WO2017114375A1 - Agent de renfort de matériau à base de ciment, et son procédé de préparation et ses applications - Google Patents

Agent de renfort de matériau à base de ciment, et son procédé de préparation et ses applications Download PDF

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WO2017114375A1
WO2017114375A1 PCT/CN2016/112249 CN2016112249W WO2017114375A1 WO 2017114375 A1 WO2017114375 A1 WO 2017114375A1 CN 2016112249 W CN2016112249 W CN 2016112249W WO 2017114375 A1 WO2017114375 A1 WO 2017114375A1
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monomer
siloxane
organic
polymerizable monomer
parts
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Chinese (zh)
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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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江苏苏博特新材料股份有限公司
南京博特新材料有限公司
博特建材（天津）有限公司
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    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08F220/10—Esters
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
    • 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
    • C08F230/08—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 containing silicon
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the invention relates to the field of admixtures for modifying cement-based materials, in particular to an enhancer which can improve the mechanical properties (including compression resistance, flexural strength and tensile strength) of cement-based materials and a preparation method thereof.
  • Cement-based materials refer to materials such as concrete, mortar, and grouting. As the most widely used building material in the world, cement-based materials continue to expand in its application fields, but complex and diverse construction and use environments are constantly demanding higher performance. Therefore, improving its mechanical properties is an inevitable trend of its development.
  • Ordinary cement-based material is a typical brittle material, which has high compressive strength, and is resistant to bending and tensile strength. In actual use, it is easy to generate various cracks or damages due to stress concentration or uneven force. The durability is reduced, which limits its application. For example, the surface layer of the cement pavement is prone to premature failure of the board and surface structure, thus limiting its application in high-grade roads.
  • the existing main modified components include fibers (organic polymers, steel fibers). And glass fiber) and polymer particles (emulsion or dry powder).
  • the principle of fiber toughening is: (1) limit the development of micro-cracks. When the fibers are evenly distributed in the concrete matrix, it is assumed that there is a tendency for microcracks to occur inside the concrete matrix. When any micro-cracks occur and may develop in any direction, the fibers are not farther than the fiber average in the concrete matrix. Within the distance of the center distance, the crack will encounter a fiber that traverses in front of it. When the crack is generated, due to the high modulus of the fiber and the high tensile strength of the single root, the further development of the crack can be prevented, and a closed cavity similar to a harmless hole or a hole having a very small inner diameter can be formed only in the concrete matrix. (2) The toughness of high-strength fiber itself is much higher than that of concrete. The strength of fiber-modified concrete is the superposition of the properties of concrete phase and fiber phase, so its toughness is higher than that of ordinary concrete.
  • the polymer particles act as admixtures to improve the bond between the concrete components. Dispersion and film formation of polymer particles are the main reason for their modification. Due to the presence of the polymer film, the mechanical properties (especially toughness) of the concrete material are more excellent.
  • the physical interaction or partial chemical bonding between the polymer and the inorganic material that is, the modification of the cement mortar in the form of particles or membranes, or the formation of a more dense chelating body combined by coordination, Thereby improving the performance of the polymer cement concrete.
  • the introduction of reactive groups such as -OH, -COOH, -COOR into the polymer can coordinate with the cement hydration product, change the bond type of the cement material with silicon-oxygen bond, and add organic hydrocarbon.
  • the bond type of the bond significantly enhances the structure, forming a double-stack network structure with overlapping layers, improving the interface between the interfaces and improving the interface fracture energy and toughness (Bulletin of the Chinese Ceramic Society, 2014, 33, 365).
  • the fiber tends to agglomerate when the concrete is stirred, is difficult to disperse, and cannot be uniformly distributed in the concrete.
  • the performance of fiber-modified concrete is closely related to the dispersion and orientation of fibers. Therefore, the concrete preparation process has a great influence on the performance of concrete, and its preparation is more difficult than conventional concrete.
  • the agglomeration makes the concrete workability poor, pumping difficult, and difficult to construct.
  • the failure mode of the steel fiber during use is mainly pulled out without being broken, which indicates that the adhesion of the steel fiber to the concrete is insufficient, which affects the effect of improving the tensile strength of the concrete.
  • the density of the synthetic fiber is small, the diameter of the monofilament is small, and there is a thickening effect, which is not conducive to the vibration compaction of the concrete. Due to the poor alkali resistance of glass fibers, the application of glass fiber reinforced concrete is limited.
  • the cement-based material toughening method disclosed in the patent CN101891417B requires uniform dispersion of the components (including fibers) of the formulation by stirring, and the stirring time is long (25-35 min).
  • the patent CN101913188B adds a magnetic field to make the steel fiber single-phase distribution and improve the flexural strength of the steel fiber concrete, which undoubtedly complicates the preparation of the concrete.
  • Patent US7192643 prepares a readily dispersible organic fiber membrane for toughening cement-based materials by a special method.
  • the patents EP0488577, US5993537, and US4524101 all require the addition of so-called wetting agents or inorganic binding agents to allow the fibers to disperse. These patents typically require the preparation of the desired fibrous material or corresponding modified concrete by specific means or equipment.
  • the polymer blending amount in the polymer modified concrete is too high. Since polymer modified concrete is more likely to form a polymer network, it is equivalent to improving the performance of concrete through the form of material blending.
  • the polymer network itself has limited adhesion to cement-based materials, so the modification performance is not high at low dosage. Obviously, it is necessary to add a higher amount, which makes it costly.
  • Polymer emulsions may also accumulate in the environment of high alkali and high salt of concrete, affecting its function (the emulsion of anionic emulsifier synthesis is easy to coagulate, Journal of Materials in Civil Engineering 2011, 23, 1412).
  • Patent CN102276764B provides a chemical modification method for polymer powder modification, which is chemically grafted on a surface of a polymer powder by a coupling agent to improve the interaction between the powder and the matrix, thereby improving the impact resistance of the modified mortar. But it does not solve the problem of dispersion of polymer powder itself.
  • the polymer emulsion (Handbook of polymer-modified concrete and mortars, 1995, 55) has an effect on the setting time of cement-based materials. It is related to the type and amount of polymer emulsion used, and generally delays the setting time. Ten minutes - hours).
