CN100358825C - Acrylic acid series multiple copolymer analog high efficiency water reducing agent and its synthesis method - Google Patents
Acrylic acid series multiple copolymer analog high efficiency water reducing agent and its synthesis method Download PDFInfo
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- CN100358825C CN100358825C CNB2006100181799A CN200610018179A CN100358825C CN 100358825 C CN100358825 C CN 100358825C CN B2006100181799 A CNB2006100181799 A CN B2006100181799A CN 200610018179 A CN200610018179 A CN 200610018179A CN 100358825 C CN100358825 C CN 100358825C
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical class OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 32
- 229920001577 copolymer Polymers 0.000 title claims abstract description 17
- 238000001308 synthesis method Methods 0.000 title abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 83
- -1 polyoxy Polymers 0.000 claims abstract description 43
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 29
- 150000001336 alkenes Chemical class 0.000 claims abstract description 27
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003999 initiator Substances 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 14
- 230000032050 esterification Effects 0.000 claims description 30
- 238000005886 esterification reaction Methods 0.000 claims description 30
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 27
- 239000000376 reactant Substances 0.000 claims description 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 9
- 238000010189 synthetic method Methods 0.000 claims description 9
- 239000004160 Ammonium persulphate Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 229920000151 polyglycol Polymers 0.000 claims description 7
- 239000010695 polyglycol Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- 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 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003921 oil Substances 0.000 claims description 3
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 2
- 239000003112 inhibitor Substances 0.000 abstract 2
- 150000003460 sulfonic acids Chemical class 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 229920001515 polyalkylene glycol Polymers 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004567 concrete Substances 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Abstract
The present invention relates to water reducing agent and a synthesis method thereof, particularly to acrylic acid series multi-copolymer series high-efficiency water reducing agent, which is characterized in that the water reducing agent is prepared by raw material which is composed of acrylic acid or derivative thereof, polyoxy alkene, sulfonic acid series derivative, deionized water solvent, NaOH solution, catalyst, polymerization inhibitor, isopropanol chain transfer agent and initiator. The present invention has the quality portions of the raw material that the acrylic acid or the derivative thereof is 100 portions; the polyoxy alkene is from 150 to 450 portions; the sulfonic acid series derivative is from 10 to 80 portions; the deionized water solvent is from 450 to 800 portions; the catalyst is from 0.5 to 6 portions; the polymerization inhibitor is from 0.1 to 5 portions; the isopropanol chain transfer agent is from 5 to 30 portions; the initiator is from 0.5 to 5 portions. The addition quantity of the NaOH enables the pH value of the product to reach from 6 to 8. The present invention has the advantages of simple synthesis technology of the product, easy control of reaction conditions, stable performance, high water reducing rate and environmental protection.
Description
Technical field
The invention belongs to technical field of concrete additives, be specifically related to a kind of water reducer and synthetic method thereof.
Technical background
Admixture based on water reducer is one of requisite component of concrete, and the cement water reducing agent of China is that product is a main flow with naphthalene system and melamine at present, and there are problems such as water-reducing rate is not high, slump-loss big, contaminate environment, modification difficulty in this series products.And polycarboxylic acid series high efficiency water reducing agent can be brought into play low-dosage polymolecularity, slump retaining good (not having slump-loss in the 90min substantially), and easily modification, so its high performance potentiality are big, is considered to the regeneration product of high efficiency water reducing agent.
External polycarboxylic acid series high efficiency water reducing agent is used widely in concrete works, and product type is main with maleic anhydride mainly.With Japan is example, and the product synthetic method is mainly: the first step, under the nitrogen protection condition, methyl alcohol and oxyethane react under 140 ℃, 0.05～0.5MPa, add NaOH again in reaction vessel, 110 ℃, the dehydration of 20mmHg pressure.Subsequently, in mixture, add a certain amount of chlorallylene, when mixture basicity is reduced to a stationary value, use the HCl neutralise mixt, separate obtaining allyl ethers.Second the step: with toluene as solvent; under nitrogen protection; in having the reaction vessel of condensation; the allyl ethers and the maleic anhydride that are generated with the first step reaction carry out polyreaction; polymerization temperature is 80 ℃; churning time is 4 hours, steams and removes toluene solvant, obtains maleic anhydride series high performance concrete water reducer.
