CN105254819A - Preparation method of normal-temperature early-strength polycarboxylate superplasticizer - Google Patents
Preparation method of normal-temperature early-strength polycarboxylate superplasticizer Download PDFInfo
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 32
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- 238000000034 method Methods 0.000 claims abstract description 28
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
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- 239000011718 vitamin C Substances 0.000 claims description 8
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- 230000011218 segmentation Effects 0.000 claims description 7
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- 238000007334 copolymerization reaction Methods 0.000 claims description 3
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
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- AOAGVPIEEAAAOL-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;hydrogen peroxide Chemical compound OO.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O AOAGVPIEEAAAOL-RXSVEWSESA-N 0.000 abstract 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 229940051841 polyoxyethylene ether Drugs 0.000 abstract 1
- 229920000056 polyoxyethylene ether Polymers 0.000 abstract 1
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000004568 cement Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
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- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
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- 150000003254 radicals Chemical class 0.000 description 3
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- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
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- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZHCGVAXFRLLEFW-UHFFFAOYSA-N 2-methyl-3-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)CNC(=O)C=C ZHCGVAXFRLLEFW-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- CAQWNKXTMBFBGI-UHFFFAOYSA-N C.[Na] Chemical compound C.[Na] CAQWNKXTMBFBGI-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
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- 150000002170 ethers Chemical class 0.000 description 1
- NPUKDXXFDDZOKR-LLVKDONJSA-N etomidate Chemical compound CCOC(=O)C1=CN=CN1[C@H](C)C1=CC=CC=C1 NPUKDXXFDDZOKR-LLVKDONJSA-N 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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Abstract
The invention discloses a preparation method of a normal-temperature early-strength polycarboxylate water reducer, which is prepared by copolymerizing 80-90 wt% of methyl alkenyl polyoxyethylene ether, 6-13 wt% of acrylic acid and 4-7 wt% of acrylamide three water-soluble monomers, preferably sodium methallyl sulfonate as a chain transfer agent at normal temperature by using a single-tank segmented dropping method and a redox initiation system of hydrogen peroxide-vitamin C. The invention adopts a normal-temperature one-step method for production, has simple production process and low requirement on production equipment, and is suitable for the production of the zero-heat-source early-strength polycarboxylate superplasticizer. The early-strength polycarboxylate superplasticizer prepared by the method has high water reducing rate and good early-strength effect, and is suitable for producing concrete needing early-strength performance, such as subway segments and other prefabricated parts.
Description
Technical field
The present invention relates to concrete admixture field, be specifically related to a kind of preparation method of normal temperature Early-strength polycarboxylate superplasticizer.
Background technology
Concrete, as conventional construction substrate, along with the develop rapidly of its technology and constantly perfect, is all widely used in every field.The consequent is improving constantly the requirement of concrete performance.Workability energy is excellent, pumping construction convenient, and the performances such as super hardening, high strength, high-durability are subject to extensive concern.Early strong, super high-early concrete has market application foreground widely in prestressed high-strength tubing string, bridge, highway, harbour and maintenance thereof and reinforcing.In traditional Concrete Design, generally by reducing water-cement ratio, improve the strength grade of cement, the quality etc. that increases cement amount and improve sand material improves concrete intensity.But no matter from conservation of resources or energy-saving and emission-reduction, these methods all do not have sustainable developability, so need development new technology to realize early powerful.
High-performance poly carboxylic acid water reducing agent volume is low, water-reducing rate is high, little loss of slump, institute concrete batching excellent durability good with cement adaptability, greatly enhances concrete performance, greatly facilitates the development of concrete technology.But on the other hand, it has significantly delayed the aquation of cement, has affected the development of early age strength of concrete, use in engineering and cold environment in the winter time and be restricted.In prefabricated components, delayed coagulation lengthens the production cycle, extends curing time, improves maintenance power consumption, substantially increases production cost, reduce production efficiency.Therefore, the polycarboxylate high performance water-reducing agent with more high early strength need be researched and developed.This is not only conducive to research and development functional polyalkylene carboxylic acid water reducing agent, and all has great practice significance and theory significance to the promotion and application of poly carboxylic acid series water reducer.
