CN102604006A - Preparation method for acidic silica sol in-situ modified acrylate emulsion - Google Patents
Preparation method for acidic silica sol in-situ modified acrylate emulsion Download PDFInfo
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Abstract
A preparation method for acidic silica sol in-situ modified acrylate emulsion includes the steps: firstly, diluting acidic silica sol with deionized water prior to adding small molecular alcohol, and then adding organo-siloxane with mixing to obtain modified acidic silica sol; then, utilizing the modified acidic silica sol, emulsifier, nuclear-layer monomers, deionized water and sodium bicarbonate to prepare seed pre-emulsion by means of pre-emulsification, adding the seed pre-emulsion into a reactor, heating up and adding initiator to initiate polymerization so that seed emulsion is prepared; and finally, adding emulsifier, shell monomers, initiator and deionized water into the reactor to prepare pre-emulsion by means of pre-emulsification, adding the pre-emulsion into the seed emulsion, replenishing initiator to hold, filtering after cooling to the normal temperature, and adjusting a pH (potential of hydrogen) value so that the modified acrylate emulsion is prepared. By the aid of the method, secondary dispersion of nano silica is avoided, stability of the emulsion is enhanced, and hardness, resistance to ultraviolet ageing and resistance to high temperature of an emulsion coating film are enhanced.
Description
Technical field
The present invention relates to kind of the method for the in-situ modified acrylic ester emulsion of acidic silicasol, especially a kind of with the preparing acrylate emulsion method of nano silicon through original position/seeded emulsion polymerization technology synthetic water-based thermally cross-linkable.
Background technology
Traditional physical blending is that nano silicon is directly carried out dispersing and mixing and one type of matrix material obtaining in emulsion; Because organic phase is relatively poor with inorganic consistency mutually; So nano-silicon dioxide particle is difficult to obtain homodisperse in organism, also exist problem such as interface affinity difference and package stability difference between propenoate and nano material particle.Technology afterwards has good consistency in order to make silicon-dioxide and vinyl resin, earlier nano silicon is carried out surface-treated usually, generally is to utilize the esterification of its hydroxy functional group or condensation reaction to carry out.For example a kind of silicon sol and acrylate composite emulsion; It is characterized in that being dispersed with in the composite emulsion the inorganic phase of nano silicon; Wherein nano silicon account for the acrylate monomer quality ratio at 0.1%-5%; And used nano silicon is through surface-treated; Nano-silicon dioxide modified used organosilicon content has also produced very big influence to the stability and the physical strength of emulsion, and seeing publication number for details is CN1654533 " nano silicon dioxide/acrylate composite emulsion and preparation method thereof ".Publication number be CN102030873A's " a kind of preparation method of nano silicon/poly acrylate composite emulsion "; Introduced the method for modifying of nano silicon in detail; Mainly be that tetraethoxy is used emulsifying agent, silane coupling agent and monomer at ambient temperature; Reaction obtained in 8-24 hour in the acidic aqueous solution of regulating with hydrochloric acid, but its method exists the problem of nano silicon " secondary agglomeration ", and what influence letex polymerization normally carries out the stability with emulsion.The many of usefulness is in-situ emulsion polymerization; For example publication number is " a kind of preparation method of room temperature self-crosslinking acrylic ester emulsion modified by inorganic nano particle " of CN 1908022; Set forth with tetraethoxy and in ethanol, prepared behind the nano silicon with organic-silicon-modified; Thereby and then it is dispersed in carries out in-situ emulsion polymerization in the acrylate monomer and make nano-silicon dioxide modified acrylic ester emulsion; Adopt the method for in-situ emulsion polymerization can make nano silicon homodisperse in polymkeric substance, improved the physical and mechanical property of polymkeric substance to a certain extent, but the modified technique of existing nano silicon is complicated; When the nano silicon of modification is used for polymerization also easily " secondary agglomeration ", thereby the stability of emulsion and normally carrying out of polymerization process have been influenced.Publication number be CN1654489's " preparation method of nano silicon dioxide-acrylate composite emulsion "; Set forth nano silicon and to have stirred in its verivate that is dispersed in benzene and with silane coupler modified; After the spinning, use acetone rinsing again, used organic solvent in the modifying process; Be unfavorable for environmental protection, operation is also complicated." a kind of preparation method of acrylic ester copolymer emulsion for pressure-sensitive adhesive " of patent CN101412783; Invented a kind of seed emulsion of only not having other polymerisable monomers with nano silicon, gradient adding shell monomers is carried out polymerization on this basis, has synthesized the silicon dioxide-acrylate copolymer emulsion; Can infer that silicon hydroxyl in the silicon-dioxide is that effect has taken place for reactive group carboxyl with the succinate sodium 2-ethylhexyl emulsifying agent; Make silicon-dioxide obtain modification, otherwise because the high-specific surface area of silicon-dioxide, silicon-dioxide is autohemagglutination highly; Polyreaction is difficult to carry out, to the requirement of emulsifying agent also than higher.
