CN104497228A - Method for mixing polyester-ether macromonomers for preparation of polycarboxylic acid water reducer - Google Patents
Method for mixing polyester-ether macromonomers for preparation of polycarboxylic acid water reducer Download PDFInfo
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 66
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 4
- 239000002253 acid Substances 0.000 title abstract description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 13
- 229920000570 polyether Polymers 0.000 claims abstract description 13
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 229920005646 polycarboxylate Polymers 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 229920000728 polyester Polymers 0.000 claims description 41
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- -1 polyoxyethylene Polymers 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 17
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 claims description 12
- 229950007687 macrogol ester Drugs 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 230000002829 reductive effect Effects 0.000 claims description 10
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical group CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 claims description 8
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 8
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 8
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000004160 Ammonium persulphate Substances 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 4
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- 238000004220 aggregation Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 abstract description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- 229920001223 polyethylene glycol Polymers 0.000 abstract 1
- 239000004567 concrete Substances 0.000 description 18
- 239000004568 cement Substances 0.000 description 8
- 239000004927 clay Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 0 CC(C)(*)O[N+](**[N+](*)[O-])[O-] Chemical compound CC(C)(*)O[N+](**[N+](*)[O-])[O-] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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- Macromonomer-Based Addition Polymer (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a method for mixing polyester-ether macromonomers for preparation of a polycarboxylic acid water reducer, and belongs to the field of a water reducer. According to the method, two macromonomers and maleic anhydride polyethylene glycol are taken as raw materials to produce the polycarboxylic acid water reducer through multiple polymerization in the presence of acrylic acid, a chain transfer agent and a reducing agent. By use of influence of the structure and performance of the polycarboxylic acid water reducer by structure difference of polyether macromonomers and ester macromonomers, water reducing ratio and slump retention property of the polycarboxylic acid water reducer can be balanced, and air entraining ratio of the polycarboxylic acid water reducer can be effectively reducted by use of ester ether mixed structure. The method has the advantages of simple process, convenient control, easy industrialization, low cost, safety and environmental protection.
Description
Technical field
The invention belongs to water reducer field, be specifically related to a kind of method that mixed polyester ether polymeric monomer prepares polycarboxylate water-reducer.
Background technology
Polycarboxylic acid series (PC) water reducer, as the new high performance water-reducing agent released after naphthalene system, fatty family and sulfamate based water reducer, has that water-reducing rate is high, cement granules good dispersity, volume are low, cement adaptability good, slump retaining is good and does not extend the performance characteristics such as concrete setting and harden time, intensity are high, environmental protection.At present, polycarboxylate water-reducer has been widely used in a series of Important Project such as high ferro, bridge, tunnel, is 21 century one of cement additive with application prospect most.
Polycarboxylate water-reducer can improve concrete mobility, and can reduce concrete Water usage, has a kind of effect that can improve concrete intensity and weather resistance etc.But in actual applications, except consideration is to except concrete water-reducing property, also to consider, in the workability at the concrete scene of operation, therefore to need a kind of polycarboxylate water-reducer that can reach balance between both.And existing polycarboxylate water-reducer dispersive ability good (high diminishing) or retentivity good (high-thin arch dam) in the early stage, be difficult to take into account scene to concrete construction requirement, and adopt keeps balancing in this by both composite concrete that make with other water reducers more in prior art, more loaded down with trivial details, serious have impact on applying and performance of polycarboxylate water-reducer.In addition, in actual application, the result of use impact of the clay contained in aggregate on PC is fairly obvious.In concrete production process, the clay contained in aggregate is inevitably mixed in cementitious material system.Along with the increase of clay content, water-reducing rate and the function of slump protection of PC obviously decline, and fresh concrete even can be made to lose flowability completely.The susceptibility of PC result of use to clay has a strong impact on concrete pumping, builds and construction effect.In addition, the polycarboxylate water-reducer of current commercial type is in compound process, stronger to the selectivity of air entrapment agent, defoamer, the monomer type used during the polymerization of the polycarboxylate water-reducer of different manufacturer production and technique are not quite similar, and the polycarboxylate water-reducer bleed gender gap therefore produced is very large.Poly carboxylic acid inherently has certain air-entraining effect, easily introduces more larger-size bubble, affects concrete serviceability, visual appearance, intensity and weather resistance.
