CN101993210A - Prenyl polyether polycarboxylate water reducing agent and synthesis method thereof - Google Patents
Prenyl polyether polycarboxylate water reducing agent and synthesis method thereof Download PDFInfo
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- CN101993210A CN101993210A CN 201010119880 CN201010119880A CN101993210A CN 101993210 A CN101993210 A CN 101993210A CN 201010119880 CN201010119880 CN 201010119880 CN 201010119880 A CN201010119880 A CN 201010119880A CN 101993210 A CN101993210 A CN 101993210A
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- prenyl
- water reducing
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- acid
- reducing agent
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 title claims abstract description 25
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 24
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 21
- 229920000570 polyether Polymers 0.000 title claims abstract description 20
- 239000004721 Polyphenylene oxide Substances 0.000 title abstract description 6
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 239000000178 monomer Substances 0.000 claims abstract description 22
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 10
- -1 polyoxyethylene propylene ether Polymers 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 37
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 13
- 235000019154 vitamin C Nutrition 0.000 claims description 12
- 239000011718 vitamin C Substances 0.000 claims description 12
- 238000009413 insulation Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000010189 synthetic method Methods 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
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 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
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- 125000003368 amide group Chemical group 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
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 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
- 239000000126 substance Substances 0.000 claims description 2
- ACTRVOBWPAIOHC-UHFFFAOYSA-N succimer Chemical compound OC(=O)C(S)C(S)C(O)=O ACTRVOBWPAIOHC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical group OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 238000007334 copolymerization reaction Methods 0.000 abstract description 6
- 239000012966 redox initiator Substances 0.000 abstract description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract 2
- 230000005494 condensation Effects 0.000 abstract 2
- 229920000056 polyoxyethylene ether Polymers 0.000 abstract 2
- 229940051841 polyoxyethylene ether Drugs 0.000 abstract 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 21
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 15
- 239000004568 cement Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 7
- 229960005070 ascorbic acid Drugs 0.000 description 7
- 238000009835 boiling Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 238000010907 mechanical stirring Methods 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- ACIAHEMYLLBZOI-ZZXKWVIFSA-N Unsaturated alcohol Chemical compound CC\C(CO)=C/C ACIAHEMYLLBZOI-ZZXKWVIFSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007046 ethoxylation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a prenyl polyether polycarboxylate water reducing agent which is a polymer of prenyl polyoxyethylene ether or prenyl polyoxyethylene propylene ether (big monomer A) and unsaturated carboxylic acid and derivatives thereof (small monomer B), belonging to the field of concrete additives. A synthesis method of the water reducing agent comprises the following steps of: with water as a solvent, initiating the big monomer A and the small monomer B by adopting a redox initiation system under the lower temperature, and carrying out copolymerization under the action of a chain transfer agent to obtain the finished product. The water reducing agent overcomes the defects of low water reducing rate, poor slump loss resistance, long condensation time, and the like of a water reducing agent synthesized by allyl polyoxyethylene ether and has the advantages of high slump loss resistance, plenty water reducing and small influence on the condensation time of concrete.
Description
Technical field
The present invention relates to cement water reducing agent, specifically belong to a kind of prenyl polyethers polycarboxylate dehydragent and synthetic method thereof.
Background technology
Water reducer is used for concrete, can reduce the needed moisture of hardening of cement, and cement is had very strong dissemination, make solidify the back concrete physical structure more even, improve concrete intensity.The development of water reducer mainly contains three phases: the first-generation is to be the ordinary water-reducing agent of representative with sulfonated lignin; The s-generation is to be the high efficiency water reducing agent of representative with the naphthalenesulfonate; The third generation is to be the high-performance water reducing agent of representative with the polycarboxylate.
The polycarboxylate dehydragent that has polyether lateral chain is present newest research results, and it just has higher dispersing property, good function of slump protection under low-dosage; In addition, its degree of freedom on molecular structure is big, and the synthetic technology method is various, obtains high performance having a high potential.
