CN105669913B - A kind of preparation method of the controllable star-like poly carboxylic acid series water reducer of molecular structure - Google Patents

A kind of preparation method of the controllable star-like poly carboxylic acid series water reducer of molecular structure Download PDF

Info

Publication number
CN105669913B
CN105669913B CN201610122454.5A CN201610122454A CN105669913B CN 105669913 B CN105669913 B CN 105669913B CN 201610122454 A CN201610122454 A CN 201610122454A CN 105669913 B CN105669913 B CN 105669913B
Authority
CN
China
Prior art keywords
preparation
reducer
star
halogen radical
polyethylene glycol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201610122454.5A
Other languages
Chinese (zh)
Other versions
CN105669913A (en
Inventor
钱珊珊
张岭
丁蓓
王毅
姜海东
郑春扬
郭兆来
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Olite New Materials Co., Ltd.
Original Assignee
Jiangsu China Railway ARIT New Materials Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jiangsu China Railway ARIT New Materials Co Ltd filed Critical Jiangsu China Railway ARIT New Materials Co Ltd
Priority to CN201610122454.5A priority Critical patent/CN105669913B/en
Publication of CN105669913A publication Critical patent/CN105669913A/en
Application granted granted Critical
Publication of CN105669913B publication Critical patent/CN105669913B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C04B24/16—Sulfur-containing compounds
    • C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • 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
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
    • 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
    • C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
    • C04B24/2658—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles containing polyether side chains
    • 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
    • C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
    • C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers 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
    • 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
    • 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
    • C04B2103/302—Water reducers
    • 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
    • C08F2438/00—Living radical polymerisation
    • C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP

Abstract

A kind of preparation method of the controllable star-like poly carboxylic acid series water reducer of molecular structure, it is comprised the following steps that：By the organic molecule containing more alcoholic extract hydroxyl groups and halogen acyl halide organic molecule, 30~90min of esterification is carried out at 0~25 DEG C, obtains multiterminal halogen radical ATRP initiators；Then by multiterminal halogen radical ATRP initiators, unsaturated acids minor comonomer, unsaturated polymeric monomer and transient metal complex, 30~240min is reacted at 50~80 DEG C, it is 6~7 to add alkali adjustment pH value, that is, obtains the controllable star-like polycarboxylate water-reducer of molecular structure；The inventive method adjusts properties of product by controlling the molecular weight of temperature, monomer ratio and polymeric monomer, is swift in response, is efficiency high, simple to operate.The poly carboxylic acid series water reducer prepared with the inventive method is a kind of functional polycarboxylic acid series high efficiency water reducing agent, and properties of product are stable.

