CN101215120A - Method for preparing polycarboxylate water reducing agent - Google Patents
Method for preparing polycarboxylate water reducing agent Download PDFInfo
- Publication number
- CN101215120A CN101215120A CNA2007103026107A CN200710302610A CN101215120A CN 101215120 A CN101215120 A CN 101215120A CN A2007103026107 A CNA2007103026107 A CN A2007103026107A CN 200710302610 A CN200710302610 A CN 200710302610A CN 101215120 A CN101215120 A CN 101215120A
- Authority
- CN
- China
- Prior art keywords
- component
- polycarboxylate dehydragent
- molecular weight
- preparation
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 31
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 238000013019 agitation Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 3
- 230000000977 initiatory effect Effects 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 10
- 229920001427 mPEG Polymers 0.000 claims description 9
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 9
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- -1 ammonium radical ion Chemical class 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012966 redox initiator Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 238000006902 nitrogenation reaction Methods 0.000 claims description 4
- 229920000151 polyglycol Polymers 0.000 claims description 4
- 239000010695 polyglycol Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 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 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 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 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 238000012661 block copolymerization Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 abstract 1
- YYEHOLBIXGDEGT-UHFFFAOYSA-N ethenoxyethene;sulfuric acid Chemical compound C=COC=C.OS(O)(=O)=O YYEHOLBIXGDEGT-UHFFFAOYSA-N 0.000 abstract 1
- 239000011976 maleic acid Substances 0.000 abstract 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 abstract 1
- 239000004568 cement Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 12
- 239000004567 concrete Substances 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000008187 granular material Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000004873 anchoring Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 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
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 239000008030 superplasticizer Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a process for preparing polycarboxylate water reducing agent which is prepared by copolymerization reaction of comonomers in solvent under the condition of existing initiating agent, nitrogen adding and agitation, wherein of the comonomers, component A is vinyl ether sulfate, component B includes at least one of methacrylic acid, acrylic acid, maleic acid and maleic anhydride, the mass of component A is not lower than 50% of the monomer gross mass, and the finally obtained water reducing agent forms a comb type structure. The process is most characterized in that 1, both the relative proportion of big monomer A and monomer B and the performance of the polycarboxylate water reducing agent can be adjusted by adjusting self molecular weight of the big monomer A. 2, the preparing process is environment-friendly and harmless to environment.
Description
Technical field
The present invention relates to a kind of concrete admixture, be specifically related to a kind of preparation method of polycarboxylate dehydragent.
Background technology
Along with the fast development of concrete industry, utilize concrete admixture to prepare the attention that high performance concrete more and more obtains people.Cement water reducing agent is a kind of tensio-active agent, and its molecular structure is made of jointly multiple hydrophilic group and hydrophobic group etc., belongs to water soluble dispersing agent.
Since at first having developed naphthalene sulfonic acidformaldehyde condensation product high efficiency water reducing agent and West Germany's exploitation trimeric cyanamide series high-efficiency water-reducing agent in 1964 from Japan in 1963, the exploitation and the application period of high efficiency water reducing agent have been entered, effectively promoted the development of concrete technology, the outstanding feature of these two serial water reducers is water-reducing rate height, the cement dispersion effect is good, it mainly acts on is to reduce unit consumption of water or unit cement consumption significantly, is used to dispose high strength, superstrength, high durability concrete.
At present, the cement water reducing agent of domestic use is based on naphthalene water reducer, its mature production technology, low price, but its fatal shortcoming is that slump-loss is big, good inadequately with the cement suitability, poor durability, and these condensation polymer type water reducers mostly adopt the vitriol oil of formaldehyde and severe corrosive, inevitably environment are polluted, and are detrimental to health.
By comparison, the polycarboxylic acid series high efficiency water reducing agent of the Japan exploitation eighties in 20th century because have low-dosage, good dispersity, high water reducing rate, the cement suitability is good, slump retaining is good, molecular structure is variable etc., and advantage is developed rapidly.
Wherein, polycarboxylate dehydragent is the focus of studying both at home and abroad in recent years, and it has the advantage of a lot of uniquenesses, such as this water reducer good relatively adaptability can be arranged with different cement; When volume is low, can make concrete have good flowability; When low water-cement ratio, have low viscosity, good relatively slump retentivity and workability; Environmentally friendly or the like.Current, along with development and national economy, the construction of heavy construction is more and more, thereby poly carboxylic acid series water reducer is had higher requirement, urgent requires us to develop new poly carboxylic acid series water reducer, constantly improve and improve every performance of novel poly carboxylic acid series water reducer, to satisfy the needs of economic construction.
