CN101602834B - Preparation method of polycarboxylic acid concrete dispersers - Google Patents
Preparation method of polycarboxylic acid concrete dispersers Download PDFInfo
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Abstract
The invention relates to a preparation method of polycarboxylic acid concrete dispersers, comprising the following steps: (1) free radical copolymerization is carried out: a monomer A and a monomer C carry out free radical copolymerization under a condition that a monomer B is used as solvent according to mole ratio of 1.01 : 1 to 1.5 : 1, wherein the monomer A is (alkyl) vinyl alkyl acid ester, the monomer B is mono-alkoxy poly alkylene glycol ether, and the monomer C is maleic anhydride; the mole ratio of the monomer B and the monomer C is 0.1 : 1 to 1 : 1; (2) esterification grafting reaction is carried out: the polymer prepared by the step 1 is warmed up and esterified, so as to graft monomer B on a acid anhydride group led in by the monomer C; (3) after the esterification reaction is finished, reaction product is added with water for dilution, and alkalinity substances are added in for adjusting the pH value to 6.0 to 8.0. Organic solvent with toxic substances is not used, thereby effectively avoiding volatile organic solvents from damaging the environment and human body; in addition, the production cost is low, the process is simple and the production efficiency is high.
Description
Technical field
The present invention relates to a kind of preparation method of the polycarboxylic acid concrete dispersers based on maleic anhydride, belong to technical field of concrete additives.
Background technology
At present, high-performance water reducing agent has become the indispensable component of preparation high performance concrete.In numerous water reducer kinds, the poly carboxylic acid series water reducer of comb shaped structure have water-reducing rate height, slump through the time loss little, advantage such as volume is low becomes the focus of domestic and international research.The side chain that main chain that the polycarboxylate water-reducer of comb shaped structure all is made up of groups such as carboxyl, hydroxyl, sulfonic groups and polyalkylene glycol ethers macromole are formed constitutes.Main chain provides the absorption to cement granules, and dispersion repulsion is provided; Long side chain has increased space steric effect, and forms thicker adsorbed film of water, makes polycarboxylate water-reducer more obvious to the stably dispersing effect of cement granules, improves slump hold facility.
Ester class side chain all is that mode by esterification or transesterify is grafted on polyalkylene glycol ethers on the main chain in the polycarboxylate water-reducer, esterification technique need use a large amount of solvents as the band aqua, reaction needs solvent to be separated and reclaim after finishing, this solvation mode of production production cycle is long, energy consumption is big, it is big to pollute, this a series of process has increased production cost and has reduced production efficiency again, is unfavorable for Sustainable development.
Maleic anhydride is one of carboxylic-acid unsaturated monomer commonly used in the polycarboxylate water-reducer, and the anhydride group on its molecule has good esterification activity to alcohols material, and the maleic anhydride polyether ester has worldwide had certain research as the cement water reducing agent raw material.
Chinese patent CN 1712381A has reported a kind of with the Zelan 338 sulfonation, use the way of polyoxyethylene glycol addition synthesizing polyether grafting polyocarboxy acid type cement water reducing agent on the anhydride group of maleic anhydride again, this method is divided into three steps: at first use maleic anhydride and vinylbenzene synthesizing styrene copolymer-maleic anhydride in solvent; Second step removed the back of desolvating and with sulphur trioxide or SULPHURYL CHLORIDE vinylbenzene is carried out the sulfonation processing; The 3rd step was carried out grafting according to a certain percentage with polyoxyethylene glycol and sulfonated phenylethylene copolymer-maleic anhydride in solvent.Whole processing process is long, and the first step and the 3rd step operation all need carry out in solvent, has increased difficulty of processing, and has been unfavorable for environment protection.
