CN105713125B - A kind of cement-based material reinforcing agent and its preparation method and application - Google Patents

A kind of cement-based material reinforcing agent and its preparation method and application Download PDF

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CN105713125B
CN105713125B CN201511028806.2A CN201511028806A CN105713125B CN 105713125 B CN105713125 B CN 105713125B CN 201511028806 A CN201511028806 A CN 201511028806A CN 105713125 B CN105713125 B CN 105713125B
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monomer
organic
siloxanes
polymerisable monomer
parts
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CN105713125A (en
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舒鑫
刘加平
杨勇
冉千平
李申桐
赵红霞
曹攀攀
翟树英
张志勇
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Sobute New Materials Co Ltd
Nanjing Bote Building Materials Co Ltd
Bote Building Materials Tianjin Co Ltd
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Sobute New Materials Co Ltd
Nanjing Bote Building Materials Co Ltd
Bote Building Materials Tianjin Co Ltd
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Priority to PCT/CN2016/112249 priority patent/WO2017114375A1/en
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/02—Agglomerated materials, e.g. artificial aggregates
    • C04B18/022—Agglomerated materials, e.g. artificial aggregates agglomerated by an organic binder
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/0004—Microcomposites or nanocomposites, e.g. composite particles obtained by polymerising monomers onto inorganic materials
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    • C08F2/00—Processes of polymerisation
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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  • Chemical & Material Sciences (AREA)
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Abstract

Application the invention discloses a kind of organic inorganic hybridization particle and preparation method thereof and in cement-based material modification.Organic inorganic hybridization particle of the present invention is made of organic component and inorganic component, is mutually connected with each other between organic component and inorganic component with covalent bond, not nucleocapsid, but mutually interspersed, is attached between each other with covalent chemical bond.Organic inorganic hybridization particle of the present invention, organic component are used to improve the mechanical property of cement-based material, are fully connected organic constituents by covalent bond and CSH particles by inorganic component, improve the efficiency that organic constituents play toughness properties；And volume of the organic inorganic hybridization particle of the present invention in cement-based material is higher, the mechanical property promotion of cement-based material is more apparent.

Description

A kind of cement-based material reinforcing agent and its preparation method and application
Technical field
The present invention relates to the additive fields being modified for cement-based material, and in particular to one kind can improve cement-based material Reinforcing agent of mechanical property (including resistance to compression, anti-folding and tensile strength) and preparation method thereof.
Background technology
Cement-based material refers to the materials such as concrete, mortar, slip casting.Cement-based material conduct is most popular in the world Construction material, the continuous expansion of application field, but complicated and diversified construction and use environment constantly propose higher to its performance It is required that therefore, improve the inexorable trend that its mechanical property is its development.
Ordinary cement sill is a kind of typical fragile material, and compression strength is high, and bend resistance, tensile strength are substantially not Foot, in actual use, easily because stress concentration or unbalance stress generate various crackles or damage so that durability declines, So as to limit its application, for example, the diseases such as disconnected plate and surface texture destruction easily occurs too early in the surface layer of cement pavement, thus limit Its application in high-grade highway is made.
People have carried out substantial amounts of research in terms of cement-based material brittleness is improved, such as：By add modified component from And the bend resistance of concrete, tensile strength are improved, existing main modified component includes fiber (organic polymer, steel fibre and glass Glass fiber) and polymer particle (lotion or dry powder) etc..
Fiber reinforced principle is：(1) microcrack development is limited.When fiber is evenly distributed among concrete substrate, It is assumed that there are the tendency that microcrack occurs inside concrete substrate, when any microcrack occurs and may be to arbitrary When direction is developed, farthest no more than fiber in concrete substrate fiber mean center away from distance within, the crack will meet To the fiber to lie across in front of it.After crack generates, high-modulus and single high-tensile due to fiber can hinder The further development of crack arrest seam, can only form the closed cavity for being similar to harmless hole or internal diameter very in concrete substrate Tiny hole.(2) high strength fibre toughness itself is far above concrete, the intensity of fibre modification concrete be concrete phase and The superposition of fiber phase performance, thus its toughness is higher than normal concrete.
Polymer particle can improve the combination between concrete component as additive.Polymer particle scattered and Film forming is their ability to the main reason for modified.Due to the presence of polymer film, the mechanical property for making concrete material is (especially tough Property) more excellent.Physical action or the effect of part chemical bonding are generated between polymer and inorganic material, i.e., polymer is with grain The form of son or film is modified cement mortar, can also form the more fine and close chelating of the structure combined with coordination Body, so as to improve the performance of polymer cement concrete.Active group such as-OH ,-COOH ,-COOR are introduced into polymer Coordination can be generated with hydrolysis product of cement, change bond type of the cement material based on silicon oxygen bond, add organic C-H bond Bond type, structure is remarkably reinforced, folded double set network structures repeatedly staggeredly is formed, improves the combination between interface, raising Interphase fracture energy and toughness (Bulletin of the Chinese Ceramic Society, 2014,33,365).
But all there is apparent deficiency in Yi Shang technology：
(1) fiber easy conglomeration when concrete stirs, it is difficult to scattered, it is impossible to be uniformly distributed in concrete.Fiber changes Property the performance of concrete and the scattered of fiber and orientation have substantial connection, thus concrete preparation process influences concrete performance It is larger, it prepares more more difficult than conventional concrete.Conglomeration makes concrete workability poor, and pumping difficulties are difficult to construct.Steel fibre Damage -form is mainly pulled out in use, and without being pulled off, this illustrates steel fibre with concrete adhesiveness Deficiency, this can influence the effect for improving concrete tensile strength.Synthetic fibers density is small, and filament diameter is smaller, there is thickening effect Should, the vibrations for being unfavorable for concrete are closely knit.Since glass fibre alkali resistance is poor, the application of glass concrete is limited System.
The toughening cement-based materials method that patent CN101891417B is disclosed by stirring, it is necessary to be formulated each component (including fiber) is uniformly dispersed, and mixing time is longer (25-35min).Patent CN101913188B adds magnetic field to make steel fibre single-phase Distribution improves Flexural Strength of Steel Fibers Concrete, this undoubtedly causes the preparation of concrete to complicate.Patent US7192643 passes through Specific process prepares easily scattered organic fiber film and is used for toughening cement-based materials.Patent EP0488577, US5993537, US4524101 is both needed to add the limited meanses such as so-called wetting agent or inorganic coupling reagent (binding agent) and enables fiber It is scattered.These patents usually require to prepare required fibrous material or corresponding modified concrete by specific means or equipment.
(2) polymer volume is excessively high in polymer modification concrete.Since polymer modification concrete is more formed Polymer network, be equivalent to by material be blended form improve concrete performance, polymer network in itself with cement-based material Cohesive force is limited, thus performance unobvious are modified in low-dosage, it is necessary to add compared with high additive, this so that its cost is higher. Polymer emulsion is also possible to that coagulation occurs in concrete highly basic environment with high salt, and it is (anionic emulsifying to influence its effect performance The easy coagulation of lotion of agent synthesis, Journal of Materials in Civil Engineering 2011,23,1412).Specially Sharp CN102276764B provides the chemical modification method that a kind of polymer powder is modified, and passes through coupling on polymer powder surface Agent carries out chemical graft, and to improve the interaction of powder and matrix, so as to improve the shock resistance of modified mortar, but it is originally There is no the scattering problems for solving polymer powder for body.
Although polymer adds flexural strength and toughness, the compression strength of high additive polymer modification concrete is apparent It reduces.Even if (with ratio of mud condition or even in view of polymer breast under conditions of polymer volume relatively low (5wt%) The water-reduction of liquid, the lower ratio of mud of use also have slight intensity and decline), concrete crushing strength also has in various degree Decline, amplitude is even up to 15~50% (Journal of Jilin Institute of Architecture＆ Civil Engineering 2012,29,7；Cement and Concrete Research 2005,35,900 etc.).
Polymer emulsion (Handbook of polymer-modified concrete and mortars, 1995,55) The setting time of cement-based material is influenced, the polymer emulsion species used is related with dosage, can generally postpone Setting time (dozens of minutes-a few hours).
In addition, patent CN103130436A and CN101239800B are reported respectively using graphene (graphene oxide) and carbon The modified cement-based material of nanotube promotes resistance to compression tension flexural strength, but its cost is excessively high.Patent CN103274620A passes through Common metakaolin mineral of the kaolin families clay mineral generation with certain pattern of heating and calcining, enhancing cement-based material are strong Degree.It is nanocrystalline that EP2695850A1 discloses one kind nucleating growth calcium silicates (wollastonite) in situ in cement-based material The method of body is used for toughening.The modifying agent of these patent reports is required for the conditions such as specific temperature, pressure, and difficulty is brought to preparation Degree.
