CN105669913A - Preparation method of star polycarboxylate water reducing agent with controllable molecular structure - Google Patents
Preparation method of star polycarboxylate water reducing agent with controllable molecular structure Download PDFInfo
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Abstract
The invention discloses a preparation method of a star polycarboxylate water reducing agent with a controllable molecular structure. The method comprises the following specific steps: performing an esterification reaction between polyalcoholic hydroxyl-containing organic molecules and halogenacylhalide organic molecules for 30-90min at 0-25 DEG C to obtain a multi-terminal halogen ATRP initiator; enabling the multi-terminal halogen ATRP initiator, an unsaturated acid small monomer, an unsaturated macromonomer and a transition metal complex to react for 30-240min at 50-80 DEG C; and adding alkali to adjust the pH value to 6-7 to obtain the star polycarboxylate water reducing agent with a controllable molecular structure. According to the method disclosed by the invention, the product performance is adjusted by controlling the temperature, monomer proportion and molecular weight of the macromonomer, the reaction is quick, the efficiency is high, and the operation is simple. The polycarboxylate water reducing agent prepared by the method is a functional polycarboxylate high-efficiency water reducing agent, and the product performance is stable.
Description
Technical field
The present invention relates to the technical field of a kind of cement concrete poly carboxylic acid series water reducer, particularly to the preparation method of the controlled star-like poly carboxylic acid series water reducer of a kind of molecular structure.
Background technology
Along with the development of building trade, in engineer applied, the requirement of water reducer being stepped up, the polycarboxylate water-reducer meeting different construction requirement and application characteristic is researched and developed in succession. Aggregate is indispensable important component part in concrete, and its quality directly affects concrete performance. A large amount of engineerings are actual to be shown with research, can concrete performance be had a negative impact when clay content of gathering materials is higher, is mainly manifested in the diminishing dispersive property reducing water reducer and the workability affecting concrete mix. In order to avoid the negative effect that concrete is caused by the clay content height that gathers materials, high the gathering materials of clay content is mainly rinsed or surpasses mixing water reducer by solution conventional at present. Although higher the gathering materials of clay content is rinsed fundamentally solving the attached impact containing mud on concrete performance of gathering materials, but aggregate grading when rinsing, can be damaged, rinse and also can increase operation, affect the construction period. Though super water reducer of mixing can solve to gather materials the negative effect that clay content height causes to a certain extent; but sometimes for ensureing that concrete mix still had good workability in several hours; super water reducer of mixing would generally make concrete bleeding and isolation initially occur, and super mix water reducer and also can increase cost. Therefore, the concrete admixture used in the past can not meet modern construction demand, therefore solves site operation problem in the urgent need to a high performance polycarboxylate water-reducer at present.
Owing to the designability of polycarboxylate water-reducer molecular structure is strong, control backbone polymerization degree by the optimum organization of difference in functionality construction unit, side chain lengths, functional group's kind realize the high performance of poly carboxylic acid series water reducer, prepare and there is high performance polycarboxylate water-reducer, to solve site operation problem.The multifunctionality of the polycarboxylic admixture of different structure, high reaction activity and bigger spatial volume, be increasingly subject to the favor of researcheres. Therefore we design the polycarboxylate water-reducer of synthesis star structure, form star-like multi-arm copolymer, thus ensureing the space steric effect with more high energy efficiency. This polymer not only has the various performances of traditional comb polymer, also has the various special natures of star polymer simultaneously, has very big application potential.
