CN102070730B - A kind of method of preparing emulsion with multivariate particle size distribution in situ - Google Patents
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Abstract
The present invention relates in a kind of letex polymerization and effectively control latex particle component, size and distribution, thus control the solid content of emulsion and the method for viscosity, it is during monomer dropping, in suitable temperature range, disposable to system injection compound emulsifying agent stage by stage, then monomer nucleation is again dripped, by the number of times of disposable injection compound emulsifying agent and concentration hierarchy of control latex particle size and distribution thereof, inject and just can form N+1 unit's size distribution emulsion wherein desirable natural number 2 being greater than 2 of N for N time, 3, 4 ... this method is that original position is prepared composite emulsion and realized the effective way of latex particle design, because its technique is simple, controlling efficiency is high, can be used as preparation of industrialization multimodel particle size distribution high solids content, the general method of low viscosity composite emulsion.
Description
Technical field
This programme belongs to patent of invention, relates to macromolecule emulsion, specifically a kind of method of preparing emulsion with multivariate particle size distribution in situ.
Background technology
The effective means realizing particle design is not only in the diversification distribution of particle diameter, is also prepare high solid content emulsion, the effective way of the special type latex goods such as composite emulsion.Compared with conventional emulsions, the distribution of multivariate particle size is to product emulsion glossiness, and emulsion film forming etc. all show obvious advantage.Especially, in particle design and modifying process, the same In-situ reaction crossing the latex particle of unlike material, significantly can improve material property.Therefore, the performance of its uniqueness of emulsion with multivariate particle size distribution causes the extensive concern of people.At coating, sizing agent, biological capsule and medicament slow release, the application aspect of Nano microsphere etc. is significant.
The existing method preparing emulsion with multivariate particle size distribution mainly contains: 1, the emulsion physical blending of different-grain diameter.Such as Chu [1], Greenwood [2,3], the people such as Berend [4] are by two kinds or three kinds of monodisperse polymer emulsion mixing, and then distillation or the method with differential pressure infiltration dewater, and finally obtain the emulsion of binary or ternary size distribution.But this method adopts the mode of physical blending completely, the problem of consistency have impact on the performance of final emulsion to a certain extent; 2, utilize mini-emulsion polymerization to prepare wide particle diameter distribution emulsion.Such as Leiza J.R [5], Arbina [6], K.Ouzineb [7] utilizes the mini-emulsion polymerization long nucleation period to be conducive to widening the feature of size distribution, has prepared the wide particle diameter distribution emulsion of solid content at 60wt%; 3, (as the people such as Liu Jianping [8,9], KennethL [10] passes through constantly extracting emulsion from reactor, and then the form of returning again in injecting reactor adds the distribution of system wide particle diameter constantly to return injecting reactor again from reactor extracting emulsion; 4 add a certain amount of small particle size seed emulsion by half-continuous process.Such as store up [11,12,13] such as Fu Xiang, SchneiderM. [14,15].Wherein store up the research paper [13] being entitled as " research 2 of high solids content polydispersion size distribution emulsion, the binary seed law prepares binary dispersion size distribution emulsion " that the people such as Fu Xiang delivered in " bonding " in 2000.They are by the method for injection two generation seed, realize the control to particle diameter and size distribution, namely first prepare seed emulsion I with the half-continuous process dripping continuously pre-emulsification monomer and initiator, when monomer dropping is to total monomer amount 60%, disposablely add seed emulsion II.Wherein I with II preparation method is identical, but the diameter of I is 130nm, and solid content is 24%; The diameter of II is 75nm, and solid content is 50%.By controlling the amount of small particle size seed emulsion II in certain limit adjustment size of particles and distribution of sizes.Subsequently, have studied the critical emulsifier concentration of secondary nucleation and critical area coverage, and utilize secondary nucleation and add the high solid content emulsion that seed latex obtains the distribution of ternary particle size dispersion.Wherein macroparticle is formed by increasing by seed emulsion I, and middle particle is formed by increasing by small particle size seed emulsion II; Small-particle is formed by secondary nucleation.Mainly through to small particle size seed emulsion II and the method injecting emulsifier simultaneously, control size of particles and particle distribution.