Report a kind of polycarboxylic acid series water reducing agents for efficient aerocrote among the Chinese invention patent CN1316398A, but after it produces end, needed to adopt the mode of underpressure distillation, solvent-the butanone of copolyreaction is removed, complex process, energy consumption height, and contaminate environment.
Reported a kind of multi-functional carboxylic acid comb grafted copolymer concrete high efficiency water reducing agent among the Chinese invention patent CN1721361A, when the big monomer of preparation their defoaming function, the catalyzer of choosing comprises the vitriol oil, phosphoric acid and tosic acid, therefore has problem of environmental pollution equally.
Summary of the invention
The object of the invention provides a kind of preparation method of polycarboxylate high-efficiency water reducing agent, with obtain steady quality, slump retaining is good, the polycarboxylate dehydragent of water-reducing rate height and environmental protection; And the material of contaminate environment is not used, do not produced to this method.
For achieving the above object, the technical solution used in the present invention is: a kind of preparation method of polycarboxylate dehydragent,, carried out copolyreaction and get under the condition that initiator exists by each comonomer in solvent under logical nitrogen and agitation condition;
Described comonomer is made of component A and component B, and the quality of component A accounts for 50%～70% of monomer total mass, wherein,
Component A: molecular weight is 400～3000 alkene ether sulphate, and its structural formula is
R
1O(R
2O)
nSO
3M
R in the formula
1The thiazolinyl of expression carbonatoms 3～6; (R
2O)
nBe the polymkeric substance of two kinds of oxyalkylene groups of carbonatoms 2 and 3, wherein carbonatoms is that 3 oxyalkylene group and carbonatoms are that the mol ratio of 2 oxyalkylene group is 1: 2～1: 6; N represents the average addition mole number of oxyalkylene group; M is a kind of in hydrogen ion, sodium ion, potassium ion, the ammonium radical ion;
Component B: be component B
1, perhaps component B
1With component B
2Mixture,
Wherein, component B
1Be selected from one or both the mixture in methacrylic acid, vinylformic acid, toxilic acid, the maleic anhydride;
Component B
2Be selected from one or both the mixture in methoxy poly (ethylene glycol) ether acrylate, methoxy poly (ethylene glycol) ether metacrylic acid ester, methoxy poly (ethylene glycol) ether toxilic acid monoesters, the allyl polyglycol ether, its molecular weight is 400～2500;
When component B by component B
1With component B
2Mix when constituting B
1With B
2The molar mass ratio be 1: 0.2～1: 0.8;
Described solvent is a water; Described copolyreaction temperature is 40～60 ℃, 4～8 hours time;
After polyreaction is finished, in copolymerization product, add the sodium hydroxide neutralization, regulate pH value to 7.5～8.5.
In the technique scheme, (R among the described component A
2O)
nBe polymerized by the mode of two kinds of oxyalkylene groups with block copolymerization or random copolymerization.
The initiation mode that optimized technical scheme, described copolyreaction adopt is a redox initiation, and initiator is made of Oxidizing and Reducing Agents, wherein is selected from a kind of in Sodium Persulfate, ammonium persulphate, Potassium Persulphate or the hydrogen peroxide for oxygenant; Reductive agent is selected from one or more the mixture in oxalic acid, xitix, ferrous sulfate, sodium bisulfite, S-WAT, glucose, the fructose; The consumption of redox initiator is 0.1～8% of a monomer total mass in reaction system.Usually, when carrying out redox initiation, the consumption of Oxidizing and Reducing Agents is mol ratio 1: 1.
Optimized technical scheme, the quality of described component A accounts for 60%～70% of monomer total mass; Thus obtained polycarboxylate dehydragent has higher water-reducing rate.
In the technique scheme, the weight-average molecular weight of the polycarboxylate dehydragent product that makes is 10000～20000.
In the technique scheme, the hybrid mode of each comonomer and water can have following two kinds:
1. before the copolymerization, in reactor, put into water in advance, under logical nitrogen and agitation condition, water is warming up to the copolyreaction temperature,, carry out copolyreaction then with each monomer or partly or entirely add in advance in the still.
2. before the copolymerization, in reactor, put into water in advance, under logical nitrogen and agitation condition, water is warming up to the copolyreaction temperature, then each active comonomer is added drop-wise in the still, carry out copolyreaction.Also need be incubated 1 hour after the dropping, soaking time is long more, reacts complete more.