Patent CN102887979A reports a kind of method of synthesizing polycarboxylic acid concrete high-performance water reducing agent. The method adopts polyhydric alcohol and (methyl) acrylic acid as esterification primary raw material, star high performance water reducing agent of polyocarboxy acid material is prepared by being first esterified the method for post polymerization, namely with (methyl) acrylic acid and polyhydric alcohol for reactant, under catalyst action, first prepare star polymerizable activity end by esterification, then prepared by Raolical polymerizable under the effect of initiator with unsaturated polyoxyethylene ether, molecular weight regulator, unsaturated carboxylic acid monomer. This invention obtains star polymer and not only has the various performances of traditional comb polymer, also has the space steric effect of more high energy efficiency, also has the various special natures of star polymer simultaneously. This invention existing esterification of gained water reducer also has polyreaction, the polycarboxylate high performance water-reducing agent of star-type multi-arm comb shaped structure can be realized, but there is the shortcomings such as complex process, complex operation, preparation cost height, severe reaction conditions and products collection efficiency are low, do not possess some unique advantages of conventional polycarboxylate water-reducer, it is impossible to high-volume is formal to be produced.
Patent CN103482897A reports a kind of method adopting atom transfer radical polymerization (ATRP) to prepare block polycarboxylate water-reducer. The method adopts two-step method, the first step: ATRP initiator is first polymerized the macromole ATRP initiator generating unsaturated acids minor comonomer or unsaturated polymeric monomer with unsaturated acids minor comonomer or unsaturated polymeric monomer; Second step: the macromole ATRP initiator of generation is polymerized with unsaturated polymeric monomer or unsaturated acids minor comonomer and prepares block polycarboxylate water-reducer. This invention obtains block polycarboxylate water-reducer and effectively controls polycarboxylic acid structure's regularity and molecular weight distribution thereof, and is applied in cement dispersive process. Solve the difficult problems such as polycarboxylic acids molecular weight is uncontrollable, molecular weight distribution is wider, molecular structure can not design, but the method exists inefficient, complex process and the shortcoming such as products collection efficiency is low, can there is, when regulating second step reaction, the defect that part macromole evocating agent lost efficacy in the macromole ATRP initiator that in two-step method reaction, the first step generates, can cause that part macromole evocating agent cannot cause. Secondly when ATRP initiator causes this step of unsaturated polymeric monomer, the problems such as unsaturated polymeric monomer is sterically hindered greatly, and polymerization efficiency is low. The performance and the development space that are difficult to reach conventional combed polycarboxylate water-reducer are little.
Most the reinforcement of concrete water reducers described in patent realize excellent performance mainly through transformationreation raw material or process conditions, and seldom realize its excellent cement concrete application performance by the method for Molecular Design change polymer architecture. Fact proved that the work efficiency and application performance that improve polymer are had obvious effect by the density of texture changing polymer.
Summary of the invention
The preparation method of the star-like poly carboxylic acid series water reducer that the invention aims to improve the deficiencies in the prior art and provide a kind of molecular structure controlled.
The preparation method that the technical scheme is that the controlled star-like poly carboxylic acid series water reducer of a kind of molecular structure, it specifically comprises the following steps that
1) preparation of multiterminal halogen radical ATRP initiator: the organic molecule containing many alcoholic extract hydroxyl groups and halogen acyl halide organic molecule are carried out esterification 30～90min at 0～25 DEG C, obtains multiterminal halogen radical ATRP initiator;The mol ratio of the wherein said organic molecule containing many alcoholic extract hydroxyl groups and halogen acyl halide organic molecule is 1:(3～8);
2) preparation of the star-like polycarboxylate water-reducer that molecular structure is controlled: by step 1) the multiterminal halogen radical ATRP initiator obtained, unsaturated acids minor comonomer, unsaturated polymeric monomer and transient metal complex react 30～240min at 50～80 DEG C, adding alkali adjustment pH value is 6～7, namely obtains the star-like polycarboxylate water-reducer that molecular structure is controlled; Its middle-end halogen radical ATRP initiator, 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 many alcoholic extract hydroxyl groups be 3-methyl isophthalic acid, 3,5-penta triol, 1,2,5-penta triol, 1,2,3-penta triol, Pehanorm, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, glycerol, 1,2,4-butantriol, 1,2,6-hexanetriol, 1, one or more combinations of 2,7-triol in heptan, tetramethylolmethane, Bis(pentaerythritol) or tripentaerythritol.
