CN104446102B - A kind of admixture and its preparation method promoting the anti-folding of cement-based material and tensile strength - Google Patents

Abstract

The present invention discloses a kind of admixture and its preparation method that promote the anti-folding of cement-based material and tensile strength. Promoting the admixture of the anti-folding of cement-based material and tensile strength, be the aqueous dispersions of the hybrid inorganic-organic particle of nucleocapsid structure, the mass content of the hybrid inorganic-organic particle of nucleocapsid structure in aqueous dispersions is 5-40%; The hybrid inorganic-organic particle of nucleocapsid structure forms by three layers, is innermost layer, middle layer and outermost layer from inside to outside successively; Innermost layer is organic polymer core, and middle layer is the silica shell that silicon-dioxide or organo-functional group replace, and outermost layer is the electronegativity organic polyelectrolyte of one layer of long side chain of band. The present invention promotes the admixture of the anti-folding of cement-based material and tensile strength for cement-based material modification, volume is more high, its folding strength and tension (split and draw) intensity improve more obvious, volume is even to reach 30-40% under 5% condition, simultaneously to its ultimate compression strength almost without negative impact (ultimate compression strength reduce degree < 5%) or slightly improve.

Description

A kind of admixture and its preparation method promoting the anti-folding of cement-based material and tensile strength

Technical field

The invention belongs to the admixture field of cement-based material modification, it is specifically related to a kind of admixture and its preparation method that promote the anti-folding of cement-based material and tensile strength.

Background technology

" concrete " represents the cement-based materials such as concrete, mortar or slip casting.

Portland cement concrete is a kind of typical hard brittle material, its ultimate compression strength height, bend resistance, tensile strength are obviously not enough, in actual use, it is easy to because stress is concentrated or unbalance stress produces various crackle or damage so that weather resistance declines, thus limit its application, such as, it is applied to cement pavement surface layer and the disconnected disease such as plate and surface tissue destruction easily occurs too early, thus limit its application in high-grade highway.

People have carried out big quantifier elimination improving in concrete fragility, particularly by adding modified component thus improve the method for concrete bend resistance, tensile strength, existing main modified component comprises fiber (organic polymer, steel fiber and glass fibre) and polymer particle (emulsion or dry powder) etc.

Fiber reinforced principle is: (1) restriction microfracture development. When fiber is evenly distributed among concrete substrate, assuming that concrete substrate inside has the tendency that microfracture occurs, when any microfracture occurs and may develop to any direction, within the distance being the farthest no more than fiber fiber mean center distance in concrete substrate, this crack will run into the fiber lain across in its front. After crack produces, due to the high-modulus of fiber and the high-tensile of single root, further developing of crack can be stoped, the enclosed cavity being similar to harmless hole or the very tiny hole of internal diameter can only be formed in concrete substrate. (2) toughness of high strength fibre own is far above concrete, and the concrete intensity of fibre modification is the coagulation soil phase and the superposition of fiber phase performance, and thus its toughness is higher than normal concrete.

Polymer particle is as admixture, it is possible to improve the combination between concrete component. The dispersion of polymer particle and film forming are that it can the major cause of modification. Due to the existence of polymeric film, make the mechanical property (especially toughness) of concrete material more excellent. Physical action or part chemical bonding effect is created between polymkeric substance and inorganic materials, namely sand-cement slurry is carried out modification with the form of particle or film by polymkeric substance, the chelating body that the structure with coordination combination is more fine and close can also be formed, thus improve the performance of polymer cement concrete. In polymkeric substance, introduce active group such as-OH ,-COOH ,-COOR etc. can produce coordination with hydrated cementitious product, change the key type of cement material based on siloxane bond, add the key type of organic C-H bond, structure is obviously strengthened, forms folded repeatedly staggered two cover network structures, improve the combination between interface, improve interphase fracture energy and toughness (BulletinoftheChineseCeramicSociety, 2014,33,365).

But all there is obvious deficiency in above technology:

(1) fiber easy conglomeration when concrete stirs, it is difficult to dispersion, can not be uniformly distributed in concrete. Dispersion and the orientation of the concrete performance of fibre modification and fiber have substantial connection, and thus concrete preparation technology is relatively big on concrete performance impact, and its preparation is more more difficult than conventional concrete. Conglomeration makes concrete workability poor, pumping difficulty, be difficult to construction. Steel fiber in use damage-form be mainly pulled out, and can not be pulled off, this illustrates the not enough with concrete adhesivity of steel fiber, and this can affect the effect improving concrete tensile strength. Synthon density is little, and filament diameter is less, there is thickening effect, is unfavorable for that concrete vibrations are closely knit. Glass fibre due to alkali resistance poor, the application of glass fiber reinforced concrete is restricted.

The toughening cement-based materials method that patent CN101891417B discloses needs to be uniformly dispersed by stirring each component (comprising fiber) of being filled a prescription, churning time longer (25-35min). Patent CN101913188B adds magnetic field makes the single-phase distribution of steel fiber improve Steel Fiber Reinforced Concrete folding strength, and this makes concrete preparation complicated undoubtedly. The organic fibre film that patent US7192643 is easily disperseed by special methods preparation is used for toughening cement-based materials. Patent EP0488577, US5993537, US4524101 all need to add the so-called specific means such as wetting agent or inorganic coupling reagent (bindingagent) and fiber can be disperseed. These patents need to be prepared required filamentary material or corresponding modified concrete by specific means or equipment usually.

(2) in polymer modification concrete, polymkeric substance volume is too high. Owing to polymer modification concrete is more formation polymer network, be equivalent to the form by material is blended and improve concrete performance, polymer network itself is limited with cement-based material cohesive force, thus when low-dosage, modification performance is not obvious, must adding relatively high additive, this makes its cost higher. It is poly-heavy that polymer emulsion also likely occurs in the environment of concrete highly basic height salt, affects its effect and plays (emulsion of anionic emulsifier synthesis is easily poly-heavy, JournalofMaterialsinCivilEngineering2011,23,1412). Patent CN102276764B provides the chemical modification method of a kind of polymer powder modification, chemical graft is carried out by coupling agent on polymer powder surface, to improve the interaction of powder and matrix, thus improve the shock resistance of modified mortar, but it itself does not solve the scattering problem of polymer powder.

In addition, although polymkeric substance adds folding strength and toughness, but the ultimate compression strength of high additive polymer-modified cementitious materials obviously reduces. Even if when polymkeric substance volume relatively low (5wt%) (with water cement ratio condition, even consider the water-reduction of polymer emulsion, adopt lower water cement ratio also may have slight decrease in strength), cement-based material ultimate compression strength also has decline in various degree, its amplitude even can reach��15-50% (JournalofJilinInstituteofArchitecture&CivilEngineering20 12,29,7; CementandConcreteResearch2005,35,900 etc.).

In addition, patent CN103130436A and CN101239800B reports respectively and adopts Graphene (graphene oxide) and carbon nano-tube modification cement-based material, is promoted by resistance to compression tension folding strength, but its cost is too high. It is tough for increasing that EP2695850A1 discloses one method of original position nucleating growth Calucium Silicate powder (wollastonite) nanocrystal in cement-based material, it is necessary to the conditions such as specific temperature, pressure, brings difficulty to preparation.

Summary of the invention

In order to solve the technical barrier that toughness in prior art (comprising folding strength and tensile strength) and ultimate compression strength can not ensure simultaneously, the present invention provides a kind of admixture and its preparation method that promote the anti-folding of cement-based material and tensile strength.

For solving the problems of the technologies described above, the invention of this reality adopts following technical scheme:

Promoting an admixture for the anti-folding of cement-based material and tensile strength, be the aqueous dispersions of the hybrid inorganic-organic particle of nucleocapsid structure, the mass content of the hybrid inorganic-organic particle of nucleocapsid structure in aqueous dispersions is 5-40%; The hybrid inorganic-organic particle of nucleocapsid structure forms by three layers, is innermost layer, middle layer and outermost layer from inside to outside successively; Innermost layer is organic polymer core, and middle layer is the silica shell that silicon-dioxide or organo-functional group replace, and outermost layer is the electronegativity organic polyelectrolyte of one layer of long side chain of band. Solid content is

Above-mentioned innermost layer is the homopolymer that formed of one or more polymerizations in the univalent metal salt of the acrylate by vinylbenzene, substituted phenylethylene, vinylformic acid, methacrylic acid, acrylate, replacement, the acrylamide monomer of replacement, the methyl acrylamide monomer of replacement, methacrylic ester, the methacrylic ester of replacement, acrylic acid univalent metal salt or methacrylic acid or multipolymer. Above-mentioned polymerization can be carry out when linking agent presence or absence.

Innermost layer is for adding hydroxyl, amino or carboxylic polymerisable monomer in the preparation.

Hydroxyl, amino or carboxyl functional group can be introduced like this on organic polymer core surface, when middle layer covers, these hydroxyls, amino or carboxyl functional group are as reaction site, and reaction site with middle layer, reaction occurs thus plays the effect being connected middle layer with covalent linkage.

Middle layer is by siloxanes or water glass hydrolysis preparation. The surface in such middle layer is full of hydroxy functional group, and these hydroxyls with outermost layer, reaction occur thus play and be connected outermost effect with covalent linkage.

Outermost layer is prepared from by the product obtained by acrylic acid or the like or the acrylic monomer of replacement and the polymerisable monomer of the long Soxylat A 25-7 chain of band and polymerisable silicone monomer. Generating-Si-O-structure by the hydroxyl generation linked reaction of silicone functionalities and interlayer surfaces like this is formed covalently bound.