Therefore, research polycarboxylate water-reducer has good function of slump protection in a long time, and keep water-reducing rate and slump retaining to balance, the method reducing polycarboxylate water-reducer bleed is necessary.
Summary of the invention
The object of the invention is the limitation in order to overcome existing poly carboxylic acid, providing a kind of mixed polyester ether polymeric monomer to prepare the method for polycarboxylate water-reducer.
Object of the present invention is achieved through the following technical solutions: a kind of mixed polyester ether polymeric monomer prepares the method for polycarboxylate water-reducer, with two kinds of polyether macromonomer and maleic anhydride macrogol ester for raw material, through multiple aggregation, under vinylformic acid, chain-transfer agent and reductive agent existent condition, generate polycarboxylate water-reducer.
The desirable molecular structural formula of mixed ester ether polycarboxylate water-reducer:
Described a kind of mixed polyester ether polymeric monomer prepares the method for polycarboxylate water-reducer, specifically comprises the following steps:
(1) polyoxyethylene glycol, maleic anhydride are added in reactor with the mol ratio of 1:1.1 ~ 1.5, nitrogen is passed into closed reactor 30 ~ 60min with 40 ~ 50L/h simultaneously, air is arranged light, subsequently the flow of nitrogen is turned down to 20 ~ 30L/h, temperature of reaction kettle is increased to 58 ~ 62 DEG C, by the time after material all melts, stir, make mixed solution A;
(2) by temperature-stable at 50 ~ 60 DEG C, in mixed solution A, be slowly incorporated as 98% vitriol oil of weight of material 0.3 ~ 0.5%, stir 8 ~ 12min, temperature is increased to 100 ~ 130 DEG C, is incubated 3 ~ 6h at such a temperature, obtains mixing solutions B;
(3) insulation terminates, and is cooled to 48 ~ 52 DEG C, and close nitrogen, in mixing solutions B, add water, be the maleic anhydride polyoxyethylene glycol ester solution of 45 ~ 55% by its furnishing solid content;
(4) by polyether macromonomer A, polyether macromonomer B, maleic anhydride macrogol ester with the mol ratio of 1:0.2 ~ 0.6:0.1 ~ 0.3, be placed in reactor, be mixed polyester ether, note weight part is 100, add water dissolution, be warming up to 30 ~ 60 DEG C, stir, obtain mixed polyester ethereal solution;
(5) add initiator, drip the mixing solutions that vinylformic acid, chain-transfer agent, reductive agent and water are formed simultaneously, time for adding is 1 ~ 3h;
(6) continue holding temperature 1 ~ 1.5h, carry out slaking to the mixed polyester ethereal solution after dripping, be down to room temperature subsequently, add sodium hydroxide, being adjusted to pH is 6.5 ~ 7.0, obtains polycarboxylate water-reducer.
Described polyoxyethylene glycol comprise molecular weight be in 400,600,800,1000 any one or a few.
The chemical structural formula of described maleic anhydride macrogol ester is:
wherein, n is 8 ~ 22.
Described polyether macromonomer A is methacrylic Soxylat A 25-7, i.e. HPEG, and chemical structural formula is:
wherein, m is 40 ~ 66, and molecular-weight average is 1800 ~ 3000.
Described polyether macromonomer B is isopentenol polyoxyethylene ether, i.e. TPEG, and chemical structural formula is:
wherein, m is 40 ~ 66, and molecular-weight average is 1814 ~ 3014.
The weight part of the water described in step (4) is 40 ~ 60.
The weight part of each component in initiator described in step (5) and mixing solutions: initiator 0.5 ~ 2, vinylformic acid 8 ~ 15, chain-transfer agent 0.2 ~ 1, reductive agent 0.1 ~ 0.4, water 40 ~ 60.