Chinese patent CN 1792960A has reported a kind of preparation method of maleic anhydride series concrete water-reducing agent.This method is having stopper, catalyzer, toluene to make under the condition of solvent pyroreaction 10～15 hours with maleic anhydride and methoxy poly (ethylene glycol) according to a certain percentage, obtain toxilic acid mono methoxy polyethylene glycol ester and the big monomer mixture of toxilic acid Varonic DM 55 ester, again with 2-acrylamide-2-methylpropene sodium sulfonate with it copolymerization obtain product.Operating process still needs to use solvent, and toxilic acid esterification thing polymerization activity in the aqueous solution is not high, has partial monosomy and remains in the product, causes the waste of raw material.
Chinese patent CN 1948209A has reported a kind of with polyoxyethylene glycol and the synthetic toxilic acid esterification thing of maleic anhydride, then obtains a kind of poly carboxylic acid series water reducer with vinylformic acid, methylpropene sodium sulfonate copolymerization in the aqueous solution.The first step maleic anhydride of this method adopts during the esterification polyoxyethylene glycol method of decompression can cause the distillation of maleic anhydride under hot conditions, cause waste of raw materials, and can inevitably generate a part of dibasic acid esters, the improper meeting of control causes gel in polymerization process, and there are the insufficient shortcoming of toxilic acid esterification thing polymerization activity in the aqueous solution, the space that has a distinct increment equally.
Summary of the invention
For overcoming the problem that above-mentioned prior art exists, the invention provides a kind of polycarboxylic acid concrete dispersers based on maleic anhydride and preparation method thereof, the product of producing has the advantage that water-reducing property is good, slump-loss is little, reinforced effects is obvious, cheap, easy to operate.
Investigator of the present invention finds that through a large amount of experiments the polyethers alcohols material has good solubility property to the reaction raw materials of carboxylic-acid polymkeric substance, propose to use the polyethers alcohols material of one of copolymer reaction monomer as solvent, for other monomeric copolyreaction provide the place, can effectively avoid the injury of volatile organic solvent to environment and human body.
Polycarboxylic acid concrete dispersers of the present invention can be prepared from by the following step:
(1) free radicals copolymerization reaction: monomer A and monomer C are to carry out free radicals copolymerization reaction in monomers B under as the condition of solvent in 1.01: 1～1.5: 1 according to the A/C molar ratio, wherein:
Monomer A is represented with general formula (1):
What general formula (1) was represented is (alkyl) vinyl alkyl acid esters, R in the formula
1Represent hydrogen atom or methyl, n is the number of methylene radical, is 0～2 integer.The monomer A of general formula (1) representative can be vinyl-acetic ester, propionate, vinyl butyrate, different propylene acetic ester, different propylene propionic ester, different propylene butyric ester, and these monomers can use separately or two kinds or two or more form of mixtures use with arbitrary proportion.
Monomers B is represented with general formula (2):
What general formula (2) was represented is the monoalkoxy polyalkylene glycol ethers, R in the formula
2Represent the alkyl of 1～20 carbon atom; The addition quantity of p representative ring oxidative ethane is 1～200 integer; The addition quantity of q representative ring Ethylene Oxide is 0～25 integer.It mainly provides dispersive ability and disperses hold facility in multipolymer.
General formula (2) if in q equal 0, then monomers B is the linear polymer of oxyethane; When q greater than 0 the time, monomers B is the polymkeric substance of oxyethane and propylene oxide, they can be linear polymer, random or segmented copolymer.Among the present invention, monomers B can make the monoalkoxy polyalkylene glycol ethers material of a certain type use separately, also can be that two or more different monoalkoxy polyalkylene glycol ethers materials mix use with arbitrary proportion.
Monomer C refers to maleic anhydride, and its anhydride group provides the esterification ability with alcohols material, and the hydroxy-acid group that generates after its open loop provides adsorption site and electric repulsion in multipolymer.
Among the present invention, the molar ratio of monomer A/C keeps monomer A excessive a little in 1.01: 1～1.5: 1 scopes, can guarantee the transformation efficiency of monomer C but does not influence the water-soluble of product.The molar ratio of monomers B/C can be selected corresponding suitable B/C ratio according to the length of side chain in the multipolymer in 0.1: 1～1: 1 scope, to guarantee dispersive ability and to disperse to keep the balance of performance.