CN104446091A, CN103787609A and CN104119014A describe several concrete and subtract jelly respectively, lead to The chelation for crossing enhancing cement granules improves cement degree of scatter, so as to improve its degree of hydration, but considers simultaneously from principle The brittleness of cement-based material cannot fundamentally be improved.
Based on organic phase and the principle of inorganic phase interaction is increased, coordination is substituted with Covalently attached interaction, CN104609759A and CN104446102A respectively describe it is a kind of can increase cement-based material it is anti-folding and tensile strength it is additional Agent, these additive active ingredients are a kind of particles of nucleocapsid, because organic phase only has core with the inorganic site being connected The inside and outside bed boundary of shell structure, Covalently attached interaction depend on nucleocapsid inner layer sheet area, what this was limited by, thus It is also subject to certain restrictions the improvement degree of Mechanical Properties of Cement-based Materials, and two kinds of additives are to Compressive Strength of Cement-based Materials It influences smaller.
The content of the invention
Existing additive can not fundamentally solve the brittleness problems of cement-based material and enable to delay to a certain extent The problem is solved, there is also the preparation process that drags down the intensity of cement-based material either additive is complicated or cost is excessively high, with And the various defects that application is restricted etc..To solve problem above, the present invention provides a kind of organic inorganic hybridization particles And preparation method thereof, the reinforcing agent of the aqueous dispersions of the organic inorganic hybridization particle as cement-based material can carry simultaneously Rise cement-based material resistance to compression, anti-folding and tension (or resist and split drawing) intensity.
Tension and split tensile strength are the parameters that test method is slightly different, and usually, split tensile strength is high, and tensile strength should This is also higher.Index used is split tensile strength in the present invention, for replacing tensile strength.
Organic inorganic hybridization particle of the present invention, is mutually mutually interconnected between organic component and inorganic component with covalent bond It connects, not nucleocapsid, but mutually interspersed, is attached between each other with covalent chemical bond, but organic component and without unit / without large scale split-phase boundary, herein split-phase boundary refer to similar clearly line of demarcation between stratum nucleare and shell.
The organic moiety is formed by long ethylene glycol segment, intermediate segment and siloxanes segment by being covalently attached Organic polymer network, wherein siloxanes segment do not include alkoxy and alkoxy the silicon oxygen bond that hydrolysis is formed occurs Part；
The intermediate segment refers to by styrene or substituted phenylethylene, acrylic acid, methacrylic acid, acrylates, methyl It is any number of in acrylates, acrylate or substituted acrylate, methacrylate or substituted methacrylate The homopolymerization segment or cosegment that Type of Collective is formed；
The organic component is under the conditions of existing for the polymeric monomer and siloxanes containing long glycol chain, by styrene or is taken For styrene, acrylic acid, methacrylic acid, acrylate or substituted acrylate, methacrylate or substituted methyl Any kind in acrylate polymerize the homopolymerization segment or cosegment to be formed.
Siloxanes is the key that connection organic component and inorganic component, and the siloxanes can contain or not contain double Key, but it is certain containing there are three more than silicone functionalities；Silicone functionalities hydrolysis can be connected on inorganic component, if Containing double bond, then double-bond polymerization can be connected on organic component, if not containing double bond, silicone functionalities with it is organic Hydroxyl or the amino reaction that polymers compositions contains make it be connected on organic component.
Inorganic component is the network that silicon oxygen bond is formed, and is hydrolyzed and prepared by siloxanes.
It should be noted that the silane containing three or more alkoxy substitutions is also used in the present invention, such as methyl trimethoxy Oxysilane, wherein methyl are also organo-functional group, but the methyl is smaller on the performance influence of hybrid particle.
The effect of the organic inorganic hybridization particle each component is respectively：
Organic component：When material incorporation cement-based material is modified, play the role of being crosslinked node, due to having Machine object has excellent tensile property, can undertake part external force, to promote the flexural strength of cement-based material and tensile strength； Simultaneously polymeric monomer in hybrid particle preparation process constantly by graft polymerization to hybrid particle, so as to by providing space bit Hybrid particle is stablized in resistance, prevents hybrid particle coagulation.
Inorganic component：It can be chemically reacted in the environment of cement-based material strong basicity, with main gelling therein Component hydrated calcium silicate gel (CSH) generates covalent key connection, so as to be connected organic component and CSH particles by covalent chemical bond It picks up and, giving full play to organic component improves the effect of Mechanical Properties of Cement-based Materials；Meanwhile play the role of CSH nodes, it improves CSH gel contents in cement-based material promote Mechanical Properties of Cement-based Materials (such as compression strength).
The organic inorganic hybridization particle for cement-based material when being modified, the alkaline environment of particle and cement-based material It reacts, and hydrated product is promoted to be crystallized by core of particle, so as to play the role of being crosslinked node, connect hydrated product Particle promotes Mechanical Properties of Cement-based Materials.
Organic component is being compared the smaller scale covalent linkage of nucleocapsid by this hybrid structure with inorganic component, into one Step improves the joint efficiency of organic component and inorganic component, is conducive to improve the mechanical property of hybrid particle in itself, meanwhile, it uses When cement-based material is modified, compared to the joint efficiency that organic component is further increased in nucleocapsid, so as to improve its increasing Add the ability of cement-based material resistance to compression, tension and flexural strength.
The organic inorganic hybridization particle is spheroidal particle, and diameter is less than 1000nm；Its all directions stress is more equal than fiber It is even, because orientation problem may be not present.
The preparation method of organic inorganic hybridization particle water dispersion liquid of the present invention, specifically comprises the following steps：
A part of addition polymerisable monomer A, polymerisable monomer B, a part of crosslinking agent C, siloxanes D into reactor A part and water, be thoroughly mixed, obtain mixed liquor；It is 2-12 that mixed liquor, which is adjusted to pH, and N is led into mixed liquor2Except O2, Reactor is risen to 20-90 DEG C, adding in initiator into reactor under stirring condition triggers polymerization, starts simultaneously at into reactor Remainder, the remainder of crosslinking agent C, the remainder of siloxanes D and the polymerisable monomer E of polymerisable monomer A is added dropwise, from Timing when initiator is initially added into, reacts 4-24h at reaction conditions, removes inert atmosphere protection, and cooling decompression extraction can wave The organic molecule of hair obtains hybrid particle dispersion liquid.
Polymerisable monomer A is added at twice, and the monomer A that reaction is initially directly added into reactor accounts for whole use of monomer A The 10-50% of amount.
Crosslinking agent C is added at twice, and the ratio of wherein first time addition accounts for the 0-100% of whole crosslinking agent C.
Siloxanes D is added at twice, and the ratio of wherein first time addition accounts for the 0-100% of whole siloxanes D.
The polymerisable monomer A is the one kind met in below general formula ((1)-(2)) organic matter：
R1、R2And R3Separately represent H or CH3, R4Represent the alkyl of 6-30 carbon atom；X1、X2And X3It is only respectively On the spot represent O or NH；A and b separately refers to ethyoxyl-CH2CH2The average repeat unit number of O- chain links, the value of a, b Scope is 4-50；
The too small then autoemulsification of a and b values is weak, and the steric hindrance provided is smaller, unfavorable to stablizing hybrid particle, and Value is excessive then too low compared to monomer B and crosslinking agent C polymerization activities, so as to cause largely to residue in polymerization because being difficult to be copolymerized In system.
On the one hand polymerisable monomer A can be used for acting on class with stable hybrid particle in application process in the synthesis process Like the polymerisable emulsifier in conventional emulsion polymerizations, on the other hand, the small molecular weight polymer that monomer A preliminary polymerizations are formed can be with Micella is formed, follow-up polymerisable monomer B, crosslinking agent C and siloxanes D can be swollen.Its dosage is equally to first stage synthesis The size of organic polymer nuclear particle has close influence, is initially added that the dosage of reactor is higher, and particle size is smaller.
The polymerisable monomer B is by functional group's type monomer and non-functional group type monomer composition, functional group's type monomer in monomer B The 1-5% of monomer B gross masses is accounted for, remaining is non-functional group type monomer.
Monomer is one kind or more than one any combination in following all monomers.