The domestic relevant report that polycarboxylic acid series high efficiency water reducing agent is also arranged in recent years.Its use raw material generally by unsaturated carboxylic acid class (vinylformic acid, methacrylic acid, maleic anhydride), polyoxy alkene (polyoxyethylene, polyoxyethylene glycol etc.), unsaturated carboxylate type, contain the unsaturated monomer of sulfonic acid group etc.; Its synthesis step generally all be divided into two the step carry out.Make catalyzer as the polycarboxylic acid series water reducing agents for efficient aerocrote of reporting among the CN1316398A at tosic acid, Resorcinol is done under the stopper condition, make methyl methacrylate and methyl Soxylat A 25-7 generation transesterification reaction, generate the big monomer of ester class, be solvent again with the butanone, under the dibenzoyl peroxide initiation conditions,, after finishing substantially, question response obtains bleed type high efficiency water reducing agent except that desolvating with the methacrylic acid polymerization reaction take place.The water reducer that this method makes is only soluble in alkali lye and is insoluble in water, brings very big inconvenience to use; Select for use butanone to make solvent in this synthesis technique in addition, need just to get product, make process complications through underpressure distillation.
Summary of the invention
The object of the present invention is to provide a kind of acrylic acid series multiple copolymer analog high efficiency water reducing agent and synthetic method thereof, this product synthesis technique is simple, easily-controlled reaction conditions, stable performance, water-reducing rate height, environmental protection.
To achieve these goals, technical scheme of the present invention is: a kind of acrylic acid series multiple copolymer analog high efficiency water reducing agent, it is characterized in that it is mainly by the vinylformic acid or derivatives thereof, the polyoxy alkene, sulfonic acid is derivative, deionized water solvent, NaOH solution, catalyzer, stopper, Virahol chain-transfer agent and initiator feedstock production form, the shared mass fraction of each raw material is: 100 parts of vinylformic acid or derivatives thereofs, 150～450 parts of polyoxy alkenes, sulfonic acid is 10～80 parts in derivative, 450～800 parts of deionized water solvents, 0.5～6 part of catalyzer, 0.1～5 part of stopper, 5～30 parts of Virahol chain-transfer agents, 0.5～5 part of initiator, the add-on of NaOH solution are to make the pH value of product reach 6～8.
Described acrylic acid derivative is a methacrylic acid.
Described polyoxy alkene is poly glycol monomethyl ether, polyoxyethylene glycol or polyoxyethylene.
Described sulfonic acid is that derivative is sodium allyl sulfonate, methylpropene sodium sulfonate, 2-Methacrylamide-2-propene sulfonic acid or Sodium styrene sulfonate.
Described catalyzer is tosic acid, phosphoric acid or the vitriol oil.
Described stopper is Resorcinol or quinhydrones.
Described initiator is ammonium persulphate or Sodium Persulfate.
Aforesaid propylene acid is the synthetic method of multiple copolymer analog high efficiency water reducing agent, it is characterized in that it comprises the steps:
1). choosing of raw material: be: 100 parts of vinylformic acid or derivatives thereofs by the shared mass fraction of each raw material, 150～450 parts of polyoxy alkenes, sulfonic acid is 10～80 parts in derivative, 450～800 parts of deionized water solvents, 0.5～6 part of catalyzer, 0.1～5 part of stopper, 5～30 parts of Virahol chain-transfer agents, 0.5～5 part of initiator, the add-on of NaOH solution are to make the pH value of product reach 6～8; Choose vinylformic acid or derivatives thereof, polyoxy alkene, sulfonic acid and be derivative, deionized water solvent, NaOH solution, catalyzer, stopper, Virahol chain-transfer agent and initiator raw material, standby;
2). graft esterification:
10～60 parts of vinylformic acid or derivatives thereofs and polyoxy alkene under catalyzer and stopper condition, are carried out esterification 2～6 hours under 70～150 ℃ condition, obtain a kind of esterification products;
3). polyreaction:
With above-mentioned gained esterification products, remaining vinylformic acid or derivatives thereof, sulfonic acid is that derivative, Virahol chain-transfer agent (or being called molecular weight regulator), initiator (mass concentration is 2%～30%) carry out radical polymerization in deionized water solvent under 35～95 ℃ of conditions, polymerization time is 2～6 hours, gets polymerization reactant;
4). polymerization reactant is cooled to room temperature, regulates its pH value to 6～8 for 10-40%NaOH solution, obtain the thickness transparent liquid, promptly get product with mass concentration.