  • Patents CN103130436A and CN101239800B respectively report the use of graphene (graphene oxide) and carbon nanotube modified cement-based materials to improve the compression and tensile strength, but the cost is too high.
  • Patent CN103274620A generates metamorphic kaolin minerals with a certain morphology by heating and calcining ordinary kaolin clay minerals, and strengthening the strength of cement-based materials.
  • EP 2 695 850 A1 discloses a method for the in situ nucleation of growing calcium silicate (wollastonite) nanocrystals in a cementitious material for toughening. The modifiers reported in these patents require specific conditions such as temperature and pressure, which make preparation difficult.
  • CN104446091A, CN103787609A and CN104119014A respectively introduce several concrete reducers, which increase the degree of cement dispersion by enhancing the cementation of cement particles, thereby improving the degree of hydration, but in principle, it cannot fundamentally improve the cement-based materials. brittleness.
  • CN104609759A and CN104446102A each introduce an admixture which can increase the flexural strength and tensile strength of the cement-based material.
  • the active ingredient is a core-shell structure particle, because the organic phase and the inorganic phase are connected to the inner and outer interfaces of the core-shell structure, and the covalent bonding depends on the inner surface area of the core-shell structure, which is limited. Therefore, the degree of improvement of the mechanical properties of cement-based materials is also limited, and the two admixtures have little effect on the compressive strength of cement-based materials.
  • the present invention provides an organic-inorganic hybrid particle and a preparation method thereof, and the aqueous dispersion of the organic-inorganic hybrid particle as a reinforcing agent for a cement-based material can simultaneously improve the compressive and anti-pressure resistance of the cement-based material. Fold and tensile (or anti-pull) strength.
  • Tensile and anti-pull strength are slightly different parameters of the test method. Generally, the tensile strength is high and the tensile strength should be high.
  • the index used in the present invention is the tensile strength, which is used instead of the tensile strength.
  • the organic component and the inorganic component are mutually connected by a covalent bond, not a core-shell structure, but interpenetrated with each other, and are linked by a covalent chemical bond, but the organic group
  • the phase separation boundary refers to a clear boundary between the core layer and the shell layer.
  • the organic moiety is an organic polymer network formed by covalently linking a long ethylene glycol segment, an intermediate segment, and a siloxane segment, wherein the siloxane segment does not comprise an alkoxy group and the alkoxy group occurs. a silicon-oxygen bond portion formed by the hydrolysis reaction;
  • the intermediate segment means styrene or substituted styrene, acrylic acid, methacrylic acid, acrylate, methyl propyl a homopolymeric segment or a copolymerized segment formed by polymerization of any of a acrylate, acrylate or substituted acrylate, methacrylate or substituted methacrylate;
  • the organic component is styrene or substituted styrene, acrylic acid, methacrylic acid, acrylate or substituted acrylate, methyl in the presence of a long monomer and siloxane containing a long ethylene glycol chain.
  • Siloxanes are the key to linking organic and inorganic components.
  • the siloxanes may or may not contain double bonds, but must contain more than three siloxane functional groups; siloxane functional groups can be hydrolyzed to link them to none.
  • the double bond polymerization can be attached to the organic component. If it does not contain a double bond, the siloxane functional group reacts with the hydroxyl group or amino group contained in the organic polymer component to cause it to be attached. On the organic component.
  • the inorganic component is a network of silicon-oxygen bonds prepared by hydrolyzing the siloxane.
  • a silane containing three or more alkoxy groups such as methyltrimethoxysilane, wherein the methyl group is also an organic functional group, is used in the present invention, but the methyl group has less influence on the performance of the hybrid particles. .
  • Organic component When the material is incorporated into the cement-based material for modification, it functions as a cross-linking node. Due to the excellent tensile properties of the organic material, it can bear part of the external force to improve the flexural strength of the cement-based material. And tensile strength; at the same time, the macromonomer is continuously grafted onto the hybrid particles during the preparation of the hybrid particles, thereby stabilizing the hybrid particles by providing steric hindrance and preventing the hybrid particles from coagulation.
  • Inorganic component a chemical reaction can occur in a strongly alkaline environment of a cement-based material, and a covalent bond is formed with the main gelling component hydrated calcium silicate gel (CSH) to thereby organically bond through a covalent chemical bond.
  • the components are connected with the CSH particles, and the organic components are fully utilized to improve the mechanical properties of the cement-based materials.
  • the CSH junction function is acted upon to increase the CSH gel content in the cement-based material and improve the mechanical properties of the cement-based material (eg, Compressive strength).
  • the particles react with the alkaline environment of the cement-based material, and the hydrated product is crystallized by the particles, thereby functioning as a cross-linking node.
  • the hydrated product particles are connected to improve the mechanical properties of the cement-based material.
  • the hybrid structure covalently connects the organic component and the inorganic component to a smaller scale than the core-shell structure, further improves the connection efficiency of the organic component and the inorganic component, and is beneficial to improve the mechanics of the hybrid particle itself. Performance, at the same time, when used in the modification of cement-based materials, the connection efficiency of organic components is further increased compared with the core-shell structure, thereby improving its ability to increase the compressive, tensile and flexural strength of cement-based materials.
  • the organic-inorganic hybrid particles are spherical particles having a diameter of less than 1000 nm; their forces in all directions are more uniform than fibers, and thus there is no problem of orientation.
  • the preparation method of the organic-inorganic hybrid particle aqueous dispersion of the present invention specifically comprises the following steps:
  • a part of the polymerizable monomer A, a polymerizable monomer B, a part of the crosslinking agent C, a part of the siloxane D, and water are added to the reactor, and the mixture is thoroughly stirred and mixed to obtain a mixed solution; the mixture is adjusted to pH.
  • the polymerizable monomer A is added in two portions, and the monomer A directly added to the reactor at the initial stage of the reaction accounts for 10-50% of the total amount of the monomer A.
  • the cross-linking agent C was added in two portions, wherein the ratio of the first addition amount was 0-100% of the total cross-linking agent C.