The patent documentation of polycarboxylate high performance dehydragent mainly is the polyethers polycarboxylate dehydragent of unsaturated alcohol both at home and abroad at present.(methyl) acrylic acid esterification class water reducer water-reducing rate is higher, slump retaining might as well, but the big monomer of polyester at first will carry out the esterification of macromolecular alcohol and small molecules unsaturated acid, this step, synthetic difficulty was big, intermediate section is from the purge process more complicated, the macromonomer raw material instability that synthesizes, the industrialization cost is higher.And the synthesis technique of the polyethers polycarboxylate dehydragent of unsaturated alcohol is simple, the big monomer of unsaturated polyether is mainly undertaken by industrial ethoxylation equipment, only need carry out a step ring-opening polymerization, need not separate, product purity is very high, follow-up polymerization technique is simple, product in the market mainly is an allyl polyethenoxy ether, such polyethers activity is lower, can only carry out copolymerization preferably with maleic anhydride, synthetic product water-reducing rate is low, and function of slump protection is general and because two carboxyls of maleic anhydride, such polycarboxylate dehydragent that makes influences bigger to the aquation of cement; The product that report is arranged at present is the methacrylic Soxylat A 25-7, and such polyethers activity is higher, can carry out copolymerization preferably with the acrylic acid or the like minor comonomer, and synthetic water reducer water-reducing rate is higher, and function of slump protection is good, and is good with various cement adaptabilities.Employed initiator was a methallyl alcohol synthesis technique complexity when but it was synthetic, and price is higher, belongs to fine chemical product, had limited its large-scale popularization and had used.
Summary of the invention
The purpose of this invention is to provide a kind of prenyl polyethers polycarboxylate dehydragent and synthetic method thereof, the big monomer that this water reducer uses is not only active higher, can carry out copolymerization preferably with the acrylic acid or the like minor comonomer, synthetic water reducer water-reducing rate is higher, function of slump protection is good, and is good with various cement adaptabilities, and its big monomer when synthetic employed initiator synthesis technique simple, price is lower, is easy to promote.
A kind of prenyl polyethers polycarboxylate dehydragent provided by the invention, it is the polymkeric substance of prenyl Soxylat A 25-7 or prenyl polyoxyethylene propylene ether (A) and unsaturated carboxylic acid or derivatives thereof (B), represent big monomer A with formula (1), B is as follows with formula (2) expression minor comonomer:
Wherein: R
1-hydrogen atom or C atomicity are 1～5 alkyl group
The m-number of repeat unit is 5～200
The n-number of repeat unit is 0～100,
Wherein: R
2-hydrogen atom or C atomicity are 1～5 alkyl group
R
3-hydroxyl, amido or C atomicity are 1～5 alkyl group.
Synthetic above-mentioned polycarboxylate high performance dehydragent is to adopt redox initiation system to cause big monomer A and minor comonomer B, gets through copolyreaction under the chain-transfer agent effect.
Concrete steps comprise: big monomer A is dissolved in the deionized water, warming while stirring, when temperature is raised to 30-50 ℃, add oxygenant, when temperature reaches 60-80 ℃, drip the mixed aqueous solution of the minor comonomer B aqueous solution and reductive agent and chain-transfer agent simultaneously, the minor comonomer B aqueous solution dropping time was controlled at 2～4 hours, and the mixed aqueous solution dropping time of reductive agent and chain-transfer agent was controlled at 2.5～5 hours, after dropwising, continue insulation 0.5～2 hour, be cooled to then below 40 ℃, add aqueous sodium hydroxide solution and neutralize, the control product concentration is 20～50%, pH=6～8 finally obtain light yellow hyalomucoid;
The mol ratio of described big monomer A and minor comonomer B is 1: 1～5;
Total consumption of described Oxidizing and Reducing Agents accounts for 0.2～5% of big monomer A and minor comonomer B gross weight;
Described chain-transfer agent consumption accounts for 0.05～0.25% of big monomer A and minor comonomer B gross weight.
Described chain-transfer agent is mercaptoethanol, Thiovanic acid, thiohydracrylic acid or dimercaptosuccinic acid.
Described oxygenant can be in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, the hydrogen peroxide one or more.
Described reductive agent can be in vitamins C, S-WAT, oxalic acid, the glucose one or more.
The polycarboxylate dehydragent performance test is according to GB8076-2008 and GB8077-2000
The polycarboxylate dehydragent molecular weight detects with the water gel chromatograph, molecular weight 5000～200000.
Advantage compared with prior art of the present invention and effect: the big monomer that the present invention uses is the prenyl Soxylat A 25-7, not only active higher, can carry out copolymerization preferably with the acrylic acid or the like minor comonomer, synthetic water reducer water-reducing rate is higher, and function of slump protection is good, and is good with various cement adaptabilities, and its big monomer when synthetic employed initiator be isoprene alcohol, synthesis technique is simple, and price is lower, is easy to promote.The present invention has adopted redox initiation system, is that solvent has synthesized a kind of polycarboxylate high performance dehydragent of polyethers efficiently with water, and its production technique is simple, and polymerization temperature is low, gained polycarboxylate dehydragent superior performance.