Water reducer of the present invention (solid content is 18～25%) need not to purify through separating, and directly obtains product, and synthesis technique is simple.Temperature of reaction is constant, and side reaction is few, easily-controlled reaction conditions.Products obtained therefrom is water-soluble good, is soluble in alkali; Compare with the flowability and the slump-loss of naphthalene water reducer (FDN-1) and the clean slurry of blank sample making cement, it starches degree of mobilization only and protect plasticity is significantly improved than other products, stable performance.When its volume be cement weight 0.20% the time, its mixture slump can reach 19cm, making its water-reducing rate of reference with FDN-1 can be up to more than 30%, workability does not have the segregation excreting water phenomenon well, and 2 hours slumps of concrete are not lost substantially, and no air pocket produces, bleed is good, the water-reducing rate height.And do not use formaldehyde and other harmful starting material in the synthetic production process of the present invention, in production and the life-time service process HUMAN HEALTH is not had harm, environment has not been caused any pollution.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
With molecular weight 750 poly glycol monomethyl ether 37.5g, tosic acid 0.30g, Resorcinol 0.20g puts into four-hole boiling flask, stirring heating, and (acrylic acid total amount is 12ml to slow dropwise addition of acrylic acid 5ml under 100～120 ℃ of temperature, be divided into two parts, portion is 5ml, and portion is 7ml), dripped off in 60 minutes, reacted 2～3 hours, and generated polyalkylene glycol acrylate monomethyl ether ester (esterification products).Adding 4.32g sodium allyl sulfonate, 80ml deionized water, 3ml Virahol carry out stirring heating in esterification products, in a dropping funnel, add 7ml vinylformic acid, in another dropping funnel, add 15ml ammonium persulfate solution (mass concentration is 2%), when temperature rises to 55 ℃, beginning slowly drips ammonium persulphate and vinylformic acid, dripped off in 100 minutes, and kept 55～85 ℃ of temperature to carry out polyase 13～4 hour, polymerization reactant.Polymerization reactant is cooled to room temperature, regulates its pH value to 6～8 for 30%NaOH solution, obtain mass concentration and be 20% thickness transparent liquid, promptly get product with mass concentration.
Embodiment 2:
With molecular weight 750 poly glycol monomethyl ether 37.5g, catalyzer vitriol oil 0.30g, Resorcinol 0.20g puts into four-hole boiling flask, stirring heating, slow dropwise addition of acrylic acid 5ml under 100～120 ℃ of temperature, dripped off in 60 minutes, reacted 2～3 hours, generate polyalkylene glycol acrylate monomethyl ether ester (esterification products).Adding 4.32g sodium allyl sulfonate, 80ml deionized water, 3ml Virahol carry out stirring heating in esterification products, in a dropping funnel, add 7ml vinylformic acid, in another dropping funnel, add 15ml ammonium persulfate solution (mass concentration is 2%), when temperature rises to 55 ℃, beginning slowly drips ammonium persulphate and vinylformic acid, dripped off in 100 minutes, and kept 55～85 ℃ of temperature to carry out polyase 13～4 hour, polymerization reactant.Polymerization reactant is cooled to room temperature, regulates its pH value to 6～8, obtain mass concentration and be about 20% thickness transparent liquid, promptly get product with 30%NaOH solution.
Embodiment 3:
With molecular weight 750 poly glycol monomethyl ether 37.5g, tosic acid 0.30g, Resorcinol 0.20g puts into four-hole boiling flask, stirring heating, slow dropwise addition of acrylic acid 5ml under 100～120 ℃ of temperature, dripped off in 60 minutes, reacted 2～3 hours, generate polyalkylene glycol acrylate monomethyl ether ester (esterification products).Adding 2.88g sodium allyl sulfonate, 80ml deionized water, 3ml Virahol carry out stirring heating in esterification products, in a dropping funnel, add 7ml vinylformic acid, in another dropping funnel, add 15ml ammonium persulfate solution (mass concentration is 2%), when temperature rises to 55 ℃, beginning slowly drips ammonium persulphate and vinylformic acid, dripped off in 100 minutes, and kept 55～85 ℃ of temperature to carry out polyase 13～4 hour, polymerization reactant.Polymerization reactant is cooled to room temperature, regulates its pH value to 6～8 for 30%NaOH solution, obtain mass concentration and be about 20% thickness transparent liquid, promptly get product with mass concentration.