  • the siloxane D was added in two portions, wherein the proportion of the first addition amounted to 0-100% of the total siloxane D.
  • the polymerizable monomer A is one of the following general formula ((1)-(2)):
  • R 1 , R 2 and R 3 each independently represent H or CH 3 , and R 4 represents an alkyl group of 6 to 30 carbon atoms;
  • X 1 , X 2 and X 3 each independently represent O or NH;
  • a and b respectively Independently refers to the average number of repeating units of the ethoxy-CH 2 CH 2 O-chain, a, b ranges from 4 to 50;
  • the values of a and b are too small, the self-emulsification is weak, and the steric hindrance provided is small, which is unfavorable for stabilizing the hybrid particles.
  • the value is too large, the polymerization activity is too low compared to the monomer B and the crosslinking agent C. Therefore, a large amount remains in the polymerization system because it is difficult to copolymerize.
  • the polymerizable monomer A can be used on the one hand to stabilize the hybrid particles during the synthesis process and in the application process, and the effect is similar to the polymerizable emulsifier in the conventional emulsion polymerization.
  • the small molecular weight polymer formed by the preliminary polymerization of the monomer A Micellars can be formed which can swell the subsequent polymerizable monomer B, crosslinker C and siloxane D.
  • the amount thereof also has a close influence on the size of the organic polymer core particles synthesized in the first stage, and the higher the amount of the initial addition to the reactor, the smaller the particle size.
  • the polymerizable monomer B is composed of a functional group monomer and a non-functional monomer.
  • the functional group monomer in the monomer B accounts for 1-5% of the total mass of the monomer B, and the rest is a non-functional monomer.
  • the functional group monomer is one or more than any one of all of the following functional group monomers.
  • the amino group-containing polymerizable monomer includes 3-aminostyrene, 4-aminostyrene, 2-(tert-butylamino)ethyl methacrylate, aminoethyl methacrylate, and hydrochloride of these monomers. Or sulfonate;
  • the hydroxyl group-containing polymerizable monomer is a hydroxy acrylate or methacrylate, hydroxy acrylamide or hydroxymethyl acrylamide monomer, and includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
  • HEMA 2-hydroxypropyl acrylate
  • 4-hydroxybutyl acrylate 2-hydroxypropyl methacrylate
  • 4-hydroxybutyl methacrylate N-methylol acrylamide
  • HEMA 2-hydroxypropyl acrylate
  • 4-hydroxybutyl acrylate 2-hydroxypropyl methacrylate
  • 4-hydroxybutyl methacrylate N-methylol acrylamide
  • N- Hydroxyethyl acrylamide N-(2-hydroxypropyl) acrylamide
  • N-methylol methacrylamide N-(2-
  • the non-functional monomer is one or more than any one of styrene and a monomer represented by the following formula (3).
  • R 5 represents H or CH 3
  • R 6 represents H, Na, K or an alkyl group of 1 to 12 carbon atoms.
  • the polymerizable monomer B is the most important component of the organic polymer core particles, and its role is to provide a better tough organic substrate for ultimately improving the flexural strength and tensile strength of the cement-based material.
  • the crosslinking agent C is divinylbenzene and any one of the structures represented by the following formula (4).
  • R 7 represents H or CH 3
  • X represents a saturated alkyl group of 2 to 12 carbon atoms or a structure of (CH 2 CH 2 O) c CH 2 CH 2 wherein c is an ethylene oxide structure (-CH 2 CH 2 O-)
  • c is an ethylene oxide structure (-CH 2 CH 2 O-)
  • the average molar addition number, c ranges from 1-44. If the value of c is too large, the polymerization activity is low, which is disadvantageous for the full performance of the crosslinking property.
  • the cross-linking agent C assists in forming an organic polymer network, improves the mechanical strength of the organic polymer network, and reduces the solubility of the organic polymer component in water, thereby promoting nucleation.
  • the siloxane D is a silane substituted with three or more alkoxy groups, which may form a network of siloxane bonds, and may be one or more of a radically polymerizable siloxane and/or a non-radical polymerizable siloxane. In any combination of one.
  • the radically polymerizable siloxane may be vinyltrimethoxysilane, vinyltriethoxysilane (VTES), methacryloxypropyltrimethoxysilane (MAPTMS), methacryloxypropane Triethoxysilane (MAPTES), methacryloxymethyltriethoxysilane (AAPTES), acryloxymethyltrimethoxysilane (AAMTMS), acryloxypropyltrimethoxy Any of silane (AAPTMS).
  • the non-radically polymerizable siloxane is any one of the structures represented by the following formula (5).
  • R 8 , R 9 and R 10 each independently represent a saturated alkyl group of 1 to 4 carbon atoms, and R 11 represents a phenyl group (-C 6 H 5 ) or a saturated alkyl group of 1 to 12 carbon atoms or 1 A saturated alkoxy group of 4 carbon atoms.
  • Siloxane D is the main source of the inorganic component of the organic-inorganic hybrid particles, and the silicon-oxygen bonds generated by the hydrolysis reaction are connected to each other to react with Ca(OH) 2 in the alkaline environment of the cement-based material.
  • the hydrolysis process produces volatile organic small molecule alcohols which are extracted by depressurization after the reaction is completed.
  • the siloxane D may be added at a time before or after the addition of the initiator during the reaction, or may be added in two portions at any ratio.
  • the polymerizable monomer E is composed of a functional group type monomer and a non-functional group type monomer.
  • the functional group monomer in the monomer E accounts for 1-10% of the total mass of the monomer E, and the rest is a non-functional monomer.
  • the functional group monomer in the polymerizable monomer E is one or more than any one of all the functional group monomers described in the foregoing polymerizable monomer B; the non-functional monomer is styrene and One or more than any one of the monomers represented by the formula (4); the composition of the polymerizable monomer E may be the same as or different from the polymerizable monomer B.
  • the ratio of the amount of the polymerizable monomer A, the polymerizable monomer B, the crosslinking agent C, the siloxane D, and the polymerizable monomer E is required to satisfy the following conditions:
  • the alkoxy group of siloxane D is hydrolyzed to produce a volatile small molecule organic alcohol.
