CN106146755A - A kind of preparation method of high solids content silicone acrylic emulsion - Google Patents
A kind of preparation method of high solids content silicone acrylic emulsion Download PDFInfo
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Abstract
The present invention relates to the preparation method of a kind of high solids content silicone acrylic emulsion, be particularly useful for the silicone acrylic emulsion of high-grade exterior coating preparation.First the inventive method prepares the emulsion Han vinyl polysiloxane with octamethylcy-clotetrasiloxane, t etram-ethyltetravinylcyclotetrasiloxane, DBSA, dodecylbenzene sodium sulfonate, nonionic emulsifier NP-40 and deionized water by acid catalysis open loop, under thermal initiator effect, carry out silicone acrylic emulsion combined polymerization with acrylic ester monomer the most again, prepare stable silicon third copolymer emulsion with higher solids content, higher silicone content and low emulsifier.Effectively solve silicone content in silicone acrylic emulsion preparation and cannot obtain substantive raising, and solid content is relatively low and problem that emulsifier is higher.The excellent performances such as this product not only weather resisteant, stain resistance, resistance to water, and cost performance is high, greatly expands its range of application.
Description
Technical field
The present invention relates to the preparation method of a kind of high solids content silicone acrylic emulsion, be particularly useful for the silicone acrylic emulsion of high-grade exterior coating preparation.
Technical background
Polyacrylate dispersion is widely used in the production of Architectural Emulsion Paints with advantages such as its good film-forming property, intensity height and caking property are strong, but there is the shortcomings such as weather resisteant, resistance to water and stain resistance simultaneously, limits its further application.Along with people's greenization, high performance and multifunction requirement to coating products, Acrylic emulsion coating meets requirement the most slowly, especially as building external paint, it is necessary to have good weatherability, resistance to water and stain resistance.Fluorine richness and organosilicon-modified acrylate emulsion become the representative of high-weatherability latex paint in recent years, particularly organosilicon-modified acrylate emulsion, owing to organosilicon has the features such as Si-O key bond energy is big, surface energy is low, molecular flexibility is big, there is many unique surface propertys, the two is combined and can obtain having concurrently the New Emulsion material of both excellent properties.And compared with fluorine carbon emulsion; the weatherability of silicon the third latex paint can compare favourably with fluorine carbon emulsion paint; stain resistance is then better than fluorine carbon emulsion paint; production cost is also low compared with fluorine carbon emulsion; the process equipment produced is close with acrylic acid ester emulsion; it is easily achieved the transformation to acrylic acid ester emulsion and large-scale production, is the main development direction of high-performance weather-proof water paint.
At present, in the silicone acrylic emulsion provided on domestic and international market, organosilicon composition content is generally less than the 10% of polymer quality, even if being in terms of 50% by silicone acrylic emulsion in emulsion paint, in film, the actual content of organosilicon is also below 3%, can not represent its due various combination properties well.Additionally, the existing silicone acrylic emulsion shortcomings such as generally to there is emulsifier higher, system solid content low (＜ 50%), this high emulsifier, the shortcoming of low polymer content also limit its extensive application in the industrial production.Therefore, reduce emulsifier, improve polymer content, and organosilicon substantial levels in raising polymer, prepare and there is high solids content height silicone content and low emulsifier, the silicone acrylic emulsion of excellent combination property simultaneously, be the key of preparation high-grade paint.