Described initiator to comprise in hydrogen peroxide, ammonium persulphate, Potassium Persulphate, potassium permanganate any one or a few.
Described chain-transfer agent comprises a kind of in Thiovanic acid, thiohydracrylic acid or their mixture.
Described reductive agent to comprise in xitix, rongalite, ferrous sulfate, sodium bisulfite any one or a few.
The present invention has following beneficial effect:
(1) the present invention is by the Structure and Properties of the structural difference influences polycarboxylate water-reducer of polyether macromonomer and ester class polymeric monomer: the molecular structure of HPEG ensure that the initial dispersion of polycarboxylate water-reducer; The molecular structure of TPEG ensure that the dispersion retention of polycarboxylate water-reducer; The introducing of ester class polymeric monomer, at aquation later stage ester linkage breaking, discharges more water reducer molecule, makes polycarboxylate water-reducer still have good function of slump protection in a long time; Acting in conjunction between HPEG, TPEG and ester class polymeric monomer, makes the relation between the water-reducing rate of polycarboxylate water-reducer and slump retaining better be balanced.
(2) the ester ether mixed structure that in the present invention, polyether macromonomer and ester class polymeric monomer are formed effectively can reduce the bleed of polycarboxylate water-reducer, reduce the introducing of the bad bubble of large-size, concrete work performance is stablized, reliable in quality, intensity increases, and has more weather resistance.
(3) the present invention with methacrylic Soxylat A 25-7, isopentenol polyoxyethylene ether and maleic anhydride macrogol ester for raw material, multiple aggregation prepares polycarboxylate water-reducer, whole technological process is simple, building-up process is easily controlled, is easy to realize suitability for industrialized production.
(4), in whole preparation process of the present invention, safety and environmental protection, cleanliness without any pollution, be raw materials usedly easy to get, low production cost.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, and protection scope of the present invention is not limited to the following stated.
Embodiment 1: a kind of mixed polyester ether polymeric monomer prepares the method for polycarboxylate water-reducer, and it comprises the following steps:
(1) by molecular weight be 1000 polyoxyethylene glycol and maleic anhydride add in reactor with the mol ratio of 1:1.1, nitrogen is passed into closed reactor 30min with 40h/L simultaneously, air is arranged light, subsequently the flow of nitrogen is turned down to 20h/L, temperature of reaction kettle is increased to 58 DEG C, by the time after material all melts, stir, make mixed solution A;
(2) by temperature-stable at 50 DEG C, in mixed solution A, be slowly incorporated as 98% vitriol oil of weight of material 0.3%, stir 8min, temperature is increased to 100 DEG C, is incubated 6h at such a temperature, obtains mixing solutions B;
(3) insulation terminates, and is cooled to 48 DEG C, and close nitrogen, in mixing solutions B, add water, be the maleic anhydride polyoxyethylene glycol ester solution of 45% by its furnishing solid content;
(4) by molecular weight be 1832 methacrylic Soxylat A 25-7, molecular weight be 1846 isopentenol polyoxyethylene ether and molecular weight be that the maleic anhydride macrogol ester of 482 is with the mol ratio of 1:0.2:0.1, be placed in reactor, be mixed polyester ether, note weight part is 100, add the water dissolution that weight part is 40, be warming up to 30 DEG C, stir, obtain mixed polyester ethereal solution;
(5) hydrogen peroxide that weight part is 0.5 is added, drip the mixing solutions that vinylformic acid, Thiovanic acid, xitix and water are formed simultaneously, time for adding is 1h, wherein, acrylic acid weight part is 8, the weight part of Thiovanic acid is 0.2, and the weight part of xitix is 0.1, and the weight part of water is 40;
(6) continue holding temperature 1h, carry out slaking to the mixed polyester ethereal solution after dripping, be down to room temperature subsequently, add sodium hydroxide, being adjusted to pH is 6.5, obtains polycarboxylate water-reducer.
After the polycarboxylate water-reducer obtained is deposited 30 days at 6 DEG C, measure its implementation result: the dispersiveness had and slump retaining; Be blended in cement, concrete work performance is stablized, and intensity increases.