The amino-containing polymerisable monomer includes 3- aminostyryls, 4- aminostyryls, 2- (tert-butylamino) first The hydrochloride or sulfonate of base ethyl acrylate, aminoethyl methacrylate and these monomers；
The polymerisable monomer of the hydroxyl is hydroxy acrylate or methacrylate, hydroxyacrylamide or hydroxyl Methacryl amine monomer, including acrylic acid -2- hydroxyl ethyl esters, 2-hydroxyethyl methacry-late (HEMA), acrylic acid -2- hydroxyls Base propyl ester, acrylic acid -4- hydroxybutyls, methacrylic acid -2- hydroxy propyl esters, methacrylic acid -4- hydroxybutyls, N- methylols Acrylamide, N- hydroxyethyl acrylamides, N- (2- hydroxypropyls) acrylamide, N- methylol methacrylamides and N- (2- hydroxyls Propyl) Methacrylamide；
Non-functional group's type monomer is one kind or more than one arbitrary group in monomer shown in styrene and below general formula (3) It closes.
R5Represent H or CH3, R6Represent the alkyl of H, Na, K or 1-12 carbon atoms.
Polymerisable monomer B is the main ingredient of organic polymer nuclear particle, and its role is to provide toughness preferably to have Machine object matrix, for finally promoting the flexural strength of cement-based material and split tensile strength.
The crosslinking agent C is any one in structure shown in divinylbenzene and below general formula (4).
R7Represent H or CH3, the saturated alkyl or (CH of X 2-12 carbon atom of expression2CH2O)cCH2CH2Structure, Middle c is ethylene oxide structure (- CH2CH2O-) molar average adduct number, the value range of c is 1-44.The numerical value of c is crossed senior general and is caused Polymerization activity is relatively low, is unfavorable for giving full play to for its cross-linking properties.
Crosslinking agent C assists to form organic polymer network, improves organic polymer network mechanical strength, reduces organic polymer The dissolubility of object component in water, so as to promote to be nucleated.
The siloxanes D is the silane of three or more alkoxy substitutions, can form silicon oxygen bond network, can be free redical One kind or more than one any combination in the siloxanes of polymer siloxane and/or not free redical polymerization.
Free redical polymerization siloxanes can be vinyltrimethoxysilane, vinyltriethoxysilane (VTES), Methacryloxypropyl trimethoxy silane (MAPTMS), methacryloxypropyl (MAPTES), methacryloxymethyl triethoxysilane (AAPTES), acryloyloxymethyl trimethoxy silane (AAMTMS), any one in acryloxypropyl trimethoxy silane (AAPTMS).
The siloxanes of free redical polymerization is not any one in structure shown in below general formula (5).
R8、R9、R10Separately represent the saturated alkyl of 1-4 carbon atom, R11Represent phenyl (- C6H5) or 1-12 The saturated alkyl of carbon atom or the saturation alkoxy containing 1-4 carbon atom.
Siloxanes D is the main source of the organic inorganic hybridization particulate inorganic component, passes through the silicon of hydrolysis generation Oxygen key is connected with each other, can be with the Ca (OH) of cement-based material alkaline environment2Reaction.Hydrolytic process can generate volatilizable organic Small molecule alcohol is extracted out after the completion of reaction by depressurizing.
Siloxanes D can once be added in before initiator adds in or after adding in during the reaction, can also be arbitrarily to compare Example adds at twice.
The polymerisable monomer E is by functional group's type monomer and non-functional group type monomer composition.Functional group's type monomer in monomer E The 1-10% of monomer E gross masses is accounted for, remaining is non-functional group type monomer.
All monomers when functional group's type monomer in polymerisable monomer E is polymerisable monomer B described previously In one kind or more than one any combination；Non-functional group's type monomer is styrene and one kind in monomer shown in general formula (4) Or more than one any combination；The composition of the polymerisable monomer E can it is identical with the polymerisable monomer B or Different.
Polymerisable monomer A, polymerisable monomer B, crosslinking agent C, the usage ratio of siloxanes D and polymerisable monomer E need to meet The following conditions：
The alkoxy of siloxanes D, which can hydrolyze, in reaction process generates volatilizable small molecule organic alcohols, complete in alkoxy Under the conditions of fully hydrolyzed, the effective mass of siloxanes D (is denoted as D0) to deduct these remaining titanium dioxides of small molecule organic alcohols Silicon or the silica of organo-functional group substitution calculate.Using tetraalkoxy substitute silane and tri-alkoxy substitution silane as Example, is described as follows：
In above formula (6), left side reactant is tetraethoxysilane (TEOS), ethyl alcohol is generated after complete hydrolysis, ethyl alcohol subtracts It can be extracted out during pressure, remaining effective mass is SiO2, computational methods are that the matter of ethyl alcohol is deducted with the gross mass of TEOS and water Amount.In above formula (7), left side reactant is methyltrimethoxysilane (MTMOS), methanol is generated after complete hydrolysis, methanol exists It can be extracted out in decompression process, remaining effective mass is methyl substituted siloxane network, and computational methods are with MTMOS and water Gross mass deducts the quality of methanol.
On the basis of deducting all aqueous dispersions quality of volatilizable small molecule organic alcohols, polymerisable monomer A, B, E, Crosslinking agent C and siloxanes D used in amounts cause in aqueous dispersions can not volatile component (that is, active principle, hybrid particle) account for moisture The scope of dispersion liquid gross mass is 5-40% (mass fraction).Specifically, effecting reaction object gross mass (A+B+C+E+D0) account for water The 5-40% of dispersion liquid final mass.Aqueous dispersions final mass refers to herein, total matter of the aqueous dispersions obtained after reaction The gross mass of all species deducts the quality of all volatilizable small molecule organic alcohols in amount, that is, reaction.
Wherein, monomer A occupies validity response object gross mass (A+B+C+E+D0) 1-10%, crosslinking agent C occupies validity response object Gross mass (A+B+C+E+D0) 0-5%, monomer B and E (B+E) occupy validity response object gross mass (A+B+C+E+D0) 20- 70%, and polymerisable monomer B accounts for the gross mass ratio of B and E (B+E) not less than 10%.
Monomer A is equivalent to the dispersant of autohemagglutination mould assembly emulsifier and hybrid particle simultaneously, and dosage is too low, cannot be formed point Scattered hybrid particle, hybrid particle will reunite in nucleation process to be precipitated, and hybrid particle may be in cement in application process Unstable and coagulation in sill highly basic environment with high salt.Similarly, monomer A has the tensile property contribution of hybrid particle in itself Limit, it is smaller to organic polymer backbones (main polymer chain) contribution after polymerization because its double bond content is relatively low, thus need to limit Its dosage is not higher than 5%.The amount ranges for the monomer A that limited reactions are initially directly added into reactor be in order to：(a) maintain just Begin to promote nucleation and the autohemagglutination co-emulsifier minimum amount of swelling；(b) maintain constantly to connect by adding in reaction in reaction process Branch arrives the minimum flow of the long side chain of particle surface, so as to stable particle.
Limitation crosslinking agent C is that the excessively high hybrid particle of crosslinking degree is in preparation process the reason for dosage is not higher than 5% In, morphotropism is smaller, and monomer swell degree is relatively low so that hydrolysis and polymerisation may occur outside particle, generate Homogeneous organic polymer particle or inorganic polymer particle.
The sum of the dosage of limitation monomer B and E scope is to ensure in hybrid particle organic component and inorganic in 20-80% Otherwise the minimum content of component is difficult to give full play to the mechanical property of hybrid particle.
The 10% of gross mass of the limitation polymerisable monomer B dosages not less than B and E is to not dissolved in initial reaction stage formation The polymer of water, so as to promote particle nucleation.There is more water-soluble monomer A in initial reaction stage system, if reaction initial monomer A Autohemagglutination forms water-soluble polymer, then nucleation can not be precipitated, and consume the A as emulsifier in reaction process；In the presence of B Under, B and A can form amphoteric polymer and form the degree of polymerization increase of B in micella or polymer so that shape is precipitated in polymer Into particle.
The dosage upper limit of functional group's type monomer is since functional group's type monomer is usually water solubility in limitation monomer B and E , a large amount of uses may cause hybrid particle to be partially dissolved in water, be unfavorable for hybrid particle nucleating growth, while these are dissolved Polymer on the one hand increase system viscosity, reduce hybrid particle content, on the other hand may mutually tangle and cause coagulation.But Monomer B due to adding in polymerization system, participation nucleation process at the very start, thus its monomer's ratio upper limit will compared with monomer E It is lower.And it is to ensure effective covalent linkage between organic component and inorganic component to limit its dosage lower limit.
It should be noted that the effective mass for limiting polymerisable monomer A, B, E, crosslinking agent C and siloxanes D is not less than moisture The 5% of the total effective mass of dispersion liquid is because when the additive is modified for cement-based material, mixes the solid active ingredient of system Dosage should be no less than the 0.5% of total glue material, otherwise its contribution unobvious to mechanical property.And if additive total solid content mistake It is low, then possibly it can not meet requirement.In fact, even below 5%, which is also that can succeed what is carried out.