Above-mentioned interlayer institute role is respectively: innermost layer: when this material mixing cement-based material and carries out modification, play the effect of crosslinked node, owing to organism has excellent tensile property, it is possible to undertake part external force, in order to promote folding strength and the split tensile strength of cement-based material. Middle layer: be interconnected with covalent linkage between this layer and innermost layer organism core, this layer has double effect: a. is in the environment of cement-based material strong basicity, chemical reaction can be there is in this mineral shell, produce covalent linkage with main bonding component hydrated calcium silicate gel (CSH) wherein to be connected, thus by covalent chemical bond, whole organic polymer is connected with CSH particle, give full play to the effect that innermost layer organism improves cement-based material mechanical property; B. play CSH node effect, it is to increase CSH gel content in cement-based material, promote cement-based material mechanical property (such as ultimate compression strength). Outermost layer: in electrolyte solution, by Coulomb repulsion and space stability ultimate load hybrid particle, enables fully to disperse in the cement-based material of highly basic height salt.

This admixture material is connected in order to improve the organic constituents of cement-based material mechanical property with CSH particle by covalent linkage by inorganic component, improves the efficiency that organic constituents plays toughness properties; Simultaneously, layer structure is by stronger electrostatic repulsion and space steric effect these particles of abundant stable dispersion, enable to be scattered in cement-based material pore solution with (soilless sticking) form of single dispersing, further improve particle for efficiency during cement-based material modification.

This admixture effective constituent is spheroidal particle, its all directions by force rate fiber evenly, thus there is not orientation problem. Compared to simple polymer-modified cementitious materials or polymer fiber and modified cement-based material, admixture dosage of the present invention can much slower (core-shell particles consumption is the 0.5-5.0% relative to total glue material amount), with traditional polymer emulsion when same volume cement-based material fracture resistance and tension (or split draw) performance boost is more obvious, overcome traditional polymer modified cement sill because polymkeric substance volume height thus affect the defect of cement-based material ultimate compression strength. Even further, owing to the inorganic component introduced can produce more CSH bonding component, cement-based material ultimate compression strength is promoted to some extent.

The preparation method of the admixture of the above-mentioned anti-folding of lifting cement-based material and tensile strength, it is preferable that, comprise the following steps that order connects:

(1) preparation of innermost layer:

In reactor, add the polymerisable monomer A of institute's requirement, polymerisable monomer B, the 0-100% of linking agent C and institute's requirement water, fully it is uniformly mixed, obtains mixed solution, logical N in mixed solution₂Except O₂, reactor is risen to 20-90 DEG C, in reactor, under agitation condition, adds initiator initiated polymerization, the mixed solution simultaneously dripping the residue part and polymerisable monomer D that add linking agent C in reactor carries out copolymerization, adding fashionable timing from initiator, reaction 2-8h, obtains organic polymer core dispersion liquid;

The quality of polymerisable monomer A, B, D and linking agent C and account for the 5-45% of polymerization system total mass in step (1), wherein, the quality of polymerisable monomer A accounts for polymerisable monomer A, B, D and the 0-5% of linking agent C total mass, the quality of linking agent C accounts for polymerisable monomer A, B, D and the 0-5% of linking agent C total mass, and the ratio of the total mass that the quality of polymerisable monomer B accounts for polymerisable monomer B and D is not less than 10%;

Wherein, the one of polymerisable monomer A for meeting in following general formula ((1)-(3)) organism:

R₁��R₂��R₃And R₅It is respectively H or CH₃, R₄For the alkyl of 6-30 carbon atom, X₁��X₂��X₃And X₄Being respectively O or NH, a, b are the integer of 4-50, and c is the integer of 6-12;

Polymerisable monomer B is made up of monomer and non-functional single group body, and wherein, monomer accounts for the 0.5-5% of polymerisable monomer B total mass, and all the other are non-functional single group body;

Linking agent C is the mixture of one or more any proportionings in Vinylstyrene, vinyltrimethoxy silane, vinyltriethoxysilane (VTES), methacryloxypropyl trimethoxy silane (MAPTMS), methacryloxypropyl triethoxyl silane (MAPTES), methacryloxypropyl ylmethyl triethoxyl silane, acryloxy methyltrimethoxy silane or acryloxy propyl trimethoxy silicane:

Polymerisable monomer D is made up of functional group's type monomer and non-functional single group body, and wherein, monomer accounts for the 0.5-5% of polymerisable monomer D total mass, and all the other are non-functional single group body.

Initiator is thermal decomposition initiating or redox initiator, and according to thermal decomposition initiating, then initiator quality consumption is polymerisable monomer A, B, D and the 0.05-3% of linking agent C total mass; According to redox initiator, then consumption calculates with side's total mass that molar weight in Oxidizing and Reducing Agents is lower, is the 0.05-3% of polymerisable monomer A, B, D and linking agent C total mass;

Thermal decomposition initiating is azo-initiator or persulfuric acid salt initiator; Redox initiator comprises Oxidizing and Reducing Agents, and the mol ratio of oxygenant and reductive agent is 0.5-2.0, and oxygenant is H₂O₂, or persulphate, reductive agent is the mixture of one or more any proportionings in vitamins C, rongalite, S-WAT, sodium bisulfite or Sodium Pyrosulfite; If thermal decomposition initiating, then directly once add or slowly evenly add polymerization system; If redox initiator, then first oxygenant is added polymerization system, then reductive agent is slowly evenly added polymerization system, and should not add before polymerisable monomer A, B, D and linking agent C all add reaction system;

(2) the coated middle layer of innermost surface:

The organic polymer core dispersion liquid of preparation in step (1) is regulated required pH, at 30-80 DEG C, dripping in organism E or silicon containing component F one or both under agitation condition in organic polymer core dispersion liquid, dropwise reaction 1-24 hour, must be coated with the dispersion liquid in middle layer; If only using organism E, then required pH is 2-12, if only using silicon containing component F or organism E and silicon containing component F all used times, then required pH is 2-8;

Wherein, organism E is the silane that more than three alkoxyl groups replace; Silicon containing component F is made up of water glass and reactant K, and reactant K is the mixture of one or more any proportionings in ammonium nitrate, ammonium sulfate, ammonium acetate or acetic acid, drips the added-time, and water glass and reactant K separately drip and add; The mol ratio of water glass and reactant K is (ammonium ion+acetic acid)/water glass is 2.0-2.2;

In organism E and silicon containing component F, contained element silicon total mass is the 2-20% of first stage gained organic polymer core total mass, and the total mass that in silicon containing component F, contained element silicon quality accounts for element silicon in organism E and silicon containing component F is no more than 25%;

(3) at the coated outermost layer of interlayer surfaces:

Gained dispersion liquid in step (2) is adjusted pH to 4-12, when temperature is 40-90 DEG C, in reaction system, it is added with organic polymer G, dropwise reaction 1-5h, volatilizable organic molecule is extracted in decompression out, must promote the admixture of the anti-folding of cement-based material and tensile strength; The quality consumption of organic polymer G is the 2-50% of gained particle total mass in step (2);

Wherein, organic polymer G is the polymkeric substance prepared by radical copolymerization by monomer H, I and J; The molar fraction that monomer H, I and J account for total monomer (H+I+J) is respectively m₁��n₁��p₁, m₁+n₁+p₁=100%, and 2%��m₁�� 80%, 0.5%��n₁�� 96%, 2%��p₁�� 30%;

Monomer H is the one in vinylformic acid, methacrylic acid, acrylic acid sodium salt or sylvite, the sodium salt of methacrylic acid or sylvite; Monomer I is monomethyl polyethylene glycol acrylate ester, polyethylene glycol monomethyl ethermethacrylic acid esters, allyl polyethenoxy ether, methacrylic Soxylat A 25-7, butenyl Soxylat A 25-7, methyl butene base Soxylat A 25-7 or vinyl Soxylat A 25-7; Monomer J is vinyltrimethoxy silane, vinyltriethoxysilane (VTES), methacryloxypropyl trimethoxy silane (MAPTMS), methacryloxypropyl triethoxyl silane (MAPTES), methacryloxypropyl ylmethyl triethoxyl silane, acryloxy methyltrimethoxy silane or acryloxy propyl trimethoxy silicane.

In step (1), a, b are the integer of 4-50, and c is the integer of 6-12; A, b refer to oxyethyl group-CH in organism shown in general formula (1) and (2) respectively₂CH₂O-chain link average repeat unit number, for commercial goods and synthetics, these two kinds of organism are generally the polymkeric substance of small-molecular-weight instead of the pure compound of single variety, and such as, A may be by oxyethyl group-CH₂CH₂The mixture of five kinds of compounds of O-chain link number of repeat unit 40,41,42,43 and 44, and the average repeat unit number of these five kinds of compounds is 42. But c should be the compound of small molecules synthesis, and non-CH₂The mean value of-chain number, it is definite.

In step (1), it is because when this admixture is for cement-based material modification that the total mass of restriction polymerisable monomer A, B, D and linking agent C is not less than 5%, the solid effective ingredient consumption mixing system should be no less than the 0.5% of total glue material, otherwise it is not obvious to the contribution of mechanical property. And if admixture total solid content is too low, then possibly cannot meet service requirements. In fact, even if when polymerisable monomer A, B, D and linking agent C consumption are lower than total polymerization system 5% solid content, this reaction also can successfully carry out.

Polymerization system in step (1) comprises polymerisable monomer A, B, D, linking agent C, initiator and water.

It is weak that a, b and c value in above-mentioned polymerisable monomer A crosses little then self-emulsifying action, and value is excessive then too low compared to polymerisable monomer B and linking agent C polymerization activity, thus causes residuing in polymerization system in a large number because being difficult to copolymerization. Polymerisable monomer A is for stablizing the organic polymer nuclear particle of first stage synthesis, and it acts on the polymerisable emulsifier in the polymerization of similar conventional emulsion.

The effect of linking agent C is to promote the mechanical strength of polymer beads daughter nucleus, reduces the solvability of polymer beads daughter nucleus in water.