Embodiment 2: a kind of mixed polyester ether polymeric monomer prepares the method for polycarboxylate water-reducer, and it comprises the following steps:
(1) by molecular weight be 400 polyoxyethylene glycol and maleic anhydride add in reactor with the mol ratio of 1:1.5, nitrogen is passed into closed reactor 60min with 50L/h simultaneously, air is arranged light, subsequently the flow of nitrogen is turned down to 30L/h, temperature of reaction kettle is increased to 62 DEG C, by the time after material all melts, stir, make mixed solution A;
(2) by temperature-stable at 60 DEG C, in mixed solution A, be slowly incorporated as 98% vitriol oil of weight of material 0.5%, stir 12min, temperature is increased to 130 DEG C, is incubated 3h at such a temperature, obtains mixing solutions B;
(3) insulation terminates, and is cooled to 52 DEG C, and close nitrogen, in mixing solutions B, add water, be the maleic anhydride polyoxyethylene glycol ester solution of 55% by its furnishing solid content;
(4) by molecular weight be 2976 methacrylic Soxylat A 25-7, molecular weight be 2990 isopentenol polyoxyethylene ether and molecular weight be that the maleic anhydride macrogol ester of 1098 is with the mol ratio of 1:0.6:0.3, be placed in reactor, be mixed polyester ether, note weight part is 100, add the water dissolution that weight part is 60, be warming up to 60 DEG C, stir, obtain mixed polyester ethereal solution;
(5) add the ammonium persulphate that weight part is 2, drip the mixing solutions that vinylformic acid, thiohydracrylic acid, rongalite and water are formed simultaneously, time for adding is 3h, wherein, acrylic acid weight part is 15, and the weight part of thiohydracrylic acid is 1, the weight part of rongalite is 0.4, and the weight part of water is 60;
(6) continue holding temperature 1.5h, carry out slaking to the mixed polyester ethereal solution after dripping, be down to room temperature subsequently, add sodium hydroxide, being adjusted to pH is 7.0, obtains polycarboxylate water-reducer.
After the polycarboxylate water-reducer obtained is deposited 33 days at 9 DEG C, measure its implementation result: the dispersiveness had and slump retaining; Be blended in cement, concrete work performance is stablized, and intensity increases.
Embodiment 3: a kind of mixed polyester ether polymeric monomer prepares the method for polycarboxylate water-reducer, and it comprises the following steps:
(1) by molecular weight be 600 polyoxyethylene glycol and maleic anhydride add in reactor with the mol ratio of 1:1.3, nitrogen is passed into closed reactor 40min with 42L/h simultaneously, air is arranged light, subsequently the flow of nitrogen is turned down to 23L/h, temperature of reaction kettle is increased to 60 DEG C, by the time after material all melts, stir, make mixed solution A;
(2) by temperature-stable at 53 DEG C, in mixed solution A, be slowly incorporated as 98% vitriol oil of weight of material 0.4%, stir 10min, temperature is increased to 110 DEG C, is incubated 4.5h at such a temperature, obtains mixing solutions B;
(3), after insulation, close nitrogen, being cooled to 50 DEG C, adding water to mixing solutions B, is the maleic anhydride polyoxyethylene glycol ester solution of 48% by its furnishing solid content;
(4) by molecular weight be 2272 methacrylic Soxylat A 25-7, molecular weight be 2286 isopentenol polyoxyethylene ether and molecular weight be that the maleic anhydride macrogol ester of 570 is with the mol ratio of 1:0.4:0.2, be placed in reactor, be mixed polyester ether, note weight part is 100, add the water dissolution that weight part is 45, be warming up to 40 DEG C, stir, obtain mixed polyester ethereal solution;
(5) potassium permanganate that weight part is 1 is added, drip the mixing solutions that vinylformic acid, thiohydracrylic acid, ferrous sulfate and water are formed simultaneously, time for adding is 2h, wherein, acrylic acid weight part is 10, and the weight part of thiohydracrylic acid is, 0.4, the weight part of ferrous sulfate is 0.18, and the weight part of water is 45;
(6) continue holding temperature 1.5h, carry out slaking to the mixed polyester ethereal solution after dripping, be down to room temperature subsequently, add sodium hydroxide, being adjusted to pH is 6.7, obtains polycarboxylate water-reducer.