Description

A kind of preparation method of the controllable star-like poly carboxylic acid series water reducer of molecular structure
Technical field
The present invention relates to a kind of technical field of cement concrete poly carboxylic acid series water reducer, more particularly to a kind of molecule knot The preparation method of the controllable star-like poly carboxylic acid series water reducer of structure.
Background technology
With the development of building trade, the requirement in engineer applied to water reducer steps up, and meets different construction requirements And the polycarboxylate water-reducer of application characteristic is researched and developed in succession.Aggregate is indispensable important component in concrete, its Quality directly affects concrete performance.A large amount of engineerings are actual and research shows, can be to coagulation when clay content of gathering materials is higher Soil nature can have a negative impact, and be mainly manifested in the diminishing dispersive property for reducing water reducer and the work for influenceing concrete mix Property.In order to avoid clay content high negative effect to caused by concrete of gathering materials, currently used solution is mainly to clay content It is high gather materials be rinsed or super mix water reducer.Although gather materials higher to clay content, which is rinsed, can fundamentally solve to collect Expect attached containing influence of the mud to concrete performance, but aggregate grading can be damaged when rinsing, flushing can also increase process, influence to construct Duration.Can solve negative effect caused by clay content height of gathering materials to a certain extent though surpassing and mixing water reducer, sometimes for guarantee coagulation Native mixture still has good workability within a few houres, it is super mix water reducer would generally make concrete initially occur bleeding and from Analysis, and super mix water reducer and can also increase cost.Therefore, the concrete admixture used in the past can not meet modern construction need Ask, therefore there is an urgent need to a high performance polycarboxylate water-reducer at present to solve the problems, such as site operation.
Because the designability of polycarboxylate water-reducer molecule structure is strong, pass through the optimum organization control of difference in functionality construction unit Backbone polymerization degree processed, side chain lengths, functional group's species realize the high performance of poly carboxylic acid series water reducer, are prepared with height The polycarboxylate water-reducer of performance, to solve the problems, such as site operation.The multifunctionality of the polycarboxylic admixture of different structure, high reaction Active and larger spatial volume, is increasingly favored by researchers.Therefore we design the poly- carboxylic of synthesis star structure Sour water reducer, star-like multi-arm copolymer is formed, so as to ensure the space steric effect with more high energy efficiency.The polymer is not only Various performances with traditional comb polymer, while also there are the various special natures of star polymer, there is very big application Potentiality.
Patent CN102887979A reports a kind of method of synthesizing polycarboxylic acid concrete high-performance water reducing agent.This method Using polyalcohol and (methyl) acrylic acid as esterification primary raw material, star polycarboxylic acids is prepared by being first esterified the method polymerizeing afterwards High-performance water reducing agent material, i.e., using (methyl) acrylic acid and polyalcohol as reactant, pass through esterification under catalyst action The polymerizable active end of star is first prepared, then is being triggered with unsaturated APEO, molecular weight regulator, unsaturated carboxylic acid monomer It is made in the presence of agent by Raolical polymerizable.The invention, which obtains star polymer, not only has traditional comb polymer Various performances, also there is the space steric effect of more high energy efficiency, while also there are the various special natures of star polymer.The hair The bright existing esterification of gained water reducer also has polymerisation, it is possible to achieve the polycarboxylic acid series high-performance of star-type multi-arm comb shaped structure Water reducer, but exist complex process, it is cumbersome, prepare cost high, severe reaction conditions and the shortcomings such as products collection efficiency is low, no Possess some unique advantages of conventional polycarboxylate water-reducer, in high volume can not formally produce.
Patent CN103482897A reports one kind and prepares block polycarboxylic acids using ATRP (ATRP) The method of water reducer.This method uses two-step method, the first step：ATRP initiators are first big with unsaturated acids minor comonomer or unsaturation The macromolecular ATRP initiators of monomer polymerization generation unsaturated acids minor comonomer or unsaturated polymeric monomer；Second step：What is generated is big Molecule ATRP initiators polymerize with unsaturated polymeric monomer or unsaturated acids minor comonomer again prepares block polycarboxylate water-reducer.The hair The bright block polycarboxylate water-reducer that obtains effectively controls polycarboxylic acid structure's regularity and its molecular weight distribution, and applied to cement point During dissipating.Solve the problems such as polycarboxylic acids molecular weight is uncontrollable, molecular weight distribution is wider, molecular structure can not design, still Inefficient, the shortcomings such as complex process and products collection efficiency are low, the macromolecular that the first step generates in two-step method reaction be present in this method ATRP initiators can have the defects of part macromole evocating agent failure when adjusting second step reaction, can cause part macromolecular Initiator can not trigger.Secondly when ATRP initiators trigger unsaturated this step of polymeric monomer, unsaturated polymeric monomer steric hindrance Greatly, the problems such as polymerization efficiency is low.The performance and development space for being difficult to reach conventional combed polycarboxylate water-reducer are little.