The initiator is thermal decomposition initiation system as described below or redox initiation system：
Thermally decompose initiation system：Azo (VA044 or V50), persulfuric acid salt (ammonium persulfate, potassium peroxydisulfate and over cure Sour sodium)；
Or redox initiation system：H2O2With reducing agent (such as vitamin C, rongalite), persulfate (mistake Ammonium sulfate, sodium peroxydisulfate and potassium peroxydisulfate) in one kind with low price Sulfates (sodium sulfite, sodium hydrogensulfite, pyrosulfurous acid Sodium, rongalite) in one kind.The dosage of oxidant and reducing agent meets oxidant/reducing agent between 0.5-2.0 (molar ratio).
Initiator amount (redox system is calculated with the relatively low side of mole in Oxidizing and Reducing Agents)；For monomer The 0.05-3% of gross mass.
If the oxidant mole added in is low, just with the Mass Calculation of oxidant, oxidant quality is the total matter of monomer The 0.05-3% of amount, it is on the contrary then calculated with reducing agent.
Initiator amount may so that organic monomer conversion ratio is insufficient less than 0.05% monomer mass, if initiator amount is high In 3%, then cruelly poly- it may make reaction failure (will appear from largely precipitation or gel) because initial velocity of initiation is too fast.
For thermal decomposition initiating, it directly can once add in, can also slowly be uniformly added into；For Redox Initiator Required quality oxide agent is first added in polymerization system by agent, and reducing agent solution is slowly then uniformly added into polymerization system, and should not It is added before monomer all adds in reaction system.Because the presence of half-life period, thermal decomposition initiating elicitation procedure is relatively gentle, therefore And can once add in, it can also slowly be uniformly added into.But for redox initiation system, general activation energy is relatively low, such as Fruit once adds in initiation, then not only can be too low because of later stage number of free radical so that conversion ratio is relatively low, early stage number of free radical mistake Height is easy to cause the too fast precipitation for causing system appearance not redispersible of reaction speed.
Reaction temperature (initiation, polymerization and hydrolysis temperature) is applicable in as 20-90 DEG C, this field researcher can be according to other Document and the suitable initiation temperature using initiator used in experience judgement, redox initiation system initiation temperature is relatively low, even Close to room temperature, thermal decomposition initiation system initiation temperature can be determined according to its half-life period.Polymerization time is longer, and conversion ratio is higher.From Initiator starts timing when adding in, and this system reaction time generally can be controlled in 4-24h, usually, therefore, to assure that initiator exists Polymerization complete when substantially completely decompose, in addition, in hybrid particle preparation process comprising polymerization with hydrolyze two synchronously carry out it is anti- Should, wherein hydrolysis usually requires the long period, all to react all as complete as possible in order to avoid dividing gained hybrid particle afterwards Dispersion liquid storage use has an impact.
The initial required pH scopes of reaction system are 2-12 in the reaction step.It will under the scope, acid condition The a large amount of equal aerosils of generation, and polymerisable monomer A cannot fully cover all hybrid particles because of reaction speed deficiency, Make hybrid particle coagulation；The similary either too fast coagulation of hydrolysis or particle are in itself because and reaction environment under alkaline condition In high concentration OH-It reacts and loss of stability.
Application process of the dispersion liquid of organic inorganic hybridization particle of the present invention as the reinforcing agent of cement-based material, system During standby cement-based material, the organic inorganic hybridization particle is once added in directly during mix and participates in stirring；Hydridization Particle dosage is the 0.5-5.0% of total glue material quality.
Compared to simple polymer-modified cementitious materials or polymer fiber and modified cement-based material, significantly reduce The volume of polymer modification component carries cement-based material tension fracture resistance under the conditions of same volume with traditional polymer lotion It rises and becomes apparent from, overcome the modified cement-based material of traditional polymer because of polymer volume height so as to influence cement-based material resistance to compression The defects of intensity.
Organic inorganic hybridization particle of the present invention, organic component are used to improve the mechanical property of cement-based material, lead to It crosses inorganic component fully to connect organic constituents by covalent bond and CSH particles, it is tough to improve organic constituents performance The efficiency of property performance.
Simultaneously as the inorganic component introduced can generate more CSH bonding components, and nano-particle passing through in itself It is high to learn the degree of key connection, improves nano-particle itself mechanical strength (compression strength), thus cement base can be promoted more significantly The compression strength of material.
It is of the present invention compared to simple polymer-modified cementitious materials or polymer fiber and modified cement-based material (0.5-5.0% that hybrid particle dosage is total glue material quality) can be greatly reduced in admixture dosage, with traditional polymer lotion Or the organic inorganic hybridization particle of nucleocapsid is compared, since organic polymer passes through with inorganic polymer in finer scale Covalent bond is connected with each other, itself can more give full play to the advantage of the mechanical property of organic polymer and inorganic polymer, is mixed same Folding anti-to cement-based material and tension (or splitting drawing) performance boost become apparent under the conditions of amount, while can effectively promote its pressure resistance Degree overcomes the modified cement-based material of traditional polymer because of polymer volume height so as to influence Compressive Strength of Cement-based Materials Defect.
Volume of the present invention refers to active ingredient (hybrid inorganic-organic grain in the aqueous dispersions that the present invention finally synthesizes Son) quality compared with glue material quality in cement-based material ratio.
The hybrid particle is modified for cement-based material, volume is higher, and (resistance to compression, anti-folding and tension are strong for mechanical property Degree) improve it is more apparent.To calculate volume (%bwoc) compared with the ratio of cementitious material gross mass, under the conditions of volume 5bwoc%, Compression strength can improve 14-41%, and flexural strength improves 20-44%, and tensile strength improves 25-53%.
Description of the drawings
Fig. 1：For the transmission electron microscope picture of gained hybrid particle in embodiment 2.
Specific embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, these implementations Example is only used for explaining the present invention, is not intended to limit the scope of the present invention..
In addition, usually, under the conditions of high solids content, these synthetic reactions are more difficult, for example, easily because reaction speed mistake 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.With Lower embodiment is illustrated and compared with the preparation of high solids content sample.
Unit used in material is mass parts in following synthesis step.
It is corresponding structural formula of respectively abridging in embodiment in attached sheet 1.
1. the preparation of hybrid particle aqueous dispersions
Polymerisable monomer used below is commercial goods or synthesizes the gained (source of polymerisable monomer A according to document： (1) it is commercially available；(2) macromolecule is circulated a notice of, and 2008,16；Polymer Bulletin 1999,42,287；Journal of Applied Polymer Science 2000,77,2768)。
4- aminostyryls hydrochloride (4-VBAH) is composite, and reference literature synthesizes gained (Analytical Chemistry 2012,84,3500)。
Embodiment 1
A part (number A1, polyethylene glycol methacrylate-styrene polymer, the poly- second two of polymerisable monomer A is added in into reactor - CH in alcohol chain2CH2O- average repeat units number is 6, and end group is hydroxyl, 1.0 parts of dosage), polymerisable monomer B (4- hydroxyls butyl third 3.96 parts of 0.04 part of olefin(e) acid ester (4-HBA) and styrene (St)) and 270 parts of water, with 1mol/LNaOH by pH of mixed adjust to 10, it is thoroughly mixed；Lead to N into mixed liquor2Except O2, temperature of reactor is risen to 80 DEG C, under stirring condition into reactor one It is secondary addition initiator (0.1 part of ammonium persulfate APS is dissolved in 15 parts of water) trigger polymerization, start simultaneously at into reactor be added dropwise can Aqueous solution (A1,1.0 parts are dissolved in 14.9 parts of water), the siloxanes D (vinyl triethoxyls of the remainder of polymerized monomer A 246.67 parts of 38.01 parts of silane (VTES), 180.2 parts of tetramethoxy-silicane (TMOS) and tetraethoxysilane (TEOS)) and can Polymerized monomer E (4-VBAH0.36 parts and St35.64 parts), timing when self-initiating agent is initially added into reactor, polymerisable monomer A is remained 3h is added dropwise in aqueous solution, siloxanes D and the polymerisable monomer E of remaining part point, is added dropwise and continues to keep the temperature 3h, then removes inert atmosphere Protection, decompression extract volatilizable organic molecule out, obtain hybrid particle aqueous dispersions AE01.