Preferred steps 1) described in halogen acyl halide organic molecule be 2-bromo isobutyl acylbromide, 2-bromo isobutyryl chloride, 2-chloro isobutyryl chloride, 2-chloro-propanoyl chloride or 2-bromo propionyl chloride one or more combination.
Preferred steps 2) described in unsaturated acids minor comonomer be acrylic acid, maleic anhydride, fumaric acid, methacrylic acid, sodium acrylate, Sodium methacrylate., methoxy acrylic acid potassium, sodium allylsulfonate, vinylbenzenesulfonic acid sodium, methallylsulfonic acid sodium, methoxyallyl sodium sulfonate, allyl sulphonic acid potassium, styrene sulfonic acid potassium, vinyl sulfonic acid potassium, methallylsulfonic acid potassium, methyl allyloxy potassium sulfonate, 2-acrylic amide-2-methyl propane sulfonic acid (AMPS), the one or more combination of methacrylic acid potassium or methoxy acrylic acid.
Preferred steps 2) described in unsaturated polymeric monomer be: allyl polyglycol, methacrylic Polyethylene Glycol, 3-methyl-3-butene-1-Polyethylene Glycol or 2-methacrylic Polyethylene Glycol, methoxy poly (ethylene glycol) monomethyl ether (methyl) acrylate, methoxy polyethylene glycol acrylate, polyethylene glycol acrylate or polyethylene glycol methacrylate-styrene polymer one or more combination, its molecular weight is 300～8000g/mol. If unsaturated polymeric monomer meet below general formula also can: R1O(EO)n(PO)mOR2Or R3COO(EO)p(PO)qOR4Represent, wherein R1, R3It is the ethylenic unsaturation alkyl of 3～8 carbon atoms, R2, R4For the alkyl of H or 1～6 carbon atom, n, p is 15～100, m, and q is 0～100.
Preferred steps 2) described in transient metal complex be CuBr-pentamethyl-diethylenetriamine (PMDETA), CuCl-HMTETA, CuBr-tetra-[(2-pyridine radicals) methyl] ethylenediamine (TPEN), CuBr-tri-[2-(dimethylamino) ethyl] amine (Me6TREN), CuCl-pentamethyl-diethylenetriamine (PMDETA), CuBr-HMTETA, CuCl-tetra-[(2-pyridine radicals) methyl] ethylenediamine (TPEN), CuCl-tri-[2-(dimethylamino) ethyl] amine (Me6TREN) one or more combination. It is 1%～5% that preferred transition metal accounts for the mol ratio of transient metal complex.
Preferred steps 2) described in alkali be sodium hydroxide, potassium hydroxide or calcium hydroxide.
The method that this patent adopts is swift in response and productivity high efficiency is high, simple to operate. The inventive method is first to adopt carboxylic acid halides to carry out esterification synthesis multiterminal halogen radical ATRP initiator, again multiterminal halogen radical ATRP initiator, the little molecule of unsaturated acids and unsaturated polyether macromole are carried out ATRP and star-type multi-arm polycarboxylate water-reducer is synthesized, technique is simple, it is a kind of new method synthesizing water reducer, and imparts the function that water reducer is new.
Beneficial effect:
1. the abundant raw material source that the inventive method utilizes, all industrialization of each step, method is ripe.
2. the inventive method is with atom transition free radical polymerization reaction (ATRP), it is possible to obtain controlled molecular weight and very narrow molecular weight distribution.
3. the inventive method carboxylic acid halides element carries out esterification, substantially reduces the response time and improves reaction yield.
4. the polycarboxylate water-reducer that prepared by the inventive method so that it is give new function and simplify.
5. the polycarboxylate water-reducer that prepared by the inventive method carries out ATRP to mix one-step method, at the single-enter polymer that polymerization initial activity is bigger, carrying out along with reaction, the monomer concentration that activity is bigger declines, and the relatively low monomer of activity enters polymers chain more, the gradient copolymer that material is thus formed comonomer prolongation in time and change in gradient, is conducive to it to use in practice.
