CN100345874C - Organosilicon modified acrylate emulsion for ambient temperature crosslinked aqueous paint and method for preparing same - Google Patents
Organosilicon modified acrylate emulsion for ambient temperature crosslinked aqueous paint and method for preparing same Download PDFInfo
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- CN100345874C CN100345874C CNB2005100378976A CN200510037897A CN100345874C CN 100345874 C CN100345874 C CN 100345874C CN B2005100378976 A CNB2005100378976 A CN B2005100378976A CN 200510037897 A CN200510037897 A CN 200510037897A CN 100345874 C CN100345874 C CN 100345874C
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Abstract
The present invention relates to organosilicon modified acrylate emulsion for environmental temperature crosslinking aqueous paint. The present invention is characterized in that the emulsion is obtained by the following steps that firstly, organosilicon prepolymers are synthesized; secondly, surface modified silicon dioxide nanometer particles are synthesized by adopting a collosol-gelatin technique after the organosilicon prepolymers react with tetraethyl orthosilicate; seed emulsion is used as a core by adopting a polymerization process of seed emulsion; silicon dioxide nanometer particles whose surfaces are coated with organosilicon prepolymers and a mixture which is composed of organosilicon monomers, hard monomers, soft monomers and functional monomers are used as a shell; finally, the organosilicon modified acrylate emulsion is obtained by the network polyreaction of interpenetrating polymer of the core and the shell. A preparing method comprises the following steps that: (1) organosilicon prepolymers are synthesized; (2) silicon dioxide nanometer particles are prepared; (3) seed emulsion is prepared; (4) silicone acrylic emulsion is synthesized; the product is obtained. The present invention greatly improves the abrasion resisting performance, the alkali resisting performance, the water resisting performance, the weathering performance, the dirt resisting performance, etc. of an emulsion film.
Description
Technical field
The invention belongs to the chemical coating field, be specifically related to a kind of organosilicon modified acrylate emulsion for ambient temperature crosslinked aqueous paint, and the preparation method of this emulsion.Emulsion of the present invention is mainly used in the emulsion of top-grade building exterior coating, water-borne wood coating, waterproof paint and metal alloy sheet material decoration coating and the contour performance environment-friendly type coating of aqueous adhesive.
Background technology
The emulsion (filmogen) of one of exterior wall latex coating main component is mostly based on benzene emulsion and pure-acrylic emulsion etc. at present.And the thermoplasticity of the molecule of these emulsions own is limit, and linear molecule lacks cross-linking set again, is difficult to form three-dimensional cross-linked reticulated structure, therefore, easily high temperature be clamminess, binding dust, and lack flexibility the embrittlement of filming during low temperature.So prepare the more superior exterior coating of over-all properties, the crucial filmogen superior (resin or emulsion) of still need studying with production performance.As water-based fluorocarbon resin or emulsion, organosilicon crylic acid latex and modification pure-acrylic emulsion.And fluorocarbon resin is owing to cost an arm and a leg, and present in addition synthetic technology is immature, has been subjected to very big restriction in application process.Organosilicon-modified acrylate emulsion has improved the deficiency of ACRYLIC EMULSION " hot sticky cold crisp " then with the performance of ACRYLIC EMULSION and organic silicon emulsion.And owing to the performance of present organosilicon crylic acid latex also exists such as weathering resistance, resistance to soiling, the more unfavorable problem of tensile strength, so be badly in need of wanting excellent combination property, as the research of cross-linked type latex emulsion and the listing of product.
The preparation difficult point of current generally acknowledged organosilicon-modified acrylate emulsion is to occur problems such as gelatin phenomenon and package stability be not good enough when synthetic.This all is to cause owing to hydrolysis very easily takes place the organo-siloxane in the macromolecular chain.Current organosilicon-modified acrylic emulsion mainly contains following several preparation method:
(1) cold spelling;
(2) add water decomposition siloxanes and polyacrylic acid ester condensation grafting;
(3) the direct and hydroxyl polyacrylic acid ester condensation grafting of dimethyl polysiloxane;
(4) contain technological line preparations such as vinyl group organo-siloxane and acrylic ester monomer copolymerization.