Azo-initiator is preferably VA044 or V50; Persulfuric acid salt initiator is preferably ammonium persulphate, Potassium Persulphate or Sodium Persulfate. Persulphate is preferably ammonium persulphate, Sodium Persulfate or Potassium Persulphate;

Initiator amount is lower than 0.05%, it is possible to make organic monomer transformation efficiency not enough, if initiator amount is higher than 3%, then cruelly poly-because initial velocity of initiation is too fast may make reaction failure (a large amount of precipitation or gel will occur).

Because the existence of transformation period, thermal decomposition initiating elicitation procedure is relatively mild, so can once add, it is also possible to slowly evenly add. But for redox initiation system, general activation energy is lower, if once adding initiation, then not only transformation efficiency can be made on the low side because of later stage number of free radical is too low, and early stage number of free radical is too high easily causes that speed of response is too fast makes system not redispersible precipitation occur.

The application's temperature of reaction (initiation and polymerization temperature) is 20-90 DEG C, and redox initiation system kick off temperature is lower, and even close to normal temperature, thermolysis initiator system kick off temperature can determine according to its transformation period. Polymerization time is more long, and transformation efficiency is more high, and body series polymerization time generally can be controlled in 2-8h, generally needs to guarantee that initiator decomposes in order to avoid being had an impact by synthesis step afterwards substantially completely when being polymerized.

In step (2), dropwise reaction 1-24 hour refers to start from organism E or silicon containing component F to drip and adds timing to reacting complete time. E and F drips simultaneously and adds, and drips that to add the time identical, drips and adds that to terminate the moment identical.

In step (2), organism E is the silane that a kind of more than three alkoxyl groups replace, and can form siloxane bond network. Water glass hydrolysis produces silicon-dioxide, and reactant K is slightly acidic or partial neutral, for water glass hydrolysis provides hydrogen ion, does not adopt the reason of strongly-acid material to be that the initial pH of reaction system is had bigger impact.

If element silicon total amount is too low in organism E used and silicon containing component F, then it is difficult to the silicon dioxide layer of coated adequate thickness on organic polymer nuclear particle; Consumption is too high, then when this admixture being used for cement-based material modification, it is necessary to corresponding raising volume could introduce enough organic constituentses so that when low-dosage, this admixture is not obvious to the improvement of folding strength and tension (or split draw) intensity. Silicon containing component F can generate a large amount of inorganic salt in reaction process, and therefore its used in amounts to be controlled.

In step (2), pH exceeds institute's limited range, sourer then will generate a large amount of homogeneous phase silicon-dioxide, more alkali is then reacted slow (for silicon containing component F), or particle itself is because occurring to react and loss of stability with the high density OH-in reaction environment.

Component E and silicon containing component F is in reaction process evenly to drip add, and silicon containing component F drips the added-time, water glass and reactant K are made generally in the aqueous solution, and these two kinds of components are dripped, and to add the time preferably identical, the dripping of silicon containing component F adds the time and too short will generate homogeneous phase silicon-dioxide in a large number, but not is coated on the shell of first stage gained organic polymer nuclear particle. During system temperature height, speed of response increases, and can adopt the relatively short reaction time; When temperature is low, the general employing relatively long reaction times.

In step (2), in organism E and silicon containing component F, contained element silicon total mass is the 2-20% of first stage gained organic polymer core total mass, and organic polymer core total mass does not comprise water herein.

In step (3), organic polymer G consumption is too low can not play stabilization, and consumption is too high affects when final admixture described in this patent is used for cement-based material modification the lifting to folding strength and tension (or split draw) intensity. Dropwise reaction 1-5h refers to start to drip from organic polymer G add timing to reacting complete time.

In step (3), pH is too low, and polymkeric substance G may be suppressed to ionize, and causes product particle poly-heavy in electrolyte solution, too high then particle itself because of with the high density OH in reaction environment^-Occur to react and loss of stability.

In step (3), organic polymer G feed postition adds for dripping, once add and poly-heavy phenomenon then relatively easily occurs, drip and add the time for being no more than 3h, too much going bad more than the silicone functionalities in 3h then polymkeric substance H and cause playing a role, temperature of reaction is selected higher than normal temperature to increase siloxane reactions speed.

Applicant finds after deliberation, adds if polymkeric substance G is disposable, and single polymers G can react from different particles simultaneously, is interconnected by different particles, particle is increased, and then poly-heavy; Polymkeric substance G drips that to add then polymkeric substance G not enough relative to particle far away, and a small amount of polymkeric substance G of a large amount of particle contention, polymkeric substance G tend to and single particle reaction, and it is heavy not assemble.

The synthetic method of organic polymer G can refer to document JournaloftheChineseCeramicSociety, and 2014,42,635; CementandConcreteResearch2012,42,166.

Above-mentioned monomer H provides electronegativity functional group, monomer I provides long side chain (space steric hindrance), monomer J provides silicone functionalities, makes organic polymer G be connected to the particle surface prepared by step (2) by hydrolysis reaction with covalent linkage form.

The molar fraction of monomer H, I and J is too low is all unfavorable for that corresponding monomer effectively plays a role. Control monomer H molar fraction is not that the molar fraction in order to control monomer I and J is not less than 20% higher than 80%, so that the functional group's (from monomer I) having enough offer space steric hindrances is covalently attached to the particle surface prepared by step (2), make particle more stable. Monomer J molar fraction height, the then covalently bound efficiency height of polymkeric substance G, but monomer J molar fraction is too high, and polymkeric substance G may be caused to be insoluble to water.

In step (3), the quality consumption of organic polymer G is the 2-50% of gained particle total mass in step (2); In step (2), gained particle refers to the particle being made up of (for the three-layer nuclear shell particle of final gained) polymer core and middle layer synthesized, do not comprise also not coated outer polyelectrolyte, in the particle dispersion of step (2) gained except particle (being made up of polymer core and middle layer), also has the inorganic salt by-product (sodium salt, as water glass and ammonium nitrate produce SODIUMNITRATE, ammonia and silicon-dioxide) produced in step (2) inorganic salt hydrolysis reaction.

In step (1), the monomer in polymerisable monomer B and polymerisable monomer D is the polymerisable monomer of hydroxyl, amino or carboxyl; Non-functional group type monomer in polymerisable monomer B and polymerisable monomer D is the mixture of one or more any proportionings in monomer shown in vinylbenzene and following general formula (4);

R₆Represent H or CH₃, R₇Represent the alkyl of 1-12 carbon atom.

Polymerisable monomer B and polymerisable monomer D is the main composition of organic polymer nuclear particle, its role is to provide the good organism matrix of toughness, for finally promoting folding strength and the split tensile strength of cement-based material. The composition of polymerisable monomer B and polymerisable monomer D both can identical also can be different.

Preferably, the above-mentioned polymerisable monomer containing amino is hydrochloride or the sulfonate of 3-amino-benzene ethene, 4-amino-benzene ethene, 2-(tert-butylamino) ��-dimethyl-aminoethylmethacrylate, aminoethyl methacrylate or above-mentioned monomer; Carboxylic polymerisable monomer is the univalent metal salt of vinylformic acid, methacrylic acid, acrylic acid univalent metal salt or methacrylic acid; The polymerisable monomer of hydroxyl is hydroxy acrylate, methacrylic ester, hydroxyacrylamide, hydroxymethylacrylamide class monomer. The univalent metal salt of aforesaid propylene acid or the univalent metal salt of methacrylic acid are preferably sodium salt or sylvite.

Further preferably, the polymerisable monomer of hydroxyl is vinylformic acid-2-hydroxyl second ester, 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate, vinylformic acid-4-hydroxybutyl, methacrylic acid-2-hydroxy propyl ester, methacrylic acid-4-hydroxybutyl, N hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, N-(2-hydroxypropyl) acrylamide, N-methylol methacrylamide or N-(2-hydroxypropyl) Methacrylamide. Can ensure that products obtained therefrom can take into account folding strength and toughness and ultimate compression strength simultaneously so further.

Preferably, in step (2), organism E is tetraethoxysilane, tetramethoxy-silicane, vinyltrimethoxy silane, vinyltriethoxysilane, methacryloxypropyl trimethoxy silane (MAPTMS), methacryloxypropyl triethoxyl silane (MAPTES), ��-mercaptopropyl trimethoxysilane or (3-aminopropyl) triethoxyl silane. Can further ensure that products obtained therefrom can take into account folding strength and toughness and ultimate compression strength simultaneously like this.

Preferably, in step (3), repeating unit-CH in polyglycol chain in monomer I structure₂CH₂The numerical value span of O-is 4-55. The too low effect being difficult to play its space steric hindrance thus stable dispersion liquid particles of above-mentioned value, too high then its polymerization activity of value is low, and residual quantity is higher, and impact this admixture final is applied to the air content of cement-based material.

Preferably, in step (3), polymkeric substance G weight-average molecular weight is 5000-100000. Molecular weight is too low then too low for siloxanes covalent linkage ligation efficiency time step (3), and molecular weight is too high, can obviously increase system viscosity. Polymkeric substance G may change in placement process, therefore needs in post synthesis to use at once.

In the application, volume refers to the ratio of the quality of pure effective constituent (core-shell particles) in the aqueous dispersions that this patent finally synthesizes relative to glue material amount in cement-based material.

The technology that the present invention does not mention is all with reference to prior art.

Compared with prior art, the present invention has following advantage:

The present invention promotes the admixture of the anti-folding of cement-based material and tensile strength for cement-based material modification, volume is more high, its folding strength and tension (split and draw) intensity improve more obvious, volume is even to reach 30-40% under 5% condition, simultaneously to its ultimate compression strength almost without negative impact (ultimate compression strength reduce degree < 5%) or slightly improve.

