CN103865005A - Water-soluble comb-like polymer and synthesis method thereof - Google Patents
Water-soluble comb-like polymer and synthesis method thereof Download PDFInfo
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- CN103865005A CN103865005A CN201410024128.1A CN201410024128A CN103865005A CN 103865005 A CN103865005 A CN 103865005A CN 201410024128 A CN201410024128 A CN 201410024128A CN 103865005 A CN103865005 A CN 103865005A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title abstract 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 15
- 229920001807 Urea-formaldehyde Polymers 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 18
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 18
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 238000010189 synthetic method Methods 0.000 claims description 11
- 239000004160 Ammonium persulphate Substances 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000012986 chain transfer agent Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 claims description 5
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical group FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 239000004159 Potassium persulphate Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 40
- 239000004567 concrete Substances 0.000 abstract description 25
- 239000004568 cement Substances 0.000 abstract description 13
- 238000002156 mixing Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 229920005646 polycarboxylate Polymers 0.000 description 11
- 238000011160 research Methods 0.000 description 11
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- -1 acrylate monomethyl ether ester Chemical class 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical group OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a water reducing agent for concrete and a synthesis method thereof, and specifically relates to a water-soluble comb-like polymer and a synthesis method thereof. The synthesis method of the water-soluble comb-like polymer comprises the following steps: preparing materials, blending materials, dropwise adding, curing and neutralizing. The water-soluble comb-like polymer prepared by the synthesis method is characterized in that the main chain of the polymer is polymerized from vinyl carboxylic acids such as acrylic acid and methylacrylic acid, while the side chain of the same is constructed by a water-soluble linear urea resin; the polymer is simple in synthesis process, has excellent cement dispersibility and can be taken as a novel concrete water reducing agent.
Description
Technical field
The present invention relates to the reinforcement of concrete water reducer and synthetic method, specifically, relate to a kind of water-soluble comb-shaped polymer and synthetic method.
Background technology
Concrete admixture refers to and mixes in concrete, is not more than cement quality 5%, and can improve on request or improve the additive of concrete mixture characteristic or properties of hardened concrete.In concrete admixture, usage quantity maximum be water reducer, it can be in the water consumption that ensures significantly reduce under the prerequisite of normal construction concrete mix, thereby improves concrete strength, reduces folk prescription concrete cement consumption, reduces costs.According to market statistics, water reducer accounts for 70%～80% of concrete admixture total amount on market.
According to size and the raw material sources etc. of the development course of water reducer, water-reducing rate, generally water reducer product is divided into three generations: first-generation called after ordinary water-reducing agent, taking calcium lignin sulphonate, sodium lignosulfonate as representative, comprise Weibull, brown coal etc., water-reducing rate is less than 10%; The s-generation is referred to as high efficiency water reducing agent, and water-reducing rate is greater than 18%, taking naphthalene series high-efficiency water-reducing agent as representative, comprises sulfamate water reducer, melmac water reducer, aliphatic water reducing agent etc.; Third generation water reducer is called after high-performance water reducing agent in GB8076-2008, and water-reducing rate is greater than 25%, because its currently available products is polycarboxylate series products, is called again high performance water reducing agent of polyocarboxy acid.This three generations's water reducer respectively has performance characteristics, has application in the market.
Compared with the first-generation, s-generation water reducer, polycarboxylic acid series high efficiency water reducing agent has advantages of following outstanding: to the dispersed ability of cement is stronger, higher, the concrete Slump Time losing of Large of water-reducing rate is less, concrete wraps, workability good, high-grade concrete viscosity is little; Concrete gain in strength is large, shrink little, impervious good, resistance to corrosion is strong.In addition, polycarboxylate water-reducer itself not contains sodium sulfate, containing ammonia, containing formaldehyde, without chlorine, alkali-free almost.Therefore, can say, polycarboxylate water-reducer is high performance modern water reducer product truly.At present, high-grade concrete on market, self-leveling concrete, overlength pump concrete, maritime concrete, concrete for railway, concrete for airport, for highway, concrete, water resources dam, water power all use polycarboxylate water-reducer configuration with concrete etc., by statistics in 2013, normal concrete used poly carboxylic acid to exceed 50%.