Concrete described in most patents is mainly realized excellent with water reducer by transformationreation raw material or process conditions Performance, and seldom by Molecular Design change polymer architecture method realize its excellent cement concrete application Energy.It fact proved that the density of texture for changing polymer has obvious effect to the work efficiency and application performance that improve polymer Fruit.
The content of the invention
There is provided a kind of molecular structure controllable star-like poly- carboxylic the invention aims to improve the deficiencies in the prior art The preparation method of sour based water reducer.
The technical scheme is that：A kind of preparation method of the controllable star-like poly carboxylic acid series water reducer of molecular structure, its Comprise the following steps that：
1) preparation of multiterminal halogen radical ATRP initiators：By the organic molecule containing more alcoholic extract hydroxyl groups and halogen acyl halide organic molecule 30~90min of esterification is carried out at 0~25 DEG C, obtains multiterminal halogen radical ATRP initiators；It is wherein described containing more alcoholic extract hydroxyl groups The mol ratio of organic molecule and halogen acyl halide organic molecule is 1：(3~8)；
2) preparation of the controllable star-like polycarboxylate water-reducer of molecular structure：The multiterminal halogen radical ATRP that step 1) obtains is drawn Send out agent, unsaturated acids minor comonomer, unsaturated polymeric monomer and transient metal complex and react 30~240min at 50~80 DEG C, add Alkali adjustment pH value is 6~7, that is, obtains the controllable star-like polycarboxylate water-reducer of molecular structure；Its middle-end halogen radical ATRP initiators, Unsaturated acids minor comonomer, unsaturated polymeric monomer and transient metal complex mol ratio are 1：(100~300)：(200~600)： (0.01~0.1).
Preferred steps 1) described in the organic molecule containing more alcoholic extract hydroxyl groups be 3- methyl isophthalic acids, the triols of 3,5- penta, 1,2,5- penta Triol, the triols of 1,2,3- penta, Pehanorm, trimethylolethane, trimethylolpropane, 1,2,6- hexanetriols, glycerine, 1, 2,4- butantriols, 1,2,6- hexanetriols, 1,2,7- triols in heptan, pentaerythrite, bipentaerythrite or tripentaerythritol one kind or Two or more combinations.
Preferred steps 1) described in halogen acyl halide organic molecule for 2- bromo isobutyls acylbromide, 2- bromos isobutyryl chloride, 2- One or more kinds of combinations of chloro isobutyryl chloride, 2- chloro-propanoyl chlorides or 2- bromo propionyl chlorides.
Preferred steps 2) described in unsaturated acids minor comonomer for acrylic acid, maleic anhydride, fumaric acid, metering system Acid, PAA, Sodium methacrylate, methoxy acrylic acid potassium, ALS, vinylbenzenesulfonic acid sodium, methallyl Base sodium sulfonate, methoxyallyl sodium sulfonate, allyl sulphonic acid potassium, styrene sulfonic acid potassium, vinyl sulfonic acid potassium, methacrylic Potassium sulfonate, methyl allyloxy potassium sulfonate, 2- acrylic amide -2- methyl propane sulfonic acids (AMPS), methacrylic acid potassium or methoxy The one or more combination of base acrylic acid.
Preferred steps 2) described in unsaturated polymeric monomer be：Allyl polyglycol, methacrylic polyethylene glycol, 3- Methyl -3- butene-1s-polyethylene glycol or 2- methacrylics polyethylene glycol, methoxy poly (ethylene glycol) monomethyl ether (methyl) acrylic acid Ester, methoxy polyethylene glycol acrylate, the one or two of polyethylene glycol acrylate or polyethylene glycol methacrylate-styrene polymer Combination of the above, its molecular weight are 300~8000g/mol.Also may be used if unsaturated polymeric monomer meets below general formula：R1O(EO)n (PO)mOR2Or R3COO(EO)p(PO)qOR4Represent, wherein R1, R3For the ethylenic unsaturation alkyl of 3~8 carbon atoms, R2, R4For The alkyl of H or 1~6 carbon atom, n, p are 15~100, m, and q is 0~100.
Preferred steps 2) described in transient metal complex for CuBr- pentamethyl-diethylenetriamines (PMDETA), CuCl- HMTETA, CuBr- tetra- [(2- pyridine radicals) methyl] ethylenediamine (TPEN), CuBr- tri- [2- (dimethylamino) ethyl] amine (Me6TREN), CuCl- pentamethyl-diethylenetriamines (PMDETA), CuBr-HMTETA, CuCl- tetra- [(2- pyridine radicals) methyl] second Diamines (TPEN), CuCl- tri- [2- (dimethylamino) ethyl] amine (Me6TREN one or more combination).It is preferred that transition metal The mol ratio for accounting for transient metal complex is 1%~5%.
Preferred steps 2) described in alkali be sodium hydroxide, potassium hydroxide or calcium hydroxide.
The method that this patent uses is swift in response and yield high efficiency is high, simple to operate.The inventive method is first to use acyl Halogen carries out esterification synthesis multiterminal halogen radical ATRP initiators, then by multiterminal halogen radical ATRP initiators, small point of unsaturated acids Son and unsaturated polyether macromolecular carry out ATRP reaction synthesis star-type multi-arm polycarboxylate water-reducers, and technique is simple, is a kind of synthesis The new method of water reducer, and impart the new function of water reducer.
Beneficial effect：
1. the raw material sources that the inventive method is utilized enrich, each step has all industrialized, and method is ripe.
2. the inventive method with atom transition free radical polymerization reaction (ATRP), can obtain controllable molecular weight and very narrow Molecular weight distribution.
3. the inventive method carries out esterification with carboxylic acid halides element, substantially reduce the reaction time and improve reaction yield.
4. polycarboxylate water-reducer prepared by the inventive method, it is assigned new function and simplify.
