CN105330793B - A kind of preparation method of ethers polycarboxylic acid water reducing agent - Google Patents
A kind of preparation method of ethers polycarboxylic acid water reducing agent Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 37
- 150000002170 ethers Chemical class 0.000 title claims abstract description 18
- 239000002253 acid Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011259 mixed solution Substances 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 238000010792 warming Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 238000010926 purge Methods 0.000 claims abstract description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000012188 paraffin wax Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- 238000007599 discharging Methods 0.000 claims abstract description 10
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 10
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229920000570 polyether Polymers 0.000 claims abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 4
- 229940124024 weight reducing agent Drugs 0.000 claims description 24
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 6
- -1 hydroxyl methyl Chemical class 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 5
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 5
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- GGOFGLKJLBSIHK-UHFFFAOYSA-N [K].C(CCC)OC(CC)S(=O)(=O)O Chemical compound [K].C(CCC)OC(CC)S(=O)(=O)O GGOFGLKJLBSIHK-UHFFFAOYSA-N 0.000 claims description 4
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 claims description 4
- 229960001748 allylthiourea Drugs 0.000 claims description 4
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- 239000013585 weight reducing agent Substances 0.000 claims description 3
- CEFDWZDNAJAKGO-UHFFFAOYSA-N 2-hydroxy-2-sulfoacetic acid Chemical compound OC(=O)C(O)S(O)(=O)=O CEFDWZDNAJAKGO-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims 1
- 229920005646 polycarboxylate Polymers 0.000 abstract description 7
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 abstract 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 abstract 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 239000004567 concrete Substances 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- HVCNQTCZNBPWBV-UHFFFAOYSA-N 2-hydroxy-2-sulfinoacetic acid Chemical class OC(=O)C(O)S(O)=O HVCNQTCZNBPWBV-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 208000014903 transposition of the great arteries Diseases 0.000 description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical group OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- DRKDJDUPOFSMEU-UHFFFAOYSA-N acetic acid;potassium Chemical compound [K].[K].CC(O)=O DRKDJDUPOFSMEU-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- FWABLCJJBXRYBK-UHFFFAOYSA-N potassium;propane-1-sulfonic acid Chemical compound [K].CCCS(O)(=O)=O FWABLCJJBXRYBK-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008126 allyl sulfides Chemical class 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- OPGYRRGJRBEUFK-UHFFFAOYSA-L disodium;diacetate Chemical compound [Na+].[Na+].CC([O-])=O.CC([O-])=O OPGYRRGJRBEUFK-UHFFFAOYSA-L 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009149 molecular binding Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012032 thrombin generation assay Methods 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Detergent Compositions (AREA)
Abstract
The invention discloses a kind of preparation method of ethers polycarboxylic acid water reducing agent.Comprise the following steps：(1) unsaturated polyether, acrylic acid, unsaturated sulfonic acid salt, paraffin, disodium EDTA and water are added in reactor, stirs lower dissolving, be configured to react bed material, the maintaining nitrogen purge under the liquid level of reaction bed material, while be warming up to 30~40 DEG C；(2) hydrogen peroxide is disposably added in step (1) resulting material, the first mixed solution and the second mixed solution are added dropwise simultaneously, control rate of addition, time for adding is 1~2.5h, after being added dropwise, reaction system is warming up to 50~60 DEG C, the disposable hydrogen peroxide that adds continues to react, (3) SDD is added in step (2) resulting material with terminating reaction, and add sodium hydroxide solution and neutralized, 40~50 DEG C are cooled to, discharging, obtains ethers polycarboxylic acid water reducing agent.The preparation method of the present invention is advantageous to avoid gel from generating, while can greatly improve the bin stability of obtained polycarboxylate water-reducer.
Description
Technical field
The invention belongs to building material technical field, and in particular to a kind of preparation method of ethers polycarboxylic acid water reducing agent.
Background technology
It is various industry with civil buildings, road and rail bridge, airfield runway, mine construction, hydro-structure, ocean development,
The construction of many engineerings such as geothermal engineering and military affairs all be unable to do without concrete.At present, as concrete is to high performance and more
The direction of functionalization is developed, it is desirable to which concrete has high workability, high intensity, high-durability, and can meet in many special feelings
Application under condition.Polycarboxylate water-reducer with ultra-dispersed performance oneself turn into high performance concrete in indispensable component.