Wherein, the shortcoming of first three methods is to be easy to generate two to be separated, and storage period is short.And (2) and (3) in the kind method, and the organosilicon polymer active group is whole grafting inactivations before this, and does not have chemical bond to link to each other between acrylate copolymer and the base material, improves little to weathering resistance and sticking power.The coating of (4) kind method preparation, when drying and forming-film, siloxanes hydrolysis, condensation can form interpenetrating(polymer)networks and the structural form by the silica cross-link bond between polymkeric substance and base material, making films has excellent weathering resistance, pollution resistance, water tolerance and sticking power.In the middle of several years that the exterior coating big area is used, construction quality has occurred having had a strong impact on the attractive in appearance of exterior wall such as quality problems such as ftractureing, stain.So rising year by year of elastic emulsion demand.But at present elastic emulsion exists resistance to soiling difference and the not good enough deficiency that waits of tensile strength.The present invention utilizes the little characteristics of organosilicon surface tension, adopts hud polymerization technology and interpenetrating polymer networks polymerization technique to combine the silicon acrylate elastic emulsion that synthesizes, the problems referred to above of Xie Jueing effectively.
In addition, when emulsion exists second-order transition temperature high at present, the corresponding high deficiency of film-forming temperature, this use to China's different areas exterior coating has brought the difficulty of construction.Aspect polymerization technique, the maximum difference of the emulsion that core-shell emulsion polymerization and conventional emulsion polymerization obtain is: the anti-after-tackiness of the emulsion that core-shell emulsion polymerization obtains is good, minimum film-forming temperature is low, better film-forming properties, stability and more superior mechanical property.Nucleocapsid interpenetrating polymer networks polymerization technique is a new developing technology on the seeded emulsion polymerization basis in recent years.This polymerization technique has proposed the new ideas of " particle design ", promptly changes the emulsion particle structure under the prerequisite that does not change emulsion monomer composition, thereby improves emulsion property.Connection situation between the nucleocapsid has very big influence to particle shape and emulsion property.
At present, nano modification coating is that inorganic nano-particle mixes with the simple of conventional each component of coating, after the coating film forming, the nanoparticle state how with and the effect brought into play ageing etc. do not have reliable according to confirming.The real improved performance of coating of realizing also needs the modification of the nanoparticle of atomic level to superpolymer.
The preparation of nanoemulsions is as patent (publication number: 1424353; Publication number: 1431234; Publication number: 1385447; Publication number: 1394888) report is the pure-acrylic emulsion of first synthesis of nano size, is nuclear then with the pure-acrylic emulsion, is shell with organosilicon and acrylate, has made organosilicon crylic acid latex.Zhi Bei emulsion just in the emulsion film forming process, produces partial crosslinked or Intermolecular Forces between the molecule in molecular structure like this.Such result is that ageing resistance and the resistance to soiling and the mechanical property etc. of pure-acrylic emulsion are not significantly improved.At present also there is weak point in organosilicon crylic acid latex at aspects such as some performance such as freeze-thaw stability, Calcium ion stability, package stabilities.
Summary of the invention
In view of above situation, task of the present invention provides a kind of new organosilicon crylic acid latex, this emulsion will be on the basis of thermoplastic acrylic emulsion and grafting organosilicon crylic acid latex in the past, introduce linked and nanoparticle, adopt active emulsifier, by nucleocapsid interpenetrating polymer networks polymerization technique, make between emulsion particle stratum nucleare and the shell produce certain crosslinked.This will improve wear-resisting, alkaline-resisting, water-fast, weather-proof, resistant, perviousness, solvent resistance and tensile strength behind the polymer film forming, bonding strength, chemical stability, freeze-thaw stability etc. greatly.Exterior coating by this series emulsion preparation has performances such as more excellent weathering resistance, resistance to soiling, scrub resistance and physical strength.
The technical scheme of finishing the foregoing invention task is: organosilicon modified acrylate emulsion for ambient temperature crosslinked aqueous paint also can be called: inorganic nano particle modified organosilicon-modified acrylate emulsion, and the preparation method of this emulsion.Be respectively described below:
Organosilicon modified acrylate emulsion for ambient temperature crosslinked aqueous paint (inorganic nano particle modified organosilicon-modified acrylate emulsion) is characterized in that this emulsion is obtained by following method:
Elder generation's synthesizing organo-silicon prepolymer after reacting with tetraethoxy then, adopts sol-gel technique to synthesize the Nano particles of silicon dioxide of surface modification; Be nuclear then to adopt seeded emulsion polymerization technology to obtain seed emulsion, coating the Nano particles of silicon dioxide of organosilicon preformed polymer and by unsaturated organosilicon monomer, hard monomer, soft monomer with above-mentioned surface, and the mixture that function monomer is formed is a shell, nucleocapsid interpenetrating polymer networks polyreaction through 3-5 hour obtains inorganic nano particle modified organosilicon crylic acid latex at last.