Embodiment 4:
With molecular weight 650 poly glycol monomethyl ether 32.5g, tosic acid 0.30g, Resorcinol 0.20g puts into four-hole boiling flask, stirring heating, slow dropwise addition of acrylic acid 5ml under 100～120 ℃ of temperature, dripped off in 60 minutes, reacted 2～3 hours, generate polyalkylene glycol acrylate monomethyl ether ester (esterification products).Adding 4.32g sodium allyl sulfonate, 80ml water, 3ml Virahol carry out stirring heating in esterification products, in a dropping funnel, add 7ml vinylformic acid, in another dropping funnel, add 15ml ammonium persulfate solution (mass concentration is 2%), when temperature rises to 55 ℃, beginning slowly drips ammonium persulphate and vinylformic acid, dripped off in 100 minutes, and kept 55～85 ℃ of temperature to carry out polyase 13～4 hour, polymerization reactant.Polymerization reactant is cooled to room temperature, regulates its pH value to 6～8 for 30%NaOH solution, obtain mass concentration and be about 20% thickness transparent liquid, promptly get product with mass concentration.
Embodiment 5:
With molecular weight 750 poly glycol monomethyl ether 37.5g, tosic acid 0.30g, Resorcinol 0.20g puts into four-hole boiling flask, stirring heating, slow dropwise addition of acrylic acid 5ml under 100～120 ℃ of temperature, dripped off in 60 minutes, reacted 2～3 hours, generate polyalkylene glycol acrylate monomethyl ether ester (esterification products).Adding 4.32g sodium allyl sulfonate, 80ml water, 3ml Virahol carry out stirring heating in esterification products, in a dropping funnel, add 10ml vinylformic acid, in another dropping funnel, add 15ml ammonium persulfate solution (mass concentration is 2%), when temperature rises to 55 ℃, beginning slowly drips ammonium persulphate and vinylformic acid, dripped off in about 100 minutes, and kept 55～85 ℃ of temperature to carry out polyase 13～4 hour, polymerization reactant.Polymerization reactant is cooled to room temperature, regulates its pH value to 6～8 for 30%NaOH solution, obtain mass concentration and be about 20% thickness transparent liquid, promptly get product with mass concentration.
Embodiment 6:
The synthetic method of acrylic acid series multiple copolymer analog high efficiency water reducing agent, it comprises the steps: 1). choosing of raw material: be: 100 parts of acrylic acid derivatives by the shared mass fraction of each raw material, 150 parts of polyoxy alkenes, sulfonic acid is 10 parts in derivative, 450 parts of deionized water solvents, 0.5 part of catalyzer, 0.1 part of stopper, 5 parts of Virahol chain-transfer agents, 0.5 part of initiator, the add-on of NaOH solution is to make the pH value of product reach 6; Choose acrylic acid derivative, polyoxy alkene, sulfonic acid and be derivative, deionized water solvent, NaOH solution, catalyzer, stopper, Virahol chain-transfer agent and initiator raw material, standby; Described acrylic acid derivative is a methacrylic acid, and described polyoxy alkene is a polyoxyethylene glycol, and described sulfonic acid is that derivative is a methylpropene sodium sulfonate, and described catalyzer is a phosphoric acid, and described stopper is a quinhydrones, and described initiator is a Sodium Persulfate.
2). graft esterification:
10 parts of acrylic acid derivatives and polyoxy alkene under catalyzer and stopper condition, are carried out esterification 2～6 hours under 70～150 ℃ condition, obtain a kind of esterification products;
3). polyreaction:
With above-mentioned gained esterification products, remaining acrylic acid derivative (90 parts), sulfonic acid is that derivative, Virahol chain-transfer agent, initiator (mass concentration is 2%～30%) carry out radical polymerization in deionized water solvent under 35～95 ℃ of conditions, polymerization time is 2～6 hours, gets polymerization reactant.