5. polycarboxylate water-reducer prepared by the inventive method carries out ATRP to mix one-step method, larger in polymerization initial stage activity Single-enter polymer, with the progress of reaction, the larger monomer concentration of activity declines, and the relatively low monomer of activity more enters Enter polymers chain, material is thus formed the gradient copolymer that comonomer changes in gradient with the extension of time, be advantageous to its Use in practice.
6. the inventive method is safe and reliable in the polycarboxylate water-reducer product whole preparation process of preparation, operating procedure letter Folk prescription just advantage.
Embodiment
Technical solution of the present invention is described in further detail below by embodiment.
Embodiment 1
1) preparation of three end halogen radical ATRP initiators：By 1mol 3- methyl isophthalic acids, the triols of 3,5- penta and 3mol 2- bromos 0 DEG C of isobutyl acylbromide carries out esterification 90min and obtains three end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The three end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 10mol acrylic acid, 20mol methacrylics polyethylene glycol (300g/mol) and 0.01mol CuBr- pentamethyl-diethylenetriamines (PMDETA) (CuBr molar content is 1%), 50 DEG C of reaction 240min, hydrogenation sodium oxide molybdena adjustment pH value obtain for 7 A kind of (Trident Type) star-like polycarboxylate water-reducer.
Embodiment 2
1) preparation of three end halogen radical ATRP initiators：By the triols of 1mol 1,2,5- penta and 3.1mol 2- bromo isobutyryls 25 DEG C of chlorine carries out esterification 30min and obtains three end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The three end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 10mol maleic anhydrides, 30mol allyl polyglycols (500g/mol) and 0.001molCuCl-HMTETA (moles the hundred of CuCl Divide content for 1%), 80 DEG C of reaction 30min, hydrogenation sodium oxide molybdena adjustment pH value obtains a kind of (Trident Type) star-like polycarboxylic acids for 7 Water reducer.
Embodiment 3：
1) preparation of three end halogen radical ATRP initiators：By the triols of 1mol 1,2,3- penta and 3.01mol 2- chloro isobutyls 20 DEG C of acyl chlorides carries out esterification 70min and obtains three end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The three end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 10mol fumaric acid, 30mol3- methyl -3- butene-1s-polyethylene glycol (800g/mol) and [(the 2- pyridines of 0.002molCuBr- tetra- Base) methyl] ethylenediamine (TPEN) (CuBr molar content is 5%), 60 DEG C of reaction 120min, hydrogenation sodium oxide molybdena adjustment pH It is worth and obtains a kind of (Trident Type) star-like polycarboxylate water-reducer for 6.
Embodiment 4：
1) preparation of three end halogen radical ATRP initiators：By 1mol Pehanorms and 3.05mol 2- bromo propionyl chlorides 5 DEG C carry out esterification 30min and obtain three end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The three end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 10mol methacrylic acids, 40mol2- methacrylics polyethylene glycol (2000g/mol) and [2- (diformazans of 0.003molCuBr- tri- Amino) ethyl] amine (Me6TREN) (CuBr molar content is 3%), 70 DEG C of reaction 80min, hydrogenation potassium oxide adjustment pH It is worth and obtains a kind of (Trident Type) star-like polycarboxylate water-reducer for 7.
Embodiment 5：
1) preparation of three end halogen radical ATRP initiators：By 1mol trimethylolethanes and 3.05mol 2- bromo isobutyryls 10 DEG C of bromine carries out esterification 90min and obtains three end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The three end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 10mol PAAs, 50mol methoxy poly (ethylene glycol)s monomethyl ether (methyl) acrylate (1000g/mol) and 0.004molCuCl- pentamethyl-diethylenetriamines (PMDETA) (CuCl molar content is 2%), 80 DEG C of reaction 50min, Hydrogenation sodium oxide molybdena adjustment pH value obtains a kind of (Trident Type) star-like polycarboxylate water-reducer for 6.
Embodiment 6：
1) preparation of three end halogen radical ATRP initiators：By 1mol trimethylolpropanes and 3.04mol 2- chloro isobutyryls 15 DEG C of chlorine carries out esterification 80min and obtains three end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The three end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 10mol Sodium methacrylates, 60mol methoxy polyethylene glycol acrylates (1200g/mol) and 0.005molCuBr-HMTETA (CuBr molar content is 2%), 40 DEG C of reaction 100min, hydrogenation sodium oxide molybdena adjustment pH value obtain a kind of (trident for 7 Type) star-like polycarboxylate water-reducer.
Embodiment 7：
1) preparation of three end halogen radical ATRP initiators：By 1mol 1,2,6- hexanetriols and 3.03mol 2- chloro propionyl 25 DEG C of chlorine carries out esterification 60min and obtains three end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The three end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 10mol methoxy acrylic acids potassium, 20mol polyethylene glycol acrylates (1500g/mol) and [(the 2- pyridines of 0.006molCuCl- tetra- Base) methyl] ethylenediamine (TPEN) (CuCl molar content is 1%), 70 DEG C of reaction 90min, hydrogenation calcium oxide adjustment pH It is worth and obtains a kind of (Trident Type) star-like polycarboxylate water-reducer for 6.
Embodiment 8：
1) preparation of three end halogen radical ATRP initiators：By the 0 DEG C of progress of 1mol glycerine and 3.02mol 2- bromos propionyl chloride Esterification 40min obtains three end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The three end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 30mol methallylsulfonic acids potassium, 30mol polyethylene glycol methacrylate-styrene polymers (2400g/mol) and 0.007molCuCl- tri- [2- (dimethylamino) ethyl] amine (Me6TREN) (CuCl molar content is 1.5%), 80 DEG C of reaction 110min, hydrogenation Sodium oxide molybdena adjustment pH value obtains a kind of (Trident Type) star-like polycarboxylate water-reducer for 7.
Embodiment 9：