Accompanying drawing explanation

Fig. 1 is structural formula corresponding to each abbreviation in embodiment.

Fig. 2 is the transmission electron microscope picture of the nucleocapsid structure of synthesis in embodiment 2.

Fig. 3 is infrared spectra (FT-IR) figure of the particle that step (1)-(3) in embodiment 2 (Step (1)-Step (3)) obtain.

Fig. 4 is the dynamic light scattering size distribution figure of the particle that step (1)-(3) in embodiment 2 (Step (1)-Step (3)) obtain.

Embodiment

In order to understand the present invention better, illustrate the content of the present invention further below in conjunction with embodiment, but the content of the present invention is not only confined to the following examples.

Generally, when high solids content, building-up reactions is more difficult, and such as, easily because speed of response too fast and out of control (particle aggregation occur), high solids content can synthesize, then the aqueous dispersions of corresponding low-solid content can also obtain. Following examples are all described with the preparation of high solids content sample and contrast.

Unit used is mass parts below, and all compound used therefors are business product, or the synthetics (accompanying drawing 1) of document report.

1, the synthesis of polymkeric substance G:

The synthesis of polymkeric substance G and molecular weight determination reference (JournaloftheChineseCeramicSociety, 2014,42,635; CementandConcreteResearch2012,42,166).

(1) polymkeric substance G01 (m₁/n₁/p₁=2/96/2):

To being equipped with in the round-bottomed flask of thermometer, agitator, dropping funnel and nitrogen conduit to add 50 parts of distilled water and 0.5 part of mass concentration is the hydrogen peroxide of 30%, stir and holding temperature is 30 DEG C; By 0.58 part of vinylformic acid (AA), 97.44 parts of methoxy polyethylene glycol acrylate (-CH₂CH₂O-average repeat unit number 4; AAM4), 1.98 parts of methacryloxypropyl trimethoxy silane (MAAPTMS), 0.388 part of vitamins C (VC), 0.42 part of Thiovanic acid (MEA) and 100 parts of water are fully uniformly mixed; under nitrogen protection; the aqueous dispersions adding AA/AAM4/MAAPTMS/VC/MEA is evenly dripped in flask; drip and add the time and be controlled to 5h; drip to add and terminate to continue the aqueous solution that insulation 1h can obtain polymkeric substance G02; polymkeric substance effective solid content 40%; actual measurement solid content 40.4%, weight-average molecular weight 43700. This aqueous solution directly uses at once in follow-up preparation, non-separation and purification.

(2) polymkeric substance G02 (m₁/n₁/p₁=69/1/30):

50 parts of distilled water, 9.14 parts of methacrylic polyoxyethylene glycol (-CH are added to being equipped with in the round-bottomed flask of thermometer, agitator, dropping funnel and nitrogen conduit₂CH₂O-average repeat unit number 25, HPEG25), 44.51 parts of vinyltriethoxysilanes (VTES) and 0.5 part of mass concentration be the hydrogen peroxide of 30%, stir and holding temperature is 40 DEG C. 46.34 parts of methacrylic acids (MAA), 0.388 part of VC, 0.14 part of MEA and 100 part of water are fully uniformly mixed; under nitrogen protection; the aqueous dispersions adding MAA/VC/MEA is evenly dripped in flask; drip and add the time and be controlled to 3h; drip to add and terminate to continue the aqueous solution that insulation 1h can obtain polymkeric substance G01; polymkeric substance effective solid content 40%, actual measurement solid content 40.3%, weight-average molecular weight 96300. This aqueous solution directly uses at once in follow-up preparation, non-separation and purification.

(3) polymkeric substance G03 (m₁/n₁/p₁=80/10/10):

In the round-bottomed flask that thermometer, agitator, dropping funnel and nitrogen conduit are housed, add 50 parts of distilled water, 71.24 parts of methyl butene base polyoxyethylene glycol (-CH₂CH₂O-average repeat unit number 52, IPEG52) and 0.5 part of mass concentration is the hydrogen peroxide of 30%, stirring also holding temperature is 45 DEG C, preparation is containing 22.58 parts of sodium acrylates (AANa), 6.18 parts of acryloxy methyltrimethoxy silanes (AAMTMS), 0.388 part of vitamins C, the dispersion liquid of 1.11 parts of Thiovanic acids and 100 parts of water is also fully uniformly mixed, under nitrogen protection, the aqueous dispersions adding AANa/IPEG52/AAMTMS is evenly dripped in flask, drip and add the time and be controlled to 2h, drip to add and terminate to continue the aqueous solution that insulation 1h can obtain polymkeric substance G03, polymkeric substance effective solid content 40%, actual measurement solid content 40.3%, weight-average molecular weight 12600. this aqueous solution directly uses at once in follow-up preparation, non-separation and purification.

(4) polymkeric substance G04 (m₁/n₁/p₁=60/30/10):

In the round-bottomed flask that thermometer, agitator, dropping funnel and nitrogen conduit are housed, add 50 parts of distilled water and 0.5 part of mass concentration is the hydrogen peroxide of 30%, stir and holding temperature is 10 DEG C. Preparation is containing 17.67 parts of methacrylic acid potassium (MAAK), 76.10 parts of methoxy polyethylene glycol methacrylate-styrene polymer (-CH₂CH₂O-average repeat unit number 22; MAAM22), the dispersion liquid of 6.22 parts of methacryloxypropyls ylmethyl triethoxyl silane (MAAMTES), 0.388 part of vitamins C, 1.26 parts of Thiovanic acids and 100 parts of water and be fully uniformly mixed; under nitrogen protection; the aqueous dispersions adding MAAK/MAAM22/MAAMTES is evenly dripped in flask; drip and add the time and be controlled to 5h; drip to add and terminate to continue the aqueous solution that insulation 1h can obtain polymkeric substance G04; polymkeric substance effective solid content 40%; actual measurement solid content 40.5%, weight-average molecular weight 5400. This aqueous solution directly uses at once in follow-up preparation, non-separation and purification.

The synthesis of the admixture of 2 lifting cement-based material folding strengths and split tensile strength:

Polymerisable monomer used is commercial goods below, or according to the document synthesis gained (source of polymerisable monomer A: (1) is commercially available; (2) polymer circular, 2008,16; PolymerBulletin1999,42287; JournalofAppliedPolymerScience2000,77,2768; (3) Langmuir2001,17,6077.)

4-amino-benzene ethene hydrochloride (4-VBAH) is synthetics, with reference to AnalyticalChemistry2012,84,3500.

The theoretical solid content of effective constituent (the organo-mineral complexing particle of nucleocapsid three-decker) calculates according to throwing material, containing the inorganic salt produced in reaction in actual measurement solid content, this part is non-active ingredients also, and historical facts or anecdotes surveys solid content higher than the theoretical solid content of effective constituent.

Embodiment 1

(1) in reactor, polymerisable monomer A (numbering A1, polyethylene glycol methacrylate-styrene polymer ,-CH in polyglycol chain is added₂CH₂O-average repeat unit number is 6, end group is hydroxyl, consumption 0.1 part), polymerisable monomer B (0.29 part, vinylformic acid (AA) and methyl methacrylate (MMA) 9.22 parts), linking agent C (Vinylstyrene (DVB) 5 parts, commodity DVB comprise between position and para-isomeride) and 92.22 parts of water, be fully uniformly mixed; In mixed solution, logical N2 is except O2, temperature of reactor is risen to 80 DEG C, in reactor, initiator (0.05 part of ammonium persulphate APS is dissolved in 30 parts of water) initiated polymerization is once added under agitation condition, start to drip in reactor simultaneously and add polymerisable monomer D (4.28 parts, vinylformic acid and MMA81.13 part), drip and add 5h. Timing when starting to add reactor from initiator, reacts 6h under polymerizing condition, then removes inert atmosphere protection, obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temperature is down to 30 DEG C, slowly drip wherein and add the NaOH aqueous solution (0.1M), pH is adjusted to 11.0, add 34.21 parts of water wherein, in organic polymer nuclear particle dispersion liquid, organism E (the tetraethoxysilane TEOS adding institute's requirement is evenly dripped under agitation condition, 14.86 parts, silicon content 2 parts), dropwise reaction 24h.

(3) in gained dispersion liquid in step (2), slow dripping adds the NaOH aqueous solution (0.1M), pH is adjusted to 10.0, temperature is risen to 70 DEG C, the 5.21 parts of organic polymer G01 aqueous solution prepared are added in reaction system, drip and stop after adding 2h, volatilizable organic molecule is extracted in decompression out, can obtain the required admixture W01 promoting cement-based material folding strength and split tensile strength.

The theoretical solid content 40.0% of effective constituent, actual measurement solid content 40.2%.

Embodiment 2

(1) in reactor, polymerisable monomer A (numbering A2, monomethyl polyethylene glycol acrylate ester ,-CH in polyglycol chain is added₂CH₂O-average repeat unit number is 22, end group is methyl, consumption is 2.00 parts), polymerisable monomer B (4-amino-benzene ethene hydrochloride (4-VBAH) 0.49 part and vinylbenzene (St) 97.51 parts), 3 parts of APS and 92.22 part of water, be fully uniformly mixed; Logical N in mixed solution₂Except O₂, temperature of reactor is risen to 70 DEG C, evenly drips in reactor under agitation condition and add initiator (1.71 parts of sodium bisulfite SBS are dissolved in 30 parts of water) initiated polymerization, drip and add 6h. Timing when starting to add reactor from initiator, reacts 7h under polymerizing condition, then removes inert atmosphere protection, obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temperature is down to 60 DEG C, slowly drip wherein and add H₂SO₄The aqueous solution (0.05M), is adjusted to 2.5 by pH, adds 59.92 parts of water wherein, in organic polymer nuclear particle dispersion liquid, organism E (the tetramethoxy-silicane TMOS adding institute's requirement is dripped under agitation condition, 54.29 parts, silicon content 10 parts), dropwise reaction 4h.