6. the inventive method safe and reliable, simple and convenient advantage of operating procedure in the whole preparation process of polycarboxylate water-reducer product of preparation.
Detailed description of the invention
By the examples below technical solution of the present invention is described in further detail.
Embodiment 1
1) preparation of three end halogen radical ATRP initiators: by 1mol3-methyl isophthalic acid, 3,5-penta triol and 3mol2-bromo isobutyl acylbromide 0 DEG C carry out esterification 90min and obtain three end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the three end halogen radical ATRP initiators, 10mol acrylic acid, 20mol methacrylic Polyethylene Glycol (300g/mol) and the 0.01molCuBr-pentamethyl-diethylenetriamine (PMDETA) (molar content of CuBr is 1%) that obtain, 50 DEG C of reaction 240min, it is 7 namely obtain one (Trident Type) star-like polycarboxylate water-reducer that hydro-oxidation sodium adjusts pH value.
Embodiment 2
1) preparation of three end halogen radical ATRP initiators: 1mol1,2,5-penta triol and 3.1mol2-bromo isobutyryl chloride 25 DEG C are carried out esterification 30min and obtains three end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the three end halogen radical ATRP initiators, 10mol maleic anhydride, 30mol allyl polyglycol (500g/mol) and the 0.001molCuCl-HMTETA (molar content of CuCl is 1%) that obtain, 80 DEG C of reaction 30min, it is 7 namely obtain one (Trident Type) star-like polycarboxylate water-reducer that hydro-oxidation sodium adjusts pH value.
Embodiment 3:
1) preparation of three end halogen radical ATRP initiators: 1mol1,2,3-penta triol and 3.01mol2-chloro isobutyryl chloride 20 DEG C are carried out esterification 70min and obtains three end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the three end halogen radical ATRP initiators, 10mol fumaric acid, 30mol3-methyl-3-butene-1-Polyethylene Glycol (800g/mol) and 0.002molCuBr-tetra-[(2-pyridine radicals) methyl] ethylenediamine (TPEN) (molar content of CuBr is 5%) that obtain, 60 DEG C of reaction 120min, it is 6 namely obtain one (Trident Type) star-like polycarboxylate water-reducer that hydro-oxidation sodium adjusts pH value.
Embodiment 4:
1) preparation of three end halogen radical ATRP initiators: 1mol Pehanorm and 3.05mol2-bromo propionyl chloride 5 DEG C are carried out esterification 30min and obtains three end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the three end halogen radical ATRP initiators, 10mol methacrylic acid, 40mol2-methacrylic Polyethylene Glycol (2000g/mol) and 0.003molCuBr-tri-[2-(dimethylamino) ethyl] amine (Me6TREN) (molar content of CuBr is 3%) that obtain, 70 DEG C of reaction 80min, it is 7 namely obtain one (Trident Type) star-like polycarboxylate water-reducer that hydro-oxidation potassium adjusts pH value.
Embodiment 5:
1) preparation of three end halogen radical ATRP initiators: 1mol trimethylolethane and 3.05mol2-bromo isobutyl acylbromide 10 DEG C are carried out esterification 90min and obtains three end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the three end halogen radical ATRP initiators, 10mol sodium acrylate, 50mol methoxy poly (ethylene glycol) monomethyl ether (methyl) acrylate (1000g/mol) and the 0.004molCuCl-pentamethyl-diethylenetriamine (PMDETA) (molar content of CuCl is 2%) that obtain, 80 DEG C of reaction 50min, it is 6 namely obtain one (Trident Type) star-like polycarboxylate water-reducer that hydro-oxidation sodium adjusts pH value.