Summary of the invention
The technical problem that the present invention will solve is to use disperses homogeneous and the less acidic silicasol of particle diameter; Under simple technical flow; Mode with environmental protection is carried out graft modification to nano silicon; Utilize the method for original position/seeded emulsion polymerization to synthesize the propenoate strawberry type or the pomegranate type emulsion particle of clad nano silicon-dioxide; And in polymerization process, added the reactive monomer that can produce the heat cross-linking effect, purpose has provided the in-situ modified preparing acrylate emulsion method of a kind of acidic silicasol.
Provide the method for the in-situ modified acrylic ester emulsion of a kind of acidic silicasol based on above-mentioned purpose, follow these steps to during its method carry out:
(1) silica sol modified
Under 45～55 ℃, get 100 parts of acidic silicasols, after 0～80 part of deionized water dilution, add 5～25 parts of small molecular alcohols, add 1.0～1.5 parts of organo-siloxanes at last and stirred 3 hours, obtain modified silicasol;
(2) ACRYLIC EMULSION is synthetic
(1) the seeded emulsion polymerization stage: get 40～85 parts of modified silicasols, 2～4 parts of emulsifying agents, 16～24 parts of nuclear layer monomer, 30～65 parts of deionized waters and 0.8 part of sodium hydrogencarbonate in the above-mentioned steps (); Emulsification is 1 hour in advance, processes the seed pre-emulsion, then it is added reaction kettle; Be warming up to 70～75 ℃; Add 0.1～0.3 part of initiator initiated polymerization again, after reaction half a hour, be warming up to 80～85 ℃ and be incubated half a hour;
(2) the letex polymerization stage: 1～3 part of emulsifying agent, 60～80 parts of shell monomers, 0.4～0.6 part of initiator and 30～50 parts of deionized waters are added reaction kettle; Pre-emulsion was processed in emulsification in 1 hour in advance; In 3 hours, it is added in the seed emulsion, add 0.0004 part of initiator of total monomer amount and be incubated 1 hour, drop to normal temperature and filter discharging; Transfer PH to 8～9 at last, make modified acrylate emulsion.
In the above-mentioned technical scheme, described emulsifying agent is that CO-436 or CO-458:CO-897 or CO-630 are by portion rate 1
:1.5～1
:3.5 the composite use of ratio; Described nuclear layer monomer is Bing Xisuandingzhi and TEB 3K; Described shell monomers is that in TEB 3K, Bing Xisuandingzhi, vinylformic acid, methylacrylic acid, the Hydroxyethyl acrylate one or more mix by arbitrary proportion, wherein contains reactive group monomer Hydroxyethyl acrylate and accounts for 0.03～0.2 part of total monomer amount; Described organo-siloxane is γ-(methacryloxypropyl) propyl trimethoxy silicane: KH-570, γ-An Bingjisanyiyangjiguiwan: KH-550 and γ-glycidyl ether oxygen propyl trimethoxy silicane: one or more among the KH-560 are pressed arbitrary proportion and are mixed, and the organo-siloxane consumption accounts for 0.04～0.06 part of nano silicon solids content in the silicon sol; Described initiator is a kind of in ammonium persulfate, the Potassium Persulphate-sodium sulfite anhy 96, and consumption accounts for 0.003～0.012 part of total monomer quality; Described small molecular alcohol is one or more in ethanol, propyl alcohol and the terepthaloyl moietie; Described acidic silicasol, particle diameter are 10～20nm, and solid content is 25%～26%.
Advantage and positively effect that technique scheme of the present invention is brought are; Avoided " the secondary dispersion " of nano silicon; Being beneficial to the emulsion synthetic carries out smoothly; Improve the stability of emulsion, also improved hardness, water tolerance, oil-proofness, anti-ultraviolet aging ability and the resistance to elevated temperatures of emulsion film.