In the scope of the invention, radical polymerization process is most important, and it can be described as: add the monomers B of a part in being connected with the batching flask of nitrogen, dropping into monomer C, initiator and chain-transfer agent more successively, stirring and dissolving is made material G.Monomers B with residual content feels secure in being connected with the reaction vessel of nitrogen, is warming up to temperature of reaction, drips monomer A and material G simultaneously, and the dropping time is 2～3 hours, and the insulation reaction time is 2 hours.
The polymerization starter that the present invention is suitable for can be one or more mixtures with arbitrary proportion in superoxide (as benzoyl peroxide or lauroyl peroxide), azo compound (as Diisopropyl azodicarboxylate) or the hydroperoxide (as cumene hydroperoxide).All initiator amount accounts for 0.5～5% of reactant A+B+C gross weight.
The present invention is by using the effectively molecular weight of controlling polymers of chain-transfer agent, is suitable for chain-transfer agent of the present invention and can selects a kind of of Dodecyl Mercaptan, 16 mercaptan, mercaptoethanol, Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid or two kinds for use or be used in combination more kinds of chain-transfer agents with arbitrary proportion.The consumption of polymeric chain transfer agent is 0.1～2.0% of monomer A+C gross weight.
The present invention uses the monoalkoxy polyalkylene glycol ethers class material of general formula (2) representative as solvent, and the bottoming part accounts for 20～90% of monomers B gross weight.The preparation temperature of material G is chosen in 20～60 ℃, if temperature is too low, then monomers B self can not well be dissolved; Temperature is too high, then can cause decomposition of initiator to lose efficacy, and perhaps causes the generation of side reactions such as monomers B and monomer C antedating response.
The Raolical polymerizable temperature range is chosen between 60～100 ℃ among the present invention.Temperature is too low, then causes half-lives of initiators long, the excessively slow or well polymerization of material of described polyreaction; Temperature too Gao Zehui causes the volatilization of monomer A and causes reaction too violent, is not easy control.
(2) graft esterification reaction: in other words grafted monomer B on the anhydride group of monomer C is exactly with above-mentioned free radical reaction product intensification esterification 1～3 hour.
The temperature of esterification is preferably at 100～160 ℃.Temperature helps the carrying out of esterification in suitable scope, and can guarantee not occur the situation that reaction product is oxidized and polyether segment ruptures as far as possible.If temperature of reaction is lower than 100 ℃, well grafting of polyethers (monomers B) causes the reaction times to prolong, and perhaps causes percentage of grafting to reduce, thereby wastes starting material, influences the performance of comb-shaped copolymer; Temperature surpasses 160 ℃, has then increased to destroy the possibility of unsaturated link(age) and polyether segment, and can make the product color burn.
After esterification finishes, to reaction product thin up to mass concentration is 60%, and adding basic cpd, to adjust pH value be 6.0～8.0, oxyhydroxide or its carbonate of described basic cpd selection ammoniacal liquor, organic amine, monovalent metal or divalent metal.
The weight-average molecular weight of the concrete dispersion agent that employing the present invention makes is controlled at 10,000～80, between 000, if molecular weight is too little, water-reducing property not only occurring descends, and its guarantor ability of collapsing also descends significantly, descend if water-reducing property too greatly not only appears in molecular weight, and its guarantor ability of collapsing also descends significantly.
Compare with existing polycarboxylic acids dehydragent production technology, advantage of the present invention is obvious:
1. the present invention makes solvent with monomer, fully need not toxic property organic solvent, and the injury of effectively having avoided volatile organic solvent to bring for environment and human body.
Reaction density was 100% when 2. the present invention produced, and had improved production efficiency, had omitted the concentrated subsequent technique of Denging, had saved follow-up spendings such as packing, freight charges.