Embodiment 2
A part (number A2, monomethyl polyethylene glycol acrylate ester, the poly- second of polymerisable monomer A is added in into reactor - CH in glycol chains2CH2O- average repeat units number is 22, and end group is methyl, and dosage is 1.8 parts), polymerisable monomer B (4- VBAH1.8 parts, 58.2 parts of methacrylic acid (MAA)), a part of crosslinking agent C (number C2, glycol diacrylate ,- CH2CH2O- average repeat units number be 45,2 parts), a part (the methacryloxypropyl trimethoxy silicon of siloxanes D (MAPTMS) 1.25 parts and TMOS20.53 parts), 6 parts of APS and 270 part of water, be thoroughly mixed；It will be mixed with 1mol/LNaOH Liquid pH is adjusted to 10, and N is led into mixed liquor2Except O2, temperature of reactor is risen to 70 DEG C, under stirring condition into reactor uniformly Be added dropwise the aqueous solution (4.2 parts of A2 are dissolved in 3 parts of water) of the remainder of polymerisable monomer A, crosslinking agent C remainder (C2,2 Part), the remainder of siloxanes D (MAPTMS11.22 part with TMOS184.76 parts), polymerisable monomer E (methacrylic acid ammonia second 38 parts of 2 parts of ester hydrochloride (AEMH) and methyl methacrylate) and initiator solution (3.28 parts of sodium hydrogensulfite SBS are dissolved in In 23.72 parts of water) trigger polymerization, timing when self-initiating agent is initially added into reactor, initiator solution, polymerisable monomer A are remaining 4h is added dropwise in partial aqueous solution, the remainder of crosslinking agent C, the remainder of siloxanes D and polymerisable monomer E, drips Bi Jixu keeps the temperature 2h, then removes inert atmosphere protection, and volatilizable organic molecule is extracted in decompression out, obtains hybrid particle aqueous dispersions AE02。
Gained hybrid particle TEM figures are shown in Fig. 1, gained particle diameter about 50-400nm, and the contrast of particle shown in figure is equal It is even continuously to change, any split-phase such as nucleocapsid interface is had no, illustrates that the hydridization level of organic phase and inorganic phase at least uses general T EM It can not observe.
Embodiment 3
Added in into reactor polymerisable monomer A a part (number A3, polyethylene glycol monomethyl ethermethacrylic acid esters, - CH in polyglycol chain2CH2O- average repeat units number be 45, dosage be 1 part), polymerisable monomer B (acrylic acid -2- hydroxyl second 26.6 parts of 1.4 parts of ester (HEA) and acrylic acid lauryl alcohol ester (LA)), crosslinking agent C (10 parts of divinylbenzene (DVB), commodity DVB bags Containing meta position and para-isomer), a part (the methacryloxypropyl triethoxysilicane (MAPTES) 16.21 of siloxanes D 4.06 parts and TEOS27.75 parts of part, methyltrimethoxysilane (MTMOS)) and 270 parts of water, it is thoroughly mixed；Use 1mol/ LH2SO4PH of mixed is adjusted to 3, N is led into mixed liquor2Except O2, temperature of reactor is risen to 60 DEG C, to anti-under stirring condition It answers and initiator (2 parts of azo diisobutyl amidine hydrochloride V50 are dissolved in 23 parts of water) initiation polymerization is once added in device, while to Aqueous solution (9 parts of A3 are dissolved in 5 parts of water), the remainder of siloxanes D of the remainder of polymerisable monomer A are added dropwise in reactor Divide (MAPTES16.21 parts, MTMOS4.06 parts and TEOS27.75 parts) and polymerisable monomer E (HEA11.2 parts and LA100.8 Part), timing when self-initiating agent is initially added into reactor, aqueous solution, the remainder of siloxanes D of polymerisable monomer A remainders Point and polymerisable monomer E be added dropwise 8 it is small when, be added dropwise that the reaction was continued 4 it is small when, then remove inert atmosphere protection, decompression extraction can Volatilize organic molecule, obtains hybrid particle aqueous dispersions AE03.
Embodiment 4
Into reactor, (number A4, N- poly glycol monomethyl ether-acrylamide gathers a part of addition polymerisable monomer A - CH in glycol chain2CH2O- average repeat units number be 45,0.6 part of dosage), polymerisable monomer B (4-VBAH3 parts and acrylic acid 57 parts of N-butyl (BA)), a part (36.72 parts of vinyltrimethoxysilane (VTMS)) of siloxanes D and 270 parts of water, fill Divide and be stirred；Use 1mol/LH2SO4PH of mixed is adjusted to 3.5, N is led into mixed liquor2Except O2, by temperature of reactor liter To 50 DEG C, initiator (4 parts of two isobutyl imidazoline hydrochloride VA044 of azo dissolvings are dropped evenly under stirring condition into reactor In 22 parts of water) trigger polymerization, start simultaneously at the remainder aqueous solution (dosage 1.4 that polymerisable monomer A is added dropwise into reactor Part be dissolved in 4 parts of water), polymerisable monomer E (4 parts and St36 part of 2-hydroxypropyl acrylate (HPA)) and siloxanes D remain Remaining part point (VTES146.9 part), timing when self-initiating agent is initially added into reactor, dropwise addition 6h, initiator, polymerisable monomer A 6h is added dropwise in the aqueous solution of remainder, the remainder of siloxanes D and polymerisable monomer E, is added dropwise and continues to keep the temperature 6h, then Inert atmosphere protection is removed, decompression extracts volatilizable organic molecule out, obtains hybrid particle aqueous dispersions AE04.
Embodiment 5
Added in into reactor polymerisable monomer A (number A1, polyethylene glycol methacrylate-styrene polymer, in polyglycol chain- CH2CH2O- average repeat units number is 6, and end group is hydroxyl, and dosage is 0.6 part), polymerisable monomer B (AEMH1.4 parts and propylene Sour 138.6 parts of n-octyl (n-OctA)), crosslinking agent C (number C3, ethylene glycol dimethacrylate ,-CH2CH2O- is averagely repeated Unit number is 45,1.6 parts), siloxanes D (VTES108.27 parts and 6.56 parts of dodecyl trimethoxy silane (DTMOS)), The H of 0.26 part of mass fraction 30%2O2Aqueous solution and 269.74 parts of water, are thoroughly mixed；With 1mol/LNaOH by pH of mixed It adjusts to 11, N is led into mixed liquor2Except O2, temperature of reactor is maintained 20 DEG C, is uniformly dripped into reactor under stirring condition Add initiator (0.2 part of vitamin C (VC) is dissolved in 2 parts of water) trigger polymerization, start simultaneously at be added dropwise into reactor it is polymerizable The aqueous solution (5.4 parts of A1 are dissolved in 27.8 parts of water) of monomer A remainders, the remainder (C3,2.4 parts) of crosslinking agent C, from Timing when initiator is initially added into reactor, the residue of initiator, the aqueous solution of polymerisable monomer A remainders and crosslinking agent C 6h is added dropwise in part.It being added dropwise and continues to keep the temperature 18h, then remove inert atmosphere protection, volatilizable organic molecule is extracted in decompression out, Obtain hybrid particle aqueous dispersions AE05.
Embodiment 6
Polymerisable monomer A is added in into reactor, and (number A6, dodecyl-poly glycol monomethyl ether-maleic acid are double Ester ,-CH2CH2O- average repeat units number 45, dosage be 5 parts), polymerisable monomer B (HPA0.12 part with methyl acrylate 3.88 Part), a part (number C4, the ethylene glycol dimethacrylate ,-CH of crosslinking agent C2CH2O- average repeat units number is 22,8 Part), a part (VTES67.37 parts) of siloxanes D, 4.8 parts of sodium peroxydisulfates (SPS) and 265.2 parts of water, be thoroughly mixed； Use 1mol/LH2SO4PH of mixed is adjusted to 2, N is led into mixed liquor2Except O2, temperature of reactor is maintained 60 DEG C, stirring Under the conditions of dropped evenly into reactor initiator (2 parts of sodium pyrosulfites (SMBS) are dissolved in 23 parts of water) trigger polymerization, together When be added dropwise into reaction system the aqueous solutions (5 parts of A6 are dissolved in 5 parts of water) of polymerisable monomer A remainders, crosslinking agent C it is surplus The remainder (VTES269.47 parts) and polymerisable monomer E of remaining part point (C4,2 parts) and siloxanes D (4-VBAH1.8 parts with BA34.2 parts), timing when self-initiating agent is initially added into reactor, initiator solution, the remainder of siloxanes D and polymerizable list 3h is added dropwise in body E, is added dropwise and continues to keep the temperature 1h, then removes inert atmosphere protection, and volatilizable organic molecule is extracted in decompression out, is obtained To hybrid particle aqueous dispersions AE06.