Embodiment
Specific embodiments of the invention is explained as follows:
The present invention has simplified in the prior art with tetraethoxy as starting raw material, the flow process of the organo-siloxane graft modification nano silicon through ultra-sonic dispersion, modification, purification, redispersion, and avoided pilot process to use the organic solvent except that small molecule alcohol; Environmental protection more as starting raw material, has been found out a kind of technology of the modified manometer silicon dioxide that is fit to this letex polymerization of excellence with silicon sol; At first disperse homogeneous, stable,, avoided described in the background technology owing to the secondary agglomeration that repeatedly disperses to produce through also being the characteristic of steady state after the modification by means of acidic silicasol; Further obtain modification and dispersion simultaneously with after monomer, the emulsifier mix, thereby guaranteed steadily carrying out of letex polymerization, secondly; Because the silicon sol particle diameter is very little, the nano silicon of modification is easy to get in the micella, through in-situ emulsion polymerization; Final pomegranate type or the strawberry type spheroidal colloidal particles that forms clad nano silicon-dioxide; Shell contains the monomeric adding of reactive group makes emulsion at high temperature be cross-linked to form reticulated structure, has improved water tolerance and hardness, suitable nucleocapsid monomer ratio; Make synthetic emulsion particle diameter narrowly distributing; And be in nano level, thereby guaranteed the transparent and high gloss of filming, proposed a kind of effective technology for solving acrylic ester emulsion hardness problem low, that wear no resistance.
The present invention focuses on the rigidity of effectively utilizing the inorganic nano silicon dioxide granule, the mode that hardness combines with the toughness of macromolecular material; Obtained the acrylic ester emulsion of satisfactory mechanical property through the chemically modified modification; The adding of nano silicon has not only improved the tensile strength and the elongation at break of filming; Strengthen wearability, stain resistance, water-resistant capacity, also improved the anti-ultraviolet aging ability.
Nano silicon in the silicon sol of the present invention at emulsifying stage, to the further modification in the surface of nano silicon, can carry out polymerization by emulsifying agent, monomer through after organosilicon grafted and modified smoothly.Method of modifying is more comparatively environmental protection; In the mixing solutions of the deionized water of certain volume and small molecular alcohol, add a certain amount of acidic silicasol (commercially available), add organo-siloxane and whip modified at a certain temperature again; Such method had both been simplified direct flow process with the tetraethyl silicate modified manometer silicon dioxide; Avoided dispersion once more again, thereby reduced the probability of nano silicon " secondary agglomeration ", improved technical process modified manometer silicon dioxide.
The reactive group of acrylic ester emulsion of the present invention is from the carboxyl of emulsion particle shell and hydroxyl; Heat cross-linking self takes place in emulsion particle on the one hand; On the other hand again can with aminoresin generation heat cross-linking; Form tridimensional network, further improve the water-oil resistance and the hardness of coating, and effectively reduced of the pollution of organism volatile matter environment.
Wherein, the stability of silicon sol depends on interaction and tensio-active agent, the acid of nanoparticle or the space steric effect that alkali provided, and therefore when the potential of hydrogen of colloidal sol and temperature change to some extent, can break original balance and cause gel or reunion.Show that through experiment acidic silicasol is more remarkable through effect after the modification of silane coupling agent; Because of the activity of silicon hydroxyl in the specific activity alkaline silica sol of silicon hydroxyl in its sour environment is eager to excel; Utilize the sour environment of acidic silicasol itself; Eliminate nano silicon during to its modification and changed the influence of reuniting owing to acid-basicity; And the silicon sol after the modification is electrically charged opposite with anionic emulsifier institute when carrying out preparatory emulsification, also can carry out the part coating modification to it through the electrostatic interaction partial emulsifier, thereby improve the lipophilic modification degree of nano silicon; Higher temperature can cause the fierceness collision between nano silicon, produces and reunites, and the reunion degree receives the influence of nano silicon percentage of grafting; The very few percentage of grafting of organosilyl consumption is less, and reunite along with the increase of organosilicon consumption more; The percentage of grafting on nano-silicon dioxide particle surface rises, and reunites certainly and reduces, and particle diameter reduces; Good stability continues to increase, and can cause again on the contrary reuniting and increase; Influence disperses, and the modification temperature of acidic silicasol is 45 ℃～55 ℃, and wherein the consumption of organo-siloxane is 0.04～0.06 part of nano silicon solids content in the acidic silicasol.
