CN104609759B

CN104609759B - Additive capable of improving bending strength and tensile strength of cement base material and its preparation method

Info

Publication number: CN104609759B
Application number: CN201410690674.9A
Authority: CN
Inventors: 冉千平; 舒鑫; 刘浩; 杨勇; 于诚; 刘金芝; 刘加平
Original assignee: Sobute New Materials Co Ltd
Current assignee: Sobute New Materials Co Ltd
Priority date: 2014-11-25
Filing date: 2014-11-25
Publication date: 2017-04-12
Anticipated expiration: 2034-11-25
Also published as: CN104609759A

Abstract

The invention discloses an additive capable of improving bending strength and tensile strength of a cement base material. The additive is an aqueous dispersion of organic-inorganic hybrid particles with core-shell structures. Each organic-inorganic hybrid particle is composed of inner and outer layers, wherein the inner layer is an organic polymer core; the outer layer is an inorganic composite oxide or an inorganic composite oxide covalently connected with an organic functional group; the inorganic composite oxide is a silicon-calcium composite oxide or a silicon-magnesium composite oxide or a silicon-calcium-magnesium composite oxide; and the outer layer is in covalent connection with an electronegative organic polyelectrolyte internally. Compared to the mixing amount of a polymer or polymer fiber in a pure polymer-modified cement base material or a polymer fiber-modified cement base material, the mixing amount of the additive in the cement base material can be greatly reduced; and the additive can more obviously improve the splitting tensile and bending resistant performances of the cement base material in comparison with a traditional polymer emulsion in the same mixing amount. Therefore, the additive overcomes the disadvantage that the high polymer mixing amount of the traditional polymer modified cement base material affects the compressive strength of the cement base material, and can effectively improve the bending strength and tensile strength (or splitting tensile strength) of the cement base material.

Description

A kind of additive and its preparation for improving the anti-folding of cement-based material and tensile strength Method

Technical field

The present invention relates to be used for the modified additive field of cement-based material, and in particular to one kind can improve cement-based material The additive of anti-folding and tensile strength.

Background technology

The cement matrixs such as concrete, mortar or slip casting are represented used in term " concrete " herein is generally indiscriminate Material, this is also suitable in elsewhere herein.

Portland cement concrete is a kind of typical fragile material, and its comprcssive strength is high, and bend resistance, tensile strength are substantially not Foot, in actual use, easily because stress concentration or unbalance stress produce various crackles or damage so that durability declines, So as to limit its application, for example, it is applied to cement pavement surface layer and easily occurs the disease such as disconnected plate and surface texture destruction too early, because And limit its application in high-grade highway.

People have carried out substantial amounts of research in terms of Brittleness of Concrete is improved, especially by addition modified component so as to carrying The method of high concrete bend resistance, tensile strength, existing main modified component includes fiber (organic polymer, steel fibre and glass Glass fiber) and polymer particle (emulsion 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 any When direction is developed, it is farthest less than fiber in concrete substrate fiber mean center away from distance within, the crack will meet To the fiber lain across in front of it.After crack produces, due to the high-moduluss and single high-tensile of fiber, can hinder Crack arrest seam further development, can only be formed in concrete substrate similar to harmless hole closed cavity or internal diameter very 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.The dispersion of polymer particle and Film forming is their ability to modified main cause.Due to the presence of polymeric film, make the mechanical property of concrete material (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 to cement mortar, it is also possible to formed with the more fine and close chelating of the structure of coordination combination Body, so as to improve the performance of polymer cement concrete.Active group such as-OH ,-COOH ,-COOR are introduced in polymer Coordination can be produced with hydrolysis product of cement, change of bonding of the cement material based on siliconoxygen bond, add organic C-H bond Of bonding, be remarkably reinforced structure, form folded double set network structures repeatedly staggeredly, improve the combination between interface, raising Interphase fracture energy and toughness (Bulletin of the Chinese Ceramic Society, 2014,33,365).

But all there is obvious deficiency in above technology：

(1) fiber easy conglomeration in concrete-agitating, it is difficult to disperse, it is impossible in being uniformly distributed in concrete.Fiber changes Property the performance of concrete and the dispersion of fiber and orientation have substantial connection, thus concrete preparation technology affects on concrete performance Larger, its preparation is more increasingly difficult than conventional concrete.Conglomeration makes concrete workability poor, pumping difficulties, is difficult to construct.Steel fibre In use damage -form is mainly pulled out, without being pulled off, the adhesiveness with concrete of this explanation steel fibre Deficiency, this can affect the effect for improving concrete tensile strength.Synthetic fibers density is little, and filament diameter is less, there is thickening effect Should, it is unfavorable for that the vibrations of concrete are closely knit.Glass fibre is poor due to alkali resistance, and the application of glass concrete is limited System.

The toughening cement-based materials method that patent CN101891417B is disclosed needs (to wrap its formula each component by stirring Include fiber) it is uniformly dispersed, mixing time longer (25-35min).Patent CN101913188B adds magnetic field to make the single-phase distribution of steel fibre Flexural Strength of Steel Fibers Concrete is improved, this undoubtedly causes the preparation of concrete to complicate.Patent US7192643 passes through special side Method prepares easily scattered organic fiber film is used for toughening cement-based materials.Patent EP0488577, US5993537, US4524101 It is both needed to add the limited means such as so-called wetting agent or inorganic coupling reagent (binding agent) and fiber is disperseed.These Patent generally needs to prepare required fibrous material or corresponding modified concrete by specific means or equipment.

(2) polymer volume is too high in polymer modification concrete.Because polymer modification concrete is more formed Polymer network, equivalent to the form being blended by material concrete performance, polymer network itself and cement-based material are improved Cohesive force is limited, thus the performance that is modified in low-dosage is not obvious, it is necessary to which compared with high additive, this causes its relatively costly for addition. Polymer emulsion is also possible to coagulation in the environment of concrete highly basic high salt, affects its effect to play (anionic emulsifying The easy coagulation of emulsion 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, on polymer powder surface by being coupled 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 Body does not solve the scattering problem of polymer powder.

Although polymer increased rupture strength and toughness, the comprcssive strength of high additive polymer modification concrete is obvious Reduce.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, also has slight intensity and declines using the lower ratio of mud), concrete crushing strength also has in various degree Decline, its amplitude even up to～15-50% (Journal of Jilin Institute of Architecture＆ Civil Engineering2012,29,7；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 affected, the polymer emulsion species by using is relevant with consumption, typically can postpone Setting time (several tens minutes-a few hours).

In addition, patent CN103130436A and CN101239800B report respectively using Graphene (graphene oxide) and Carbon nano-tube modification cement-based material, is lifted to resistance to compression tension rupture strength, but its high cost.EP2695850A1 is disclosed A kind of method in cement-based material situ nucleating growth calcium silicates (wollastonite) nanocrystal is used for toughness reinforcing, needs The conditions such as specific temperature, pressure, to preparation difficulty is brought.

The content of the invention

Goal of the invention：The invention aims to solve the above problems, there is provided one kind can improve the anti-folding of cement-based material With the additive of tensile strength.

Technical scheme：The additive for improving the anti-folding of cement-based material and tensile strength of the present invention, the additive It is a kind of aqueous dispersions of the hybrid inorganic-organic particle with nucleocapsid structure, the hybrid inorganic-organic particle is by inside and outside Two-layer is constituted, and internal layer is the inorganic compounding of organic polymer core, outer layer inorganic composite oxide or organo-functional group covalent attachment Oxide, affiliated inorganic composite oxide is silicon-calcium composite oxides or silicon-Magnesium coumpoud oxide or silicon-calcium-magnesium combined oxidation Thing, being covalently attached in the layer of the outer layer has elecrtonegativity organic polyelectrolyte.

The effect of the inside and outside materials at two layers of the hybrid inorganic-organic particle is respectively：

When hybrid inorganic-organic particle incorporation cement-based material is modified, internal layer plays a part of to be crosslinked node, due to Organic substance has excellent tensile property, can undertake part external force, to lift the rupture strength of cement-based material and split drawing by force Degree；

It is connected with each other with covalent bond between outer layer and internal layer Organic substance core, outer layer has triple role, strong in cement-based material In the environment of alkalescence, the mineral shell can induce the main bonding component hydrated calcium silicate gel (CSH) of cement-based material In particle surface crystallization, on the one hand, greatly accelerate heat evolution velocity, the development of cement-based material early strength is promoted (but not affect material The final mechanical property of material), on the other hand (it is covalent that-OH alkaline reactions generate silica with CSH gels generation ionic bond and covalent bond Key) connection, whole organic polymers are coupled together with CSH granules so as to pass through chemical bond, because monodispersed particle is in water It is significantly increased compared to polymeric film with the bond area of Binder Materials in mud system, thus internal layer Organic substance can be given full play to Improve the effect of Mechanical Properties of Cement-based Materials, such that it is able to lift the rupture strength and tension of cement-based material in low-dosage (or splitting drawing) intensity.