3. the steric influence of long side chain has effectively been avoided in the present invention's polymerization of carrying out main chain before grafting, has guaranteed monomeric polymerization activity, has improved monomer conversion.
4. grafting process of the present invention is produced simple, and the time is short, and the percentage of grafting height has been saved the energy, has simplified production technique.
5. the present invention's toxilic acid class polycarboxylate water-reducer of cleaning explained hereafter does not prolong concrete coagulating time, helps winter construction.
6. the present invention has made full use of the high reactivity of acid anhydrides to the alcohols material addition, has omitted the solvent esterification process, has shortened Production Flow Chart, has improved production efficiency.
Embodiment
Following examples more detailed description the method according to this invention prepare the process of polymerisate, and these embodiment provide in the mode of explanation, its purpose is to allow the personage who is familiar with this technology can understand content of the present invention and enforcement according to this, but these embodiment never limit the scope of the invention.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
In the embodiment of the invention, the weight-average molecular weight Mw of polymkeric substance adopts Wyatt technology corporation gel permeation chromatograph to measure (miniDAWN Tristar laser light scattering detector).
In the Application Example of the present invention, remove and specify that the cement that is adopted is little wild field 52.5R.P.II cement, sand is the medium sand of fineness modulus Mx=2.6, and stone is that particle diameter is the rubble of 5～20mm continuous grading.The flowing degree of net paste of cement test is carried out with reference to the GB/T8077-2000 standard, and amount of water is 87g, stirs and measures flowing degree of net paste of cement after 3 minutes on sheet glass.Air content, water-reducing rate test method are carried out with reference to the relevant regulations of GB8076-97 " concrete admixture ".The slump and slump-loss are carried out with reference to JC473-2001 " concrete pump-feed agent " relevant regulations.
Use the listed code name of table 1 in an embodiment:
The monomeric code name of table 1
Synthetic embodiment 1
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 150gB-1, be connected be heated to 45 ℃ under the condition of nitrogen after, add 98gC, stirring and dissolving.Then 1.8g chain-transfer agent D-1,18g initiator E-1 are joined in the reaction flask successively, stirring and dissolving obtains ruddy solution G1.
Other 50gB-1 packs in another is equipped with the glass flask of thermometer, agitator, dropping funnel, nitrogen inlet pipe and reflux exchanger, be connected be heated to 60 ℃ under the condition of nitrogen after, drip solution G1 and 90gA-1 simultaneously, the dropping time is 2 hours, dropwise the back and be warming up to 120 ℃ of esterifications 2 hours after 2 hours, finish building-up reactions in insulation under this temperature.Reactant is cooled to below 60 ℃, and thin up to concentration is 60%, adds 190g30%NaOH solution neutralization reactant and equals 7 to pH, obtains polymkeric substance 1, and this polymkeric substance is that 22800 aqueous solutions of polymers is formed by weight-average molecular weight.
Synthetic embodiment 2
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 400gB-2, be connected be heated to 20 ℃ under the condition of nitrogen after, add 98gC, stirring and dissolving.Then 2g chain-transfer agent D-1,3g chain-transfer agent D-2,25g initiator E-2 are joined in the reaction flask successively, stirring and dissolving obtains ruddy solution G2.
Other 200gB-2 packs in another is equipped with the glass flask of thermometer, agitator, dropping funnel, nitrogen inlet pipe and reflux exchanger, be connected be heated to 80 ℃ under the condition of nitrogen after, drip solution G2 and 170gA-2 simultaneously, the dropping time is 2 hours, dropwise the back and be warming up to 100 ℃ of esterifications 3 hours after 2 hours, finish building-up reactions in insulation under this temperature.Reactant is cooled to below 60 ℃, and thin up to concentration is 60%, adds 190g30%NaOH solution neutralization reactant and equals 7 to pH, obtains polymkeric substance 2, and this polymkeric substance is that 25500 aqueous solutions of polymers is formed by weight-average molecular weight.