  • the effective mass of siloxane D (referred to as D 0 ) is deducted from these small amounts. Calculation of the remaining silica or organofunctional substituted silica of the molecular organic alcohol. Taking a tetraalkoxy-substituted silane and a trialkoxy-substituted silane as an example, the description is as follows:
  • the left reactant is tetraethoxysilane (TEOS), which is completely hydrolyzed to produce ethanol.
  • TEOS tetraethoxysilane
  • the ethanol can be extracted during decompression, and the remaining effective mass is SiO 2 .
  • the calculation method is TEOS and water.
  • the total mass is deducted from the quality of the ethanol.
  • the left reactant is methyltrimethoxysilane (MTMOS), which is completely hydrolyzed to produce methanol.
  • MTMOS methyltrimethoxysilane
  • the methanol can be extracted during the decompression process, and the remaining effective mass is a methyl-substituted siloxane network. Calculated by subtracting the mass of methanol from the total mass of MTMOS and water.
  • the amount of polymerizable monomers A, B, E, crosslinker C and siloxane D should be such that the non-volatile components of the aqueous dispersion are based on the mass of the aqueous dispersion minus all volatile small organic alcohols. That is, the effective component, the hybrid particle) accounts for 5-40% (mass fraction) of the total mass of the aqueous dispersion. Specifically, the total mass of the effective reactant (A+B+C+E+D 0 ) accounts for 5-40% of the final mass of the aqueous dispersion.
  • the final mass of the aqueous dispersion herein means the total mass of the aqueous dispersion obtained after the end of the reaction, that is, the total mass of all species in the reaction minus the mass of all volatile small molecule organic alcohols.
  • monomer A accounts for 1-10% of the total mass of the effective reactant (A+B+C+E+D 0 )
  • crosslinker C accounts for the total mass of the effective reactant (A+B+C+E+D 0 0-5%
  • monomers B and E (B+E) account for 20-70% of the total mass of the active reactant (A+B+C+E+D 0 )
  • the polymerizable monomer B accounts for B and
  • the total mass ratio of E(B+E) is not less than 10%.
  • Monomer A is equivalent to a dispersant of self-polymerizing emulsifier and hybrid particles. When the amount is too low, dispersed hybrid particles cannot be formed. The hybrid particles will agglomerate and precipitate during nucleation, and hybridized during application. The particles may be unstable and coagulate in the environment where the cement-based material is strong in alkali and high in salt. Similarly, monomer A contributes a limited amount to the tensile properties of the hybrid particles themselves because of their low double bond content and less contribution to the organic polymer backbone (polymer backbone) after polymerization. At 5%.
  • Limiting the amount of monomer A directly added to the reactor at the beginning of the reaction is to: (a) maintain the minimum amount of self-polymerizing emulsifier that initially promotes nucleation and swelling; (b) continuously graft by the addition reaction during the maintenance of the reaction. The minimum amount of long side chains to the surface of the particle, thereby stabilizing the particles.
  • the reason for limiting the amount of cross-linking agent C to not more than 5% is that the hybridized particles with too high degree of cross-linking have less deformability during preparation, and the degree of swelling of the monomers is low, so that the hydrolysis reaction and the polymerization reaction may be Occurrence occurs outside the particle, producing homogeneous organic polymer particles or inorganic polymer particles.
  • the sum of the amounts of the monomers B and E is limited to a range of 20-80% in order to ensure the minimum content of the organic component and the inorganic component in the hybrid particles, otherwise it is difficult to fully exert the mechanical properties of the hybrid particles.
  • Limiting the amount of the polymerizable monomer B to not less than 10% of the total mass of B and E is to form a water-insoluble polymer at the initial stage of the reaction, thereby promoting particle nucleation.
  • the initial stage of the reaction there are many water-soluble monomers A. If the initial monomer A is self-polymerized to form a water-soluble polymer, nucleation cannot be precipitated, and A as an emulsifier in the reaction process is consumed; in the presence of B B and A may form an amphoteric polymer to form micelles or an increase in the degree of polymerization of B in the polymer to cause the polymer to precipitate to form particles.
  • the upper limit of the amount of the functional group monomer in the monomers B and E is limited because the functional group monomer is generally water-soluble, and the large amount of use may cause the hybrid particles to partially dissolve in water, which is disadvantageous for the nucleation growth of the hybrid particles, and these
  • the dissolved polymer on the one hand increases the viscosity of the system, reduces the content of hybrid particles, and on the other hand may entangle each other to cause coagulation.
  • the upper limit of the functional group monomer ratio is lower than that of the monomer E.
  • the lower limit of the amount is limited to ensure an effective covalent bond between the organic component and the inorganic component.
  • the effective mass of the polymerizable monomers A, B, E, crosslinker C and siloxane D is not less than 5% of the total effective mass of the aqueous dispersion because the admixture is used for the modification of cement-based materials.
  • the amount of solid active ingredient incorporated into the system should be no less than 0.5% of the total gum, otherwise its contribution to mechanical properties is not significant.
  • the total solid content of the admixture is too low, the use requirements may not be met. In fact, even below 5%, the reaction can be successfully carried out.
  • the initiator is a thermal decomposition initiation system or a redox initiation system as follows:
  • Thermal decomposition initiation system azo (VA044 or V50), persulfate (ammonium persulfate, potassium persulfate and Sodium sulfate);
  • Or redox initiation system one of H 2 O 2 and a reducing agent (such as vitamin C, sodium formaldehyde sulfoxylate), persulfate (ammonium persulfate, sodium persulfate and potassium persulfate) and low-priced sulfate
  • a reducing agent such as vitamin C, sodium formaldehyde sulfoxylate
  • persulfate ammonium persulfate, sodium persulfate and potassium persulfate
  • low-priced sulfate One of the classes (sodium sulfite, sodium hydrogen sulfite, sodium metabisulfite, sodium formaldehyde sulfoxylate).
  • the amount of oxidizing agent and reducing agent is such that the oxidizing agent/reducing agent is between 0.5 and 2.0 (molar ratio).
  • the amount of initiator (the redox system is calculated as the lower molar amount of the oxidizing agent and the reducing agent); it is 0.05-3% of the total mass of the monomer.
