride 8.0g, 0.5h drip off continuously, add B component behind the insulation 2h, continue insulation 2h; Suction filtration then, recovery part solvent and unreacted monomer; Be cooled at last below 40 ℃, in polymerization reaction kettle, add the 27.0g triethylamine and neutralize, and the reaction product water is disperseed, can make cation type organic silicon-acrylate water dispersion.The performance of the cation type organic silicon that makes-acrylate water dispersion sees Table 1.
Embodiment 2
Vinyltriethoxysilane 5.0g, vinylbenzene 11.0g, vinylformic acid 22.0g, methyl methacrylate 24.0g, butyl acrylate 28.0g, benzoyl peroxide 1.5g, Dodecyl Mercaptan 1.0g are mixed, stir, be mixed with combination A; Then benzoyl peroxide 0.3g is dissolved in the 3.0g mibk, is mixed with combination B; The 30.0g mibk is added in the polymerization reaction kettle, be warming up to 96 ℃, add 10.0g combination A, behind the reaction 30min, drip remaining combination A, after 3.5h drips off, then drip methylacryoyloxyethyl trimethyl ammonium chloride 10.0g, 0.5h drip off, add B component behind the insulation 2h, continue insulation 2h; Suction filtration then, recovery part solvent and unreacted monomer; Be cooled at last below 40 ℃, in polymerization reaction kettle, add the 24.7g triethylamine and neutralize, and the reaction product water is disperseed, can make cation type organic silicon-acrylate water dispersion.The performance of the cation type organic silicon that makes-acrylate water dispersion sees Table 1.
Embodiment 3
Propenyl Trimethoxy silane 12.0g, vinylbenzene 13.0g, vinylformic acid 20.0g, methyl methacrylate 21.0g, butyl acrylate 22.0g, benzoyl peroxide 2.0g, mercaptoethanol 1.0g are mixed, stir, be mixed with combination A; Then benzoyl peroxide 0.5g is dissolved in the 5.0g n-propyl alcohol, is mixed with combination B; The 30.0g n-propyl alcohol is added in the polymerization reaction kettle, be warming up to 90 ℃, add 10.0g combination A, behind the reaction 30min, drip remaining combination A, after 3h drips off, then drip methylacryoyloxyethyl trimethyl ammonium chloride 12.0g, 1h drips off, and adds B component behind the insulation 2h, continues insulation 2h; Suction filtration then, recovery part solvent and unreacted monomer; Be cooled at last below 40 ℃, in polymerization reaction kettle, add 31.1g ammoniacal liquor and neutralize, and the reaction product water is disperseed, can make cation type organic silicon-acrylate water dispersion.The performance of the cation type organic silicon that makes-acrylate water dispersion sees Table 1.
Embodiment 4
Gamma-methyl allyl acyloxypropyl trimethoxysilane 12.0g, vinylbenzene 9.0g, methacrylic acid 18.0g, methyl methacrylate 25.0g, butyl acrylate 22.0g, benzoyl peroxide 2.0g are mixed, stir, be mixed with combination A; Then benzoyl peroxide 0.5g is dissolved in the 5.0g dioxane, is mixed with combination B; The 50.0g dioxane is added in the polymerization reaction kettle, be warming up to 96 ℃, add 10.0g combination A, behind the reaction 30min, drip remaining combination A, after 3h drips off, then drip methylacryoyloxyethyl trimethyl ammonium chloride 14.0g, 1h drips off, and adds B component behind the insulation 2h, continues insulation 2h; Suction filtration then, recovery part solvent and unreacted monomer; Be cooled at last below 40 ℃, in polymerization reaction kettle, add 23.4g ammoniacal liquor and neutralize, and the reaction product water is disperseed, can make cation type organic silicon-acrylate water dispersion.The performance of the cation type organic silicon that makes-acrylate water dispersion sees Table 1.
Embodiment 5
Gamma-methyl allyl acyloxypropyl trimethoxysilane 11.0g, vinylbenzene 12g, methacrylic acid 18g, methyl methacrylate 22.0g, butyl acrylate 22.0g, Propylene glycol monoacrylate 1.0g, azo-bis-isobutyl cyanide 1.0g, mercaptoethanol 1.0g are mixed, stir, be mixed with combination A; Then benzoyl peroxide 0.2g is dissolved in the 2.0g isopropylcarbinol, is mixed with combination B; The 50.0g isopropylcarbinol is added in the polymerization reaction kettle, be warming up to 80 ℃, add 20.0g combination A, behind the reaction 40min, drip remaining combination A, after 3h drips off, then drip methylacryoyloxyethyl trimethyl ammonium chloride 14.0g, 1h drips off, and adds B component behind the insulation 2h, continues insulation 2h; Suction filtration then, recovery part solvent and unreacted monomer; Be cooled at last below 40 ℃, in polymerization reaction kettle, add 23.4g ammoniacal liquor and neutralize, and the reaction product water is disperseed, can make cation type organic silicon-acrylate water dispersion.The performance of the cation type organic silicon that makes-acrylate water dispersion sees Table 1.