Principle of the present invention is: component A and component B carry out copolyreaction and produce polycarboxylate dehydragent.Because two keys of each molecule carry out polyreaction under the exciting of initiator, generated organic high molecular polymer, its weight-average molecular weight is 10000-20000.This organic high molecular polymer is a comb-shaped polymer, is connected to more active group on the main chain, relies on these active groups, water reducer can " anchoring " on cement granules; The side chain possess hydrophilic property can stretch in liquid phase, thereby forms huge three-dimensional arrangement at particle surface, produces space steric effect, stops the cohesion of cement granules; At many chain ends strong polar group---sulfate groups is arranged, they also " anchoring " on cement granules, side chain is fixed between the cement granules like this, the performance supporting role, stoped coalescent mutually between cement granules, the maintenance of concrete slump is guaranteed.Adjust big monomeric molecular weight, can change the length of polymkeric substance pectination broach; The mol ratio of adjusting big monomer and minor comonomer can change the broach density of polymkeric substance pectination, thereby changes polymer properties.
Because the technique scheme utilization, the present invention compared with prior art has following advantage:
1, owing to selects for use this new raw material of big monomer A alkene ether sulphate to come synthesizing polycarboxylate superplasticizer as main raw material, can be by regulating big monomer A self molecular weight, regulate the relative proportion of big monomer A and monomers B, make synthetic polycarboxylate dehydragent and cement keep good consistency, the mortar water-reducing rate can remain on more than 23%;
2, the excellent product performance of the present invention's preparation, because there is strong polar group at comb-shaped polymer broach two ends, make polycarboxylate dehydragent " anchoring " between cement granules, there is the multistage oxyalkyl chain centre, certain supporting and space is provided, has improved the slump retaining of polycarboxylate dehydragent;
3, do not use, do not produce harmful material owing in this product preparation process, as: formaldehyde, aromatic hydrocarbons etc., thereby the diminishing city that obtains is a kind of product of environment-friendly type.
Embodiment
Below in conjunction with embodiment the present invention is further described:
In order to simplify statement, below represent to have R with APEGS
1O (R
2O)
nSO
3The big monomer A (alkene ether sulphate) of M structure can be selected for example Emulsogenv5127 of development area, Tianjin state Longhua worker company limited (allyl polyglycol ether ammonium sulfate) or Emulsogen K 208 (polyoxyethylene glycol Vinyl Ether) etc. for use; MPEGMA represents " methoxy poly (ethylene glycol) ether metacrylic acid ester "; MPEGAA represents " methoxy poly (ethylene glycol) ether acrylate "; MPEGMMA represents " methoxy poly (ethylene glycol) ether toxilic acid monoesters "; APEG represents " allyl polyglycol ether "; MAA represents " methacrylic acid "; AA represents " vinylformic acid "; MA represents " maleic anhydride ".
Embodiment one:
(molecular weight is 1000 with 150 gram APEGS, the mol ratio of PO and EO is 1: 3) and 25 the gram MA join fill 150 the gram water reactor in, feed nitrogen, under agitation be heated to 50 ℃, the solution that drips 100 gram MPEGMA (molecular weight is 1000), 20 gram MAA and 150 gram water is in reactor, the potassium persulfate solution of Dropwise 53 grams 5% and 53 restrains 2% S-WAT respectively simultaneously, drips in 5 hours, and constant temperature is 1 hour again.PH value to 8 is regulated with 50% sodium hydroxide solution in the cooling back, is the polycarboxylate dehydragent product.
Embodiment two:
(molecular weight is 1000 with 220 gram APEGS, the mol ratio of PO and EO is 1: 3) and 25 the gram MA join fill 200 the gram water reactor in, feed nitrogen, under agitation be heated to 50 ℃, the solution that drips 100 gram MPEGMA (molecular weight is 1000), 20 gram MAA and 150 gram water is in reactor, the potassium persulfate solution of Dropwise 53 grams 5% and 53 restrains 2% S-WAT respectively simultaneously, drips in 5 hours, and constant temperature is 1 hour again.PH value to 8 is regulated with 50% sodium hydroxide solution in the cooling back, is the polycarboxylate dehydragent product.
