CN101121771A - Acryloxyalkoxysilicane modified acrylic acid ester polymerization emulsion and its preparation method and application - Google Patents
Acryloxyalkoxysilicane modified acrylic acid ester polymerization emulsion and its preparation method and application Download PDFInfo
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Abstract
The utility model discloses one or more than one Acryloyl alkoxy silane-modified acrylic emulsion with controllable latex particle form and the manufacturing method. The emulsion of the utility model is the emulsion gathering of the (meth) Acryloyl alkoxy silane and acrylic acid alkyl ester, without the use of methyl acrylate monomer of high volatility and toxicity, benzene ethylene and other types of unsaturated monomers comprising unsaturated acid. In use of the reactivity relationship in the Kinetics and through the control on the reaction raw materials, copolymer of various emulsion particle morphology can be achieved through the emulsion polymerization. The polymerization product generated by the method is of significantly-improved mechanical properties. The emulsion can be used in buffer coating, adhesives, sealants, gaskets, inks, and cleaning agents. The sealant manufactured by the latex is of good stability, and can be stored stably under the room temperature. The utility model can be widely used in the sealing, coating and bonding of automobile materials, building materials, and the daily products.
Description
Technical field
The present invention relates to the alkoxysilane-modified acrylate copolymer emulsion of one or more acryloxies, its preparation method and application thereof, Zhi Bei emulsion can be used for buffer coating, tackiness agent, seal gum, pad, printing ink and clean-out system thus.
Background technology
Acrylic ester emulsion has many outstanding advantages, as the photostabilization of excellence, and weathering resistance, resistance to acids and bases, erosion resistance and good oil-proofness.Simultaneously low in part because of its cost, this emulsion is widely used in fields such as automobile, building, electronic product.But because acrylic ester emulsion thermotolerance, winter hardiness, water-fast and solvent borne need to improve, still there is shortcoming in this emulsion.
Excellent properties such as silicone resin has submissive, high temperature resistant, low temperature resistant, weather-proof and ageing-resistant and surface energy is low is used for acrylic resin modified product and helps eliminating its inherent defect, significantly promotes its performance.The organic silicon modified propenoic ester copolymer emulsion has had a lot of achievements in research to deliver, method of modifying commonly used as: utilize polyphosphazene polymer silicone-modified (referring to Smith D., Macromolecules, 1992,25 (10): 2575), come modification (referring to Maeda K. with the copolymerization of wetting ability silica gel emulsifying agent, Paint Coating Bus., 1996,6:37) and organosilicon oligopolymer grafted and modified acrylic resin resin coating (referring to Wang Jian, Wang Chen, the Chinese patent application CN 1155635C of Chen Dequan, Granted publication day is on June 30th, 2004) etc.
In recent years, with the unsaturated silane monomer carry out modification also have successively report (referring to DwightW., Macromolecules, 1988,21 (9): 2689; Robert N T., U.S3575910,1971).Can improve the tensile strength of filming with the alkoxysilane-modified acrylic ester emulsion of acryloxy, wear resistance, solvent resistance and water tolerance etc., but existing technology or complex process (as needs seeding polymerization or radiation-initiated polymerization: referring to: Sima Wenlong, Song Lei, the Anhui chemical industry, Vol.136,2005 (4), 23), can reach comparatively satisfied effect in the time of perhaps must mixing other types unsaturated monomer (comprising the methacrylate monomer that volatility height and toxicity are big) and use quite a large amount of silane monomers (referring to " research of γ-methacryloxypropyl trimethoxy silane modified acrylate emulsion ", Gong Xingyu, Fan Xiaodong, polymer material science and engineering, Vol.19, No.1, Jan.2003:62; Gui Qiang, etc., chemical building material, the fourth phase, 2004 (10): 8; And Wang Jian, Wang Chen, the Chinese patent application CN1155635C of Chen Dequan and CN1130437C are respectively on June 30th, 2004 and on December 10th, 2003 Granted publication day).Along with now more and more higher to environment protection and the requirement that reduces cost, so the simple water-borne coatings of development technology or sealing agent have become various countries researchist's target.But because the existence of water is arranged in the emulsion reaction, the alkoxyl group hydrolysis-condensation reaction can take place (referring to " structural form of the copolymerized emulsion of organic silicon acrylic ester and performance ", polymer material science and engineering, Gong Xingyu, Vol.20, NO.2,2004.3), the instability of emulsion and the decline of transformation efficiency are that the problem of outwardness is (referring to " research of organosilicon acrylic ester copolymerization thing emulsion property ", Li Wei, Chen Liqiong, colloid and polymkeric substance, Vol 22, NO.3,2004.9).
Summary of the invention
The inventor obtains emulsion particle form acrylate copolymer emulsion controlled, stable, that the acryloxy organoalkoxysilane is monomer modified by a kind of method and overcomes the problems referred to above, and does not need to adopt the other types unsaturated monomer of the methacrylate monomer, vinylbenzene and the unsaturated acid that comprise that volatility height and toxicity are big.
The present invention also provides a kind of specific alkoxysilane-modified acrylate copolymer emulsion of new acryloxy, it is different from the alkoxysilane-modified acrylate copolymer emulsion of acryloxy that present being suitable for forms top coat, and it is specially adapted to buffer coating (non-top coat), tackiness agent, seal gum, pad, printing ink and clean-out system.
Acrylic ester emulsion of the present invention is a kind of alkoxysilane-modified acrylate copolymer emulsion of acryloxy with nucleocapsid clad structure.With respect to bigger organosilicon molecule and other unsaturated organosilicon monomers, acryloxy organoalkoxysilane reactive behavior is big, phase interface tension force in polymerization process is little, and and acrylate monomer has suitable reactivity ratio (referring to E.Bourgeat-Lami, I.Tissot, and F.Lefebvre, Macromolecules, 2002,35:6185-6191).Acryloxy organoalkoxysilane monomer neither influences speed of response like this, again can be effectively and acrylate monomer generation copolymerization, thus improve the weather resistance of emulsion significantly.In addition, the variation by addition sequence can make the form of emulsion particle form clad structure, even the multilayer clad structure.
But the group in the acryloxy organoalkoxysilane (Si-O-R) can produce hydrolysis and exist with the form of Si-OH in aqueous environment.And thereby Si-OH can react each other and forms Si-O-Si and form crosslinked.And in the monomeric letex polymerization with identity function group (acryloyl-oxy base class), the molar weight of silane is less relatively, with respect to the system that has big water gaging, because Si-OH content is few relatively, showing more is wetting ability, hydrolysis reaction can reach a kind of balance with polyreaction, (osmanthus is strong, etc., chemical building material and can not be cross-linked to form gel in advance, the fourth phase, 2004; With Silane Coupling Agent Chemistry, BarryArkles, Petrarch System Inc., Silicon Compounds Register andReview, 2nd edition, Page 54).