Embodiment 6
Vinyltriethoxysilane 7.0g, vinylbenzene 12.0g, methacrylic acid 16.0g, methyl methacrylate 22.0g, butyl acrylate 26.5g, Propylene glycol monoacrylate 0.5g, azo-bis-isobutyl cyanide 1.0g, Dodecyl Mercaptan 1.0g are mixed, stir, be mixed with combination A; Then azo-bis-isobutyl cyanide 0.2g is dissolved in the 2.0g espeleton, is mixed with combination B; The 40.0g espeleton is added in the polymerization reaction kettle, be warming up to 85 ℃, add 20.0g combination A, behind the reaction 40min, drip remaining combination A, after 3h drips off, then drip methylacryoyloxyethyl trimethyl ammonium chloride 16.0g, 1h drips off, and adds B component behind the insulation 2h, continues insulation 2h; Suction filtration then, recovery part solvent and unreacted monomer; Be cooled at last below 40 ℃, in polymerization reaction kettle, add 20.8g ammoniacal liquor and neutralize, and the reaction product water is disperseed, can make cation type organic silicon-acrylate water dispersion.The performance of the cation type organic silicon that makes-acrylate water dispersion sees Table 1.
Embodiment 7
Vinyltrimethoxy silane 13.0g, vinylbenzene 5.0g, vinylformic acid 14.0g, methyl methacrylate 29.0g, butyl acrylate 20.0g, Hydroxyethyl acrylate 1.0g, azo-bis-isobutyl cyanide 1.0g, mercaptoethanol 1.0g are mixed, stir, be mixed with combination A; Then benzoyl peroxide 0.2g is dissolved in the 2.0g Virahol, is mixed with combination B; The 40.0g Virahol is added in the polymerization reaction kettle, be warming up to 80 ℃, add 20.0g combination A, behind the reaction 30min, drip remaining combination A, after 2.5h drips off, then drip methylacryoyloxyethyl trimethyl ammonium chloride 18.0g, 1.5h drip off, add B component behind the insulation 2h, continue insulation 2h; Suction filtration then, recovery part solvent and unreacted monomer; Be cooled at last below 40 ℃, in polymerization reaction kettle, add the 15.7g triethylamine and neutralize, and the reaction product water is disperseed, can make cation type organic silicon-acrylate water dispersion.The performance of the cation type organic silicon that makes-acrylate water dispersion sees Table 1.
Embodiment 8
Vinyltriethoxysilane 12.0g, vinylbenzene 12.0g, vinylformic acid 12.0g, methyl methacrylate 22.0g, butyl acrylate 21.5g, Hydroxyethyl acrylate 0.5g, azo-bis-isobutyl cyanide 1.0g are mixed, stir, be mixed with combination A; Then benzoyl peroxide 0.2g is dissolved in the 2.0g isopropylcarbinol, is mixed with combination B; The 30.0g isopropylcarbinol is added in the polymerization reaction kettle, be warming up to 85 ℃, add 20.0g combination A, behind the reaction 30min, drip remaining combination A, after 2.5h drips off, then drip methylacryoyloxyethyl trimethyl ammonium chloride 20.0g, 1.5h drip off, add B component behind the insulation 2h, continue insulation 2h; Suction filtration then, recovery part solvent and unreacted monomer; Be cooled at last below 40 ℃, in polymerization reaction kettle, add the 13.5g triethylamine and neutralize, and the reaction product water is disperseed, can make cation type organic silicon-acrylate water dispersion.The performance of the cation type organic silicon that makes-acrylate water dispersion sees Table 1.
The performance of gained cation type organic silicon-acrylate water dispersion sees Table 1.
The various performance parameters of table 1 cation type organic silicon-acrylate water dispersion
Various performance parameters detection data are as follows in the table 1:
1) outward appearance: range estimation;
2) viscosity: adopt the DV-2 of Shanghai Nirun Intelligent Technology Co., Ltd.