Based on present on problem, domestic and international researcher has been also carried out substantial amounts of research work, Patents and document and has also had been reported that.Patent CN1546542A discloses the new technology of a kind of silicone acrylic emulsion synthesizing high silicone content (15%～25%), prepared emulsion film has the strongest hydrophobicity, but the radical polymerization that its method uses ring-opening polymerisation and the vinyl monomer of cyclosiloxane is Tong Bu carried out, and both require difference to reaction medium pH value, the former needs to carry out in acidity or alkaline medium, the latter then needs to carry out under micro-neutrallty condition, silicone content in silicone acrylic emulsion product so will certainly be caused cannot to obtain substantive raising, solid content is only about 40% simultaneously, and emulsifier is monomer consumption 4%, also added a certain amount of co-emulsifier, these can affect the raising of combination property of emulsion to a great extent.Patent CN1796428A discloses using alkoxy silane coupling agent as organic silicon monomer, mini-emulsion polymerization is used to synthesize a kind of high-performance high silane content modified polyacrylate emulsion, but silicone content is monomer total amount 10%, and solid content is 47%, also with the addition of a certain amount of co-emulsifier.CN1629202A discloses with VTES, acrylic acid and acrylate as monomer; under the protective effect of protecting colloid and hydrolysis inhibitor; synthesize a kind of silicone content nucleocapsid structure silicone acrylic emulsion more than 15%; but solid content is also below 50%; and emulsifier reaches 8%; the consumption of protecting colloid and hydrolysis inhibitor is the highest, will have a strong impact on the water resistance of film, and also be unfavorable for environmental protection.Patent CN101781390A discloses the preparation method of a kind of nucleocapsid structure high silicon content silicone acrylic emulsion used for building exterior wall, it is prepared unsaturated organosilicon oxygen alkane oligomer emulsion by cyclosiloxane and carrys out modified polyacrylate, and the highest addition of its organosilicon can account for the 20% of siloxane-acrylate copolymer.But its product solid content is only between 36%～45%, and emulsifier is the highest.Patent CN101798369A also discloses that the preparation method of a kind of high silicon content silicone acrylic emulsion, in gained emulsion, silicone content accounts for more than the 10% of emulsion system, it is using alkoxy silane coupling agent as organic silicon monomer, by adding hydrolysis inhibitor and using redox initiator to implement, but solid content is also below 50%, have also been introduced some auxiliary agents simultaneously, be unfavorable for the raising of combination property.Kingdom builds etc. and to use hydrolysis suppression method in " development of study of silicone-acrylate emulsion with high amount of siloxane " that 2 phases of volume 43 " Shanghai coating " in January, 2005 deliver, carry out emulsion with the vinylsiloxane monomer of not facile hydrolysis with acrylate monomer to be polymerized, prepared silicone content reaches the silicone acrylate emulsion of 20%, but emulsifier is compared with big and solid content is relatively low.Tang Minfeng etc. use the reactive organic silicon monomer with branched structure to carry out emulsion copolymerization with MPS silane coupler and acrylic ester monomer in " synthesis of branching type organosilicon acrylic ester copolymerization emulsion and the performance thereof " that the 1st phase of volume 24 " fine chemistry industry " in January, 2007 delivers, synthesize the highest silicone content and reach the stable high silicon content silicone acrylic emulsion of 10%, but there is also same problem, solid content is less than 50%.Additionally, also have other some researcheres to have also been made " room temperature prepares the research of high silicon content VTES/St/MMA copolymer emulsion " that similar research work, such as Yin Chang Jie etc. are delivered in the 1st phase of volume 30 " modern chemical industry " in January, 2010；" the low temperature synthesis of silicon the-the third core shell emulsion and the stability " that Ge Chengyue etc. delivered in the 4th phase of volume 25 " polymer material science and engineering " in April, 2009；" development of study of silicone-acrylate emulsion with high amount of siloxane " that Hu Zhongyu delivered in volume 36 the 1st phase " New Chemical Materials " in January, 2008 etc., all synthesize silicone content silicone acrylic emulsion between 10%-15%, but all there is identical problem: solid content is relatively low, partial emulsifier consumption is higher.
Existing technology shows, when silicone content is relatively low, improves limited to the performance of silicone acrylic emulsion, does not reaches the effect of modification；Very little, when increasing silicone content or solid content XOR the two content simultaneously, emulsion intercalation method is deteriorated, easily condenses emulsifier；If but be to increase silicone content and reduce solid content, then can increase production and the cost such as transport, and limit silicone acrylic emulsion and the most extensively apply；Emulsifier is many, have impact on the hydrophobicity effect of organic silicon monomer the most to a certain extent, causes emulsion film resistance to water to reduce.
Summary of the invention
The primary and foremost purpose of the present invention is to overcome the deficiencies in the prior art and defect, the preparation method of a kind of high solids content silicone acrylic emulsion is provided, the high performance silicon emulsion stablized, this silicone acrylic emulsion has the features such as weatherability, resistance to water and the contaminated resistance of excellence, and good with the compatibility of color stuffing, it is particularly suited for configuring the base material of high-grade exterior coating.
Another object of the present invention also provides for the preparation method of above-mentioned silicone acrylic emulsion.