The invention provides a kind of novel alkoxysilane-modified acrylate copolymer emulsion of acryloxy, shown in the following general formula of the structure of wherein said multipolymer (I):
Wherein: R is selected from the alkyl of C1-C16, the aryl of C6-C20, the aralkyl of C7-C20 and the alkaryl of C7-C20, R
1Be hydrogen atom or methyl, R
2, R
3Be selected from the alkyl of C1-C16, the aralkyl of C7-C20 and the alkaryl of C7-C20 separately, wherein n is the integer of 1-10, and y is the integer of 0-2, and p, q respectively are 1-1000.
The present invention uses (methyl) acryloxy organoalkoxysilane as modified monomer (hereinafter referred to as monomers B), shown in the following general formula of its structure (II):
Wherein: R
1Be hydrogen atom or methyl, R
2, R
3Respectively be selected from the alkyl of C1-C16, the aralkyl of C7-C20 and the alkaryl of C7-C20, wherein n is the integer of 1-10, and y is the integer of 0-2.
In the present invention, the raw material monomer that adopts in the preparation emulsion is composed of the following components basically:
Monomer A.Vinylformic acid hydrocarbyl carbonate monomer, preferred vinylformic acid C1-C14 hydrocarbyl carbonate, more preferably vinylformic acid C1-C10 hydrocarbyl carbonate, wherein said alkyl is preferably alkyl.
The limiting examples of monomer A has: methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, vinyl acrylate, ethyl acrylate, Hydroxyethyl acrylate, vinylformic acid-2-ethylamino ester and combination thereof.Its consumption is preferably the 13.5-59.9 weight % that accounts for the emulsion total amount; And preferably account for the 90.0-99.9 weight % of total overall reaction monomer (A+B) total amount, wherein 93.0-99.9 weight % more preferably is preferably 95.0-99.9 weight % again.
Monomers B.(methyl) acryloxy organoalkoxysilane of general formula (II) includes but not limited to: γ-acryloxy propyl trimethoxy silicane, γ-acryloxy propyl group methyl dimethoxysilane, γ-acryloxy propyl-triethoxysilicane, γ-acryloxy propyl group methyldiethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl triethoxyl silane, γ-methacryloxypropyl methyldiethoxysilane, α-acryloxy methylene tri methoxy silane, α-acryloyl-oxy methylene methyl dimethoxysilane, α-acryloxy methylene tri Ethoxysilane, α-acryloyl-oxy methylene methyldiethoxysilane, Alpha-Methyl acryloxy methylene tri methoxy silane, Alpha-Methyl acryloyl-oxy methylene methyl dimethoxysilane, Alpha-Methyl acryloxy methylene tri Ethoxysilane, Alpha-Methyl acryloyl-oxy methylene methyldiethoxysilane, γ-methacryloxypropyl three (beta-methoxy-oxyethyl group) silane, and combination.
The content of monomers B is preferably the 0.1-6 weight % that accounts for the emulsion total amount; And preferably account for the 0.1-10 weight % of total overall reaction monomer (A and B), more preferably content is 0.1-7 weight %, and preferred content is 0.1-5 weight % again.
Further preferably, the total content of above-mentioned total overall reaction monomer (A and B) is the 15-60 weight % of emulsion total amount.
Also adopt following functional reagent in the letex polymerization of the present invention.
C. emulsifying agent: the present invention can adopt the conventional emulsifier in the acrylic ester emulsion polymerization.But the emulsifying agent that the present invention preferably uses is anion surfactant, the perhaps compound emulsifying agent of anion surfactant and nonionogenic tenside, and the HLB value all is preferably 8-40.The emulsifying agent consumption is preferably the 0.15-6.0 weight % of emulsion total amount, and preferably accounts for the 1-10 weight % of total overall reaction monomer (A+B).For example: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, alkyl aryl ether sulfate, amber sulfonate, polyoxyethylene nonylphenol ether, fatty alcohol-polyoxyethylene ether, and composition thereof etc.
D. water: the water yield described in the emulsion of the present invention is the 38-83 weight % of emulsion total amount.Preferred emulsion of the present invention is the emulsion of oil-in-water-type.
E. chain-transfer agent: the present invention can adopt the conventional chain-transfer agent in the acrylic ester emulsion polymerization to regulate the molecular weight of emulsion polymerization.Chain-transfer agent preferably just adds when polymerization begins.The present invention preferably adopts the alkyl sulfhydryl of C1-C14, as mercaptoalcohol, 2-mercaprol, butanethiol, lauryl mercaptan etc., perhaps hydrosulphonyl silane.Consumption is preferably the 0.015-1.8 weight % of emulsion total amount, preferably accounts for the 0.1-3 weight % of total overall reaction monomer (A and B).
F. initiator: the present invention can adopt the normal starter in the acrylic ester emulsion polymerization.The initiator that the present invention preferably adopts is persulphate and derivative thereof, as Potassium Persulphate, ammonium persulphate etc.Initiator preferably adds when needs cause letex polymerization again.Initiator F preferably accounts for the 0.015-2.4 weight % of emulsion total amount, preferably accounts for the 0.1-4 weight % of total overall reaction monomer (A+B).Preferably initiator F is formulated as the aqueous solution that concentration is 0.001-0.12g/ml, can disposablely adds, perhaps in 0.5-1.5 hour, drop in the system gradually.
G. nonessential buffer reagent: in emulsion polymerization process of the present invention, can adopt the pH value during buffer reagent is regulated letex polymerization in case of necessity, can when letex polymerization begins or between polymerization period, add.Preferred reducing agents of the present invention is a basic metal, the carbonate of alkaline-earth metal or ammonium, and supercarbonate, phosphoric acid salt, hydrophosphate, vitriol or hydrosulfate are as yellow soda ash, sodium bicarbonate, potassiumphosphate, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate etc.The consumption of buffer reagent G is preferably the 0.015-2.4% of emulsion total amount, preferably accounts for the 0.10-4.0 weight % of total overall reaction monomer (A+B).
H. nonessential curing catalyst: the alkoxysilane-modified acrylate copolymer emulsion of acryloxy of the present invention has the film forming performance of self-crosslinking under the moisture condition, also can quicken its film forming speed as organic metallic compound by adding curing catalyst H.Promotor can just add when letex polymerization begins or between polymerization period, or adds after letex polymerization is finished.This promotor includes but not limited to: two sad dibutyl tins, toxilic acid dibutyl tin, dibutyl tin laurate, two lauric acid dioctyl tins, dibutyltin diacetate, titanium isopropylate, the poly-titanic acid ester of n-butyl, 2-sec.-propyl-2-trolamine base titanium, two propoxy-diacetyl acetate ester titanium mixtures etc., the consumption of vulkacit H is preferably the 0.015-2.4 weight % of emulsion total amount, preferably accounts for the 0.10-4.0 weight % of total overall reaction monomer (A+B).