  • the mass of the oxidizing agent is calculated as the mass of the oxidizing agent, and the mass of the oxidizing agent is 0.05-3% of the total mass of the monomer, and vice versa.
  • the amount of the initiator is less than 0.05%, the monomer mass may cause insufficient conversion of the organic monomer. If the amount of the initiator is more than 3%, the reaction may fail due to excessive initial polymerization rate (a large amount of precipitation or condensation will occur). gum).
  • the thermal decomposition initiator may be added directly or in a slow and uniform manner; for the redox initiator, the desired mass of the oxidant is first added to the polymerization system, and then the reducing agent solution is slowly and uniformly added to the polymerization system, and should not be in the monomer. Add all before adding to the reaction system. Because of the half-life, the thermal decomposition initiator is relatively gentle, so it can be added at one time or slowly and evenly. However, for the redox initiation system, the activation energy is generally low. If the addition is initiated, the conversion rate will be low because the late radical concentration is too low. The early radical concentration is too high, which may cause the reaction rate to be too fast. Redispersed precipitate.
  • Applicable reaction temperature is 20-90 ° C
  • the redox initiation system initiated temperature is lower, even close to normal temperature
  • the thermal decomposition initiation system initiation temperature can be determined based on its half-life. The longer the polymerization time, the higher the conversion rate.
  • the reaction time of the system can be generally controlled at 4-24h. Generally, it is necessary to ensure that the initiator is substantially completely decomposed when the polymerization is completed.
  • the hybrid particle preparation process includes two synchronizations of polymerization and hydrolysis. The reaction is carried out in which the hydrolysis reaction usually takes a long time, and all the reactions are as complete as possible so as not to affect the storage use of the resulting hybrid particle dispersion.
  • the initial pH of the reaction system in the reaction step is in the range of 2-12. Beyond this range, a large amount of homogeneous silica will be formed under acidic conditions, and the polymerizable monomer A cannot sufficiently cover all the hybrid particles due to insufficient reaction rate to cause the hybrid particles to coagulate; the same or hydrolysis reaction under alkaline conditions The coagulation is too fast, or the particles themselves lose stability due to reaction with a high concentration of OH - in the reaction environment.
  • the method for applying the dispersion of the organic-inorganic hybrid particles of the present invention as a reinforcing agent for a cement-based material when preparing the cement-based material, directly adding the organic-inorganic hybrid particles to the stirring process in the mixing process;
  • the amount of the particles used is 0.5 to 5.0% of the total mass of the rubber.
  • the organic-inorganic hybrid particle according to the invention is used for improving the mechanical properties of the cement-based material, and the organic component is fully connected with the CSH particle through the covalent bond through the inorganic component, thereby improving the toughness of the organic component. Performance efficiency.
  • the introduced inorganic component can generate more CSH gelling components, and the nanoparticle itself is connected by chemical bonding to a high degree, the mechanical strength (compressive strength) of the nanoparticle itself is improved, so that the cement base can be significantly improved.
  • the compressive strength of the material since the introduced inorganic component can generate more CSH gelling components, and the nanoparticle itself is connected by chemical bonding to a high degree, the mechanical strength (compressive strength) of the nanoparticle itself is improved, so that the cement base can be significantly improved.
  • the compressive strength of the material since the introduced inorganic component can generate more CSH gelling components, and the nanoparticle itself is connected by chemical bonding to a high degree, the mechanical strength (compressive strength) of the nanoparticle itself is improved, so that the cement base can be significantly improved.
  • the compressive strength of the material since the introduced inorganic component can generate more CSH gelling components, and the nanoparticle itself is connected by chemical bonding to a high degree, the mechanical strength (compressive strength) of the nano
  • the admixture dosage of the invention can be greatly reduced (the amount of hybrid particles is 0.5-5.0% of the total rubber material quality), Compared with organic polymer-inorganic hybrid particles of traditional polymer emulsion or core-shell structure, organic polymers and inorganic polymers can fully utilize organic polymers and inorganic polymers because they are interconnected by covalent bonds at a finer scale.
  • the advantages of mechanical properties, the flexural and tensile (or tensile) performance of cement-based materials are more obvious under the same dosage conditions, and the compressive strength can be effectively improved, and the traditional polymer modified cement-based materials are overcome. Because of the high amount of polymer, it affects the defects of the compressive strength of cement-based materials.
  • the amount of the present invention refers to the ratio of the mass of the active ingredient (organic-inorganic hybrid particles) in the finally synthesized aqueous dispersion of the present invention to the mass of the rubber in the cement-based material.
  • the hybrid particles are used for the modification of cement-based materials, and the higher the blending amount, the more obvious the mechanical properties (compression, flexural strength and tensile strength) are improved.
  • Figure 1 is a transmission electron micrograph of the hybrid particles obtained in Example 2.
  • the attached structure 1 corresponds to the structural formula corresponding to each abbreviation in the embodiment.
  • polymerizable monomers used below are either commercially available or synthesized according to literature (source of polymerizable monomer A: (1) commercially available; (2) Polymer Bulletin, 2008, 16; Polymer Bulletin 1999, 42, 287; Journal Of Applied Polymer Science 2000, 77, 2768).
  • 4-Aminostyrene hydrochloride (4-VBAH) is a synthetic product obtained by reference to literature synthesis (Analytical Chemistry 2012, 84, 3500).
  • a part of the polymerizable monomer A was added to the reactor (No. A1, polyethylene glycol methacrylate, -CH 2 CH 2 O in the polyethylene glycol chain - the average repeating unit number was 6, and the terminal group was a hydroxyl group.
  • TMOS tetramethoxysilane
  • TEOS tetraethoxysilane
  • polymerizable monomer E 4-VBAH 0.36 parts and St.35.64 parts
  • a part of the polymerizable monomer A was added to the reactor (No. A2, polyethylene glycol monomethyl ether acrylate, -CH 2 CH 2 O in the polyethylene glycol chain - the average repeating unit number was 22, and the terminal group was A Base, dosage: 1.8 parts), polymerizable monomer B (4-VBAH 1.8 parts, methacrylic acid (MAA) 58.2 parts), part of crosslinker C (No.