The synthesis patent of the domestic high-early strength type polycarboxylic acids dehydragent found all adopts high―temperature nuclei technique at present, and some patent needs first esterification, repolymerization.And major part also needs composite organic or inorganic micromolecular accelerating component.A kind of preparation method of high-early strength type polycarboxylic acids dehydragent is disclosed in patent CN102432776A, modification polyoxyalkylenes ether containing unsaturated double-bond, (methyl) vinylformic acid, undersaturated sulfonate, acrylamide four kinds of monomers under molecular weight regulator existent condition, are carried out aqueous solution copolymerization by free radical initiation and form by this patent.The method needs to be polymerized under the high temperature of 50 ~ 70 DEG C, and needs the polyoxyalkylenes ether adopting modification, limits the popularization of the method.In patent CN103396028A, disclose a kind of preparation method of high Early-strength polycarboxylate superplasticizer, be polymerized under the effect of molecular weight chain initiator, chain-transfer agent by monomers such as methacrylic Soxylat A 25-7, acrylamide, methylpropene sodium sulfonate, vinylformic acid, acroleic acid esterification hydramine.The method needs to carry out esterification at 100 ~ 140 DEG C, at 65 ~ 80 DEG C, carry out polyreaction, and adopt high temperature two-step approach to produce, complex manufacturing, is not suitable for the popularization on a large scale of suitability for industrialized production.A kind of preparation method of ethers Early-strength polycarboxylate superplasticizer is disclosed in patent CN103450408A, by unsaturated ester, di-alcohol monoisopropanolamine, 2-acrylamido-methyl propanesulfonic acid and methacrylic polyoxyethylene poly-oxygen propylene aether etc. are as primary chemical synthesis material, at catalyzer, initiator, under the effect of chain-transfer agent etc., be prepared from through amidation and polymerization process under certain condition, the method needs to carry out amidate action at 70 ~ 100 DEG C, copolyreaction is carried out at 50 ~ 70 DEG C, polymerization technique is complicated, production cycle is long, be not suitable for suitability for industrialized production.
Summary of the invention
The object of the invention is the defect existed for above-mentioned technology, provide a kind of water-reducing rate high, early effective by force, be applicable to the production method of normal temperature Early-strength polycarboxylate superplasticizer suitability for industrialized production, this production method technique is simple, and production cost is low.
For realizing foregoing invention, the present invention adopts following technical scheme:
A kind of preparation method of normal temperature Early-strength polycarboxylate superplasticizer, it is characterized in that: it by methyl thiazolinyl Soxylat A 25-7, vinylformic acid, acrylamide three kinds of water-soluble monomers at normal temperatures, preferable methyl sodium allylsulfonate is as chain-transfer agent, adopt single tank segmentation dripping method, " hydrogen peroxide-vitamins C " redox initiation system copolymerization is utilized to form, the mass percent of described three kinds of monomers is: monomer methyl thiazolinyl Soxylat A 25-7 80 ~ 90%, monomeric acrylic 6 ~ 13%, monomeric acrylamide 4 ~ 7%.
The preparation method of described normal temperature Early-strength polycarboxylate superplasticizer, is characterized in that, specifically comprise the steps:
(1) joined in reactor by methyl thiazolinyl Soxylat A 25-7, then add a certain amount of softening water, stir, the add-on of described softening water is (90 ~ 100) % of above-mentioned monomer mass;
(2) be that the aqueous solution of hydrogen peroxide of (20 ~ 50) % joins in reactor by concentration, stir, reactor temperature is 10 ~ 30 DEG C, and the add-on of aqueous hydrogen peroxide solution is (0.5 ~ 1.7) % of methyl thiazolinyl Soxylat A 25-7, vinylformic acid and acrylamide three kinds of monomer total masses;
(3) in concentration is the vinylformic acid of (10 ~ 15) % and the aqueous solution of acrylamide two kinds of monomers, vitamins C and methylpropene sodium sulfonate is added, stir, form and drip solution, adopt single tank segmentation dripping method, dropping solution is added drop-wise in reactor, continuous stirring, require that the time for adding dripping solution controls at 3 ~ 3.2h, front 1h drips the dropping solution of half quality, drip the dropping solution of second half quality remaining time, drip solution and dropwise follow-up continuation of insurance about temperature 1h, the add-on of methylpropene sodium sulfonate is (1.5 ~ 2.2) % of methyl thiazolinyl Soxylat A 25-7 quality, ascorbic add-on is methyl thiazolinyl Soxylat A 25-7, (0.10 ~ 0.25) % of vinylformic acid and acrylamide three kinds of monomer total masses,
(4) pH value regulating product is 6 ~ 7, can obtain target product.