(3) in gained dispersion liquid in step (2), slow dripping adds H₂SO₄The aqueous solution (0.05M), pH is adjusted to 4.0, temperature is risen to 50 DEG C, the 151.79 parts of organic polymer G02 aqueous solution prepared are added in reaction system, drip and stop after adding 3h, volatilizable organic molecule is extracted in decompression out, can obtain the required admixture W02 promoting cement-based material folding strength and split tensile strength.

The theoretical solid content 40.0% of effective constituent, actual measurement solid content 40.4%.

Can obviously finding out by Fig. 2, its innermost layer and middle layer are high-visible, and outermost layer organic polyelectrolyte, owing to being subject to the restriction of grafting density, cannot be observed directly by TEM.

Fig. 3 is the infrared spectra (FT-IR) of the particle that step (1)-(3) in embodiment 2 (Step (1)-Step (3)) obtain, and the sample that all FT-IR test is all through dialysis purifying. can obviously find out by Fig. 3, 1581cm-1 and 1603cm-1 in Step (1) spectrogram, and the multiplet (can pointed out as unsaturated c h bond) within the scope of 3000cm-1-3120cm-1 proves phenyl ring (polystyrene agent structure), Step (2) is compared with Step (1), only absorb near 1120cm-1 and obviously increase, this is the stretching vibration of the Si-O of increase, prove that step (2) adds SiO2 layer, Step (3) is compared with Step (2), an absorption peak is increased near 1650cm-1, it is attributed to carboxylic acid (salt) carbonylic stretching vibration peak, belong to the stretching vibration peak of C-H within the scope of 2800-3000cm-1 simultaneously, this region ratio that unsaturated C-H vibrates relative within the scope of 3000cm-1-3120cm-1 increases to some extent, prove that saturated c h bond increases to some extent, contrast synthesis condition is confirmed as organic polymer G and is connected on particle in step (3).

Fig. 4 is the dynamic light scattering size distribution figure of the particle that step (1)-(3) in embodiment 2 (Step (1)-Step (3)) obtain, and each step particle radii all increase to some extent than back.

Embodiment 3

(1) in reactor, polymerisable monomer A (numbering A3, polyethylene glycol monomethyl ethermethacrylic acid esters ,-CH in polyglycol chain is added₂CH₂O-average repeat unit number is 45, consumption is 5.00 parts), polymerisable monomer B (1.38 parts, vinylformic acid-2-hydroxyl second ester (HEA), n-butyl acrylate (n-BuA) 17.12 and lauryl acrylate (LA) 9.10 parts), linking agent C (1 part of DVB) and 92.22 parts of water, be fully uniformly mixed; Logical N in mixed solution₂Except O₂Temperature of reactor is risen to 60 DEG C, in reactor, initiator (1 part of azo diisobutyl amidine hydrochloride V50 is dissolved in 30 parts of water) initiated polymerization is once added under agitation condition, starting to drip in reactor to add residue part linking agent C (2 parts of DVB) polymerisable monomer D (4-VBAH1.29 part and MMA63.11 part), residue part linking agent C and polymerisable monomer D drips and adds 3h simultaneously. Timing when starting to add reactor from initiator, reacts 4h under polymerizing condition, then removes inert atmosphere protection, obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temperature rises to 80 DEG C, slowly drip wherein and add the NaOH aqueous solution (0.1M), pH is adjusted to 9.0, add 120.99 parts of water wherein, in organic polymer nuclear particle dispersion liquid, organism E (the vinyltriethoxysilane VTES135.71 part adding institute's requirement is dripped under agitation condition, silicon content 20 parts), dropwise reaction 12h.

(3) in gained dispersion liquid in step (2), slow dripping adds the NaOH aqueous solution (0.1M), pH is adjusted to 11.0, temperature is risen to 50 DEG C, the 40.54 parts of organic polymer G03 aqueous solution prepared are added in reaction system, drip and stop after adding 1h, volatilizable organic molecule is extracted in decompression out, can obtain the required admixture W03 promoting cement-based material folding strength and split tensile strength.

The theoretical solid content 40.0% of effective constituent, actual measurement solid content 40.4%.

Embodiment 4

(1) in reactor, add polymerisable monomer A (numbering A4, N-poly glycol monomethyl ether-acrylamide ,-CH in polyglycol chain₂CH₂O-average repeat unit number is 45, consumption 0.1 part), polymerisable monomer B (0.75 part, vinylformic acid, methacrylic acid (MAA) 1.73 parts and n-BuA46.93 part) and 92.22 parts of water, be fully uniformly mixed; Logical N in mixed solution₂Except O₂Temperature of reactor is risen to 50 DEG C, evenly drip in reactor under agitation condition and add initiator (2 parts of different fourth imidazoline hydrochloride VA044 of azo two are dissolved in 30 parts of water) initiated polymerization, starting to drip in reactor to add linking agent C (1 part of DVB) and polymerisable monomer D (0.25 part of 2-hydroxypropyl acrylate (HPA), 24.61 parts of MMA and 24.64 part of St), initiator, linking agent C and polymerisable monomer D all drip and add 6h simultaneously. Timing when starting to add reactor from initiator, reacts 8h under polymerizing condition, then removes inert atmosphere protection, obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temperature rises to 80 DEG C, slowly drip wherein and add H₂SO₄The aqueous solution (0.05M), pH is adjusted to 3.0, in organic polymer nuclear particle dispersion liquid, organism E (the methyltrimethoxy silane MTMOS7.29 part adding institute's requirement is dripped under agitation condition, silicon content 1.5 parts) and the aqueous solution of silicon containing component F (water glass 2.18 parts is dissolved in 25.33 parts of water, silicon content 0.5 part; 2.89 parts of ammonium nitrate are dissolved in 10 parts of water), dropwise reaction 3h.

(3) in gained dispersion liquid in step (2), slow dripping adds the NaOH aqueous solution (0.1M), pH is adjusted to 9.0, temperature is risen to 60 DEG C, the 37.9 parts of organic polymer G04 aqueous solution prepared are added in reaction system, drip and stop after adding 3h, volatilizable organic molecule is extracted in decompression out, can obtain the required admixture W04 promoting cement-based material folding strength and split tensile strength.

The theoretical solid content 40.0% of effective constituent, actual measurement solid content 41.2%.

Embodiment 5

(1) in reactor, polymerisable monomer A (numbering A5 is added, the just pungent oxygen base benzene sulfonic acid sodium salt of 4-(8-acryloyl-oxy), consumption is 3.00 parts), polymerisable monomer B (methacrylic acid-2-amino ethyl ester hydrochloride (AEMH) 0.18 part and vinylformic acid n-octyl (n-OctA) 9.02 parts), linking agent C (0.2 part of vinyltriethoxysilane (VTES) and 0.3 part of DVB), 0.13 part of massfraction 30% H₂O₂The aqueous solution and 92.22 parts of water, be fully uniformly mixed; Logical N in mixed solution₂Except O₂Temperature of reactor is maintained 20 DEG C, evenly drip in reactor under agitation condition and add initiator (0.1 part of vitamins C (VC) is dissolved in 30 parts of water) initiated polymerization, starting to drip in reactor simultaneously and add residue part linking agent C (1.8 parts of VTES and 2.7 part of DVB) and polymerisable monomer D (3-amino-benzene ethene (3-VBA) 0.41 part and n-BuA82.39 part), initiator, residue part linking agent C and polymerisable monomer D all drip and add 2h. Timing when starting to add reactor from initiator, reacts 3h under polymerizing condition, then removes inert atmosphere protection, obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temperature rises to 30 DEG C, slowly drip wherein and add H₂SO₄The aqueous solution (0.05M), pH is adjusted to 8.0, in organic polymer nuclear particle dispersion liquid, organism E (the tetramethoxy-silicane TMOS40.71 part adding institute's requirement is dripped under agitation condition, silicon content 7.5 parts) and the aqueous solution of silicon containing component F (water glass 10.89 parts is dissolved in 35 parts of water, silicon content 2.5 parts; 12.92 parts of ammonium sulfate are dissolved in 24.92 parts of water), dropwise reaction 24h.

(3) in gained dispersion liquid in step (2), slow dripping adds the NaOH aqueous solution (0.1M), pH is adjusted to 9.0, temperature is risen to 60 DEG C, the 26.34 parts of organic polymer G04 aqueous solution prepared are added in reaction system, drip and stop after adding 4h, volatilizable organic molecule is extracted in decompression out, can obtain the required admixture W05 promoting cement-based material folding strength and split tensile strength.

The theoretical solid content 40.0% of effective constituent, actual measurement solid content 45.9%.

Embodiment 6

(1) in reactor, add polymerisable monomer A (numbering A6, dodecyl-poly glycol monomethyl ether-maleic acid diester ,-CH₂-CH₂O-average repeat unit number 45, consumption is 5.00 parts), polymerisable monomer B (2-hydroxypropyl acrylate (HPA) 0.47 part and methyl acrylate (MA) 92.54 parts), linking agent C (2 parts of VTES), 2.4 parts of Sodium Persulfate SPS and 92.22 part of water, be fully uniformly mixed; Logical N in mixed solution₂Except O₂, temperature of reactor is maintained 60 DEG C, evenly drips in reactor under agitation condition and add initiator (1 part of Sodium Pyrosulfite (SMBS) is dissolved in 30 parts of water) initiated polymerization, drip and add 3.5h. Timing when starting to add reactor from initiator, reacts 4h under polymerizing condition, then removes inert atmosphere protection, obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temperature is down to 40 DEG C, slowly drip wherein and add H₂SO₄The aqueous solution (0.05M), pH is adjusted to 5.0, in organic polymer nuclear particle dispersion liquid, organism E (the TEOS111.43 part adding institute's requirement is dripped under agitation condition, silicon content 15 parts) and the aqueous solution of silicon containing component F (water glass 21.79 parts is dissolved in 62.06 parts of water, silicon content 5 parts; 29.65 parts of ammonium acetates are dissolved in 30 parts of water), dropwise reaction 20h.