Embodiment three:
(molecular weight is 2000 with 150 gram APEGS, the mol ratio of PO and EO is 1: 4) and 145 the gram MA join fill 150 the gram water reactor in, feed nitrogen, under agitation be heated to 50 ℃, the potassium persulfate solution of Dropwise 53 grams 5% and 53 restrains 2% S-WAT respectively simultaneously, dripped in 5 hours, constant temperature is 1 hour again.PH value to 8 is regulated with 50% sodium hydroxide solution in the cooling back, is the polycarboxylate dehydragent product.
Embodiment four:
(molecular weight is 2000 with 185 gram APEGS, the mol ratio of PO and EO is 1: 4) and 115 the gram MA join fill 150 the gram water reactor in, feed nitrogen, under agitation be heated to 50 ℃, the potassium persulfate solution of Dropwise 53 grams 5% and 53 restrains 2% S-WAT respectively simultaneously, dripped in 5 hours, constant temperature is 1 hour again.PH value to 8 is regulated with 50% sodium hydroxide solution in the cooling back, is the polycarboxylate dehydragent product.
Embodiment five:
(molecular weight is 1500 with 150 gram APEGS, the mol ratio of PO and EO is 1: 5) and 25 the gram MA join fill 150 the gram water reactor in, feed nitrogen, under agitation be heated to 50 ℃, the solution that drips 100 gram MPEGAA (molecular weight is 600), 20 gram AA and 150 gram water is in reactor, the potassium persulfate solution of Dropwise 53 grams 5% and 53 restrains 2% S-WAT respectively simultaneously, drips in 5 hours, and constant temperature is 1 hour again.PH value to 8 is regulated with 50% sodium hydroxide solution in the cooling back, is the polycarboxylate dehydragent product.
Embodiment six:
(molecular weight is 1500 with 220 gram APEGS, the mol ratio of PO and EO is 1: 5) and 45 the gram MA join fill 200 the gram water reactor in, feed nitrogen, under agitation be heated to 50 ℃, drip 100 gram MPEGMMA (molecular weight is 600) and 150 and restrain the solution of water in reactor, the potassium persulfate solution of Dropwise 53 grams 5% and 53 restrains 2% S-WAT respectively simultaneously, drips in 5 hours, and constant temperature is 1 hour again.PH value to 8 is regulated with 50% sodium hydroxide solution in the cooling back, is the polycarboxylate dehydragent product.
Embodiment seven:
(molecular weight is 1500 with 220 gram APEGS, the mol ratio of PO and EO is 1: 5) and 35 the gram MA join fill 200 the gram water reactor in, feed nitrogen, under agitation be heated to 50 ℃, drip 105 gram APEG (molecular weight is 1200) and 150 and restrain the solution of water in reactor, the potassium persulfate solution of Dropwise 53 grams 5% and 53 restrains 2% S-WAT respectively simultaneously, drips in 5 hours, and constant temperature is 1 hour again.PH value to 8 is regulated with 50% sodium hydroxide solution in the cooling back, is the polycarboxylate dehydragent product.
Use reference cement by embodiment one to seven prepared polycarboxylate water-reducer, measure its mortar water-reducing rate and mortar degree of mobilization and the degree of mobilization retentivity after 1 hour thereof.(volume folding be admittedly cement 0.2%).
The sand-cement slurry water-reducing rate and the degree of mobilization of each example are listed in the table below:
| Embodiment | One | Two | Three | Four | Five | Six | Seven |
| Water-reducing rate % | 25 | 27 | 23 | 26 | 25 | 27 | 27 |
| Initial flow degree mm | 184 | 184 | 183 | 179 | 181 | 179 | 183 |
| Mm after 1 hour | 171 | 180 | 170 | 182 | 173 | 182 | 187 |
As can be seen from the table, produce polycarboxylate dehydragent by alkene ether sulphate, mortar water-reducing rate height, minimum 23%, the highest by 27%, and retentivity is good.
