WO2022000306A1 - 超高性能混凝土用多官能团超塑化剂及其制备方法 - Google Patents

超高性能混凝土用多官能团超塑化剂及其制备方法 Download PDF

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WO2022000306A1
WO2022000306A1 PCT/CN2020/099415 CN2020099415W WO2022000306A1 WO 2022000306 A1 WO2022000306 A1 WO 2022000306A1 CN 2020099415 W CN2020099415 W CN 2020099415W WO 2022000306 A1 WO2022000306 A1 WO 2022000306A1
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acid
superplasticizer
parts
side chains
structure shown
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PCT/CN2020/099415
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English (en)
French (fr)
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刘加平
舒鑫
冉千平
杨勇
王涛
张倩倩
刘建忠
周栋梁
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江苏苏博特新材料股份有限公司
博特建材（天津）有限公司
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Priority to US18/013,266 priority Critical patent/US20230278926A1/en
Publication of WO2022000306A1 publication Critical patent/WO2022000306A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/243—Phosphorus-containing polymers
    • C04B24/246—Phosphorus-containing polymers containing polyether side chains
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2688—Copolymers containing at least three different monomers
    • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
    • 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
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • 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
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (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
    • C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
    • 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
    • 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
    • C08F230/02—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 phosphorus
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/08—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to polyphenylene oxides
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • 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
    • C08F30/00—Homopolymers and 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
    • C08F30/02—Homopolymers and 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 phosphorus
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/32—Superplasticisers
    • 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
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/40—Chemical modification of a polymer taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains
    • 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 present application relates to the field of superplasticizers for concrete, in particular to a superplasticizer that can be used for ultra-high performance concrete and a preparation method thereof.
  • concrete as used herein generally and indiscriminately refers to concrete such as concrete, mortar, or grout, as is applicable elsewhere herein.
  • the polycarboxylate superplasticizer is a comb-shaped structure, which is generally prepared by free radical polymerization of vinyl-containing monomers, and its main chain (usually -CH 2 -CH 2 - structure or functional group-substituted -CH 1 -CH 2 - structure) is connected with charged functional groups (such as carboxyl groups, sulfonic acid groups, etc.), and the corresponding side chains are mostly water-soluble polyether side chains. Adsorbed on it, and the corresponding long side chains prevent the cement particles from approaching each other and agglomerate through steric hindrance (repulsion), release the wrapped water, improve the workability of concrete, and reduce the water-cement ratio.
  • Ultra-high performance concrete (compressive strength of 100 MPa and above) has attracted widespread attention due to its excellent service performance.
  • its water-to-binder ratio is extremely low, generally not higher than 0.2
  • its cementitious material components include silica fume, ultrafine ore
  • the content of ultrafine powder such as solid particles with hydration activity is extremely high, often reaching 30% or even more than 40% of the total mass of the cementitious material, and the size of the ultrafine powder is generally in the nanometer range (10 1 nm-10 0 ⁇ m), smaller than the cement particles ( ⁇ 10 1 ⁇ m), so that the ultra high performance concrete which compared to ordinary concrete product flowability is poor, the viscosity, one of the key challenges in the construction constraints.
  • the interface characteristics of ultrafine powder are different from those of cement particles.
  • the traditional polycarboxylate superplasticizer designed for cement has insufficient adsorption affinity for these particles. It has poor versatility and insufficient performance in the coagulation material system, and it is difficult to meet its basic requirements for fluidity and low viscosity.
  • the design scheme of the water reducing agent of EP1775271A2 is that it can reduce the viscosity of concrete and has good slump retention performance, but it is designed for ordinary concrete and is difficult to apply in high/ultra-high strength concrete.
  • CN106467604A reports a viscosity-reducing polycarboxylate water reducer prepared by copolymerizing difunctional unsaturated carboxylate monomer and unsaturated phosphate monomer with unsaturated acid anhydride and polyether monomer.
  • CN103553413A discloses a viscosity-adjusting water reducer incorporating viscosity-adjusting monomers (unsaturated alkyl esters, fluorine-containing esters, alkyl acrylamides or their concretes), which can effectively reduce the viscosity of concrete. Air function.
  • viscosity-adjusting monomers unsaturated alkyl esters, fluorine-containing esters, alkyl acrylamides or their concretes
  • CN106431060A reports that a viscosity-reducing polycarboxylate water-reducing agent for high-strength concrete adopts a compound scheme of a water-reducing agent, a viscosity-reducing agent, and a slump-retaining agent, which can reduce the viscosity of high-strength concrete to varying degrees.
  • CN10147533 discloses an early-strength polycarboxylate compound water-reducing agent, which uses a compounded viscosity-reducing component polyethylene glycol, which can significantly reduce the viscosity of concrete and meet the fluidity requirements of the concrete construction process.
  • CN103865007A discloses a method for preparing a viscosity-reducing polycarboxylic acid-based water-reducing agent. A certain amount of hydrophobic units and hydrophobic groups are introduced and controlled in the molecular structure of a carboxylic acid copolymer to reduce the effect of the water-reducing agent on cement bases. The role of material viscosity, the performance is superior.
  • CN105367721A discloses a preparation method and application of a viscosity-reducing polycarboxylic acid superplasticizer, mainly introducing a branched side chain-containing monomer b and a rigid ring group-containing monomer c into the structure for free radical Polymerization can greatly reduce the water-binder ratio of concrete and effectively reduce the viscosity of concrete.
  • CN106397683A reports a kind of polycarboxylate water reducer for reducing the viscosity of high-grade concrete and its preparation method, which consists of terminal alkenyl polyoxyethylene ether, unsaturated acid (benzenesulfonic acid, benzoic acid, acrylic acid, etc.), unsaturated ester ( Unsaturated hydroxy ester) is prepared by molecular rearrangement through viscosity reducing regulator after free radical polymerization, and has the effects of high water reduction rate and good viscosity reduction effect.
  • CN104262550A discloses a preparation method of a viscosity-reducing polycarboxylic acid-based water-reducing agent, which is prepared into unsaturated quaternary ammonium salts by using unsaturated primary amine small monomers, organic small molecules with epoxy groups and halogen-containing groups , and then copolymerized with an unsaturated acid, the prepared viscosity-reducing polycarboxylate water-reducing agent has a simple reaction and is easy to control, and can effectively reduce the viscosity of concrete.
  • CN104371081A discloses a method for preparing a rapidly dispersing viscosity-reducing polycarboxylate cement dispersant.
  • the hyperbranched polycarboxylate cement dispersant is obtained by using an unsaturated monomolecular monomer containing a tertiary amino group as a reducing agent that can participate in polymerization. Great improvement.
  • the concrete viscosity reducer reported in CN106008784A is made by polymerizing 4-hydroxybutyl vinyl polyether, unsaturated amide and unsaturated phosphate, which can reduce the viscosity of concrete without affecting its fluidity and improve the pumping construction performance.
  • the concrete viscosity modifier reported by CN105837740B is a terpolymer obtained by radical polymerization of monomers prepared from glycidyl methacrylate and iminodiacetic acid, acrylic acid/methacrylic acid and cationic monomers, which effectively reduces the C50 concrete viscosity.
  • the viscosity-reducing polycarboxylic acid reported by CN105732911B is prepared by the polymerization of unsaturated acid, unsaturated polyether macromonomer and N-(4-vinylbenzyl)-N,N-dialkylamine. The reaction is simple and easy to use. Preparation, high water-reducing rate, can be used for high-strength ( ⁇ 0.3) concrete viscosity reduction.
  • the polycarboxylic acid concrete admixture disclosed by CN100402457C is prepared by free radical polymerization of alkyl (meth)acrylate monomer, specific polyalkylene glycol unsaturated macromonomer and unsaturated acid monomer, wherein the introduced
  • the third monomer alkyl acrylate monomer with hydrophobic effect can effectively help the water reducer to reduce the yield stress and viscosity of concrete.
  • CN105367721B reports the preparation method and application of viscosity-reducing polycarboxylate superplasticizer.
  • the superplasticizer adopts branched side-chain polyether to increase the thickness of the water film layer, and at the same time introduces other monomers with rigid rings such as vinylpyrrolidone. It increases the degree of molecular conformation extension, thereby greatly reducing the viscosity of high- and ultra-high-strength concrete.
  • the concrete viscosity modifier reported by CN104973817B that is suitable for use with water reducing agent is mainly composed of clay stabilizer, air-entraining agent, foam stabilizer and thickener, which can reduce the ineffective adsorption of water reducing agent and stabilize air bubbles. It is suitable for C30 -C50 concrete, improve workability.
  • CN104031217B reported a loose and anti-sticking high-performance polycarboxylic acid admixture, which is composed of ester-type or ether-type macromonomers, unsaturated carboxyl monomers, organic phosphate compounds and acrylic acid-lignin polymer through aqueous solution polymerization. It can enhance the adsorption of water molecules and effectively reduce the viscosity of high-strength concrete.
  • CN109535341A reported a polycarboxylate superplasticizer prepared by containing terminal hydrophobically modified polyethylene glycol, which has excellent viscosity reducing performance.
  • Patent CN108623756A reports a polycarboxylic acid prepared by polymerization of N-ethyl perfluorooctyl sulfonamide acrylate, which can be used in ultra-high performance concrete.
  • the terminal hydrophobically modified functional groups greatly affect the adsorption conformation of the polymer, thereby affecting its steric hindrance, especially in cement-based materials with extremely low water-to-binder ratios, so its dispersibility is limited.
  • the fluidity of concrete depends on the fluidity of its slurry, and its viscosity is positively correlated with the viscosity of the slurry.
  • the fluidity of the slurry is in the range of 10 1 nm-10 2 ⁇ m with the scale of cement, ultrafine powder, mineral admixture, stone powder, etc. Nano-micron particles are closely related.
  • the water reducing agent is attached to the surface of the particles by adsorption, which can effectively disperse the particles and increase the fluidity.
  • the mutual friction determines that the surface coating of the particles by the polymer can effectively weaken the mutual friction between the particles, thereby reducing the viscosity.
  • the present application provides a superplasticizer with a novel structure and a preparation method thereof.
  • the superplasticizer comprehensively enhances the adhesion ability, thereby weakening the particle friction, and can significantly improve the fluidity of ultra-high performance concrete and reduce its viscosity compared with the prior art.
  • the main chain of the multifunctional superplasticizer is an alkyl chain, and in addition to several side chains whose terminals are carboxylic acid or carboxylate, several polyether side chains, there are also several terminals which are phosphoric acid or phosphorous acid.
  • Substituted polyolamine side chain the terminal is phosphoric acid or phosphorous acid substituted polyolamine side chain is connected to the main chain through phenyl or alkyl of 1-9 carbons, and the terminal is carboxylic acid or carboxyl
  • the ratio of the number of side chains of the acid salt to the total number of side chains is greater than or equal to zero, and ⁇ 0.8; the ratio of the number of side chains of the polyether to the total number of side chains is ⁇ 0.1 and ⁇ 0.9.
  • R 15 represents H or a saturated alkyl group containing 1-4 carbon atoms.
  • R 15 in the structure shown by each chain segment can be the same or different;
  • R 16 , R 20 and R 22 independently represent -PO 3 H 2 or -PO 2 H 2 ;
  • Y 0 , Y 0 ′ and Y 0 ′′ are product functional groups in which a hydroxyl-containing polyol functional group reacts with a sufficient or insufficient amount of a phosphorylating reagent, and the hydroxyl H is replaced by a phosphoric acid group, and Y 0 , Y 0 ′ and Y 0 ′′ are connected to the structural formula through carbon-carbon bonds, and the original structure of the hydroxyl-containing polyol may have a carboxyl group or a phosphoric acid group.
  • the phosphorylation reagent is a commonly used phosphorylation reagent. (referred to by J hereinafter).
  • Y 0 , Y 0 ′ and Y 0 ′′ are alkyl polyol residues with a carboxyl, carboxylate, phosphate or phosphate functional group attached to the end, and Y 0 , Y 0 ′ and Y 0 " is connected to the remaining structure shown in structural formula (2) through carbon-carbon bonds; or alkyl polyol residues partially or fully substituted by carboxyl, carboxylate, phosphate or phosphate functional groups; and carboxyl replaces carbon-hydrogen bonds
  • the H atom position of the phosphate group is substituted for the carbon-hydrogen bond or the H atom position of the hydroxyl group.