The present invention also provides the preparation method of the additive, and step is as follows：

(1) polymerisable monomer A, polymerisable monomer B, Part I cross-linking agent C and water are added in reactor, is sufficiently stirred for Mixing；Lead to N in mixed liquor₂Except O₂, reactor is risen to into reaction temperature, add initiator to draw in reactor under stirring condition Polymerization is sent out, starting simultaneously at the mixed liquor of Deca Part II cross-linking agent C and polymerisable monomer D in reactor carries out copolymerization, institute It is arbitrary proportion to state Part I cross-linking agent C and Part II cross-linking agent C, and reaction end obtains the dispersion of organic polymer nuclear particle Liquid；

(2) organic polymer nuclear particle dispersion liquid prepared by step (1) is adjusted to temperature required, to having under stirring condition Organic substance E, organic polymer G and inorganic component F are added in machine polymer core particle dispersion, are reacted in reaction condition, Volatilizable organic molecule is extracted in decompression out, and cooling is improved the additive of the anti-folding of cement-based material and tensile strength.

The polymerisable monomer A is to meet the one kind in below general formula (1)-(3) Organic substance：

Wherein, R₁、R₂、R₃And R₅Separately represent H or CH₃, R₄Represent the alkyl of 6-30 carbon atom, X₁、X₂、X₃With X₄O or NH is separately represented, a, b are ethyoxyl (- CH₂CH₂O) chain link average repeat unit number, span is 4-50, c Span be 6-12.The too small then autoemulsification of a, b and c value is weak, and value is excessive then compared to monomer B and cross-linking agent C Polymerization activity is too low, so as to cause to residue in a large number in polymerization system because being difficult to copolymerization.Polymerisable monomer A is used to stablize first The organic polymer nuclear particle of stage synthesis, the polymerisable emulsifier in the similar conventional emulsion polymerizations of its effect.Its consumption is same There is impact closely to the size of the organic polymer nuclear particle of first stage synthesis, its consumption is higher, and particle size is less.

The polymerisable monomer B and polymerisable monomer D can be gathered by functional group's type monomer and non-functional group type monomer composition The 0.5-5% that the monomer in monomer B accounts for polymerisable monomer B gross masses is closed, the monomer in polymerisable monomer D accounts for The 0.5-5% of polymerisable monomer D gross masses, the monomer for hydroxyl, amino or carboxyl polymerisable monomer, be with Under one kind in all monomers or more than one combination in any：Monomer's (containing amino) includes 3- aminobenzene second The salt of alkene, 4- aminostyryls, 2- (tert-butylamino) ethyl methacrylate, aminoethyl methacrylate and these monomers Hydrochlorate or sulfonate；Monomer's (containing carboxyl) includes the acid of acrylic acid, methacrylic acid and acrylic or methacrylic Univalent metal salt (sodium salt and potassium salt)；Monomer's (hydroxyl) is hydroxy acrylate or methacrylate, hydroxyl third Acrylamide or hydroxymethylacrylamide class monomer, including acrylic acid -2- hydroxyl ethyl esters, 2-hydroxyethyl methacry-late (HEMA), 2-hydroxypropyl acrylate, acrylic acid -4- hydroxybutyls, methacrylic acid -2- hydroxy propyl esters, methacrylic acid -4- hydroxyl fourths Ester, N hydroxymethyl acrylamide, N- hydroxyethyl acrylamides, N- (2- hydroxypropyls) acrylamide, N- hydroxymethyl, methyl acryloyls Amine and N- (2- hydroxypropyls) Methacrylamide.

The non-functional group type monomer is the one kind in styrene and monomer shown in formula (4) or more than one any group Close：

Wherein, 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 preferable Organic substance matrix of toughness, for the final rupture strength and split tensile strength for lifting cement-based material.Polymerisable monomer D's Composition can be identical from polymerisable monomer B, or different.

Organic polymer nuclear particle adds hydroxyl, amino or carboxylic polymerizable list when prepared by polymerization process Body, so as to introduce hydroxyl, amino or carboxyl functional group on its surface, when intermediate layer covers, these amino or carboxyl official Can roll into a ball and be reacted so as to play a part of with covalent bonded intermediate layer as reaction site part and outer layer, remaining site is received Limit to reaction efficiency and do not change.

The cross-linking agent C is one kind or more than one combination in any in following material：Divinylbenzene, vinyl three Methoxy silane, VTES, methacryloxypropyl trimethoxy silane, methacryloxy third Ethyl triethoxy silicane alkane, methacryloxymethyl triethoxysilane, acryloyloxymethyl trimethoxy silane, propylene Acryloxypropylethoxysilane trimethoxy silane.The effect of cross-linking agent C is the mechanical strength for lifting polymer beads daughter nucleus, reduces polymer Dissolubility of the particle core in water.

The initiator is to thermally decompose initiator system initiator or the one kind in redox initiation system initiator, described Thermal decomposition initiator system initiator is the isobutyl imidazoline hydrochloride (VA044) of azo two, double (the 2- methyl-prop amidines) two of 2,2'- azos One kind in hydrochlorate (V50), Ammonium persulfate., potassium peroxydisulfate or sodium peroxydisulfate, in the redox initiation system initiator Oxidant be H₂O₂, reducing agent is vitamin C or rongalite.

The redox initiation system initiator is also possible that oxidant is Ammonium persulfate., sodium peroxydisulfate or persulfuric acid One kind in potassium, reducing agent is the one kind in sodium sulfite, sodium sulfite, sodium pyrosulfite or rongalite.

The oxidant of the redox initiation system initiator is 0.5-2.0 with the consumption mol ratio of reducing agent.

For thermal decomposition initiating, directly can once add, it is also possible to be slowly uniformly added into；For redox initiation Agent, first adds polymerization system by required quality oxide agent, and then reductant solution is slowly uniformly added into polymerization system, and should not Add before monomer all adds reaction system.Because the presence of half-life, thermal decomposition initiating elicitation procedure is relatively gentle, therefore And can once add, it is also possible to slowly it is uniformly added into.But for redox initiation system, general activation energy is relatively low, such as Fruit once adds and causes, then not only can be too low because of later stage number of free radical so that conversion ratio is low, early stage number of free radical mistake Height is easily caused more serious gel effect so that polymeric viscosity is excessive.

The Organic substance E is the silane that a kind of more than three alkoxyls replace, and is tetraethoxysilane, tetramethoxy-silicane Alkane, vinyltrimethoxy silane, VTES, methacryloxypropyl trimethoxy silane, methyl Appointing in acryloxypropyl triethoxysilane, γ-mercaptopropyl trimethoxysilane or 3- aminopropyl triethoxysilanes Meaning is a kind of.Organic substance E produces in the reaction organic siliconoxygen bond, passes through-Si-O- tetrahedral frameworks with sodium silicate and soluble inorganic The inorganic composite of silicon-calcium-magnesium oxide that calcium salt and magnesium salt reaction are produced is connected with each other.

The inorganic component F is made up of sodium silicate and soluble inorganic salt, and affiliated soluble inorganic salt is by soluble inorganic One or two compositions in calcium salt or soluble inorganic magnesium salt, mole total amount and silicon of the soluble inorganic salt cationic The ratio of the mole of sour sodium be 0.8-1.0, the soluble inorganic calcium salt be calcium nitrate, calcium chloride, calcium acetate in one kind or Several arbitrary proportion mixture, the soluble inorganic magnesium salt be magnesium acetate, magnesium chloride, magnesium nitrate or magnesium sulfate in one kind or Several arbitrary proportion mixture.Calcium salt and magnesium sulfate can be used separately in same reaction and cannot be used in mixed way.

The gross mass of described polymerisable monomer A, B, D and cross-linking agent C and account for the 5- of polymerization system gross mass in step (1) 45%, the quality of the polymerisable monomer A accounts for the 0-5% of the gross mass of described polymerisable monomer A, B, D and cross-linking agent C, described The quality of cross-linking agent C accounts for the 0-5% of the gross mass of described polymerisable monomer A, B, D and cross-linking agent C, the polymerisable monomer B's Quality accounts for the ratio of the gross mass of polymerisable monomer B and D not less than 10%, the quality of the initiator account for polymerisable monomer A, B, The 0.05-3% of D and cross-linking agent C gross masses.

