CN105175740B - A kind of preparation method of high workability esters polycarboxylate water-reducer - Google Patents
A kind of preparation method of high workability esters polycarboxylate water-reducer Download PDFInfo
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- CN105175740B CN105175740B CN201510526485.2A CN201510526485A CN105175740B CN 105175740 B CN105175740 B CN 105175740B CN 201510526485 A CN201510526485 A CN 201510526485A CN 105175740 B CN105175740 B CN 105175740B
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 32
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 24
- 150000002148 esters Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920001400 block copolymer Polymers 0.000 claims abstract description 14
- 239000010695 polyglycol Substances 0.000 claims abstract description 10
- 229920000151 polyglycol Polymers 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 230000000977 initiatory effect Effects 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 11
- -1 acryloyl-oxy Hydroxypropyl phosphate ester Chemical class 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical class COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 claims description 6
- 235000021317 phosphate Nutrition 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical class OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- SKKXTPQPJYBUEF-UHFFFAOYSA-N 3-phosphonooxypropyl prop-2-enoate Chemical compound OP(O)(=O)OCCCOC(=O)C=C SKKXTPQPJYBUEF-UHFFFAOYSA-N 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 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
- 238000002156 mixing Methods 0.000 claims description 2
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical group OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- CIIWMXSMCCRQEQ-UHFFFAOYSA-N 3-phosphonooxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOP(O)(O)=O CIIWMXSMCCRQEQ-UHFFFAOYSA-N 0.000 claims 1
- SQILDHVCFVBFQL-UHFFFAOYSA-N C(C)P(O)(O)=O.C(C=C)(=O)[O] Chemical group C(C)P(O)(O)=O.C(C=C)(=O)[O] SQILDHVCFVBFQL-UHFFFAOYSA-N 0.000 claims 1
- MKOQAXOMCIQUJY-UHFFFAOYSA-N pent-4-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCC=C MKOQAXOMCIQUJY-UHFFFAOYSA-N 0.000 claims 1
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical compound [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 claims 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims 1
- 239000003930 superacid Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 12
- 230000032050 esterification Effects 0.000 abstract description 8
- 238000005886 esterification reaction Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 2
- 238000013461 design Methods 0.000 abstract description 2
- 230000001066 destructive effect Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MZAVSXJJSQTGRK-UHFFFAOYSA-N [Cl-].C=C.C[NH+](C)C Chemical compound [Cl-].C=C.C[NH+](C)C MZAVSXJJSQTGRK-UHFFFAOYSA-N 0.000 description 3
- 239000000159 acid neutralizing agent Substances 0.000 description 3
- 230000003467 diminishing effect Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000019260 propionic acid Nutrition 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- HWNSTNONJFVIJR-UHFFFAOYSA-N 3-[hydroxy(3-hydroxypropoxy)phosphoryl]oxypropyl 2-methylprop-2-enoate Chemical class CC(=C)C(=O)OCCCOP(=O)(O)OCCCO HWNSTNONJFVIJR-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- CDGOGRINGXZSJO-UHFFFAOYSA-N [Cl-].C[NH+](C)C.C(C=C)(=O)OC=C Chemical compound [Cl-].C[NH+](C)C.C(C=C)(=O)OC=C CDGOGRINGXZSJO-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229960003511 macrogol Drugs 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical class [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 238000009440 infrastructure construction Methods 0.000 description 1
- 229920001427 mPEG Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical compound [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of preparation method of high workability esters polycarboxylate water-reducer, first mixed by the high activated monomer of acrylic acid and workability, add oxidant and aided initiating, the mixed liquor of unsaturated monomer, chain-transferring agent, reducing agent and water is added dropwise at low temperature, reaction obtains block copolymer intermediate, poly glycol monomethyl ether is added afterwards and carries out graft esterification with catalyst, is finally neutralized and is made.High workability esters polycarboxylate water-reducer prepared by the present invention introduces the good activated monomer of workability, the method for taking high temperature esterification after first low temperature polymerization by Molecular Design, this method double bond destructive rate is low, copolymerization degree is high, and the water reducer workability of production is good, and water-reducing rate is high；Industrialized producing technology is simple, the production cycle greatly shortens, production process environmental protection, pollution-free.