Polycarboxylate water-reducer contains the functional groups such as carboxylic acid group, sulfonic group, ester group, in the molecular binding process of polymer,
Different monomers make molecule have comb-type structure with random or regularly condense together, and it is excellent for its special structures shape
More performance.Polycarboxylate water-reducer can cut out design principle according to polymer molecule, can be gathered by free radical copolymerization
Close construction unit synthesis predetermined structure and performance water reducer, by adjust monomer component and its between proportionate relationship, choose
High reaction activity monomer and initiator etc., main chain, the side chain containing preferable molecular structure that can meet specific demand are finally given,
And make it have the polymer of certain charge density and molecular conformation molecular structure.
In the correlative study of polycarboxylate water-reducer, numerous enterprises and R＆D institution are primarily upon carrying for polycarboxylic acids performance
The lifting of liter or cost performance, or the functionalized design of product, and the research for polycarboxylate water-reducer production process is less.It is poly-
The synthesis of carboxylic acid water reducer is typically polymerize using aqueous free radical, during the course of the reaction with the consumption of reaction monomers, monomer
The raising of conversion ratio, the viscosity of system also increase therewith, i.e. the molecular weight of product gradually steps up, and due to reaction system mass transfer
The heterogencity of heat transfer, cause sudden and violent poly- phenomenon may locally occur in system, therefore gelatin phenomenon can be caused to occur, actual production
During particularly be very easy to agglomerate gel occur on kettle wall and agitating paddle, often cause reactor discharging opening and product
The blocking of pipeline in course of conveying.
The content of the invention
It is an object of the invention to overcome prior art defect, there is provided a kind of preparation method of ethers polycarboxylic acid water reducing agent.
The concrete technical scheme of the present invention is as follows：
A kind of preparation method of ethers polycarboxylic acid water reducing agent, comprises the following steps：
(1) by 100 parts by weight unsaturated polyethers, 2~11 parts by weight of acrylic acid, 1~6 parts by weight unsaturated sulfonic acid salt,
0.01~0.6 parts by weight paraffin, 1~6 parts by wt EDTA-disodium salt and 50 parts by weight water are added in reactor, stirring
Lower dissolving, it is configured to react bed material, 12~20min of maintaining nitrogen purge under the liquid level of reaction bed material, while is warming up to 30~40
℃；Above-mentioned unsaturated polyether is methacrylic polyoxyethylene ether or isopentene group polyoxyethylene ether；
(2) maintaining nitrogen purge under the liquid level of step (1) resulting material, and continuously stir, disposably add 1~6 weight
Part hydrogen peroxide, while the first mixed solution and the second mixed solution is added dropwise, rate of addition is controlled, time for adding is 1~2.5h,
After being added dropwise, reaction system is warming up to 50~60 DEG C, 0.2~1.0 parts by weight hydrogen peroxide is disposably added and continues to react,
Reaction time is 0.8~1.2h；Wherein the first mixed solution is by 4~11 parts by weight unsaturated carboxylic acids, 1~6 parts by weight pi-allyl
Thiocarbamide, 0.2~1.5 parts by weight chain-transferring agent and 30 parts by weight water are formulated, and the second mixed solution is by 0.05~1.2 parts by weight
Reducing agent, 0.05~0.6 parts by weight help reducing agent tetramethylethylenediamine and 30 parts by weight water to be formulated；
(3) 0.01~0.06 parts by weight SDD is added in step (2) resulting material with end
Only react, and add the sodium hydroxide solution that 8~22 parts by weight mass concentrations are 30% and neutralized, be cooled to 40~50 DEG C,
Discharging, obtains ethers polycarboxylic acid water reducing agent.
In a preferred embodiment of the invention, the step (1) is：By 100 parts by weight unsaturated polyethers, 3~
10 parts by weight of acrylic acid, 1~5 parts by weight unsaturated sulfonic acid salt, 0.01~0.5 parts by weight paraffin, 1~5 parts by weight ethylenediamine tetraacetic
Acetic acid disodium salt and 50 parts by weight water are added in reactor, stir lower dissolving, are configured to react bed material, in the liquid level of reaction bed material
Lower maintaining nitrogen purge 15min, while it is warming up to 30~40 DEG C.
In a preferred embodiment of the invention, the step (2) is：Under the liquid level of step (1) resulting material
Maintaining nitrogen purge, and continuously stir, 1~5 parts by weight hydrogen peroxide is disposably added, while the first mixed solution and second is added dropwise
Mixed solution, rate of addition being controlled, time for adding is 1~2h, and after being added dropwise, reaction system is warming up into 50~60 DEG C, one
Secondary property adds 0.2~0.8 parts by weight hydrogen peroxide and continues to react, reaction time 1h.