  • Y 0 , Y 0 ′ and Y 0 ′′ in the shown structure respectively independently represent any one or more of the structures shown in the following general formula (3).
  • each chain unit Y 0 , Y 0 ′ and Y 0 ′′ may be the same or different in the structures shown, respectively, where all carbon atoms have any chirality:
  • R 23 represents H or -PO 3 H 2 or any one or more of the functional groups represented by the following general formula (4)
  • R 24 represents H or -CH 2 OPO 3 H 2 or -COOH or -COONa or - Any one or more of COOK or -CH 2 OPO 3 Na 2 or -CH 2 OPO 3 K 2
  • x 4 represents a positive integer between 2-6, including 2 and 6; and each Y 0 , Y
  • Each of the 0 ' and Y 0 " functional groups can only have at most one functional group represented by the general formula (4).
  • R 25 and R 26 independently represent H or -PO 3 H 2
  • x 6 represents a positive integer between 1 and 4, including 1 and 4.
  • the side chain whose end is a carboxylic acid or a carboxylate is any one of the following structural formulas:
  • R 18 represents H or methyl
  • M 1 + , M 2 + , M 3 + , M 4 + and M 5 + independently represent H + or NH 4 + or Na + or K + , respectively .
  • the polyether segments through a carbonyl group, a phenyl group, -OCH 2 CH 2 -, - OCH 2 CH 2 CH 2 CH 2 -, - CO-NH-CH 2 CH 2 - or - (CH 2) pp - connected to The main chain, where pp is an integer between 1 and 6, including 1 and 6.
  • the multifunctional superplasticizer is a comb polymer, and its structure is shown in the following general formula (8), and the chirality of all carbon atoms in the general formula is not limited:
  • the average number of R 11 mers in the structure shown is aa
  • R 12 , R 13 , R 14 and R 19 independently represent -H or methyl
  • Z 0 represents carbonyl or phenyl or -OCH 2 CH 2 - or -OCH 2 CH 2 CH 2 CH 2 - or -CO-NH-CH 2 CH 2 - or -(CH 2 ) pp -, wherein pp is an integer between 1 and 6, inclusive.
  • mm and nn represent the number of repeating units of isopropoxy and ethoxy, respectively, which may or may not be integers.
  • the value of (mm+nn) ranges from 8 to 114, and mm/(mm+ nn) is not more than 1/2, so as to ensure the water solubility of the polyether and the extensibility of its molecular chain in the aqueous solution.
  • the structure shown in general formula (0) does not limit the connection order of ethoxy and isopropoxy repeating units, which can be block or random;
  • X 0 and X 0 ' each independently represent a saturated alkyl or phenyl group containing 1-9 carbon atoms
  • R 15 represents H or a saturated alkyl group containing 1-4 carbon atoms, in the same polymer molecule, R 15 in the structure shown by each chain segment can be the same or different;
  • R 16 , R 20 and R 22 independently represent -PO 3 H 2 or -PO 2 H 2 or the corresponding sodium and potassium salt forms;
  • aa, bb, cc, and cc' represent the average number of corresponding chain units of the polymer, respectively.
  • the ratio of cc and cc' is arbitrary.
  • the values of aa, bb, cc, and cc' need to satisfy the following conditions at the same time: ( 1) 0 ⁇ aa/(aa+bb+cc+cc') ⁇ 0.8; (2) 0.1 ⁇ bb/(aa+bb+cc+cc') ⁇ 0.9; (3) the superplasticizer polymer
  • the weight average molecular weight range is 2000-100000.
  • terminal alkenylamine B, polyhydroxy aldehyde C and phosphorus-containing composition E are firstly copolymerized to obtain an intermediate, and then an intermediate is obtained by copolymerization.
  • the multifunctional superplasticizer is prepared by radical polymerization with unsaturated carboxylic acid F and unsaturated polyether G in aqueous solution.
  • Described solvent A is any one in water, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dioxane or its Mixtures in any ratio.
  • Described terminal alkenylamine B is in conformity with the structure shown in following general formula (9) or its corresponding hydrochloride, sulfate in one or more than one arbitrary mixture:
  • R 1 represents -H or methyl
  • X represents a saturated alkyl or phenyl group containing 1-9 carbon atoms
  • R 2 represents H or a saturated alkyl group containing 1-4 carbon atoms.
  • the polyhydroxy aldehyde C is a terminal aldehyde group small molecule sugar containing 3-14 carbon atoms, or an organic molecule conforming to the structure shown in the following general formula (10), any one of the two or more than An arbitrary mix of one:
  • Y represents any one of the structures represented by the following general formula (11), wherein the configuration of any chiral carbon atom is not limited:
  • R 4 represents H or -CH 2 OPO 3 H 2 or -COOH or -COONa or -COOK or -CH 2 OPO 3 Na 2 or -CH 2 OPO 3 K 2 or in the structure represented by the following general formula (12) any kind.
  • x 1 is a positive integer between 2 and 6, including 2 and 6; x 2 is a positive integer between 1 and 4, including 1 and 4.
  • the acid catalyst D is a strong acid, including but not limited to any of p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, sodium hydrogen sulfate, potassium hydrogen sulfate, and ammonium hydrogen sulfate. A sort of.
  • Described phosphorus-containing composition E is the mixture of component I and component J, and component I is a kind of phosphorous acid, potassium dihydrogen phosphite, sodium dihydrogen phosphite, hypophosphorous acid, sodium hypophosphite and potassium hypophosphite Or any mixture of more than one, component J is a mixture of one or more than one of phosphoric acid, polyphosphoric acid, pyrophosphoric acid, phosphorus pentoxide and water.
  • Component I reacts with the aldehyde groups of B and C; J reacts with the hydroxyl groups of C, and the amount of I and J is determined by the amount of B and the content of hydroxyl groups in C.
  • Component J is a mixture prepared by reacting an anhydride of phosphoric acid with water, which cannot be purified and separated, and is reactive.
  • Described unsaturated carboxylic acid F is one or more in acrylic acid, methacrylic acid, maleic acid, fumaric acid, maleic anhydride, fumaric anhydride, itaconic acid or its corresponding sodium, potassium and ammonium salts. any combination of one.
  • the unsaturated polyether G is an arbitrary mixture of one or more than one of the structures shown in the following general formula (13):
  • R 6 and R 7 independently represent -H or methyl
  • Z represents carbonyl or phenyl or -OCH 2 CH 2 - or -OCH 2 CH 2 CH 2 CH 2 - or -CO-NH-CH 2 CH 2 - or -(CH 2 ) p -, where p is an integer in the range 1-6, inclusive.
  • n and n represent the number of repeating units of isopropoxy and ethoxy, respectively, which may or may not be integers.
  • (m+n) ranges from 8 to 114, and m/(m+n) is not greater than 1/2, so as to ensure the water solubility of polyether and the extensibility of its molecular chain in aqueous solution.
  • the structure represented by the general formula (13) does not limit the connection order of the ethoxy and isopropoxy repeating units, which may be block or random.
  • the value of (m+n) reflects the length of the side chain. If the value is too small, the side chain will be shorter. This does not mean that the dispersant of this structure cannot be prepared, but because the short side chain will lead to poor dispersion performance. If the value is too high, the preparation difficulty of the plasticizer itself will be increased, the reaction efficiency will be difficult to improve, and the conversion rate will be low. In addition, the excessively long side chain will also cause the adsorption group to be shielded by the side chain, which is not conducive to improving the surface of the solid particles to a certain extent. adhesion ability.
  • the initiator H is a conventional free radical polymerization initiating system adopted by those skilled in the art.
  • the initiator can be thermally initiated or a redox initiator.
  • the initiator can be added at one time, or it can be added continuously and uniformly within a certain period of time.
  • the agent must meet the following conditions: the initiator can be dissolved in the solvent at the corresponding temperature and successfully initiate the polymerization, and the initiator is sufficiently decomposed during the reaction to prevent changes after the reaction and affect the stability of the polymer.
  • the initiators described in this application include but are not limited to the initiator systems listed below:
  • the thermal initiators are azobisisobutyronitrile, azobisisoheptanenitrile, azobisisobutyramidine hydrochloride, azobisisobutylimidazoline hydrochloride, ammonium persulfate, potassium persulfate and persulfate. any one in sodium sulfate;
  • the redox initiator is composed of an oxidizing agent and a reducing agent, and the oxidizing agent is any one of hydrogen peroxide, ammonium persulfate, potassium persulfate and sodium persulfate;
  • the reducing agent can be any combination of one or more than one of saturated alkyl mercaptan containing 2-6 carbon atoms, mercaptoacetic acid, ascorbic acid or mercaptopropionic acid, in addition , can also include or not include one or more than one arbitrary combination in ferrous acetate, ferrous sulfate or ferrous ammonium sulfate as catalyst, the catalyst is measured with the molar amount of Fe element, and its consumption is not higher than the above-mentioned reduction 10% of the molar amount of the agent. Excessive amounts of catalyst may result in runaway polymer molecular weights.
  • the reducing agent is any one of the following compositions: (1) in thioglycolic acid, ascorbic acid, white powder or mercaptopropionic acid
  • One or more than one arbitrary combination in addition, can also comprise or not comprise one or more than one arbitrary combination in ferrous acetate, ferrous sulfate or ferrous ammonium sulfate as catalyzer, catalyzer with Fe
  • the molar amount of the element is measured, and the amount thereof is not higher than 10% of the molar amount of the above-mentioned reducing agent. Too high catalyst dosage may cause the polymer molecular weight to run out of control; (2) any combination of one or more than one of sodium bisulfite, sodium sulfite and sodium metabisulfite.
  • the amount of the initiator is calculated based on the following method. If it is a thermal initiator, the mass of the initiator is 0.2-4% of the total mass of the terminal alkenylamine B, unsaturated carboxylic acid F and unsaturated polyether G; if it is redox Initiator, calculated on the one with the larger molar amount of oxidant and reducing agent, accounts for 0.2-4% of the total molar amount of terminal alkenylamine B, unsaturated carboxylic acid F and unsaturated polyether G, the mole of oxidizing agent and reducing agent The ratio is 0.25-4.
  • the chain transfer agent K is a conventional free radical polymerization chain transfer agent used by those skilled in the art, and is only used to adjust the molecular weight of the product superplasticizer, so that the weight-average molecular weight of the product superplasticizer is between 2,000 and 100,000.
  • the chain transfer agent K used includes but is not limited to: (1) small organic molecules containing sulfhydryl groups, including but not limited to saturated alkyl mercaptans containing 2-6 carbon atoms, mercaptoethanol, mercaptoethylamine, cysteine, Thioglycolic acid or mercaptopropionic acid; (2) sodium bisulfite, sodium sulfite and sodium metabisulfite.
  • the dosage can be adjusted according to the target molecular weight of the product, and is generally between 0.1-15% of the total molar amount of polymerizable double bonds in the reaction system.
  • the total molar amount of the polymerizable double bonds is numerically equivalent to the total molar amount of the alkenyl-terminated amine B, the polyether G, and the unsaturated carboxylic acid F.
  • the preparation method of the superplasticizer described in this application specifically comprises the following steps:
  • the multifunctional superplasticizer is prepared by radically polymerizing all the intermediate mixtures prepared in step (1) with unsaturated carboxylic acid F and unsaturated polyether G in an aqueous solution at 0°C-90°C .
  • the way of adding the intermediate mixture, unsaturated carboxylic acid and unsaturated polyether to the reaction is to add it at one time before the reaction starts or during the reaction, add it in batches, or add it continuously and uniformly within a certain reaction time.
  • the way of adding the initiator to the reaction is to add it at one time before the start of the reaction or during the reaction, add it in batches, or add it continuously and uniformly within a certain reaction time.
  • the reaction is timed since the initiator is added, and the reaction is carried out for a period of time. When the reaction is stopped, the solution of the desired polymer superplasticizer is obtained.
  • step (1) the reaction temperature of the first stage is 70-120° C., and the reaction time is 1-12 h.
  • the reaction temperature of the second stage is 60-120° C., and the reaction time is 1-12 h.
  • the reaction time required for each step depends on the reaction rate and conversion rate, and the reaction time is generally longer at lower temperatures.
  • the reaction temperature is 0°C-90°C, and the time is counted from the time when the initiator starts to be added, and the cumulative reaction time is 1-12h.