Say that more specifically and more optimally this organosilicon modified acrylate emulsion for ambient temperature crosslinked aqueous paint (inorganic nano particle modified organosilicon-modified acrylate emulsion) is obtained by following method:
(1), organosilicon preformed polymer is synthetic: Virahol and potassium hydroxide react, and add octamethylcyclotetrasiloxane again and carry out ring-opening polymerization, obtain organosilicon preformed polymer A, and is standby;
(2), the preparation of Nano particles of silicon dioxide: in tetraethoxy, drip deionized water and Glacial acetic acid, temperature reaction, add organosilicon preformed polymer A then, obtain the Nano particles of silicon dioxide that the surface is coating organosilicon preformed polymer after the temperature reaction, be called organosilicon preformed polymer B;
(3), the preparation of seed emulsion: after deionized water, emulsifying agent, PH conditioning agent, initiator emulsification, add acrylate mixing monomer and organosilicon preformed polymer B and carry out emulsification, be warming up to 70-75 ℃, system is cooled to about 75 ℃ when being warming up to 80-85 ℃ rapidly, constant temperature 30 minutes obtains seed emulsion;
(4), organosilicon-modified acrylate emulsion is synthetic:
Soft monomer, hard monomer and function monomer and organosilicon preformed polymer B were splashed in the reactor at 3-5 hour, regularly add initiator, emulsifying agent and PH conditioning agent simultaneously in batches, be warming up to 80 ℃, add the butyl acrylate that is dissolved with benzoyl peroxide, continue reaction, last system temperature rises to 90 ℃, constant temperature 60 minutes, cooling adds auxiliary agents such as defoamer, frostproofer, antimildew disinfectant, waterproofing agent of organosilicon, after being lower than under 40 ℃ of conditions neutralization, discharging.
The preparation method of above-mentioned emulsion of the present invention is that first synthesizing organo-silicon prepolymer after reacting with tetraethoxy then, adopts sol-gel technique to synthesize the Nano particles of silicon dioxide of surface modification.Be nuclear then to adopt seeded emulsion polymerization technology to obtain seed emulsion, coating the Nano particles of silicon dioxide of organosilicon preformed polymer and by unsaturated organosilicon monomer, hard monomer, soft monomer with above-mentioned surface, and the monomer mixture that function monomer is formed is a shell, nucleocapsid interpenetrating polymer networks polyreaction (shell monomers splashes in the reactor in batches) through 3-5 hour obtains inorganic nano particle modified organosilicon crylic acid latex at last.
The inventive method specifically may further comprise the steps:
(1), organosilicon preformed polymer is synthetic: Virahol and potassium hydroxide react, and add octamethylcyclotetrasiloxane again and carry out ring-opening polymerization, obtain organosilicon preformed polymer A, and is standby;
(2), the preparation of Nano particles of silicon dioxide: in tetraethoxy, drip deionized water and Glacial acetic acid, temperature reaction, add organosilicon preformed polymer A then, obtain the Nano particles of silicon dioxide that the surface is coating organosilicon preformed polymer after the temperature reaction, be called organosilicon preformed polymer B;
(3), the preparation of seed emulsion: after deionized water, emulsifying agent, PH conditioning agent, initiator emulsification, add acrylate mixing monomer and organosilicon preformed polymer B and carry out emulsification, be warming up to 70-75 ℃, system is cooled to about 75 ℃ when being warming up to 80-85 ℃ rapidly, constant temperature 30 minutes obtains seed emulsion;
(4), organosilicon crylic acid latex is synthetic:
Soft monomer, hard monomer and function monomer and organosilicon preformed polymer B were splashed in the reactor at 3-5 hour, regularly add initiator, emulsifying agent and PH conditioning agent simultaneously in batches, be warming up to 80 ℃, add the butyl acrylate that is dissolved with benzoyl peroxide, continue reaction, last system temperature rises to 90 ℃, constant temperature 60 minutes, cooling adds auxiliary agents such as defoamer, frostproofer, antimildew disinfectant, waterproofing agent of organosilicon, after being lower than under 40 ℃ of conditions neutralization, discharging.