The gross mass for limiting polymerisable monomer A, B, D and cross-linking agent C is because the additive not less than 5% for cement based During material modification, mixing the solid effective ingredient consumption of system should be no less than the 0.5% of total glue material, and otherwise it is to mechanical property Contribution it is unobvious.And if additive total solid content is too low, possibly use requirement cannot be met.Even if in fact, polymerizable , less than under the conditions of total polymerization system solid content 5%, the reaction also can be successfully to carry out for monomer A, B, D and cross-linking agent C consumptions.

Initiator amount for monomer gross mass 0.05-3%, according to thermal decomposition initiating, then initiator quality consumption For polymerisable monomer A, B, D and the 0.05-3% of cross-linking agent C gross masses；According to redox initiator, then consumption is aoxidizing Side's gross mass that mole is relatively low in agent and reducing agent is calculated, and is polymerisable monomer A, B, D and cross-linking agent C gross masses 0.05-3%.Initiator amount may cause organic monomer conversion ratio not enough less than 0.05% monomer mass, if initiator amount Higher than 3%, then may cruelly gather because initial velocity of initiation is too fast makes reaction failure (a large amount of precipitations or gel occur).

The gross mass of contained element silicon accounts for the organic polymer obtained in step (1) in the Organic substance E and inorganic component F The 2-20% of particle gross mass, contained element silicon amount accounts for element silicon in Organic substance E and inorganic component F in the inorganic component F The 0-25% of gross mass, if element silicon total amount is too low in Organic substance E used and inorganic component F, is difficult in organic polymer core The silicon dioxide layer of adequate thickness is coated on particle；Consumption is too high, then when the additive is modified for cement-based material, need The corresponding volume that improves could introduce enough organic constituentses so that the additive is to rupture strength under the conditions of low-dosage and splits drawing The improvement of intensity is not obvious.Extra inorganic salt can be generated in inorganic component F courses of reaction, therefore its used in amounts will be controlled.Institute The quality for stating organic polymer G accounts for the 2-50% of the organic polymer particle gross mass obtained in step (1).Organic polymer G Consumption is too low can not to play Stabilization, when final additive described in the too high impact this patent of consumption is modified for cement-based material Performance boost amplitude.

The organic polymer G is the elecrtonegativity organic polyelectrolyte of long side chain, the Weight-average molecular of the organic polymer G Amount scope is 5000≤Mw≤100000.Too low then siloxanes covalent bond coupled reaction efficiency when for step (2) of molecular weight Too low, molecular weight is too high, can significantly increase system viscosity.The inside and surface of the inorganic composite shell has by silicon The elecrtonegativity organic polyelectrolyte of the belt length side chain that oxygen key is covalently attached, by Coulomb repulsion and space stability ultimate load hydridization grain Son, enables fully dispersed in the cement-based material of highly basic high salt.

Organic polymer G is that (synthetic method can refer to for the polymer that prepared by radical copolymerization by monomer H, I and J Document Journal of the Chinese Ceramic Society, 2014,42,635；Cement and Concrete Research 2012,42,166)。

Monomer H is acrylic acid, methacrylic acid or corresponding sodium salt and the one kind in potassium salt, and monomer I is polyethyleneglycol Methyl ether acetate, polyethylene glycol monomethyl ethermethacrylic acid esters, allyl polyethenoxy ether, methacrylic Polyethylene oxide One kind in ether, cyclobutenyl polyoxyethylene ether, methyl butene base polyoxyethylene ether, vinyl polyoxyethylene ether, monomer J is ethylene Base trimethoxy silane, VTES (VTES), methacryloxypropyl trimethoxy silane (MAPTMS), methacryloxypropyl (MAPTES), methacryloxymethyl triethoxysilicane One kind in alkane, acryloyloxymethyl trimethoxy silane, acryloxypropyl trimethoxy silane.

Polyglycol chain average repeat unit (- CH in monomer I structures₂CH₂O-) number span is 4-55, and value is too low Its is sterically hindered so as to the effect of stable dispersion liquid particles to be difficult to performance, and too high then its polymerization activity of value is low, and residual quantity is higher, Air content when affecting final dispersion liquid to be applied to cement-based material.

The molar fraction for accounting for total monomer (H+I+J) of monomer H, I and J is m₁、n₁、p₁, its span meets m₁+n₁+p₁ =100% and 2%≤m₁≤ 80%, 0.5%≤n₁≤ 96%, 2%≤p₁≤ 30%.Monomer H provides elecrtonegativity functional group, single Body I provides long side chain (sterically hindered effect), and monomer J provides silicone functionalities, make polymer G can by hydrolysis with- The form of Si-O- is connected to the inorganic composite inside and surface that silicon-calcium-magnesium oxide is main body.

The molar fraction of H, I and J is too low to be unfavorable for that corresponding monomer effectively plays a role.Control monomer H molar fractions are not It is that molar fraction in order to control I and J is not less than 20% higher than 80%, so that there is the sterically hindered functional group of enough offers (from monomer I) is covalently attached on the particle prepared by step (2), makes particle more stable.J molar fractions are high, then polymer G Efficiency high is covalently attached, but J molar fractions are too high, and polymer G may be caused water insoluble.

Reaction temperature in the step (1) is 20-90 DEG C, and the response time is 2-8h, and this area research worker can be with root Judge the suitable initiation temperature of initiator used according to other documents and using experience, redox initiation system initiation temperature compared with It is low, or even close room temperature, thermal decomposition initiator system initiation temperature can be according to its half-life decision.Polymerization time is longer, conversion ratio It is higher.Body series polymerization time control in 2-8h, be usually necessary to ensure that initiator substantially completely decompose when polymerization is completed with Exempt from the synthesis step on after and produce impact.

Reaction temperature in the step (2) is 40-90 DEG C, and the response time is 3-8h.Organic substance E, inorganic component F and have Machine polymer G is in course of reaction uniform Deca, and in inorganic component F two kinds of components separate Deca (be made generally in aqueous solution, And both component time for adding are identical), Organic substance E, inorganic component F and organic polymer G time for adding are controlled in 3-8h. When temperature is high, response speed increases, and can adopt the relatively short response time；When temperature is low, typically using during relatively long reaction Between.Time for adding is too short will in a large number to generate particle precipitation (silicon-calcium-magnesium inorganic composite and polymer G coupling polymer particles Core), rather than the outer shell for being coated on step (1) gained organic polymer nuclear particle.The long then organic polymer G of time for adding holds It is perishable, it is difficult to produce covalently bonded.

Beneficial effect：Additive of the present invention, will be to improve Mechanical Properties of Cement-based Materials by inorganic component Organic constituentses coupled together with CSH granules by covalent bond, improve organic constituentses play toughness properties efficiency；Together When, layer structure can pass through that stronger electrostatic repulsion and space steric effect are substantially stabilized to disperse these particles, enable with Monodispersed (soilless sticking) form is scattered in cement-based material pore solution, further improves particle for cement matrix Efficiency when material is modified.In addition, the outer layer of additive core-shell particles is with the composite oxides of silicon-calcium-magnesium as main component Shell, can play a part of CSH gels induction nucleation and crystallization during hydrated cementitious, thus can greatly accelerate early stage Hydrated cementitious, rather than extend the setting time of cement-based material, cement-based material early stage mechanical strength can be greatly improved.

Additive effective ingredient of the present invention is spheroidal particle, its all directions stress than fiber evenly, thus not There are problems that orientation.

It is of the present invention compared to simple polymer-modified cementitious materials or polymer fiber and modified cement-based material Admixture dosage can be greatly reduced (0.5-5.0% that core-shell particles consumption is total glue material quality), with traditional polymer emulsion Cement-based material fracture resistance and tension (or splitting drawing) performance boost are become apparent under the conditions of same volume, overcomes conventional polymeric The modified cement-based material of thing is because the high defect so as to affect Compressive Strength of Cement-based Materials of polymer volume.Even more enter one Step, because the inorganic component for introducing can produce more CSH bonding components, has been lifted to Compressive Strength of Cement-based Materials.

Volume of the present invention refers to pure effective ingredient (hybrid inorganic-organic in the final aqueous dispersions for synthesizing of the invention Particle) quality relative to glue material quality in cement-based material ratio.

The additive is modified for cement-based material, volume is higher, its rupture strength and tension (splitting drawing) intensity are improved More obvious, the lifting amplitude of cement-based material rupture strength and tension (or splitting drawing) intensity is even up under the conditions of volume 5% More than 25%, while to its comprcssive strength almost without negative effect.