After the polycarboxylate water-reducer obtained is deposited 32 days at 7 DEG C, measure its implementation result: the dispersiveness had and slump retaining; Be blended in cement, concrete work performance is stablized, and intensity increases.
Embodiment 4: a kind of mixed polyester ether polymeric monomer prepares the method for polycarboxylate water-reducer, and it comprises the following steps:
(1) by molecular weight be 800 polyoxyethylene glycol and maleic anhydride add in reactor with the mol ratio of 1:1.4, nitrogen is passed into closed reactor 50min with 45L/h simultaneously, air is arranged light, subsequently the flow of nitrogen is turned down to 25L/h, temperature of reaction kettle is increased to 61 DEG C, by the time after material all melts, stir, make mixed solution A;
(2) by temperature-stable at 57 DEG C, in mixed solution A, be slowly incorporated as 98% vitriol oil of weight of material 0.4%, stir 11min, temperature is increased to 120 DEG C, is incubated 4h at such a temperature, obtains mixing solutions B;
(3) insulation terminates, and is cooled to 51 DEG C, and close nitrogen, in mixing solutions B, add water, be the maleic anhydride polyoxyethylene glycol ester solution of 52% by its furnishing solid content;
(4) by molecular weight be 2712 methacrylic Soxylat A 25-7, molecular weight be 2726 isopentenol polyoxyethylene ether and molecular weight be that the maleic anhydride macrogol ester of 790 is with the mol ratio of 1:0.5:0.3, be placed in reactor, be mixed polyester ether, note weight part is 100, add the water dissolution that weight part is 50, be warming up to 50 DEG C, stir, obtain mixed polyester ethereal solution;
(5) Potassium Persulphate that weight part is 1.3 is added, drip the mixing solutions that vinylformic acid, Thiovanic acid, sodium bisulfite and water are formed simultaneously, time for adding is 2.5h, wherein, acrylic acid weight part is 12, the weight part of Thiovanic acid is 0.6, and the weight part of sodium bisulfite is 0.25, and the weight part of water is 50;
(6) continue holding temperature 1.5h, carry out slaking to the mixed polyester ethereal solution after dripping, be down to room temperature subsequently, add sodium hydroxide, being adjusted to pH is 6.8, obtains polycarboxylate water-reducer.
After the polycarboxylate water-reducer obtained is deposited 32 days at 8 DEG C, measure its implementation result: the dispersiveness had and slump retaining; Be blended in cement, concrete work performance is stablized, and intensity increases.
Embodiment 5: a kind of mixed polyester ether polymeric monomer prepares the method for polycarboxylate water-reducer, and it comprises the following steps:
(1) by molecular weight be 600 polyoxyethylene glycol, molecular weight be 800 polyoxyethylene glycol and maleic anhydride add in reactor with the mol ratio of 1:1:2.4, nitrogen is passed into closed reactor 45min with 48L/h simultaneously, air is arranged light, subsequently the flow of nitrogen is turned down to 28L/h, temperature of reaction kettle is increased to 60 DEG C, by the time after material all melts, stir, make mixed solution A;
(2) by temperature-stable at 57 DEG C, in mixed solution A, be slowly incorporated as 98% vitriol oil of weight of material 0.4%, stir 11min, temperature is increased to 120 DEG C, is incubated 4h at such a temperature, obtains mixing solutions B;
(3) insulation terminates, and is cooled to 51 DEG C, and close nitrogen, adding water to mixing solutions B, is the maleic anhydride polyoxyethylene glycol ester solution of 52% by its furnishing solid content;
(4) by molecular weight be 2712 methacrylic Soxylat A 25-7, molecular weight be 2726 isopentenol polyoxyethylene ether and molecular weight be that the maleic anhydride macrogol ester of 790 is with the mol ratio of 1:0.5:0.3, be placed in reactor, be mixed polyester ether, note weight part is 100, add the water dissolution that weight part is 55, be warming up to 50 DEG C, stir, obtain mixed polyester ethereal solution;
(5) adding weight part is the ammonium persulphate of 1.7 and the mixture of potassium permanganate, wherein, ammonium persulphate and potassium permanganate weight ratio are 1:1, drip vinylformic acid simultaneously, chain-transfer agent, the mixing solutions that reductive agent and water are formed, time for adding is 2.5h, wherein, in this mixing solutions, acrylic acid weight part is 14, chain-transfer agent is the mixture of Thiovanic acid and thiohydracrylic acid, weight part is 0.8, Thiovanic acid, thiohydracrylic acid weight ratio is 1:1, reductive agent is the mixture of xitix and sodium bisulfite, weight part is 0.35, xitix, sodium bisulfite weight ratio is 1:1, the weight part of water is 55,
(6) continue holding temperature 1.5h, carry out slaking to the mixed polyester ethereal solution after dripping, be down to room temperature subsequently, add sodium hydroxide, being adjusted to pH is 6.8, obtains polycarboxylate water-reducer.