The large monomer difference using according to polycarboxylate water-reducer, high performance water reducing agent of polyocarboxy acid can be subdivided into again: 1, ester class high performance water reducing agent of polyocarboxy acid, the large monomer of use is methacrylic acid, polyalkylene glycol acrylate monomethyl ether ester); 2, ethers high performance water reducing agent of polyocarboxy acid, the large monomer of use is vinyl carbinol polyglycol ether, methallyl alcohol polyglycol ether, prenol polyglycol ether etc.By these large monomers, we can find out, existing polycarboxylic acid series high efficiency water reducing agent side chain is polyoxyethylene, and different is only the on-link mode (OLM) of polyoxyethylene and main chain.
Abroad Japan to high performance water reducing agent of polyocarboxy acid research and application country the earliest.As catalyst company, flower king, wheat think of top grade have had polycarboxylate water-reducer product very early.The Chinese patent that relates to polycarboxylate water-reducer of Nippon Shokubai Co., Ltd's application has CN97126334, CN97126334, CN99127479, CN200580023517, CN200410033714, CN200610071910, CN200610071910, CN200980117278 etc., and these patents have comprised many poly carboxylic acid and synthesized and compounded technology.Korea S is also polycarboxylate water-reducer research and application country early, as LG chemistry, Qing Dou Co., Ltd. etc., almost all uses polycarboxylate water-reducer to Korea S in 2006 except solid water reducer.The ground recent two decades such as America and Europe come the research of carboxylic acid water reducing agent aspect always more deep, and the use of poly carboxylic acid is more extensive, and the Chinese patent of application has the CN200880111132 of BASF AG, the CN201080005070 of W. R. Grace & Co etc.
The middle and later periods nineties 20th century, the novel water reducer that more domestic colleges and universities, institute etc. at the non-naphthalene of research are all.Although the actual quantity that domestic relevant article is delivered is many, few in aspect researchs such as the impacts of the mechanism of action, Water-reducing Admixtures To Cements aquation and slurry microstructure, only in the academic dissertation of some colleges and universities, slightly inquire into.Synthetic product also mainly rests on laboratory stage, also has suitable distance from suitability for industrialized production.After 2005, the domestic research boom that rises polycarboxylate water-reducer, many investigators constantly explore the synthetic method of high-performance water reducing agent by molecular designing approach, the development research of polycarboxylate high performance water-reducing agent makes great progress, in Beijing, Shanghai, suitability for industrialized production has been realized on the ground such as Jiangsu and Zhejiang Provinces, as Shanghai architecture science research institute, Architecture Science Inst. of Jiangsu Prov., Shandong architecture science research institute, Chinese Research Institute for Building Sciences etc., the patent of application has China Building Material Scientific Research General Institute CN200910077550 in recent years, CN200910077550, Beijing Architectural Engineering Inst CN200810134808, the CN200810134808 of Architecture Science Inst. of Jiangsu Prov., CN200710190296, CN200710190295, CN200710190297, CN200710190297, CN200710190296, CN200710131423, CN200710131423, CN200710024393, CN200710024393 etc.
Summary of the invention
The object of the invention is to, it is to be polymerized by the vinyl carboxylic acid such as vinylformic acid, methacrylic acid that a kind of main chain is provided, and side chain is water-soluble comb-shaped polymer and the synthetic method of water-soluble linear urea-formaldehyde resin.
The present invention is achieved through the following technical solutions:
A kind of water-soluble comb-shaped polymer, is characterized in that: this polymer repeat unit and molecular formula can be represented by following general formula:
Wherein R
1for H or CH
3, m=40～45, n=15～20, L=10～15.