The preparation method of described normal temperature Early-strength polycarboxylate superplasticizer, it is characterized in that: described methyl thiazolinyl Soxylat A 25-7 is block structure, outward appearance is that white is to light yellow sheet, degree of unsaturation >=0.3, hydroxyl value is 23.4 ~ 26.7mgKOH/g, the pH value of the 1% methyl thiazolinyl Soxylat A 25-7 aqueous solution is 5.0 ~ 7.0, double bond retention rate >=85.0%, and its chemical structural formula is as follows:
Molecular weight is 2000 ~ 5000, and wherein m value is the arbitrary integer in 32 ~ 86, and n value is the arbitrary integer in 0 ~ 10.
The preparation method of described normal temperature Early-strength polycarboxylate superplasticizer, it is characterized in that: described single tank segmentation dripping method refers to all dropping monomers all in same dropping tank, polymerization drips monomer dropping speed soon early stage, and it is slow that the polymerization later stage drips monomer dropping speed.
The polycarboxylate water-reducer that the inventive method is obtained.
Normal temperature Early-strength polycarboxylate superplasticizer obtained by the inventive method, do not need heating installation, production technique is simple, low in raw material price, be applicable to the production of zero thermal source high-early strength type polycarboxylic acids dehydragent, there is significant economic benefit, social benefit and huge promotional value.
The following beneficial effect that the present invention compared with prior art has:
(1) the present invention adopts hydrogen peroxide-ascorbic normal temperature oxidation reduction initiating system, when namely temperature of reaction is the normal temperature of 10 ~ 30 DEG C, adopts the suitability for industrialized production of this initiator system all without the need to heating, polyreaction can be made normally to carry out.Therefore the production technique of the water reducer of patent of the present invention is more simple, lower to the requirement of equipment, is particularly suitable for the production of zero thermal source Early-strength polycarboxylate superplasticizer.
(2) the present invention adopts normal temperature single stage method to prepare Early-strength polycarboxylate superplasticizer, and the production cycle is shorter, improves the utilization ratio of production unit.
(3) the present invention adopts single tank to drip, and simplifies production equipment and process.Reaction monomers kind used is few, and Easy dosing, very easily operates and implement.
(4) the present invention's method of adopting segmentation to drip, early stage, monomer dropping speed was fast, made up the polymerization mechanism that free radical causes slowly, and late monomer rate of addition is slow, because free radical increases and the speed of termination is fast.The Early-strength polycarboxylate superplasticizer structure utilizing this dropping method to produce is more even, early the excellent property such as strong, water-reducing rate, flowing retentivity.
(5) production technique of the present invention compares patent CN102432776A, does not need heating.Compare patent CN103396028A and Patents, adopt One-step production, production technique is easier, and use range is wider.
(6) the present invention is directed to normal temperature Early-strength polycarboxylate superplasticizer and invent, also the production of high temperature Early-strength polycarboxylate superplasticizer is applicable to after regulating the ratio between each monomer, the production technique of Early-strength polycarboxylate superplasticizer has been enriched in its preparation and invention, is that the production of zero thermal source high-early strength type polycarboxylic acids dehydragent provides technical guarantee.
The method of concrete enforcement
Example 1
By molecular weight be 2900 methyl thiazolinyl Soxylat A 25-7 2400kg add in reactor, then add 2400kg softening water make it dissolve, add the aqueous hydrogen peroxide solution 44.6kg of 28.9% until completely dissolved.After stirring, at temperature is 10 ~ 30 DEG C, the mixing dripping vinylformic acid, acrylamide, vitamins C, methylpropene sodium sulfonate and water drips solution 2222.2kg, in this dropping liquid, vinylformic acid is 217kg, acrylamide is 107kg, vitamins C is 5.8kg, and methylpropene sodium sulfonate is 52.4kg, and water is 1840kg.The time for adding of this dropping liquid controls at 3 ~ 3.2h, and front 1h drips the dropping liquid of half quality, and drip the dropping liquid of second half quality remaining time, dropping liquid dropwises follow-up continuation of insurance temperature 1h.Adopt 30%NaOH solution to regulate the pH value of product to be 7, obtained product is the high-early strength type polycarboxylic acids dehydragent of ordinary temperature production.