The preparation method of a kind of high solids content silicone acrylic emulsion, is achieved through the following technical solutions, including step:
(1) preparation containing vinyl polysiloxane emulsion:
Octamethylcy-clotetrasiloxane 30%～40%, t etram-ethyltetravinylcyclotetrasiloxane 10%～20%, DBSA 1%～10%, dodecylbenzene sodium sulfonate 1%～5%, emulsifying agent NP-401%～5%, deionized water 40%～60% is taken by quality；
DBSA, dodecylbenzene sodium sulfonate, emulsifying agent NP-40 and deionized water are joined in reactor and stir, warming-in-water is to 60～85 DEG C, organic silicon monomer mixture is added in 2h-3h, insulation continues reaction 3h, stop heating, naturally cool to room temperature, be neutralized to neutrality with 10% aqueous sodium carbonate, obtain containing vinyl polysiloxane emulsion
(2) preparation of silicon the third copolymer emulsion:
Take following component by quality: step 1) prepare containing vinyl polysiloxane emulsion 40-60%, acrylic ester monomer 40-50%, initiator 0.1-0.5%, pH value regulator 0.01-0.1%, molecular weight regulator 1%, deionized water 30-40%；
By in 20% addition containing vinyl polysiloxane emulsion, the 15% of the total amount of acrylic ester monomer mixture, initiator and pH value regulator total amount to reactor, it is warming up to 75-85 DEG C, isothermal reaction about 30min now blue light is sufficient and produces without backflow monomer, then constant temperature drips the mixture of remaining organosilicon and the mixture of acrylic ester monomer and remaining initiator and pH value regulator, and time for adding is about 2.5-3.5h；Drip complete isothermal reaction 0.5h, then heat to 85-95 DEG C, continue reaction 1-1.5h, stop heating, obtain described silicone acrylic emulsion.
Described organic silicon monomer mixture by octamethylcy-clotetrasiloxane and tetramethyl four ethylene cyclotetrasiloxane with 9: the mass ratio of 1-5: 1 forms, concrete consumption or proportioning determine according to the purposes of product, the former consumption increase can improve the flexibility of product, tolerance to cold, and the latter's consumption increase can improve the rigidity of product, thermostability；
Described acrylic ester monomer refers to two or more the mixture in acrylic acid, methacrylic acid, methyl methacrylate, acrylic acid methyl ester., ethyl acrylate, propyl acrylate, butyl acrylate or Isooctyl acrylate monomer, concrete consumption or proportioning determine according to the purposes of product, acrylic acid and methacrylic acid consumption increase can improve the stability of product, reduce the consumption of emulsifying agent, but the resistance to water of product can be reduced；Methyl methacrylate increases the rigidity of product glued membrane, and remaining monomer increase can improve the flexibility of product glued membrane successively；
Described compound emulsifying agent is dodecylbenzene sodium sulfonate, sodium lauryl sulphate or the Anionic-nonionic emulsifying agent of octyl group polyoxyethylene ether apoplexy due to endogenous wind at least two material composition, and the proportioning of anion and nonionic is 4: 1～2: 1；
Described catalyst is DBSA, acrylic or methacrylic acid, they are both as the acid catalyst of ring-opening polymerisation, the most also have the emulsification of surfactant concurrently, especially the latter due to as participating in the surface active monomer of backbone polymerization, can be greatly reduced the total consumption of emulsifying agent ensureing on the premise of polymer emulsion product is stable；
Described initiator is persulfate, mainly Ammonium persulfate. or potassium peroxydisulfate, and depending on its consumption can be according to polymerization temperature, consumption generally improves with selected polymerization temperature and reduces.
Described molecular weight regulator is lauryl mercaptan；
Described PH buffer agent is sodium bicarbonate, disodium hydrogen phosphate or sodium dihydrogen phosphate；
Compared with prior art, the present invention has a characteristic that
1, extensive due to the organic silicon monomer raw material sources used in the present invention, price is less expensive, under same performance, can effectively reduce emulsion production cost.