1) preparation of three end halogen radical ATRP initiators：By 1mol 1,2,4- butantriols and 3.01mol 2- chloro propionyl 10 DEG C of chlorine carries out esterification 50min and obtains three end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The three end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 30mol allyl sulphonic acids potassium, 40mol methoxy polyethylene glycol methacrylate-styrene polymers (3000g/mol) and 0.008molCuCl- tetra- [(2- pyridine radicals) methyl] ethylenediamine (TPEN) (CuCl molar content is 2%), 80 DEG C of reaction 200min, hydrogenation oxidation Potassium adjustment pH value obtains a kind of (Trident Type) star-like polycarboxylate water-reducer for 6.
Embodiment 10：
1) preparation of three end halogen radical ATRP initiators：By 1mol 1,2,6- hexanetriols and 3.1mol 2- bromo isobutyryls 5 DEG C of bromine carries out esterification 60min and obtains three end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The three end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 25mol styrene sulfonic acids potassium, 50mol methoxy polyethylene glycol acrylates (4000g/mol) and 0.009molCuBr-HMTETA (CuBr molar content is 1%), 50 DEG C of reaction 240min, hydrogenation sodium oxide molybdena adjustment pH value obtain a kind of (trident for 6 Type) star-like polycarboxylate water-reducer.
Embodiment 11：
1) preparation of three end halogen radical ATRP initiators：By 1mol 1,2,7- triols in heptan and 3mol2- bromo isobutyl acylbromides 20 DEG C carry out esterification 50min and obtain three end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The three end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 10molAMPS, 60mol2- methacrylic polyethylene glycol (5000g/mol) and [2- (dimethylamino) second of 0.01molCuCl- tri- Base] amine (Me6TREN) (CuCl molar content is 1%), 80 DEG C of reaction 100min, hydrogenation potassium oxide adjustment pH value is 7 Obtain a kind of (Trident Type) star-like polycarboxylate water-reducer.
Embodiment 12：
1) preparation of four end halogen radical ATRP initiators：1mol pentaerythrites are entered for 20 DEG C with 4mol2- bromo isobutyls acylbromide Row esterification 50min obtains four end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The four end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 10mol AMPS, 60mol 2- methacrylics polyethylene glycol (8000g/mol) and [2- (dimethylamino) of 0.01molCuCl- tri- Ethyl] amine (Me6TREN) (CuCl molar content is 1%), 80 DEG C of reaction 100min, being hydrogenated with sodium oxide molybdena adjustment pH value is 7 obtain a kind of (cross) star-like polycarboxylate water-reducer.
Embodiment 13：
1) preparation of six end halogen radical ATRP initiators：By 20 DEG C of 1mol bipentaerythrites and 6mol2- bromo isobutyls acylbromide Carry out esterification 50min and obtain six end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The six end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 10mol AMPS, 60mol 2- methacrylics polyethylene glycol (3000g/mol) and [2- (dimethylamino) of 0.01molCuCl- tri- Ethyl] amine (Me6TREN) (CuCl molar content is 3%), 80 DEG C of reaction 100min, hydrogenation sodium oxide molybdena adjustment pH value are 7 obtain a kind of (diesis type) star-like polycarboxylate water-reducer.
Embodiment 14：
1) preparation of eight end halogen radical ATRP initiators：By 20 DEG C of 1mol tripentaerythritols and 8mol2- bromo isobutyls acylbromide Carry out esterification 50min and obtain eight end halogen radical ATRP initiators；
2) preparation of star-like polycarboxylate water-reducer：The eight end halogen radical ATRP initiators that are obtained in 0.1mol steps 1), 10mol AMPS, 60mol 2- methacrylics polyethylene glycol (1000g/mol) and [2- (dimethylamino) of 0.01molCuCl- tri- Ethyl] amine (Me6TREN) (CuCl molar content is 1%), 80 DEG C of reaction 100min, hydrogenation sodium oxide molybdena adjustment pH value are 7 obtain a kind of (three is cross) star-like polycarboxylate water-reducer.
Paste flowing degree is tested：With reference to GB8077-2000《Methods for testing uniformity of concrete admixture》, to embodiment 1 Paste flowing degree test is carried out to the gained sample of embodiment 14.W/C is 0.29, and the solid volume of additive folding is cement consumption 0.08%, 1h loss are hardly lost；
The paste flowing degree and gradual loss of 1 different samples of table
Testing concrete performance：With reference to GB8076-2008《Concrete admixture》The gained sample of embodiment 14 is arrived to embodiment 1 Product carry out slump-loss, concrete strength inspection.(relative to cement consumption) when the solid volume of additive folding is 0.8wt%, subtract Water rate is above 40%, and 3 days compression strength, which improves, is all higher than 85%, and 7 days compression strength, which improves, is all higher than 70%, 28 days pressure resistances Degree raising is all higher than 75%.
The concrete slump retaining performance and mechanical property of 2 different samples of table
Paste flowing degree is tested：With reference to GB8077-2000《Methods for testing uniformity of concrete admixture》, to embodiment 1 Paste flowing degree test is carried out to the gained sample of embodiment 11.W/C is 0.29, and the solid volume of additive folding is cement consumption 0.10%, 2 grams of bentonites.From following table as can be seen that to the addition of the embodiment 1 of additive to the institute of embodiment 14 compared with blank Obtaining sample paste flowing degree has significant change, illustrates that this anti-chamotte mould polycarboxylate water-reducer confrontation mud has obvious effect.
The paste flowing degree and gradual loss of 3 different samples of table
Testing concrete performance：With reference to GB8076-2008《Concrete admixture》The gained sample of embodiment 14 is arrived to embodiment 1 Product carry out concrete strength inspection., can from following table (relative to cement consumption) when the solid volume of additive folding is 0.11wt% Going out, arriving 14 gained sample of embodiment 3 days to the addition of bentonitic embodiment 1 compared with blank, 7 days, compression strength was equal within 28 days Have a significant effect, illustrate this anti-anti- mud of chamotte mould water reducer while concrete strength is significantly improved.
The mechanical performance of concrete of 4 different samples of table