The used emulsion of the present invention is through in-situ emulsion polymerization nano silicon to be coated in the propenoate emulsion particle; Adding nano silicon can not only make the tensile strength and the elongation at break of filming be multiplied; And the adding of silicon sol utilizes its polyhydric characteristic; Strengthen wearability, stain resistance and water tolerance, also had good anti-ultraviolet aging ability.Carry out physical mixed in the acrylic ester emulsion and nano silicon directly added to as filler, disperse comparatively difficulty and mixed stability not good enough.Nano-silicon dioxide modified purpose is the hydrophilic silicon hydroxyl of nano-silica surface through carrying out grafting with other the compound esterification that contains lipophilic group, condensation or through electrostatic interaction; Make it become oleophilicity by wetting ability; Be easier to coated by emulsifying agent; The percentage of grafting of nano-silica surface hydroxyl is limited, and when with the hydroxyl after the organosilyl hydrolysis silicon hydroxyl of nano silicon being carried out graft modification, organosilyl addition can not be very few; Otherwise percentage of grafting is incomplete; In-situ emulsion polymerization reaction back gel fraction increases, and can produce autohemagglutination owing to the organosilyl existence that is imbued with at most and cross, and the steady qualitative and water tolerance of emulsion is reduced.
The used organo-siloxane of the present invention is: γ-(methacryloxypropyl) propyl trimethoxy silicane: KH-570, γ-An Bingjisanyiyangjiguiwan: KH-550 and γ-glycidyl ether oxygen propyl trimethoxy silicane: one or more among the KH-560 are pressed arbitrary proportion and are mixed.
The used small molecule alcohol of the present invention is: one or more in ethanol, propyl alcohol and the terepthaloyl moietie.
The used initiator efficiency of initiation of the present invention is relevant with initiator concentration, and initiator concentration is excessive, causes that rate of polymerization is too fast; Even implode, initiator concentration is too low, and rate of polymerization is too slow; Polymerization is incomplete; Transformation efficiency is low, also will feed nitrogen protection in the polymerization process, prevents that radical is by oxygen depletion.Said initiator is: a kind of in ammonium persulfate and the Potassium Persulphate-sodium sulfite anhy 96, consumption is 0.003～0.012 part of monomer total amount umber.
The used anionic emulsifier of the present invention makes the particle decentralized stabilization with electrostatic double layer and the effect that shields stabilization, and nonionic emulsifier then increases the stability of emulsion with the shielding stabilization; The advantage of anionic emulsifier and the composite use of nonionic emulsifying agent is: the sterically hindered effect of the charge stability of anionic emulsifier and nonionic emulsifying agent can produce coordinating effect; Improve the stability of emulsion particle; The present invention is negatively charged ion and the composite use of nonionic emulsifying agent in polymerization process; Like this in the stability and the water tolerance that guarantee can to significantly improve under the prerequisite of emulsifying effectiveness emulsion, said emulsifying agent is that CO-436 or CO-458:CO-897 or CO-630 are by portion rate 1
:1.5～1
:3.5 the composite use of ratio.
The in-situ modified preparing acrylate emulsion method of a kind of acidic silicasol of the present invention, this method follows these steps to carry out:
(1) silica sol modified
Under 45～55 ℃, at first get 100 parts of acidic silicasols, after 0～80 part of deionized water dilution, add 5～25 parts of small molecular alcohols then, add 1.0～1.5 parts of organo-siloxanes at last and stirred 3 hours, obtain modified silicasol;
(2) ACRYLIC EMULSION is synthetic
(1) the seeded emulsion polymerization stage: get 40～85 parts of modified silicasols, 2～4 parts of emulsifying agents, 16～24 parts of nuclear layer monomer, 30～65 parts of deionized waters and 0.8 part of sodium hydrogencarbonate in the above-mentioned steps (); Emulsification is 1 hour in advance, processes the seed pre-emulsion, then it is added reaction kettle; The temperature of reaction kettle is 70～75 ℃; Add 0.1～0.3 part of initiator initiated polymerization again, after reaction half a hour, be warming up to 80～85 ℃ and be incubated half a hour;
(2) the letex polymerization stage: 1～3 part of emulsifying agent, 60～80 parts of shell monomers, 0.4～0.6 part of initiator and 30～50 parts of deionized waters are added reaction kettle; Emulsification is 1 hour in advance, processes pre-emulsion, in 3 hours, it is added in the seed emulsion; Add 0.0004 part of initiator of total monomer amount and be incubated 1 hour; Drop to normal temperature and filter discharging, transfer PH to 8～9 at last, make modified acrylate emulsion.
Nuclear layer monomer of the present invention is Bing Xisuandingzhi, TEB 3K; Shell monomers is a TEB 3K; Bing Xisuandingzhi, vinylformic acid, methylacrylic acid; In the Hydroxyethyl acrylate one or more are pressed arbitrary proportion and are mixed, and wherein contain reactive group monomer Hydroxyethyl acrylate and account for 0.03～0.2 part of total monomer umber.