Embodiment 7
Added in into reactor polymerisable monomer A (number A2, monomethyl polyethylene glycol acrylate ester, in polyglycol chain- CH2CH2O- average repeat units number is 22, and end group is methyl, and dosage is 1 part), polymerisable monomer B (N hydroxymethyl acrylamides (N-HMAAm) 1.2 parts and 38.8 parts of lauryl methacrylate (LMA)), a part (acryloxypropyl three of siloxanes D 82.19 parts of 21.84 parts of methoxy silane (AAPTMS) and tetra-n-butyl silane (TBOS)), the H of 4.04 parts of mass fractions 30%2O2 Aqueous solution and 265.96 parts of water, are thoroughly mixed；Use 1mol/LH2SO4PH of mixed is adjusted to 3.5, is led into mixed liquor N2Except O2, temperature of reactor is maintained 30 DEG C, drops evenly initiator (5 parts of formaldehyde sulfoxylates under stirring condition into reactor Hydrogen sodium (SFA) is dissolved in 23 parts of water) trigger polymerization, it starts simultaneously at and polymerisable monomer A remainders is added dropwise into reactor Aqueous solution (1 part of A2 is dissolved in 2 parts of water), crosslinking agent C (number C5, glycol diacrylate ,-CH2CH2O- averagely repeats list First number is 22,4 parts) and siloxanes D remainder (AAPTMS87.37 part with TBOS328.76 parts), self-initiating agent starts to add Timing when entering reactor, the remainder of initiator, the aqueous solution of polymerisable monomer A remainders and siloxanes D are added dropwise 12h is dripped and is continued to keep the temperature 12h, then removes inert atmosphere protection, and volatilizable organic molecule is extracted in decompression out, obtains hydridization grain Sub- aqueous dispersions AE07.
Embodiment 8
Polymerisable monomer A (number A8, polyethylene glycol monomethyl ethermethacrylic acid esters, polyethylene glycol are added in into reactor - CH in chain2CH2O- average repeat units number is 22, and end group is methyl, and dosage is 3 parts), polymerisable monomer B (2- (tertiary butyl ammonia Base) 0.5 part of ethyl methacrylate (t-BAEMA) and MMA9.5 parts), a part of crosslinking agent C (number C6,1,12- ten two pair Alcohol dimethylacrylate, 5 parts), siloxanes D (VTES4.04 parts and TEOS23.31 parts) and 270 parts of water, be thoroughly mixed； PH of mixed is adjusted to 12 with 1mol/LNaOH, N is led into mixed liquor2Except O2, temperature of reactor is maintained 90 DEG C, stirring Under the conditions of dropped evenly into reactor initiator (6 parts of SPS are dissolved in 16 parts of water) trigger polymerization, start simultaneously to reactor It is middle be added dropwise the aqueous solutions (3 parts of A8 are dissolved in 4 parts of water) of polymerisable monomer A remainders, crosslinking agent C remainder (C6,5 Part), (N-HMAAm0.9 parts molten by the remainder of siloxanes D (VTES36.38 part with TEOS309.82 parts) and polymerisable monomer E In 4 parts of water and LMA89.1 parts, the two is added dropwise solution simultaneously respectively), timing when self-initiating agent is initially added into reactor, initiator, 2h is added dropwise in the aqueous solution of polymerisable monomer A remainders, the remainder of siloxanes D and polymerisable monomer E, be added dropwise after Continue insurance temperature 2h, then removes inert atmosphere protection, and volatilizable organic molecule is extracted in decompression out, obtains hybrid particle aqueous dispersions AE08。
Embodiment 9
Added in into reactor polymerisable monomer A a part (number A3, polyethylene glycol monomethyl ethermethacrylic acid esters, - CH in polyglycol chain2CH2O- average repeat units number be 45, dosage be 3 parts), polymerisable monomer B (N-HMAAm0.84 part with MMA83.16 parts), a part (PhTEOS88.4 parts of phenyl triethoxysilane) of siloxanes D and 270 parts of water, be sufficiently stirred mixed It closes；PH of mixed is adjusted to 11 with 1mol/LNaOH, N is led into mixed liquor2Except O2, temperature of reactor is maintained 85 DEG C, is stirred Initiator (0.2 part of potassium peroxydisulfate KPS is dissolved in 16.8 parts of water) is dropped evenly into reactor under the conditions of mixing and trigger polymerization, together When start to be added dropwise the aqueous solutions (7 parts of A3 are dissolved in 3 parts of water) of polymerisable monomer A remainders, siloxanes D into reactor (N-HMAAm2.8 parts are dissolved in 10 parts of water and MMA53.2 parts, two by remainder (PhTEOS4.65 parts) and polymerisable monomer E Person simultaneously respectively be added dropwise), timing when self-initiating agent is initially added into reactor, initiator, polymerisable monomer A remainders it is water-soluble 5h is added dropwise in liquid, the remainder of siloxanes D and polymerisable monomer E, is added dropwise and continues to keep the temperature 1h, then removes inert atmosphere guarantor Shield, decompression extract volatilizable organic molecule out, obtain hybrid particle aqueous dispersions AE09.
Embodiment 10
Polymerisable monomer A is added in into reactor, and (number A6, dodecyl-poly glycol monomethyl ether-maleic acid are double Ester ,-CH2-CH2O- average repeat units number 45, dosage be 0.4 part), (2.52 parts 4-VBAH and 81.48 part of polymerisable monomer B BA), a part (C1, ethylene glycol dimethacrylate, 9 parts) of crosslinking agent C and (TMOS30.41 parts of a part of siloxanes D With MTMOS31.89 parts of methyltrimethoxysilane) and 270 parts of water, it is thoroughly mixed；Use 1mol/LH2SO4By pH of mixed It adjusts to 3, N is led into mixed liquor2Except O2, temperature of reactor is maintained 80 DEG C, is once added in into reactor under stirring condition Initiator (6 parts of APS are dissolved in 20 parts of water) triggers polymerization, while drops evenly polymerisable monomer A remainders thereto Remainder (C1,1 part), the remainder of siloxanes D of aqueous solution (1.6 parts of A6 are dissolved in 4 parts of water), crosslinking agent C (TMOS30.41 parts and MTMOS31.89 parts) and polymerisable monomer E (AEMH0.56 parts and 55.44 parts of St).Self-initiating agent starts Timing when adding in reactor, siloxanes D and polymerisable monomer E drop evenly 6h, the reaction was continued after being added dropwise 6h, then removes lazy Property atmosphere protection, decompression extracts volatilizable organic molecule out, obtains hybrid particle aqueous dispersions AE10.
Embodiment 11
Added in into reactor polymerisable monomer A a part (number A10, dodecyl-poly glycol monomethyl ether- Maleic acid diester ,-CH2-CH2O- average repeat units number 6, dosage be 0.6 part), polymerisable monomer B (3- aminostyryls (3- VBA) and 38 parts of St) and siloxanes D a part (TBOS82.19 parts) and 250 parts of water, be thoroughly mixed；Use 1mol/ LH2SO4PH of mixed is adjusted to 3, N is led into mixed liquor2Except O2, temperature of reactor is maintained 70 DEG C, under stirring condition to Initiator is dropped evenly in reactor, and (1 part of APS is dissolved in 14 parts of water；1.1 parts of sodium sulfite SS are dissolved in 13.9 parts of water, The two is added dropwise respectively) trigger polymerization, start simultaneously at (5.4 parts of the aqueous solution that polymerisable monomer A remainders are added dropwise into reactor A10 is dissolved in 25 parts of water) and siloxanes D remainder (TBOS739.71 parts), when self-initiating agent is initially added into reactor Timing, initiator, the aqueous solution of polymerisable monomer A remainders and remainder siloxanes D are added dropwise 2h, continuation are added dropwise 2h is kept the temperature, then removes inert atmosphere protection, volatilizable organic molecule is extracted in decompression out, obtains hybrid particle aqueous dispersions AE11.
Embodiment 12
A part (number A7, the dodecyl-hydroxyl polyethylene glycol groups-horse of polymerisable monomer A is added in into reactor Come acid diester ,-CH2-CH2O- average repeat units number 32, dosage be 5 parts), (0.1 part HEMA and 9.9 part of polymerisable monomer B LMA), crosslinking agent C (C2,0.8 part) and 270 parts of water, are thoroughly mixed；PH of mixed is adjusted to 11 with 1mol/LNaOH, Lead to N into mixed liquor2Except O2, temperature of reactor is maintained 60 DEG C, drops evenly initiator (2 under stirring condition into reactor Part V50 is dissolved in 28 parts of water) trigger polymerization, it starts simultaneously at and the water-soluble of polymerisable monomer A remainders is added dropwise into reactor Liquid (5 parts of A10 are dissolved in 25 parts of water), the remainder (C2,3.2 parts) of crosslinking agent C, siloxanes D (TEOS298.36 parts) and Polymerisable monomer E (9 parts of HEMA and 81 part of LA), timing when self-initiating agent is initially added into reactor, initiator, siloxanes D and can 3h is added dropwise in polymerized monomer E, is added dropwise and continues to keep the temperature 3h, then removes inert atmosphere protection, and decompression extraction is volatilizable organic small Molecule obtains hybrid particle aqueous dispersions AE12.