  • ethylene glycol diacrylate, -CH 2 CH 2 O-average repeat unit number is 45,2 parts
  • part of siloxane D (1.25 parts of methacryloxypropyltrimethoxysilane (MAPTMS) and 20.53 parts of TMOS), 6 parts of APS and 270 parts of water, thoroughly stirred and mixed; with 1mol / LNaOH the mixture was adjusted to pH 10, drops of N 2 through the mixture evenly into the reactor in addition to O 2, the reactor temperature was raised to 70 °C, under stirring to An aqueous solution of the remainder of the polymerizable monomer A (4.2 parts of A2 dissolved in 3 parts of water), the remainder of the crosslinking agent C (C2, 2 parts), and the remainder of the siloxane D (MAPTMS 11.22 parts and TMOS 184) .76 parts), polymerizable monomer E (2 parts of aminoethyl methacrylate hydrochloride (AEMH) and 38 parts of methyl methacrylate) and initiator solution (3.28 parts of
  • the TEM image of the obtained hybrid particles is shown in Fig. 1.
  • the obtained particles have a diameter of about 50-400 nm, and the contrast of the particles shown in the figure changes uniformly and continuously without any phase separation such as the core-shell interface, indicating the miscibility of the organic phase and the inorganic phase.
  • the level of hierarchy is at least observable with ordinary TEM.
  • a part of the polymerizable monomer A was added to the reactor (No. A3, polyethylene glycol monomethyl ether methacrylate, and -CH 2 CH 2 O in the polyethylene glycol chain - the average repeating unit number was 45, and the amount was 1 part), polymerizable monomer B (1.4 parts of 2-hydroxyethyl acrylate (HEA) and 26.6 parts of dodecyl acrylate (LA)), crosslinker C (divinylbenzene (DVB) 10 parts, Commercial DVB contains meta and para isomers), part of siloxane D (methacryloxypropyltriethoxysilane (MAPTES) 16.21 parts, methyltrimethoxysilane (MTMOS) 4.06 parts and TEOS27.75 parts) and 270 parts of water, mixing thoroughly stirred; the pH was adjusted to 3 with 1mol / LH 2 SO 4 the mixture to N 2 through the mixture in addition to O 2, the reactor temperature was raised to 60 °C, The initiator was added to the reactor
  • Aqueous solution (9 parts of A3 dissolved in 5 parts of water), the remainder of siloxane D (MAPTES 16.21 parts, MTMOS 4.06 parts and TEOS 27.75 parts) and polymerizable monomer E (HEA 11.2 parts and LA 100.8) Part), starting from the initiator
  • the aqueous solution of the remaining part of the polymerizable monomer A, the remainder of the siloxane D, and the polymerizable monomer E are added dropwise for 8 hours, and the reaction is continued for 4 hours after the dropwise addition, and the inert atmosphere protection is removed, and the pressure is extracted under reduced pressure.
  • the organic small molecule can be volatilized to obtain an aqueous dispersion of hybrid particles AE03.
  • a part of the polymerizable monomer A was added to the reactor (No. A4, N-polyethylene glycol monomethyl ether-acrylamide, and -CH 2 CH 2 O in the polyethylene glycol chain - the average repeating unit number was 45, the amount 0.6 parts), polymerizable monomer B (4 parts of 4-VBAH and 57 parts of n-butyl acrylate (BA)), a part of siloxane D (36.72 parts of vinyltrimethoxysilane (VTMS)) and 270 parts of water, sufficiently stirred and mixed; with 1mol / LH 2 SO 4 the mixture was adjusted to pH 3.5, passed through a mixture of N 2 addition to O 2, the reactor temperature was raised to 50 °C, even to the reactor dropwise with stirring to the initiator
  • the agent (4 parts of azobisisobutyrazoline hydrochloride VA044 dissolved in 22 parts of water) initiates polymerization, and at the same time, the remaining aqueous solution of the polymerizable monomer A
  • polymerizable monomer E (4-hydroxypropyl acrylate (HPA) 4 parts and St36 parts) and the remainder of siloxane D (VTES 146.9 parts), timed from the start of the initiator to the reactor, dripping After adding 6h, the initiator, the remaining part of the polymerizable monomer A, the remaining part of the siloxane D and the polymerizable monomer E were added dropwise for 6 hours, and the addition was continued for 6 hours, and then withdrawn. Protective inert atmosphere, under reduced pressure and extracted volatile small organic molecules, to obtain an aqueous dispersion of hybrid particles AE04.
  • HPA 4-hydroxypropyl acrylate
  • VTES 146.9 parts siloxane D
  • polymerizable monomer A to the reactor (No. A1, polyethylene glycol methacrylate, -CH 2 CH 2 O in the polyethylene glycol chain - the average repeating unit number is 6, the terminal group is hydroxyl group, the amount is 0.6 parts), polymerizable monomer B (1.4 parts of AEMH and 138.6 parts of n-octyl acrylate), crosslinker C (No.
  • polymerizable monomer A to the reactor (No. A6, n-dodecyl-polyethylene glycol monomethyl ether-maleic acid diester, -CH 2 CH 2 O - average repeating unit number 45, in an amount of 5 Part), polymerizable monomer B (HPA 0.12 part and methyl acrylate 3.88 parts), part of crosslinker C (No.
  • polymerizable monomer A No. A2, polyethylene glycol monomethyl ether acrylate, -CH 2 CH 2 O in the polyethylene glycol chain - the average repeating unit number was 22, and the terminal group was methyl group.