In addition, the people [16 ~ 18] such as Salima Boutti delivered three sections of articles continuously in 2005 and reports its method preparing the high solid content emulsion of binary size distribution on Polymer magazine.Ai Zhaoquan describes a kind of method preparing binary size distribution high-solid-content and low-viscosity acrylics copolymer emulsion respectively at 2004 publish thesis on " polymer journal " [19] again.Published thesis on " Journal ofApplied Polymer Science " magazine in 2007 again subsequently [20] describe a kind of method preparing high-solid-content and low-viscosity binary composite emulsion.Preparation method that AiZhaoquan introduces all adopts two-step approach to prepare, and first prepares Large stone seed (particle diameter is greater than 485nm), then carries out second time polymerization as medium.Compared with the present invention, the control of above-mentioned several method to emulsion system size and distribution thereof is obviously inadequate, it is to be noted, aforesaid method generally also can only reach binary size distribution emulsion, according to the literature, the preparation of current ternary size distribution emulsion or by physical blending, or small particle size seed emulsion is introduced in original system.Therefore, be that " algebraically " control is inadequate to the unit time of emulsion, from document, can not check the in-situ preparation method of the composite emulsion with ternary or the above size distribution of ternary especially.
Based on preparation method of the present invention, be there is by the method preparation generating multivariate particle size in position the polymer emulsion of N elementary particle, and its size and distribution are designed and controls, to improve space availability ratio when emulsion particle is piled up, not only can improve the overall high solids content of system, low viscous characteristic can also be kept.
By the emulsion modified effective way that the In-situ reaction of unlike material emulsion particle expands especially.Then can latex particle first time, size and distribution be designed and be controlled, carry out the design of latex particle chemical constitution
[1]Chu F，Guillot J.and Guyot A..Colloid Polym Sci，1998，276(4)：305-312.
[2]Greenwood R.，Luckham P.F.，Gregory T.J Colloids Interf Sci，1997，191(1：)11-21.
[3]Greenwood R.，Luckhamand P.F.，Gregory T..Colloid Surface A，1998，144(1)：139-147.
[4]Klaus Berend and Walter Richtering.Colloid Surface A，1995，99(2)：101-109.
[5]Leiza J.R，Sudol E.D，El-aasser M.S..J Appl Polym Sci，1997，64(9)：1797-1809.
[6]I.Aizpurua，J.I.Amalvy，J.C.de la Cal，M.J.Barandiaran.2001，42：1417-1427
[7]K.Ouzineb.C.Graillat，T.F.McKenna..J Appl Polym Sci，2005，97：745-752
[8] Liu Jianping, Sun Yanlin, Wang Hong, Zhao Xing. Kunming University of Science and Technology's journal (science and engineering version), 2007,5 (32): 5-8.
[9] Liu Jianping, Sun Yanlin, Wang Hong, Liu Lang, Zhao Xing. polymer material science and engineering, 2008,7 (24): 93-96.
[10]Kenneth L.Hoy，Roland H.Peterson.US Patent 4，130，523；1978-11.
[11]Fuxiang Chu，Guillot J，Guyot A..Polym Adv Technol，1998，9(12)：851-857.
[12]Fuxiang Chu，Christian Graillat，Alain Guyot.J Appl Polym Sci，1998，70(13)：2667-2677.
[13] Chu Fuxiang, Tang Chuanbing, Guyot A. is bonding, and 2000 (2): 1-9.
[14]Schneider M.，Graillat C.，Guyot A..J Appl Polym Sci，2002，84(10)：1935-1948.
[15]Schneider M，Claverie J，Guyot A，McKenna TF.J Appl PolymSci，2002，84(10)：1878-1896.
[16]Boutti S.，Graillat C.，McKenna T.F..Polymer，2005，4(46)：1189-1210.
[17]Boutti S.，Graillat C.，McKenna T.F..Polymer，2005，4(46)：1211-1222.
[18]Boutti S.，Graillat C.，McKenna T.F..Polymer，2005，4(46)：1211-1222.
[19] Ai Zhaoquan, Zhou Qilong, Zhang Hongtao, thanks long-living. polymer journal, 2005, (5): 754-759.