Claims (7)

1. a kind of preparation method of the controllable star-like poly carboxylic acid series water reducer of molecular structure, it is comprised the following steps that：
1) preparation of multiterminal halogen radical ATRP initiators：By the organic molecule containing more alcoholic extract hydroxyl groups and halogen acyl halide organic molecule 0 ~25 DEG C of progress 30~90min of esterification, obtain multiterminal halogen radical ATRP initiators；It is wherein described containing the organic of more alcoholic extract hydroxyl groups The mol ratio of molecule and halogen acyl halide organic molecule is 1：(3~8)；
2) preparation of the controllable star-like polycarboxylate water-reducer of molecular structure：The multiterminal halogen radical ATRP that step 1) is obtained triggers Agent, unsaturated acids minor comonomer, unsaturated polymeric monomer and transient metal complex react 30~240min at 50~80 DEG C, add alkali It is 6~7 to adjust pH value, that is, obtains the controllable star-like polycarboxylate water-reducer of molecular structure；Its middle-end halogen radical ATRP initiators, no Saturated species minor comonomer, unsaturated polymeric monomer and transient metal complex mol ratio are 1：(100~300)：(200~600)： (0.01~0.1).
2. preparation method according to claim 1, it is characterised in that organic point containing more alcoholic extract hydroxyl groups described in step 1) Son is 3- methyl isophthalic acids, the triols of 3,5- penta, the triols of 1,2,5- penta, the triols of 1,2,3- penta, Pehanorm, trimethylolethane, Trimethylolpropane, 1,2,6- hexanetriols, glycerine, 1,2,4- butantriols, 1,2,7- triols in heptan, pentaerythrite, bipentaerythrite Or one or more kinds of combinations of tripentaerythritol.
3. preparation method according to claim 1, it is characterised in that the halogen acyl halide organic molecule described in step 1) is 2- bromo isobutyls acylbromide, 2- bromos isobutyryl chloride, 2- chloros isobutyryl chloride, one kind of 2- chloro-propanoyl chlorides or 2- bromo propionyl chlorides Or two or more combinations.
4. preparation method according to claim 1, it is characterised in that the unsaturated acids minor comonomer described in step 2) is Acrylic acid, maleic anhydride, fumaric acid, methacrylic acid, PAA, Sodium methacrylate, methoxy acrylic acid potassium, pi-allyl Sodium sulfonate, vinylbenzenesulfonic acid sodium, methallylsulfonic acid sodium, methoxyallyl sodium sulfonate, allyl sulphonic acid potassium, styrene Potassium sulfonate, vinyl sulfonic acid potassium, methallylsulfonic acid potassium, methyl allyloxy potassium sulfonate, 2- acrylamide -2- methyl-prop sulphurs The one or more combination of acid, methacrylic acid potassium or methoxy acrylic acid.
5. preparation method according to claim 1, it is characterised in that the unsaturated polymeric monomer described in step 2) is allyl Base polyethylene glycol, methacrylic polyethylene glycol, 3- methyl -3- butene-1s-polyethylene glycol, 2- methacrylics polyethylene glycol, The one or more of methoxy polyethylene glycol acrylate, polyethylene glycol acrylate or polyethylene glycol methacrylate-styrene polymer Combination, its molecular weight is 300~8000g/mol.
6. preparation method according to claim 1, it is characterised in that the transient metal complex described in step 2) is CuBr- pentamethyl-diethylenetriamines (PMDETA), CuCl-HMTETA, CuBr- tetra- [(2- pyridine radicals) methyl] ethylenediamine (TPEN), CuBr- tri- [2- (dimethylamino) ethyl] amine (Me6TREN), CuCl- pentamethyl-diethylenetriamines (PMDETA), CuBr-HMTETA, CuCl- tetra- [(2- pyridine radicals) methyl] ethylenediamine (TPEN), CuCl- tri- [2- (dimethylamino) ethyl] amine (Me6TREN one or more combination).
7. preparation method according to claim 1, it is characterised in that the alkali described in step 2) is sodium hydroxide, hydroxide Potassium or calcium hydroxide.
CN201610122454.5A 2016-03-03 2016-03-03 A kind of preparation method of the controllable star-like poly carboxylic acid series water reducer of molecular structure Active CN105669913B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610122454.5A CN105669913B (en) 2016-03-03 2016-03-03 A kind of preparation method of the controllable star-like poly carboxylic acid series water reducer of molecular structure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610122454.5A CN105669913B (en) 2016-03-03 2016-03-03 A kind of preparation method of the controllable star-like poly carboxylic acid series water reducer of molecular structure