  • the reaction temperature in this step depends on the initiating system used. Generally, the reaction temperature is relatively low when the redox initiating system is used. Due to the high rate of free radical generation, the reaction rate is fast and the reaction time is short; The temperature is relatively high and the reaction time is long. Those skilled in the art can adjust it according to experience.
  • step (1) the effective reactants account for 50-90% of the total mass of the system, and the effective reactants are terminal alkenylamine B, polyhydroxy aldehyde C and phosphorus-containing composition E.
  • the effective reactant concentration of the step (2) is the concentration of the conventional free radical polymerization system adopted by those skilled in the art, which can be adjusted according to economy, monomer feeding sequence, etc.
  • the typical effective reactant concentration range is 30-80wt%
  • the effective reactant is the sum of the intermediate mixture, polyether G and unsaturated carboxylic acid F.
  • the ratio n(B)/n(C) of the terminal alkenylamine B to the molar amount of the polyhydroxy aldehyde C is calculated based on the molar amount of the H atom connected to the N atom, and ranges from 0.8 to 1.2.
  • the amount of polyhydroxy aldehyde C higher than this ratio has no significant adverse effect on the reaction of step (1) and step (2), the reaction can be carried out as it is, but it remains in the final product superplasticizer, which may have Relatively obvious retardation characteristics, so it is limited here.
  • the ratio of the amount of active protons (strongly ionized hydrogen ions) in the acid catalyst D to the molar amount of the terminal alkenylamine B (calculated in terms of the molar amount of H atoms linked to N atoms) ranges from 0.5 to 2.0. Both too high and too low acid dosages are unfavorable to improve the conversion rate of the reaction in step (1).
  • step (1) the consumption of component I is calculated with the molar amount of phosphorus element, and the ratio of its total amount and the molar amount of polyhydroxy aldehyde C is 1-2, and the ratio of hypophosphorous acid and phosphorous acid in component I is arbitrary, The amount of hypophosphorous acid or phosphorous acid in component I can be zero.
  • n(JH) The molar amount of hydrogen element in component J
  • n(JP) the molar amount of phosphorus element
  • the number of effective reactive sites is calculated as [1.5 ⁇ n(JP)-0.5 ⁇ n(JH) )]
  • the dosage of component J should satisfy the following conditions at the same time: 1 ⁇ n(JH)/n(JP) ⁇ 3, and [1.5 ⁇ n(JP)-0.5 ⁇ n(JH)] and n(OH)
  • the value of the ratio ranges from 0.2 to 1.2.
  • n(OH) is the total number of moles of hydroxyl groups in the polyhydroxy aldehyde C.
  • the amount of unsaturated carboxylic acid F used in step (2) is equivalent to 0-80% of the total molar amount of alkenyl-terminated amine B, unsaturated carboxylic acid F and polyether G.
  • the amount of unsaturated carboxylic acid F should not be too high, otherwise the content of the characteristic adsorption group (connected to the superplasticizer molecule through the terminal alkenyl group B) in the product superplasticizer is too low, and its adsorption capacity on the surface of the negatively charged powder is too low. Limited, its dispersing ability and economy cannot reflect the advantages in ultra-high performance concrete.
  • the amount of polyether G used in step (2) is equivalent to 10%-90% of the total molar amount of alkenyl-terminated amine B, unsaturated carboxylic acid F and polyether G. If the value is too high, the adsorption capacity of the product superplasticizer will be weak; if the value is too low, the steric hindrance provided by the superplasticizer after adsorption will be small.
  • the superplasticizer described in this application is used in ultra-high performance concrete (the water-binder ratio is not higher than 0.2) compared with the commercially available ordinary superplasticizer, referring to the examples.
  • the dosage of the chemical agent can be reduced by 16-42%, the viscosity can be effectively reduced, and the shear viscosity can be reduced by 17-42%.
  • the maximum dispersing ability of the superplasticizer described in this application is significantly better than that of the commercially available superplasticizer. Under the condition of extremely low water-to-binder ratio (often not higher than 0.16), it can effectively improve the fluidity of concrete, while the commercially available superplasticizer can effectively improve the fluidity of concrete. No amount of plasticizers can achieve effective flow of concrete. It should be noted that the superplasticizer described in this application may be increased in the amount required to achieve the same fluidity in ordinary commercial concrete compared to the superplasticizer in the market.
  • the sources of solvent A, alkenyl amine B, polyhydroxy aldehyde C, acid catalyst D, polyether G (except G3 and G6), unsaturated carboxylic acid F, initiator H and chain transfer agent K are all commercially available ( Bailingwei reagent, TCI reagent, Sigma-Aldrich, Huntsman and Ron reagent, etc.).
  • Some polyethers are industrial products, which are prepared by anionic ring-opening polymerization of ethylene oxide catalyzed by terminal alkenyl alcohol bases, and are produced by Subote Company.
  • Polyethers G3 and G6 are prepared by dehydration condensation of corresponding polyethylene glycol or substituted polyethylene glycol ether with unsaturated carboxylic acid:
  • Acrylic acid (7.56 g, 0.105 mol) and amino poly(ethylene oxide-propylene oxide) monomethyl ether (number average molecular weight 2000, 200 g, 0.1 mol) were dissolved in 1000 mL of dichloromethane, to which was added DMAP (0.122 g , 1 mmol), DCC (22.67 g, 0.11 mol) dissolved in dichloromethane (200 mL) was added dropwise to it at room temperature, added dropwise for 4 h, continued to stir for 6 h after the dropwise addition was completed, and the white solid precipitate was removed by filtration, and the pressure was reduced.
  • G6 prepared by the reaction of methacrylic acid with amino polyethylene glycol (O-(2-aminoethyl) polyethylene glycol, number average molecular weight 5000, ethylene glycol repeating unit number about 113, derived from Sigma) .
  • amino polyethylene glycol O-(2-aminoethyl) polyethylene glycol, number average molecular weight 5000, ethylene glycol repeating unit number about 113, derived from Sigma
  • Methacrylic acid (0.0903 g, 0.00105 mol) and the above amino polyethylene glycol (5 g, 0.01 mol) were dissolved in 50 mL of dichloromethane, DMAP (0.00122 g, 0.01 mmol) was added thereto, and added dropwise to it at room temperature
  • a solution of DCC (0.2267 g, 0.001 mol) dissolved in dichloromethane (5 mL) was added dropwise for 12 h. A white precipitate appeared in the system.
  • stirring was continued for 12 h, filtered, and distilled under reduced pressure.
  • the obtained solid was diluted with dichloromethane. Dissolve, precipitate with ether, filter, repeat the precipitation of the obtained solid with dichloromethane/ether for 2 times, and vacuum dry the final product to obtain polyether G6 with a yield of 77%.
  • the molecular weight of the product was tested by Shimadzu GPC (LC-20A), the gel chromatographic column was the TSK-GELSW series of TOSOH company, the differential refraction detector was used, the mobile phase was 0.1M NaNO 3 aqueous solution, and polyethylene glycol was used as the molecular weight determination benchmark.
  • step (2) Add water (60 parts), polyether G1 (400 parts) and the intermediate mixture prepared in step (1) to the flask, adjust the temperature of the reactor to 70°C, stir and mix evenly, and add azo to it once 0.462 parts of diisobutyronitrile powder, then an aqueous solution (67.98 parts of water) of methacrylic acid (4.3 parts) and sodium acrylate (4.7 parts) was uniformly added dropwise to it, and added dropwise for 4 hours. Starting from the monomer dropwise addition, every half 0.462 parts of azobisisobutyronitrile powder was added to it at one time for 8 batches. After feeding, the reaction was continued for 4 hours, the temperature was adjusted to room temperature, and the reaction was stopped to obtain a superplasticizer sample PCE-MP01 with a weight average molecular weight. 43.2kDa.
  • N,N-dimethylformamide (84.02 parts) was added to the reactor, B3 (9.356 parts), C3 (57.05 parts) and trifluoroacetic acid (11.402 parts) were sequentially added thereto, and the reactor was adjusted to 100° C., stirring and reacting for 6 h, the reactor was adjusted to 80° C., and phosphorous acid (8.2 parts), potassium hypophosphite (10.4 parts), phosphorus pentoxide (12.62 parts) and water (1.6 parts) were added thereto. , continue to stir the reaction for 12h, stop the reaction, remove the solvent in vacuo to obtain the intermediate mixture.
  • N,N-dimethylacetamide (49.28 parts) was added to the reactor, B4 (11.32 parts), C4 (14.42 parts) and methanesulfonic acid (11.533 parts) were sequentially added thereto, and the reactor was adjusted to 70°C, stir evenly for 3 hours, adjust the reactor to 100°C, add hypophosphorous acid (6.6 parts), phosphorus pentoxide (6.6 parts) and pyrophosphoric acid (28.48 parts), continue to stir the reaction for 4h, stop The reaction was carried out and the solvent was removed in vacuo to give the intermediate mixture.
  • N-methylpyrrolidone (37.24 parts) was added to the reactor, B6 (11.916 parts), C6 (43.14 parts) and sulfuric acid (5 parts, 98%) were sequentially added thereto, and the reactor was adjusted to 100° C. , after stirring for 6 hours, the reactor was adjusted to 90°C, and potassium dihydrogen phosphite (12.0 parts), phosphorous acid (16.4 parts), phosphorus pentoxide (52.59 parts) and anhydrous phosphoric acid (36.3 parts) were added thereto. ), continue to stir the reaction for 6h, stop the reaction, and remove the solvent in vacuo to obtain the intermediate mixture.
  • step (1) (2) Add water (677.41 parts), polyether G6 (505 parts) and the intermediate mixture prepared in step (1) to the flask, adjust the temperature of the reactor to 35°C, stir and mix evenly, and add azo to it at one time 1.034 parts of diisobutylimidazoline hydrochloride was continuously reacted for 12h, the temperature was adjusted to room temperature, and the reaction was stopped to obtain a superplasticizer sample PCE-MP06 with a weight average molecular weight of 97.8kDa.
  • Conch cement (P ⁇ O ⁇ 42.5) was used for the clean slurry, Jiangnan Onotian cement (P ⁇ II ⁇ 52.5) was used for the concrete, Aiken 97 silica fume was used for the silica fume, and S95 mineral powder was used for the mineral powder. All materials were kept at a constant temperature before the experiment. temperature required.
  • the comparative sample is a common commercially available polycarboxylic acid superplasticizer (commercially available 1 is ester type, commercially available 2 is ether type, side chain length 2400). It should be noted that all the percentages expressed below are for comparison with the corresponding indicators in the commercially available samples.
  • the fluidity of cement paste was measured according to GB/T8077-2000 "Test method for homogeneity of concrete admixtures", and all dispersant dosages were percentages (wt%) of pure solids relative to cement mass.
  • the cement paste was prepared with 270 g of cement and 30 g of silica fume, and the water consumption was fixed at 51 g. The cement and silica fume are pre-mixed with a mixer to ensure uniformity.
  • the maximum dispersing ability of all the samples in the table is much larger than that of the commercially available samples, which shows the super dispersing ability of the samples prepared in the examples of the present application.
  • the required content of the samples of the present application is 0.1-0.2 wt% lower than that of the commercial samples (corresponding to a percentage reduction of 16-42%).
  • the sample PCE-MP01-12 prepared in the examples of this application can reduce the shear viscosity by 17-42%, V The funnel time can be shortened by 14-40%, which fully demonstrates the viscosity reducing properties of the samples.
  • Ultra-high performance concrete (UHPC) test concrete, fiber-containing
  • Onoda cement P II 52.5
  • the sand is ordinary river sand
  • the fiber is steel fiber with an aspect ratio of 30 and a length of 50 mm
  • the dosage of superplasticizer PCE-MP01-12, commercially available 1 and commercially available 2 is to gel Material-based calculation of solids (unit: mass percentage, wt%), during the test, the slump ((20 ⁇ 1)cm) and expansion ((45 ⁇ 2) of UHPC were controlled by adjusting the amount of superplasticizer. cm)
  • the defoamer used is the common and conventional PXP-I concrete defoamer sold by Jiangsu Subote New Materials Co., Ltd., and the gas content of UHPC in each group is basically the same as controlled by the defoamer.