Below through embodiment further explain embodiment of the present invention:
Embodiment one
The in-situ modified preparing acrylate emulsion method of a kind of acidic silicasol that embodiment of the present invention provided, press step and carry out:
The first step, silica sol modified.In the reaction kettle of volume 50L, add deionized water 16 ㎏; Acidic silicasol 20 ㎏ of solid content 25% mix, and add then slowly to add 0.3 ㎏ KH-560 behind the 4 ㎏ ethanol mixings in reaction kettle; 50 ℃ of following stirring reactions 3 hours obtain the silicon sol of modification.
In second step, seed emulsion is synthetic.In the reaction kettle of volume 100L; 0.167 ㎏ anionic emulsifier CO-436 and 0.334 ㎏ nonionic emulsifying agent CO-897 are added in the 4.5 ㎏ deionized waters; Add 14 ㎏ modified silicasols again and stir 15min down at 30 ℃; Add 2.4 ㎏ TEB 3Ks (MMA), 0.8 ㎏ Bing Xisuandingzhi (BA) emulsification half a hour in advance then, regulate PH to 7～8, add 0.16 ㎏ NaHCO with ammoniacal liquor
3The damping fluid that is made into 2 ㎏ deionized waters; Continue emulsification half a hour, pre-emulsion is added in the 100 L reaction kettles, be warmed up to 75 ℃ under the nitrogen protection; In reaction kettle, add then and be dissolved in the aqueous solution that 1 ㎏ deionized water is made into 0.023 ㎏ ammonium persulphate; Reaction half a hour is warming up to 83 ℃ and be incubated half a hour, obtains seed emulsion.
In the 3rd step, emulsion is synthetic.With 6.3 ㎏ TEB 3Ks (MMA), 4.1 ㎏ Bing Xisuandingzhis (BA), 1.4 ㎏ Hydroxyethyl acrylates (HEA), 0.7 ㎏ methylacrylic acid (MAA): wherein methylacrylic acid transfers pH value to 7～8,0.082 ㎏ CO-436,0.164 ㎏ CO-897,0.1 ㎏ ammonium persulphate to add that preparatory emulsification obtained pre-emulsion in 1 hour in the 8 ㎏ deionized waters with 1 ㎏ deionized water dilution back with ammoniacal liquor or AMP-95 earlier; In 3 hours, add pre-emulsion in the above-mentioned seed emulsion; The seed emulsion temperature is 83 ℃, is warmed up to 85 ℃ of initiators of adding total monomer amount 0.00628 ㎏, is incubated one hour; The cold filtration discharging; Regulate pH value and be 8～9 and obtain emulsion, the viscosity of this emulsion is 14s, the blue light foot; Hardness of film is 4H, water-intake rate 3%.
Embodiment two
This embodiment compares with embodiment one; The consumption of emulsifying agent and initiator changes; The CO-436 in seeded emulsion polymerization stage and the consumption of CO-897 are respectively 0.16 ㎏ and 0.56 ㎏; The amount of initiator is 0.02 ㎏, and letex polymerization stage CO-436 and CO-897 consumption are respectively 0.12 ㎏ and 0.42 ㎏, and initiator is 0.072 ㎏.
Embodiment three
Silica sol modified method is different:
Silica sol modified 1.In the reaction kettle of volume 50L, add deionized water 0 ㎏; Acidic silicasol 20 ㎏ of solid content 25% mix, and add then slowly to add 0.3 ㎏ KH-550 behind the 4 ㎏ ethanol mixings in reaction kettle; 50 ℃ of following stirring reactions 3 hours obtain the silicon sol of modification.
Silica sol modified 2.In the reaction kettle of volume 50L, add deionized water 16 ㎏; Acidic silicasol 20 ㎏ of solid content 25% mix, and add then slowly to add 0.25 ㎏ KH-560 behind the 4 ㎏ ethanol mixings in reaction kettle; 50 ℃ of following stirring reactions 3 hours obtain the silicon sol of modification.
Silica sol modified 3.In the reaction kettle of volume 50L, add deionized water 16 ㎏; Acidic silicasol 20 ㎏ of solid content 25% mix, and add then slowly to add 0.3 ㎏ KH-560 behind the 5 ㎏ ethanol mixings in reaction kettle; 45 ℃ of following stirring reactions 3 hours obtain the silicon sol of modification.
Silica sol modified 4.In the reaction kettle of volume 50L, add deionized water 16 ㎏; Acidic silicasol 20 ㎏ of solid content 25% mix, and add then slowly to add 0.2 ㎏ KH-560 behind the 1 ㎏ ethanol mixing in reaction kettle; 55 ℃ of following stirring reactions 3 hours obtain the silicon sol of modification.