2. reinforcing agent is modified test for cement-based material
Application Example 1
Improvement to mortar mechanical property：(the small wild water in field mud in Jiangnan is limited using small wild field PII52.5 cement for mortar Company), iso standard sand prepare, aggregate-to-cement ratio 3:1, the ratio of mud 0.36, reinforcing agent AE01-AE12, W01, W05, PE01-02 Volume measure calculating (unit admittedly for folding on the basis of cementitious material：Mass percent, %bwoc), antifoaming agent used is Jiangsu The PXP-I concrete antifoaming agent of the commercially available normal conventional of Su Bote new materials limited company is controlled each by antifoaming agent dosage Group mortar air content is basically identical, and water-reducing agent used is the polycarboxylate water-reducer of Su Bote companies market normal conventionals Control each group Mortar'S Flowability basically identical by water-reducing agent dosage.Specimen molding is placed on 25 DEG C, more than 95% damp condition Lower maintenance.Test method bibliography (Construction and Building Materials, 2013,49,121).
PE01：Carboxy (SD622S) lotion of Shanghai Gaoqiao BASF dispersions Co., Ltd；
PE02：BASF styrene-acrylic emulsions (Acronal S 400).
W01：With reference to patent CN104446102A embodiments W01 synthesis；
W05：With reference to patent CN104446102A embodiments W05 synthesis.
1 mortar performance of table tests table
Note：AE01-AE12 volumes refer to pure active ingredient in the aqueous dispersions that various embodiments of the present invention finally synthesize (it is organic- Inorganic hybridization particle) quality compared with glue material quality in cement-based material ratio.
By experimental result in table as it can be seen that under the conditions of the identical ratio of mud, synthesis organic inorganic hybridization shown in the embodiment of the present invention Particle AE01-AE12 is when for modifying mortar：
(1) (compared with the 1.0% of cement consumption) under the conditions of low-dosage, hybrid particle synthesized by this patent resists mortar Pressure, anti-folding and split tensile strength have certain improvement result, and 28 days compression strength promotes 10-18%, and (promotion of 52.5MPa highests is arrived 61.8MPa), flexural strength promotes 10-24% (9.98MPa highests are promoted to 12.41MPa), and tensile strength promotes 11-23% (4.77MPa highests are promoted to 5.87MPa).In contrast, using common polymer emulsion (commercially available or synthesis, PE01, PE02) only slightly promoted.The nucleocapsid particle reported using patent CN104446102A, although its flexural strength and tension are strong Degree makes moderate progress, but improvement amplitude is smaller (5-14%), and the compression strength of mortar is not improved.
(2) volumes such as AE01 are promoted to 2.5%, AE01, AE05, AE10 and AE12, which can be equally obviously improved, resists mortar Press anti-folding and tensile strength (intensity promotes 13-25%, 16-30% and 18-35% respectively within 28 days).In contrast, using common Polymer emulsion (commercially available or synthesis, PE01, PE02) confrontation folding and tensile strength promotion effect it is weaker (2-5%).Using The nucleocapsid particle of patent CN104446102A reports, although its flexural strength and tensile strength make moderate progress (6-23%), But its compression strength is still not improved.
(3) volumes such as AE01 are promoted to 5.0%, hybrid particle synthesized by this patent is strong to mortar resistance to compression, anti-folding and tension Degree is significantly improved, and 28 days test specimen compression strength promotes 17-49%, and flexural strength promotes 22-52%, and tensile strength carries Rise 29-59%.The additive (W01 and W05) of the nucleocapsid of patent CN104446102A reports is although resist mortar specimen Folding intensity (promoting 11-25%) also makes moderate progress with tensile strength (promoting 23-31%), but compared to the hydridization grain of this patent report Son is without any advantage, it is often more important that, it is smaller (general to improve degree to compression strength<10%).
In contrast, using common polymer emulsion (commercially available or synthesis, PE01-PE02), no matter resistance to compression, anti-folding or Tensile strength, modified effect are markedly less than AE01-AE12.
It can be seen that AE01, AE05, AE10 and AE12 volume in the 1-2.5% of cement consumption to the anti-folding of mortar and tensile strength Promotion can reach performances of the addition PE01-PE02 when polymer emulsions 5%, while compared to W01 and W05, hydridization Particle can improve the pressure-proof and snap-resistent and tensile strength of mortar comprehensively, show apparent advantage.
Application Example 2
Mechanical performance of concrete experiment is carried out with reference to GB/T50080-2002 and GB/T50081-2002, using reference cement (Qufu Zhonglian Cement Co., Ltd.), II grades of flyash, modulus of fineness be 2.6 river sand, the rubble of 5-25mm continuous gradings.It is mixed Solidifying soil match ratio is shown in Table 2, and concrete test the results are shown in Table 3.
2 concrete mix (kg/m of table3)
Cement Flyash Sand Stone Water
373 77 700 1130 145
The volume of additive AH01-AH12, W01, W05, PE01-02 measure calculating admittedly for the folding on the basis of cementitious material (unit：Mass percent, %bwoc), antifoaming agent used is the commercially available normal conventional of Jiangsu Subotexin Material Co., Ltd PXP-I concrete antifoaming agent, control each group mortar air content basically identical by antifoaming agent, water-reducing agent used is public for Su Bote Take charge of the polycarboxylate water-reducer of commercially available normal conventionalEach group slump basic one is controlled by water-reducing agent dosage It causes (20 ± 1cm).Specimen molding is placed on 25 DEG C, conserves under more than 95% damp condition.
3 testing concrete performance table of table
Note：AE01-AE12 volumes refer to pure active ingredient in the aqueous dispersions that various embodiments of the present invention finally synthesize (it is organic- Inorganic hybridization particle) quality compared with glue material quality in cement-based material ratio.
By experimental result in table as it can be seen that under the conditions of the identical ratio of mud, synthesis organic inorganic hybridization shown in the embodiment of the present invention Particle AE01-AE12 is when for concrete：
(1) it is anti-to concrete anti-compression to roll over and split drawing by force (compared with the 1.0%bwoc of cement amount) under the conditions of low-dosage Degree has certain improvement.Compression strength promotes 7-15%, and flexural strength promotes 8-20%, and tensile strength promotes 9-22%.Compared to it Under, it is obviously improved using common polymer emulsion (commercially available or synthesis, PE01, PE02) nothing.Core-shell particles W01 and W05 pairs Its compression strength has no significant effect.
(2) volumes such as AE01 are promoted to 2.5%, AE01, AE05, AE10 and AE12 promote 28 days compression strength of concrete 11-22%, flexural strength promote 13-28%, and split tensile strength promotes 15-31%.Similarly, using common polymer emulsion (commercially available or synthesis, PE01, PE02) improves anti-folding and the effect of split tensile strength is relatively weak.And core-shell particles are then to compression strength It is not improved.
(3) volumes such as AE01 are promoted to 5.0%, hybrid particle synthesized by this patent is to concrete anti-compression, anti-folding and splits drawing Intensity is significantly improved, and 28 days test specimen compression strength promotes 14-41%, and flexural strength promotes 20-44%, split tensile strength Promote 25-53%.The additive (W01 and W05) of the nucleocapsid of patent CN104446102A reports is although to concrete sample Flexural strength (15-22%) also make moderate progress with split tensile strength (19-24%), but compared to this patent report hybrid particle without Any advantage, it is often more important that, compression strength is not improved (1-7%).
In contrast, using common polymer emulsion (commercially available or synthesis, PE01-PE02), no matter resistance to compression, anti-folding or Split tensile strength, modified effect are markedly less than AE01-AE12.
It can be seen that AE01, AE05, AE10 and AE12 volume roll over agent on crack resistance of concrete in the 1-2.5% of cement consumption and split drawing by force The promotion of degree, which substantially reaches, even better than adds performances of the PE01-PE02 when polymer emulsions 5%, at the same compared to W01 and W05, hybrid particle can improve the pressure-proof and snap-resistent and split tensile strength of concrete, show apparent advantage comprehensively.
It should be noted that for mortar specimen, general experiment can measure tensile strength；For concrete sample, lead to Tensile splitting strength, the value and being proportionate property of tensile strength are often measured, but (it is strong to be typically slightly above tension not equal to tensile strength Degree), tensile splitting strength is higher, and tensile strength is higher.