Description
Technical field
The invention belongs to the technical field of construction material, more particularly to a kind of system of high workability esters polycarboxylate water-reducer
Preparation Method.
Background technology
In recent years, with the development that China 12 plans, government is for infrastructure construction, people's livelihood engineering, environmental protection etc.
Various aspects can put into substantial contribution, water conservancy, tunnel, the construction of bridge Large Infrastructure Projects, and high performance water reducing agent of polyocarboxy acid is still
It is among a higher market demand.
Polycarboxylate water-reducer has obtained faster development because of its raw material supply convenience, simple production process, product stabilization.
But in actual application due to the particularity of domestic many engineerings and the change in season substantially, and different zones
Sand, stone material quality are uneven, big containing mud, powder containing quantity difference so that many polycarboxylate water-reducers answering in some engineerings
With occurring that workability is poor, expect relatively to glue, the poor problem of the service behaviour such as easy bleeding.
CN102826784A discloses a kind of polycarboxylate water-reducer and preparation method thereof, by polymeric monomer, unsaturated carboxylic acid, acyl
Amine or acid anhydrides, insatiable hunger sulfonate monomer, and oxidant and water, add reducing agent at 45 DEG C, are incubated 3-5 hours, use liquid caustic soda
Neutralization obtains target product.There is Slump Time losing of Large greatly in the product of the technique, the problem of workability is poor.
CN103450411A discloses a kind of preparation method of high-slump-retentionpolycarboxylate polycarboxylate water reducer, first by methoxy poly (ethylene glycol)
Monomethyl ether and methacrylic acid obtain being esterified polymeric monomer MP with carrying out being esterified under catalyst at high temperature, then by MP, unsaturated sulphur
Hydrochlorate, (methyl) esters of acrylic acid unsaturated monomer and chain-transferring agent are polymerize in aqueous, are eventually adding liquid caustic soda neutralization
Obtain target product.The target product workability of the technique is general, and the polymerization inhibitor that adds of esterification process have to polymerization process compared with
Big influence, and the two-step reaction cycle is longer.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of preparation side of high workability esters polycarboxylate water-reducer
Method, overcomes problems of the prior art and deficiency, so as to have high workability, adaptability good, scattered there is provided a kind of
Excellent performance, and with short production cycle, the simple and environmentally-friendly free of contamination high-performance water reducing agent of technique.
In order to solve the above technical problems, the technical solution of the present invention is：
A kind of preparation method of high workability esters polycarboxylate water-reducer comprises the following steps：
(1) in parts by mass, by 100 parts of acrylic acid, 2~10 parts of unsaturated phosphates, 2~8 parts of methacryloxypropyl second
Alkene trimethyl ammonium chloride and 50 parts of water mix dissolving and in being reacted at 15 DEG C -35 DEG C, sequentially add 0.5~1.0 part of oxidation
Agent and 0.3~2.0 part of aided initiating, then be added dropwise by 10~20 parts of acrylic acid, 0.5~2.0 part of chain-transferring agent, 0.1~1.0 part also
The mixed liquor of former agent and the formation of 50 parts of water and in 0.5~1.0 hour completion of dropping, it is common that follow-up continuation of insurance temperature obtains block for 0.5 hour
Polymers intermediate；
(2) in parts by mass, by the block copolymer obtained by 100 parts of poly glycol monomethyl ethers, 10~60 parts of steps 1
Mesosome and the mixing of 0.15~2 part of catalyst, are warming up to 80 DEG C~100 DEG C, stir and vacuumize simultaneously make its 0.01MPa~
React 4~5 hours, after question response terminates, cool to less than 60 DEG C under 0.04MPa vacuum, add 10~30 parts of matter
Amount concentration obtains the high workability esters polycarboxylate water-reducer for 30% sodium hydroxide neutralization.
In a preferred embodiment of the invention, described unsaturated phosphate be acrylyl oxy-ethyl phosphate,
Acryloxypropyl phosphate, acryloyl-oxy Hydroxypropyl phosphate ester, methylacryoyloxyethyl phosphate, methacryloxypropyl third
The combination of one or both of base phosphate or methacryloxypropyl Hydroxypropyl phosphate ester.
In a preferred embodiment of the invention, described oxidant is hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate
One or both of combination.