(3) in gained dispersion liquid in step (2), slow dripping adds the NaOH aqueous solution (0.1M), pH is adjusted to 9.0, temperature is risen to 60 DEG C, the 41.52 parts of organic polymer G03 aqueous solution prepared are added in reaction system, drip and stop after adding 3h, volatilizable organic molecule is extracted in decompression out, can obtain the required admixture W06 promoting cement-based material folding strength and split tensile strength.

The theoretical solid content 40.0% of effective constituent, actual measurement solid content 49.9%.

Embodiment 7

(1) in reactor, add the H of polymerisable monomer B (sodium acrylate 0.14 part and lauryl methacrylate(LMA) (LMA) 28.36 parts), linking agent C (4 parts of VTES), 2.02 parts of massfractions 30%₂O₂The aqueous solution and 92.22 parts of water, be fully uniformly mixed; Logical N in mixed solution₂Except O₂Temperature of reactor is maintained 30 DEG C, evenly drip in reactor under agitation condition and add initiator (2.5 parts of rongalites (SFA) are dissolved in 30 parts of water) initiated polymerization, starting to drip in reactor to add residue part linking agent C (1 part of DVB) polymerisable monomer D (AEMH0.92 part, 3-VBA0.41 part, LMA12.74 part and St52.43 part), initiator, residue part linking agent C and polymerisable monomer D all drip and add 5h simultaneously. Timing when starting to add reactor from initiator, reacts 6h under polymerizing condition, then removes inert atmosphere protection, obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temperature rises to 60 DEG C, slowly drip wherein and add H₂SO₄The aqueous solution (0.05M), pH is adjusted to 2.5, in organic polymer nuclear particle dispersion liquid, organism E (the MTMOS8.74 part adding institute's requirement is dripped under agitation condition, silicon content 1.8 parts) and the aqueous solution of silicon containing component F (water glass 0.87 part is dissolved in 15.56 parts of water, silicon content 0.2 part; 0.89 part of acetate dissolution is in 20 parts of water), dropwise reaction 12h.

(3) in gained dispersion liquid in step (2), slow dripping adds the NaOH aqueous solution (0.1M), pH is adjusted to 9.0, temperature is risen to 90 DEG C, the 5.26 parts of organic polymer G02 aqueous solution prepared are added in reaction system, drip and stop after adding 1h, volatilizable organic molecule is extracted in decompression out, can obtain the required admixture W07 promoting cement-based material folding strength and split tensile strength.

The theoretical solid content 40.0% of effective constituent, actual measurement solid content 40.7%.

Embodiment 8

(1) in reactor, polymerisable monomer A (numbering A8, polyethylene glycol monomethyl ethermethacrylic acid esters ,-CH in polyglycol chain is added₂CH₂O-average repeat unit number is 22, end group is methyl, consumption is 2.00 parts), polymerisable monomer B (aminoethyl methacrylate hydrochloride (AEMH) 0.41 part, methacrylic acid-2-t-butylaminoethyl (t-BAEMA) 2.01 parts and methyl methacrylate (MMA) 46.55 parts) and 92.22 parts of water, be fully uniformly mixed; Logical N in mixed solution₂Except O₂Temperature of reactor is maintained 90 DEG C, evenly drip in reactor under agitation condition and add initiator (3 parts of SPS are dissolved in 30 parts of water) initiated polymerization, starting to drip in reactor to add polymerisable monomer D (MAA2.45 part and LMA46.55 part), initiator and polymerisable monomer D all drip and add 2h simultaneously. Timing when starting to add reactor from initiator, reacts 4h under polymerizing condition, then removes inert atmosphere protection, obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temperature is down to 70 DEG C, slowly drip wherein and add H₂SO₄The aqueous solution (0.05M), pH is adjusted to 8.0, in organic polymer nuclear particle dispersion liquid, organism E (the 3-aminopropyl trimethoxysilane APTMS115.07 part adding institute's requirement is dripped under agitation condition, silicon content 18 parts) and the aqueous solution of silicon containing component F (water glass 8.71 parts is dissolved in 77.99 parts of water, silicon content 2 parts; 11.84 parts of ammonium nitrate are dissolved in 70 parts of water), dropwise reaction 6h.

(3) in gained dispersion liquid in step (2), slow dripping adds the NaOH aqueous solution (0.1M), pH is adjusted to 10.0, temperature is risen to 70 DEG C, the 225.18 parts of organic polymer G01 aqueous solution prepared are added in reaction system, drip and stop after adding 3h, volatilizable organic molecule is extracted in decompression out, can obtain the required admixture W08 promoting cement-based material folding strength and split tensile strength.

The theoretical solid content 40.0% of effective constituent, actual measurement solid content 42.9%.

Embodiment 9

(1) in reactor, polymerisable monomer A (numbering A9 is added, 4-(10-acryloyl-oxy) n-decyloxy benzene sulfonic acid sodium salt, consumption is 5.00 parts), polymerisable monomer B (N hydroxymethyl acrylamide (N-HMAAm) 0.18 part and MMA9.02 part), linking agent C (2.7 parts of methacryloxypropyl trimethoxy silane MAAPTMS and 0.3 part of VTES) and 92.22 parts of water, be fully uniformly mixed; Logical N in mixed solution₂Except O₂Temperature of reactor is maintained 85 DEG C, evenly drip in reactor under agitation condition and add initiator (0.1 part of Potassium Persulphate KPS is dissolved in 30 parts of water) initiated polymerization, starting to drip in reactor simultaneously and add polymerisable monomer D (methacrylic acid-2-hydroxy methacrylate (HEMA) 1.66 parts and MMA81.14 part), initiator and polymerisable monomer D all drip and add 5h. Timing when starting to add reactor from initiator, reacts 8h under polymerizing condition, then removes inert atmosphere protection, obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temperature is down to 60 DEG C, slowly drip wherein and add H₂SO₄The aqueous solution (0.05M), pH is adjusted to 2.5, in organic polymer nuclear particle dispersion liquid, organism E (the Union carbide A-162 MTEOS50.94 part adding institute's requirement is dripped under agitation condition, silicon content 8 parts) and the aqueous solution of silicon containing component F (water glass 8.71 parts is dissolved in 35.92 parts of water, silicon content 2 parts; 9.77 parts of ammonium sulfate are dissolved in 30 parts of water), dropwise reaction 8h.

(3) in gained dispersion liquid in step (2), slow dripping adds the NaOH aqueous solution (0.1M), pH is adjusted to 11.0, temperature is risen to 90 DEG C, the 47.04 parts of organic polymer G02 aqueous solution prepared are added in reaction system, drip and stop after adding 1h, volatilizable organic molecule is extracted in decompression out, can obtain the required admixture W09 promoting cement-based material folding strength and split tensile strength.

The theoretical solid content 40.0% of effective constituent, actual measurement solid content 44.1%.

Embodiment 10

(1) in reactor, add polymerisable monomer B (MAA5 part and t-BuA95 part) and 92.22 parts of water, fully it is uniformly mixed; Logical N in mixed solution₂Except O₂, temperature of reactor is maintained 80 DEG C, in reactor, under agitation condition, once adds initiator (3 parts of APS are dissolved in 30 parts of water) initiated polymerization. Timing when starting to add reactor from initiator, reacts 4h under polymerizing condition, then removes inert atmosphere protection, obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temperature is down to 60 DEG C, slowly drip wherein and add H₂SO₄The aqueous solution (0.05M), pH is adjusted to 3.0, in organic polymer nuclear particle dispersion liquid, organism E (the VTES64.46 part adding institute's requirement is dripped under agitation condition, silicon content 9.5 parts) and the aqueous solution of silicon containing component F (water glass 2.18 parts is dissolved in 43.66 parts of water, silicon content 0.5 part; 3 parts of ammonium acetates are dissolved in 30 parts of water), dropwise reaction 12h.

(3) in gained dispersion liquid in step (2), slow dripping adds H₂SO₄The aqueous solution (0.05M), pH is adjusted to 4.0, temperature is risen to 60 DEG C, the 32.65 parts of organic polymer G01 aqueous solution prepared are added in reaction system, drip and stop after adding 3h, volatilizable organic molecule is extracted in decompression out, can obtain the required admixture W10 promoting cement-based material folding strength and split tensile strength.

The theoretical solid content 40.0% of effective constituent, actual measurement solid content 41.2%.

Embodiment 11

(1) in reactor, add polymerisable monomer A (numbering A10, dodecyl-poly glycol monomethyl ether-maleic acid diester ,-CH₂-CH₂O-average repeat unit number 6, consumption is 3.00 parts), polymerisable monomer B (3-amino-benzene ethene (3-VBA) 0.57 part and St27.93 part) and 92.22 parts of water, be fully uniformly mixed; Logical N in mixed solution₂Except O₂, temperature of reactor is maintained 70 DEG C, evenly drips in reactor under agitation condition and add initiator (0.5 part of APS is dissolved in 15 parts of water; 0.55 part of S-WAT SS is dissolved in 15 parts of water, both drip respectively and add) initiated polymerization, starting to drip in reactor to add linking agent C (2 parts of acryloxy methyltrimethoxy silane AAMTMS) polymerisable monomer D (AEMH2 part and LA64.51 part), initiator, residue part linking agent C and polymerisable monomer D all drip and add 2.5h simultaneously. Timing when starting to add reactor from initiator, reacts 3h under polymerizing condition, then removes inert atmosphere protection, obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temperature is down to 30 DEG C, slowly drip wherein and add H₂SO₄The aqueous solution (0.05M), pH is adjusted to 3.0, in organic polymer nuclear particle dispersion liquid, organism E (the TEOS29.71 part adding institute's requirement is dripped under agitation condition, silicon content 4 parts) and the aqueous solution of silicon containing component F (water glass 4.36 parts is dissolved in 23.85 parts of water, silicon content 1 part; 4.6 parts of acetate dissolutions are in 20 parts of water), dropwise reaction 24h.