+ PRODigital viscometer is tested;
3) sticking power: test according to standard GB 1720-1979 (89);
4) water-intake rate: the polymers soln that takes a morsel is evenly coated on the polyfluortetraethylene plate, dries film forming down at 130 ℃, takes by weighing glued membrane quality m
1, in deionized water, flood 48h under the room temperature, wipe surperficial moisture content away with filter paper, m weighs
2, the water-intake rate of glued membrane is:
5) stability: be placed in 50 ℃ of constant temperature vacuum drying ovens and test;
6) 180 ° of stripping strengths: adopt electronic tension tester to test according to GB 2792-1995 standard;
From above-mentioned test chart as can be seen, a kind of cation type organic silicon that makes in the embodiment of the invention 1～8-acrylate water dispersion appearance transparent, look shallow, viscosity is lower, and water-intake rate is lower, sticking power is better, 180 ° of stability in storagies that stripping strength is stronger and good.In sum, the present invention adopts semi-batch technology, use the methylacryoyloxyethyl trimethyl ammonium chloride, organosilane monomer, a kind of cation type organic silicon that vinylbenzene and (methyl) acrylic ester monomer make-acrylate water dispersion homogeneous, transparent, has good storage stability, excellent properties such as strong adhesive power and strong water-repellancy, and polymerization technique is simple, atmospheric pressure environment and temperature are lower, safe and energy-conservation for production, its product can be applicable to coating, sizing agent, hide finishes, papermaking, water treatment, fields such as fabric finishing agent.
Above-described embodiment is preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. the preparation method of cation type organic silicon-acrylate water dispersion is characterized in that, comprises the steps:
(1) in parts by weight, with 5.0 ~ 13.0 parts of organosilane monomers, 5.0 ~ 13.0 parts of vinylbenzene, 56.0 ~ 74.0 parts of acrylic ester monomers, 1.0 ~ 2.0 parts of initiators, 0 ~ 1.0 part of mixing of chain-transfer agent, stir, be mixed with combination A;
(2) 0.2 ~ 0.5 part of initiator is dissolved in 2.0 ~ 5.0 parts of solvents, is mixed with combination B;
(4) 30.0 ~ 50.0 parts of solvents are added in the polymerization reaction kettle, be warming up to 80 ~ 100 ℃, add 10.0 ~ 20.0 parts of combination A earlier, behind reaction 20 ~ 40min, drip remaining combination A again, 2.5 after ~ 3.5h drips off continuously, then drip 8.0 ~ 20.0 parts of methylacryoyloxyethyl trimethyl ammonium chlorides, 0.5 ~ 1.5h drips off continuously, insulation 1 ~ 2 h, add combination B again, after continuing to be incubated 1 ~ 2 h, be cooled to again below 40 ℃;
(4) in polymerization reaction kettle, add 13.5 ~ 31.1 parts of amine substances and neutralize, and the reaction product water is disperseed, can make required a kind of cation type organic silicon-acrylate water dispersion.
2. preparation method according to claim 1, it is characterized in that, described organosilane monomer be in vinyltrimethoxy silane, vinyltriethoxysilane, propenyl Trimethoxy silane and the gamma-methyl allyl acyloxypropyl trimethoxysilane any one or more than.
3. preparation method according to claim 1 and 2 is characterized in that, described acrylic ester monomer be in methyl methacrylate, vinylformic acid, butyl acrylate, methacrylic acid, Hydroxyethyl acrylate and the Propylene glycol monoacrylate any one or more than.
4. preparation method according to claim 3 is characterized in that, described initiator is dibenzoyl peroxide or azo-bis-isobutyl cyanide.
5. preparation method according to claim 4 is characterized in that, described chain-transfer agent is Dodecyl Mercaptan or mercaptoethanol.
6. preparation method according to claim 5 is characterized in that, described solvent be in n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, dioxane, espeleton and the mibk any one or more than.
7. preparation method according to claim 6 is characterized in that, described amine substance is ammoniacal liquor or triethylamine.
8. cation type organic silicon-acrylate water dispersion is characterized in that, is prepared from by any described method of claim 1 to 7.
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| CN104059190A (en) * | 2013-04-25 | 2014-09-24 | 中国船舶重工集团公司第七二五研究所 | Organosilicon acrylate resin for gradient connection paint and preparation method thereof |
| CN103396718B (en) * | 2013-08-02 | 2016-01-20 | 武汉双虎涂料有限公司 | A kind of preparation method of fastener cathode electrophoretic paint |
| CN103936920A (en) * | 2014-04-30 | 2014-07-23 | 陕西农产品加工技术研究院 | Preparation method of cationic fluorine silicon polyacrylate soap-free emulsion |
| CN103965706B (en) * | 2014-05-21 | 2016-08-31 | 马鞍山市九和化工科技有限公司 | A kind of Treatment of Metal Surface polymer complex emulsions and preparation method thereof |
| CN109370401A (en) * | 2018-09-28 | 2019-02-22 | 河北晨阳工贸集团有限公司 | A kind of high temperature resistant cathode electrophoresis dope and preparation method thereof |
| CN110157364B (en) * | 2019-04-30 | 2022-02-11 | 青岛光电医疗科技有限公司 | Medical conductive pressure-sensitive adhesive, preparation method thereof and electrode slice prepared from same |
| 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 |
| CN111206457A (en) * | 2020-01-15 | 2020-05-29 | 黄细英 | Waterproof stain-resistant corrugated carton and preparation process thereof |
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