In a preferred embodiment of the invention, the step (3) is：Added in step (2) resulting material
0.01~0.05 parts by weight SDD is added 10~20 parts by weight mass concentrations and is with terminating reaction
30% sodium hydroxide solution is neutralized, and is cooled to 45 DEG C, discharging, is obtained ethers polycarboxylic acid water reducing agent.
It is further preferred that the unsaturated sulfonic acid salt is 2- hydroxyl -3- allyloxys propanesulfonate, 2- hydroxyl -3- alkene
Propoxyl group propane sulfonic acid potassium, 2- hydroxyl -4- alkene butoxy propanesulfonates or 2- hydroxyl -4- alkene butoxy propane sulfonic acid potassium.
It is further preferred that the unsaturated carboxylic acid is acrylic acid, methyl acrylate, ethyl acrylate, acrylic acid hydroxyl first
At least one of ester, hydroxy-ethyl acrylate and itaconic acid.
It is further preferred that the chain-transferring agent is mercaptoethanol, TGA or mercaptopropionic acid.
It is further preferred that the reducing agent is 2- hydroxyls -2- sulfinatoacetic acids di-potassium or 2- hydroxyl -2- sulfonic groups
Acetic acid di-potassium.
The beneficial effects of the invention are as follows：
1st, preparation method of the invention is advantageous to avoid gel from generating：Before adding reaction monomers, it is passed through nitrogen and removes dereaction
Air in kettle, to provide the oxygen-free environment of polymerisation；Paraffin is added in reaction, can reduce or prevent attachment of polymers as far as possible
On the reactor part such as kettle wall or agitating paddle；The unsaturated sulfonic acid of introducing, contain three functional groups in its structure, be a kind of high
Hydrophilic functional monomer is spent, the hydrophily of polymer can be increased, is advantageous to avoid the generation of gelatinous mass.
2nd, preparation method of the invention can greatly improve the bin stability of obtained polycarboxylate water-reducer, will not produce
Raw gel or white gels shape floating object：Introduced allylthiourea, the group with anti-oxidation function, product can be prevented
Crosslinking and degraded, can improve the service efficiencies of antioxidant groups, due between antioxidant group and main polymer chain by covalent
Key is bonded, and is not in separation effect；The SDD added can be with the chain that is remained in reaction system
Radical reaction, chain free radical activity is set to disappear so that reaction terminating.
Embodiment
Technical scheme is further detailed and described below by way of embodiment.
Embodiment 1
(1) by 100 parts by weight methacrylic polyoxyethylene ethers, 5 parts by weight of acrylic acid, 1 parts by weight 2- hydroxyl -3- alkene
Propoxyl group propanesulfonate, 0.01 parts by weight paraffin, 1 parts by wt EDTA-disodium salt and 50 parts by weight water add reactor
In, lower dissolving is stirred, is configured to react bed material, the maintaining nitrogen purge 15min under the liquid level of reaction bed material, while be warming up to 40
℃；
(2) maintaining nitrogen purge under the liquid level of step (1) resulting material, and continuously stir, it is disposable to add 4 parts by weight mistakes
Hydrogen oxide, while the first mixed solution and the second mixed solution is added dropwise, rate of addition is controlled, time for adding 2h, is added dropwise
Afterwards, reaction system is warming up to 55 DEG C, the disposable 0.8 parts by weight hydrogen peroxide that adds continues to react, reaction time 1h；Wherein
First mixed solution is matched somebody with somebody by 5 parts by weight of acrylic acid, 3 parts by weight allylthioureas, 0.2 parts by weight mercaptoethanol and 30 parts by weight water
System forms, and the second mixed solution helps reducing agent tetramethyl by 1 parts by weight 2- hydroxyl -2- sulfinatoacetic acids di-potassium, 0.5 parts by weight
Base ethylenediamine and 30 parts by weight water are formulated；
(3) 0.01 parts by weight SDD is added in step (2) resulting material with terminating reaction,
And add the sodium hydroxide solution that 13 parts by weight mass concentrations are 30% and neutralized, 45 DEG C are cooled to, discharging, ethers is obtained and gathers
Carboxylic acid water reducer.