Description of the drawings

Fig. 1 is the nucleocapsid structure transmission electron microscope picture of organic inorganic hybridization particle of the present invention.

Fig. 2 is gained particle energy dispersive x-ray spectroscopy (EDS) collection of illustrative plates of the embodiment of the present invention 2.

Fig. 3 is the infrared spectrogram (FT-IR) after the separated purification of each synthesis step of the embodiment of the present invention 2 gained particle.

Fig. 4 is the dynamic light scattering grain size distribution of each synthesis step of the embodiment of the present invention 2 gained particle.

Specific embodiment

In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, these enforcements Example is only used for the explanation present invention, does not constitute limiting 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 response 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 be obtained.With Lower embodiment is illustrated and contrasted with the preparation of high solids content sample.

1. the synthesis of organic polymer G

The synthesis of polymer G and molecular weight determination list of references (Journal of the Chinese Ceramic Society,2014,42,635；Cement and Concrete Research 2012,42,166).

(1) organic polymer G01 (m_1/n₁/p₁=2/96/2)：

50 parts of distilled water and 0.5 are added in the round-bottomed flask equipped with thermometer, agitator, Dropping funnel and nitrogen conduit Part mass concentration is 30% hydrogen peroxide, stirs and maintain temperature to be 30 DEG C.By 0.58 part of acrylic acid (AA), 97.44 parts of first Epoxide polyethylene glycol acrylate (- CH₂CH₂O- average repeat units number 4, AAM4), 1.98 parts of methacryloxypropyls three Methoxy silane (MAAPTMS), 0.388 part of vitamin C (VC), 0.42 part of TGA (MEA) and 100 parts of water are sufficiently stirred for mixing Close, under nitrogen protection, the aqueous dispersions of uniform Deca AA/AAM4/MAAPTMS/VC/MEA in flask, time for adding control For 5h, completion of dropwise addition continues insulation 1h can obtain the aqueous solution of polymer G02, and polymer effective solid content 40% surveys solid content 40.4%, weight average molecular weight 43700.This aqueous solution is directly used at once in follow-up preparation, is not isolated and purified.

(2) organic polymer G02 (m_1/n₁/p₁=69/1/30)：

Add in the round-bottomed flask equipped with thermometer, agitator, Dropping funnel and nitrogen conduit 50 parts of distilled water, 9.14 Part methacrylic Polyethylene Glycol (- CH₂CH₂O- average repeat units number 25, HPEG25), 44.51 parts of vinyl triethoxyl silicon Alkane (VTES) and 0.5 part of mass concentration are 30% hydrogen peroxide, stir and maintain temperature to be 40 DEG C.By 46.34 parts of methyl-props Olefin(e) acid (MAA), 0.388 part of VC, 0.14 part of MEA and 100 part of water are thoroughly mixed, under nitrogen protection, uniform in flask The aqueous dispersions of Deca MAA/VC/MEA, time for adding is controlled to 3h, and completion of dropwise addition continues insulation 1h can obtain the water of polymer G01 Solution, polymer effective solid content 40% surveys solid content 40.3%, weight average molecular weight 96300.This aqueous solution is subsequently being prepared In directly use at once, do not isolate and purify.

(3) organic polymer G03 (m_1/n₁/p₁=80/10/10)：

In the round-bottomed flask equipped with thermometer, agitator, Dropping funnel and nitrogen conduit, 50 parts of distilled water of addition, 71.24 parts of methyl butene base Polyethylene Glycol (- CH₂CH₂O- average repeat units number 52, IPEG52) and 0.5 part of mass concentration be 30% hydrogen peroxide, stirs and maintains temperature to be 45 DEG C.Prepare and contain 22.58 parts of sodium acrylate (AANa), 6.18 parts of acryloyls Epoxide MTMS (AAMTMS), 0.388 part of vitamin C, 1.11 parts of TGAs and 100 parts of water dispersion liquid simultaneously It is thoroughly mixed, under nitrogen protection, the aqueous dispersions of uniform Deca AANa/IPEG52/AAMTMS in flask, during Deca Between be controlled to 2h, completion of dropwise addition continues to be incubated 1h can obtain the aqueous solution of polymer G03, polymer effective solid content 40%, actual measurement Solid content 40.3%, weight average molecular weight 12600.This aqueous solution is directly used at once in follow-up preparation, is not isolated and purified.

(4) organic polymer G04 (m_1/n₁/p₁=60/30/10)：

In the round-bottomed flask equipped with thermometer, agitator, Dropping funnel and nitrogen conduit, add 50 parts of distilled water and 0.5 part of mass concentration is 30% hydrogen peroxide, stirs and maintain temperature to be 10 DEG C.Prepare and contain 17.67 parts of methacrylic acid potassium (MAAK), 76.10 parts of methoxy polyethylene glycol methacrylate-styrene polymer (- CH₂CH₂O- average repeat units number 22, MAAM22), 6.22 parts of methacryloxymethyl triethoxysilanes (MAAMTES), 0.388 part of vitamin C, 1.26 parts of TGAs and The dispersion liquid of 100 parts of water is simultaneously thoroughly mixed, under nitrogen protection, uniform Deca MAAK/MAAM22/ in flask The aqueous dispersions of MAAMTES, time for adding is controlled to 5h, and completion of dropwise addition continues insulation 1h can obtain the aqueous solution of polymer G04, gather Compound effective solid content 40%, surveys solid content 40.5%, weight average molecular weight 5400.This aqueous solution is straight at once in follow-up preparation Connect and use, do not isolate and purify.

2. the synthesis of additive

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 circular, 2008,16；Polymer Bulletin 1999,42287；Journal of Applied Polymer Science 2000,77,2768；(3)Langmuir 2001,17,6077-6085.).

4- aminostyryl hydrochlorates (4-VBAH) is composite, and reference literature synthesizes gained (Analytical Chemistry 2012,84,3500)。

Embodiment 1

(1) polymerisable monomer A (numbering A1, polyethylene glycol methacrylate-styrene polymer, polyglycol chain are added in reactor In-CH₂CH₂O- average repeat units number is 6, and end group is hydroxyl, 0.1 part of consumption), polymerisable monomer B (AA0.29 parts and methyl 9.22 parts of acrylic acid methyl ester. (MMA)), (5 parts of divinylbenzene (DVB), commodity DVB includes meta and para-position isomery to cross-linking agent C Body) and 92.22 parts of water, it is thoroughly mixed；Lead to N in mixed liquor₂Except O₂, temperature of reactor is risen to into 80 DEG C, under stirring condition Once add in reactor initiator (0.05 part of Ammonium persulfate. APS is dissolved in 30 parts of water) cause polymerization, start simultaneously to Deca polymerisable monomer D (4.28 parts of acrylic acid and MMA81.13 parts), Deca 5h in reactor.Self-initiating agent is initially added into reaction Timing during device, 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 temp is down to 40 DEG C, be added thereto to 19.69 parts of water, stir Under the conditions of in organic polymer nuclear particle dispersion liquid the uniform the desired amount of Organic substance E of Deca (tetraethoxysilane TEOS, 13.37 parts, 1.8 parts of silicon content), (0.87 part of sodium silicate is dissolved in 5.00 parts of water, 0.2 part of silicon content to inorganic component F；One hydration vinegar 1.01 parts of sour calcium is dissolved in 10.00 parts of water) and 25.00 parts of organic polymer G01 aqueous solutions having prepared, dropwise reaction 8h.Reaction Volatilizable organic molecule is extracted in decompression after end out, and the additive of the anti-folding of cement-based material and tensile strength is improved needed for can obtaining W01。

Embodiment 2

(1) polymerisable monomer A (numbering A2, monomethyl polyethylene glycol acrylate ester, polyglycol chain are added in reactor In-CH₂CH₂O- average repeat units number is 22, and end group is methyl, and consumption is 2.00 parts), polymerisable monomer B (4- aminobenzene second 97.51 parts of 0.49 part of pinene hyhrochloride (4-VBAH) and styrene (St)), 3 parts of APS and 92.22 part of water, be thoroughly mixed；To Lead to N in mixed liquor₂Except O₂, temperature of reactor is risen to into 70 DEG C, under stirring condition in reactor uniform Deca initiator (1.71 Part sodium sulfite SBS is dissolved in 30 parts of water) cause polymerization, Deca 6h.Timing when self-initiating agent is initially added into reactor, in 7h is reacted under polymerizing condition, then removes inert atmosphere protection, obtain organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temp is down to 60 DEG C, to organic polymer core under stirring condition The desired amount of Organic substance E of Deca in particle dispersion (tetramethoxy-silicane TMOS, 48.86 parts, 9.0 parts of silicon content), without unit Divide F (4.36 parts of sodium silicate is dissolved in 20.00 parts of water, 1.0 parts of silicon content；6.29 parts of Calcium diacetate monohydrate is dissolved in 42.92 parts of water) and 37.50 parts of organic polymer G02 aqueous solutions, dropwise reaction 4h.Volatilizable organic molecule is extracted in decompression after reaction terminates out, can The additive W02 of the anti-folding of cement-based material and tensile strength is improved needed for obtaining.