[20]Zhao-Quan Ai，Qi-Long Zhou et al..J Appl Polym Sci，2007，3(103)：1815-1825.
Summary of the invention
The present invention is in order to solve above institute produced problem, under the condition not introducing other emulsion seeds, adopt the way injecting after emulsifying agent constantly original position nucleation again, a latex particle generation generation is constantly grown (each designate is a unit time), the simple and effective effect playing control latex particle size and distribution.Namely during monomer dropping, in suitable temperature range, disposable (compound) emulsifying agent is injected to system, then drip monomer nucleation again, by the number of times of disposable injection (compound) emulsifying agent and concentration hierarchy of control latex particle size and distribution thereof.Just can generate a collection of new latex particle owing to often adding an emulsifying agent, and the emulsion particle subnumber that the amount injecting emulsifying agent each time generates more at most is more; Inject the number of times of emulsifying agent more, the unit of newly-generated latex particle is time more, inject just can be formed for N time the first size distribution emulsion of N+1 (wherein N can get natural number 1,2,3 ...).Because its technique is simple, controlling efficiency is high, can be used as the excellent process of preparation of industrialization emulsion with multivariate particle size distribution.
Now the object of the present invention (i.e. seed emulsion) mentioned in this claim 1 and 2 is described as follows:
Can be the commercial emulsion (being all called seed emulsion here) of emulsion or the purchase prepared, also can be the work in-process in emulsion preparation process, and namely this law also can be interted and to complete in conventional emulsion preparation process.But must ensure that in (seed) emulsion, in aqueous phase, residual emulsifying agents content is less than micelle-forming concentration (CMC).Because when residual emulsifying agents content in emulsion aqueous phase is more than or equal to micelle-forming concentration (CMC), many new micellas can be formed in aqueous phase, once have monomer to add also initiated polymerization will form many new latex particles.So residual emulsifying agents directly results in the uncontrollability of nucleation.Popular, after emulsion polymerisation process obtains general polymer emulsion routinely, as long as aqueous emulsifier phase concentration is less than its critical micell viscosity, for reaching this requirement, by great many of experiments experience, we sum up, and general requirement emulsifying agent total amount accounts for monomer total amount massfraction and is less than 2%.
Now " specific time (stage) " mentioned in claim 1 is described as follows:
Specific time (stage) essence refers to and to control by adding the size of amount of monomer to latex particle.Add the oversize or too short growth that all can affect emulsion particle of time of monomer, latex particle size controls by injecting the add-on of monomer before and after emulsifying agent.When after injection high-concentration-emulsifier, then add monomer, then monomer solubilising madam micella becomes nuclear reaction immediately, the latex particle of generation.Theoretical according to letex polymerization, the monomer newly added will be mainly used in the small-particle increasing new nucleation.The amount of monomer added after each injection emulsifying agent is more, then for long larger of the small-particle of new nucleation, show small-particle particle diameter and increase rapidly, and now large and small particle diameter ratio (dL/dS) reduces gradually.
As mentioned in claim 1 and 3, now how to make system again become nuclear reaction to the present invention, forming latex particle of new generation and do following explanation:
After add a certain amount of added emulsifier in system, part emulsifying agent is used for the stability of emulsion particle, excessive emulsifying agent is assembled in aqueous phase, after emulsifier concentration reaches micelle-forming concentration (CMC) value, the emulsifying agent added again just exists (obviously, the object of our disposable injection added emulsifier will cause the new micella of System forming exactly) with the form of new micella.Due to constantly adding of monomer following closely and initiator, theoretical according to Harkins letex polymerization Micellar nucleation, monomer can be initiated and immediately at micelle formation new emulsion particle.The number of times of nucleation is more again, then latex particle " generation " number grown is more, although the continuous formation of new particle from one generation to the next, old particle does not reduce.In other words, often add an emulsifying agent and just can generate a collection of new latex particle, and the latex particle that the amount injecting emulsifying agent each time generates more at most is more; Inject the number of times of emulsifying agent more, the unit of newly-generated latex particle is time more, inject just can be formed for N time the first size distribution of N+1 (wherein N can get 1,2,3 ... natural number).