2, in the present invention preparation containing vinyl polysiloxane emulsion, monomer conversion is high, even particle size distribution, good emulsion stability, its chemical constitution is to have the line style unsaturated polyester siloxanes of certain chain length, side chain is vinyl, methyl, effectively reduce organosilicon ring body structurc sterically hindered, it is more beneficial for carrying out copolymerization with acrylic ester monomer, increase introduction volume and the chain length thereof of Si-O-Si key in acrylate polymer simultaneously, giving full play to its premium properties, its highest addition accounts for the 20% of siloxane-acrylate copolymer；Meanwhile, the polysiloxanes generated has fine emulsifying effectiveness, can effectively reduce the consumption of emulsifying agent in silicone acrylic emulsion, reduces the generation of condensation product, strengthens emulsion intercalation method, and can also increase biphase between the compatibility.
3, use the polymerization of open loop emulsion and radical polymerization substep to carry out, meet the polyreaction requirement to reaction medium so that in silicone acrylic emulsion, silicone content can obtain substantive raising.
4, due in the silicone acrylic emulsion of the present invention solid content and silicone content the highest, be so possible not only to be substantially reduced the cost of production and transport, expand its range of application, and with its prepared coating, there is good stain resistance and weatherability.Under conditions of being converted into identical solid content, saving of labor of the present invention, material-saving, the energy that saves time, saves advantage the most notable.
5, product silicone acrylic emulsion of the present invention has that solid content is high, silicone content high, emulsifier is low and storage is stable, not only has performances such as excellent weatherability, stain resistance, stain resistance, and be dried rapidly, the advantage such as the transparency and good fluidity.
Detailed description of the invention
In order to the present invention is better described, the technology to the present invention gives to illustrate further in conjunction with the embodiments, but the present invention is not limited in following embodiment.
Embodiment 1:
1) preparation containing vinyl polysiloxane emulsion: first 4g DBSA, 2g dodecylbenzene sodium sulfonate, 2g NP-40,60g deionized water are joined in reactor, stirring is fully dissolved, it is warming up to 80 DEG C afterwards, then 30g octamethylcy-clotetrasiloxane, 10g t etram-ethyltetravinylcyclotetrasiloxane mixing organic silicon monomer are slowly added dropwise in reactor in 3h, insulation reaction 3h, naturally cool to room temperature, finally it is neutralized to neutrality with 10% aqueous sodium carbonate, vinyl polysiloxane emulsion must be contained.
Gained emulsion solid content is more than 35%, molecular weight 2000-5000, and bin stability is more than 3 months.
2) preparation of silicon the third copolymer emulsion:
Joining in single port flask by 35g containing vinyl polysiloxane emulsion, 42.5g butyl acrylate, 42.5g methyl methacrylate, 3g acrylic acid and 20g deionized water, to obtain pre-emulsion stand-by for pre-emulsification 0.5h under high velocity agitation；Add 0.4g Ammonium persulfate., 0.1g sodium bicarbonate and 15g deionized water in another flask to obtain initiator solution stand-by simultaneously.
In the four mouthfuls of round-bottomed flasks being configured with thermometer, agitator, reflux condensing tube and constant pressure funnel, by 15g deionized water and 25g, the emulsion Han vinyl polysiloxane is added thereto and stirs, it is warming up to 80 DEG C after logical nitrogen 0.5h, put into pre-emulsion and 15% initiator solution of 10% simultaneously, reaction 0.5h starts to be simultaneously added dropwise remaining pre-emulsion and initiator solution, in 3h, dropping is complete, it is warming up to 85 DEG C after insulation 0.5h and continues reaction 1h, stop heating, naturally cool to room temperature, filter discharging, i.e. obtain described silicon the third copolymer emulsion.
Embodiment 2:
1) preparation containing vinyl polysiloxane emulsion: first 4g DBSA, 2g dodecylbenzene sodium sulfonate, 2g NP-40,60g deionized water are joined in reactor, stirring is fully dissolved, it is warming up to 80 DEG C afterwards, then 25g octamethylcy-clotetrasiloxane, 15g t etram-ethyltetravinylcyclotetrasiloxane mixing organic silicon monomer are slowly added dropwise in reactor in 3h, insulation reaction 3h, naturally cool to room temperature, finally it is neutralized to neutrality with 10% aqueous sodium carbonate, vinyl polysiloxane emulsion must be contained.
Gained emulsion solid content is more than 35%, molecular weight 2000-5000, and bin stability is more than 3 months.
2) preparation of silicon the third copolymer emulsion:
Joining in single port flask by 30g containing vinyl polysiloxane emulsion, 45.5g butyl acrylate, 45.5g methyl methacrylate, 3g acrylic acid and 25g deionized water, to obtain pre-emulsion stand-by for pre-emulsification 0.5h under high velocity agitation；Add 0.4g Ammonium persulfate., 0.1g sodium bicarbonate and 15g deionized water in another flask to obtain initiator solution stand-by simultaneously.