(3) in gained dispersion liquid in step (2), slow dripping adds the NaOH aqueous solution (0.1M), pH is adjusted to 9.0, temperature is risen to 60 DEG C, the 138.39 parts of organic polymer G04 aqueous solution prepared are added in reaction system, drip and stop after adding 2h, volatilizable organic molecule is extracted in decompression out, can obtain the required admixture W11 promoting cement-based material folding strength and split tensile strength.

The theoretical solid content 40.0% of effective constituent, actual measurement solid content 42.0%.

Embodiment 12

(1) in reactor, add polymerisable monomer A (numbering A7, dodecyl-hydroxyl polyethylene glycol groups-maleic acid diester ,-CH₂-CH₂O-average repeat unit number 32, consumption is 5.00 parts), polymerisable monomer B (HEMA0.23 part and LMA44.78 part), linking agent C (2.5 parts of VTES) and 92.22 parts of water, be fully uniformly mixed; Logical N in mixed solution₂Except O₂Temperature of reactor is maintained 60 DEG C, evenly drip in reactor under agitation condition and add initiator (1 part of V50 is dissolved in 30 parts of water) initiated polymerization, starting to drip in reactor to add residue part linking agent C (2.5 parts of VTES) and polymerisable monomer D (HEMA0.23 part and LMA44.78 part), initiator, residue part linking agent C and polymerisable monomer D all drip and add 4h simultaneously. Timing when starting to add reactor from initiator, reacts 6h under polymerizing condition, then removes inert atmosphere protection, obtains organic polymer nuclear particle dispersion liquid.

(2) maintaining gained organic polymer nuclear particle dispersion liquid temperature is 60 DEG C, slowly drips wherein and adds H₂SO₄The aqueous solution (0.05M), pH is adjusted to 2.5, in organic polymer nuclear particle dispersion liquid, organism E (the TEOS118.86 part adding institute's requirement is dripped under agitation condition, silicon content 16 parts) and the aqueous solution of silicon containing component F (water glass 17.43 parts is dissolved in 62.06 parts of water, silicon content 4 parts; 17.19 parts of acetate dissolutions are in 30 parts of water), dropwise reaction 8h.

(3) in gained dispersion liquid in step (2), slow dripping adds the NaOH aqueous solution (0.1M), pH is adjusted to 9.0, temperature is risen to 60 DEG C, the 7.14 parts of organic polymer G03 aqueous solution prepared are added in reaction system, drip and stop after adding 2h, volatilizable organic molecule is extracted in decompression out, can obtain the required admixture W12 promoting cement-based material folding strength and split tensile strength.

The theoretical solid content 40.0% of effective constituent, actual measurement solid content 47.1%.

The admixture promoting cement-based material folding strength and split tensile strength is used for cement-based material modification test:

Application Example 1

Improvement to mortar mechanical property: mortar adopts little wild field P II 52.5 cement, the preparation of iso standard sand, sand-lime is than being 3:1, water cement ratio is 0.36, the volume of admixture W01-W12, PE01-PE04 is be that the solid gauge of folding of benchmark is calculated taking gelling material, defoamer used is the PXP-I concrete defoamer of the commercially available normal conventional of Jiangsu Subotexin Material Co., Ltd, controlling each group of mortar air content by defoamer consumption basically identical, water reducer used is the polycarboxylate water-reducer of the commercially available normal conventional of Su Bote companyEach group of mortar degree of mobilization is controlled basically identical by water reducer consumption. Specimen molding is placed on 25 DEG C, maintenance under more than 95% humidity condition.

Carboxyl butylbenzene (SD622S) emulsion of PE01: Shanghai Gaoqiao BASF dispersion company limited;

PE02:PAlatex, synthesizes (JournalofMaterialsinCivilEngineering2011,23,1412) according to document, and its stability is slightly poor, and it is poly-heavy to occur in cement filtrate; It is heavy that W01-W12 does not assemble in cement filtrate;

PE03:BASF pure-acrylic emulsion (AcronalPA237);

PE04:BASF benzene emulsion (AcronalS400).

Table 1 mortar performance test table

From experimental result in table, when identical water cement ratio, admixture W01-W12 is when for modifying mortar in synthesis shown in the embodiment of the present invention:

(1) when low-dosage (relative to the 1.0% of cement consumption), to mortar ultimate compression strength without negative impact, to its tension and have (the 28 days strength enhancing 4-11% of lifting to a certain degree, 3.87MPa is the highest rises to 4.31MPa), folding strength also has certain lifting (28 days strength enhancing 10-14%, 10.2MPa is the highest rises to 11.6MPa). By contrast, adopt common polymer emulsion (commercially available or synthesis, PE01, PE02) all without obviously promoting.

(2) volumes to 2.5% such as W01 are promoted, W01, W05 and W09 to mortar ultimate compression strength substantially without negative impact, its tensile strength is had (the 28 days strength enhancing 10-19% of lifting to a certain degree, 3.87MPa is the highest rises to 4.59MPa), folding strength also has certain lifting (28 days strength enhancing 19-27%, 10.2MPa is the highest rises to 13.0MPa). By contrast, adopt common polymer emulsion (commercially available or synthesis, PE01, PE02) action effect relatively weak.

(3) volumes to 5.0% such as W01 are promoted, mortar ultimate compression strength without negative impact or is promoted (0-15%) by W01-W12 to some extent, its tensile strength has lifting to a certain degree (28 days strength enhancing 13-33%) simultaneously, and folding strength also has certain lifting (28 days strength enhancing 20-50%). By contrast, adopt common polymer emulsion (commercially available or synthesis, PE01-PE02), although the tension folding strength of mortar promote to some extent (lifting amplitude is respectively��10% and 10-15%, but its ultimate compression strength has reduction in various degree (��10%).

The performance when lifting of the anti-folding of mortar and tensile strength can have been reached polymer emulsions 5% such as adding PE01-PE04 when the 1-2.5% of cement consumption by visible W01, W05 and W09 volume, W01, W05 and W09 to mortar ultimate compression strength and have no adverse effect simultaneously, show obvious advantage.

Application Example 2

Carrying out mechanical performance of concrete test with reference to GB/T50080-2002 and GB/T50081-2002, adopt reference cement, II level flyash, fineness modulus is the river sand of 2.6, the rubble of 5-25mm continuous grading. Concrete mix the results are shown in Table 3 in table 2, concrete test.

Table 2 concrete mix (kg/m³)

Cement	Flyash	Sand	Stone	Water
					373	77	700	1130	145

The volume of admixture W01-W12, PE01-PE04 is be that the solid gauge of folding of benchmark is calculated taking gelling material, defoamer used is the PXP-I concrete defoamer of the commercially available normal conventional of Jiangsu Subotexin Material Co., Ltd, controlling each group of mortar air content by defoamer basically identical, water reducer used is the polycarboxylate water-reducer of the commercially available normal conventional of Su Bote companyEach group of slump basically identical (20 �� 1cm) is controlled by water reducer consumption. Specimen molding is placed on 25 DEG C, maintenance under more than 95% humidity condition.

Table 3 testing concrete performance table

From experimental result in table, when identical water cement ratio, admixture W01-W12 is when for concrete in synthesis shown in the embodiment of the present invention:

(1) when low-dosage (relative to the 1.0 of cement consumption), to concrete crushing strength without negative impact, it is split and draws and folding strength also has certain lifting. By contrast, adopt common polymer emulsion (commercially available or synthesis, PE01, PE02) all without obviously promoting.

(2) volumes to 2.5% such as W01 are promoted, W01, W05 and W09 to mortar ultimate compression strength substantially without negative impact, its split tensile strength is had (the 28 days strength enhancing 8-22% of lifting to a certain degree, 4.67MPa is the highest rises to 5.72MPa), folding strength also has certain lifting (28 days strength enhancing 14-25%, 7.99MPa is the highest rises to 9.98MPa). By contrast, adopt common polymer emulsion (commercially available or synthesis, PE01, PE02) action effect relatively weak.

(3) volumes to 5.0% such as W01 are promoted, W01-W12 to concrete crushing strength substantially without negative impact or to some extent promote (0-16%), its split tensile strength has obvious lifting (28 days strength enhancing 15-37%) simultaneously, and folding strength also has certain lifting (28 days strength enhancing 24-44%). By contrast, adopt common polymer emulsion (commercially available or synthesis, PE01-PE02), although concrete tension folding strength promote to some extent (lifting amplitude is respectively��10% and 10-15%, but its ultimate compression strength has reduction in various degree.

The performance when lifting of concrete split tensile strength and tensile strength can have been reached polymer emulsions 5% such as adding PE01-PE04 when the 1-2.5% of cement consumption by visible W01, W05 and W09 volume, W01, W05 and W09 to concrete crushing strength and have no adverse effect simultaneously, show obvious advantage.

Claims (10)

1. one kind promotes the admixture of the anti-folding of cement-based material and tensile strength, it is characterised in that: being the aqueous dispersions of the hybrid inorganic-organic particle of nucleocapsid structure, the mass content of the hybrid inorganic-organic particle of nucleocapsid structure in aqueous dispersions is 5-40%; The hybrid inorganic-organic particle of nucleocapsid structure forms by three layers, is innermost layer, middle layer and outermost layer from inside to outside successively; Innermost layer is organic polymer core, and middle layer is the silica shell that silicon-dioxide or organo-functional group replace, and outermost layer is the electronegativity organic polyelectrolyte of one layer of long side chain of band.