The synthetic method of described water-soluble comb-shaped polymer, comprises the steps:
1, get the raw materials ready: liquid caustic soda and water that the macromonomer aqueous solution, initiator, chain-transfer agent, minor comonomer, the concentration that concentration is 50% is 30%, the mass percent of above-mentioned various raw materials is respectively: the macromonomer aqueous solution 62%, initiator 0.25%-0.3%, chain-transfer agent 0.2%-0.42%, minor comonomer 3.4%-4%, liquid caustic soda 6%, surplus are water;
2, batching
2A, in conversion unit, add the macromonomer aqueous solution, open and stir, and be warming up to 60 DEG C-85 DEG C, stand-by;
2B, be equivalent by moisture two parts, a copy of it and initiator fully dissolve, and the solution of making adds in a dropping equipment; Another part fully dissolves with chain-transfer agent and minor comonomer, and the solution of making joins in No. two dropping equipment;
It should be noted that: in blending process, accurate measurement, the solution in the solution in a dropping equipment and No. two dropping equipment can not be in contact with one another, if be in contact with one another, also can react even if temperature is very low, causes end product quality variation; In addition, temperature will be controlled at design temperature ± 2 DEG C;
3, drip
Solution in solution in a dropping equipment and No. two dropping equipment is at the uniform velocity added drop-wise in conversion unit simultaneously, time for adding is 3 hours, ensure that, after 3 hours, the material in the material in a dropping equipment and No. two dropping equipment is all added drop-wise in conversion unit; In dropping process, temperature maintains 60 DEG C-85 DEG C;
4, slaking: after being added dropwise to complete, holding temperature is constant, insulation slaking 1 hour;
5, neutralization: be cooled to 45 DEG C, to conversion unit, time for adding 20 minutes, ensures that after 20 minutes, liquid caustic soda is all added drop-wise in conversion unit by slow liquid caustic soda underframe.
say further:
The described macromonomer aqueous solution is the double bond containing water-soluble linear urea-formaldehyde resin of the end group oligopolymer aqueous solution, and the repeating unit of this oligopolymer and molecular formula are:
Described initiator is ammonium persulphate, Sodium Persulfate or Potassium Persulphate, and wherein, ammonium persulphate decomposition temperature is minimum, decomposition rate is the fastest, and Sodium Persulfate takes second place, and Potassium Persulphate decomposition temperature is the highest, decomposition rate is the slowest.
Described chain-transfer agent is sodium allyl sulfonate, methallylsulfonic acid sodium, Thiovanic acid or thiohydracrylic acid, and their chain transfer activity raises according to above-mentioned order, and consumption successively reduces.
Described minor comonomer is acrylic or methacrylic acid.
beneficial effect:the water-soluble comb-shaped polymer that adopts the present invention to prepare, main chain is to be polymerized by the vinyl carboxylic acid such as vinylformic acid, methacrylic acid, and side chain is water-soluble linear urea-formaldehyde resin, and the synthesis technique of this polymkeric substance is simple, there is good cement dispersiveness, can be as a kind of novel cement water reducing agent.
Embodiment
Below with reference to specific embodiment, the present invention is described further.
embodiment 1
1, in the there-necked flask that is 1000ml at capacity, adding 620g concentration is the urea-formaldehyde resin oligopolymer aqueous solution of 50% acrylamide end-blocking, opens and stirs, and is warming up to 60～65 DEG C;
A expects configuration: in a 250ml beaker, add 2.5g ammonium persulphate and 140g water, stirring and dissolving; B expects configuration: in another 250ml beaker, add 2g thiohydracrylic acid, 34g vinylformic acid and 140g water, stirring and dissolving;
2, in there-necked flask, drip A material and B material simultaneously, within 3 hours, drip off, in dropping process, holding temperature is constant;
3, after being added dropwise to complete, holding temperature is constant, insulation slaking 1 hour;
4, be cooled to 45 DEG C, adding concentration is 30% sodium hydroxide 60g, slowly drips, and within 20 minutes, drips off.
embodiment 2
1, in the there-necked flask that is 1000ml at capacity, adding 620g concentration is the urea-formaldehyde resin oligopolymer aqueous solution of 50% acrylamide end-blocking, opens and stirs, and is warming up to 60～65 DEG C;
A expects configuration: in a 250ml beaker, add 2.5g ammonium persulphate and 140g water, stirring and dissolving.B expects configuration: in another 250ml beaker, add 2.5g Thiovanic acid, 34g vinylformic acid and 140g water, stirring and dissolving;
2, in there-necked flask, drip A material and B material simultaneously, within 3 hours, drip off, in dropping process, holding temperature is constant;
3, after being added dropwise to complete, holding temperature is constant, insulation slaking 1 hour;
4, be cooled to 45 DEG C, adding concentration is 30% sodium hydroxide 60g, slowly drips, and within 20 minutes, drips off.