Embodiment 6:
1) preparation of three end halogen radical ATRP initiators: 1mol trimethylolpropane and 3.04mol2-chloro isobutyryl chloride 15 DEG C are carried out esterification 80min and obtains three end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the three end halogen radical ATRP initiators, 10mol Sodium methacrylate., 60mol methoxy polyethylene glycol acrylate (1200g/mol) and the 0.005molCuBr-HMTETA (molar content of CuBr is 2%) that obtain, 40 DEG C of reaction 100min, it is 7 namely obtain one (Trident Type) star-like polycarboxylate water-reducer that hydro-oxidation sodium adjusts pH value.
Embodiment 7:
1) preparation of three end halogen radical ATRP initiators: 1mol1,2,6-hexanetriol and 3.03mol2-chloro-propanoyl chloride 25 DEG C are carried out esterification 60min and obtains three end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the three end halogen radical ATRP initiators, 10mol methoxy acrylic acid potassium, 20mol polyethylene glycol acrylate (1500g/mol) and 0.006molCuCl-tetra-[(2-pyridine radicals) methyl] ethylenediamine (TPEN) (molar content of CuCl is 1%) that obtain, 70 DEG C of reaction 90min, it is 6 namely obtain one (Trident Type) star-like polycarboxylate water-reducer that adding calcium hydroxide adjusts pH value.
Embodiment 8:
1) preparation of three end halogen radical ATRP initiators: 1mol glycerol and 3.02mol2-bromo propionyl chloride 0 DEG C are carried out esterification 40min and obtains three end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the three end halogen radical ATRP initiators, 30mol methallylsulfonic acid potassium, 30mol polyethylene glycol methacrylate-styrene polymer (2400g/mol) and 0.007molCuCl-tri-[2-(dimethylamino) ethyl] amine (Me that obtain6TREN) (molar content of CuCl is 1.5%), 80 DEG C of reaction 110min, it is 7 namely obtain one (Trident Type) star-like polycarboxylate water-reducer that hydro-oxidation sodium adjusts pH value.
Embodiment 9:
1) preparation of three end halogen radical ATRP initiators: 1mol1,2,4-butantriol and 3.01mol2-chloro-propanoyl chloride 10 DEG C are carried out esterification 50min and obtains three end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the three end halogen radical ATRP initiators, 30mol allyl sulphonic acid potassium, 40mol methoxy polyethylene glycol methacrylate-styrene polymer (3000g/mol) and 0.008molCuCl-tetra-[(2-pyridine radicals) methyl] ethylenediamine (TPEN) (molar content of CuCl is 2%) that obtain, 80 DEG C of reaction 200min, it is 6 namely obtain one (Trident Type) star-like polycarboxylate water-reducer that hydro-oxidation potassium adjusts pH value.
Embodiment 10:
1) preparation of three end halogen radical ATRP initiators: 1mol1,2,6-hexanetriol and 3.1mol2-bromo isobutyl acylbromide 5 DEG C are carried out esterification 60min and obtains three end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the three end halogen radical ATRP initiators, 25mol styrene sulfonic acid potassium, 50mol methoxy polyethylene glycol acrylate (4000g/mol) and the 0.009molCuBr-HMTETA (molar content of CuBr is 1%) that obtain, 50 DEG C of reaction 240min, it is 6 namely obtain one (Trident Type) star-like polycarboxylate water-reducer that hydro-oxidation sodium adjusts pH value.
Embodiment 11:
1) preparation of three end halogen radical ATRP initiators: 1mol1,2,7-triol in heptan and 3mol2-bromo isobutyl acylbromide 20 DEG C are carried out esterification 50min and obtains three end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the three end halogen radical ATRP initiators, 10molAMPS, 60mol2-methacrylic Polyethylene Glycol (5000g/mol) and 0.01molCuCl-tri-[2-(dimethylamino) ethyl] amine (Me that obtain6TREN) (molar content of CuCl is 1%), 80 DEG C of reaction 100min, it is 7 namely obtain one (Trident Type) star-like polycarboxylate water-reducer that hydro-oxidation potassium adjusts pH value.