I. nonessential solid packing: the present invention also can come the performance of fortified milk liquid product after curing by adding solid packing I, and this solid packing can just add when letex polymerization begins or between polymerization period, or adds after letex polymerization is finished.Solid packing I includes but not limited to: white carbon black, lime carbonate, quartz, diatomite, metal oxide, etc.The consumption that adds solid packing I is preferably the 0.50-30 weight % of emulsion total amount.
The alkoxysilane-modified acrylate copolymer emulsion of acryloxy of the present invention both can at room temperature carry out above-mentioned curing, also can accelerate the curing process by suitable heating.The Heating temperature scope is preferably 25-85 ℃.
Put down in writing according to document, compete in the aggressiveness system at (methyl) acryloxy organoalkoxysilane and acrylate monomer, the reactivity ratio of butyl acrylate (BA) and γ-methacryloxypropyl trimethoxy silane (MPS) is respectively 0.005 and 0.007 by for example calculating, because the two reactivity ratio in system is all much smaller than 1, reflecting has bigger alternating copolymerization tendency (referring to K.F.Ni between two kinds of monomers, G.R.Shan, Z.X.Weng, N.Sheibat-Othman, Macromolecules 2005,38:7321-7329).When the present invention adopts the redox initiator initiated polymerization, mainly utilized the relation of its reactivity ratio, sequencing that adds by acrylate monomer A and (methyl) acryloxy organoalkoxysilane monomers B and add-on different form and have the different acrylate copolymer emulsions that coat the form emulsion particles.In other words, on the particle design aspect, on the latex radial direction, form different polymerization gradients, make the microscopic pattern of silanization acrylate copolymer emulsion particle to regulate, and operation is simple.
Is example as monomer A with MPS as monomers B with BA, and a kind of method of emulsion copolymerization is that BA and MPS adding are simultaneously at the very start carried out copolymerization.Because the amount less relatively (only accounting for the 1.0-10% of monomer total amount) of MPS, and the tendency of both copolymerization is bigger as mentioned above, and therefore, the copolyreaction meeting is preferentially carried out, and forms the BA+MPS multipolymer earlier.After the MPS reaction was finished, autohemagglutination can take place in BA, therefore can form a BA+MPS multipolymer and be nuclear, and the BA homopolymer is the nucleocapsid structure superpolymer of shell.(the left figure of Fig. 1)
Another kind method then is to allow BA homopolymerization for some time earlier, and then adds MPS and carry out copolymerization, and forming one is nuclear with the BA homopolymer, and the BA+MPS multipolymer is the nucleocapsid structure superpolymer (the right figure of Fig. 1) of shell.
Therefore, adopt two kinds of different interpolation monomer methods to form different nucleocapsid clad structures, below describe in detail.
The preparation method 1.In one embodiment, with vinylformic acid hydrocarbyl carbonate monomer A, (methyl) acryloxy organoalkoxysilane monomers B, required above-mentioned functions reagent and water stir together and make it fully emulsified.Heat up then, add the initiator initiated polymerization, obtaining with acrylate and acryloxy alkoxyl silicone alkyl copolymer is nuclear, and Voncoat R 3310 is the nucleocapsid clad structure of shell.Particularly, this method may further comprise the steps:
1.1. being put into stirred autoclave, acrylate monomer A, (methyl) acryloxy organoalkoxysilane monomers B, emulsifying agent C, water D, chain-transfer agent E and nonessential buffer reagent G, curing catalyst H and solid packing I carry out emulsification;
Carry out polyreaction 1.2. add initiator F, and keep to be stirred to react and finish; With
1.3. cooling back discharging.
In above-mentioned steps 1.1, preferably under 5-45 ℃ temperature, agitator preferably preferably stirs under the rotating speed of 100-1000rpm and carried out emulsification in 10-40 minute.Reactor has well heater, thermometer, filling tube, reflux exchanger.In above-mentioned steps 1.2, preferably under 50-65 ℃ temperature, add initiator F; Wherein, preferably initiator F is formulated as the aqueous solution that concentration is 0.001-0.12g/ml, can disposablely adds, perhaps in 0.5-1.5 hour, be added dropwise in the system gradually.Temperature of reaction preferably maintains between 65-85 ℃, more preferably 75-80 ℃; Stirring velocity is preferably at 100-1000rpm, and the reaction times preferably was controlled at 1-8 hour, more preferably 3-5 hour.Preferably, keep 75-80 ℃ of temperature of reaction next and before cooling, more preferably heat, and kept stirring velocity preferably under the 500-1500rpm rotating speed preferred 0.5-1 hour, make sufficient reacting to 85 ℃.Keep the pH value in the reaction process preferably at 6.0-7.5, more preferably 6.5-7.0.
In above-mentioned steps 1.3, naturally cooling or water of condensation cool to room temperature; More preferably, regulating pH value is discharging behind the 8-9, preserves in encloses container.
The preparation method 2.Vinylformic acid hydrocarbyl carbonate monomer A and required above-mentioned functions reagent and water stirred together make it fully emulsified.Heat up then, add initiator and carry out polyreaction; And then, proceed polyreaction with the adding of (methyl) acryloxy organoalkoxysilane monomers B, and obtaining with the Voncoat R 3310 is nuclear, acrylate and acryloxy alkoxyl silicone alkyl copolymer are the nucleocapsid clad structure of shell.Particularly, this method may further comprise the steps:
2.1. with acrylate monomer A, emulsifying agent C, water D, chain-transfer agent E, and nonessential buffer reagent G, curing catalyst H and solid packing I put into stirred autoclave and carry out emulsification;
Carry out polyreaction 2.2. add initiator F, and keep stirring;
2.3. (methyl) acryloxy organoalkoxysilane monomers B is added to carries out copolymerization in the reactor and finish until reaction; With
2.4. cooling back discharging.
In above-mentioned steps 2.1, operation condition is with the step 1.1 in the above-mentioned method 1, except monomers B does not add.