2. the as claimed in claim 1 admixture promoting the anti-folding of cement-based material and tensile strength, it is characterised in that: innermost layer is the homopolymer that formed of one or more polymerizations in the univalent metal salt of the acrylate by vinylbenzene, substituted phenylethylene, vinylformic acid, methacrylic acid, acrylate, replacement, the acrylamide monomer of replacement, the methyl acrylamide monomer of replacement, methacrylic ester, the methacrylic ester of replacement, acrylic acid univalent metal salt or methacrylic acid or multipolymer.

3. the admixture promoting the anti-folding of cement-based material and tensile strength as claimed in claim 1 or 2, it is characterised in that: middle layer is by siloxanes or water glass hydrolysis preparation.

4. the as claimed in claim 1 or 2 admixture promoting the anti-folding of cement-based material and tensile strength, it is characterised in that: outermost layer is prepared from by the product obtained by acrylic acid or the like or the acrylic monomer of replacement and the polymerisable monomer of the long Soxylat A 25-7 chain of band and polymerisable silicone monomer.

5. the preparation method of the admixture of the anti-folding of lifting cement-based material described in claim 1-4 any one and tensile strength, it is characterised in that: comprise the following steps that order connects:

(1) preparation of innermost layer:

In reactor, add the polymerisable monomer A of institute's requirement, polymerisable monomer B, the 0-100% of linking agent C and institute's requirement water, fully it is uniformly mixed, obtains mixed solution, logical N in mixed solution₂Except O₂, reactor is risen to 20-90 DEG C, in reactor, under agitation condition, adds initiator initiated polymerization, the mixed solution simultaneously dripping the residue part and polymerisable monomer D that add linking agent C in reactor carries out copolymerization, adding fashionable timing from initiator, reaction 2-8h, obtains organic polymer core dispersion liquid;

The quality of polymerisable monomer A, B, D and linking agent C and account for the 5-45% of polymerization system total mass in step (1), wherein, the quality of polymerisable monomer A accounts for polymerisable monomer A, B, D and the 0-5% of linking agent C total mass, the quality of linking agent C accounts for polymerisable monomer A, B, D and the 0-5% of linking agent C total mass, and the ratio of the total mass that the quality of polymerisable monomer B accounts for polymerisable monomer B and D is not less than 10%;

Wherein, the one of polymerisable monomer A for meeting in following general formula (1)-(3) organism:

R₁��R₂��R₃And R₅It is respectively H or CH₃, R₄For the alkyl of 6-30 carbon atom, X₁��X₂��X₃And X₄Being respectively O or NH, a, b are the integer of 4-50, and c is the integer of 6-12;

Polymerisable monomer B is made up of monomer and non-functional single group body, and wherein, monomer accounts for the 0.5-5% of polymerisable monomer B total mass, and all the other are non-functional single group body;

Linking agent C is the mixture of one or more any proportionings in Vinylstyrene, vinyltrimethoxy silane, vinyltriethoxysilane (VTES), methacryloxypropyl trimethoxy silane (MAPTMS), methacryloxypropyl triethoxyl silane (MAPTES), methacryloxypropyl ylmethyl triethoxyl silane, acryloxy methyltrimethoxy silane or acryloxy propyl trimethoxy silicane:

Polymerisable monomer D is made up of functional group's type monomer and non-functional single group body, and wherein, monomer accounts for the 0.5-5% of polymerisable monomer D total mass, and all the other are non-functional single group body;

Initiator is thermal decomposition initiating or redox initiator, and according to thermal decomposition initiating, then initiator quality consumption is polymerisable monomer A, B, D and the 0.05-3% of linking agent C total mass; According to redox initiator, then consumption calculates with side's total mass that molar weight in Oxidizing and Reducing Agents is lower, is the 0.05-3% of polymerisable monomer A, B, D and linking agent C total mass;

Thermal decomposition initiating is azo-initiator or persulfuric acid salt initiator; Redox initiator comprises Oxidizing and Reducing Agents, and the mol ratio of oxygenant and reductive agent is 0.5-2.0, and oxygenant is H₂O₂Or persulphate, reductive agent is the mixture of one or more any proportionings in vitamins C, rongalite, S-WAT, sodium bisulfite or Sodium Pyrosulfite; If thermal decomposition initiating, then directly once add or slowly evenly add polymerization system; If redox initiator, then first oxygenant is added polymerization system, then reductive agent is slowly evenly added polymerization system, and should not add before polymerisable monomer A, B, D and linking agent C all add reaction system;

(2) the coated middle layer of innermost surface:

The organic polymer core dispersion liquid of preparation in step (1) is regulated required pH, at 30-80 DEG C, dripping in organism E or silicon containing component F one or both under agitation condition in organic polymer core dispersion liquid, dropwise reaction 1-24 hour, must be coated with the dispersion liquid in middle layer; If only using organism E, then required pH is 2-12, if only using silicon containing component F or organism E and silicon containing component F all used times, then required pH is 2-8;

Wherein, organism E is the silane replaced containing more than three alkoxyl groups; Silicon containing component F is made up of water glass and reactant K, and reactant K is the mixture of one or more any proportionings in ammonium nitrate, ammonium sulfate, ammonium acetate or acetic acid, drips the added-time, and water glass and reactant K separately drip and add; The mol ratio of water glass and reactant K is (ammonium ion+acetic acid)/water glass is 2.0-2.2;

In organism E and silicon containing component F, contained element silicon total mass is the 2-20% of first stage gained organic polymer core total mass, and the total mass that in silicon containing component F, contained element silicon quality accounts for element silicon in organism E and silicon containing component F is no more than 25%;

(3) at the coated outermost layer of interlayer surfaces:

Gained dispersion liquid in step (2) is adjusted pH to 4-12, when temperature is 40-90 DEG C, in reaction system, it is added with organic polymer G, dropwise reaction 1-5h, volatilizable organic molecule is extracted in decompression out, must promote the admixture of the anti-folding of cement-based material and tensile strength; The quality consumption of organic polymer G is the 2-50% of gained particle total mass in step (2);

Wherein, organic polymer G is the polymkeric substance prepared by radical copolymerization by monomer H, I and J; The molar fraction that monomer H, I and J account for total monomer (H+I+J) is respectively m₁��n₁��p₁, m₁+n₁+p₁=100%, and 2%��m₁�� 80%, 0.5%��n₁�� 96%, 2%��p₁�� 30%;

Monomer H is the one in vinylformic acid, methacrylic acid, acrylic acid sodium salt or sylvite, the sodium salt of methacrylic acid or sylvite; Monomer I is monomethyl polyethylene glycol acrylate ester, polyethylene glycol monomethyl ethermethacrylic acid esters, allyl polyethenoxy ether, methacrylic Soxylat A 25-7, butenyl Soxylat A 25-7, methyl butene base Soxylat A 25-7 or vinyl Soxylat A 25-7; Monomer J is vinyltrimethoxy silane, vinyltriethoxysilane (VTES), methacryloxypropyl trimethoxy silane (MAPTMS), methacryloxypropyl triethoxyl silane (MAPTES), methacryloxypropyl ylmethyl triethoxyl silane, acryloxy methyltrimethoxy silane or acryloxy propyl trimethoxy silicane.

6. preparation method as claimed in claim 5, it is characterised in that: in step (1), the monomer in polymerisable monomer B and polymerisable monomer D is the polymerisable monomer of hydroxyl, amino or carboxyl; Non-functional group type monomer in polymerisable monomer B and polymerisable monomer D is the mixture of one or more any proportionings in monomer shown in vinylbenzene and following general formula (4);

R₆Represent H or CH₃, R₇Represent the alkyl of 1-12 carbon atom.

7. preparation method as claimed in claim 6, it is characterised in that: it is hydrochloride or the sulfonate of 3-amino-benzene ethene, 4-amino-benzene ethene, 2-(tert-butylamino) ��-dimethyl-aminoethylmethacrylate, aminoethyl methacrylate or above-mentioned monomer containing the polymerisable monomer of amino;

Carboxylic polymerisable monomer is the univalent metal salt of vinylformic acid, methacrylic acid, acrylic acid univalent metal salt or methacrylic acid;

The polymerisable monomer of hydroxyl is hydroxy acrylate, hydroxyl-metacrylate, hydroxyacrylamide, hydroxymethylacrylamide class monomer.

8. preparation method as claimed in claim 7, it is characterised in that: the polymerisable monomer of hydroxyl is vinylformic acid-2-hydroxyl second ester, 2-hydroxyethyl methacrylate (HEMA), 2-hydroxypropyl acrylate, vinylformic acid-4-hydroxybutyl, methacrylic acid-2-hydroxy propyl ester, methacrylic acid-4-hydroxybutyl, N hydroxymethyl acrylamide, N-hydroxyethyl acrylamide, N-(2-hydroxypropyl) acrylamide, N-methylol methacrylamide or N-(2-hydroxypropyl) Methacrylamide.

9. preparation method as described in claim 5-8 any one, it is characterized in that: in step (2), organism E is tetraethoxysilane, tetramethoxy-silicane, vinyltrimethoxy silane, vinyltriethoxysilane, methacryloxypropyl trimethoxy silane (MAPTMS), methacryloxypropyl triethoxyl silane (MAPTES), ��-mercaptopropyl trimethoxysilane or (3-aminopropyl) triethoxyl silane.

10. preparation method as described in claim 5-8 any one, it is characterised in that: in step (3), in monomer I structure, repeating unit-CH in polyglycol chain₂CH₂The quantity span of O-is 4-55; In step (3), polymkeric substance G weight-average molecular weight is 5000-100000.