Embodiment
The used big monomer A of copolymerization in the following example of the present invention:
IB-500: prenyl Soxylat A 25-7, molecular-weight average are 500;
IB-1000: prenyl Soxylat A 25-7, molecular-weight average are 1000;
IB-1500: prenyl Soxylat A 25-7, molecular-weight average are 1500;
IB-2000: prenyl Soxylat A 25-7, molecular-weight average are 2000;
IB-2500: prenyl Soxylat A 25-7, molecular-weight average are 2500;
IB-3000: prenyl Soxylat A 25-7, molecular-weight average are 3000;
IB-5000: prenyl polyoxyethylene propylene ether, molecular-weight average is 4000;
Used minor comonomer B is acrylic or methacrylic acid in the following example.
Embodiment 1
Mechanical stirring is being housed, temperature regulator, add 150gIB-500 in the 1000ml four-hole boiling flask of dropper, add the 120g deionized water simultaneously, heat up in stirring and dissolving limit, limit, when temperature is raised to 50 ℃, the hydrogen peroxide that adds 1.1g30%, when temperature reaches 60 ℃, mixing solutions (the 0.5g vitamins C of beginning while dropwise addition of acrylic acid solution (22g vinylformic acid is dissolved in the 10g deionized water) and vitamins C and Thiovanic acid, 0.3g Thiovanic acid is dissolved in the 60g deionized water), the dropping time of acrylic acid solution was controlled at 2.5 hours, the dropping time of vitamin c solution is controlled at 3h, and temperature of reaction is controlled at 60 ± 2 ℃.After dropwising, continue insulation 0.5 hour, be cooled to then below 40 ℃, add aqueous sodium hydroxide solution (the 6.9g dissolution of sodium hydroxide is in the 71.1g deionized water) and neutralize, obtaining concentration is 40%, the light yellow hyalomucoid of pH=7.5.Molecular-weight average is 40000 after tested, and density is 1.07g/ml.
Embodiment 2
Mechanical stirring is being housed, temperature regulator, add 155gIB-1000 in the 1000ml four-hole boiling flask of dropper, add the 120g deionized water simultaneously, heat up in stirring and dissolving limit, limit, when temperature is raised to 50 ℃, the hydrogen peroxide that adds 1.0g30%, when temperature reaches 60 ℃, mixing solutions (the 0.4g S-WAT of beginning while dropwise addition of acrylic acid solution (16g vinylformic acid is dissolved in the 10g deionized water) and S-WAT and Thiovanic acid, 0.2g thiohydracrylic acid is dissolved in the 60g deionized water), the dropping time of acrylic acid solution was controlled at 2.5 hours, the dropping time of vitamin c solution is controlled at 3h, and temperature of reaction is controlled at 60 ± 2 ℃.After dropwising, continue insulation 0.5 hour, be cooled to then below 40 ℃, add aqueous sodium hydroxide solution (the 5.0g dissolution of sodium hydroxide is in the 68.6g deionized water) and neutralize, obtaining concentration is 40%, the light yellow hyalomucoid of pH=7.5.Molecular-weight average is 43000 after tested, and density is 1.07g/ml.
Embodiment 3
Mechanical stirring is being housed, temperature regulator, add 156gIB-1500 in the 1000ml four-hole boiling flask of dropper, add the 120g deionized water simultaneously, heat up in stirring and dissolving limit, limit, when temperature is raised to 50 ℃, the hydrogen peroxide that adds 1.1g30%, when temperature reaches 60 ℃, beginning drips mixing solutions (the 0.52g vitamins C of methacrylic acid solution (the 17g methacrylic acid is dissolved in the 10g deionized water) and vitamins C and Thiovanic acid simultaneously, 0.26g Thiovanic acid is dissolved in the 60g deionized water), the dropping time of acrylic acid solution was controlled at 2.5 hours, the dropping time of vitamin c solution is controlled at 3h, and temperature of reaction is controlled at 60 ± 2 ℃.After dropwising, continue insulation 0.5 hour, be cooled to then below 40 ℃, add aqueous sodium hydroxide solution (the 5.3g dissolution of sodium hydroxide is in the 71.9g deionized water) and neutralize, obtaining concentration is 40%, the light yellow hyalomucoid of pH=7.5.Molecular-weight average is 44000 after tested, and density is 1.07g/ml.