In above-mentioned steps 2.2, operation condition is with the step 1.2 in the above-mentioned method 1;
In above-mentioned steps 2.3, preferably under 65-85 ℃ temperature, more preferably under 75-80 ℃, keep stirring velocity preferably under the 500-1500rpm rotating speed, to stir, preferably in 1-4 hour copolyreaction time, in more preferably 2-3 hour copolyreaction time, (methyl) acryloxy silane monomer B is dripped gradually or add in the reactor respectively in batches.In the method, reach at 60% to 95% o'clock, add monomers B and carry out copolymerization at the transformation efficiency of monomer A.Preferably, keep 75-80 ℃ of temperature of reaction next and before cooling, more preferably heat, and kept stirring velocity preferably under the 500-1500rpm rotating speed 0.5-1 hour, make sufficient reacting to 85 ℃.
In above-mentioned steps 2.4, operational condition is with the step 1.3 in the above-mentioned method 1.
The preparation process of emulsion of the present invention does not have special requirement to the pressure of each step, as long as it can not influence the preparation process of emulsion of the present invention significantly unfriendly, preferably carries out under normal pressure.
In above-mentioned preparation method 1 and method 2, control each amounts of components to prepare stable oil-in-water-type silanization acrylate copolymer emulsion.Emulsion solid content of the present invention is preferably 15-60%, more preferably 30-50 weight %.
Other processing condition of not mentioning in the preparation process of the invention described above emulsion but may relating to can be with the preparation condition of conventional Silanization polymer emulsion.
The emulsion that aforesaid method 1 makes, the emulsion that emulsion particle distribution ratio method 2 makes be (referring to Fig. 3 and Fig. 4) more evenly.Sample after the curing presents the character of glass gel.Because the introducing of silane, temperature tolerance is improved significantly.
The emulsion that method 2 makes, the sample after the curing is an elastomerics, the solidified sample that ratio method 1 obtains is in mechanical property, as all increasing significantly on rupture stress, the Young's modulus, particularly elongation at break.The emulsion of method 2, its emulsion particle top layer enrichment the crosslinked group of silanization, there are the crosslinked of acrylate and two kinds of crosslinking methods of silicon hydroxyl condensation simultaneously, and crosslinked number is compared greatly with method 1 and has been increased, solidify the back and form successive crosslinking structure (referring to Fig. 2), make the ultimate tensile strength of film and modulus all improve greatly.
Adopt the alkoxysilane-modified acrylate copolymer emulsion of the acryloxy with nucleocapsid clad structure of the present invention's preparation, have the following advantages:
1. employed among the present invention (methyl) acryloxy organoalkoxysilane monomers B is very easy to and the acrylate monomer copolymerization, and the siloxane groups in the monomers B (Si-O-R) is rare in the wetting ability Si-OH concentration that hydrolysis obtains.Hydrolysis reaction and letex polymerization can balances, impelled the stable of emulsion on the contrary, and can not be cross-linked to form a large amount of gels in advance, and the consumption of silane B is few, saves cost, and stability is high.Therefore the emulsion of preparation is comparatively stable, can preserve more than 1 year under the room temperature, does not have visible to be separated.
2. only adopt acrylate monomer and (methyl) acryloxy organoalkoxysilane monomer as polymerization reaction monomer, and do not use volatility height and big methacrylate monomer and other unsaturated monomers such as vinylbenzene, unsaturated acid of toxicity, meet the trend requirement of health environment-friendly;
3. according to the adjusting of monomer addition order and feeding quantity, the emulsion particle form and the polymerization degree of polymkeric substance can easily be regulated, and can form the nucleocapsid clad structure, even the multi-layer core-shell clad structure.
4. this preparation method need not to adopt complicated technologies such as seeding polymerization or ray initiation based on the conventional emulsion polymerization technique, and process is simple, is easy to control.Advantages such as adopt method of emulsion polymerization, used solvent is a water, and the prepared emulsion that goes out has environmental protection, and is nonflammable had both helped environment protection, can reduce production costs again.
5. under the prerequisite that keeps the acrylic ester polymer low Tg, significantly improve the mechanical property of solidifying the back product, increased the temperature tolerance and the weathering resistance of product.The sealing agent good stability that uses this emulsion to make can be stablized under the room temperature and place more than 1 year.Can be widely used in automobile, building materials, the sealing of daily product etc., coating and bonding.
Unless otherwise, all per-cents used herein and ratio are all by weight; Components contents is all in the gross weight of emulsion.
The publication that this paper quotes is incorporated herein by reference for all purposes.
The accompanying drawing summary
Fig. 1 is the contrast synoptic diagram of the obtained nucleocapsid structure emulsion particle of preparation method of two kinds of emulsions of the present invention.
Fig. 2 is the contrast synoptic diagram of the cross-linking effect of the emulsion that obtains of two kinds of square preparation methods.
Fig. 3. the reinforced jointly emulsion particle transmission electron microscope observation photo that forms of BA among the embodiment 3 and MPS.
Fig. 4. add the emulsion particle transmission electron microscope observation photo of formation behind the MPS among the embodiment 4.
Embodiment
The following example has further described and has proved the preferred embodiment in the scope of the invention.These embodiment that given only are illustrative, and are unintelligible for being limitation of the present invention.
Below each step among each embodiment all under normal pressure, carry out, temperature is a normal temperature, relative humidity is 50%, unless otherwise.
Raw material sources:
Butyl acrylate (BA): analytical pure, Tianjin chemical reagent institute; Address: Tianjin Dongli District Xu village; Postcode: 315451; Network address: www.chemreagent.com.cn
Methyl methacrylate (MMA): analytical pure, Tianjin chemical reagent institute;
γ-methacryloxypropyl trimethoxy silane (MPS): U.S. Gelest company; 11 East
Steel Rd.Morrisville，PA19067 Phone：(215)547-1015
Potassium Persulphate (KPS): chemical pure, Beijing Chemical Plant; Address: No. 1, stable town, Daxing District, the BeiJing, China city stable South St in industrial Sector East; Phone: 086-010-80239083; Fax: 086-010-80239716, postcode: 102607
Sodium lauryl sulphate (SDS): analytical pure, Jiangsu China Kanggong department;
Lauryl mercaptan (SDA): analytical pure, Tianjin chemical reagent institute.
SODIUM PHOSPHATE, MONOBASIC: analytical pure, Tianjin chemical reagent institute;
Wherein, acrylate monomer before using through overweight steaming.Initiator is purified through recrystallization.Other reagent are direct use.Actual amount after material consumption in following examples is all handled by the above.