Embodiment 2
(1) by 100 parts by weight isopentene group polyoxyethylene ethers, 8 parts by weight of acrylic acid, 2 parts by weight 2- hydroxyl -3- allyls
Epoxide propane sulfonic acid potassium, 0.01 parts by weight paraffin, 4 parts by wt EDTA-disodium salt and 50 parts by weight water add reactor
In, lower dissolving is stirred, is configured to react bed material, the maintaining nitrogen purge 15min under the liquid level of reaction bed material, while be warming up to 30
℃；
(2) maintaining nitrogen purge under the liquid level of step (1) resulting material, and continuously stir, it is disposable to add 2 parts by weight mistakes
Hydrogen oxide, while the first mixed solution and the second mixed solution is added dropwise, rate of addition is controlled, time for adding 2h, is added dropwise
Afterwards, reaction system is warming up to 55 DEG C, the disposable 0.5 parts by weight hydrogen peroxide that adds continues to react, reaction time 1h；Wherein
First mixed solution is by 4 parts by weight of acrylic acid, 1 parts by weight of acrylic acid hydroxyl ethyl ester, 1 parts by weight allylthiourea, 0.4 parts by weight mercapto
Base ethanol and 30 parts by weight water are formulated, and the second mixed solution is by 0.4 parts by weight 2- hydroxyl -2- sulfinatoacetic acid dipotassiums
Salt, 0.5 parts by weight help reducing agent tetramethylethylenediamine and 30 parts by weight water to be formulated；
(3) 0.04 parts by weight SDD is added in step (2) resulting material with terminating reaction,
And add the sodium hydroxide solution that 17 parts by weight mass concentrations are 30% and neutralized, 45 DEG C are cooled to, discharging, ethers is obtained and gathers
Carboxylic acid water reducer.
Embodiment 3
(1) by 100 parts by weight isopentene group polyoxyethylene ethers, 3 parts by weight of acrylic acid, 3 parts by weight 2- hydroxyl -4- alkene fourths
Epoxide propanesulfonate, 0.5 parts by weight paraffin, 4 parts by wt EDTA-disodium salt and 50 parts by weight water are added in reactor,
Stirring is lower to dissolve, and is configured to react bed material, the maintaining nitrogen purge 15min under the liquid level of reaction bed material, while be warming up to 40 DEG C；
(2) maintaining nitrogen purge under the liquid level of step (1) resulting material, and continuously stir, it is disposable to add 1 parts by weight mistake
Hydrogen oxide, while the first mixed solution and the second mixed solution is added dropwise, rate of addition is controlled, time for adding 1h, is added dropwise
Afterwards, reaction system is warming up to 60 DEG C, the disposable 0.5 parts by weight hydrogen peroxide that adds continues to react, reaction time 1h；Wherein
First mixed solution is by 3 parts by weight of acrylic acid, 7 parts by weight itaconic acids, 1 parts by weight allylthiourea, 1.2 parts by weight TGAs
It is formulated with 30 parts by weight water, the second mixed solution is by 1 parts by weight 2- hydroxyl -2- sulfinatoacetic acids di-potassium, 0.05 weight
Amount part helps reducing agent tetramethylethylenediamine and 30 parts by weight water to be formulated；
(3) 0.02 parts by weight SDD is added in step (2) resulting material with terminating reaction,
And add the sodium hydroxide solution that 10 parts by weight mass concentrations are 30% and neutralized, 45 DEG C are cooled to, discharging, ethers is obtained and gathers
Carboxylic acid water reducer.
Embodiment 4
(1) by 100 parts by weight methacrylic polyoxyethylene ethers, 10 parts by weight of acrylic acid, 5 parts by weight 2- hydroxyls -4-
Alkene butoxy propane sulfonic acid potassium, 0.1 parts by weight paraffin, 5 parts by wt EDTA-disodium salt and 50 parts by weight water add reaction
In kettle, lower dissolving is stirred, is configured to react bed material, the maintaining nitrogen purge 15min under the liquid level of reaction bed material, while be warming up to 35
℃；
(2) maintaining nitrogen purge under the liquid level of step (1) resulting material, and continuously stir, it is disposable to add 5 parts by weight mistakes
Hydrogen oxide, while the first mixed solution and the second mixed solution is added dropwise, rate of addition is controlled, time for adding 1h, is added dropwise
Afterwards, reaction system is warming up to 50 DEG C, the disposable 0.2 parts by weight hydrogen peroxide that adds continues to react, reaction time 1h；Wherein
First mixed solution is by 2 parts by weight of acrylic acid, 2 parts by weight of acrylic acid hydroxyl ethyl esters, 1 parts by weight itaconic acid, 5 parts by weight allyl sulfides
Urea, 0.5 parts by weight mercaptopropionic acid and 30 parts by weight water are formulated, and the second mixed solution is by 0.05 parts by weight 2- hydroxyl -2- sulphurs
Acidic group acetic acid di-potassium, 0.1 parts by weight help reducing agent tetramethylethylenediamine and 30 parts by weight water to be formulated；
(3) 0.05 parts by weight SDD is added in step (2) resulting material with terminating reaction,
And add the sodium hydroxide solution that 20 parts by weight mass concentrations are 30% and neutralized, 45 DEG C are cooled to, discharging, ethers is obtained and gathers
Carboxylic acid water reducer.