The further optimization of aforesaid method is following preparation method:
(1), organosilicon preformed polymer is synthetic:
Virahol and potassium hydroxide are under refluxad reacted, boil off excessive Virahol.Add octamethylcyclotetrasiloxane (D again
4), under 100-120 ℃, carry out ring-opening polymerization, cooling adds Glacial acetic acid, stirs, and vacuumizes, and removes the small molecules thing, filters, and removes Potassium ethanoate, obtains organosilicon preformed polymer A, and is standby;
(2), the preparation of Nano particles of silicon dioxide:
In reactor, add tetraethoxy, drip deionized water and Glacial acetic acid, temperature reaction, take out residual water and Glacial acetic acid and small amount of ethanol with water pump then, add organosilicon preformed polymer A, slowly after the temperature reaction, vacuumize, cooling obtains the Nano particles of silicon dioxide that the surface is coating organosilicon preformed polymer, is called organosilicon preformed polymer B.
(3), the preparation of seed emulsion:
After dissolving in deionized water, emulsifying agent, PH conditioning agent, the initiator adding emulsification still, powerful emulsification, slowly add acrylate mixing monomer and organosilicon preformed polymer B, carry out emulsify at a high speed, move in the reactor, begin to be warming up to 70-75 ℃, this moment, system was warming up to 80-85 ℃ rapidly, take combination of inner and outside cooling means, temperature is reduced to about 75 ℃, and constant temperature 30 minutes obtains outward appearance and is blue seed emulsion;
(4), the synthetic of organosilicon crylic acid latex splashed into remaining soft monomer, hard monomer and function monomer and organosilicon preformed polymer B in the reactor at 3-5 hour, regularly adds solution such as initiator, emulsifying agent and PH conditioning agent simultaneously in batches.After dripping off, be warming up to 80 ℃, add the butyl acrylate that is dissolved with benzoyl peroxide, continue reaction, last system temperature rises to 90 ℃, constant temperature 60 minutes.Cooling adds auxiliary agents such as defoamer, frostproofer, antimildew disinfectant, waterproofing agent of organosilicon, is being lower than under 40 ℃ of conditions after the neutralization discharging, packing.
The organosilane monomer kind that the present invention selects for use mainly contains unsaturated organosilicon monomer, octamethylcyclotetrasiloxane (D4), organosilicon preformed polymer and tetraethoxy etc.
The unsaturated organosilicon monomer that the present invention selects for use comprises vinyl triethoxyl siloxanes, vinyl trimethoxy siloxanes, vinyl three isopropoxy siloxanes, methacryloxypropyl triethoxy silica alkane etc.Consumption is the 5-20% of monomer total amount.
The hard monomer that the present invention selects for use comprises methyl methacrylate, n-BMA, vinylbenzene etc.Consumption is the 20-45% of monomer total amount.
The soft monomer that the present invention selects for use comprises methyl acrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, 2-EHA etc., and consumption is the 30-50% of monomer total amount.
The function monomer that the present invention selects for use comprises vinylformic acid, methacrylic acid, vinyl cyanide, acrylamide, N-methylol acrylic acid amides, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate or Rocryl 410 etc.Consumption is the 5-10% of monomer total amount.
The polymerization technique that the present invention adopts comprises seeding polymerization technology, pre-emulsification technology, interpenetrating polymer networks polymerization technique and hud polymerization technology etc.
The second-order transition temperature of emulsion has influence on the resistance to soiling of emulsion paint.Second-order transition temperature is too high, can influence the film forming and the cost of emulsion, because preparation is during coating, the film coalescence aid amount can corresponding increase.And for organosilicon crylic acid latex, because emulsion own belongs to the self-crosslinking structure, along with the prolongation of time, the hardness of filming can increase.The design of second-order transition temperature is different.
Content of the present invention comprises the relation of emulsion second-order transition temperature and organosilicon content.Organosilyl content is 5-20% (accounting for monomeric weight percentage) in the emulsion, and second-order transition temperature is at-18-35 ℃, and minimum film-forming temperature is at 0-20 ℃.