Synthetic embodiment 3
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 400gB-3, be connected be heated to 60 ℃ under the condition of nitrogen after, add 98gC, stirring and dissolving.Then 4g chain-transfer agent D-2,5g initiator E-1,24g initiator E-2 are joined in the reaction flask successively, stirring and dissolving obtains ruddy solution G3.
Other 600gB-3 packs in another is equipped with the glass flask of thermometer, agitator, dropping funnel, nitrogen inlet pipe and reflux exchanger, be connected be heated to 100 ℃ under the condition of nitrogen after, drip solution G3 and 110gA-3 simultaneously, the dropping time is 2 hours, dropwise the back and be warming up to 160 ℃ of esterifications 1 hour after 2 hours, finish building-up reactions in insulation under this temperature.Reactant is cooled to below 60 ℃, and thin up to concentration is 60%, adds 190g30%NaOH solution neutralization reactant and equals 7 to pH, obtains polymkeric substance 3, and this polymkeric substance is that 28500 aqueous solutions of polymers is formed by weight-average molecular weight.
Synthetic embodiment 4
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 300gB-4, be connected be heated to 40 ℃ under the condition of nitrogen after, add 98gC, stirring and dissolving.Then 0.4g chain-transfer agent D-1,10gE-2 are joined in the reaction flask successively, stirring and dissolving obtains ruddy solution G4.
Other 300gB-4 packs in another is equipped with the glass flask of thermometer, agitator, dropping funnel, nitrogen inlet pipe and reflux exchanger, be connected be heated to 80 ℃ under the condition of nitrogen after, drip solution G4 and 145gA-4 simultaneously, the dropping time is 2 hours, dropwise the back and be warming up to 120 ℃ of esterifications 2 hours after 2 hours, finish building-up reactions in insulation under this temperature.Reactant is cooled to below 60 ℃, and thin up to concentration is 60%, adds 190g30%NaOH solution neutralization reactant and equals 7 to pH, obtains polymkeric substance 4, and this polymkeric substance is that 33000 aqueous solutions of polymers is formed by weight-average molecular weight.
Synthetic embodiment 5
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 500gB-5, be connected be heated to 60 ℃ under the condition of nitrogen after, add 98gC, stirring and dissolving.Then 3.4g chain-transfer agent D-1,15.4gE-1 are joined in the reaction flask successively, stirring and dissolving obtains ruddy solution G5.
Other 300gB-5 packs in another is equipped with the glass flask of thermometer, agitator, dropping funnel, nitrogen inlet pipe and reflux exchanger, be connected be heated to 80 ℃ under the condition of nitrogen after, drip the mixed monomer solution of solution G5 and 51.6gA-1 and 76.8g A-5 simultaneously, the dropping time is 2 hours, dropwise the back and be warming up to 140 ℃ of esterifications 2 hours after 2 hours, finish building-up reactions in insulation under this temperature.Reactant is cooled to below 60 ℃, and thin up to concentration is 60%, adds 190g30%NaOH solution neutralization reactant and equals 7 to pH, obtains polymkeric substance 5, and this polymkeric substance is that 31500 aqueous solutions of polymers is formed by weight-average molecular weight.
Synthetic embodiment 6
In the glass flask that thermometer, agitator, nitrogen inlet pipe are housed, add 300gB-6, be connected be heated to 60 ℃ under the condition of nitrogen after, add 98gC, stirring and dissolving.Then 2g chain-transfer agent D-2,6gE-1 and 4.5gE-2 are joined in the reaction flask successively, stirring and dissolving obtains ruddy solution G6.