Comparative Examples 1. monobasic systems: set of monomers becomes butyl acrylate, and the prescription of emulsion is as follows:
| Numbering | Component |
| 1 acrylate monomer A, 2 emulsifying agent C, 3 water D, 4 initiator F, 5 chain-transfer agent E, 6 buffer reagent G | Butyl acrylate sodium lauryl sulphate water Potassium Persulphate lauryl mercaptan SODIUM PHOSPHATE, MONOBASIC |
With butyl acrylate 39.60g, emulsifier sodium lauryl sulfate 0.90g, water 84.00g, (the pH value is 7 NaH for lauryl mercaptan 0.04g and buffer reagent
2PO
4-NaOH the aqueous solution) 1.00g adds and has well heater, thermometer, and filling tube is in the reactor of reflux exchanger.450rpm stirred 20 minutes down under the room temperature, was warming up to 60 ℃ then, added initiator 0.08g, and temperature is risen to 75 ℃.Keep the pH value in the reaction process 7, regulate with the NaOH aqueous solution or the HCl aqueous solution of 0.1mol/L.React after 3 hours, be warmed up to 85 ℃, continue reaction 30min.Naturally cool to the room temperature after-filtration, regulate pH value to 8 with ammoniacal liquor.Emulsion solid content is 33.5 weight %.
The butyl acrylate of Comparative Examples 2. silanizations-methylmethacrylate copolymer samples of latex: adopt the method for terpolymer, introduce alkyl methacrylate as one of comonomer:
| Numbering | Component |
| 1 acrylate monomer A, 2 methacrylate monomer, 3 acryloxy organoalkoxysilane B, 4 emulsifying agent C, 5 water D, 6 chain-transfer agent E, 7 initiator F, 8 buffer reagent G | Butyl acrylate methyl methacrylate γ-methacryloxypropyl trimethoxy silane (MPS) sodium lauryl sulphate water lauryl mercaptan Potassium Persulphate SODIUM PHOSPHATE, MONOBASIC |
With butyl acrylate 33.26g, methyl methacrylate 6.24g, emulsifier sodium lauryl sulfate 1.00g, water 84.00g, (the pH value is 6.8 NaH for lauryl mercaptan 0.05g and buffer reagent 1.20g
2PO
4The aqueous solution) adding has well heater, thermometer, filling tube, in the reactor of reflux exchanger, at room temperature 480rmp stirred 20 minutes, be warming up to 60 ℃ then, add initiator potassium persulfate 0.09g, temperature is risen to 75 ℃ of reactions 2 hours, simultaneously stirring velocity is controlled at 400rmp, keep the pH value in the reaction process 7, regulate with the NaOH aqueous solution or the HCl aqueous solution of 0.1mol/L.Join in the system MPS1.98g is disposable then, reacted again 2 hours.Naturally cool to the room temperature after-filtration, ammoniacal liquor is regulated pH value to 8, the solid content 32.4 weight % of emulsion, promptly be able to acrylate, methacrylic ester copolymer for examining, acrylate, methacrylic ester and acryloxy organoalkoxysilane terpolymer are the alkoxysilane-modified acrylic ester emulsion of acryloxy of the nucleocapsid clad structure of shell.
Embodiment 1: binary system: set of monomers becomes butyl acrylate and γ-methacryloxypropyl trimethoxy silane (MPS), and the prescription of emulsion is as follows:
| Numbering | Component |
| 1 acrylate monomer A, 2 acryloxy organoalkoxysilane B, 3 emulsifying agent C, 4 water D, 5 chain-transfer agent E, 6 initiator F, 7 buffer reagent G | Butyl acrylate γ-methacryloxypropyl trimethoxy silane (MPS) sodium lauryl sulphate distilled water lauryl mercaptan Potassium Persulphate SODIUM PHOSPHATE, MONOBASIC |
With butyl acrylate 39.60g, γ-methacryloxypropyl trimethoxy silane (MPS) 1.98g, emulsifier sodium lauryl sulfate 0.90g, water 84.00g, (the pH value is 6.8 NaH for lauryl mercaptan 0.04g and buffer reagent
2PO
4The aqueous solution) 1.00g adds and has well heater, thermometer, filling tube, in the reactor of reflux exchanger, 480rpm stirred 20 minutes down under the room temperature, was warming up to 60 ℃ then, added initiator 0.10g, temperature is risen to 75 ℃, keep the pH value in the reaction process 7, regulate, react after 6 hours with the NaOH aqueous solution or the HCl aqueous solution of 0.1mol/L, naturally cool to the room temperature after-filtration, regulate pH value to 8 with ammoniacal liquor.Monomer conversion reaches 95%.The solid content 33.3% of emulsion, promptly being able to acrylate and acryloxy alkoxyl silicone alkyl copolymer is the alkoxysilane-modified acrylic ester emulsion of acryloxy of the nucleocapsid clad structure of shell for nuclear, Voncoat R 3310.
Embodiment 2: binary system: set of monomers becomes butyl acrylate and γ-methacryloxypropyl trimethoxy silane (MPS), and the prescription of emulsion is as follows:
| Numbering | Component |
| 1 acrylate monomer A, 2 acryloxy organoalkoxysilane B, 3 emulsifying agent C, 4 water D, 5 chain-transfer agent E, 6 initiator F, 7 buffer reagent G | Butyl acrylate γ-methacryloxypropyl trimethoxy silane (MPS) sodium lauryl sulphate distilled water lauryl mercaptan Potassium Persulphate SODIUM PHOSPHATE, MONOBASIC |
With butyl acrylate 39.60g, emulsifier sodium lauryl sulfate 0.90g, water 84.00g, (the pH value is 6.80 NaH for lauryl mercaptan 0.05g and buffer reagent
2PO
4The aqueous solution) 1.01g adds and has well heater, thermometer, filling tube, in the reactor of reflux exchanger, stirring at room 20 minutes, stirring velocity is at 480rpm, be warming up to 60 ℃ then, add initiator potassium persulfate 0.08g, temperature is risen to 75 ℃, react after 2 hours, the transformation efficiency of monomer A reaches at 70% o'clock, stirring velocity is controlled at 380rpm, joins in the system acryloxy organoalkoxysilane B1.98g is disposable, keep the pH value in the reaction process 7, the NaOH aqueous solution or the HCl aqueous solution with 0.1mol/L are regulated, react after 2 hours, naturally cool to the room temperature after-filtration, regulate pH value to 8 with ammoniacal liquor.Monomer conversion reaches 90%.The solid content of emulsion is 33.3%.Promptly be able to Voncoat R 3310 and be nuclear, acrylate and acryloxy alkoxyl silicone alkyl copolymer are the acryloxy organoalkoxysilane acrylic ester emulsion of the nucleocapsid clad structure of shell.
Embodiment 3 (being used for electron microscopy observation): binary system: set of monomers becomes butyl acrylate and γ-methacryloxypropyl trimethoxy silane.