The emulsification system that the present invention adopts is ternary composite emulsifying systems such as active emulsifier, anionic emulsifier and nonionic emulsifying agent.
Active emulsifier is selected among the present invention: sodium vinyl sulfonate, acrylamide stearic acid sodium salt, alkyl vinylformic acid-2-ethanesulfonic acid sodium salt etc.
Anionic emulsifier is selected among the present invention: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, Nonyl pheno base (4) ether ammonium sulfate etc.
Nonionic emulsifying agent is selected among the present invention: Nonyl pheno base ether (the ethene radix is at 10-70) etc.
Organosilicon crylic acid latex industrial scale of the present invention is in 100L-10000L reactor scale.
Initiator comprises Potassium Persulphate, ammonium persulphate, sodium bisulfite-Potassium Persulphate, benzoyl peroxide, dicumyl peroxide, tert-butyl peroxide, Diisopropyl azodicarboxylate etc. among the present invention.
The usage quantity of emulsion of the present invention in the external wall latex coating is 20-40%.
The present invention utilizes ternary compound emulsifying agent system, has improved above-mentioned performance greatly.
It is as shown in the table for concrete outcome.
The leading indicator of the exterior wall silicon-acrylic coatings of emulsion preparation is among the present invention: artificial ageing resistance performance, 3000 hours; 0 grade of efflorescence; 1 grade of variable color; Resistance to soiling＜5; Scrub resistance＞20000 time.
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Embodiment
Embodiment 1: inorganic nano particle modified organosilicon-modified acrylate emulsion
The preparation method is as follows:
(1), organosilicon preformed polymer is synthetic:
400 kilograms of Virahols and 8.4 kilograms of exsiccant potassium hydroxide are added in the reactor, be heated to backflow, and 350 kilograms of Virahols are steamed.Add 148 kilograms of octamethylcyclotetrasiloxane (D again
4), reacted 120 minutes down at 100-120 ℃, be cooled to 70-80 ℃ then, add 10 kilograms of Glacial acetic acid, stirred 60 minutes, vacuumize again, remove the small molecules thing, filter, remove Potassium ethanoate, obtain organosilicon preformed polymer A.Standby.
(2), in reactor, add 70 kilograms of tetraethoxys, drip 6 kilograms of deionized waters and 0.2 kilogram of Glacial acetic acid, 90 ℃ the reaction 60 minutes after, take out residual water, Glacial acetic acid and small amount of ethanol in the system with water pump then, add organosilicon preformed polymer A then, slowly be warming up to 130-150 ℃ of reaction after 120-180 minute, vacuumize, remove the small molecules thing, cooling obtains the Nano particles of silicon dioxide that the surface is coating organosilicon preformed polymer.
(3), organosilicon crylic acid latex is synthetic:
(1) compositing formula unit: kilogram
(2) technology
After dissolving in the component A adding 500L emulsification still, powerful emulsification, slowly add component C1, carried out emulsify at a high speed 15-30 minute with mulser.Move in the reactor, be warming up to 70-75 ℃, this moment, system was warming up to 80-85 ℃ rapidly, taked combination of inner and outside cooling means, and temperature is reduced to about 75 ℃, constant temperature 30-60 minute, obtained outward appearance and was blue seed emulsion.
(4), component C2 and component C3 were splashed in 180-300 minute in the 1000L reactor successively, respectively added once solution such as remaining initiator, emulsifying agent and PH conditioning agent every 30 minutes.After dripping off, be warming up to 80 ℃, add component D, continue reaction 30 minutes.System temperature is risen to 90 ℃ at last, isothermal reaction 60 minutes.Cooling adds auxiliary agents such as defoamer, frostproofer, antimildew disinfectant, waterproofing agent of organosilicon, under being lower than 40 ℃ of conditions with in the ammoniacal liquor and after, move into storage tank, discharging, packing.
Embodiment 2, and is identical with the technology of embodiment 1, and raw material is formed basic identical, but following change is arranged:
Compositing formula unit: kilogram
Embodiment 3, and is identical with the technology of embodiment 1, and raw material is formed basic identical, but following change is arranged:
Compositing formula unit: kilogram
Embodiment 4, and is basic identical with above embodiment 1, but following change is arranged:
Organosilane monomer is used methacryloxypropyl triethoxy silica alkane instead, and consumption is 10% of a monomer total amount;
Hard monomer is selected methyl methacrylate for use, and consumption is 45% of a monomer total amount;
Soft monomer is selected ethyl propenoate for use, and consumption is 40% of a monomer total amount;
Function monomer is selected vinylformic acid for use, and consumption is 5% of a monomer total amount.