Other 500gB-6 packs in another is equipped with the glass flask of thermometer, agitator, dropping funnel, nitrogen inlet pipe and reflux exchanger, be connected be heated to 75 ℃ under the condition of nitrogen after, drip the mixed monomer solution of solution G6 and 45gA-2 and 80gA-4 simultaneously, the dropping time is 2 hours, dropwise the back and be warming up to 120 ℃ of esterifications 3 hours after 2 hours, finish building-up reactions in insulation under this temperature.Reactant is cooled to below 60 ℃, and thin up to concentration is 60%, adds 190g30%NaOH solution neutralization reactant and equals 7 to pH, obtains polymkeric substance 6, and this polymkeric substance is that 29000 aqueous solutions of polymers is formed by weight-average molecular weight.
Application Example 1
Comparative Examples 1 is commercially available methacrylic acid and the multipolymer of methoxy polyethylene glycol methacrylate-styrene polymer (being called for short PE-1), and Comparative Examples 2 is naphthalenesulfonate formaldehyde condensation compound water reducer (being called for short FDN).For the dispersing property and the slump of estimating synthetic 1～6 synthetic toxilic acid of embodiment concrete dispersers keeps performance, carried out the flowing degree of net paste of cement test with reference to the GB/T8077-2000 standard, cement 300g, amount of water is 87g, stir and on sheet glass, measure flowing degree of net paste of cement after 3 minutes, and test clean slurry degree of mobilization after 1 hour, wherein except that the FDN volume be cement consumption 0.5%, other multipolymer volume is fixed as 0.2% of cement consumption, and experimental result sees Table 2.
Table 2 flowing degree of net paste of cement
The comb-shaped copolymer of table 2 data declaration the present invention preparation has good dispersive ability to cement, and good dispersion hold facility is arranged.
Carried out the mensuration of water-reducing rate, air content with reference to the relevant regulations test method of GB8076-97 " concrete admixture ".The slump and slump-loss have been measured with reference to JC473-2001 " concrete pump-feed agent " relevant regulations, wherein except that the FDN volume be cement consumption 0.5%, other multipolymer volume is fixed as 0.2% of cement consumption, and adjusting water consumption, to make the initial slump of fresh concrete be 21 ± 1cm, and experimental result sees Table 3.
Table 3 concrete performance
When comb-shaped graft copolymer cement dispersant volume of the present invention be cement 0.20% the time, all has the water-reducing rate more than 25%, its water-reducing rate and commercially available polycarboxylate water-reducer are suitable, and considerably beyond the level of general naphthalene series high-efficiency water-reducing agent (FDN) in the market.Not only addition ratio FDN is a half abovely, and it is very little to add the fresh concrete 1h slump-loss of concrete dispersion agent of the present invention.Above-mentioned test shows, adopts the concrete superplasticizer of the inventive method preparation just can obtain the very high slump under lower volume, and has good slump hold facility.
Claims (12)
1. the preparation method of a polycarboxylic acid concrete dispersers is characterized in that comprising the following steps:
(1) free radicals copolymerization reaction: monomer A and monomer C be according to 1.01: 1～1.5: 1 mol ratio, carrying out free radicals copolymerization reaction with monomers B under as the condition of solvent, wherein:
Monomer A is (alkyl) vinyl alkyl acid esters, represents with general formula (1):
In the general formula (1), R
1Represent hydrogen atom or methyl, n is the number of methylene radical, is 0～2 integer;
Monomers B is the monoalkoxy polyalkylene glycol ethers, represents with general formula (2):
In the general formula (2), R
2Represent the alkyl of 1～20 carbon atom; The addition quantity of p representative ring oxidative ethane is 1～200 integer; The addition quantity of q representative ring Ethylene Oxide is 0～25 integer;
Monomer C is a maleic anhydride, and its anhydride group provides the esterification ability with alcohols material, and the hydroxy-acid group that generates after its open loop provides adsorption site and electric repulsion in multipolymer;
The molar ratio of monomers B and monomer C is 0.1: 1～1: 1;
(2) graft esterification reaction: the polymkeric substance intensification esterification that step 1) is made, with grafted monomer B on the anhydride group of introducing by monomer C;
(3) after esterification finished, to the reaction product thin up, and adding alkaline matter adjustment pH value was 6.0～8.0.