Embodiment 12:
1) preparation of four end halogen radical ATRP initiators: 1mol tetramethylolmethane and 4mol2-bromo isobutyl acylbromide 20 DEG C are carried out esterification 50min and obtains four end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the four end halogen radical ATRP initiators, 10molAMPS, 60mol2-methacrylic Polyethylene Glycol (8000g/mol) and 0.01molCuCl-tri-[2-(dimethylamino) ethyl] amine (Me6TREN) (molar content of CuCl is 1%) that obtain, 80 DEG C of reaction 100min, it is 7 namely obtain one (cross) star-like polycarboxylate water-reducer that hydro-oxidation sodium adjusts pH value.
Embodiment 13:
1) preparation of six end halogen radical ATRP initiators: 1mol Bis(pentaerythritol) and 6mol2-bromo isobutyl acylbromide 20 DEG C are carried out esterification 50min and obtains six end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the six end halogen radical ATRP initiators, 10molAMPS, 60mol2-methacrylic Polyethylene Glycol (3000g/mol) and 0.01molCuCl-tri-[2-(dimethylamino) ethyl] amine (Me that obtain6TREN) (molar content of CuCl is 3%), 80 DEG C of reaction 100min, it is 7 namely obtain one (diesis type) star-like polycarboxylate water-reducer that hydro-oxidation sodium adjusts pH value.
Embodiment 14:
1) preparation of eight end halogen radical ATRP initiators: 1mol tripentaerythritol and 8mol2-bromo isobutyl acylbromide 20 DEG C are carried out esterification 50min and obtains eight end halogen radical ATRP initiators;
2) preparation of star-like polycarboxylate water-reducer: 0.1mol step 1) in the eight end halogen radical ATRP initiators, 10molAMPS, 60mol2-methacrylic Polyethylene Glycol (1000g/mol) and 0.01molCuCl-tri-[2-(dimethylamino) ethyl] amine (Me that obtain6TREN) (molar content of CuCl is 1%), 80 DEG C of reaction 100min, it is 7 namely obtain one (three is cross) star-like polycarboxylate water-reducer that hydro-oxidation sodium adjusts pH value.
Paste flowing degree is tested: with reference to GB8077-2000 " Methods for testing uniformity of concrete admixture ", to embodiment 14 gained sample, embodiment 1 is carried out paste flowing degree test. W/C is 0.29, and the solid volume of additive folding is the 0.08% of cement consumption, and 1h loss is lost hardly;
The paste flowing degree of the different sample of table 1 and gradual loss
Testing concrete performance: embodiment 1 is carried out slump-loss, concrete strength inspection to embodiment 14 gained sample with reference to GB8076-2008 " concrete admixture ".When the solid volume of additive folding is 0.8wt% (relative to cement consumption), water-reducing rate is above 40%, and comprcssive strength raising in 3 days is all higher than 85%, and comprcssive strength raising in 7 days is all higher than 70%, and comprcssive strength raising in 28 days is all higher than 75%.
The concrete slump retaining performance of the different sample of table 2 and mechanical property
Paste flowing degree is tested: with reference to GB8077-2000 " Methods for testing uniformity of concrete admixture ", to embodiment 11 gained sample, embodiment 1 is carried out paste flowing degree test. W/C is 0.29, and the solid volume of additive folding is the 0.10% of cement consumption, 2 grams of bentonite. From the table below it can be seen that with the addition of the embodiment 1 of additive with blank phase comparison have significant change to embodiment 14 gained sample paste flowing degree, illustrate that this anti-chamotte mould polycarboxylate water-reducer resists mud and has obvious effect.