  • Amount of 1 part polymerizable monomer B (N-hydroxymethyl acrylamide (N-HMAAm) 1.2 parts and lauryl methacrylate (LMA) 38.8 parts), part of siloxane D (acryloyloxy group) 21.84 parts of propyltrimethoxysilane (AAPTMS) and 82.19 parts of tetra-n-butylsilane (TBOS), 4.04 parts by weight of 30% aqueous solution of H 2 O 2 and 265.96 parts of water, mixed well; 1 mol/L H 2 SO 4 the mixture was adjusted to pH 3.5, to the mixture through the other N 2 O 2, the reaction temperature was maintained at 30 °C, uniformly added dropwise with stirring to the reactor an initiator (5 parts of sodium s
  • polymerizable monomer A No. A8, polyethylene glycol monomethyl ether methacrylate, -CH 2 CH 2 O in the polyethylene glycol chain - the average repeating unit number was 22, and the terminal group was A Base, the amount is 3 parts
  • polymerizable monomer B (2-(tert-butylamino)ethyl methacrylate (t-BAEMA) 0.5 parts and MMA 9.5 parts)
  • crosslinking agent C No.
  • a part of the polymerizable monomer A was added to the reactor (No. A3, polyethylene glycol monomethyl ether methacrylate, and -CH 2 CH 2 O in the polyethylene glycol chain - the average repeating unit number was 45, and the amount was 3 parts), polymerizable monomer B (N-HMAAm 0.84 parts and MMA 83.16 parts), a part of siloxane D (phenyl triethoxysilane PhTEOS 88.4 parts) and 270 parts of water, thoroughly stirred and mixed ; the pH was adjusted to 11 with 1mol / LNaOH the mixture to N 2 through the mixture in addition to O 2, the reaction temperature was maintained at 85 °C, uniformly added dropwise with stirring to the reactor initiator (persulfate 0.2 parts Potassium KPS was dissolved in 16.8 parts of water to initiate polymerization, and an aqueous solution of the remainder of the polymerizable monomer A was dropwise added to the reactor (7 parts of A3 dissolved in 3 parts of water), and
  • polymerizable monomer A No. A6, n-dodecyl-polyethylene glycol monomethyl ether-maleic acid diester, -CH 2 -CH 2 O - average repeating unit number 45, the amount is 0.4 parts
  • polymerizable monomer B (2.52 parts of 4-VBAH and 81.48 parts of BA)
  • part of crosslinker C C1, ethylene glycol dimethacrylate, 9 parts
  • siloxane D TMOS30.41 parts methyltrimethoxysilane and MTMOS31.89 parts
  • a part of the polymerizable monomer A was added to the reactor (No. A10, n-dodecyl-polyethylene glycol monomethyl ether-maleic acid diester, -CH 2 -CH 2 O - average repeating unit number 6, Amount of 0.6 parts), a polymerizable monomer B (3-aminostyrene (3-VBA) and 38 parts of St) and a part of siloxane D (TBOS82.19 parts) and 250 parts of water, mixed well; 1mol / LH 2 SO 4 the mixture was adjusted to pH 3 to N 2 through the mixture in addition to O 2, the reaction temperature was maintained at 70 °C, uniformly added dropwise with stirring to the reactor initiator (APS 1 part Dissolved in 14 parts of water; 1.1 parts of sodium sulfite SS dissolved in 13.9 parts of water, respectively, were added dropwise) to initiate polymerization, and at the same time, the aqueous solution of the remainder of the polymerizable monomer A was added dropwise to
  • a part of the polymerizable monomer A was added to the reactor (No. A7, n-dodecyl-hydroxypolyethylene glycol-maleic acid diester, -CH 2 -CH 2 O - average repeating unit number 32, amount 5 parts), polymerizable monomer B (0.1 parts HEMA and 9.9 parts LMA), cross-linking agent C (C2, 0.8 parts) and 270 parts water, mixed well; adjust the pH of the mixture to 11 with 1 mol/L NaOH , N 2 through the mixture in addition to O 2, the reaction temperature was maintained at 60 °C, stirring uniformly added dropwise into the reactor initiator (V50 were dissolved in 2 parts of water 28 parts of) the polymerization initiator, while the reaction began to An aqueous solution of the remainder of the polymerizable monomer A was dropwise added (5 parts of A10 dissolved in 25 parts of water), the remainder of the crosslinking agent C (C2, 3.2 parts), siloxane D (TEOS 298.36 parts) and Polymerization
  • Mortar is prepared by Onodada P ⁇ II ⁇ 52.5 cement (Jiangnan Xiaoyetian Cement Co., Ltd.) and ISO standard sand.
  • the sand-ash ratio is 3:1
  • the water-cement ratio is 0.36
  • the dosage of W05 and PE01-02 is calculated based on the amount of solidification based on the cementitious material (unit: mass percentage, %bwoc).
  • the defoaming agent used is commercially available from Jiangsu Subote New Material Co., Ltd.
  • PXP-I concrete defoamer the gas content of each group of mortar is basically controlled by the amount of defoaming agent.
  • the water reducing agent used is a conventional polycarboxylate water reducing agent commercially available from Subote.
  • the fluidity of each group of mortar was basically the same through the amount of water reducing agent. After the test piece is formed, it is cured at 25 ° C and 95% humidity. Test Methods Reference (Construction and Building Materials, 2013, 49, 121).
  • PE01 carboxylated butylbenzene (SD622S) emulsion of Shanghai Gaoqiao BASF Dispersion Co., Ltd.;
  • PE02 BASF styrene-acrylic emulsion (Acronal S 400).
  • W01 refer to the patent CN104446102A embodiment W01 synthesis
  • the AE01-AE12 dosage refers to the ratio of the mass of the pure active ingredient (organic-inorganic hybrid particles) in the finally synthesized aqueous dispersion of the examples of the present invention to the quality of the rubber material in the cement-based material.
  • the hybrid particles synthesized in this patent can improve the compressive strength, flexural strength and tensile strength of the mortar, and the 28-day compressive strength is improved by 10 -18% (52.5MPa up to 61.8MPa), flexural strength increased by 10-24% (9.98MPa up to 12.41MPa), tensile strength increased by 11-23% (4.77MPa up to 5.87MPa).
  • the use of ordinary polymer emulsions commercial or synthetic, PE01, PE02
  • the core-shell structure particles reported by the patent CN104446102A have improved the flexural strength and tensile strength, but the improvement is small (5-14%), and the compressive strength of the mortar is not significantly improved.
  • AE01, AE05, AE10 and AE12 can also significantly improve the compressive and flexural strength and tensile strength of the mortar (28-day strength increased by 13-25%, 16-30% and 18-35%).