embodiment 3
1, in the there-necked flask that is 1000ml at capacity, adding 620g concentration is the urea-formaldehyde resin oligopolymer aqueous solution of 50% acrylamide end-blocking, opens and stirs, and is warming up to 60～65 DEG C;
A expects configuration: in a 250ml beaker, add 2.5g ammonium persulphate and 140g water, stirring and dissolving; B expects configuration: in another 250ml beaker, add 3.66g methallylsulfonic acid sodium, 34g vinylformic acid and 140g water, stirring and dissolving;
2, in there-necked flask, drip A material and B material simultaneously, within 3 hours, drip off, in dropping process, holding temperature is constant;
3, after being added dropwise to complete, holding temperature is constant, insulation slaking 1 hour;
4, be cooled to 45 DEG C, adding concentration is 30% sodium hydroxide 60g, slowly drips, and within 20 minutes, drips off.
embodiment 4
1, in the there-necked flask that is 1000ml at capacity, adding 620g concentration is the urea-formaldehyde resin oligopolymer aqueous solution of 50% acrylamide end-blocking, opens and stirs, and is warming up to 60～65 DEG C;
A expects configuration: in a 250ml beaker, add 2.5g ammonium persulphate and 140g water, stirring and dissolving.B expects configuration: in another 250ml beaker, add 4.2g sodium allyl sulfonate, 36g vinylformic acid and 140g water, stirring and dissolving;
2, in there-necked flask, drip A material and B material simultaneously, within 3 hours, drip off, in dropping process, holding temperature is constant;
3, after being added dropwise to complete, holding temperature is constant, insulation slaking 1 hour;
4, be cooled to 45 DEG C, adding concentration is 30% sodium hydroxide 60g, slowly drips, and within 20 minutes, drips off.
embodiment 5
1, in the there-necked flask that is 1000ml at capacity, adding 620g concentration is the urea-formaldehyde resin oligopolymer aqueous solution of 50% acrylamide end-blocking, opens and stirs, and is warming up to 70～75 DEG C;
A expects configuration: in a 250ml beaker, add 2.7g Sodium Persulfate and 140g water, stirring and dissolving.B expects configuration: in another 250ml beaker, add 3.89g methallylsulfonic acid sodium, 40g vinylformic acid and 140g water, stirring and dissolving;
2, in there-necked flask, drip A material and B material simultaneously, within 3 hours, drip off, in dropping process, holding temperature is constant;
3, after being added dropwise to complete, holding temperature is constant, insulation slaking 1 hour;
4, be cooled to 45 DEG C, adding concentration is 30% sodium hydroxide 60g, slowly drips, and within 20 minutes, drips off.
embodiment 6
1, in the there-necked flask that is 1000ml at capacity, adding 620g concentration is the urea-formaldehyde resin oligopolymer aqueous solution of 50% acrylamide end-blocking, opens and stirs, and is warming up to 70～75 DEG C;
A expects configuration: in a 250ml beaker, add 2.7g Sodium Persulfate and 140g water, stirring and dissolving.B expects configuration: in another 250ml beaker, add 4.2g sodium allyl sulfonate, 40g vinylformic acid and 140g water, stirring and dissolving;
2, in there-necked flask, drip A material and B material simultaneously, within 3 hours, drip off, in dropping process, holding temperature is constant;
3, after being added dropwise to complete, holding temperature is constant, insulation slaking 1 hour;
4, be cooled to 45 DEG C, adding concentration is 30% sodium hydroxide 60g, slowly drips, and within 20 minutes, drips off.
embodiment 7
1, in the there-necked flask that is 1000ml at capacity, adding 620g concentration is the urea-formaldehyde resin oligopolymer aqueous solution of 50% acrylamide end-blocking, opens and stirs, and is warming up to 80～85 DEG C;
A expects configuration: in a 250ml beaker, add 3.0g Potassium Persulphate and 140g water, stirring and dissolving; B expects configuration: in another 250ml beaker, add 4.2g sodium allyl sulfonate, 40g vinylformic acid and 140g water, stirring and dissolving;
2, in there-necked flask, drip A material and B material simultaneously, within 4.5 hours, drip off, in dropping process, holding temperature is constant;
3, after being added dropwise to complete, holding temperature is constant, insulation slaking 1 hour;
4, be cooled to 45 DEG C, adding concentration is 30% sodium hydroxide 60g, slowly drips, and within 20 minutes, drips off.