In a preferred embodiment of the invention, described aided initiating is iron ammonium sulfate, ferrous sulfate, tetramethyl
The combination of one or both of ammonium chloride.
In a preferred embodiment of the invention, described chain-transferring agent is mercaptoethanol, TGA, 3~mercapto
The combination of one or both of base propionic acid, lauryl mercaptan, thioglycerin, thiomalic acid.
In a preferred embodiment of the invention, described reducing agent is L-AA, formaldehyde conjunction bisulphite
The combination of one or both of sodium, sodium hydrogensulfite.
In a preferred embodiment of the invention, described macrogol monomethyl ether be molecular weight for 600,
1200th, in 2200,3000 macrogol monomethyl ether the combination of any one or two kinds.
In a preferred embodiment of the invention, described catalyst is solid super-strong acid SO4 2-/TiO2/La3+、
SO4 2-/TiO2/Sm3+、S2O8 2-/ZrO2One of which or two kinds of combinations.
The preparation method for the high workability esters polycarboxylate water-reducer that the present invention is provided, is grafted using Post functionalization, i.e., first
Two step synthetic reaction routes are esterified after polymerization.Compared to other Patents, this patent has the obvious of the following aspects
Feature：
(1) present invention introduces the unsaturated phosphate of the good activated monomer of workability and methyl-prop by Molecular Design
Alkene acyl-oxygen ethene trimethyl ammonium chloride, and block copolymer intermediate molecule amount is controlled in the range of 5000-20000, then it is and poly-
Glycol monoethyl ether is esterified, and the method for taking high temperature esterification after first low temperature polymerization, this method double bond destructive rate is low, copolymerization degree
It is high；Obtained product workability is good, water-reducing rate is high, excellent working performance.It is of the present invention compared with past esterification technique
Polymerization inhibitor need not be added during esterification technique is anti-, it is to avoid produce influence, and production technology on product quality because adding polymerization inhibitor
Simply, the production cycle greatly shortens, production process environmental protection, pollution-free.
(2) copolyreaction activity can be improved by adding the aided initiating of reproducibility, greatly shortened the reaction time, improved reaction
Efficiency.
(3) under the catalysis of solid esterification catalyst, the activation energy of esterification can be reduced, reaction rate, contracting is improved
The short reaction cycle；And it is easily separated after completion of the reaction, it is reusable, it is small to consersion unit and environmental corrosion.
Following examples are described in further detail to the present invention；But a kind of high workability esters polycarboxylic acids of the present invention subtracts
The preparation method of aqua is not limited to embodiment.
Embodiment
Embodiment 1
(1) step one：In parts by mass, by 100 parts of acrylic acid, 6 parts of acrylyl oxy-ethyl phosphates, 3 parts of metering systems
Acyl-oxygen ethene trimethyl ammonium chloride and 50 parts of water are placed in reaction unit, stirring and dissolving, 25 DEG C reaction, by 0.8 part of hydrogen peroxide,
0.3 part of iron ammonium sulfate is put into reaction unit successively with tetramethyl ammonium chloride mixed liquor, by 10 parts of acrylic acid, 1.0 parts of 3~mercaptos
Base propionic acid, 0.4 part of L-AA and 50 parts of water are placed in Dropping feeder, and 1.0 hours completion of dropping, follow-up continuation of insurance temperature 0.5 is small
When obtain block copolymer intermediate.
(2) step 2：In parts by mass, by 100 parts of poly glycol monomethyl ethers (MPEG-1200), 20 parts of (institutes in step one
Obtain) block copolymer intermediate, 0.3 part of solid super-strong acid (SO4 2-/TiO2/La3+) put into reaction unit, it is warming up to 90
DEG C, stir and vacuumize simultaneously, it is ensured that vacuum is reacted 4 hours in 0.02MPa.After question response terminates, cool to 60 DEG C
Hereinafter, 10 parts of mass concentrations are added and obtain certain density high workability esters polycarboxylic acids diminishing for 30% sodium hydroxide neutralization
Agent.