  • the fluidity of the concrete is difficult to reach the above indexes, the fluidity when the superplasticizer dosage is 1.0 wt% is uniformly investigated, and the fluidity of the concrete is examined. At this output, the sample dispersing ability has reached its limit, and the concrete fluidity is difficult to enhance by adding superplasticizer.
  • the commercially available superplasticizers can no longer meet the fluidity requirements of concrete with such a low water-to-binder ratio, while the superplasticizer samples prepared in the examples can endow the concrete with a water-to-binder ratio of 0.148 with good fluidity.
  • the dispersion performance of the commercially available superplasticizer is not good, and the strength is slightly lower than that of the sample prepared in the example, which may be caused by the slightly poor uniformity of the slurry and aggregate.

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Abstract

一种超高性能混凝土用多官能团超塑化剂及其制备方法。所述超高性能混凝土用多官能团超塑化剂的主链为烷基链，侧链除了数个末端为羧酸或羧酸盐的侧链，数个聚醚侧链，还具有数个末端为磷酸或亚磷酸取代的多元醇胺基侧链，所述末端为磷酸或亚磷酸取代的多元醇胺基侧链通过苯基或1-9个碳的烷基连接到主链上，且末端为羧酸或羧酸盐的侧链个数相比侧链总个数的比例为大于等于零，≤0.8；所述聚醚侧链的个数相比侧链总个数的比例为≥0.1，且≤0.9。所述超高性能混凝土用超塑化剂全面增强了对所有胶凝材料的附着能力，从而削弱颗粒摩擦，相比现有技术，能够显著提高超高性能混凝土流动性，降低其粘度。

Description

[根据细则37.2由ISA制定的发明名称]　超高性能混凝土用多官能团超塑化剂及其制备方法
本申请要求于2020年6月29日提交中国专利局，发明名称为“一种超高性能混凝土用多官能团超塑化剂及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本申请涉及用于混凝土超塑化剂领域，具体涉及一种可用于超高性能混凝土的超塑化剂及其制备方法。
背景技术
用在此处的术语“混凝土”通常不加选择地表示混凝土、砂浆或注浆等混凝土，这在本文的其他地方也适用。
高性能减水剂(特别是聚羧酸减水剂或聚羧酸超塑化剂)自发明以来，得到了广泛应用于巨大的发展，它已成为混凝土中必不可少的组分。一般地，聚羧酸减水剂为一种梳型结构，一般由含乙烯基单体通过自由基聚合制备，其主链(一般为-CH 2-CH 2-结构或官能团取代的-CH 1-CH 2-结构)上连接有带电官能团(如羧基、磺酸基等)，而相应侧链多为水溶性的聚醚侧链，在混凝土中，通过带电官能团与水泥颗粒表面的静电相互作用吸附于其上，而相应长侧链则通过空间位阻(排斥作用)阻止水泥颗粒相互靠近而团聚，释放被包裹的水分，改善混凝土工作性，降低水灰比。
超高性能混凝土(抗压强度100MPa及以上)由于其优异的服役性能受到广泛关注，然而，其水胶比极低，一般不高于0.2，其胶凝材料组分中硅灰、超细矿粉等具有水化活性的固体颗粒等超细粉体含量极高，往往可达胶凝材料总质量的30％甚至40％以上，所述超细粉体的尺寸一般在纳微米范围(10 1nm-10 0μm)，比水泥颗粒(～10 1μm)尺寸更小，其使得超高性能混凝土相比普通商品混凝土流动性差，粘度大，成为制约施工的关键难题之一。此外，超细粉体界面特性与水泥颗粒不同，在混凝土浆体溶液环境中，面向水泥设计的传统聚羧酸超塑化剂针对这些颗粒的吸附亲和性不足，在超高性能混凝土复杂胶凝材料体系中通用性较差，性能不足，难以满足其对流动性和低粘度的基本需求。
针对此类问题，人们发展了大量降低混凝土水胶比、降低剪切阻力、提高工作性的减水剂新技术。
EP1775271A2的减水剂设计方案为可以降低混凝土粘度，具有良好的保坍性能，但其针对普通混凝土设计，在高/超高强混凝土中难以适用。
CN106467604A报道了一种采用双官能度的不饱和羧酸酯单体和不饱和磷酸酯单体与不饱和酸酐、聚醚单体共聚制备降粘型聚羧酸减水剂。
CN103553413A公开了一种引入调粘单体(不饱和烷基酯、含氟酯、烷基丙烯酰胺或其混凝土)的调粘型减水剂，可有效降低混凝土粘度，但其不同程度上 存在引气功能。
CN106431060A报道了一种用于高强混凝土的降粘型聚羧酸减水剂采用了减水剂、降粘剂、以及保坍剂复配的方案，可以不同程度降低高强混凝土粘度。
CN10147533公开的一种早强型聚羧酸盐复配减水剂，采用复配降粘组分聚乙二醇，明显降低混凝土粘度，满足混凝土施工过程的流动性要求。
CN103865007A公开了一种降粘型聚羧酸系减水剂制备方法，在羧酸共聚物分子结构中引入和控制一定量的疏水单元和疏水基团，起到降低该减水剂作用下水泥基材料粘度的作用，性能优越。
CN105367721A公开了一种降粘型聚羧酸超塑化剂的制备方法及应用，主要在结构中引入了含支化型侧链的单体b与含刚性环基团的单体c进行自由基聚合，能大幅降低混凝土水胶比且能有效降低混凝土粘度。
CN106397683A报道了一种降低高标号混凝土粘度的聚羧酸减水剂及其制备方法，由端烯基聚氧乙烯醚、不饱和酸(苯磺酸、苯甲酸、丙烯酸等)、不饱和酯(不饱和羟基酯)自由基聚合后通过降粘调节剂通过分子重排制备，具有减水率高、降粘效果好等效果。
CN104262550A公开了一种降粘型聚羧酸系减水剂的制备方法，采用不饱和伯胺类小单体，有环氧基团的有机小分子和含卤素基团制备成不饱和季铵盐，然后与不饱和酸共聚，制备的降粘型聚羧酸减水剂反应简单易于控制，能有效降低混凝土粘度。
CN104371081A公开的快速分散降粘型聚羧酸水泥分散剂的制备方法，使用含叔氨基的不饱和单分子单体作为可参与聚合还原剂获得超支化聚羧酸水泥分散剂，对混凝土粘度有较大改善。
CN106008784A报道的混凝土降粘剂采用4-羟丁基乙烯基聚醚、不饱和酰胺及不饱和磷酸酯聚合而成，可以降低混凝土粘度而不影响其流动性，提高泵送施工性能。
CN105837740B报道的混凝土粘度调节剂为由甲基丙烯酸缩水甘油酯和亚氨基二乙酸制备的单体、丙烯酸/甲基丙烯酸和阳离子单体通过自由基聚合得到的三元共聚物，有效降低了C50混凝土粘度。
CN105732911B报道的降粘型聚羧酸由不饱和酸、不饱和聚醚大单体和N-(4-乙烯基苄基)-N,N-二烷基胺聚合制备而成，反应简单，易于制备，减水率高，可用于高强(～0.3)混凝土降粘。
CN100402457C公布的多羧酸混凝土外加剂由(甲基)丙烯酸烷基酯单体、特定的聚亚烷基二醇不饱和大单体和不饱和酸单体通过自由基聚合反应制备，其中引入的具有疏水作用的第三单体丙烯酸烷基酯单体可以有效帮助减水剂降低混凝土屈服应力和粘度。
CN105367721B报道了降粘型聚羧酸超塑化剂的制备方法及应用，该超塑化剂采用了支化的侧链聚醚增加水膜层厚度，同时引入乙烯基吡咯烷酮等刚性环的其他单体，提高分子构象伸展程度，从而大幅降低高与超高强混凝土的粘度。
CN104973817B报道的适于与减水剂配伍使用的混凝土粘度调节剂主要是黏土稳定剂、引气剂、稳泡剂和增稠剂复配，可以减少减水剂无效吸附，稳定气泡，适用于C30-C50的混凝土，改善工作性。
CN104031217B报道了一种疏松抗粘型高性能聚羧酸外加剂，其由酯型或醚型大单体、不饱和羧基单体、有机磷酸盐类化合物以及丙烯酸-木质素聚合物通过水溶液聚合最终制备，可以增强吸附水分子，可以有效降低高强混凝土粘度。
CN109535341A报道了一种含有末端疏水改性的聚乙二醇制备的聚羧酸超塑化剂，其降粘性能优异。专利CN108623756A报道了一种采用N-乙基全氟辛基磺酰胺丙烯酸酯聚合制备的聚羧酸，可用于超高性能混凝土。然而根据发明人的研究，末端疏水改性官能团非常影响聚合物吸附构象，从而影响其空间位阻，特别是在极低水胶比水泥基材料中，因此其分散能力是受到限制的。
根据发明人的研究，混凝土流动性取决于其浆体流动性，其粘度与浆体粘度正相关，浆体粘度越高，混凝土剪切粘度等操作阻力越大。在骨料、胶凝材料、水胶比等配合比固定的条件下，浆体流动性与其中包括水泥、超细粉体、矿物掺合料、石粉等尺度处于10 1nm-10 2μm的纳微米颗粒密切相关，减水剂通过吸附作用附着于颗粒表面，可以有效分散颗粒，增加流动性；浆体粘度反映了浆体剪切时产生的阻力，由浆体中纳微米颗粒之间的相互摩擦决定，通过聚合物对颗粒进行表面覆盖可以有效削弱颗粒间相互摩擦，从而降低粘度。
普通减水剂在硅灰等纳微米级颗粒表面的附着作用较弱，并不能在所有粉体颗粒表面进行有效覆盖。在一般混凝土中，水胶比高，浆体中硅灰等纳微米颗粒含量相对较低，普通减水剂应用性能良好；但在超高性能混凝土中，水胶比极低，纳微米颗粒含量极高，减水剂能否附着于颗粒表面对流动性和粘度的影响十分显著，此时普通减水剂表现为性能不足，混凝土流动性低，颗粒间摩擦削弱程度低，浆体粘度高，施工较为困难。
而上述现有新技术(减水剂产品)未能从根本上解决问题，这些减水剂未经过特殊设计，其针对硅灰等纳米颗粒的表面附着作用较弱，并不能在所有颗粒表面进行有效覆盖，因此浆体絮凝结构较多，流动性差且粘度高，减水剂效果十分有限，其报道的混凝土水胶比多为0.2-0.35之间，属于常规高强混凝土，对超高强混凝土鲜有涉及。
申请内容
为了解决传统减水剂在超高性能混凝土中分散能力差、减水率低、降粘效果不足的问题，本申请提供了一种新型结构的超塑化剂及其制备方法。该超塑化剂全面增强了附着能力，从而削弱颗粒摩擦，相比现有技术，能够显著提高超高性能混凝土流动性，降低其粘度。
所述多官能团超塑化剂的主链为烷基链，侧链除了数个末端为羧酸或羧酸盐的侧链，数个聚醚侧链，还具有数个末端为磷酸或亚磷酸取代的多元醇胺基侧链，所述末端为磷酸或亚磷酸取代的多元醇胺基侧链通过苯基或1-9个碳的烷基连接 到主链上，且末端为羧酸或羧酸盐的侧链个数相比侧链总个数的比例为大于等于零，≤0.8；所述聚醚侧链的个数相比侧链总个数的比例为≥0.1，且≤0.9。
所述磷酸或亚磷酸取代的多元醇胺基侧链的下述两种结构式以任意比例组合：
Figure PCTCN2020099415-appb-000001