The temperature range that reaction as mentioned in claim 1 and 4 is carried out does following explanation:
The selection of temperature of reaction: inject emulsifying agent temperature range and be advisable with 50 ~ 90 DEG C.Because in the process of letex polymerization, the generation of polyreaction and the selection of initiator have much relations.Heat decomposition type initiator, as persulphate, azo, is generally all decomposed into living radical and initiated polymerization at 50 ~ 80 DEG C.Be necessary to illustrate: comparatively speaking, high temperature contributes to the fast nucleation of latex particle, because the velocity of diffusion of monomer and free radical is all accelerated under hot environment.If select redox initiation system, because it can at lesser temps initiated polymerization, so low temperature also can complete.
Initiator as mentioned in claim 1 and 5 does following explanation:
The selection of initiator and feed postition: the initiator of emulsion system can be heat decomposition type or oxidation-reduction type, initiator also can inject with emulsifying agent or part.If initiator all adds with emulsifying agent, forming the moment of new micella, a large amount of initiators forms free radical rapidly, and trigger monomer is polymerized in micella.Form latex particle little in a large number.Compared to part injection mode, initiator is all disposable injects the new latex particle obtained with emulsifying agent, particle diameter is little, and number of particles is many.In addition, water miscible heat decomposition type initiator is as ammonium persulphate, and it can ionize out electronegative group in aqueous phase, and this free negative electricity group can increase emulsion particle surface charge, strengthens its electrostatic stabilization effect.So water miscible initiator system contributes to the stable of latex system.
Emulsifying agent as mentioned in claim 1 and 6 does following explanation:
The selection of emulsifying agent and proportioning: emulsifying agent can be single anionic emulsifier, or cloudy, nonionic emulsifying agent is in the mixed emulsifier of 10: 1 ~ 1: 10 ratios.Comparatively speaking, anionic emulsifier contributes to nucleation again.On the one hand, due to emulsifying agent ion live-wire, also can produce hydration to a certain degree simultaneously, between emulsion particle electrostatic repulsion and hydration layer sterically hindered dual function under, polymer emulsion can be made more stable; Ionic emulsifying agent is generally much smaller than nonionic ionic emulsifying agent molecular weight on the other hand, and nucleation probability is large, can generate more emulsion particle, and polymerization rate is large, and the polymericular weight obtained is high.And ionic and nonionic emulsifier compound use, two class emulsifier molecules are alternately adsorbed on emulsion particle on the surface, on the one hand owing to having widened the distance of emulsion particle on the surface between emulsifying agent ion; On the other hand due to the electrostatic shielding effect of nonionic emulsifier, increase the absorption fastness of emulsifying agent on emulsion particle with regard to the electrostatic tension greatly reduced on emulsion particle surface like this, polymer stabilisation thus can be made to improve.The synergistic effect of this emulsifying agent makes polymer emulsion have good stability.Therefore, in compound emulsifying agent, nonionic emulsifier is too much unsuitable, otherwise nucleation is difficult to occur or will experience could occur for a long time again
The polymerization single polymerization monomer that may relate to as mentioned in claim 1 and 7 does following explanation:
The selection of polymerization single polymerization monomer: in the process of nucleation again, the monomer added can be the monomer identical with latex particle before nucleation again and proportioning, also can be different monomer and proportioning thereof.The former can form the emulsion particle of polynary homogeneous, and namely no matter emulsion system presents time distribution of several unit, and except last generation is different with the size of next generation, the microtexture of emulsion particle is all the same.Latter shows that last generation is different with the not only size of next generation, and the material of emulsion particle and microtexture are also different (see diagram).So the latter can be widely used in and prepare In-situ reaction emulsion.Due to letex polymerization many employings radical polymerization, so monomer used can be one or more in following scope in preparation process of the present invention: 1, vinyl monomer, as vinylbenzene, ethene, vinyl acetate, vinylchlorid, vinylidene chloride, vinyl cyanide, acrylamide etc.; 2, conjugated diene monomer, as divinyl, isoprene, chloroprene etc.; 3, vinylformic acid and methacrylic monomers, as methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate, methyl methacrylate, butyl methacrylate etc.