As shown in figure 1, by the particle obtained by step (2) Jing process after carry out transmission electron microscope shooting, in figure some particles by The shell for causing script contrast relatively low in particle overlap is difficult to observe, but from monolayer morphology of particles, it is apparent that nucleocapsid Clear in structure is visible, has marked the outer layer A and inner layer B of particle in figure respectively.

The sample Jing dialysis purifications of step (2) are dropped on silicon chip, its EDS power spectrum (Fig. 2) is observed and tested with SEM, by High-visible C, the O and Ca element peak (K α and K β) therein of power spectrum, light element C peaks signal itself is weaker, is difficult quantitative.

Fig. 3 is the infrared spectrum (FT- of the particle that step (1)-(2) (Step (1)-Step (2)) obtain in embodiment 2 IR), the sample of all FT-IR tests is through dialysis purification.Step (1) correspondences step (1), Step (2) -1 are step (2) conjunction Into the nucleocapsid structure that midway (aqueous solution of Organic substance E, inorganic component F and organic polymer G02 Deca 3h) is taken out, Step (2) -2 is the nucleocapsid structure that embodiment 2 finally gives.

As seen from Figure 3,1581cm in Step (1) spectrogram^-1And 1603cm^-1, and 3000cm^-1-3120cm^-1In the range of (can Point out as unsaturated c h bond) multiplet prove phenyl ring (polystyrene agent structure), from Step (1) to Step (2) -1 again to Step (2) -2,920-1130cm in spectrogram^-1In the range of absorption intensity progressively strengthen in step (2), especially 965, 1070cm^-1Two are respectively belonging to Si-O (CSH, Q2) and Si-O (Si-rich phase, SiO₂) stretching vibration peak, (Cement and Concrete Research 2009,39147), spectrogram 1650cm^-1Nearby increase an absworption peak, be attributed to carboxylic acid (salt) carbonyl Base stretching vibration peak, while 2800-3000cm^-1In the range of belong to the stretching vibration peak of C-H, this region is relative to 3000cm^-1-3120cm^-1In the range of unsaturation C-H vibration ratio be increased slightly, it was demonstrated that saturation c h bond increased, contrast synthesis bar Part confirms as organic polymer G and is constantly connected to during step (2) on particle (to be wrapped in outer layer).In addition, spectrum 3240-3700cm in figure^-1Broad peak belongs to the stretching vibration of OH, should be the water of CSH phases.

Fig. 4 is the dynamic light scattering particle diameter of the particle that step (1)-(2) (Step (1)-Step (2)) obtain in embodiment 2 Scattergram, as can be seen from the figure particle radii increase in building-up process.

Embodiment 3

(1) polymerisable monomer A (numbering A3, polyethylene glycol monomethyl ethermethacrylic acid esters, poly- second two are added in reactor - CH in alcohol chain₂CH₂O- average repeat units number be 45, consumption be 5.00 parts), polymerisable monomer B (acrylic acid -2- hydroxyl ethyl esters (HEA) 9.10 parts of 1.38 parts, n-butyl acrylate (n-BuA) 17.12 and lauryl acrylate (LA)), Part I cross-linking agent C (1 part of DVB) and 92.22 parts of water, are thoroughly mixed；Lead to N in mixed liquor₂Except O₂, temperature of reactor is risen to into 60 DEG C, stirring Under the conditions of once add in reactor initiator (1 part of azo diisobutyl amidine hydrochlorate V50 is dissolved in 30 parts of water) cause Polymerization, start simultaneously in reactor Deca Part II cross-linking agent C (2 parts of DVB) polymerisable monomer D (4-VBAH1.29 parts and MMA63.11 parts), Part II cross-linking agent C and polymerisable monomer D Deca 3h.Timing when self-initiating agent is initially added into reactor, 4h is reacted under polymerizing condition, then removes inert atmosphere protection, obtain organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temp rises to 80 DEG C, to organic polymer core under stirring condition The desired amount of Organic substance E of Deca (VTES VTES101.79 parts, 15 parts of silicon content), nothing in particle dispersion (21.79 parts of sodium silicate is dissolved in 75.00 parts of water, 1.0 parts of silicon content to machine component F；37.95 parts of calcium nitrate tetrahydrate is dissolved in 52.26 parts Water) and with 5.00 parts of organic polymer G03 aqueous solutions, dropwise reaction 8h.Decompression after reaction terminates extracts volatilizable organic little out Molecule, improves the additive W03 of the anti-folding of cement-based material and tensile strength needed for can obtaining.

Embodiment 4

(1) polymerisable monomer A (numbering A4, N- poly glycol monomethyl ethers-acrylamide, poly- second two are added in reactor - CH in alcohol chain₂CH₂O- average repeat units number be 45,0.1 part of consumption), polymerisable monomer B (0.75 part of acrylic acid, metering system 1.73 parts of sour (MAA) and n-BuA46.93 parts) and 92.22 parts of water, it is thoroughly mixed；Lead to N in mixed liquor₂Except O₂, will react Device temperature rises to 50 DEG C, under stirring condition in reactor uniform Deca initiator (2 parts of isobutyl imidazoline hydrochlorides of azo two VA044 is dissolved in 30 parts of water) cause polymerization, start simultaneously at Deca cross-linking agent C (1 part of DVB) and polymerizable list in reactor Body D (0.25 part of 2-hydroxypropyl acrylate (HPA), 24.61 parts of MMA and 24.64 part of St), initiator, cross-linking agent C and can gather Close equal Deca 6h of monomer D.Timing when self-initiating agent is initially added into reactor, reacts 8h under polymerizing condition, then removes indifferent gas Atmosphere is protected, and obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temp rises to 80 DEG C, to organic polymer core under stirring condition It is the desired amount of Organic substance E of Deca (MTMS MTMOS7.29 parts, 1.5 parts of silicon content) in particle dispersion, inorganic (2.18 parts of sodium silicate is dissolved in 20.00 parts of water, 0.5 part of silicon content to the aqueous solution of component F；1.71 parts of anhydrous magnesium sulfates are dissolved in 16.19 parts of water) and 125.00 parts of organic polymer G04 aqueous solutions, dropwise reaction 3h.Reaction terminates decompression and extracts volatilizable out Organic molecule, improves the additive W04 of the anti-folding of cement-based material and tensile strength needed for can obtaining.

Embodiment 5

(1) polymerisable monomer A is added in reactor, and (numbering A5,4- (8- acryloyl-oxies) n-octyloxy benzene sulfonic acid sodium salt are used Measure as 3.00 parts), polymerisable monomer B (0.18 part of methacrylic acid -2- amino ethyl ester hydrochlorates (AEMH) and n-octyl (n-OctA) 9.02 parts), Part I cross-linking agent C (0.2 part of VTES (VTES) and 0.3 part of DVB), 0.13 The H of part mass fraction 30%₂O₂Aqueous solution and 92.22 parts of water, are thoroughly mixed；Lead to N in mixed liquor₂Except O₂, by reactor Temperature maintains 20 DEG C, under stirring condition in reactor uniform Deca initiator (0.1 part of vitamin C (VC) is dissolved in 30 parts In water) cause polymerization, start simultaneously in reactor Deca Part II cross-linking agent C (1.8 parts of VTES and 2.7 part of DVB) and can Polymerized monomer D (3- aminostyryls (3-VBA) 0.41 part and n-BuA82.39 parts), initiator, Part II cross-linking agent C and can Equal Deca 2h of polymerized monomer D.Timing when self-initiating agent is initially added into reactor, reacts 3h under polymerizing condition, then removes inertia Atmosphere protection, obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temp rises to 40 DEG C, to organic polymer core under stirring condition The desired amount of Organic substance E of Deca (tetramethoxy-silicane TMOS40.71 parts, 7.5 parts of silicon content), inorganic component in particle dispersion (10.89 parts of sodium silicate is dissolved in 35 parts of water, 2.5 parts of silicon content to the aqueous solution of F；21.08 part calcium nitrate tetrahydrate is dissolved in 32.42 parts of water) and 37.50 parts of organic polymer G04 aqueous solutions, dropwise reaction 8h.Reaction end decompression extraction is volatilizable to be had Machine small molecule, improves the additive W05 of the anti-folding of cement-based material and tensile strength needed for can obtaining.