Active emulsifier is selected sodium vinyl sulfonate for use;
Anionic emulsifier is selected sodium lauryl sulphate for use;
Nonionic emulsifying agent is selected Nonyl pheno base ether (the ethene radix is 40) for use.
Embodiment 5, and is basic identical with above embodiment 1, but following change is arranged:
Organosilane monomer is selected organosilicon preformed polymer B for use, and consumption is 20% of a monomer total amount;
Hard monomer is selected n-BMA for use, and consumption is 30% of a monomer total amount;
Soft monomer is selected methyl acrylate for use, and consumption is 40% of a monomer total amount;
Described function monomer is selected methacrylic acid and Hydroxyethyl acrylate for use, and consumption is respectively 5% and 5% of monomer total amount.
Active emulsifier is selected acrylamide stearic acid sodium salt for use;
Anionic emulsifier is selected Sodium dodecylbenzene sulfonate for use.
Embodiment 6, and is basic identical with above embodiment 1, but following change is arranged:
Organosilane monomer is selected organosilicon preformed polymer B for use, and consumption is 20% of a monomer total amount;
Hard monomer is selected methyl methacrylate and vinylbenzene for use, and consumption is respectively 35% and 5% of monomer total amount;
Soft monomer is selected butyl acrylate for use, and consumption is 30% of a monomer total amount;
Function monomer is selected vinyl cyanide for use, and consumption is 10% of a monomer total amount.
Active emulsifier is selected alkyl vinylformic acid-2-ethanesulfonic acid sodium salt for use;
Anionic emulsifier is selected disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate for use.
Embodiment 7, and is basic identical with above embodiment 1, but following change is arranged:
Organosilane monomer is selected tetraethoxy for use, and consumption is 20% of a monomer total amount;
Hard monomer is selected methyl methacrylate for use, and consumption is 20% of a monomer total amount;
Soft monomer is selected Isooctyl acrylate monomer, 2-EHA for use, and consumption is 50% of a monomer total amount;
Function monomer is selected Propylene glycol monoacrylate for use, and consumption is 10% of a monomer total amount.
Anionic emulsifier is selected Nonyl pheno base (4) ether ammonium sulfate for use.
Embodiment 8, and is basic identical with above embodiment 1, but following change is arranged:
The unsaturated organosilicon monomer is selected the vinyl triethoxyl siloxanes for use, and consumption is 10% of a monomer total amount;
Hard monomer is selected methyl methacrylate for use, and consumption is 35% of a monomer total amount;
Soft monomer is selected ethyl propenoate for use, and consumption is 50% of a monomer total amount;
Function monomer is selected acrylamide for use, and consumption is 5% of a monomer total amount.
Embodiment 9, and is basic identical with above embodiment 1, but following change is arranged:
The unsaturated organosilicon monomer is selected vinyl three isopropoxy siloxanes for use, and consumption is 5% of a monomer total amount;
Hard monomer is selected methyl methacrylate for use, and consumption is 50% of a monomer total amount;
Soft monomer is selected 2-EHA for use, and consumption is 40% of a monomer total amount;
Function monomer is selected N-methylol acrylic acid amides for use, and consumption is 5% of a monomer total amount.
Embodiment 10, and is basic identical with above embodiment 1, but following change is arranged:
The unsaturated organosilicon monomer is selected the vinyl trimethoxy siloxanes for use, and consumption is 5% of a monomer total amount;
Function monomer is selected hydroxyethyl methylacrylate for use, and consumption is 5% of a monomer total amount.
Embodiment 11, and is basic identical with above embodiment 1, but following change is arranged:
Organosilane monomer is selected octamethylcyclotetrasiloxane for use, and consumption is 20% of a monomer total amount;
Function monomer is selected Rocryl 410 for use, and consumption is 5% of a monomer total amount.