2. preparation method as claimed in claim 1, the monomer A that it is characterized in that general formula (1) representative can be vinyl-acetic ester, propionate, vinyl butyrate, different propylene acetic ester, different propylene propionic ester, different propylene butyric ester, and these monomers use separately or two kinds or two or more form of mixtures use with arbitrary proportion.
3. preparation method as claimed in claim 1, it is characterized in that general formula (2) if in q equal 0, then monomers B is the linear polymer of oxyethane; When q greater than 0 the time, monomers B is the polymkeric substance of oxyethane and propylene oxide, they are linear polymer, random or segmented copolymer; Monomers B is that the monoalkoxy polyalkylene glycol ethers material of the described arbitrary type of general formula (2) uses separately, or two or more different monoalkoxy polyalkylene glycol ethers materials mix use with arbitrary proportion.
4. as claim 1 or 2 or 3 described preparation methods, it is characterized in that in the step 1), add the monomers B of a part in being connected with the batching bottle of nitrogen, drop into monomer C, initiator and chain-transfer agent more successively, stirring and dissolving is made material G; Monomers B with residual content feels secure in being connected with the reaction vessel of nitrogen, is warming up to 60～100 ℃ of temperature of reaction, drips monomer A and material G simultaneously; The monomers B of bottoming part accounts for 20～90% of monomers B gross weight.
5. preparation method as claimed in claim 4 is characterized in that initiator is the mixture of one or more arbitrary proportions in superoxide, azo compound or the hydroperoxide, and its consumption is 0.5～5% of monomer A+B+C gross weight.
6. preparation method as claimed in claim 4, it is characterized in that chain-transfer agent is the mixture of a kind of or more than one arbitrary proportions of Dodecyl Mercaptan, 16 mercaptan, mercaptoethanol, Thiovanic acid, 2 mercaptopropionic acid or 3-thiohydracrylic acid, its consumption is 0.1～2.0% of monomer A+C gross weight.
7. preparation method as claimed in claim 4, the preparation temperature that it is characterized in that material G is 20～60 ℃.
8. preparation method as claimed in claim 4 is characterized in that the time of step 1) dropping monomer A and material G is 2～3 hours, and the time of insulation reaction is 2 hours.
9. as claim 1 or 2 or 3 described preparation methods, it is characterized in that step 2) temperature of esterification is 100～160 ℃, the time is 1～3 hour.
10. as claim 1 or 2 or 3 described preparation methods, it is characterized in that the alkaline substance of using in the step 3) is selected from oxyhydroxide or its carbonate of ammoniacal liquor, organic amine, monovalent metal or divalent metal.
11. as claim 1 or 2 or 3 described preparation methods, it is characterized in that esterification finishes after, be 60% to reaction product thin up to mass concentration.
12. as claim 1 or 2 or 3 s' preparation method, the molecular weight that it is characterized in that the final product polycarboxylic acid concrete dispersers is 10,000～80, between 000.
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| CN107759126A (en) * | 2017-10-10 | 2018-03-06 | 江苏苏博特新材料股份有限公司 | A kind of gunite concrete water reducer and preparation method thereof |
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| CN102093520B (en) * | 2010-12-22 | 2012-10-03 | 江苏博特新材料有限公司 | Preparation method of hyperbranched polycarboxylic acid copolymer cement dispersant |
| CN102674741B (en) * | 2012-05-30 | 2013-07-31 | 合肥工业大学 | Polycarboxylic water reducer and synthesis method thereof |
| CN109438714B (en) * | 2018-11-09 | 2021-12-03 | 安徽森普新型材料发展有限公司 | Comb-shaped polycarboxylic acid water reducing agent and preparation method thereof |
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| CN107759126A (en) * | 2017-10-10 | 2018-03-06 | 江苏苏博特新材料股份有限公司 | A kind of gunite concrete water reducer and preparation method thereof |
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