The paste flowing degree of the different sample of table 3 and gradual loss
Testing concrete performance: embodiment 1 is carried out concrete strength inspection to embodiment 14 gained sample with reference to GB8076-2008 " concrete admixture ". When the solid volume of additive folding is 0.11wt% (relative to cement consumption), can be seen that from the table below, with the addition of bentonitic embodiment 1 with blank phase comparison and arrive embodiment 14 gained sample 3 days, 7 days, within 28 days, comprcssive strength all has a significant effect, and illustrates that concrete strength is significantly improved by this anti-anti-mud of chamotte mould water reducer simultaneously.
The mechanical performance of concrete of the different sample of table 4
Claims (7)
1. a preparation method for the star-like poly carboxylic acid series water reducer that molecular structure is controlled, it specifically comprises the following steps that
1) preparation of multiterminal halogen radical ATRP initiator: the organic molecule containing many alcoholic extract hydroxyl groups and halogen acyl halide organic molecule are carried out esterification 30～90min at 0～25 DEG C, obtains multiterminal halogen radical ATRP initiator; The mol ratio of the wherein said organic molecule containing many alcoholic extract hydroxyl groups and halogen acyl halide organic molecule is 1:(3～8);
2) preparation of the star-like polycarboxylate water-reducer that molecular structure is controlled: by step 1) the multiterminal halogen radical ATRP initiator obtained, unsaturated acids minor comonomer, unsaturated polymeric monomer and transient metal complex react 30～240min at 50～80 DEG C, adding alkali adjustment pH value is 6～7, namely obtains the star-like polycarboxylate water-reducer that molecular structure is controlled; Its middle-end halogen radical ATRP initiator, unsaturated acids 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 step 1) described in the organic molecule containing many alcoholic extract hydroxyl groups be 3-methyl isophthalic acid, 3,5-penta triol, 1,2,5-penta triol, 1,2,3-penta triols, Pehanorm, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, glycerol, BT, 1,2,6-hexanetriol, 1,2,7-heptan triol, tetramethylolmethane, Bis(pentaerythritol) or tripentaerythritol one or more combinations.
3. preparation method according to claim 1, it is characterised in that step 1) described in halogen acyl halide organic molecule be 2-bromo isobutyl acylbromide, 2-bromo isobutyryl chloride, 2-chloro isobutyryl chloride, 2-chloro-propanoyl chloride or 2-bromo propionyl chloride one or more combination.
4. preparation method according to claim 1, it is characterized in that step 2) described in unsaturated acids minor comonomer be acrylic acid, maleic anhydride, fumaric acid, methacrylic acid, sodium acrylate, Sodium methacrylate., methoxy acrylic acid potassium, sodium allylsulfonate, vinylbenzenesulfonic acid sodium, methallylsulfonic acid sodium, methoxyallyl sodium sulfonate, allyl sulphonic acid potassium, styrene sulfonic acid potassium, vinyl sulfonic acid potassium, methallylsulfonic acid potassium, methyl allyloxy potassium sulfonate, 2-acrylic amide-2-methyl propane sulfonic acid, the one or more combination of methacrylic acid potassium or methoxy acrylic acid.
5. preparation method according to claim 1, it is characterized in that step 2) described in unsaturated polymeric monomer be allyl polyglycol, methacrylic Polyethylene Glycol, 3-methyl-3-butene-1-Polyethylene Glycol or 2-methacrylic Polyethylene Glycol, methoxy poly (ethylene glycol) monomethyl ether (methyl) acrylate, methoxy polyethylene glycol acrylate, polyethylene glycol acrylate or polyethylene glycol methacrylate-styrene polymer one or more combination, its molecular weight is 300～8000g/mol.
6. preparation method according to claim 1, it is characterised in that step 2) described in transient metal complex be CuBr-pentamethyl-diethylenetriamine (PMDETA), CuCl-HMTETA, CuBr-tetra-[(2-pyridine radicals) methyl] ethylenediamine (TPEN), CuBr-tri-[2-(dimethylamino) ethyl] amine (Me6TREN), CuCl-pentamethyl-diethylenetriamine (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 step 2) described in alkali be sodium hydroxide, alkali hydroxide or calcium hydroxide.
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