Embodiment 1~4 does not find gel on reactor wall and agitating paddle after the completion of reaction；Gained polycarboxylic acids diminishing
Agent is stored 12 months at normal temperatures, is not also found gel or white gels shape floating object, is had no hydraulic performance decline.
The product of the gained of embodiment 1~4 use into reference cement P.I 42.5, sand is the river sand of modulus of fineness 2.8, stone
For particle diameter 5-20 continuous grading rubbles.According to GB 8076-2008《Concrete admixture》, determine concrete water-reducing ratio, additive
Volume is 0.20% (being converted into solid part) of glue material quality, and the concrete water-reducing ratio of the sample of embodiment 1~4 is 30% after tested
More than.
Those of ordinary skill in the art understand, when constituent content of the invention changes in following ranges, remain to access
Same as the previously described embodiments or similar technique effect, still falls within protection scope of the present invention：
(1) by 100 parts by weight unsaturated polyethers, 2~11 parts by weight of acrylic acid, 1~6 parts by weight unsaturated sulfonic acid salt,
0.01~0.6 parts by weight paraffin, 1~6 parts by wt EDTA-disodium salt and 50 parts by weight water are added in reactor, stirring
Lower dissolving, it is configured to react bed material, 12~20min of maintaining nitrogen purge under the liquid level of reaction bed material, while is warming up to 30~40
℃；Above-mentioned unsaturated polyether is methacrylic polyoxyethylene ether or isopentene group polyoxyethylene ether；
(2) maintaining nitrogen purge under the liquid level of step (1) resulting material, and continuously stir, disposably add 1~6 weight
Part hydrogen peroxide, while the first mixed solution and the second mixed solution is added dropwise, rate of addition is controlled, time for adding is 1~2.5h,
After being added dropwise, reaction system is warming up to 50~60 DEG C, 0.2~1.0 parts by weight hydrogen peroxide is disposably added and continues to react,
Reaction time is 0.8~1.2h；Wherein the first mixed solution is by 4~11 parts by weight unsaturated carboxylic acids, 1~6 parts by weight pi-allyl
Thiocarbamide, 0.2~1.5 parts by weight chain-transferring agent and 30 parts by weight water are formulated, and the second mixed solution is by 0.05~1.2 parts by weight
Reducing agent, 0.05~0.6 parts by weight help reducing agent tetramethylethylenediamine and 30 parts by weight water to be formulated；
(3) 0.01~0.06 parts by weight SDD is added in step (2) resulting material with end
Only react, and add the sodium hydroxide solution that 8~22 parts by weight mass concentrations are 30% and neutralized, be cooled to 40~50 DEG C,
Discharging, obtains ethers polycarboxylic acid water reducing agent.
The unsaturated sulfonic acid salt is 2- hydroxyl -3- allyloxys propanesulfonate, 2- hydroxyl -3- allyloxy propane sulfonic acid
Potassium, 2- hydroxyl -4- alkene butoxy propanesulfonates or 2- hydroxyl -4- alkene butoxy propane sulfonic acid potassium.
The unsaturated carboxylic acid is acrylic acid, methyl acrylate, ethyl acrylate, acrylate, acrylic acid hydroxyl second
At least one of ester and itaconic acid.
The chain-transferring agent is mercaptoethanol, TGA or mercaptopropionic acid.
The reducing agent is 2- hydroxyls -2- sulfinatoacetic acids di-potassium or 2- hydroxyl -2- sulfonatoacetic acid di-potassiums.