Embodiment 6

(1) polymerisable monomer A (numbering A6, dodecyl-poly glycol monomethyl ether-maleic acid are added in reactor Dibasic acid esters ,-CH₂-CH₂O- average repeat units number 45, consumption be 5.00 parts), polymerisable monomer B (2-hydroxypropyl acrylates (HPA) 0.47 part and 92.54 parts of acrylic acid methyl ester. (MA)), cross-linking agent C (2 parts of VTES), 2.4 parts of sodium peroxydisulfates (SPS) and 92.22 parts Water, is thoroughly mixed；Lead to N in mixed liquor₂Except O₂, temperature of reactor is maintained into 60 DEG C, under stirring condition in reactor Uniform Deca initiator (1 part of sodium pyrosulfite (SMBS) is dissolved in 30 parts of water) causes polymerization, Deca 3.5h.Self-initiating agent is opened Timing when beginning to add reactor, 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 temp is down to 40 DEG C, to organic polymer core under stirring condition The desired amount of Organic substance E of Deca (TEOS111.43 parts, 15 parts of silicon content), the aqueous solution (silicon of inorganic component F in particle dispersion 4.36 parts of sour sodium is dissolved in 40.00 parts of water, 1 part of silicon content；4.76 parts of magnesium nitrate is dissolved in 41.13 parts of water) and 25.00 parts it is organic Polymer G03 aqueous solutions, dropwise reaction 6h.Reaction terminates decompression and extracts volatilizable organic molecule out, and water is improved needed for can obtaining The additive W06 of the anti-folding of cement-based material and tensile strength.

Embodiment 7

(1) polymerisable monomer B (0.14 part of sodium acrylate and lauryl methacrylate (LMA) are added in reactor 28.36 parts), Part I cross-linking agent C (4 parts of VTES), the H of 2.02 parts of mass fractions 30%₂O₂Aqueous solution and 92.22 parts of water, fill Divide stirring mixing；Lead to N in mixed liquor₂Except O₂, temperature of reactor is maintained into 30 DEG C, it is uniform in reactor under stirring condition Deca initiator (2.5 parts of rongalites (SFA) are dissolved in 30 parts of water) causes polymerization, starts simultaneously in reactor Deca Part II cross-linking agent C (1 part of DVB) polymerisable monomer D (AEMH0.92 parts, 3-VBA0.41 parts, LMA12.74 parts and St52.43 parts), initiator, Part II cross-linking agent C and equal Deca 5h of polymerisable monomer D.Self-initiating agent is initially added into reactor When timing, 6h is reacted under polymerizing condition, then remove inert atmosphere protection, obtain organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temp rises to 90 DEG C, to organic polymer core under stirring condition The desired amount of Organic substance E of Deca (MTMOS9.52 parts, 1.96 parts of silicon content), the aqueous solution of inorganic component F in particle dispersion (0.17 part of sodium silicate is dissolved in 15.76 parts of water, 0.04 part of silicon content；0.20 part of magnesium acetate is dissolved in 20 parts of water) and 125.00 parts Organic polymer G02 aqueous solutions, dropwise reaction 3h.Reaction terminates decompression and extracts volatilizable organic molecule out, carries needed for can obtaining The anti-additive W07 rolled over tensile strength of high cement-based material.

Embodiment 8

(1) polymerisable monomer A (numbering A8, polyethylene glycol monomethyl ethermethacrylic acid esters, poly- second two are added in reactor - CH in alcohol chain₂CH₂O- average repeat units number is 22, and end group is methyl, and consumption is 2.00 parts), polymerisable monomer B (methyl-props 0.41 part of olefin(e) acid ammonia carbethoxy hydrochloride (AEMH), 2.01 parts of methacrylic acid -2- t-butylaminoethyls (t-BAEMA) and methyl 46.55 parts of acrylic acid methyl ester. (MMA)) and 92.22 parts of water, it is thoroughly mixed；Lead to N in mixed liquor₂Except O₂, by reactor temperature Degree maintains 90 DEG C, and uniform Deca initiator (3 parts of SPS are dissolved in 30 parts of water) causes poly- in reactor under stirring condition Close, start simultaneously at Deca polymerisable monomer D (MAA2.45 parts and LMA46.55 parts), initiator and polymerizable list in reactor Equal Deca 2h of body D.Timing when self-initiating agent is initially added into reactor, reacts 4h under polymerizing condition, then removes inert atmosphere guarantor Shield, obtains organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temp is down to 70 DEG C, to organic polymer core under stirring condition The desired amount of Organic substance E of Deca (3- aminopropyl trimethoxysilane APTMS115.07 parts, silicon content 18 in particle dispersion Part), (8.71 parts of sodium silicate is dissolved in 82.28 parts of water, 2 parts of silicon content to the aqueous solution of inorganic component F；10.14 part magnesium acetate dissolves In 70 parts of water) and 5.00 parts of organic polymer G01 aqueous solutions, dropwise reaction 4h.Reaction terminates decompression and extracts volatilizable organic out Small molecule, improves the additive W08 of the anti-folding of cement-based material and tensile strength needed for can obtaining.

Embodiment 9

(1) in reactor add polymerisable monomer A (numbering A9,4- (10- acryloyl-oxies) 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 parts), cross-linking agent C (2.7 parts of methacryloxypropyl trimethoxy silanes MAAPTMS and 0.3 part of VTES) and 92.22 parts of water, are sufficiently stirred for mixing Close；Lead to N in mixed liquor₂Except O₂, temperature of reactor is maintained into 85 DEG C, uniform Deca causes in reactor under stirring condition Agent (0.1 part of potassium peroxydisulfate KPS is dissolved in 30 parts of water) causes polymerization, starts simultaneously at the Deca polymerisable monomer D in reactor (1.66 parts of methacrylic acid -2- hydroxy methacrylates (HEMA) and MMA81.14 parts), initiator and equal Deca 5h of polymerisable monomer D. Timing when self-initiating agent is initially added into reactor, reacts 8h under polymerizing condition, then removes inert atmosphere protection, obtains organic poly- Compound nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temp is down to 60 DEG C, to organic polymer core under stirring condition The desired amount of Organic substance E of Deca (MTES MTEOS54.13 parts, 8.5 parts of silicon content), nothing in particle dispersion (6.54 parts of sodium silicate is dissolved in 29.77 parts of water, 2 parts of silicon content to the aqueous solution of machine component F；5.69 parts of calcium nitrate tetrahydrate and vinegar 3.42 parts of sour magnesium is dissolved in 40 parts of water) and 5.00 parts of organic polymer G02 aqueous solutions, dropwise reaction 4h.Reaction terminates decompression and takes out Go out volatilizable organic molecule, the additive W09 of the anti-folding of cement-based material and tensile strength is improved needed for can obtaining.

Embodiment 10

(1) polymerisable monomer B (MAA5 parts and t-BuA95 parts) and 92.22 parts of water are added in reactor, is sufficiently stirred for mixing Close；Lead to N in mixed liquor₂Except O₂, temperature of reactor is maintained into 80 DEG C, once add in reactor under stirring condition and cause Agent (3 parts of APS are dissolved in 30 parts of water) causes polymerization.Timing when self-initiating agent is initially added into reactor, it is anti-under polymerizing condition 4h is answered, then removes inert atmosphere protection, obtain organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temp is down to 60 DEG C, to organic polymer core under stirring condition The desired amount of Organic substance E of Deca (VTES66.50 parts, 9.8 parts of silicon content), the aqueous solution (silicon of inorganic component F in particle dispersion 0.87 part of sour sodium is dissolved in 20.00 parts of water, 0.2 part of silicon content；0.10 part of Calcium diacetate monohydrate is dissolved in 20.00 parts of water；0.73 Part magnesium acetate is dissolved in 34.56 parts of water) and 125.00 parts of organic polymer G01 aqueous solutions, dropwise reaction 8h.Reaction terminates decompression Extract volatilizable organic molecule out, the additive W10 of the anti-folding of cement-based material and tensile strength is improved needed for can obtaining.