Embodiment 4
Mechanical stirring is being housed, temperature regulator, add 165gIB-2000 in the 1000ml four-hole boiling flask of dropper, add the 120g deionized water simultaneously, heat up in stirring and dissolving limit, limit, when temperature is raised to 50 ℃, the hydrogen peroxide that adds 1.3g30%, when temperature reaches 60 ℃, mixing solutions (the 0.48g vitamins C of beginning while dropwise addition of acrylic acid solution (16.5g vinylformic acid is dissolved in the 10g deionized water) and vitamins C and Thiovanic acid, 0.18g thiohydracrylic acid is dissolved in the 60g deionized water), the dropping time of acrylic acid solution was controlled at 2.5 hours, the dropping time of vitamin c solution is controlled at 3h, and temperature of reaction is controlled at 60 ± 2 ℃.After dropwising, continue insulation 0.5 hour, be cooled to then below 40 ℃, add aqueous sodium hydroxide solution (the 5.2g dissolution of sodium hydroxide is in the 84.2g deionized water) and neutralize, obtaining concentration is 40%, the light yellow hyalomucoid of pH=7.5.Molecular-weight average is 46000 after tested, and density is 1.07g/ml.
Embodiment 5
Mechanical stirring is being housed, temperature regulator, add 178gIB-2500 in the 1000ml four-hole boiling flask of dropper, add the 120g deionized water simultaneously, heat up in stirring and dissolving limit, limit, when temperature is raised to 50 ℃, the hydrogen peroxide that adds 1.2g30%, when temperature reaches 60 ℃, mixing solutions (the 0.53g S-WAT of beginning while dropwise addition of acrylic acid solution (16.7g vinylformic acid is dissolved in the 10g deionized water) and S-WAT and Thiovanic acid, 0.27g Thiovanic acid is dissolved in the 60g deionized water), the dropping time of acrylic acid solution was controlled at 2.5 hours, the dropping time of vitamin c solution is controlled at 3h, and temperature of reaction is controlled at 60 ± 2 ℃.After dropwising, continue insulation 0.5 hour, be cooled to then below 40 ℃, add aqueous sodium hydroxide solution (the 5.2g dissolution of sodium hydroxide is in the 104.3g deionized water) and neutralize, obtaining concentration is 40%, the light yellow hyalomucoid of pH=7.5.Molecular-weight average is 49000 after tested, and density is 1.07g/ml.
Embodiment 6
Mechanical stirring is being housed, temperature regulator, add 187gIB-3000 in the 1000ml four-hole boiling flask of dropper, add the 120g deionized water simultaneously, heat up in stirring and dissolving limit, limit, when temperature is raised to 50 ℃, the hydrogen peroxide that adds 1.3g30%, when temperature reaches 60 ℃, mixing solutions (the 0.45g vitamins C of beginning while dropwise addition of acrylic acid solution (21g vinylformic acid is dissolved in the 10g deionized water) and vitamins C and Thiovanic acid, 0.13g thiohydracrylic acid is dissolved in the 60g deionized water), the dropping time of acrylic acid solution was controlled at 2.5 hours, the dropping time of vitamin c solution is controlled at 3h, and temperature of reaction is controlled at 60 ± 2 ℃.After dropwising, continue insulation 0.5 hour, be cooled to then below 40 ℃, add aqueous sodium hydroxide solution (the 6.6g dissolution of sodium hydroxide is in the 124.5g deionized water) and neutralize, obtaining concentration is 40%, the light yellow hyalomucoid of pH=7.5.Molecular-weight average is 81000 after tested, and density is 1.07g/ml.
Embodiment 7
Mechanical stirring is being housed, temperature regulator, add 300gIB-5000 in the 1000ml four-hole boiling flask of dropper, add the 120g deionized water simultaneously, heat up in stirring and dissolving limit, limit, when temperature is raised to 50 ℃, the hydrogen peroxide that adds 1.2g30%, when temperature reaches 60 ℃, beginning drips mixing solutions (the 0.52g vitamins C of methacrylic acid solution (the 18g methacrylic acid is dissolved in the 10g deionized water) and vitamins C and Thiovanic acid simultaneously, 0.32g Thiovanic acid is dissolved in the 60g deionized water), the dropping time of acrylic acid solution was controlled at 2.5 hours, the dropping time of vitamin c solution is controlled at 3h, and temperature of reaction is controlled at 60 ± 2 ℃.After dropwising, continue insulation 0.5 hour, be cooled to then below 40 ℃, add aqueous sodium hydroxide solution (the 5.7g dissolution of sodium hydroxide is in the 289.5g deionized water) and neutralize, obtaining concentration is 40%, the light yellow hyalomucoid of pH=7.5.Molecular-weight average is 53000 after tested, and density is 1.07g/ml.