Publications (2)

Publication Number Publication Date
CN105669913A CN105669913A (en) 2016-06-15
CN105669913B true CN105669913B (en) 2018-03-13

Family

ID=56306686

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610122454.5A Active CN105669913B (en) 2016-03-03 2016-03-03 A kind of preparation method of the controllable star-like poly carboxylic acid series water reducer of molecular structure

Country Status (1)

Country Link
CN (1) CN105669913B (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106084157A (en) * 2016-07-11 2016-11-09 济南大学 A kind of three arm high-efficiency water-reducing agent of poly-carboxylic acid and preparation method thereof
CN106146859B (en) * 2016-07-11 2020-04-07 济南大学 Four-arm polycarboxylic acid high-efficiency water reducing agent and preparation method thereof
CN106188556B (en) * 2016-07-17 2019-04-05 北京工业大学 Poly carboxylic acid modified carboxylic acid halides is grafted the method that compound side chain prepares cement water reducing agent
CN106749960B (en) * 2016-11-28 2019-07-02 中科院广州化学有限公司南雄材料生产基地 Polycarboxylic acid super-plasticizer and its preparation method and application with diesis core configuration
CN106883358B (en) * 2017-02-14 2019-09-20 佛山市功能高分子材料与精细化学品专业中心 Four arm star polycarboxylic acid super-plasticizers of one kind and its preparation method and application
CN107286288B (en) * 2017-07-07 2020-05-08 江苏奥莱特新材料股份有限公司 Preparation method of retarding polycarboxylate superplasticizer
CN107987230B (en) * 2017-12-29 2022-12-20 山西黄河化工有限公司 Star-shaped polycarboxylic acid water reducing agent and preparation method thereof
CN108059697B (en) 2017-12-29 2019-12-27 江苏苏博特新材料股份有限公司 Preparation method of polycarboxylate superplasticizer with regular sequence structure
CN108948285B (en) * 2018-06-19 2021-10-22 武汉源锦建材科技有限公司 High-water-reduction high-slump-retaining type polycarboxylate superplasticizer and preparation method thereof
CN110156944B (en) * 2019-04-26 2022-04-05 中科广化（重庆）新材料研究院有限公司 Four-arm star-shaped block polycarboxylic acid superplasticizer and preparation method and application thereof
CN110922546B (en) * 2019-11-21 2022-07-05 湖北工业大学 Phenyl hydroxyl compound ATRP method modified polycarboxylic acid slump retaining agent and preparation method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002134A (en) * 2010-11-05 2011-04-06 济南大学 Hyperbranched polymer, hyperbranched type water reducing agent of polycarboxylic acid series and preparation method and application thereof
CN102239193A (en) * 2008-12-08 2011-11-09 可泰克斯有限合伙公司 Use, as an agent for improving the handleability of an aqueous formulation based on hydraulic binders, of a (meth)acrylic comb copolymer and of an associative acrylic thickener
CN102268127A (en) * 2010-06-03 2011-12-07 华东师范大学 Dendritic/hyperbranched polymer and intermediate and preparation methods thereof
CN102887979A (en) * 2012-10-22 2013-01-23 北京工业大学 Preparation method of star polycarboxylic acid high-performance water reducing agent
CN103482897A (en) * 2013-09-09 2014-01-01 江苏博特新材料有限公司 Block poly-carboxylic acid concrete high-efficiency water reducing agent and preparation method thereof
CN104371071A (en) * 2014-05-23 2015-02-25 江苏苏博特新材料股份有限公司 Preparation method for hyperbranched polycarboxylic-acid concrete efficient water reducer
CN104371077A (en) * 2014-05-23 2015-02-25 江苏省建筑科学研究院有限公司 Preparation method for starlike polycarboxylic-acid cement dispersant
CN105199050A (en) * 2015-09-11 2015-12-30 湘潭大学 Polyurethane grafted copolymer and preparation method of polyurethane grafted copolymer