embodiment 8
1, in the there-necked flask that is 1000ml at capacity, adding 620g concentration is the urea-formaldehyde resin oligopolymer aqueous solution of 50% acrylamide end-blocking, opens and stirs, and is warming up to 60～65 DEG C;
A expects configuration: in a 250ml beaker, add 2.5g ammonium persulphate and 140g water, stirring and dissolving; B expects configuration: in another 250ml beaker, add 2g thiohydracrylic acid, 30g vinylformic acid, 10g methyl-prop diluted acid and 140g water, stirring and dissolving;
2, in there-necked flask, drip A material and B material simultaneously, within 3 hours, drip off, in dropping process, holding temperature is constant;
3, after being added dropwise to complete, holding temperature is constant, insulation slaking 1 hour;
4, be cooled to 45 DEG C, adding concentration is 30% sodium hydroxide 60g, slowly drips, and within 20 minutes, drips off.
comparative example 1
1, in the there-necked flask that is 1000ml at capacity, add 310g methacrylic Soxylat A 25-7 (molecular weight 2400) and water 310g, open and stir, dissolve, be warming up to 60～65 DEG C;
A expects configuration: in a 250ml beaker, add 2.8g ammonium persulphate and 140g water, stirring and dissolving; B expects configuration: in another 250ml beaker, add 4.0g methallylsulfonic acid sodium, 40g vinylformic acid and 140g water, stirring and dissolving;
2, in there-necked flask, drip A material and B material simultaneously, within 3 hours, drip off, in dropping process, holding temperature is constant;
3, after being added dropwise to complete, holding temperature is constant, insulation slaking 1 hour;
4, be cooled to 45 DEG C, adding concentration is 30% sodium hydroxide 60g, slowly drips, and within 20 minutes, drips off.
comparative example 2
1, in the there-necked flask that is 1000ml at capacity, add 310g isopentene group Soxylat A 25-7 (molecular weight 2400) and water 310g, open and stir, dissolve, be warming up to 60～65 DEG C;
A expects configuration: in a 250ml beaker, add 2.8g ammonium persulphate and 140g water, stirring and dissolving; B expects configuration: in another 250ml beaker, add 2.4g thiohydracrylic acid, 40g vinylformic acid and 140g water, stirring and dissolving;
2, in there-necked flask, drip A material and B material simultaneously, within 3 hours, drip off, in dropping process, holding temperature is constant;
3, after being added dropwise to complete, holding temperature is constant, insulation slaking 1 hour;
4, be cooled to 45 DEG C, adding concentration is 30% sodium hydroxide 60g, slowly drips, and within 20 minutes, drips off.
[the dispersed experiment of cement]
The product of embodiment 1～7 product and comparative example 1～2 is configured to respectively to 10% solution, by 2% of cement mixing content, only starches experiment according to GB8076-2008 making cement.
Cement: standard cement, consumption 300g;
Water: deionized water, consumption 81g;
Admixture: 6g.
Dispersed experimental result is as shown in the table:
Flowing degree of net paste of cement
| Sample | Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Degree of mobilization/mm | 240 | 260 | 255 | 250 | 255 | 220 | 230 | 210 | 200 | 210 |
Claims (6)
1. a water-soluble comb-shaped polymer, is characterized in that: this polymer repeat unit and molecular formula can be represented by following general formula:
Wherein R
1for H or CH
3, m=40～45, n=15～20, L=10～15.