Silica sol modified 5.In the reaction kettle of volume 50L, add deionized water 16 ㎏; Acidic silicasol 20 ㎏ of solid content 25% mix, and add then slowly to add 0.2 ㎏ KH-570 behind the 3 ㎏ ethanol mixings in reaction kettle; 55 ℃ of following stirring reactions 3 hours obtain the silicon sol of modification.
All the other are with embodiment one.
Embodiment four
This embodiment compares with embodiment one, is to replace KH-560 that silicon sol is carried out modification with the organosilicon KH-570 of equivalent or A-171, KH-550, and all the other are with embodiment one; The synthetic emulsion viscosity is more than 35s; Solid content is lower, and gel fraction also increases, and filming of making is smooth basically.
Embodiment five
This embodiment compares with embodiment one, is to be the letex polymerization stage, and the consumption of Hydroxyethyl acrylate is risen to 3.4 ㎏, and all the other are with embodiment one, and gained emulsion gel rate increases, and water-intake rate is 4.5%.
Embodiment six
This embodiment compares with embodiment one, and the initiator that is adopted is Potassium Persulphate-sodium sulfite anhy 96 (1:1) redox initiator, and seeded emulsion polymerization stage consumption is 0.05 ㎏; Polymerization temperature is 70 ℃; Holding temperature is 75 ℃, and letex polymerization stage initiator amount is 0.18 ㎏, 80 ℃ of polymerization temperatures; Holding temperature is 83 ℃, and all the other are with embodiment one.
Embodiment seven
This embodiment compares with embodiment one, and its difference is to have substituted CO-897 and with CO-458 replaced C O-436, in the seeded emulsion polymerization stage with CO-630; The amount of CO-458 and CO-630 is respectively 0.144 ㎏ and 0.216 ㎏, and the quantitative change of initiator is 0.054 ㎏, the letex polymerization stage; The amount of CO-458 and CO-630 is respectively 0.072 ㎏ and 0.108 ㎏; The quantitative change of initiator is 0.108 ㎏, and all the other are with embodiment one, and the gel fraction of emulsion increases and Calcium ion stability descends.
Embodiment eight
This embodiment compares with embodiment one; The letex polymerization stage is only used TEB 3K (MMA) 6 ㎏, Bing Xisuandingzhi (BA) 4 ㎏, three kinds of monomers of Hydroxyethyl acrylate (HEA) 2.2 ㎏; All the other embodiment one, gained emulsion blue light foot, viscosity is with being coated with-4 glasss of 13s.
Embodiment nine
This embodiment compares with embodiment one, seeded emulsion polymerization in the stage addition of modified silicasol be reduced to 7.2 ㎏, and add 4.5 ㎏ deionized waters, the gained emulsion property slightly improves, all the other are with embodiment one.
Embodiment ten
This embodiment compares with embodiment one, and with vinylformic acid (AA) the replacement methylacrylic acid (MAA) of equivalent, all the other are with embodiment one, and the emulsion gel rate slightly rises.
Embodiment 11
This embodiment compares with embodiment one; Seeded emulsion polymerization stage MMA and BA consumption increase to 3.24 ㎏ and 1.05 ㎏ respectively; MMA in the letex polymerization stage and BA consumption increase to 6.66 ㎏ and 4.5 ㎏ respectively, and the HEA consumption increases to 1.8 ㎏, and the vinylformic acid consumption is constant; All the other are with embodiment one, and particle size of emulsion increases.
Embodiment 12
This embodiment compares with embodiment 11, and the consumption of HEA is reduced to 0.5 ㎏, and all the other are with embodiment 11, the oil-proofness of emulsion, water tolerance variation.
Claims (8)
1. the method for the in-situ modified acrylic ester emulsion of acidic silicasol, this method follows these steps to carry out:
(1) silica sol modified
Under 45～55 ℃, get 100 parts of acidic silicasols, after 0～80 part of deionized water dilution, add 5～25 parts of small molecular alcohols, add 1.0～1.5 parts of organo-siloxanes at last and stirred 3 hours, obtain modified silicasol;
(2) ACRYLIC EMULSION is synthetic
(1) the seeded emulsion polymerization stage: get 40～85 parts of modified silicasols, 2～4 parts of emulsifying agents, 16～24 parts of nuclear layer monomer, 30～65 parts of deionized waters and 0.8 part of sodium hydrogencarbonate in the above-mentioned steps (); Emulsification is 1 hour in advance, processes the seed pre-emulsion, then it is added reaction kettle; Be warming up to 70～75 ℃; Add 0.1～0.3 part of initiator initiated polymerization again, after reaction half a hour, be warming up to 80～85 ℃ and be incubated half a hour;
(2) the letex polymerization stage: 1～3 part of emulsifying agent, 60～80 parts of shell monomers, 0.4～0.6 part of initiator and 30～50 parts of deionized waters are added reaction kettle; Pre-emulsion was processed in emulsification in 1 hour in advance; In 3 hours, it is added in the seed emulsion, add 0.0004 part of initiator of total monomer amount and be incubated 1 hour, drop to normal temperature and filter discharging; Transfer PH to 8～9 at last, make modified acrylate emulsion.