In the four mouthfuls of round-bottomed flasks being configured with thermometer, agitator, reflux condensing tube and constant pressure funnel, by 20g deionized water and 20g, the emulsion Han vinyl polysiloxane is added thereto and stirs, it is warming up to 80 DEG C after logical nitrogen 0.5h, put into pre-emulsion and 15% initiator solution of 10% simultaneously, reaction 0.5h starts to be simultaneously added dropwise remaining pre-emulsion and initiator solution, in 3h, dropping is complete, it is warming up to 85 DEG C after insulation 0.5h and continues reaction 1h, stop heating, naturally cool to room temperature, filter discharging, i.e. obtain described silicon the third copolymer emulsion.
Claims (6)
1. a preparation method for high solids content silicone acrylic emulsion, is particularly useful for the silicone acrylic emulsion of high-grade exterior coating preparation, it is characterised in that preparation process includes following steps successively:
(1) preparation containing vinyl polysiloxane emulsion:
DBSA, dodecylbenzene sodium sulfonate, emulsifying agent NP-40 and deionized water are joined in reactor and stir, warming-in-water is to 60～85 DEG C, organic silicon monomer mixture is added in 2h-3h, insulation continues reaction 3h, stop heating, naturally cool to room temperature, be neutralized to neutrality with 10% aqueous sodium carbonate, obtain containing vinyl polysiloxane emulsion；
(2) preparation of silicon the third copolymer emulsion:
By in 20% addition containing vinyl polysiloxane emulsion, the 15% of the total amount of acrylic ester monomer mixture, initiator and pH value regulator total amount to reactor, it is warming up to 75-85 DEG C, isothermal reaction about 30min now blue light is sufficient and produces without backflow monomer, then constant temperature drips the mixture of remaining organosilicon and the mixture of acrylic ester monomer and remaining initiator and pH value regulator, and time for adding is about 2.5-3.5h；Drip complete isothermal reaction 0.5h, then heat to 85-95 DEG C, continue reaction 1-1.5h, stop heating, obtain described silicone acrylic emulsion.
2. preparation method as claimed in claim 1, it is characterised in that organic silicon monomer mixture by octamethylcy-clotetrasiloxane with tetramethyl four ethylene cyclotetrasiloxane with 9: the mass ratio of 1-5: 1 forms.
3. preparation method as claimed in claim 1, it is characterized in that described acrylic ester monomer refers to that two or more the mixture in acrylic acid, methacrylic acid, methyl methacrylate, acrylic acid methyl ester., ethyl acrylate, propyl acrylate, butyl acrylate or Isooctyl acrylate monomer, concrete consumption and proportioning determine according to the purposes of product.
4. preparation method as claimed in claim 1, it is characterized in that compound emulsifying agent is dodecylbenzene sodium sulfonate, sodium lauryl sulphate or the Anionic-nonionic emulsifying agent of octyl group polyoxyethylene ether apoplexy due to endogenous wind at least two material composition, and the proportioning of anion and nonionic is 4: 1～2: 1.
5. preparation method as claimed in claim 1, it is characterized in that catalyst is DBSA, acrylic or methacrylic acid, they are both as the acid catalyst of ring-opening polymerisation, the most also have the emulsification of surfactant concurrently, especially the latter due to as participating in the surface active monomer of backbone polymerization, can be greatly reduced the total consumption of emulsifying agent ensureing on the premise of polymer emulsion product is stable.
6. preparation method as claimed in claim 1, it is characterised in that initiator is persulfate, mainly Ammonium persulfate. or potassium peroxydisulfate；Molecular weight regulator is lauryl mercaptan；Described PH buffer agent is sodium bicarbonate, disodium hydrogen phosphate or sodium dihydrogen phosphate.
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| CN111362659A (en) * | 2020-03-18 | 2020-07-03 | 中科院广州化学有限公司 | Self-cleaning organic-inorganic hybrid composite coating and preparation method and application thereof |
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| CN114163583A (en) * | 2021-12-17 | 2022-03-11 | 万华化学集团股份有限公司 | Silicone-acrylate emulsion and preparation method and application thereof |
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