Claims (6)

1. a kind of organic inorganic hybridization particle, which is characterized in that it is not nucleocapsid between organic component and inorganic component, and It is mutually interspersed, is attached between each other with covalent chemical bond；
The organic moiety is had by long ethylene glycol segment, intermediate segment and siloxanes segment by what covalent linkage was formed Machine polymer network, wherein siloxanes segment do not include alkoxy and the silicon oxygen bond portion that hydrolysis is formed occurs for alkoxy Point；
The intermediate segment refers to by styrene or substituted phenylethylene, acrylic acid, methacrylic acid, acrylates, metering system Any number of in hydrochlorate, acrylate or substituted acrylate, methacrylate or substituted methacrylate is birdsed of the same feather flock together Close the homopolymerization segment or cosegment formed；
Inorganic component is the network that silicon oxygen bond is formed, and is hydrolyzed and prepared by siloxanes.
2. organic inorganic hybridization particle according to claim 1, which is characterized in that the siloxanes contains or do not contain Double bond, but it is certain containing there are three more than silicone functionalities；After silicone functionalities hydrolysis, that is, it is connected to inorganic component On, if containing double bond, double-bond polymerization can be connected on organic component, if not containing double bond, silicone functionalities Hydroxyl or the amino reaction contained with organic polymer compositions makes it be connected on organic component.
3. the preparation method of the aqueous dispersions of the organic inorganic hybridization particle of claim 1 or 2, which is characterized in that specific bag Include following steps：
A part of addition polymerisable monomer A, polymerisable monomer B, a part of crosslinking agent C, the one of siloxanes D into reactor Part and water, are thoroughly mixed, obtain mixed liquor；It is 2-12 that mixed liquor, which is adjusted to pH, and N is led into mixed liquor2Except O2, will be anti- Device is answered to rise to 20-90 DEG C, adding in initiator into reactor under stirring condition triggers polymerization, starts simultaneously at and is added dropwise into reactor The remainder of polymerisable monomer A, the remainder of crosslinking agent C, the remainder of siloxanes D and polymerisable monomer E, self-initiating Agent starts timing when adding in, and reacts 4-24h at reaction conditions, removes inert atmosphere protection, and cooling decompression extraction is volatilizable Organic molecule obtains hybrid particle dispersion liquid；
Polymerisable monomer A is added at twice, and the monomer A that reaction is initially directly added into reactor accounts for whole dosages of monomer A 10-50%；
Crosslinking agent C is added at twice, and the ratio of wherein first time addition accounts for the 0-100% of whole crosslinking agent C；
Siloxanes D is added at twice, and the ratio of wherein first time addition accounts for the 0-100% of whole siloxanes D；
The polymerisable monomer A is the one kind met in below general formula ((1)-(2)) organic matter：
R1、R2And R3Separately represent H or CH3, R4Represent the alkyl of 6-30 carbon atom；X1、X2And X3Separately Represent O or NH；A and b separately refers to ethyoxyl-CH2CH2The average repeat unit number of O- chain links, the value range of a, b For 4-50；
The polymerisable monomer B is by functional group's type monomer and non-functional group type monomer composition, and functional group's type monomer accounts for list in monomer B The 1-5% of body B gross masses, remaining is non-functional group type monomer；
Monomer is one kind or more than one any combination in following all monomers；
Monomer is the polymerisable monomer of hydroxyl or amino,
The amino-containing polymerisable monomer includes 3- aminostyryls, 4- aminostyryls, 2- (tert-butylamino) methyl-prop The hydrochloride or sulfonate of olefin(e) acid ethyl ester, aminoethyl methacrylate and these monomers；
The polymerisable monomer of the hydroxyl is hydroxy acrylate or hydroxyl-metacrylate, hydroxyacrylamide or hydroxyl Methacryl amine monomer, including acrylic acid -2- hydroxyl ethyl esters, 2-hydroxyethyl methacry-late (HEMA), acrylic acid -2- hydroxyls Base propyl ester, acrylic acid -4- hydroxybutyls, methacrylic acid -2- hydroxy propyl esters, methacrylic acid -4- hydroxybutyls, N- methylols Acrylamide, N- hydroxyethyl acrylamides, N- (2- hydroxypropyls) acrylamide, N- methylol methacrylamides and N- (2- hydroxyls Propyl) Methacrylamide；
Non-functional group's type monomer is styrene and one kind in monomer shown in below general formula (3) or more than one any combination；
R5Represent H or CH3, R6Represent the alkyl of H, Na, K or 1-12 carbon atoms；
The crosslinking agent C is any one in structure shown in divinylbenzene and below general formula (4)；
R7Represent H or CH3, the saturated alkyl or (CH of X 2-12 carbon atom of expression2CH2O)cCH2CH2Structure, wherein c is Ethylene oxide structure (- CH2CH2O-) molar average adduct number, the value range of c is 1-44；
The siloxanes D is the silane of three or more alkoxy substitutions, can form silicon oxygen bond network, be free redical polymerization silica One kind or more than one any combination in the siloxanes of alkane and/or not free redical polymerization；
Free redical polymerization siloxanes is selected from vinyltrimethoxysilane, vinyltriethoxysilane (VTES), methyl-prop Alkene acryloxypropylethoxysilane trimethoxy silane (MAPTMS), methacryloxypropyl (MAPTES), methyl Acryloyloxymethyl triethoxysilane (AAPTES), acryloyloxymethyl trimethoxy silane (AAMTMS), acryloyl Any one in oxygroup propyl trimethoxy silicane (AAPTMS)；
The siloxanes of free redical polymerization is not any one in structure shown in below general formula (5)；
R8、R9、R10Separately represent the saturated alkyl of 1-4 carbon atom, R11Represent phenyl (- C6H5) or 1-12 carbon original The saturated alkyl of son or the saturation alkoxy containing 1-4 carbon atom；
The polymerisable monomer E is by functional group's type monomer and non-functional group type monomer composition.Functional group's type monomer accounts for list in monomer E The 1-10% of body E gross masses, remaining is non-functional group type monomer；
One kind when functional group's type monomer in polymerisable monomer E is foregoing polymerisable monomer B in all monomers Or more than one any combination；Non-functional group's type monomer is styrene with one kind in monomer shown in general formula (4) or more than one Any combination of kind；The composition of the polymerisable monomer E can be identical or different from polymerisable monomer B.
4. method according to claim 3, which is characterized in that polymerisable monomer A, polymerisable monomer B, crosslinking agent C, siloxanes The usage ratio of D and polymerisable monomer E need to meet the following conditions：
The alkoxy of siloxanes D, which can hydrolyze, in reaction process generates volatilizable small molecule organic alcohols, in the complete water of alkoxy Under conditions of solution, the effective mass D of siloxanes D0To deduct these remaining silica of small molecule organic alcohols or organic official The silica that substitution can be rolled into a ball calculates；
On the basis of deducting all aqueous dispersions quality of volatilizable small molecule organic alcohols, polymerisable monomer A, B, E, crosslinking Agent C and siloxanes D used in amounts cause in aqueous dispersions can not volatile component, that is, active principle accounts for aqueous dispersions gross mass Scope is 5-40% mass fractions；Specifically, effecting reaction object gross mass (A+B+C+E+D0) account for aqueous dispersions final mass 5-40%；Aqueous dispersions final mass refers in the gross mass of the aqueous dispersions obtained after reaction, that is, reaction herein The gross mass of all species deducts the quality of all volatilizable small molecule organic alcohols；
Wherein, monomer A occupies validity response object gross mass (A+B+C+E+D0) 1-10%, crosslinking agent C occupies validity response object gross mass (A+B+C+E+D0) 0-5%, monomer B and E (B+E) occupy validity response object gross mass (A+B+C+E+D0) 20-70%, and can The gross mass ratio that polymerized monomer B accounts for B and E (B+E) is not less than 10%.
5. according to 3 or 4 the method for claim, which is characterized in that the initiator is thermal decomposition initiation system as described below Or redox initiation system：
The hot initiator system is selected from azo-initiator or persulfuric acid salt initiator, the azo-initiator refer to VA044 or V50, the persulfuric acid salt initiator refer to ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate；
Any one of the redox initiation system in following redox systems：H2O2With reducing agent, the reduction Agent is selected from vitamin C, rongalite；One kind and low price Sulfates in foregoing persulfate, the low price sulfuric acid The one kind of salt in sodium sulfite, sodium hydrogensulfite, sodium pyrosulfite, rongalite；Oxidant and reducing agent Dosage meet the molar ratio of oxidant/reducing agent between 0.5-2.0；
Initiator amount, redox system are calculated with the relatively low side of mole in Oxidizing and Reducing Agents, are the total matter of monomer The 0.05-3% of amount.
6. the application process of the organic inorganic hybridization particle of claim 1 or 2, which is characterized in that when preparing cement-based material, The organic inorganic hybridization particle is once added in directly during mix and participates in stirring；Hybrid particle dosage is total glue material The 0.5-5.0% of quality.
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