2. the method for claim 1, its said emulsifying agent are that CO-436 or CO-458:CO-897 or CO-630 are by portion rate 1
:1.5～1
:3.5 the composite use of ratio.
3. the method for claim 1, its said nuclear layer monomer is Bing Xisuandingzhi and TEB 3K.
4. the method for claim 1; Its said shell monomers is that in TEB 3K, Bing Xisuandingzhi, vinylformic acid, methylacrylic acid, the Hydroxyethyl acrylate one or more mix by arbitrary proportion, wherein contains reactive group monomer Hydroxyethyl acrylate and accounts for 0.03～0.2 part of total monomer amount.
5. the method for claim 1; Its said organo-siloxane is γ-(methacryloxypropyl) propyl trimethoxy silicane: KH-570, γ-An Bingjisanyiyangjiguiwan: KH-550 and γ-glycidyl ether oxygen propyl trimethoxy silicane: one or more among the KH-560 are pressed arbitrary proportion and are mixed, and the organo-siloxane consumption accounts for 0.04～0.06 part of nano silicon solids content in the silicon sol.
6. the method for claim 1, its said initiator are a kind of in ammonium persulfate, the Potassium Persulphate-sodium sulfite anhy 96, and consumption accounts for 0.003～0.012 part of total monomer quality.
7. the method for claim 1, its said small molecular alcohol is one or more in ethanol, propyl alcohol and the terepthaloyl moietie.
8. the method for claim 1, its described acidic silicasol, particle diameter are 10～20nm, solid content is 25%～26%.
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| CN103395790A (en) * | 2013-08-01 | 2013-11-20 | 广州大学 | Preparation method of esterified nano-SiO2 hydroxyl acrylic ester organic dispersion liquid |
| CN104448117A (en) * | 2014-11-28 | 2015-03-25 | 江门四方威凯精细化工有限公司 | Water-based organic/inorganic hybrid acrylate emulsion and preparation method thereof |
| CN104558449A (en) * | 2014-12-30 | 2015-04-29 | 北京金汇利应用化工制品有限公司 | Preparation method of high-resistance organic and inorganic composite modified water-based acrylic resin |
| CN104774579A (en) * | 2015-04-24 | 2015-07-15 | 苏州市新广益电子有限公司 | High-temperature-resistant pressure-sensitive adhesive tape and heat-resistant pressure-sensitive adhesive used by same |
| CN105368150A (en) * | 2015-12-14 | 2016-03-02 | 佛山市高明绿色德化工有限公司 | Water-based weather-resistant glass printing ink |
| CN105585272A (en) * | 2015-10-22 | 2016-05-18 | 湖州绿色建材开发有限公司 | Novel concrete reinforcing agent |
| CN107501574A (en) * | 2017-08-31 | 2017-12-22 | 浙江佑谦特种材料有限公司 | A kind of UV curable water-bornes complex emulsions and its preparation method and application |
| CN108296416A (en) * | 2017-09-27 | 2018-07-20 | 柳州市柳晶科技股份有限公司 | A kind of preparation method of 3D printing precoated sand and precoated sand obtained |
| CN108587376A (en) * | 2018-04-18 | 2018-09-28 | 东莞理工学院 | A kind of stupid acrylic emulsion Ludox composite material and preparation method |
| CN109337493A (en) * | 2018-08-22 | 2019-02-15 | 浙江天姥建设发展有限公司 | A kind of Environment-friendlyinternal internal wall paint and preparation method thereof |
| CN111534149A (en) * | 2020-05-18 | 2020-08-14 | 厦门欧化实业有限公司 | High-adhesion ink and preparation method thereof |
| CN112094509A (en) * | 2020-09-24 | 2020-12-18 | 蚌埠学院 | Organic silicon modified high-stability acidic silica sol and preparation method thereof |
| CN112126301A (en) * | 2020-09-28 | 2020-12-25 | 三棵树(上海)新材料研究有限公司 | Organic-inorganic composite emulsion for coating and preparation method thereof |
| CN113248712A (en) * | 2021-05-14 | 2021-08-13 | 深圳市冠恒新材料科技有限公司 | Fluorosilicone monomer, fluorosilicone acrylate emulsion and preparation method of emulsion |
| CN115584197A (en) * | 2022-10-20 | 2023-01-10 | 东莞市精诚体育设施有限公司 | Outdoor green road color-changing water-based paint and preparation method thereof |