所示结构中R 15表示H或者含1-4个碳原子的饱和烷基，在同一个聚合物分子中，各链节所示结构中R 15可以是相同的也可以是不同的；
所示结构中R 16、R 20和R 22分别独立地表示-PO 3H 2或者-PO 2H 2；
所示结构中，Y 0、Y 0’和Y 0”为含羟基的多元醇官能团与足量或者不足量磷酸化试剂反应，羟基H被磷酸基取代的产物官能团，且Y 0、Y 0’和Y 0”通过碳碳键连接在结构式，所述含羟基的多元醇上原本的结构，可以有羧基，也可以原本就含有磷酸基。
所述磷酸化试剂为现有常用磷酸化试剂。(后文中用J指代)。
作为改进，所示结构中Y 0、Y 0’和Y 0”为末端连接有羧基、羧酸盐、磷酸基或磷酸盐官能团的烷基多元醇残基，且Y 0、Y 0’和Y 0”通过碳碳键连接在结构式(2)所示剩余结构上；或被羧基、羧酸盐、磷酸基或磷酸盐官能团部分或全部取代的烷基多元醇残基；且羧基取代碳氢键的H原子位置，磷酸基取代碳氢键或取代羟基的H原子位置。
作为改进，所示结构中Y 0、Y 0’和Y 0”分别独立地表示以下通式(3)所示结构中的任意一种或多种，在同一个聚合物分子中，各链节所示结构中Y 0、Y 0’和Y 0”分别地可以是相同的也可以是不同的，其中所有碳原子手性可以为任意：
Figure PCTCN2020099415-appb-000002
其中R 23表示H或者-PO 3H 2或以下通式(4)所示官能团中的任意一种或多种，R 24表示H或者-CH 2OPO 3H 2或-COOH或-COONa或-COOK或-CH 2OPO 3Na 2或-CH 2OPO 3K 2中的任意一种或多种，x 4表示2-6之间的正整数，包括2和6；且每一个Y 0、Y 0’和Y 0”官能团中各自分别最多只能有一个通式(4)所示官能团。
Figure PCTCN2020099415-appb-000003
其中R 25和R 26分别独立地表示H或者-PO 3H 2，x 6表示1-4之间的正整数，包括1和4。
作为进一步的改进，所述末端为羧酸或羧酸盐的侧链为下述结构式中的任意一种：
Figure PCTCN2020099415-appb-000004
其中R 18表示H或者甲基，
M 1 +、M 2 +、M 3 +、M 4 +和M 5 +分别独立地表示H +或者NH 4 +或者Na +或者K +。
所述聚醚链段通过羰基、苯基、-OCH 2CH 2-、-OCH 2CH 2CH 2CH 2-、-CO-NH-CH 2CH 2-或者-(CH 2) pp-连接到主链，其中pp取值为1-6之间的整数，包括1和6。
所述多官能团超塑化剂是一种梳形聚合物，其结构如以下通式(8)所示，通式中所有碳原子的手性不作限定：
Figure PCTCN2020099415-appb-000005
所示结构中R 11链节的平均数为aa；
所示结构中R 12、R 13、R 14和R 19分别独立地表示-H或者甲基；
所示结构中Z 0表示羰基或者苯基或者-OCH 2CH 2-或者-OCH 2CH 2CH 2CH 2-或者-CO-NH-CH 2CH 2-或者-(CH 2) pp-，其中pp取值为1-6之间的整数，包括1和6。
所示结构中mm和nn分别表示异丙氧基和乙氧基的重复单元数，其可以是整数也可以不是，(mm+nn)的取值范围为8～114，且mm/(mm+nn)不大于1/2，如此才能保证聚醚的水溶性以及其分子链在水溶液中的伸展性。通式(0)所示结构并未限定乙氧基和异丙氧基重复单元的连接顺序，其可以是嵌段的也可以是无规的；
所示结构中X 0和X 0’分别独立地表示含有1-9个碳原子的饱和烷基或苯基，
R 15表示H或者含1-4个碳原子的饱和烷基，在同一个聚合物分子中，各链 节所示结构中R 15可以是相同的也可以是不同的；
所示结构中R 16、R 20和R 22分别独立地表示-PO 3H 2或者-PO 2H 2或对应的钠盐和钾盐形式；
所示结构中aa、bb、cc和cc’分别代表聚合物相应链节的平均数，cc和cc’的比例为任意，aa、bb、cc和cc’的取值需要同时满足如下条件：(1)0≤aa/(aa+bb+cc+cc’)≤0.8；(2)0.1≤bb/(aa+bb+cc+cc’)≤0.9；(3)所述超塑化剂聚合物重均分子量范围为2000-100000。
本申请所述的多官能团超塑化剂的制备方法，在溶剂A环境下，酸催化剂D作用下，端烯基胺B、多羟基醛C和含磷组合物E先行共聚得到中间体，再与不饱和羧酸F和不饱和聚醚G在水溶液中发生自由基聚合制得所述多官能团超塑化剂。
所述溶剂A为水、二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二氧六环中的任意一种或其任意比例的混合物。
所述端烯基胺B为符合以下通式(9)所示结构或其对应的盐酸盐、硫酸盐中的一种或多于一种的任意混合：
Figure PCTCN2020099415-appb-000006
其中，R 1表示-H或者甲基，X表示含有1-9个碳原子的饱和烷基或苯基，R 2表示H或者含1-4个碳原子的饱和烷基。
所述多羟基醛C为包含3-14个碳原子的端醛基小分子糖、或符合以下通式(10)所示结构的一种有机分子，这两者中的任意一种或多于一种的任意混合：
Figure PCTCN2020099415-appb-000007
其中Y表示以下通式(11)所示结构中的任意一种，其中任意手性碳原子构型不限：
Figure PCTCN2020099415-appb-000008
其中R 4表示H或者-CH 2OPO 3H 2或-COOH或-COONa或-COOK或-CH 2OPO 3Na 2或-CH 2OPO 3K 2或以下通式(12)所示结构中的任意一种。
Figure PCTCN2020099415-appb-000009
x 1取值为2-6之间的正整数，包括2和6；x 2表示1-4之间的正整数，包括1和4。
所述酸催化剂D为强酸，包括但不限于对甲苯磺酸、盐酸、硫酸、三氟乙酸、甲基磺酸、三氟甲磺酸、硫酸氢钠、硫酸氢钾、硫酸氢铵中的任意一种。
所述含磷组合物E为组分I和组分J的混合物，组分I为亚磷酸、亚磷酸二氢钾、亚磷酸二氢钠、次磷酸、次磷酸钠和次磷酸钾中一种或多于一种的任意混合，组分J为磷酸、多聚磷酸、焦磷酸、五氧化二磷和水中一种或多于一种的混合物。
组分I与B、C的醛基反应；J与C的羟基反应，I和J的用量由B的用量和C中羟基含量决定。
组分J是通过磷酸的酸酐与水反应制备的混合物，不能纯化和分离，具有反应活性。
所述不饱和羧酸F为丙烯酸、甲基丙烯酸、马来酸、富马酸、马来酸酐、富马酸酐、衣康酸或其对应的钠、钾和铵盐中的一种或多于一种的任意组合。
所述不饱和聚醚G为符合以下通式(13)所示结构中的一种或多于一种的任意混合：
Figure PCTCN2020099415-appb-000010
其中R 6和R 7分别独立地表示-H或者甲基，Z表示羰基或者苯基或者-OCH 2CH 2-或者-OCH 2CH 2CH 2CH 2-或者-CO-NH-CH 2CH 2-或者-(CH 2) p-，其中p取值为1-6范围内的整数，包括1和6。
m和n分别表示异丙氧基和乙氧基的重复单元数，其可以是整数也可以不是，(m+n)的取值范围为8～114，且m/(m+n)不大于1/2，如此才能保证聚醚的水溶性以及其分子链在水溶液中的伸展性。通式(13)所示结构并未限定乙氧基和异丙氧基重复单元的连接顺序，其可以是嵌段的也可以是无规的。
(m+n)的值反映了侧链长度，取值过小则侧链较短，这并非意味着这种结构的分散剂不能制备，而是因为短侧链会导致较差的分散性能，取值过高将增加该塑化剂本身的制备难度，反应效率难以提高，转化率低，另外，侧链过长也会导致吸附基团被侧链遮蔽，一定程度不利于改善在固体颗粒表面的附着能力。
所述引发剂H为本领域技术人员所采用的常规自由基聚合引发体系，引发剂可以是热引发的或者氧化还原引发剂，引发剂可以一次加入，也可以在一定时间内持续均匀加入，引发剂必须满足如下条件：引发剂在相应温度下可以溶解于溶剂并成功引发聚合，且反应过程中引发剂充分分解以防止反应结束后发生变化影响聚合物稳定性。
本申请所述引发剂包括但不限于以下列举的引发剂体系：
所述热引发剂为偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁脒盐酸盐、偶氮二异丁咪唑啉盐酸盐、过硫酸铵、过硫酸钾和过硫酸钠中的任意一种；
所述氧化还原引发剂由氧化剂与还原剂组合，所述氧化剂为过氧化氢、过硫酸铵、过硫酸钾和过硫酸钠中的任意一种；
当氧化剂为过氧化氢时，所述还原剂可以为含2-6个碳原子的饱和烷基硫醇、 巯基乙酸、抗坏血酸或巯基丙酸中的一种或多于一种的任意组合，此外，还可以包含或不包含醋酸亚铁、硫酸亚铁或硫酸亚铁铵中的一种或多于一种的任意组合作为催化剂，催化剂以Fe元素的摩尔量计量，其用量不高于上述还原剂的摩尔量的10％。催化剂用量过高可能造成聚合物分子量失控。
当氧化剂为过硫酸铵、过硫酸钾和过硫酸钠中的任意一种时，所述还原剂为以下组合物中的任意一种：(1)巯基乙酸、抗坏血酸、雕白粉或巯基丙酸中的一种或多于一种的任意组合，此外，还可以包含或不包含醋酸亚铁、硫酸亚铁或硫酸亚铁铵中的一种或多于一种的任意组合作为催化剂，催化剂以Fe元素的摩尔量计量，其用量不高于上述还原剂的摩尔量的10％。催化剂用量过高可能造成聚合物分子量失控；(2)亚硫酸氢钠、亚硫酸钠和焦亚硫酸钠中的一种或多于一种的任意组合。
所述引发剂用量基于如下方法计算，若为热引发剂，则引发剂质量为端烯基胺B、不饱和羧酸F与不饱和聚醚G总质量的0.2-4％；若为氧化还原引发剂，以氧化剂和还原剂中摩尔量较多的一方计算，占端烯基胺B、不饱和羧酸F与不饱和聚醚G总摩尔量的0.2-4％，氧化剂和还原剂的摩尔比为0.25-4。
所述链转移剂K为本领域技术人员所采用的常规自由基聚合链转移剂，仅用于调节产物超塑化剂的分子量，使得产物超塑化剂重均分子量在2000-100000之间。
所用链转移剂K包括但不限于：(1)含巯基的有机小分子，包括但不限于含2-6个碳原子的饱和烷基硫醇、巯基乙醇、巯基乙胺、半胱氨酸、巯基乙酸或巯基丙酸；(2)亚硫酸氢钠、亚硫酸钠和焦亚硫酸钠。其用量可根据产物目标分子量进行调整，一般为反应体系中可聚合双键总摩尔量的0.1-15％之间。所述可聚合双键总摩尔量数值上等同于端烯基胺B、聚醚G和不饱和羧酸F的总摩尔量。
本申请所述的超塑化剂的制备方法，具体包括如下步骤：
(1)向反应器中加入溶剂A，依次向其中加入端烯基胺B、多羟基醛C、和酸催化剂D，将反应器调节至70-120℃，搅拌均匀反应1-12h后，将反应器调节至60-120℃，向其中加入含磷组合物E，搅拌1-12h后，停止反应，真空脱除溶剂，得到中间体混合物。
(2)将步骤(1)制备的全部中间体混合物与不饱和羧酸F、不饱和聚醚G在水溶液中、0℃-90℃下发生自由基聚合制得所述多官能团超塑化剂。
中间体混合物、不饱和羧酸与不饱和聚醚加入反应的方式为在反应开始前或反应过程中一次加入、分批加入或者在一段反应时间内连续均匀加入。引发剂加入反应的方式为在反应开始前或反应过程中一次加入、分批加入或者在一段反应时间内连续均匀加入。反应自引发剂加入开始计时，反应一段时间，停止反应则得到所需聚合物超塑化剂的溶液。
步骤(1)中第一阶段反应温度为70-120℃，反应时间为1-12h。步骤(1)中第二阶段反应温度为60-120℃，反应时间为1-12h。各步骤所需反应时间取决 于反应速率和转化率，温度低一般反应时间偏长。