Accompanying drawing explanation
As shown in Figure 1, represent ternary size distribution homogeneous emulsion latex particle Mathematical Model of heaped-up, accompanying drawing 2 represents ternary size distribution composite emulsion latex particle Mathematical Model of heaped-up, and accompanying drawing 3 represents quaternary size distribution composite emulsion latex particle Mathematical Model of heaped-up.Wherein Reference numeral " 1 " represents generation latex particle; Reference numeral " 2 " represent two generation latex particle; Reference numeral " 3 " represents three generations's latex particle; Reference numeral " 4 " represent four generation latex particle.Different color and lusters represent the latex particle of unlike material.
Embodiment
Illustrate typical products formula of the present invention below.
Formula one: the high solids content ternary size distribution butyronitrile emulsion making buildings waterproof.Product can be used as high solids content waterproof glue, and after emulsion gluing, rate of drying significantly improves, and greatly can shorten construction period, particularly the weather of low temperature and high relative humidity and indoor underground construction.High solids content waterproof glue can substitute organic solvent type or no-solvent type waterproof paint completely.Compared with traditional high solid content emulsion coating, it is high that this law products made thereby has solid content, and viscosity is low, the feature that rate of drying is fast.And convenient and quick construction, smear evenly, glossiness is good.
Product the key technical indexes:
(1) outward appearance: white emulsion (2) solid content, %:72% (3) viscosity, Pas:2 ~ 6
This formula used heat decomposition type initiator ammonium sulfate to make initiator, obtained vinyl cyanide, divinyl, acrylic acid copolymer emulsion 75 DEG C of initiator system polymerizations.Wherein vinyl cyanide is as hard monomer, and divinyl is as soft monomer, and vinylformic acid is function monomer, and sodium bicarbonate is buffer reagent regulation system pH value, forms copolymerization seed emulsion.Then as medium, under 80 DEG C of conditions, by disposable injection anionic emulsifier sodium lauryl sulphate, make system emulsifying agent aqueous phase reach below micelle-forming concentration and form a large amount of micella, the adding of acrylonitrile monemer following closely, initiated polymerization forms the emulsion particle of polyacrylonitrile immediately.Anionic emulsifier sodium lauryl sulphate is injected by second time, and acrylonitrile monemer, again form the emulsion particle of polyacrylonitrile.Prepared emulsion is the composite emulsion of ternary size distribution, generation latex particle (i.e. macroparticle) is acrylonitrile/butadiene/acrylic terpolymer, two generations latex particle (i.e. median size particle) were polyacrylonitrile, and three generations's latex particle (i.e. small-particle) is polyacrylonitrile.This method products obtained therefrom, the small-particle of polyacrylonitrile is filled in macroparticle space, and make emulsion have good gloss, after film forming, latex film has good physical strength and water resistance.
Formula two: the pressure-sensitive latex of high-solid-content and low-viscosity quaternary size distribution.Make solid content up to 72% by quaternary size distribution, viscosity is 100 ~ 300mPas emulsion products only.This product not only makes the rate of drying of gluing fast, improves production efficiency, energy consumption when also saving dry.Compared with the emulsion products of about 55% solid content, be often coated with 100g film, the amount of moisture that need evaporate minimizing reaches 55%.With same volume polymer phase ratio, in its conversion unit latex, also improve more than 30% in Physical productive efficiency simultaneously.