Claims (5)
1. the preparation method of a polycarboxylate dehydragent, is carried out copolyreaction and gets under the condition that initiator exists by each comonomer in solvent under logical nitrogen and agitation condition, it is characterized in that:
Described comonomer is made of component A and component B, and the quality of component A accounts for 50%～70% of monomer total mass, wherein,
Component A: molecular weight is 400～3000 alkene ether sulphate, and its structural formula is
R
1O(R
2O)
nSO
3M
R in the formula
1The thiazolinyl of expression carbonatoms 3～6; (R
2O)
nBe the polymkeric substance of two kinds of oxyalkylene groups of carbonatoms 2 and 3, wherein carbonatoms is that 3 oxyalkylene group and carbonatoms are that the mol ratio of 2 oxyalkylene group is 1: 2～1: 6; N represents the average addition mole number of oxyalkylene group; M is a kind of in hydrogen ion, sodium ion, potassium ion, the ammonium radical ion;
Component B: be component B
1, perhaps component B
1With component B
2Mixture,
Wherein, component B
1Be selected from one or both the mixture in methacrylic acid, vinylformic acid, toxilic acid, the maleic anhydride;
Component B
2Be selected from one or both the mixture in methoxy poly (ethylene glycol) ether acrylate, methoxy poly (ethylene glycol) ether metacrylic acid ester, methoxy poly (ethylene glycol) ether toxilic acid monoesters, the allyl polyglycol ether, its molecular weight is 400～2500;
When component B by component B
1With component B
2Mix when constituting B
1With B
2The molar mass ratio be 1: 0.2～1: 0.8;
Described solvent is a water; Described copolyreaction temperature is 40～60 ℃, 4～8 hours time;
After polyreaction is finished, in copolymerization product, add the sodium hydroxide neutralization, regulate pH value to 7.5～8.5.
2. the preparation method of polycarboxylate dehydragent according to claim 1 is characterized in that: (R among the described component A
2O)
nBe polymerized by the mode of two kinds of oxyalkylene groups with block copolymerization or random copolymerization.
3. the preparation method of polycarboxylate dehydragent according to claim 1, it is characterized in that: the initiation mode that described copolyreaction is adopted is a redox initiation, initiator is made of Oxidizing and Reducing Agents, wherein is selected from a kind of in Sodium Persulfate, ammonium persulphate, Potassium Persulphate or the hydrogen peroxide for oxygenant; Reductive agent is selected from one or more the mixture in oxalic acid, xitix, ferrous sulfate, sodium bisulfite, S-WAT, glucose, the fructose; The total mass of redox initiator is 0.1～8% of a monomer total mass in reaction system.
4. the preparation method of polycarboxylate dehydragent according to claim 1, it is characterized in that: the quality of described component A accounts for 60%～70% of monomer total mass.
5. the preparation method of polycarboxylate dehydragent according to claim 1, it is characterized in that: the weight-average molecular weight of the polycarboxylate dehydragent product that makes is 10000～20000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007103026107A CN101215120B (en) | 2007-12-29 | 2007-12-29 | Method for preparing polycarboxylate water reducing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007103026107A CN101215120B (en) | 2007-12-29 | 2007-12-29 | Method for preparing polycarboxylate water reducing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101215120A true CN101215120A (en) | 2008-07-09 |
| CN101215120B CN101215120B (en) | 2010-06-16 |
Family
ID=39621640
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007103026107A Expired - Fee Related CN101215120B (en) | 2007-12-29 | 2007-12-29 | Method for preparing polycarboxylate water reducing agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101215120B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010487A (en) * | 2010-10-21 | 2011-04-13 | 安徽中铁工程材料科技有限公司 | Method for preparing polycarboxylate water reducing agent |
| CN101386490B (en) * | 2008-10-16 | 2011-10-05 | 北京建筑工程学院 | A kind of allyl polyethylene glycol ether type polycarboxylate water reducing agent and preparation method thereof |
| CN101993214B (en) * | 2009-08-12 | 2012-12-05 | 山东宏艺科技股份有限公司 | Polycarboxylic acid water reducing agent using diallyl polyethylene glycol (DAPEG) as raw material and preparation method thereof |
| CN105174783A (en) * | 2015-09-10 | 2015-12-23 | 大连市建筑科学研究设计院股份有限公司 | Slow-release type polycarboxylic water reducing agent, preparation method thereof and application |
| CN105646794A (en) * | 2015-12-31 | 2016-06-08 | 江苏苏博特新材料股份有限公司 | Preparation method and application of slump-retaining type phosphate super-plasticizer |
-
2007