In order to be increased in the contrast gradient of binary composition in the electromicroscopic photograph, the 10 weight %s of the content of γ-methacryloxypropyl trimethoxy silane have been increased to reactive monomer total amount (BA+MPS).The prescription of emulsion is as follows:
| Numbering | Component |
| 1 acrylate monomer A, 2 acryloxy organoalkoxysilane B, 3 emulsifying agent C, 4 water D, 5 chain-transfer agent E, 6 initiator F, 7 buffer reagent G | Butyl acrylate (BA) γ-methacryloxypropyl trimethoxy silane (MPS) sodium lauryl sulphate distilled water lauryl mercaptan Potassium Persulphate SODIUM PHOSPHATE, MONOBASIC |
With butyl acrylate 37.40g, γ-methacryloxypropyl trimethoxy silane (MPS) 4.18g, emulsifier sodium lauryl sulfate 1.00g, water 84.00g, (pH value is 6.8 NaH for lauryl mercaptan 0.02g and buffer reagent
2PO
4The aqueous solution) 1.00g adds in the above reactor, 480rpm stirred 20 minutes down under the room temperature, be warming up to 60 ℃ then, add initiator 0.09g, temperature is risen to 75 ℃, keep the pH value in the reaction process 7, the NaOH aqueous solution or the HCl aqueous solution with 0.1mol/L are regulated, react after 6 hours, naturally cool to the room temperature after-filtration, regulate pH value to 8 with ammoniacal liquor, promptly being able to acrylate and acryloxy silicone copolymers is the alkoxysilane-modified acrylic ester emulsion of acryloxy of the nucleocapsid clad structure of shell for nuclear, Voncoat R 3310.The solid content 34.2 weight % of emulsion.
Embodiment 4 (being used for electron microscopy observation): binary system: set of monomers becomes butyl acrylate and γ-methacryloxypropyl trimethoxy silane.
| Numbering | Component |
| 1 acrylate monomer A, 2 acryloxy organoalkoxysilane B, 3 emulsifying agent C, 4 water D, 5 chain-transfer agent E, 6 initiator F, 7 buffer reagent G | Butyl acrylate (BA) γ-methacryloxypropyl trimethoxy silane (MPS) sodium lauryl sulphate distilled water lauryl mercaptan Potassium Persulphate SODIUM PHOSPHATE, MONOBASIC |
With butyl acrylate 37.40g, emulsifier sodium lauryl sulfate 0.95g, water 84.00g, (the pH value is 6.80 NaH for lauryl mercaptan 0.03g and buffer reagent
2PO
4The aqueous solution) 1.01g adds in the above reactor, stirring at room 20 minutes, stirring velocity is warming up to 60 ℃ then at 480rpm, adds initiator potassium persulfate 0.08g, temperature is risen to 75 ℃, react after 2 hours, stirring velocity is controlled at 380rpm, join in the system acryloyl-oxy radical siloxane 4.16g is disposable, keep the pH value in the reaction process 7, regulate with the NaOH aqueous solution or the HCl aqueous solution of 0.1mol/L.Reacted 2 hours, naturally cool to the room temperature after-filtration, regulate pH value to 8 with ammoniacal liquor, promptly be able to Voncoat R 3310 and be nuclear, acrylate and acryloxy alkoxyl silicone alkyl copolymer are the alkoxysilane-modified acrylic ester emulsion of acryloxy of the nucleocapsid clad structure of shell.The solid content 33.4 weight % of emulsion.
Embodiment 1 and 2 emulsion state analysis:
1. dynamic light scattering (DLS) is analyzed the latex particle size distribution:
Dynamic light scattering device model: 90 plus particle size analyzer, Brookhaven Inc. makes; Temperature=25.0 ℃, suspension system: water external phase; Viscosity=0.890 cp; Standard reflection indicating liquid=1.330, angle=90.00; Wavelength=660.0nm.
| Sample | (effective size of grain) (nm) | (heterogeneity index) | (half-breadth) (nm) |
| Embodiment 1 | 69.5 | 0.015 | 22.4 |
| Embodiment 2 | 83.8 | 0.047 | 15.3 |
In the last table is the dynamic light scattering data of method 1 (embodiment 1) and method 2 (embodiment 2), and the emulsion that makes of method 1 is compared with method 2 as can be seen, and particle size of emulsion is littler, dispersed better.This has illustrated the nuclear inside that is wrapped in emulsion particle owing to most MPS in the method 1, the chance of itself and other MPS and particle surface crosslinking reaction is diminished, and a large amount of MPS concentrates on shell portion in the method 2, makes the chance of itself and other MPS and particle surface effect become big.Therefore emulsion particle diameter is wanted the big of ratio method 1, and it is low that dispersiveness also seems.
2. emulsion freeze-thaw stability property testing
Emulsion is got part sealing, put into-5 ℃ ± 2 ℃ cryostat, take out behind the 18h, place 6h down at 20 ± 2 ℃, after 3 times, open container so repeatedly, observe it and have or not caking, cohesion and separation phenomenon are determined its freeze-thaw stability with this.With the emulsion sealing, room temperature storage is to investigate its stability in storage then.Experimental result does not all have on embodiment 1 and the range estimation of 2 emulsion are apparent and is separated emulsion-stabilizing.
This emulsion as above room temperature placement is still stable after 6 months, and the emulsion viscosity range estimation has no significant change.
Comparative Examples 1 and 2 and the emulsion film forming of embodiment 1 and 2 solidify the back product performance and characterize as follows.
At first, the film-forming method of emulsion following (the sample film of all Comparative Examples and embodiment together): emulsion sampling 15g, pour in the culture dish of tetrafluoroethylene, 25 ℃ of room temperatures, place 24h-48h under 50% relative humidity, after put into the vacuum drying oven 24h of 60 ℃ of constant temperature, take out then and get final product.
3. the contrast of second-order transition temperature
| Sample | Tg(℃) |
| Comparative Examples 1: butyl polyacrylate solidified sample | -54.598 |
| Comparative Examples 2: ternary system solidified sample | -35.181 |
| Embodiment 1: the binary system solidified sample | -46.477 |
| Embodiment 2: the binary system solidified sample | -46.055 |
Differential thermal analysis (DSC) instrument model: DTA7; Manufacturer: U.S. PerKinElmer company (45 William Street, Wellesley, MA 02481-4078, USA); Temperature range: room temperature-1600 ℃, accuracy: 1%; Temperature rise rate: 0.1-100 ℃/min; Atmosphere: nitrogen
After all solidify sample all only have 1 Tg after tested, illustrate that product all is the chemical polymerization product, the monomer among the preparation method of the present invention has formed multipolymer, but not the simple physics mixing.