Product the key technical indexes:
(1) outward appearance: white latex (2) solid content, %:72% (3) viscosity, Pas:0.1 ~ 0.3
This formula used heat decomposition type initiator ammonium sulfate to make initiator, obtain ethyl propenoate, methyl acrylate, acrylate copolymer emulsion 75 DEG C of initiator system polymerizations, gather 20 oxygen Vinyl Ethers using anionic emulsifier sodium lauryl sulphate and nonionic emulsifier nonyl phenol composite as compound emulsifying agent.N hydroxymethyl acrylamide is protective colloid.Sodium bisulfite is as buffer reagent regulation system pH value.After reinforced complete reaction about 30min, the 78 DEG C of disposable injection sodium lauryl sulphate that heat up and nonyl phenol gather the aqueous solution of 20 oxygen Vinyl Ether compound emulsifying agents, fast drop ethyl propenoate and butyl acrylate mix monomer carry out nucleation again subsequently, generate new latex particle.Same mode, the 80 DEG C of second time that heat up are injected, and 82 DEG C of third times of heating up inject.Each injection all grows the new methyl acrylate of a new generation and ethyl acrylate copolymers emulsion particle.Finally be warmed up to 85 DEG C of complete slakings of polymerization, cooling discharging.Prepared emulsion is quaternary size distribution, generation particle is ethyl propenoate, methyl acrylate, acrylic copolymer, two generation particle be methyl acrylate and ethyl acrylate copolymer, three generations's particle is methyl acrylate and ethyl acrylate copolymer, four generation particle be methyl acrylate and ethyl acrylate copolymer.The i.e. emulsion of quaternary size distribution homogeneous.
Formula three: pack and decorate with five yuan of size distribution ethene-vinyl acetate copolymer emulsions.
Through our great many of experiments, when Aqueous Adhesives solid content reaches 65%, its bonding time of drying is suitable with organic solvent type sizing agent.Present method makes product viscosity decline to a great extent owing to adopting five yuan of particle diameter designs, and rheological is excellent, thus makes the solid content of the finished product substantially exceed 55 ~ 60% solid contents of current technology.
Product the key technical indexes:
(1) outward appearance: white latex (2) solid content, %:70% (3) viscosity, Pas:3 ~ 6
This this formula of filling a prescription used heat decomposition type initiator ammonium sulfate to make initiator, obtain ethene, acetate copolymer emulsion 75 DEG C of initiator system polymerizations, wherein gather ten oxygen Vinyl Ethers for composite emulsifying system with anionic emulsifier sodium lauryl sulphate and nonionic emulsifier nonyl phenol.Polyvinyl alcohol 1788 is protective colloid.Sodium bicarbonate is as buffer reagent regulation system pH value.Form seed emulsion.Then as medium, under 80 DEG C of conditions, by disposable injection anionic emulsifier sodium lauryl sulphate, make system emulsifying agent aqueous phase reach below micelle-forming concentration and form a large amount of micella, then vinylbenzene and butyl acrylate mix monomer is added, make system immediately secondary nucleation grow a new generation vinylbenzene and butyl acrylate emulsion copolymer grain, wherein water is for dissolving sodium lauryl sulphate and ammonium persulphate.Then as medium, under 82 DEG C of conditions, again by disposable injection anionic emulsifier sodium lauryl sulphate and vinylbenzene and butyl acrylate mix monomer, wherein ammonium persulphate is for supplementing initiator, makes system nucleation again.Same mode 83 DEG C third time injects, nucleation.84 DEG C are injected for the 4th time, and nucleation, each injection all grows the new vinylbenzene of a new generation and butyl acrylate emulsion copolymer grain.Finally be warmed up to 85 DEG C of slakings, cooling discharging.Finally, prepared emulsion is five yuan of size distribution, generation particle is ethene, acetate ethylene copolymer, two generation particle be vinylbenzene and butyl acrylate copolymer, three generations's particle is vinylbenzene and butyl acrylate copolymer, four generation particle be vinylbenzene and butyl acrylate copolymer, five generation particle be vinylbenzene and butyl acrylate copolymer.Latex particle size is certain proportion, and small-particle is packed into macroparticle gap, and closely, space availability ratio is high, presents five yuan of gradient emulsions in sized particles arrangement.Compared with equal conditions conventional emulsion, there is 70% solid content, the characteristic that viscosity is low.
Claims (8)
1. prepare the method being more than or equal to ternary size distribution emulsion for one kind, it is characterized in that residual emulsifying agents content is less than in the seed emulsion of micelle-forming concentration CMC in aqueous phase, in specific time phase, disposable to system injection emulsifying agent and initiator, temperature controls at 50-90 DEG C, drip monomer and initiator nucleation again subsequently, by the number of times of disposable injection emulsifying agent, emulsifier concentration and monomer add-on three come hierarchy of control latex particle size and distribution thereof, inject and just can form N+1 unit size distribution emulsion for N time.