The evaluation method of water reducer of the present invention is estimated according to the GB8076-2008 standard, the results are shown in Table 1 and table 2.
The clean slurry of table 1 degree of mobilization data
| Embodiment | Volume (%) | Degree of mobilization/mm | 30min degree of mobilization/mm | 60min degree of mobilization/mm |
| 1 | 0.30 | 250 | 245 | 255 |
| 2 | 0.25 | 255 | 250 | 260 |
| 3 | 0.25 | 265 | 265 | 270 |
| 4 | 0.20 | 270 | 266 | 265 |
| 5 | 0.15 | 275 | 270 | 266 |
| 6 | 0.15 | 280 | 275 | 275 |
| 7 | 0.15 | 270 | 265 | 265 |
As can be seen from Table 1, the polyether-based polycarboxylic acid salt water reducer that polycarboxylate dehydragent of the present invention is traditional relatively has better dispersiveness and disperses retentivity cement.
Table 2 concrete slump data
| Embodiment | Volume (%) | The initial slump/mm | The 30min slump/mm | The 60min slump/mm |
| 1 | 0.55 | 180 | 180 | 176 |
| 2 | 0.50 | 183 | 180 | 175 |
| 3 | 0.55 | 186 | 185 | 180 |
| 4 | 0.55 | 195 | 190 | 190 |
| 5 | 0.45 | 200 | 196 | 193 |
| 6 | 0.40 | 215 | 200 | 195 |
| 7 | 0.40 | 205 | 202 | 200 |
As can be seen from Table 2, the polyether-based polycarboxylic acid salt water reducer that polycarboxylate dehydragent of the present invention is traditional relatively has better dispersiveness and slump retentivity to concrete.
Claims (5)
1. prenyl polyethers polycarboxylate dehydragent, it is the polymkeric substance of prenyl Soxylat A 25-7 or prenyl polyoxyethylene propylene ether (A) and unsaturated carboxylic acid or derivatives thereof (B), represent big monomer A with formula (1), represent minor comonomer B with formula (2):
Wherein: R
1-hydrogen atom or C atomicity are 1～5 alkyl group
The m-number of repeat unit is 5～200
The n-number of repeat unit is 0～100,
Wherein: R
2-hydrogen atom or C atomicity are 1～5 alkyl group
R
3-hydroxyl, amido or C atomicity are 1～5 alkyl group.
2. the synthetic method of prenyl polyethers polycarboxylate dehydragent as claimed in claim 1, it is characterized in that, step comprises: big monomer A is dissolved in the deionized water, warming while stirring, when temperature is raised to 30-50 ℃, add oxygenant, when temperature reaches 60-80 ℃, beginning drips the mixed aqueous solution of the minor comonomer B aqueous solution and reductive agent and chain-transfer agent simultaneously, the minor comonomer B aqueous solution dropping time was controlled at 2～4 hours, and the mixed aqueous solution dropping time of reductive agent and chain-transfer agent was controlled at 2.5～5 hours, after dropwising, continue insulation 0.5～2 hour, be cooled to then below 40 ℃, add aqueous sodium hydroxide solution and neutralize, the control product concentration is 20～50%, pH=6～8 finally obtain light yellow hyalomucoid;
The mol ratio of described big monomer A and minor comonomer B is 1: 1～5;
Total consumption of described Oxidizing and Reducing Agents accounts for 0.2～5% of big monomer A and minor comonomer B gross weight;
Described chain-transfer agent consumption accounts for 0.05～0.25% of big monomer A and minor comonomer B gross weight.
3. the synthetic method of prenyl polyethers polycarboxylate dehydragent as claimed in claim 2 is characterized in that, described chain-transfer agent is mercaptoethanol, Thiovanic acid, thiohydracrylic acid or dimercaptosuccinic acid.
4. the synthetic method of prenyl polyethers polycarboxylate dehydragent as claimed in claim 2 is characterized in that, described oxygenant is one or more in ammonium persulphate, Potassium Persulphate, Sodium Persulfate, the hydrogen peroxide.
5. the synthetic method of prenyl polyethers polycarboxylate dehydragent as claimed in claim 2 is characterized in that, described reductive agent is one or more in vitamins C, S-WAT, oxalic acid, the glucose.
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