| CN118359778A (en) * | 2024-05-21 | 2024-07-19 | 广东励成科技有限公司 | Environment-friendly waterproof agent and preparation method thereof |
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| CN103395790B (en) * | 2013-08-01 | 2015-10-28 | 广州大学 | Esterification Nano-meter SiO_2 2the preparation method of hydroxy acrylate organic dispersions |
| CN103395790A (en) * | 2013-08-01 | 2013-11-20 | 广州大学 | Preparation method of esterified nano-SiO2 hydroxyl acrylic ester organic dispersion liquid |
| CN104448117A (en) * | 2014-11-28 | 2015-03-25 | 江门四方威凯精细化工有限公司 | Water-based organic/inorganic hybrid acrylate emulsion and preparation method thereof |
| CN104558449B (en) * | 2014-12-30 | 2019-02-19 | 北京金汇利应用化工制品有限公司 | A kind of preparation method of high patience organo-mineral complexing modified aqueous acrylic acid resin |
| CN104558449A (en) * | 2014-12-30 | 2015-04-29 | 北京金汇利应用化工制品有限公司 | Preparation method of high-resistance organic and inorganic composite modified water-based acrylic resin |
| CN104774579A (en) * | 2015-04-24 | 2015-07-15 | 苏州市新广益电子有限公司 | High-temperature-resistant pressure-sensitive adhesive tape and heat-resistant pressure-sensitive adhesive used by same |
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| CN105368150A (en) * | 2015-12-14 | 2016-03-02 | 佛山市高明绿色德化工有限公司 | Water-based weather-resistant glass printing ink |
| CN105368150B (en) * | 2015-12-14 | 2018-02-09 | 佛山市高明绿色德化工有限公司 | A kind of water-based weather-proof glass ink |
| CN107501574A (en) * | 2017-08-31 | 2017-12-22 | 浙江佑谦特种材料有限公司 | A kind of UV curable water-bornes complex emulsions and its preparation method and application |
| CN108296416B (en) * | 2017-09-27 | 2020-09-22 | 柳州市柳晶科技股份有限公司 | Preparation method of 3D printing precoated sand and prepared precoated sand |
| CN108296416A (en) * | 2017-09-27 | 2018-07-20 | 柳州市柳晶科技股份有限公司 | A kind of preparation method of 3D printing precoated sand and precoated sand obtained |
| CN108587376A (en) * | 2018-04-18 | 2018-09-28 | 东莞理工学院 | A kind of stupid acrylic emulsion Ludox composite material and preparation method |
| CN108587376B (en) * | 2018-04-18 | 2020-05-05 | 东莞理工学院 | Styrene-acrylic emulsion silica sol composite material and preparation method thereof |
| CN109337493A (en) * | 2018-08-22 | 2019-02-15 | 浙江天姥建设发展有限公司 | A kind of Environment-friendlyinternal internal wall paint and preparation method thereof |
| CN111534149A (en) * | 2020-05-18 | 2020-08-14 | 厦门欧化实业有限公司 | High-adhesion ink and preparation method thereof |
| CN111534149B (en) * | 2020-05-18 | 2022-06-03 | 厦门欧化实业有限公司 | High-adhesion ink and preparation method thereof |
| CN112094509A (en) * | 2020-09-24 | 2020-12-18 | 蚌埠学院 | Organic silicon modified high-stability acidic silica sol and preparation method thereof |
| CN112126301A (en) * | 2020-09-28 | 2020-12-25 | 三棵树(上海)新材料研究有限公司 | Organic-inorganic composite emulsion for coating and preparation method thereof |
| CN112126301B (en) * | 2020-09-28 | 2021-09-03 | 三棵树(上海)新材料研究有限公司 | Organic-inorganic composite emulsion for coating and preparation method thereof |
| CN113248712A (en) * | 2021-05-14 | 2021-08-13 | 深圳市冠恒新材料科技有限公司 | Fluorosilicone monomer, fluorosilicone acrylate emulsion and preparation method of emulsion |
| CN115584197A (en) * | 2022-10-20 | 2023-01-10 | 东莞市精诚体育设施有限公司 | Outdoor green road color-changing water-based paint and preparation method thereof |
| CN118359778A (en) * | 2024-05-21 | 2024-07-19 | 广东励成科技有限公司 | Environment-friendly waterproof agent and preparation method thereof |
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