2. preparation as claimed in claim 1 is more than or equal to the method for ternary size distribution emulsion, it is characterized in that injecting the object of emulsifying agent is that seed emulsion or single stage method are fed in raw material process emulsion system sometime, but must ensure that in emulsion, in aqueous phase, residual emulsifying agents content is less than micelle-forming concentration CMC.
3. preparation as claimed in claim 1 is more than or equal to the method for ternary size distribution emulsion, it is characterized in that the size required by target product sets with distribution i.e. unit time the interval time and the emulsifier concentration that inject emulsifying agent at every turn, often complete the dropping of an emulsifying agent and monomer thereafter, just generate a collection of new latex particle, and the latex particle that the amount injecting emulsifying agent each time generates more at most is more; The number of times injecting emulsifying agent is more, and the unit of newly-generated latex particle is secondary more, injects and just can form N+1 unit size distribution for N time.
4. preparation as claimed in claim 1 is more than or equal to the method for ternary size distribution emulsion, it is characterized in that injecting emulsifying agent temperature range with 50 ~ 90 DEG C.
5. preparation as claimed in claim 1 is more than or equal to the method for ternary size distribution emulsion, and it is characterized in that the initiator of emulsion system is heat decomposition type or oxidation-reduction type, initiator is with all or part of injection of emulsifying agent.
6. preparation as claimed in claim 1 is more than or equal to the method for ternary size distribution emulsion, it is characterized in that emulsifying agent is single anionic emulsifier, or cloudy, nonionic emulsifying agent is in the mixed emulsifier of 10: 1 ~ 1: 10 ratios.
7. preparation as claimed in claim 1 is more than or equal to the method for ternary size distribution emulsion, to it is characterized in that before and after latex particle two generation size controlled by the add-on injecting monomer before and after emulsifying agent, the amount of monomer is dripped the more after each injection emulsifying agent, each latex particle size then in this system increases larger, the monomer added is the monomer identical with latex particle before nucleation again and proportioning, or different monomer and proportioning thereof, namely the monomer of unlike material forms the new latex particle of unlike material.
8. preparation as claimed in claim 1 is more than or equal to the method for ternary size distribution emulsion, it is characterized in that monomer used in preparation process refers in vinylbenzene, ethene, vinyl acetate, vinylchlorid, vinylidene chloride, vinyl cyanide, acrylamide, divinyl, isoprene, chloroprene vinylformic acid, methacrylic acid, methyl acrylate, ethyl propenoate, butyl acrylate, ethyl acrylate, methyl methacrylate, butyl methacrylate one or more.
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| CN104277618A (en) * | 2014-09-04 | 2015-01-14 | 青阳县双龙涂料有限责任公司 | High-solid-content low-viscosity paint |
| CN108084329B (en) * | 2017-12-01 | 2020-12-22 | 华南协同创新研究院 | Vinegar-acrylic emulsion with high solid content and low viscosity and preparation method thereof |
| CN111117096B (en) * | 2020-01-03 | 2022-02-15 | 大连理工大学 | Method for preparing ABS (acrylonitrile-butadiene-styrene) toughened resin based on controllable double-particle-size-distribution latex by adopting emulsion grafting method |
| CN112521547B (en) * | 2020-12-16 | 2022-03-25 | 江苏富淼科技股份有限公司 | Inverse emulsion with double particle size distribution and preparation method and application thereof |
| CN114181336A (en) * | 2021-12-16 | 2022-03-15 | 安徽天辰化工股份有限公司 | Ultra-small particle size PVC seed and preparation method thereof |
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| US3383346A (en) * | 1965-04-07 | 1968-05-14 | Goodyear Tire & Rubber | Particle size control in seed technique emulsion polymerization using hydroxyl group-containing modifier |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3383346A (en) * | 1965-04-07 | 1968-05-14 | Goodyear Tire & Rubber | Particle size control in seed technique emulsion polymerization using hydroxyl group-containing modifier |
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| Title |
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| 高固含量低粘度P(MMA/BA/AA)乳液的制备及性能研究;艾照全等;《高分子学报》;20051031(第5期);第754-759页 * |
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