Example 2
By molecular weight be 4000 methyl thiazolinyl Soxylat A 25-7 2400kg add in reactor, then add 2400kg softening water make it dissolve, add the ammonium persulfate aqueous solution 13.4kg of 28.9% until completely dissolved.After stirring, at temperature is 10 ~ 30 DEG C, the mixing dripping vinylformic acid, acrylamide, vitamins C, methylpropene sodium sulfonate and water drips solution 1845.6kg, in this dropping liquid, vinylformic acid is 172.8kg, acrylamide is 85.2kg, vitamins C is 3.6kg, and methylpropene sodium sulfonate is 38kg, and water is 1546kg.The time for adding of this dropping liquid controls at 3 ~ 3.2h, and front 1h drips the dropping liquid of half quality, and drip the dropping liquid of second half quality remaining time, dropping liquid dropwises follow-up continuation of insurance temperature 1h.Adopt 30%NaOH solution to regulate the pH value of product to be 7, obtained product is the high-early strength type polycarboxylic acids dehydragent of ordinary temperature production.
Comparative example 3 (embodiment 1 in patent CN103396028A)
(1) esterification: by vinylformic acid and hydramine under 120 degree of conditions, with sulfuric acid as catalyzer, Resorcinol as stopper, vinylformic acid: hydramine: sulfuric acid: the molar ratio of Resorcinol is 1:1:0.03:0.005, and esterification 6h obtains the acroleic acid esterification hydramine with unsaturated link(age);
(2) be polymerized: by 120.00 parts of molecular weight be 2400 methacrylic Soxylat A 25-7 and water some, put into reaction vessel, heat up, at 70 ± 5 DEG C of temperature, stirring makes reactant dissolve completely, 10.08 parts of vinylformic acid are added again in container, 6.33 part methylpropene sodium sulfonate, 5.33 part acrylamide, 5.01 parts of acroleic acid esterification hydramine, drip again 93.00 parts of mass percents be 5% ammonium persulfate solution and 7.2 parts of mass percents be the mercaptopropionic acid of 5%, control rate of addition, dripped off at 120 ± 10 minutes, maintain the temperature at 70 ± 2 DEG C, continue reaction 2h,
(3) add sodium hydroxide solution adjustment PH=6.5 ± 5 that 2.53 parts of mass percents are 40% after cooling again, obtain high Early-strength polycarboxylate superplasticizer of the present invention.
Specific embodiment
The above-mentioned normal temperature Early-strength polycarboxylate superplasticizer that the present invention provides, the hardening accelerator of comparative example 3 and market similar-type products, according to paste flowing degree test (GB/T8077-2000): adopt reference cement, test flowing degree of net paste of cement according to GB/T8077-87, detected result is as shown in table 1 below.
Table 1 the property of neat cement grout test result
The above-mentioned normal temperature Early-strength polycarboxylate superplasticizer that the present invention provides is by carrying out concrete performance contrast with the hardening accelerator and market similar-type products of comparative example 3, and concrete formulation is: conch PO42.5 cement: flyash: sand: cobble: water: admixture=547.5:97.5:1020:1530:195:6.45.Comparing result is as shown in table 2 below.
Table 2 concrete performance comparing result
From table 1 and table 2 test result, the Early-strength polycarboxylate superplasticizer water-reducing rate synthesized by the present invention and concrete ultimate compression strength in each length of time is adopted all to be better than comparative example 3 and BASF411 hardening accelerator.
In addition to the implementation, the present invention can also have other embodiments, and as the dropping monomer adopting front 1.5h to drip 2/3rds quality, rear 1.5h drips the dropping monomer of 1/3rd quality; Change each monomer ratio, adopt pyroreaction; Adopt the methyl thiazolinyl polyoxyethylene, polyethenoxy ether etc. of other molecular weight.All employings are equal to the technical scheme of replacement or equivalent transformation formation, are the protection domain of application claims.
Claims (5)
1. the preparation method of a normal temperature Early-strength polycarboxylate superplasticizer, it is characterized in that: its by methyl thiazolinyl Soxylat A 25-7, vinylformic acid, acrylamide three kinds of water-soluble monomers as raw material, at normal temperatures, select methylpropene sodium sulfonate as chain-transfer agent, adopt single tank segmentation dripping method, " hydrogen peroxide-vitamins C " redox initiation system copolymerization is utilized to form, the mass percent of described three kinds of monomers is: monomer methyl thiazolinyl Soxylat A 25-7 80 ~ 90%, monomeric acrylic 6 ~ 13%, monomeric acrylamide 4 ~ 7%.