Embodiment 12, and present embodiment is applicable to the preparation exterior coating, and its prescription is as follows with technology:
If need to change, can adjust the consumption of raw material 11,15 and 16 in right amount.Coating (sample) store 2 years not stratified, do not sink to the bottom, free from extraneous odour, in addition after 50 ± 1 place one month, shelf-stable.</entry></row></tbody></tgroup></table></tables>
Blending process
1. under 500-800 rev/min rotating speed, add earlier raw material 1-13 successively;
2. raise rotating speed to 2000-2100 rev/min, high speed dispersion 15 minutes;
3. add raw material 14,2000-2100 rev/min of high speed dispersion 10 minutes;
4. downward modulation rotating speed to 500 rev/min adds raw material 15,16,17,19 successively;
5. after being uniformly dispersed, look its viscosity size, add an amount of raw material 18, transferring it is suitable viscosity number;
6. the back discharging is uniformly dispersed.
The exterior coating of preparing is pressed the GB9755-2001 national standard and is detected,
Leading indicator is: artificial ageing resistance performance, 0 grade of efflorescence in 3000 hours, 1 grade of variable color; Resistance to soiling,＜5%; Scrub resistance,＞20000 times.
Claims (4)
1, a kind of organosilicon modified acrylate emulsion for ambient temperature crosslinked aqueous paint is characterized in that, this emulsion is obtained by following method:
Elder generation's synthesizing organo-silicon prepolymer after reacting with tetraethoxy then, adopts sol-gel technique to synthesize the Nano particles of silicon dioxide of surface modification; Be nuclear then to adopt seeded emulsion polymerization technology to obtain seed emulsion, coating the Nano particles of silicon dioxide of organosilicon preformed polymer and by unsaturated organosilicon monomer, hard monomer, soft monomer with above-mentioned surface, and the mixture that function monomer is formed is a shell, nucleocapsid interpenetrating polymer networks polyreaction through 3-5 hour obtains inorganic nano particle modified organosilicon crylic acid latex at last;
Concrete steps are:
(1), organosilicon preformed polymer is synthetic: Virahol and potassium hydroxide react, and add octamethylcyclotetrasiloxane again and carry out ring-opening polymerization, obtain organosilicon preformed polymer A, and is standby;
(2), the preparation of Nano particles of silicon dioxide: in tetraethoxy, drip deionized water and Glacial acetic acid, temperature reaction, add organosilicon preformed polymer A then, obtain the Nano particles of silicon dioxide that the surface is coating organosilicon preformed polymer after the temperature reaction, be called organosilicon preformed polymer B;
(3), the preparation of seed emulsion: after deionized water, emulsifying agent, pH regulator agent, initiator emulsification, add acrylate mixing monomer and organosilicon preformed polymer B and carry out emulsification, be warming up to 70-75 ℃, system is cooled to about 75 ℃ when being warming up to 80-85 ℃ rapidly, constant temperature 30 minutes obtains seed emulsion;
(4), organosilicon-modified acrylate emulsion is synthetic:
Soft monomer, hard monomer and function monomer and organosilicon preformed polymer B were splashed in the reactor at 3-5 hour, regularly add initiator, emulsifying agent and pH regulator agent simultaneously in batches, be warming up to 80 ℃, add the butyl acrylate that is dissolved with benzoyl peroxide, continue reaction, last system temperature rises to 90 ℃, constant temperature 60 minutes, cooling adds auxiliary agents such as defoamer, frostproofer, antimildew disinfectant, waterproofing agent of organosilicon, after being lower than under 40 ℃ of conditions neutralization, discharging.