- 2007-12-29 CN CN2007103026107A patent/CN101215120B/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101386490B (en) * | 2008-10-16 | 2011-10-05 | 北京建筑工程学院 | A kind of allyl polyethylene glycol ether type polycarboxylate water reducing agent and preparation method thereof |
| CN101993214B (en) * | 2009-08-12 | 2012-12-05 | 山东宏艺科技股份有限公司 | Polycarboxylic acid water reducing agent using diallyl polyethylene glycol (DAPEG) as raw material and preparation method thereof |
| CN102010487A (en) * | 2010-10-21 | 2011-04-13 | 安徽中铁工程材料科技有限公司 | Method for preparing polycarboxylate water reducing agent |
| CN102010487B (en) * | 2010-10-21 | 2012-12-05 | 安徽中铁工程材料科技有限公司 | Method for preparing polycarboxylate water reducing agent |
| CN105174783A (en) * | 2015-09-10 | 2015-12-23 | 大连市建筑科学研究设计院股份有限公司 | Slow-release type polycarboxylic water reducing agent, preparation method thereof and application |
| CN105174783B (en) * | 2015-09-10 | 2017-07-11 | 大连市建筑科学研究设计院股份有限公司 | A kind of Xu puts type poly carboxylic acid series water reducer and its preparation method and application |
| CN105646794A (en) * | 2015-12-31 | 2016-06-08 | 江苏苏博特新材料股份有限公司 | Preparation method and application of slump-retaining type phosphate super-plasticizer |
| CN105646794B (en) * | 2015-12-31 | 2018-01-23 | 江苏苏博特新材料股份有限公司 | The preparation method and application of collapse protection type phosphate super plasticizer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101215120B (en) | 2010-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101333092B (en) | Cement concrete superplasticizer and method for preparing same | |
| CN101786824B (en) | Plastic retaining type polyether assemblage carboxylic acid high-performance water reducing agent and preparation method thereof | |
| CN103613306B (en) | A kind of poly carboxylic acid series water reducer containing hyperbranched polyamine-ester structure and preparation method thereof | |
| CN105367721B (en) | The preparation method and application of viscosity reduction type polycarboxylic acid super-plasticizer | |
| CN101708973B (en) | Water-plastic retaining polycarboxylic acid water reducer and method for preparing same | |
| CN102391435B (en) | Slump-retaining polycarboxylic acid type water reducing agent and preparation method thereof | |
| CN101701050B (en) | Preparation method of comb formation cement dispersant and comb formation cement dispersant | |
| CN101244907A (en) | Polycarboxylic acids series concrete high efficiency water reducing agent and synthesizing process | |
| WO2017113990A1 (en) | Method for preparing concrete superplasticizer having phosphorous acid group and use thereof | |
| CN102173642B (en) | Polyetheramine carboxylate high-efficiency water-reducing agent | |
| CN101215120B (en) | Method for preparing polycarboxylate water reducing agent | |
| CN101353397B (en) | Water-soluble grafting polycarboxylic acids dehydragent and preparation thereof | |
| CN102140018A (en) | Concrete polycarboxylate water reducer and preparation method thereof | |
| CN101817657A (en) | Polycarboxylic acid slump retaining agent | |
| CN102964533B (en) | Hyperbranched polycarboxylic acid copolymer and preparation method thereof | |
| CN101041571A (en) | Air entrained collapse-preventing type polycarboxylate concrete high efficiency water reducing agent and preparation method thereof | |
| CN102532558A (en) | Preparation method of amido polycarboxylic water-reducing agent | |
| CN101830663A (en) | Collapse protective poly-carboxylic acid water reducing agent and preparation method thereof | |
| CN102976654A (en) | Polycarboxylic superplasticizer and application thereof | |
| CN101386489A (en) | Polycarboxylate dehydragent and preparation method thereof | |
| CN102140019B (en) | Polycarboxylic acid water reducing agent and preparation method thereof | |
| CN101983975B (en) | Preparation method of polycarboxylic acid water reducer | |
| CN103373831A (en) | Early-strength polycarboxylate superplasticizer and high-early-strength cement | |
| CN101164956A (en) | Cement disperser and its preparing method | |
| CN101215119A (en) | High-performance polycarboxylic acids water reducing agent prepared by one-step method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: JIANGSU MINGHE GROUP CO., LTD. Free format text: FORMER OWNER: SUZHOU FUCLEAR NEW TYPE BUILDING MATERIAL CO., LTD. Effective date: 20120213 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 215008 SUZHOU, JIANGSU PROVINCE TO: 212021 ZHENJIANG, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20120213 Address after: Runzhou Industrial Park 212021 Zhenjiang City, Jiangsu Province, Runzhou district (five floor, Camellia) Patentee after: Jiangsu Minghe Group Co., Ltd. Address before: Golden Gate Road Jinchang District Suzhou city Jiangsu province 215008 No. 158 room 1510 Patentee before: Suzhou Fuclear New Type Building Material Co., Ltd. |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100616 Termination date: 20131229 |