2. the preparation method of normal temperature Early-strength polycarboxylate superplasticizer according to claim 1, is characterized in that, specifically comprise the steps:
(1) joined in reactor by methyl thiazolinyl Soxylat A 25-7, then add a certain amount of softening water, stir, the add-on of described softening water is 90 ~ 100% of above-mentioned monomer methyl thiazolinyl Soxylat A 25-7 quality;
(2) by concentration be 20 ~ 50% the aqueous solution of hydrogen peroxide join in reactor, stir, reactor temperature is 10 ~ 30 DEG C, and the add-on of aqueous hydrogen peroxide solution is 0.5 ~ 1.7% of methyl thiazolinyl Soxylat A 25-7, vinylformic acid and acrylamide three kinds of monomer total masses;
(3) concentration be 10 ~ 15% vinylformic acid and acrylamide two kinds of monomers the aqueous solution in add vitamins C and methylpropene sodium sulfonate, stir, form and drip solution, adopt single tank segmentation dripping method, dropping solution is added drop-wise in reactor, continuous stirring, require that the time for adding dripping solution controls at 3 ~ 3.2h, front 1h drips the dropping solution of half quality, drip the dropping solution of second half quality remaining time, drip solution and dropwise follow-up continuation of insurance about temperature 1h, the add-on of methylpropene sodium sulfonate is 1.5 ~ 2.2% of methyl thiazolinyl Soxylat A 25-7 quality, ascorbic add-on is methyl thiazolinyl Soxylat A 25-7, 0.10 ~ 0.25% of vinylformic acid and acrylamide three kinds of monomer total masses,
(4) pH value regulating product is 6 ~ 7, can obtain target product.
3. the preparation method of normal temperature Early-strength polycarboxylate superplasticizer according to claim 1 and 2, it is characterized in that: described methyl thiazolinyl Soxylat A 25-7 is block structure, outward appearance is that white is to light yellow sheet, degree of unsaturation >=0.3, hydroxyl value is 23.4 ~ 26.7mgKOH/g, the pH value of the 1% methyl thiazolinyl Soxylat A 25-7 aqueous solution is 5.0 ~ 7.0, double bond retention rate >=85.0%, and its chemical structural formula is as follows:
Molecular weight is 2000 ~ 5000, and wherein m value is the arbitrary integer in 32 ~ 86, and n value is the arbitrary integer in 0 ~ 10.
4. the preparation method of normal temperature Early-strength polycarboxylate superplasticizer according to claim 1 and 2, it is characterized in that: described single tank segmentation dripping method refers to all dropping monomers all in same dropping tank, polymerization drips monomer dropping speed soon early stage, and it is slow that the polymerization later stage drips monomer dropping speed.
5. the polycarboxylate water-reducer that obtains of the preparation method of a normal temperature Early-strength polycarboxylate superplasticizer according to claim 1.
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| CN105418856A (en) * | 2015-12-18 | 2016-03-23 | 中建商品混凝土有限公司 | Preparation method of synthesis of polycarboxylate superplasticizer at room temperature in wide temperature range |
| CN105801763A (en) * | 2016-02-25 | 2016-07-27 | 四川恒泽建材有限公司 | Early strength polycarboxylic high performance water-reducing agent and preparation method thereof |
| CN107056992A (en) * | 2016-12-31 | 2017-08-18 | 武汉理工大学 | A kind of feature ethers polycarboxylic acid water reducing agent and preparation method thereof |
| CN107446090A (en) * | 2017-09-07 | 2017-12-08 | 江苏百瑞吉新材料有限公司 | A kind of synthetic method of Early-strength polycarboxylate superplasticizer |
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| CN105418856A (en) * | 2015-12-18 | 2016-03-23 | 中建商品混凝土有限公司 | Preparation method of synthesis of polycarboxylate superplasticizer at room temperature in wide temperature range |
| CN105801763A (en) * | 2016-02-25 | 2016-07-27 | 四川恒泽建材有限公司 | Early strength polycarboxylic high performance water-reducing agent and preparation method thereof |
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| CN113968946A (en) * | 2021-10-28 | 2022-01-25 | 安徽中铁工程材料科技有限公司 | Concrete thickening and water-retaining agent and preparation method thereof |
| CN113968946B (en) * | 2021-10-28 | 2023-09-08 | 安徽中铁工程材料科技有限公司 | Concrete thickening water-retaining agent and preparation method thereof |
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