步骤(2)中反应温度为0℃-90℃，自引发剂开始加入时计时，反应时间累积为1-12h。同样地，该步骤反应温度取决于所用引发体系，一般地，采用氧化还原引发体系则反应温度相对较低，由于自由基产生速率较高，反应速率较快，反应时间短；采用热引发则所用温度相对较高，反应时间长。本领域技术人员可根据经验自行调整。
步骤(1)所述有效反应物占体系总质量的范围为50-90％，所述有效反应物为端烯基胺B、多羟基醛C和含磷组合物E。
步骤(2)所述有效反应物浓度为本领域技术人员所采用的常规自由基聚合体系浓度，可根据经济性、单体投料顺序等进行调整，典型有效反应物浓度范围为30-80wt％，所述有效反应物为中间体混合物、聚醚G和不饱和羧酸F的总和。
端烯基胺B以N原子连接的H原子摩尔量计算，与多羟基醛C的摩尔量之比n(B)/n(C)的取值范围为0.8-1.2。多羟基醛C用量高于该比例对步骤(1)和步骤(2)的反应并无显著不利影响，反应可以照样进行，但其残留于最终产物超塑化剂中，在应用中可能会有较明显的缓凝特性，因此此处进行了限定。
酸催化剂D中活性质子(强电离氢离子)量与端烯基胺B的摩尔量(以N原子连接的H原子摩尔量计算)之比范围为0.5-2.0。过高和过低的酸用量均不利于提高步骤(1)中反应的转化率。
步骤(1)中组分I的用量以磷元素的摩尔量计算，其总量与多羟基醛C的摩尔量之比为1-2，组分I中次磷酸和亚磷酸的比例为任意，组分I中次磷酸或亚磷酸的用量可以为零。
将组分J中氢元素摩尔量记作n(J-H)，磷元素摩尔量记作n(J-P)，将其有效反应活性位点数量计算为[1.5×n(J-P)-0.5×n(J-H)]，则组分J的用量需同时满足以下条件：1≤n(J-H)/n(J-P)≤3，且[1.5×n(J-P)-0.5×n(J-H)]与n(OH)的比值取值范围为0.2-1.2。其中，n(OH)为多羟基醛C中羟基总摩尔数。限制1≤n(J-H)/n(J-P)≤2.5是为了保障组分J的反应活性，高于此值活性过低，低于此值容易生成副产物。此外，[1.5×n(J-P)-0.5×n(J-H)]与n(OH)的比值过低则中间体混合物中吸附活性官能团较少，比值过高则同样会生成副产物，副产物不利于步骤(2)的聚合反应，会使得分子量难以控制。
步骤(2)中不饱和羧酸F的用量相当于端烯基胺B、不饱和羧酸F和聚醚G总摩尔量的0-80％。不饱和羧酸F的用量不能过高，否则产物超塑化剂中特性吸附基团(通过端烯基B连接到超塑化剂分子上)含量过低，其在负电性粉体表面吸附能力有限，其分散能力、经济性不能在超高性能混凝土中体现出优势。
步骤(2)中聚醚G的用量相当于端烯基胺B、不饱和羧酸F和聚醚G总摩尔量的10％-90％。取值过高则产物超塑化剂吸附能力较弱，取值过低则其吸附后提供的空间位阻较小，此外还可能因为过强的吸附能力导致混凝土早期流动性快速损失。
本申请所述超塑化剂相比市售普通超塑化剂，参照实施例，应用于超高性能 混凝土(水胶比不高于0.2)，其掺量较普通市售聚羧酸超塑化剂掺量相应可降低16-42％，粘度有效降低，可降低剪切粘度17-42％。此外，本申请所述超塑化剂最大分散能力显著优于市售超塑化剂，在极低水胶比条件下(往往不高于0.16)，可以有效改善混凝土流动性，而市售超塑化剂无论掺量如何均无法实现混凝土的有效流动性。需要注意的是，本申请所述超塑化剂相比于市售超塑化剂在普通商品混凝土中达到相同流动性所需掺量可能是增加的。
具体实施方式
为了更好地理解本申请，下面结合实施例进一步阐明本申请的内容，但本申请的内容不仅仅局限于下面的实施例。以下所用单位均为质量份，所有所用化合物均为商业品，或依据文献报道的合成品。
溶剂A、端烯基胺B、多羟基醛C、酸催化剂D、聚醚G(除G3和G6以外)、不饱和羧酸F、引发剂H和链转移剂K的来源全部为市售(百灵威试剂、TCI试剂、Sigma-Aldrich、Huntsman和罗恩试剂等)。部分聚醚为工业品，采用端烯基醇碱催化环氧乙烷阴离子开环聚合制备，由苏博特公司生产。
表1实施例所用化合物名称
Figure PCTCN2020099415-appb-000011
表1列举的化合物结构如下所示，部分化合物并未标出手性：
Figure PCTCN2020099415-appb-000012
聚醚G3和G6采用相应聚乙二醇或取代的聚乙二醇醚与不饱和羧酸脱水缩合制备：
(1)G3：由丙烯酸与氨基聚(环氧乙烷-环氧丙烷)单甲醚(数均分子量2000，m/(m+n)＝0.3，来源于Huntsman)反应制备。
将丙烯酸(7.56g，0.105mol)和氨基聚(环氧乙烷-环氧丙烷)单甲醚(数均分子量2000，200g，0.1mol)用1000mL二氯甲烷溶解，向其中加入DMAP(0.122g，1mmol)，室温条件下向其中滴加DCC(22.67g，0.11mol)溶解于二氯甲烷(200mL)的溶液，滴加4h，滴加完毕后继续搅拌6h，过滤除去白色固体沉淀，减压蒸馏，所得膏状固体用二氯甲烷溶解，再用***沉淀，离心，再将所得膏状固体重复二氯甲烷/***沉淀2次，将最终所得产物真空干燥得到单体G3，收率83％。
(2)G6：由甲基丙烯酸与氨基聚乙二醇(O-(2-氨基乙基)聚乙二醇，数均分子量5000，乙二醇重复单元数约113，来源于Sigma)反应制备。
将甲基丙烯酸(0.0903g，0.00105mol)和上述氨基聚乙二醇(5g，0.01mol)用50mL二氯甲烷溶解，向其中加入DMAP(0.00122g，0.01mmol)，室温条件下向其中滴加DCC(0.2267g，0.001mol)溶解于二氯甲烷(5mL)的溶液，滴加12h，体系中有白色沉淀出现，滴加完毕后继续搅拌12h，过滤，减压蒸馏，所得固体用二氯甲烷溶解，再用***沉淀，过滤，再将所得固体重复二氯甲烷/***沉淀2次，将最终所得产物真空干燥得到聚醚G6，收率77％。
以下是实施例的具体步骤(以下所有反应的计量均以端烯基胺B为基准，折算端烯基胺B的物质的量均为0.1摩尔份，以下实施例投料量均为质量份)，产物分子量采用岛津GPC测试(LC-20A)，凝胶色谱柱为TOSOH公司的TSK-GELSW系列，采用示差折光检测器，流动相为0.1MNaNO 3水溶液，聚乙二醇作为分子量测定基准。
实施例1
(1)向反应器中加入二甲亚砜(82.48份)，依次向其中加入B1(7.112份)、C1(22.52份)和浓硫酸(20份，98％)，将反应器调节至70℃，搅拌均匀反应1h后，将反应器调节至120℃，向其中加入亚磷酸(20.5份)、多聚磷酸(85％P 2O 5当量，51.95份)，继续搅拌反应12h，停止反应，真空脱除溶剂，得到中间体混合物。
(2)向烧瓶中加入水(60份)、聚醚G1(400份)和步骤(1)制备的中间体混合物，将反应器温度调节至70℃，搅拌混合均匀，向其中一次投入偶氮二异丁腈粉末0.462份，然后向其中均匀滴加甲基丙烯酸(4.3份)和丙烯酸钠(4.7份)的水溶液(水67.98份)，滴加4h，从单体滴加开始，每隔半小时向其中一次性加入偶氮二异丁腈粉末0.462份，共8批次，投料完毕后继续反应4h，将温度调节至室温，停止反应，得到超塑化剂样品PCE-MP01，重均分子量43.2kDa。
实施例2
(1)向反应器中加入水(11.03份)，依次向其中加入B2(16.93份)、C2(30.03份)和浓硫酸(5份，98％)，将反应器调节至100℃，搅拌均匀反应6h后，将反应器调节至60℃，向其中加入亚磷酸(16.4份)、P 2O 5(47.33份)和无水磷酸32.67份，继续搅拌反应10h，停止反应，真空脱除溶剂，得到中间体混合物。
(2)向烧瓶中加入水(122.72份)、聚醚G2(240份)和步骤(1)制备的中间体混合物，将反应器温度调节至50℃，搅拌混合均匀，向其中均匀滴加引发剂偶氮二异丁脒盐酸盐的水溶液(10.27份溶解于122.72份水)，滴加6h，滴加完毕继续反应12h，将温度调节至室温，停止反应，得到超塑化剂样品PCE-MP02，重均分子量9.8kDa。
实施例3
(1)向反应器中加入N,N-二甲基甲酰胺(84.02份)，依次向其中加入B3(9.356份)、C3(57.05份)和三氟乙酸(11.402份)，将反应器调节至100℃，搅拌均匀反应6h后，将反应器调节至80℃，向其中加入亚磷酸(8.2份)、次磷酸钾(10.4份)、五氧化二磷(12.62份)和水(1.6份)，继续搅拌反应12h，停止反应，真空脱除溶剂，得到中间体混合物。
(2)向烧瓶中加入水(185.66份)、聚醚G3(400份)和步骤(1)制备的中间体混合物，将反应器温度调节至60℃，搅拌混合均匀，同时分别向其中均 匀滴加丙烯酸(57.6份)和巯基丙酸(1.06份)的混合物、引发剂的水溶液(过硫酸铵2.28份溶解于92.83份水，亚硫酸氢钠4.16份溶解于92.83份水)，滴加5h，滴加完毕继续反应1h，将温度调节至室温，停止反应，得到超塑化剂样品PCE-MP03，重均分子量45.6kDa。
实施例4
(1)向反应器中加入N,N-二甲基乙酰胺(49.28份)，依次向其中加入B4(11.32份)、C4(14.42份)和甲磺酸(11.533份)，将反应器调节至70℃，搅拌均匀反应3h后，将反应器调节至100℃，向其中加入次磷酸(6.6份)、五氧化二磷(6.6份)和焦磷酸(28.48份)，继续搅拌反应4h，停止反应，真空脱除溶剂，得到中间体混合物。
(2)向烧瓶中加入水(300份)、聚醚G4(307.5份)和步骤(1)制备的中间体混合物，将反应器温度调节至40℃，向其中加入过氧化氢的水溶液(30wt％，1.13份)，搅拌混合均匀，同时向其中均匀滴加甲基丙烯酸(21.5份)和巯基乙醇(0.585份)的混合物、抗坏血酸的水溶液(0.88份溶解于98.75份水)，滴加45min，滴加完毕继续反应15min，将温度调节至室温，停止反应，得到超塑化剂样品PCE-MP04，重均分子量33.8kDa。
实施例5
(1)向反应器中加入水(3.864份)，依次向其中加入B5(9.917份)、C5(30.41份)和硫酸氢铵(11.511份)，将反应器调节至100℃，搅拌均匀反应3h后，将反应器调节至90℃，向其中加入亚磷酸(8.2份)、次磷酸(6.6份)、五氧化二磷(14.2份)和焦磷酸(17.8份)，继续搅拌反应6h，停止反应，真空脱除溶剂，得到中间体混合物。
(2)向烧瓶中加入水(300.43份)、聚醚G5(300份)和步骤(1)制备的中间体混合物，将反应器温度调节至45℃，向其中加入过氧化氢的水溶液(30wt％，1.13份)和硫酸亚铁(0.0695份)，搅拌混合均匀，同时向其中均匀滴加丙烯酸(3.6份)和乙硫醇(0.232份)的混合物、抗坏血酸的水溶液(0.44份溶解于100份水)，滴加2h，滴加完毕继续反应1h，将温度调节至室温，停止反应，得到超塑化剂样品PCE-MP05，重均分子量29.1kDa。
实施例6
(1)向反应器中加入N-甲基吡咯烷酮(37.24份)，依次向其中加入B6(11.916份)、C6(43.14份)和硫酸(5份，98％)，将反应器调节至100℃，搅拌均匀反应6h后，将反应器调节至90℃，向其中加入亚磷酸二氢钾(12.0份)、亚磷酸(16.4份)、五氧化二磷(52.59份)和无水磷酸(36.3份)，继续搅拌反应6h，停止反应，真空脱除溶剂，得到中间体混合物。