4. the test of mechanical property
Drawing machine, model: Instron Co. (Instron Corporation, 825University Avenue, Norwood, MA 02062-2643, USA), Series IX, Automated Materials Testing System 74.3.00
Draw speed: 50mm/min; Relative humidity: 50%; Temperature: 20 ℃
| Sample | Elongation at break (%) | Rupture stress (MPa) | Young's modulus (MPa) |
| Comparative Examples 1: butyl polyacrylate solidified sample | 120.342 | 0.124 | 0.248 |
| Comparative Examples 2: ternary system solidified sample | 299.659 | 1.157 | 2.836 |
| Embodiment 1: the binary solidified sample | 61.711 | 0.384 | 0.689 |
| Embodiment 2: the binary solidified sample | 545.689 | 2.599 | 4.777 |
The emulsion that method 1 makes, the sample after the curing presents the character of glass gel, because the introducing of silane, temperature tolerance is improved significantly.The emulsion that method 2 makes, the solidified sample is an elastomerics, the solidified sample that ratio method 1 obtains is in mechanical property, as all increasing significantly on rupture stress, the Young's modulus, particularly elongation at break.The emulsion of method 2, its emulsion particle top layer enrichment the crosslinked group of silanization, there are the crosslinked of acrylate and two kinds of crosslinking methods of silicon hydroxyl condensation simultaneously, making the number of cross-linking set compare greatly with method 1 has increased, solidify the back and form the successive crosslinking structure, make the ultimate tensile strength of film and modulus all improve greatly.
5. the test of heat resistance
Thermogravimetric analysis (TGA):
Instrument model: Pyris 1 TGA; Manufacturer: Connecticut, USA PerKinElmer company
The key technical indexes: temperature range: room temperature-1000 ℃, sensitivity: 0.1 μ g, temperature rise rate: 0.1-200 ℃/min
| Sample | Decomposition temperature T (℃) |
| Comparative Examples 1: butyl polyacrylate solidified sample | 324 |
| Comparative Examples 2: ternary system solidified sample | 397 |
| Embodiment 1: the binary solidified sample | 382 |
| Embodiment 2: the binary solidified sample | 389 |
Compare with simple poly-butylacrylic acid ester sample, all solidified sample through the alkoxysilane-modified acrylate copolymer emulsion of acryloxy have obtained significant raising aspect temperature tolerance.
6. transmission electron microscope (TEM) photo contrast
Transmission electron microscope instrument model: JEM-100s manufacturer: NEC (JEOL)
The key technical indexes: temperature range: room temperature; Acceleration voltage: 80kv
The preparation of electron microscopy observation sample: get 0.20 milliliter of samples of latex to be measured, be diluted to 10ml, mix under the stirring velocity 200rpm, fish for sample emulsion 3～4 times with copper mesh dipping with deionized water, at room temperature place 3 minutes to be measured.
By Fig. 3 and Fig. 4 more as can be seen, adopt on the emulsion particle structure of two kinds of no method gained and show notable difference, black region is the silicon rich region, as can be seen: for method 1, MPS silane mainly is enriched in the position of nuclear; And for method 2, behind the MPS added-time as can be seen silane mainly be enriched in shell portion, also further confirmed above supposition for emulsion structure.
As from the foregoing, its performance difference of core-shell emulsion that two kinds of different methods make mainly shows mechanical index such as elongation at break, Young's modulus, and the emulsion particle diameter size.Method 2 ratio method, 1 easier raising film strength and elongation at break with and temperature tolerance, still, the emulsion that method 2 makes on polymolecularity not as method 1.
Above data as can be seen, the sample after a small amount of acryloxy is alkoxysilane-modified has still kept the low Tg of acrylic ester polymer, but thermotolerance, tensile strength, modulus and elongation at break are greatly improved.Find out thus of the present inventionly to have kept the original advantage of acrylate resin, effectively overcome the deficiency of himself again with the alkoxysilane-modified acrylate copolymer emulsion of acryloxy.
Claims (40)
1. one kind with the alkoxysilane-modified acrylate copolymer emulsion of acryloxy, shown in the following general formula of the structure of wherein said multipolymer (I):
Wherein: R is selected from the alkyl of C1-C16, the aryl of C6-C20, the aralkyl of C7-C20 and the alkaryl of C7-C20, R
1Be hydrogen atom or methyl, R
2, R
3Be selected from the alkyl of C1-C16, the aralkyl of C7-C20 and the alkaryl of C7-C20 separately, wherein n is the integer of 1-10, and y is the integer of 0-2, and p, q respectively are 1-1000.
2. the described emulsion of claim 1, the used monomer component of wherein said multipolymer is made up of following monomer basically:
A) vinylformic acid hydrocarbyl carbonate monomer; With
B) (methyl) acryloxy organoalkoxysilane monomer.
3. the described emulsion of claim 2, the total content of wherein said reactive monomer A and B is the 15-60 weight % of emulsion total amount.
4. claim 1 or 2 described emulsions, wherein said emulsion is an emulsion oil-in-water.
5. claim 1 or 2 described emulsions, the pH value of wherein said emulsion is 8-9.
6. the described emulsion of claim 4, the wherein said water yield is the 38-83 weight % of emulsion total amount.
7. claim 1 or 2 described emulsions, the emulsion particle in the wherein said emulsion is the nucleocapsid clad structure.
8. the described emulsion of claim 7, wherein said multipolymer forms the stratum nucleare of emulsion particle.
9. the described emulsion of claim 7, wherein said multipolymer forms the shell of emulsion particle.
10. emulsion according to claim 2, wherein said vinylformic acid hydrocarbyl carbonate monomer A is a vinylformic acid C1-C14 hydrocarbyl carbonate.
11. the described emulsion of claim 10, wherein said monomer A is selected from: methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, vinyl acrylate, ethyl acrylate, Hydroxyethyl acrylate, vinylformic acid-2-ethylamino ester and combination thereof.
12. emulsion according to claim 2, the content of wherein said vinylformic acid hydrocarbyl carbonate monomer A are the 13.5-59.9 weight % of emulsion total amount, and account for the 90.0-99.9 weight % of reactive monomer A and B total amount.
13. emulsion according to claim 2, wherein said monomers B are (methyl) acryloxy organoalkoxysilane of following general formula (II) expression:
Wherein: R
1Be hydrogen atom or methyl, R
2, R
3Respectively be selected from the alkyl of C1-C16, the aralkyl of C7-C20 and the alkaryl of C7-C20, wherein n is the integer of 1-10, and y is the integer of 0-2.