2, the preparation method of the described organosilicon modified acrylate emulsion for ambient temperature crosslinked aqueous paint of a kind of claim 1 may further comprise the steps:
(1), organosilicon preformed polymer is synthetic: Virahol and potassium hydroxide react, and add octamethylcyclotetrasiloxane again and carry out ring-opening polymerization, obtain organosilicon preformed polymer A, and is standby;
(2), the preparation of Nano particles of silicon dioxide: in tetraethoxy, drip deionized water and Glacial acetic acid, temperature reaction, add organosilicon preformed polymer A then, obtain the Nano particles of silicon dioxide that the surface is coating organosilicon preformed polymer after the temperature reaction, be called organosilicon preformed polymer B;
(3), the preparation of seed emulsion: after deionized water, emulsifying agent, pH regulator agent, initiator emulsification, add acrylate mixing monomer and organosilicon preformed polymer B and carry out emulsification, be warming up to 70-75 ℃, system is cooled to about 75 ℃ when being warming up to 80-85 ℃ rapidly, constant temperature 30 minutes obtains seed emulsion;
(4), organosilicon crylic acid latex is synthetic:
Soft monomer, hard monomer and function monomer and organosilicon preformed polymer B were splashed in the reactor at 3-5 hour, regularly add initiator, emulsifying agent and pH regulator agent simultaneously in batches, be warming up to 80 ℃, add the butyl acrylate that is dissolved with benzoyl peroxide, continue reaction, last system temperature rises to 90 ℃, constant temperature 60 minutes, cooling adds defoamer, frostproofer, antimildew disinfectant, organic silicon water-proofing agent aid, after being lower than under 40 ℃ of conditions neutralization, discharging;
Unsaturated organosilicon monomer consumption wherein is the 5-20% of monomer total amount;
Described hard monomer consumption is the 20-40% of monomer total amount;
Described soft monomer consumption is the 30-50% of monomer total amount;
Described function monomer consumption is the 5-10% of monomer total amount.
According to the preparation method of the described organosilicon modified acrylate emulsion for ambient temperature crosslinked aqueous paint of claim 2, it is characterized in that 3, concrete steps are:
(1), organosilicon preformed polymer is synthetic:
Virahol and potassium hydroxide are under refluxad reacted, boil off excessive Virahol.Add octamethylcyclotetrasiloxane again, carry out ring-opening polymerization under 100-120 ℃, cooling adds Glacial acetic acid, stirs, and vacuumizes, and removes the small molecules thing, filters, and removes Potassium ethanoate, obtains organosilicon preformed polymer A, and is standby;
(2), the preparation of Nano particles of silicon dioxide:
In reactor, add tetraethoxy, drip deionized water and Glacial acetic acid, temperature reaction, take out residual water and Glacial acetic acid and small amount of ethanol with water pump then, add organosilicon preformed polymer A, slowly after the temperature reaction, vacuumize, cooling obtains the Nano particles of silicon dioxide that the surface is coating organosilicon preformed polymer, is called organosilicon preformed polymer B;
(3), the preparation of seed emulsion:
After dissolving in deionized water, emulsifying agent, pH regulator agent, the initiator adding emulsification still, powerful emulsification, slowly add acrylate mixing monomer and organosilicon preformed polymer B, carry out emulsify at a high speed, move in the reactor, begin to be warming up to 70-75 ℃, this moment, system was warming up to 80-85 ℃ rapidly, take combination of inner and outside cooling means, temperature is reduced to about 75 ℃, and constant temperature 30 minutes obtains outward appearance and is blue seed emulsion;
(4), the synthetic of organosilicon crylic acid latex splashed into remaining soft monomer, hard monomer and function monomer and organosilicon preformed polymer B in the reactor at 3-5 hour, regularly add initiator, emulsifying agent and pH regulator agent solution simultaneously in batches, after dripping off, be warming up to 80 ℃, add the butyl acrylate that is dissolved with benzoyl peroxide, continue reaction, last system temperature rises to 90 ℃, constant temperature 60 minutes, cooling adds defoamer, frostproofer, antimildew disinfectant, organic silicon water-proofing agent aid, is being lower than under 40 ℃ of conditions after the neutralization, discharging, packing.
4, according to the preparation method of claim 2 or 3 described organosilicon modified acrylate emulsion for ambient temperature crosslinked aqueous paint, it is characterized in that,
Described organosilane monomer is selected from: unsaturated organosilicon monomer, octamethylcyclotetrasiloxane, organosilicon preformed polymer and tetraethoxy;
Unsaturated organosilicon monomer wherein is selected from: vinyl triethoxyl siloxanes, vinyl trimethoxy siloxanes, vinyl three isopropoxy siloxanes, methacrylic triethoxy silica alkane;
Described hard monomer is selected from: methyl methacrylate, n-BMA, vinylbenzene;
Described soft monomer is selected from methyl acrylate, ethyl propenoate, butyl acrylate, Isooctyl acrylate monomer, 2-EHA;
Described function monomer is selected from: vinylformic acid, methacrylic acid, vinyl cyanide, acrylamide, N-methylol acrylic acid amides, Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate or Rocryl 410.
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