Embodiment 11

(1) polymerisable monomer A (numbering A10, dodecyl-poly glycol monomethyl ether-maleic acid are added in reactor Dibasic acid esters ,-CH₂-CH₂O- average repeat units number 6, consumption be 3.00 parts), polymerisable monomer B (3- aminostyryls (3-VBA) 0.57 part and St27.93 parts) and 92.22 parts of water, it is thoroughly mixed；Lead to N in mixed liquor₂Except O₂, temperature of reactor is maintained At 70 DEG C, under stirring condition in reactor uniform Deca initiator (0.5 part of APS is dissolved in 15 parts of water；0.55 part of sulfurous acid Sodium SS is dissolved in 15 parts of water, and both distinguish Deca) cause polymerization, start simultaneously at (2 part third of the Deca cross-linking agent C in reactor Alkene pivaloyloxymethyl trimethoxy silane AAMTMS) and polymerisable monomer D (AEMH2 parts and LA64.51 parts), initiator, residue Partial cross-linked dose of C and equal Deca 2.5h of polymerisable monomer D.Timing when self-initiating agent is initially added into reactor, under polymerizing condition Reaction 3h, then inert atmosphere protection is removed, obtain organic polymer nuclear particle dispersion liquid.

(2) treat that gained organic polymer nuclear particle dispersion liquid temp is down to 50 DEG C, to organic polymer core under stirring condition The desired amount of Organic substance E of Deca (TEOS20.06 parts, 2.7 parts of silicon content), the aqueous solution (silicon of inorganic component F in particle dispersion 1.31 parts of sour sodium is dissolved in 10.00 parts of water, 0.3 part of silicon content；0.13 part of 1.82 parts of calcium nitrate tetrahydrate and magnesium nitrate are dissolved in 27.96 parts of water) and 25.00 parts of organic polymer G04 aqueous solutions, dropwise reaction 6h.Reaction end decompression extraction is volatilizable to be had Machine small molecule, improves the additive W11 of the anti-folding of cement-based material and tensile strength needed for can obtaining.

Embodiment 12

(1) polymerisable monomer A (numbering A7, dodecyl-hydroxyl polyethylene glycol groups-maleic acid are added in reactor Dibasic acid esters ,-CH₂-CH₂O- average repeat units number 32, consumption be 5.00 parts), polymerisable monomer B (HEMA0.23 parts and LMA44.78 Part), Part I cross-linking agent C (2.5 parts of VTES) and 92.22 parts of water, be thoroughly mixed；Lead to N in mixed liquor₂Except O₂, will be anti- Device temperature is answered to maintain 60 DEG C, uniform Deca initiator (1 part of V50 is dissolved in 30 parts of water) is drawn in reactor under stirring condition Polymerization is sent out, the Deca Part II cross-linking agent C (2.5 parts of VTES) and polymerisable monomer D (HEMA0.23 in reactor is started simultaneously at Part and LMA44.78 parts), initiator, Part II cross-linking agent C and equal Deca 4h of polymerisable monomer D.Self-initiating agent is initially added into Timing during reactor, reacts 6h under polymerizing condition, then removes inert atmosphere protection, obtains the dispersion of organic polymer nuclear particle Liquid.

(2) gained organic polymer nuclear particle dispersion liquid temp is maintained to be 60 DEG C, to organic polymer core under stirring condition The desired amount of Organic substance E of Deca (TEOS118.86 parts, 16 parts of silicon content), the aqueous solution (silicon of inorganic component F in particle dispersion 17.43 parts of sour sodium is dissolved in 52.69 parts of water, 4 parts of silicon content；13.50 parts of calcium nitrate tetrahydrate is dissolved in 20 parts of water；12.17 parts Magnesium acetate is dissolved in 30 parts of water) and 7.14 parts of organic polymer G03 aqueous solutions, dropwise reaction 8h.Reaction terminates decompression extraction can The organic molecule of volatilization, improves the additive W12 of the anti-folding of cement-based material and tensile strength needed for can obtaining.

3. additive is used for the modified test of cement-based material

Application Example 1

Improvement to mortar mechanical property：Mortar is prepared using little wild field PII52.5 cement, iso standard sand, sand-lime Than for 3:1, the ratio of mud is 0.36, and the volume of additive W01-W12, PE01-PE04 is that the folding on the basis of Binder Materials is measured admittedly Calculate, basically identical by defoamer consumption control each group mortar air content, water reducer used is that Su Bote companies markets are common Conventional polycarboxylate water-reducer- I, controls each group Mortar'S Flowability basically identical by water reducer consumption.Specimen molding After be placed in 25 DEG C, conserve under more than 95% damp condition.

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

PE02：According to document synthesis (Journal of Materials in Civil Engineering 2011,23, 1412), its stability is slightly worse, and coagulation can occur in cement filtrate；W01-W12 will not coagulation in cement filtrate；

PE03：BASF pure-acrylic emulsions (Acronal PA 237)；

PE04：BASF styrene-acrylic emulsions (Acronal S 400).

The mortar performance of table 1 tests table

Note：Volume refers to pure effective ingredient (hybrid inorganic-organic grain in the aqueous dispersions that various embodiments of the present invention finally synthesize Son) quality relative to glue material quality in cement-based material ratio.

From experimental result in table, under the conditions of the identical ratio of mud, synthesis additive W01-W12 shown in the embodiment of the present invention When for modifying mortar：

(1) it is right to mortar comprcssive strength without negative effect (relative to the 1.0% of cement consumption) under the conditions of low-dosage Its tension and there is a certain degree of lifting, rupture strength also has certain lifting.By contrast, using common polymer emulsion (commercially available or synthesis, PE01, PE02) nothing is obviously improved.

(2) lift the volume such as W01 to 2.5%, W01, W05 and W09 to mortar comprcssive strength substantially without negative effect, to it Tensile strength has a certain degree of lifting (28 days strength enhancing～13%), and rupture strength also has certain lifting, and (intensity is carried within 28 days Rise～30%).By contrast, using common polymer emulsion (commercially available or synthesis, PE01, PE02), action effect is relatively It is weak.

(3) lift the volume such as W01 without negative effect or to have lifted mortar comprcssive strength to 5.0%, W01-W12 (0%-18%), while having a certain degree of lifting (28 days strength enhancing 13-33%) to its tensile strength, rupture strength also has It is certain to lift (28 days strength enhancing 22-43%).By contrast, using common polymer emulsion (commercially available or synthesis, PE01- PE02), although the tension rupture strength of mortar has been lifted and (lifted amplitude respectively～10% and 10-15%, but its pressure resistance Degree has different degrees of reduction (～10%).

(4) addition of W01-W12 is obviously promoted effect, phase to early age strength of concrete (10h resistance to compressions and anti-folding) development Than under, PE01-PE04 is to early age strength of concrete development is without facilitation or has retarding action.

It can be seen that the lifting of W01, W05 and W09 volume folding anti-to mortar and tensile strength in the 1-2.5% of cement consumption is Jing can reach the performance during polymer emulsions 5% such as addition PE01-PE04, while W01, W05 and W09 are to agent on crack resistance of concrete pressure Spend and have no adverse effect, show obvious advantage.

Application Example 2

Mechanical performance of concrete test is carried out with reference to GB/T50080-2002 and GB/T50081-2002, using reference water Mud, II level flyash, modulus of fineness is 2.6 river sand, the rubble of 5-25mm continuous gradings.Concrete mix is shown in Table 2, coagulation Native result of the test is shown in Table 3.

Concrete mix (the kg/m of table 2³)

Cement	Flyash	Sand	Stone	Water
					373	77	700	1130	145

The volume of additive W01-W12, PE01-PE04 is that the folding on the basis of Binder Materials measures calculating admittedly, by froth breaking Agent control each group mortar air content is basically identical, and water reducer used is the polycarboxylate water-reducer of Su Bote companies market normal conventionals- I, controls each group slump basically identical (20 ± 1cm) by water reducer consumption.25 are placed in after specimen molding DEG C, conserve under more than 95% damp condition.

The testing concrete performance table of table 3

From experimental result in table, under the conditions of the identical ratio of mud, synthesis additive W01-W12 shown in the embodiment of the present invention When for concrete：

(1) it is right to concrete crushing strength without negative effect (relative to the 1.0 of cement consumption) under the conditions of low-dosage It splits drawing and rupture strength also certain lifting.By contrast, using common polymer emulsion (commercially available or synthesis, PE01, PE02) nothing is obviously improved.

(2) lift the volume such as W01 to 2.5%, W01, W05 and W09 to mortar comprcssive strength substantially without negative effect, to it Split tensile strength has a certain degree of lifting (28 days strength enhancing 10-16%), and rupture strength also has certain lifting, and (intensity is carried within 28 days Rise 24-34%).By contrast, using common polymer emulsion (commercially available or synthesis, PE01, PE02), action effect is relatively It is weak.