The foregoing is only a preferred embodiment of the present invention, therefore can not limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still it belong in the range of the present invention covers.
Claims (7)
- A kind of 1. preparation method of ethers polycarboxylic acid water reducing agent, it is characterised in that：Comprise the following steps：(1) by 100 parts by weight unsaturated polyethers, 2~11 parts by weight of acrylic acid, 1~6 parts by weight unsaturated sulfonic acid salt, 0.01~ 0.6 parts by weight paraffin, 1~6 parts by wt EDTA-disodium salt and 50 parts by weight water are added in reactor, molten under stirring Solution, it is configured to react bed material, 12~20min of maintaining nitrogen purge under the liquid level of reaction bed material, while is warming up to 30~40 DEG C；On It is methacrylic polyoxyethylene ether or isopentene group polyoxyethylene ether to state unsaturated polyether；(2) maintaining nitrogen purge under the liquid level of step (1) resulting material, and continuously stir, disposably add 1~6 parts by weight mistake Hydrogen oxide, while the first mixed solution and the second mixed solution is added dropwise, rate of addition is controlled, time for adding is 1~2.5h, is added dropwise After, reaction system is warming up to 50~60 DEG C, 0.2~1.0 parts by weight hydrogen peroxide is disposably added and continues to react, react Time is 0.8~1.2h；Wherein the first mixed solution is by 4~11 parts by weight of acrylic acid, methyl acrylate, ethyl acrylate, third At least one of olefin(e) acid hydroxyl methyl esters, hydroxy-ethyl acrylate and itaconic acid, 1~6 parts by weight allylthiourea, 0.2~1.5 weight Part chain-transferring agent and 30 parts by weight water are formulated, and the second mixed solution is by 0.05~1.2 parts by weight reducing agent, 0.05~0.6 Parts by weight help reducing agent tetramethylethylenediamine and 30 parts by weight water to be formulated；(3) it is anti-to terminate that 0.01~0.06 parts by weight SDD is added in step (2) resulting material Should, and add the sodium hydroxide solution that 8~22 parts by weight mass concentrations are 30% and neutralized, 40~50 DEG C are cooled to, is discharged, Obtain ethers polycarboxylic acid water reducing agent.
- A kind of 2. preparation method of ethers polycarboxylic acid water reducing agent as claimed in claim 1, it is characterised in that：The step (1) For：By 100 parts by weight unsaturated polyethers, 3~10 parts by weight of acrylic acid, 1~5 parts by weight unsaturated sulfonic acid salt, 0.01~0.5 weight Measure part paraffin, 1~5 parts by wt EDTA-disodium salt and 50 parts by weight water to add in reactor, stir lower dissolving, prepare Into reaction bed material, the maintaining nitrogen purge 15min under the liquid level of reaction bed material, while it is warming up to 30~40 DEG C.
- 3. preparation method as claimed in claim 1, it is characterised in that：The step (2) is：In step (1) resulting material Maintaining nitrogen purge under liquid level, and continuously stir, 1~5 parts by weight hydrogen peroxide is disposably added, while the first mixed solution is added dropwise With the second mixed solution, rate of addition is controlled, time for adding is 1~2h, and after being added dropwise, reaction system is warming up into 50~60 DEG C, disposably add 0.2~0.8 parts by weight hydrogen peroxide and continue to react, reaction time 1h.
- 4. preparation method as claimed in claim 1, it is characterised in that：The step (3) is：In step (2) resulting material 0.01~0.05 parts by weight SDD is added with terminating reaction, and it is dense to add 10~20 parts by weight quality Spend and neutralized for 30% sodium hydroxide solution, be cooled to 45 DEG C, discharging, obtain ethers polycarboxylic acid water reducing agent.
- 5. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The unsaturated sulfonic acid salt For 2- hydroxyl -3- allyloxys propanesulfonate, 2- hydroxyl -3- allyloxy propane sulfonic acid potassium, 2- hydroxyl -4- alkene butoxy propane sulfonic acid Sodium or 2- hydroxyl -4- alkene butoxy propane sulfonic acid potassium.
- 6. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The chain-transferring agent is mercapto Base ethanol, TGA or mercaptopropionic acid.
- 7. the preparation method as described in any claim in Claims 1-4, it is characterised in that：The reducing agent is 2- hydroxyls Base -2- sulfinatoacetic acids di-potassium or 2- hydroxyl -2- sulfonatoacetic acid di-potassiums.
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