4). polymerization reactant is cooled to room temperature, regulates its pH value to 6 for 10%NaOH solution, obtain the thickness transparent liquid, promptly get product with mass concentration.
Embodiment 7:
The synthetic method of acrylic acid series multiple copolymer analog high efficiency water reducing agent, it comprises the steps: 1). choosing of raw material: be: 100 parts in vinylformic acid by the shared mass fraction of each raw material, 350 parts of polyoxy alkenes, sulfonic acid is 40 parts in derivative, 600 parts of deionized water solvents, 3 parts of catalyzer, 2 parts of stoppers, 10 parts of Virahol chain-transfer agents, 3 parts of initiators, the add-on of NaOH solution is to make the pH value of product reach 7; Choose vinylformic acid, polyoxy alkene, sulfonic acid and be derivative, deionized water solvent, NaOH solution, catalyzer, stopper, Virahol chain-transfer agent and initiator raw material, standby; Described polyoxy alkene is a polyoxyethylene, and described sulfonic acid is that derivative is 2-Methacrylamide-2-propene sulfonic acid, and described catalyzer is to phosphoric acid, and described stopper is a quinhydrones, and described initiator is a Sodium Persulfate.
2). graft esterification:
40 parts of vinylformic acid or derivatives thereofs and polyoxy alkene under catalyzer and stopper condition, are carried out esterification 2～6 hours under 70～150 ℃ condition, obtain a kind of esterification products;
3). polyreaction:
With above-mentioned gained esterification products, remaining vinylformic acid (60 parts), sulfonic acid is that derivative, Virahol chain-transfer agent, initiator (mass concentration is 2%～30%) carry out radical polymerization in deionized water solvent under 35～95 ℃ of conditions, polymerization time is 2～6 hours, gets polymerization reactant.
4). polymerization reactant is cooled to room temperature, regulates its pH value to 7 for 30%NaOH solution, obtain the thickness transparent liquid, promptly get product with mass concentration.
Embodiment 8:
The synthetic method of acrylic acid series multiple copolymer analog high efficiency water reducing agent, it comprises the steps: 1). choosing of raw material: be: 100 parts in vinylformic acid by the shared mass fraction of each raw material, 450 parts of polyoxy alkenes, sulfonic acid is 80 parts in derivative, 800 parts of deionized water solvents, 6 parts of catalyzer, 5 parts of stoppers, 30 parts of Virahol chain-transfer agents, 5 parts of initiators, the add-on of NaOH solution is to make the pH value of product reach 8; Choose vinylformic acid or derivatives thereof, polyoxy alkene, sulfonic acid and be derivative, deionized water solvent, NaOH solution, catalyzer, stopper, Virahol chain-transfer agent and initiator raw material, standby; Described polyoxy alkene is a polyoxyethylene, and described sulfonic acid is that derivative is a Sodium styrene sulfonate, and described catalyzer is a tosic acid, and described stopper is a Resorcinol, and described initiator is an ammonium persulphate.
2). graft esterification:
60 parts of vinylformic acid or derivatives thereofs and polyoxy alkene under catalyzer and stopper condition, are carried out esterification 2～6 hours under 70～150 ℃ condition, obtain a kind of esterification products;
3). polyreaction:
With above-mentioned gained esterification products, remaining vinylformic acid (40 parts), sulfonic acid is that derivative, Virahol chain-transfer agent, initiator (mass concentration is 2%～30%) carry out radical polymerization in deionized water solvent under 35～95 ℃ of conditions, polymerization time is 2～6 hours, gets polymerization reactant.
4). polymerization reactant is cooled to room temperature, regulates its pH value to 8 for 40%NaOH solution, obtain the thickness transparent liquid, promptly get product with mass concentration.