(3) volume such as lifting W01 without negative effect or has been carried substantially to 5.0%, W01-W12 to concrete crushing strength Rise (0%-15%), while being obviously improved (28 days strength enhancing 11-26%) to its split tensile strength, rupture strength also has necessarily Lifted (28 days strength enhancing 24-50%).By contrast, using common polymer emulsion (commercially available or synthesis, PE01- PE02), although the tension rupture strength of concrete has been lifted and (lifted amplitude respectively～10% and 10-15%, but its resistance to compression Intensity has different degrees of reduction.

It can be seen that W01, W05 and W09 volume in the 1-2.5% of cement consumption to concrete split tensile strength and tensile strength Lifting can reach the performance during polymer emulsions 5% such as addition PE01-PE04, while W01, W05 and W09 are to concrete Comprcssive strength simultaneously has no adverse effect, and shows obvious advantage.

It should be noted that for mortar specimen, general experiment can determine tensile strength；For concrete sample, lead to Tensile splitting strength, the value and being proportionate property of tensile strength are often determined, but (typically slightly above tension is strong to be not equal to tensile strength Degree), tensile splitting strength is higher, and tensile strength is higher.

The abbreviation of monomer used and initiator in the polymerizing condition of table 4 is represented

。

Claims

1. it is a kind of to improve the anti-additive rolled over tensile strength of cement-based material, it is characterised in that the additive is a kind of tool There are the aqueous dispersions of the hybrid inorganic-organic particle of nucleocapsid structure, the hybrid inorganic-organic particle is made up of inside and outside two-layer, Internal layer is organic polymer core, and outer layer is the inorganic composite oxide that inorganic composite oxide or organo-functional group are covalently attached, Affiliated inorganic composite oxide is silicon-calcium composite oxides or silicon-Magnesium coumpoud oxide or silicon-calcium-Magnesium coumpoud oxide, described Being covalently attached in the layer of outer layer has elecrtonegativity organic polyelectrolyte；

The organic polymer core is prepared from by polymerisable monomer A, polymerisable monomer B, polymerisable monomer D and cross-linking agent C, institute It is the one kind met in below general formula (1)-(3) Organic substance to state polymerisable monomer A：

Wherein, R₁、R₂、R₃And R₅Separately represent H or CH₃, R₄Represent the alkyl of 6-30 carbon atom, X₁、X₂、X₃And X₄ O or NH is separately represented, a, b are ethyoxyl (- CH₂CH₂O) chain link average repeat unit number, span is 4-50, c's Span is 6-12；

The polymerisable monomer B and polymerisable monomer D is by functional group's type monomer and non-functional group type monomer composition, polymerizable list Monomer in body B accounts for the 0.5-5% of polymerisable monomer B gross masses, and the monomer in polymerisable monomer D accounts for can be gathered Close monomer D gross masses 0.5-5%, the monomer for hydroxyl, amino or carboxyl polymerisable monomer, the non-official It is the one kind or more than one combination in any in styrene and monomer shown in formula (4) that type monomer can be rolled into a ball：

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

The cross-linking agent C is one kind or more than one combination in any in following material：Divinylbenzene, vinyl trimethoxy Base silane, VTES, methacryloxypropyl trimethoxy silane, methacryloxypropyl three Ethoxysilane, methacryloxymethyl triethoxysilane, acryloyloxymethyl trimethoxy silane, acryloyl-oxy Base propyl trimethoxy silicane.

2. it is a kind of to improve the anti-preparation method rolled over the additive of tensile strength of cement-based material, it is characterised in that step is such as Under：

(1) polymerisable monomer A, polymerisable monomer B, Part I cross-linking agent C and water are added in reactor, is sufficiently stirred for mixing Close；Lead to N in mixed liquor₂Except O₂, reactor is risen to into reaction temperature, add initiator to cause in reactor under stirring condition Polymerization, starting simultaneously at the mixed liquor of Deca Part II cross-linking agent C and polymerisable monomer D in reactor carries out copolymerization, described Part I cross-linking agent C and Part II cross-linking agent C is arbitrary proportion, and reaction end obtains the dispersion of organic polymer nuclear particle Liquid；

(2) organic polymer nuclear particle dispersion liquid prepared by step (1) is adjusted to temperature required, is gathered to organic under stirring condition Organic substance E, organic polymer G and inorganic component F are added in compound nuclear particle dispersion liquid, is reacted in reaction condition, reduced pressure Extract volatilizable organic molecule out, cooling is improved the additive of the anti-folding of cement-based material and tensile strength；

The Organic substance E is the silane that a kind of more than three alkoxyls replace；

The inorganic component F is made up of sodium silicate and soluble inorganic salt, the soluble inorganic salt cationic it is mole total Amount is 0.8-1.0 with the ratio of the mole of sodium silicate；

The organic polymer G is the elecrtonegativity organic polyelectrolyte of long side chain, weight average molecular weight range be 5000≤Mw≤ 100000；

The gross mass of described polymerisable monomer A, B, D and cross-linking agent C accounts for the 5-45% of polymerization system gross mass in step (1), institute State polymerisable monomer A quality account for described polymerisable monomer A, B, D and cross-linking agent C gross mass 0-5%, the cross-linking agent C Quality account for described polymerisable monomer A, B, D and cross-linking agent C gross mass 0-5%, the quality of the polymerisable monomer B is accounted for can The ratio of the gross mass of polymerized monomer B and D is not less than 10%, and the quality of the initiator accounts for polymerisable monomer A, B, D and crosslinking The 0.05-3% of agent C gross masses；

The gross mass of contained element silicon accounts for the organic polymer particle obtained in step (1) in the Organic substance E and inorganic component F The 2-20% of gross mass, contained element silicon amount accounts for total matter of element silicon in Organic substance E and inorganic component F in the inorganic component F The 0-25% of amount, the quality of the organic polymer G accounts for the 2- of the organic polymer particle gross mass obtained in step (1) 50%.

3. preparation method according to claim 2, it is characterised in that the initiator is thermal decomposition initiator system initiator Or the one kind in redox initiation system initiator, the thermal decomposition initiator system initiator is the isobutyl imidazoline salt of azo two One kind in double (2- methyl-prop amidines) dihydrochloride, Ammonium persulfate., potassium peroxydisulfate or the sodium peroxydisulfates of hydrochlorate, 2,2'- azos, it is described Oxidant in redox initiation system initiator is H₂O₂, reducing agent is vitamin C or rongalite.

4. preparation method according to claim 3, it is characterised in that the oxygen in the redox initiation system initiator Agent is the one kind in Ammonium persulfate., sodium peroxydisulfate or potassium peroxydisulfate, and reducing agent is sodium sulfite, sodium sulfite, burnt sulfurous One kind in sour sodium or rongalite.

5. the preparation method according to claim 3 or 4, it is characterised in that the consumption mole of the oxidant and reducing agent Than for 0.5-2.0.

6. preparation method according to claim 2, it is characterised in that the monomer is the one kind in following monomer Or more than one combination in any：3- aminostyryls, 4- aminostyryls, 2- (tert-butylamino) ethyl methacrylate, The hydrochlorate or sulfonate of aminoethyl methacrylate and above-mentioned monomer, acrylic acid, methacrylic acid and acrylic acid or first The acrylic acid univalent metal salt of base, acrylic acid -2- hydroxyl ethyl esters, 2-hydroxyethyl methacry-late, 2-hydroxypropyl acrylate, third Olefin(e) acid -4- hydroxybutyls, methacrylic acid -2- hydroxy propyl esters, methacrylic acid -4- hydroxybutyls, N hydroxymethyl acrylamide, N- hydroxyethyl acrylamides, N- (2- hydroxypropyls) acrylamide, N- methylol methacrylamides and N- (2- hydroxypropyls) methyl Acrylamide.

7. preparation method according to claim 2, it is characterised in that the soluble inorganic salt is by soluble inorganic calcium salt Or one or two compositions in soluble inorganic magnesium salt, the soluble inorganic calcium salt is in calcium nitrate, calcium chloride, calcium acetate One or more arbitrary proportion mixture, the soluble inorganic magnesium salt be magnesium acetate, magnesium chloride, magnesium nitrate or magnesium sulfate in One or more arbitrary proportion mixture.

8. preparation method according to claim 2, it is characterised in that the reaction temperature in the step (1) is 20-90 DEG C, the response time is 2-8h, and the reaction temperature in the step (2) is 40-90 DEG C, and the response time is 3-8h.