After the polycarboxylate water-reducer obtained is deposited 31 days at 9 DEG C, measure its implementation result: the dispersiveness had and slump retaining; Be blended in cement, concrete work performance is stablized, and intensity increases.
Claims (10)
1. a mixed polyester ether polymeric monomer prepares the method for polycarboxylate water-reducer, it is characterized in that, with two kinds of polyether macromonomer and maleic anhydride macrogol ester for raw material, through multiple aggregation, under vinylformic acid, chain-transfer agent and reductive agent existent condition, generate polycarboxylate water-reducer.
2. a kind of mixed polyester ether polymeric monomer according to claim 1 prepares the method for polycarboxylate water-reducer, and it is characterized in that, described preparation method specifically comprises the following steps:
(1) polyoxyethylene glycol, maleic anhydride are added in reactor with the mol ratio of 1:1.1 ~ 1.5, nitrogen is passed into closed reactor 30 ~ 60min with 40 ~ 50L/h simultaneously, air is arranged light, subsequently the flow of nitrogen is turned down to 20 ~ 30L/h, temperature of reaction kettle is increased to 58 ~ 62 DEG C, by the time after material all melts, stir, make mixed solution A;
(2) by temperature-stable at 50 ~ 60 DEG C, in mixed solution A, be slowly incorporated as 98% vitriol oil of weight of material 0.3 ~ 0.5%, stir 8 ~ 12min, temperature is increased to 100 ~ 130 DEG C, is incubated 3 ~ 6h at such a temperature, obtains mixing solutions B;
(3) insulation terminates, and is cooled to 48 ~ 52 DEG C, and close nitrogen, in mixing solutions B, add water, be the maleic anhydride polyoxyethylene glycol ester solution of 45 ~ 55% by its furnishing solid content;
(4) by polyether macromonomer A, polyether macromonomer B, maleic anhydride macrogol ester with the mol ratio of 1:0.2 ~ 0.6:0.1 ~ 0.3, be placed in reactor, be mixed polyester ether, note weight part is 100, add water dissolution, be warming up to 30 ~ 60 DEG C, stir, obtain mixed polyester ethereal solution;
(5) add initiator, drip the mixing solutions that vinylformic acid, chain-transfer agent, reductive agent and water are formed simultaneously, time for adding is 1 ~ 3h;
(6) continue holding temperature 1 ~ 1.5h, carry out slaking to the mixed polyester ethereal solution after dripping, be down to room temperature subsequently, add sodium hydroxide, being adjusted to pH is 6.5 ~ 7.0, obtains polycarboxylate water-reducer.
3. a kind of mixed polyester ether polymeric monomer according to claim 2 prepares the method for polycarboxylate water-reducer, it is characterized in that, described polyoxyethylene glycol comprise molecular weight be in 400,600,800,1000 any one or a few.