2. the synthetic method of water-soluble comb-shaped polymer as claimed in claim 1, is characterized in that: comprise the steps:
(1) get the raw materials ready: liquid caustic soda and water that the macromonomer aqueous solution, initiator, chain-transfer agent, minor comonomer, the concentration that concentration is 50% is 30%, the mass percent of above-mentioned various raw materials is respectively: the macromonomer aqueous solution 62%, initiator 0.25%-0.3%, chain-transfer agent 0.2%-0.42%, minor comonomer 3.4%-4%, liquid caustic soda 6%, surplus are water;
(2) batching
(2A) in conversion unit, add the macromonomer aqueous solution, open and stir, and be warming up to 60 DEG C-85 DEG C, stand-by;
(2B) be equivalent by moisture two parts, a copy of it and initiator fully dissolve, and the solution of making adds in a dropping equipment; Another part fully dissolves with chain-transfer agent and minor comonomer, and the solution of making joins in No. two dropping equipment;
(3) drip
Solution in solution in a dropping equipment and No. two dropping equipment is at the uniform velocity added drop-wise in conversion unit simultaneously, time for adding is 3 hours, ensure that, after 3 hours, the material in the material in a dropping equipment and No. two dropping equipment is all added drop-wise in conversion unit; In dropping process, temperature maintains 60 DEG C-85 DEG C;
(4) slaking: after being added dropwise to complete, holding temperature is constant, insulation slaking 1 hour;
(5) neutralization: be cooled to 45 DEG C, to conversion unit, time for adding 20 minutes, ensures that after 20 minutes, liquid caustic soda is all added drop-wise in conversion unit by slow liquid caustic soda underframe.
3. the synthetic method of water-soluble comb-shaped polymer according to claim 2, is characterized in that: the described macromonomer aqueous solution is the double bond containing water-soluble linear urea-formaldehyde resin of the end group oligopolymer aqueous solution, and the repeating unit of this oligopolymer and molecular formula are:
Wherein, n=10-15.
4. the synthetic method of water-soluble comb-shaped polymer according to claim 2, is characterized in that: described initiator is ammonium persulphate, Sodium Persulfate or Potassium Persulphate.
5. the synthetic method of water-soluble comb-shaped polymer according to claim 2, is characterized in that: described chain-transfer agent is sodium allyl sulfonate, methallylsulfonic acid sodium, Thiovanic acid or thiohydracrylic acid.
6. the synthetic method of water-soluble comb-shaped polymer according to claim 2, is characterized in that: described minor comonomer is acrylic or methacrylic acid.
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| CN111019060A (en) * | 2019-12-12 | 2020-04-17 | 贵州师范学院 | Preparation method of tannic acid base star-shaped polycarboxylate superplasticizer |
| CN116063685A (en) * | 2022-12-16 | 2023-05-05 | 西南林业大学 | Comb-shaped hyperbranched amino copolycondensation resin and preparation method thereof |
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| CN1702087A (en) * | 2005-06-21 | 2005-11-30 | 重庆大学 | Polyacrylic acid salts shrinkage-reducing-agent and method for making same |
| CN102199298A (en) * | 2011-03-23 | 2011-09-28 | 中国日用化学工业研究院 | Preparation method for polycarboxylic acid series comb-shaped surface active agent |
| CN103613306A (en) * | 2013-11-18 | 2014-03-05 | 济南大学 | Hyperbranched poly(amine-ester) structure-containing polycarboxylic water reducer and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1702087A (en) * | 2005-06-21 | 2005-11-30 | 重庆大学 | Polyacrylic acid salts shrinkage-reducing-agent and method for making same |
| CN102199298A (en) * | 2011-03-23 | 2011-09-28 | 中国日用化学工业研究院 | Preparation method for polycarboxylic acid series comb-shaped surface active agent |
| CN103613306A (en) * | 2013-11-18 | 2014-03-05 | 济南大学 | Hyperbranched poly(amine-ester) structure-containing polycarboxylic water reducer and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019060A (en) * | 2019-12-12 | 2020-04-17 | 贵州师范学院 | Preparation method of tannic acid base star-shaped polycarboxylate superplasticizer |
| CN116063685A (en) * | 2022-12-16 | 2023-05-05 | 西南林业大学 | Comb-shaped hyperbranched amino copolycondensation resin and preparation method thereof |
| CN116063685B (en) * | 2022-12-16 | 2023-10-20 | 西南林业大学 | Comb-shaped hyperbranched amino copolycondensation resin and preparation method thereof |
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