Claims (8)
1. acrylic acid series multiple copolymer analog high efficiency water reducing agent, it is characterized in that it is mainly by the vinylformic acid or derivatives thereof, the polyoxy alkene, sulfonic acid is derivative, deionized water solvent, NaOH solution, catalyzer, stopper, Virahol chain-transfer agent and initiator feedstock production form, the shared mass fraction of each raw material is: 100 parts of vinylformic acid or derivatives thereofs, 150～450 parts of polyoxy alkenes, sulfonic acid is 10～80 parts in derivative, 450～800 parts of deionized water solvents, 0.5～6 part of catalyzer, 0.1～5 part of stopper, 5～30 parts of Virahol chain-transfer agents, 0.5～5 part of initiator, the add-on of NaOH solution are to make the pH value of product reach 6～8.
2. a kind of acrylic acid series multiple copolymer analog high efficiency water reducing agent according to claim 1 is characterized in that: described acrylic acid derivative is a methacrylic acid.
3. a kind of acrylic acid series multiple copolymer analog high efficiency water reducing agent according to claim 1 is characterized in that: described polyoxy alkene is poly glycol monomethyl ether, polyoxyethylene glycol or polyoxyethylene.
4. a kind of acrylic acid series multiple copolymer analog high efficiency water reducing agent according to claim 1 is characterized in that: described sulfonic acid is that derivative is sodium allyl sulfonate, methylpropene sodium sulfonate, 2-Methacrylamide-2-propene sulfonic acid or Sodium styrene sulfonate.
5. a kind of acrylic acid series multiple copolymer analog high efficiency water reducing agent according to claim 1 is characterized in that: described catalyzer is tosic acid, phosphoric acid or the vitriol oil.
6. a kind of acrylic acid series multiple copolymer analog high efficiency water reducing agent according to claim 1 is characterized in that: described stopper is Resorcinol or quinhydrones.
7. a kind of acrylic acid series multiple copolymer analog high efficiency water reducing agent according to claim 1 is characterized in that: described initiator is ammonium persulphate or Sodium Persulfate.
8. the synthetic method of acrylic acid series multiple copolymer analog high efficiency water reducing agent as claimed in claim 1, it is characterized in that it comprises the steps: 1). choosing of raw material: be: 100 parts of vinylformic acid or derivatives thereofs by the shared mass fraction of each raw material, 150～450 parts of polyoxy alkenes, sulfonic acid is 10～80 parts in derivative, 450～800 parts of deionized water solvents, 0.5～6 part of catalyzer, 0.1～5 part of stopper, 5～30 parts of Virahol chain-transfer agents, 0.5～5 part of initiator, the add-on of NaOH solution are to make the pH value of product reach 6～8; Choose vinylformic acid or derivatives thereof, polyoxy alkene, sulfonic acid and be derivative, deionized water solvent, NaOH solution, catalyzer, stopper, Virahol chain-transfer agent and initiator raw material, standby;
2). graft esterification:
10～60 parts of vinylformic acid or derivatives thereofs and polyoxy alkene under catalyzer and stopper condition, are carried out esterification 2～6 hours under 70～150 ℃ condition, obtain a kind of esterification products;
3). polyreaction:
With above-mentioned gained esterification products, remaining vinylformic acid or derivatives thereof, sulfonic acid is that derivative, Virahol chain-transfer agent, initiator carry out radical polymerization in deionized water solvent under 35～95 ℃ of conditions, polymerization time is 2～6 hours, gets polymerization reactant;
4). polymerization reactant is cooled to room temperature, regulates its pH value to 6～8 for 10-40%NaOH solution, obtain the thickness transparent liquid, promptly get product with mass concentration.
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| CN102718427B (en) * | 2012-06-21 | 2015-01-28 | 马清浩 | Sulfonyl modified carboxylic acid water-reducing agent and preparation method thereof |
| CN102718426A (en) * | 2012-06-21 | 2012-10-10 | 马清浩 | Modified carboxylic acid water-reducing agent and preparation method thereof |
| CN106279573A (en) * | 2016-08-12 | 2017-01-04 | 合肥东方节能科技股份有限公司 | A kind of resistance based on ternary polycarboxylic acids rust solution and preparation method thereof |
| CN110451843A (en) * | 2019-08-03 | 2019-11-15 | 徐州巨龙新材料科技有限公司 | A kind of high efficiency water reducing agent and preparation method thereof |
| CN112708050A (en) * | 2020-08-24 | 2021-04-27 | 重庆建研科之杰建材有限公司 | Concrete water reducing agent and preparation method thereof |
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