4. a kind of mixed polyester ether polymeric monomer according to claim 2 prepares the method for polycarboxylate water-reducer, and it is characterized in that, the chemical structural formula of described maleic anhydride macrogol ester is:
wherein, n is 8 ~ 22.
5. a kind of mixed polyester ether polymeric monomer according to claim 2 prepares the method for polycarboxylate water-reducer, and it is characterized in that, described polyether macromonomer A is methacrylic Soxylat A 25-7, i.e. HPEG, and chemical structural formula is:
wherein, m is 40 ~ 66, and molecular-weight average is 1800 ~ 3000.
6. a kind of mixed polyester ether polymeric monomer according to claim 2 prepares the method for polycarboxylate water-reducer, and it is characterized in that, described polyether macromonomer B is isopentenol polyoxyethylene ether, i.e. TPEG, and chemical structural formula is:
wherein, m is 40 ~ 66, and molecular-weight average is 1814 ~ 3014.
7. a kind of mixed polyester ether polymeric monomer according to claim 2 prepares the method for polycarboxylate water-reducer, it is characterized in that, the weight part of each component in initiator described in step (5) and mixing solutions: initiator 0.5 ~ 2, vinylformic acid 8 ~ 15, chain-transfer agent 0.2 ~ 1, reductive agent 0.1 ~ 0.4, water 40 ~ 60.
8. a kind of mixed polyester ether polymeric monomer according to claim 2 or 7 prepares the method for polycarboxylate water-reducer, it is characterized in that, described initiator to comprise in hydrogen peroxide, ammonium persulphate, Potassium Persulphate, potassium permanganate any one or a few.
9. a kind of mixed polyester ether polymeric monomer according to claim 2 or 7 prepares the method for polycarboxylate water-reducer, it is characterized in that, described chain-transfer agent comprises a kind of in Thiovanic acid, thiohydracrylic acid or their mixture.
10. a kind of mixed polyester ether polymeric monomer according to claim 2 or 7 prepares the method for polycarboxylate water-reducer, it is characterized in that, described reductive agent to comprise in xitix, rongalite, ferrous sulfate, sodium bisulfite any one or a few.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102093521A (en) * | 2010-12-31 | 2011-06-15 | 四川吉龙化学建材有限公司 | Method for preparing polycarboxylic acid high slump retaining agent |
| WO2011076655A1 (en) * | 2009-12-21 | 2011-06-30 | Mapei S.P.A. | Superplasticizers for concrete and cement materials and process for producing the same |
| WO2014059674A1 (en) * | 2012-10-19 | 2014-04-24 | 江苏博特新材料有限公司 | Water reducer intermediate, preparation method therefor, and water reducer prepared by using the same |
-
2014
- 2014-11-25 CN CN201410687518.7A patent/CN104497228A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011076655A1 (en) * | 2009-12-21 | 2011-06-30 | Mapei S.P.A. | Superplasticizers for concrete and cement materials and process for producing the same |
| CN102093521A (en) * | 2010-12-31 | 2011-06-15 | 四川吉龙化学建材有限公司 | Method for preparing polycarboxylic acid high slump retaining agent |
| WO2014059674A1 (en) * | 2012-10-19 | 2014-04-24 | 江苏博特新材料有限公司 | Water reducer intermediate, preparation method therefor, and water reducer prepared by using the same |
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| CN108219079A (en) * | 2016-12-14 | 2018-06-29 | 上海东大化学有限公司 | A kind of poly carboxylic acid series water reducer and preparation method thereof and application method |
| CN108219079B (en) * | 2016-12-14 | 2020-04-28 | 上海东大化学有限公司 | Polycarboxylic acid water reducing agent, and preparation method and use method thereof |
| CN109762112A (en) * | 2017-11-09 | 2019-05-17 | 中冶建筑研究总院有限公司 | A kind of synthetic method of polycarboxylate water-reducer |
| WO2019100372A1 (en) * | 2017-11-27 | 2019-05-31 | 科之杰新材料集团有限公司 | Rapid low-temperature preparation method for mixing amount low sensitive polycarboxylic acid |
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