(2)向烧瓶中加入水(677.41份)、聚醚G6(505份)和步骤(1)制备的中间体混合物，将反应器温度调节至35℃，搅拌混合均匀，向其中一次加入偶氮二异丁咪唑啉盐酸盐1.034份，持续反应12h，将温度调节至室温，停止反应，得到超塑化剂样品PCE-MP06，重均分子量97.8kDa。
实施例7
(1)向反应器中依次加入B1(7.112份)、C1(18.02份)和盐酸(20份，36.5％水溶液，水直接充当反应溶剂)，将反应器调节至80℃，搅拌均匀反应4h后，将反应器调节至100℃，向其中加入亚磷酸(32.8份)和焦磷酸(71.2份)，继续搅拌反应4h，停止反应，真空脱除溶剂，得到中间体混合物。
(2)向烧瓶中加入水(312.26份)和步骤(1)制备的中间体混合物，将反应器温度调节至45℃，向其中一次加入过氧化氢(30％水溶液，0.227份)，搅拌混合均匀，向其中连续均匀加入聚醚G1(250份)、丙烯酸(21.6份)、衣康酸(13份)、巯基丙酸(6.36份)和抗坏血酸(0.44份)的混合溶液(溶解于312.26份水)，累积加料时间为4h，加完持续反应1h，将温度调节至室温，停止反应，得到超塑化剂样品PCE-MP07，重均分子量5.2kDa。
实施例8
(1)向反应器中加入水4.58份，然后向其中依次加入B1(7.112份)、C2(36.03份)和对甲苯磺酸(17.22份)，将反应器调节至80℃，搅拌均匀反应4h后，将反应器调节至100℃，向其中加入亚磷酸二氢钾(24.0份)、五氧化二磷(56.8份)和水(7.2份)，继续搅拌反应4h，停止反应，真空脱除溶剂，得到中间体混合物。
(2)向烧瓶中加入水(317.68份)和步骤(1)制备的中间体混合物，将反应器温度调节至60℃，向其中一次加入过硫酸铵(2.28份)，搅拌混合均匀，向其中连续均匀加入聚醚G4(1845份)、巯基丙酸(2.12份)和抗坏血酸(1.76份)的混合溶液(溶解于1000份水)，累积加料时间为4h，加完持续反应2h，将温度调节至室温，停止反应，得到超塑化剂样品PCE-MP08，重均分子量25.1kDa。
实施例9
(1)向反应器中加入N,N-二甲基甲酰胺48.45份，然后向其中依次加入B3(9.356份)、C2(40.04份)和硫酸(15份，98％)，将反应器调节至80℃，搅拌均匀反应2h后，向其中加入亚磷酸(24.6份)和多聚磷酸(115.45份，P 2O 5当量85％)，继续搅拌反应6h，停止反应，真空脱除溶剂，得到中间体混合物。
(2)向烧瓶中加入水(1000份水)和聚醚G2(720份)，将反应器温度调节至75℃，向其中一次加入过硫酸铵(2.11份)，搅拌混合均匀，向其中连续均匀加入步骤(1)制备的中间体混合物、丙烯酸(5.76份)、马来酸酐(1.96份)和巯基乙酸(0.552份)的混合溶液(溶解于382.49份水)，投料时间持续3h，在3h内，剩余过硫酸铵分6批次，每半小时向反应体系中加入2.11份，加完持续反应5h，将温度调节至室温，停止反应，得到超塑化剂样品PCE-MP09，重均分子量47.1kDa。
实施例10
(1)向反应器中加入N,N-二甲基甲酰胺39.81份，然后向其中依次加入B4(11.32份)、C2(18.02份)和三氟乙酸(6.84份)，将反应器调节至120℃，搅 拌均匀反应12h后，向其中加入亚磷酸(1.64份)、次磷酸钠(7.04份)和多聚磷酸(10.39份，P 2O 5当量85％)，继续搅拌反应12h，停止反应，真空脱除溶剂，得到中间体混合物。
(2)向烧瓶中加入水(57.2份)，将反应器温度调节至5℃，向其中一次加入过氧化氢(30％水溶液，0.567份)，搅拌混合均匀，向其中连续均匀加入步骤(1)制备的中间体混合物、聚醚G4(256.25份)、雕白粉(0.193份)和巯基乙醇(1.95份)的混合溶液(溶解于171.59份水)，投料时间持续2h，加完持续反应1h，将温度调节至室温，停止反应，得到超塑化剂样品PCE-MP10，重均分子量11.4kDa。
实施例11
(1)向反应器中加入二甲亚砜13.82份，然后向其中依次加入B5(9.917份)、C5(33.79份)和硫酸氢铵(6.91份)，将反应器调节至80℃，搅拌均匀反应4h后，将反应器调节至90℃向其中加入亚磷酸(8.2份)、次磷酸钠(4.4份)和多聚磷酸(27.71份，P 2O 5当量85％)，继续搅拌反应12h，停止反应，真空脱除溶剂，得到中间体混合物。
(2)向烧瓶中加入水(628.31份)、聚醚G2(240份)和步骤(1)制备的中间体混合物，然后向其中加入过氧化氢(0.283份，30wt％)和硫酸亚铁铵(0.002085份)，搅拌混合均匀，将反应器温度调节至40℃，在2.5h内向其中连续均匀加入丙烯酸(0.72份)、衣康酸(5.2份)和巯基乙醇(0.156份)的混合溶液(溶解于78.54份水)，同时在3h内向其中连续均匀加入抗坏血酸水溶液(0.132份抗坏血酸溶解于78.54份水)，加完持续反应1h，将温度调节至室温，停止反应，得到超塑化剂样品PCE-MP11，重均分子量55.2kDa。
实施例12
(1)向反应器中加入N,N-二甲基甲酰胺16.92份，然后向其中依次加入B6(11.916份)、C1(20.02份)和盐酸(24份，36.5wt％水溶液)，将反应器调节至80℃，搅拌均匀反应2h后，将反应器调节至120℃向其中加入亚磷酸(24.6份)和多聚磷酸(27.71份，P 2O 5当量85％)，继续搅拌反应1h，停止反应，真空脱除溶剂，得到中间体混合物。
(2)向烧瓶中加入水(100份)、聚醚G2(300份)和步骤(1)制备的中间体混合物，搅拌混合均匀，将反应器温度调节至90℃，向其中连续均匀加入丙烯酸(1.8份)、抗坏血酸(0.44份)和巯基丙酸(0.159份)的混合溶液(溶解于155.59份水)，同时向其中连续均匀加入过硫酸钠水溶液(1.19份抗坏血酸溶解于155.59份水)，加料时间为1h，加完持续反应1h，将温度调节至室温，停止反应，得到超塑化剂样品PCE-MP12，重均分子量76.1kDa。
应用实施例
下面分别采用极低水胶比水泥净浆实验和超高性能混凝土实验说明本专利所述超塑化剂的使用效果。
净浆使用海螺水泥(P·O·42.5)，混凝土采用江南小野田水泥(P·II·52.5)，硅灰为艾肯97硅灰，矿粉为S95矿粉，所有材料实验前全部恒温至所需温度。对比样品为普通市售聚羧酸超塑化剂(市售1为酯型，市售2为醚型，侧链长度2400)。需要注意的是，下文所有表述的百分比为与市售样品中相应指标较优的进行对比。
(1)水泥净浆
依照GB/T8077-2000《混凝土外加剂匀质性试验方法》测定水泥净浆流动度，所有分散剂掺量均为纯固体相对于水泥质量的百分比(wt％)。为了表征样品在极低水胶比下的分散/分散保持性能，水泥净浆采用270g水泥和30g硅灰制备，用水量固定为51g。水泥和硅灰预先采用混料机混合保证均匀。
基于标准净浆搅拌流程测试不同超塑化剂的净浆流动度，同时测试水泥净浆放置30min的流动度。将实施例中制备的样品与市售聚羧酸超塑化剂样品进行对比，结果如下：
表2水泥净浆测试结果(20℃)
Figure PCTCN2020099415-appb-000013
由表2中结果可见，尽管本申请实施例中所制备的超塑化剂的分散能力与结构参数相关，有高有低，但与市售样品相比，在0.17水胶比条件下，其分散性能远强于市售样品，除PCE-MP01和PCE-MP07外，大部分样品的流动性保持能力与市售样品2基本相当，较市售样品1更加优异。
(2)超高性能混凝土(UHPC)测试(分散性能比较，砂浆)
为了考察不同样品在不同掺量下最大分散能力，在给定配合比条件下考察极低水胶比条件下水泥砂浆的流动度。
表3 UHPC砂浆配合比(重量比)
水泥 硅灰 超细矿粉 砂 水
0.60 0.12 0.28 0.7 0.15
考察初始流动度在(240±5)mm砂浆的剪切粘度，采用流变仪(Brookfield R/S300Rheometer)测量初始浆体流变曲线(参照文献Constr.Build.Mater.2017,149,359-366，最大剪切速率25s -1)，选取15s -1的剪切粘度进行比较(该剪切速率与浆体处置如搅拌拌合的速率处于同一水平)。同时测量该流动度砂浆的V漏斗时间，结果见表4：
表4 UHPC砂浆测试结果(20℃，空白为未测试)
Figure PCTCN2020099415-appb-000014
由表4中结果可见，在测试配合比条件下，所有样品均表现出随着掺量增加砂浆流动度先增加后不再增加的趋势，部分样品流动性掺量增加略有下降，其原因为粘度增加，流动速度变慢，在测量时间内流动度略小。表中出现的最大流动度视为样品的极限减水，即无论样品掺量如何，其所能达到的最大分散程度。
表中所有样品最大分散能力均远大于市售样品，这说明了本申请实施例制备样品的超强分散能力。此外，即便比较砂浆流动度达到240mm的掺量，本申请实施例样品所需掺量也较市售样品低0.1-0.2wt％(对应于百分比降低16-42％)。
对比砂浆在(240±5)mm流动度的剪切粘度(15s -1)和V漏斗时间，本申请实施例制备的样品PCE-MP01-12可降低剪切粘度17-42％不等，V漏斗时间可缩短14-40％不等，充分说明了样品的降粘特性。
(3)超高性能混凝土(UHPC)测试(混凝土，含纤维)
更换配合比，考察本申请所制备的超塑化剂在UHPC中的应用性能，混凝土配合比如下：
表5 UHPC配合比(重量比，纤维为体积分数)
水泥 硅灰 超细矿粉 粉煤灰 砂 纤维/V％ 水
0.70 0.13 0.05 0.12 0.9 2 0.148
小野田水泥(P II 52.5)，砂为普通河砂，纤维为长径比30长50mm的钢纤维，超塑化剂PCE-MP01-12、市售1和市售2的掺量为以胶凝材料为基准的折固量计算(单位：质量百分比，wt％)，测试中，通过调整超塑化剂用量控制UHPC坍落度((20±1)cm)与扩展度((45±2)cm)相当，所用消泡剂为江苏苏博特新材料股份有限公司市售普通常规的PXP-I混凝土消泡剂，通过消泡剂控制各组UHPC含气量基本一致。若混凝土流动性难以达到上述指标，则统一考察超塑化剂掺量1.0wt％时的流动性，考察其混凝土出机流动性。在该产量下，样品分散能力已经达到极限，混凝土流动性通过增加超塑化剂难以增强。
将水泥、硅灰、粉煤灰和砂加入搅拌机搅拌2min，然后加入纤维继续搅拌3min出机，分别测试UHPC的坍落度和扩展度，记录为“初始/出机”和所用超塑化剂掺量。结果如下：
表6 UHPC表征(20℃)
Figure PCTCN2020099415-appb-000015
*“-”表示仅有坍落度，没有扩展度
可见，市售超塑化剂已经不能满足如此低水胶比混凝土的流动性需求，而采用实施例制备的超塑化剂样品可以赋予水胶比0.148的混凝土良好的流动性。对比28天混凝土抗压强度，市售超塑化剂的分散性能不佳，强度略低于实施例制备的样品，其原因可能是浆体和骨料均匀性略差所致。

Claims (11)

  1. 一种超高性能混凝土用多官能团超塑化剂，其特征在于，其主链为烷基链，侧链除了数个末端为羧酸或羧酸盐的侧链，数个聚醚侧链，还具有数个末端为磷酸或亚磷酸取代的多元醇胺基侧链，所述末端为磷酸或亚磷酸取代的多元醇胺基侧链通过苯基或1-9个碳的烷基连接到主链上，且末端为羧酸或羧酸盐的侧链个数相比侧链总个数的比例为大于等于零，≤0.8；所述聚醚侧链的个数相比侧链总个数的比例为≥0.1，且≤0.9；