  • ordinary polymer emulsions commercially available or synthetic, PE01, PE02
  • PE01, PE02 have a weaker effect on the folding and tensile strength (2-5%).
  • the core-shell structure particles reported by the patent CN104446102A although their flexural strength and tensile strength are improved (6-23%), their compressive strength is still not significantly improved.
  • the hybrid particles synthesized in this patent have obvious improvement effects on the compressive strength, flexural strength and tensile strength of the mortar, and the compressive strength of the 28-day specimen is improved by 17-49%.
  • the folding strength is increased by 22-52%, and the tensile strength is increased by 29-59%.
  • the admixtures (W01 and W05) of the core-shell structure reported by the patent CN104446102A have improved the flexural strength (11-25% increase) and tensile strength (23-31% increase) of the mortar specimen, but compared with this
  • the hybrid particles reported by the patent have no advantage and, more importantly, their degree of improvement in compressive strength is small (generally ⁇ 10%).
  • the AE01, AE05, AE10 and AE12 dosages can increase the flexural strength and tensile strength of the mortar when the amount of cement is 1-2.5%, and the performance of adding polymer emulsions such as PE01-PE02 can reach 5%, and compared with W01. And W05, hybrid particles can comprehensively improve the compressive and flexural strength and tensile strength of mortar, showing obvious advantages.
  • the dosage of admixtures AH01-AH12, W01, W05 and PE01-02 is calculated based on the amount of solidification of the cementitious material (unit: mass percentage, %bwoc).
  • the defoaming agent used is Jiangsu Subote New Material Co., Ltd. Co., Ltd. commercially available ordinary PXP-I concrete defoamer, the gas content of each group of mortar is basically controlled by defoaming agent.
  • the water reducing agent used is a conventional polycarboxylate water reducing agent commercially available from Subote.
  • the concrete slump of each group was controlled by the amount of water reducing agent (20 ⁇ 1cm). After the test piece is formed, it is cured at 25 ° C and 95% humidity.
  • the AE01-AE12 dosage refers to the ratio of the mass of the pure active ingredient (organic-inorganic hybrid particles) in the finally synthesized aqueous dispersion of the examples of the present invention to the quality of the rubber material in the cement-based material.
  • the hybrid particles synthesized in this patent have obvious improvement effects on concrete compressive strength, flexural strength and tensile strength, and the compressive strength of 28-day specimens is improved by 14-41%.
  • the folding strength is increased by 20-44%, and the tensile strength is increased by 25-53%.
  • the admixtures (W01 and W05) of the core-shell structure reported by the patent CN104446102A have improved the flexural strength (15-22%) and tensile strength (19-24%) of the concrete specimens, but compared with this patent report.
  • the hybrid particles have no advantage and, more importantly, have no significant improvement in their compressive strength (1-7%).
  • the AE01, AE05, AE10 and AE12 dosages increase the flexural strength and tensile strength of the concrete at 1-2.5% of the cement content, which is obviously better than or even better than the performance of adding 5% of the polymer emulsion such as PE01-PE02.
  • hybrid particles can comprehensively improve the compressive and flexural strength and tensile strength of concrete, showing obvious advantages.
  • the tensile strength can be measured in general experiments; for concrete specimens, the split tensile strength is usually determined, which is positively correlated with the tensile strength, but not equal to the tensile strength (generally slightly Above tensile strength), the higher the split tensile strength, the higher the tensile strength.

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Abstract

La présente invention concerne des particules hybrides organiques-inorganiques, et leur procédé de préparation et leurs applications dans la modification de matériaux à base de ciment. Les particules hybrides organiques-inorganiques de la présente invention sont constituées de composants organiques et de composants inorganiques, et les composants inorganiques et les composants organiques sont mutuellement connectés d'une manière croisée grâce à des liaisons covalentes au lieu de structures de logement par cœur. Les composants inorganiques et les composants organiques sont connectés à l'aide de liaisons covalentes. Dans les particules hybrides organiques-inorganiques de la présente invention, les composants organiques sont utilisés pour l'amélioration des propriétés mécaniques des matériaux à base de ciment; par connexion complète des composants organiques avec des particules CSH à l'aide de composants inorganiques et de liaisons covalentes, l'efficacité de la rigidité des composants organiques est améliorée; de plus, dans la mesure où plus de particules hybrides organiques-inorganiques sont dopées dans les matériaux à base de ciment, les propriétés mécaniques des matériaux à base de ciment sont bien nettement améliorées.
PCT/CN2016/112249 2015-12-31 2016-12-27 Agent de renfort de matériau à base de ciment, et son procédé de préparation et ses applications WO2017114375A1 (fr)

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US20220047518A1 (en) * 2018-09-19 2022-02-17 Moderna TX, Inc. Peg lipids and uses thereof
CN111392721A (zh) * 2020-03-26 2020-07-10 重庆永固新型建材有限公司 一种氧化石墨烯分散液及其制备方法和应用
CN112574365A (zh) * 2020-12-10 2021-03-30 桂林理工大学 一种常温合成混凝土聚羧酸系减水剂及其制备方法
WO2023164987A1 (fr) * 2022-03-02 2023-09-07 青岛理工大学 Matériau composite à base de ciment renforcé à double échelle et son utilisation
CN115490805A (zh) * 2022-09-30 2022-12-20 郑州轻工业大学 一种基于氧化还原反应引发的水凝胶
CN115490805B (zh) * 2022-09-30 2023-08-18 郑州轻工业大学 一种基于氧化还原反应引发的水凝胶
CN115651571A (zh) * 2022-10-19 2023-01-31 广州双虹建材有限公司 一种环保型有机复合注浆料及其制备方法
CN115651571B (zh) * 2022-10-19 2024-05-07 广州双虹建材有限公司 一种环保型有机复合注浆料及其制备方法
CN116477903A (zh) * 2023-04-25 2023-07-25 河北工业大学 衬砌支护结构的3d打印强韧混凝土及其制备方法
CN116477903B (zh) * 2023-04-25 2024-05-31 河北工业大学 衬砌支护结构的3d打印强韧混凝土及其制备方法

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