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102239193A (en) * 2008-12-08 2011-11-09 可泰克斯有限合伙公司 Use, as an agent for improving the handleability of an aqueous formulation based on hydraulic binders, of a (meth)acrylic comb copolymer and of an associative acrylic thickener
CN102268127A (en) * 2010-06-03 2011-12-07 华东师范大学 Dendritic/hyperbranched polymer and intermediate and preparation methods thereof
CN102002134A (en) * 2010-11-05 2011-04-06 济南大学 Hyperbranched polymer, hyperbranched type water reducing agent of polycarboxylic acid series and preparation method and application thereof
CN102887979A (en) * 2012-10-22 2013-01-23 北京工业大学 Preparation method of star polycarboxylic acid high-performance water reducing agent
CN103482897A (en) * 2013-09-09 2014-01-01 江苏博特新材料有限公司 Block poly-carboxylic acid concrete high-efficiency water reducing agent and preparation method thereof
CN104371071A (en) * 2014-05-23 2015-02-25 江苏苏博特新材料股份有限公司 Preparation method for hyperbranched polycarboxylic-acid concrete efficient water reducer
CN104371077A (en) * 2014-05-23 2015-02-25 江苏省建筑科学研究院有限公司 Preparation method for starlike polycarboxylic-acid cement dispersant
CN105199050A (en) * 2015-09-11 2015-12-30 湘潭大学 Polyurethane grafted copolymer and preparation method of polyurethane grafted copolymer

Also Published As

Publication number Publication date
CN105669913A (en) 2016-06-15

Similar Documents

Publication Publication Date Title
CN105669913B (en) A kind of preparation method of the controllable star-like poly carboxylic acid series water reducer of molecular structure
CN105669912B (en) A kind of method for preparing star-like poly carboxylic acid series water reducer
CN105906753A (en) Preparation method of polycarboxylate superplasticizer
CN104193913B (en) A kind of early-strength polycarboxylate concrete dehydragent and preparation method thereof
CN101475664B (en) Preparation of polycarboxylic acid water reducing agent for prefabricated part
CN103265201B (en) Sorbitol modified polycarboxylate-type water reducing agent and synthetic method thereof
CN104961373B (en) Slump loss resistant type polycarboxylic water reducer and preparation method thereof
CN107265907B (en) Amphoteric antibacterial polycarboxylic acid high-efficiency water reducing agent and preparation method thereof
CN103396031B (en) A kind of carboxylic acid water reducer and preparation method thereof
CN104150807B (en) A kind of prestressed high-strength concrete pile polycarboxylate water-reducer and application thereof
CN106866895A (en) A kind of high-performance poly carboxylic acid series water reducer and preparation method thereof
CN110105503A (en) A kind of efficient diminishing polycarboxylate water-reducer of viscosity reduction type and preparation method thereof
CN110105499A (en) A kind of hyperbranched polyamine -ester type high-efficiency water-reducing agent of poly-carboxylic acid and preparation method thereof
CN110358023A (en) A kind of low surface tension shrinkage type polycarboxylate water-reducer and preparation method thereof
CN104496253B (en) Special early-strength polycarboxylate superplasticizer for prefabricated parts and preparation method of special early-strength polycarboxylate superplasticizer
CN104945632B (en) A kind of preparation method of microspheric polycarboxylate water-reducer
CN105417985A (en) Multi-branched polycarboxylate superplasticizer with tertiary amine groups and preparation method of polycarboxylate superplasticizer
CN106397682B (en) The preparation method of collapse protective poly-carboxylic acid water reducing agent
CN102503221A (en) Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof
JP2021524872A (en) High melt index thermoplastic elastomer and its manufacturing method
CN107337771B (en) Triblock polycarboxylate superplasticizer and preparation method thereof
CN109280141A (en) A kind of preparation method of fluorine-containing shrinkage type polycarboxylate water-reducer
CN105968266B (en) The preparation method of superpower decentralized polycarboxylic acid series high efficiency water reducing agent
CN104628962A (en) Method for synthesizing cement disperser from acrylamide-fatty acid vinyl ester graft copolymer
CN104371075A (en) Method for preparing polycarboxylate superplasticizer synthesized at room temperature

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information

Address after: Zhongshan science and Technology Park Huixin Liuhe road Nanjing District 210048 Jiangsu province No. 22

Applicant after: JIANGSU ARIT NEW MATERIALS CO., LTD.

Address before: Zhongshan science and Technology Park Huixin Liuhe road Nanjing District 210048 Jiangsu province No. 22

Applicant before: JIANGSU ARIT NEW MATERIALS CO., LTD.

COR Change of bibliographic data
GR01 Patent grant
GR01 Patent grant
CP01 Change in the name or title of a patent holder

Address after: 210048 Huixin Road, Zhongshan science and Technology Park, Liuhe District, Nanjing, Jiangsu 22

Patentee after: Jiangsu Olite New Materials Co., Ltd.

Address before: 210048 Huixin Road, Zhongshan science and Technology Park, Liuhe District, Nanjing, Jiangsu 22

Patentee before: JIANGSU ARIT NEW MATERIALS CO., LTD.

CP01 Change in the name or title of a patent holder