    所述磷酸或亚磷酸取代的多元醇胺基侧链的下述两种结构式以任意比例组合：
    Figure PCTCN2020099415-appb-100001
    所示结构中R 15表示H或者含1-4个碳原子的饱和烷基，在同一个聚合物分子中，各链节所示结构中R 15可以是相同的也可以是不同的；
    所示结构中R 16、R 20和R 22分别独立地表示-PO 3H 2或者-PO 2H 2；
    所示结构中，Y 0、Y 0’和Y 0”为含羟基的多元醇官能团与足量或者不足量磷酸化试剂反应，羟基H被磷酸基取代的产物官能团，且Y 0、Y 0’和Y 0”通过碳碳键连接在结构式(2)所示剩余结构上；所述含羟基的多元醇上原本的结构，可以有羧基，也可以原本就含有磷酸基。
  2. 根据权利要求1所述的超高性能混凝土用多官能团超塑化剂，其特征在于，所示结构中Y 0、Y 0’和Y 0”为末端连接有羧基、羧酸盐、磷酸基或磷酸盐官能团的烷基多元醇残基；或被羧基、羧酸盐、磷酸基或磷酸盐官能团部分或全部取代的烷基多元醇残基；且羧基取代碳氢键的H原子位置，磷酸基取代碳氢键或取代羟基的H原子位置；多元醇的羟基被磷酸基取代，形成-O-PO 3H 2的结构。
  3. 根据权利要求1所述的超高性能混凝土用多官能团超塑化剂，其特征在于，所示结构中Y 0、Y 0’和Y 0”分别独立地表示以下通式(3)所示结构中的任意一种或多种，在同一个聚合物分子中，各链节所示结构中Y 0、Y 0’和Y 0”分别地可以是相同的也可以是不同的，其中所有碳原子手性可以为任意：
    Figure PCTCN2020099415-appb-100002
    其中R 23表示H或者-PO 3H 2或以下通式(4)所示官能团中的任意一种或多种， R 24表示H或者-CH 2OPO 3H 2或-COOH或-COONa或-COOK或-CH 2OPO 3Na 2或-CH 2OPO3K2中的任意一种或多种，x 4表示2-6之间的正整数，包括2和6；且每一个Y 0、Y 0’和Y 0”官能团中各自分别最多只能有一个通式(4)所示官能团。
    Figure PCTCN2020099415-appb-100003
    其中R 25和R 26分别独立地表示H或者-PO 3H 2，x 6表示1-4之间的正整数，包括1和4。
  4. 根据权利要求1所述的超高性能混凝土用多官能团超塑化剂，其特征在于，所述末端为羧酸或羧酸盐的侧链为下述结构式中的任意一种：
    Figure PCTCN2020099415-appb-100004
    其中R 18表示H或者甲基，
    M 1 +、M 2 +、M 3 +、M 4 +和M 5 +分别独立地表示H +或者NH 4 +或者Na +或者K +。
    所述聚醚链段通过羰基、苯基、-OCH 2CH 2-、-OCH 2CH 2CH 2CH 2-、-CO-NH-CH 2CH 2-或者-(CH 2) pp-连接到主链，其中pp取值为1-6之间的整数，包括1和6。
  5. 根据权利要求1所述的超高性能混凝土用多官能团超塑化剂，其特征在于，所述多官能团超塑化剂是一种梳形聚合物，其结构如以下通式(8)所示，通式中所有碳原子的手性不作限定：
    Figure PCTCN2020099415-appb-100005
    所示结构中R 11链节的平均数为aa；
    所示结构中R 12、R 13、R 14和R 19分别独立地表示-H或者甲基；
    所示结构中Z 0表示羰基或者苯基或者-OCH 2CH 2-或者-OCH 2CH 2CH 2CH 2-或 者-CO-NH-CH 2CH 2-或者-(CH 2) pp-，其中pp取值为1-6之间的整数，包括1和6；
    所示结构中mm和nn分别表示异丙氧基和乙氧基的重复单元数，其可以是整数也可以不是，(mm+nn)的取值范围为8～114，且mm/(mm+nn)不大于1/2，通式(0)所示结构并未限定乙氧基和异丙氧基重复单元的连接顺序，其可以是嵌段的也可以是无规的；
    所示结构中X 0和X 0’分别独立地表示含有1-9个碳原子的饱和烷基或苯基，
    R 15表示H或者含1-4个碳原子的饱和烷基，在同一个聚合物分子中，各链节所示结构中R 15可以是相同的也可以是不同的；
    所示结构中R 16、R 20和R 22分别独立地表示-PO 3H 2或者-PO 2H 2或对应的钠盐和钾盐形式；
    所示结构中aa、bb、cc和cc’分别代表聚合物相应链节的平均数，cc和cc’的比例为任意，aa、bb、cc和cc’的取值需要同时满足如下条件：(1)0≤aa/(aa+bb+cc+cc’)≤0.8；(2)0.1≤bb/(aa+bb+cc+cc’)≤0.9；(3)所述超塑化剂聚合物重均分子量范围为2000-100000。
  6. 权利要求1所述的超高性能混凝土用多官能团超塑化剂的制备方法，其特征在于，在溶剂A环境下，酸催化剂D作用下，端烯基胺B、多羟基醛C和含磷组合物E先行共聚得到中间体，再与不饱和羧酸F和不饱和聚醚G在水溶液中发生自由基聚合制得所述超高性能混凝土用多官能团超塑化剂；
    所述溶剂A为水、二甲基亚砜、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二氧六环中的任意一种或其任意比例的混合物；
    所述端烯基胺B为符合以下通式(9)所示结构或其对应的盐酸盐、硫酸盐中的一种或多于一种的任意混合：
    Figure PCTCN2020099415-appb-100006
    其中，R 1表示-H或者甲基，X表示含有1-9个碳原子的饱和烷基或苯基，R 2表示H或者含1-4个碳原子的饱和烷基。
    所述多羟基醛C为包含3-14个碳原子的端醛基小分子糖、或符合以下通式(10)所示结构的一种有机分子，这两者中的任意一种或多于一种的任意混合：
    Figure PCTCN2020099415-appb-100007
    其中Y表示以下通式(11)所示结构中的任意一种，其中任意手性碳原子构型不限：
    Figure PCTCN2020099415-appb-100008
    其中R 4表示H或者-CH 2OPO 3H 2或-COOH或-COONa或-COOK或-CH 2OPO 3Na 2或-CH 2OPO 3K 2或以下通式(12)所示结构中的任意一种；
    Figure PCTCN2020099415-appb-100009
    x 1取值为2-6之间的正整数，包括2和6；x 2表示1-4之间的正整数，包括1和4；
    所述酸催化剂D为强酸，包括但不限于对甲苯磺酸、盐酸、硫酸、三氟乙酸、甲基磺酸、三氟甲磺酸、硫酸氢钠、硫酸氢钾、硫酸氢铵中的任意一种；
    所述含磷组合物E为组分I和组分J的混合物，组分I为亚磷酸、亚磷酸二氢钠、亚磷酸二氢钾、次磷酸、次磷酸钠和次磷酸钾中一种或多于一种的任意混合，组分J为磷酸、多聚磷酸、焦磷酸、五氧化二磷和水中一种或多于一种的混合物；
    组分I与B、C的醛基反应；J是与C的羟基反应，I和J的用量由B的用量和C中羟基含量决定；
    所述不饱和羧酸F为丙烯酸、甲基丙烯酸、马来酸、富马酸、马来酸酐、富马酸酐、衣康酸或其对应的钠、钾和铵盐中的一种或多于一种的任意组合；
    所述不饱和聚醚G为符合以下通式(13)所示结构中的一种或多于一种的任意混合：
    Figure PCTCN2020099415-appb-100010
    其中R 6和R 7分别独立地表示-H或者甲基，Z表示羰基或者苯基或者-OCH 2CH 2-或者-OCH 2CH 2CH 2CH 2-或者-CO-NH-CH 2CH 2-或者-(CH 2) p-，其中p取值为1-6范围内的整数，包括1和6；
    m和n分别表示异丙氧基和乙氧基的重复单元数，其可以是整数也可以不是，(m+n)的取值范围为8～114，且m/(m+n)不大于1/2，通式(13)所示结构并未限定乙氧基和异丙氧基重复单元的连接顺序，其可以是嵌段的也可以是无规的。
  7. 根据权利要求6所述的方法，其特征在于，所述自由基聚合所用的引发剂H是热引发的或者氧化还原引发剂，引发剂可以一次加入，也可以在一定时间内持续均匀加入，所述引发剂包括以下列举的引发剂体系：
    所述热引发剂为偶氮二异丁腈、偶氮二异庚腈、偶氮二异丁脒盐酸盐、偶氮二异丁咪唑啉盐酸盐、过硫酸铵、过硫酸钾和过硫酸钠中的任意一种；
    所述氧化还原引发剂由氧化剂与还原剂组合，所述氧化剂为过氧化氢、过硫酸铵、过硫酸钾和过硫酸钠中的任意一种；
    当氧化剂为过氧化氢时，所述还原剂为含2-6个碳原子的饱和烷基硫醇、巯基乙酸、抗坏血酸或巯基丙酸中的一种或多于一种的任意组合，此外，还可以包含或不包含醋酸亚铁、硫酸亚铁或硫酸亚铁铵中的一种或多于一种的任意组合作为催化剂，催化剂以Fe元素的摩尔量计量，其用量不高于上述还原剂的摩尔量 的10％；
    当氧化剂为过硫酸铵、过硫酸钾和过硫酸钠中的任意一种时，所述还原剂为以下组合物中的任意一种：(1)巯基乙酸、抗坏血酸、雕白粉或巯基丙酸中的一种或多于一种的任意组合，此外，还可以包含或不包含醋酸亚铁、硫酸亚铁或硫酸亚铁铵中的一种或多于一种的任意组合作为催化剂，催化剂以Fe元素的摩尔量计量，其用量不高于上述还原剂的摩尔量的10％；(2)亚硫酸氢钠、亚硫酸钠和焦亚硫酸钠中的一种或多于一种的任意组合；
    所述引发剂用量基于如下方法计算，若为热引发剂，则引发剂质量为端烯基胺B、不饱和羧酸F与不饱和聚醚G总质量的0.2-4％；若为氧化还原引发剂，以氧化剂和还原剂中摩尔量较多的一方计算，占端烯基胺B、不饱和羧酸F与不饱和聚醚G总摩尔量的0.2-4％，氧化剂和还原剂的摩尔比为0.25-4。
  8. 根据权利要求6所述的方法，其特征在于，所述链转移剂K包括：(1)含巯基的有机小分子，含2-6个碳原子的饱和烷基硫醇、巯基乙醇、巯基乙胺、半胱氨酸、巯基乙酸或巯基丙酸；(2)亚硫酸氢钠、亚硫酸钠和焦亚硫酸钠；用量为反应体系中可聚合双键总摩尔量的0.1-15％之间；所述可聚合双键总摩尔量数值上等同于端烯基胺B、聚醚G和不饱和羧酸F的总摩尔量。
  9. 根据权利要求6所述的方法，其特征在于，具体包括如下步骤：
    (1)向反应器中加入溶剂A，依次向其中加入端烯基胺B、多羟基醛C、和酸催化剂D，将反应器调节至70-120℃，搅拌均匀反应1-12h后，将反应器调节至60-120℃，向其中加入含磷组合物E，搅拌1-12h后，停止反应，真空脱除溶剂，得到中间体混合物；
    (2)将步骤(1)制备的全部中间体混合物与不饱和羧酸F、不饱和聚醚G在水溶液中、0℃-90℃下发生自由基聚合制得所述多官能团超塑化剂。
  10. 根据权利要求9所述的方法，其特征在于，步骤(1)所述有效反应物占体系总质量的范围为50-90％，所述有效反应物为端烯基胺B、多羟基醛C和含磷组合物E。
  11. 根据权利要求9所述的方法，其特征在于，步骤(2)所述有效反应物浓度为30-80wt％，所述有效反应物为中间体混合物、聚醚G和不饱和羧酸F的总和。
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