14. emulsion according to claim 13, wherein said monomers B is selected from: γ-acryloxy propyl trimethoxy silicane, γ-acryloxy propyl group methyl dimethoxysilane, γ-acryloxy propyl-triethoxysilicane, γ-acryloxy propyl group methyldiethoxysilane, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl triethoxyl silane, γ-methacryloxypropyl methyldiethoxysilane, α-acryloxy methylene tri methoxy silane, α-acryloyl-oxy methylene methyl dimethoxysilane, α-acryloxy methylene tri Ethoxysilane, α-acryloyl-oxy methylene methyldiethoxysilane, Alpha-Methyl acryloxy methylene tri methoxy silane, Alpha-Methyl acryloyl-oxy methylene methyl dimethoxysilane, Alpha-Methyl acryloxy methylene tri Ethoxysilane, Alpha-Methyl acryloyl-oxy methylene methyldiethoxysilane, γ-methacryloxypropyl three (beta-methoxy-oxyethyl group) silane, and combination.
15. emulsion according to claim 2, wherein the content of monomers B accounts for the 0.1-6 weight % of emulsion total amount, and accounts for the 0.1-10 weight % of total overall reaction monomer A and B.
16. each described emulsion preparation method of claim 1-15, wherein the emulsion particle in the emulsion is a nuclear with vinylformic acid hydrocarbyl carbonate and acryloxy alkoxyl silicone alkyl copolymer, and vinylformic acid hydrocarbyl carbonate homopolymer is a shell, comprises following steps:
A) vinylformic acid hydrocarbyl carbonate monomer A, (methyl) acryloxy organoalkoxysilane monomers B, emulsifying agent C, water D, chain-transfer agent E and nonessential buffer reagent G, curing catalyst H and solid packing I are put into stirred autoclave and carry out emulsification;
B) add initiator F and carry out polyreaction, and keep to be stirred to react and finish; With
C) cooling back discharging.
17. the preparation method of each described emulsion of claim 1-15, wherein the emulsion particle in the emulsion is a nuclear with vinylformic acid hydrocarbyl carbonate homopolymer, and vinylformic acid hydrocarbyl carbonate and acryloxy alkoxyl silicone alkyl copolymer are shell, comprise following steps:
A) vinylformic acid hydrocarbyl carbonate monomer A, emulsifying agent C, water D, chain-transfer agent E and nonessential buffer reagent G, curing catalyst H and solid packing I are put into stirred autoclave and carry out emulsification;
B) add initiator F and carry out polyreaction, and keep stirring;
C) (methyl) acryloxy silane monomer B is added to carries out copolymerization in the reactor and finish until reaction; With
D) cooling back discharging.
18. preparation method according to claim 17, wherein the transformation efficiency in monomer A reaches at 60% to 95% o'clock, adds monomers B and carries out copolymerization.
19. preparation method according to claim 17, wherein monomers B is by dripping or adding reaction system in batches.
20. according to claim 16 or 17 described preparation methods, wherein emulsifying agent D is the anion surfactant of HLB value for 8-40, perhaps the HLB value is that 8-40 anion surfactant and HLB value are the compound emulsifying agent of 8-40 nonionogenic tenside.
21., wherein under the rotating speed of 5-45 ℃ of temperature and 100-1000rpm, stir in the step a) and carried out emulsification in 10-40 minute according to claim 16 or 17 described preparation methods.
22., wherein add initiator down at 50-65 ℃ in the step b) according to claim 16 or 17 described preparation methods.
23. according to claim 16 or 17 described preparation methods, wherein the temperature of reaction of step b) is 65-85 ℃, stirring velocity is 100-1000rpm, and the reaction times is 1-8 hour, and the pH value of reaction system is 6.0-7.5.
24. preparation method according to claim 17, wherein the copolymerization temperature of step c) is 65-85 ℃, and stirring velocity is that 500-1500rpm and reaction times are 1-4 hour.
25. according to claim 16 or 17 described preparation methods, wherein emulsifying agent C consumption is the 0.15-6.0 weight % of emulsion total amount, and accounts for the 1-10 weight % of total overall reaction monomer A and B.
26. according to claim 16 or 17 described preparation methods, wherein chain-transfer agent E is alkyl sulfhydryl or the hydrosulphonyl silane of C2-C14, consumption is the 0.015-1.8 weight % of emulsion total amount, and accounts for the 0.1-3 weight % of total overall reaction monomer A and B.
27. according to claim 16 or 17 described preparation methods, wherein initiator F is the persulphate or derivatives thereof.
28. according to claim 16 or 17 described preparation methods, wherein initiator F consumption is the 0.015-2.4 weight % of emulsion total amount, and accounts for the 0.1-4.0 weight % of total overall reaction monomer A and B.
29. according to claim 16 or 17 described preparation methods, wherein initiator F is formulated as the aqueous solution that concentration is 0.001-0.12g/ml,, perhaps in 0.5-1.5 hour, is added dropwise to reaction system with its disposable adding reaction system.
30. according to claim 16 or 17 described preparation methods, wherein buffer reagent G is carbonate, supercarbonate, phosphoric acid salt, hydrophosphate, vitriol or the hydrosulfate of basic metal, alkaline-earth metal or ammonium.
31. according to claim 16 or 17 described preparation methods, wherein the consumption of buffer reagent G is the 0.015-2.4 weight % of emulsion total amount, and accounts for the 0.1-4.0 weight % of total overall reaction monomer A and B.
32. according to claim 16 or 17 described preparation methods, wherein said curing catalyst H is selected from: two sad dibutyl tins, toxilic acid dibutyl tin, dibutyl tin laurate, two lauric acid dioctyl tins, dibutyltin diacetate and combination thereof, the consumption of curing catalyst H is the 0.015-2.4 weight % of emulsion total amount, and accounts for the 0.1-4.0 weight % of total overall reaction monomer A and B.
33. according to claim 16 or 17 described preparation methods, wherein said solid packing I is selected from: white carbon black, lime carbonate, quartz, diatomite, metal oxide and combination thereof, the consumption of solid packing I is the 0.5-30 weight % of emulsion total amount.
34. each the solidifying product of emulsion of claim 1-15.
35. the solidifying product of claim 34, wherein said curing is at room temperature carried out.
36. the solidifying product of claim 34, wherein said being solidificated under 25 ℃ to 85 ℃ carried out.
37. the solidifying product of claim 34 carries out under the wherein said existence that is solidificated in moisture.
38. the solidifying product of claim 34 carries out under the wherein said existence that is solidificated in described curing catalyst H.
39. each emulsion of claim 1 to 15 is as the application of the raw material of buffer coating, tackiness agent, seal gum, pad, printing ink, clean-out system.
40. each solidifying product of claim 34 to 38 is as the application of buffer coating, tackiness agent, seal gum, pad, printing ink, clean-out system.
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