Embodiment 2
(1) step one：In parts by mass, by 100 parts of acrylic acid, 6 parts of acrylyl oxy-ethyl phosphates, 3 parts of metering systems
Acyl-oxygen ethene trimethyl ammonium chloride and 50 parts of water are placed in reaction unit, stirring and dissolving, 25 DEG C reaction, by 0.8 part of hydrogen peroxide,
0.3 part of iron ammonium sulfate is put into reaction unit successively with tetramethyl ammonium chloride mixed liquor, by 10 parts of acrylic acid, 1.0 parts of 3~mercaptos
Base propionic acid, 0.4 part of L-AA and 50 parts of water are placed in Dropping feeder, and 1.0 hours completion of dropping, follow-up continuation of insurance temperature 0.5 is small
When obtain block copolymer intermediate.
(2) step 2：In parts by mass, by 100 parts of poly glycol monomethyl ethers (MPEG-2200), 18 parts of (institutes in step one
Obtain) block copolymer intermediate, 0.4 part of solid super-strong acid (SO4 2-/TiO2/La3+) put into reaction unit, it is warming up to 95
DEG C, stir and vacuumize simultaneously, it is ensured that vacuum is reacted 5 hours in 0.01MPa.After question response terminates, cool to 60 DEG C
Hereinafter, 10 parts of mass concentrations are added and obtain certain density high workability esters polycarboxylic acids diminishing for 30% sodium hydroxide neutralization
Agent.
Embodiment 3
(1) step one：In parts by mass, by 100 parts of acrylic acid, 10 parts of methacryloxypropyl Hydroxypropyl phosphate esters, 5 parts of first
Base acryloyl-oxy ethene trimethyl ammonium chloride and 50 parts of water are placed in reaction unit, stirring and dissolving, 25 DEG C of reactions, by 1.0 parts of mistakes
Hydrogen oxide, 0.3 part of iron ammonium sulfate and tetramethyl ammonium chloride mixed liquor are put into reaction unit successively, by 10 parts of acrylic acid, 0.7
3~mercaptopropionic acid of part, 0.6 part of L-AA and 50 parts of water are placed in Dropping feeder, 1.0 hours completion of dropping, follow-up continuation of insurance
Temperature obtains block copolymer intermediate in 0.5 hour.
(2) step 2：In parts by mass, by 100 parts of poly glycol monomethyl ether (MPEG-600：MPEG-3000=2:1)、
20 parts of (obtained by step one) block copolymer intermediates, 0.4 part of solid super-strong acid (SO4 2-/TiO2/La3+) input reaction
In device, 100 DEG C are warming up to, stirs and vacuumizes simultaneously, it is ensured that vacuum is reacted 5 hours in 0.02MPa.Question response terminates
Afterwards, cool to less than 60 DEG C, add 10 parts of mass concentrations for 30% sodium hydroxide neutralize obtain it is certain density high and
Easy property esters polycarboxylate water-reducer.
Embodiment 4
(1) step one：In parts by mass, by 100 parts of acrylic acid, 8 parts of methacryloxypropyl Hydroxypropyl phosphate esters, 6 parts of first
Base acryloyl-oxy ethene trimethyl ammonium chloride and 50 parts of water are placed in reaction unit, stirring and dissolving, 25 DEG C of reactions, by 1.0 parts of mistakes
Hydrogen oxide, 0.3 part of iron ammonium sulfate and tetramethyl ammonium chloride mixed liquor are put into reaction unit successively, by 10 parts of acrylic acid, 0.7
3~mercaptopropionic acid of part, 0.6 part of L-AA and 50 parts of water are placed in Dropping feeder, 1.0 hours completion of dropping, follow-up continuation of insurance
Temperature obtains block copolymer intermediate in 0.5 hour.
(2) step 2：In parts by mass, by 100 parts of poly glycol monomethyl ethers (MPEG-2200), 20 parts of (institutes in step one
Obtain) block copolymer intermediate, 0.4 part of solid super-strong acid (SO4 2-/TiO2/La3+) put into reaction unit, it is warming up to 95
DEG C, stir and vacuumize simultaneously, it is ensured that vacuum is reacted 5 hours in 0.01MPa.After question response terminates, cool to 60 DEG C
Hereinafter, 10 parts of mass concentrations are added and obtain certain density high workability esters polycarboxylic acids diminishing for 30% sodium hydroxide neutralization
Agent.
Embodiment 5
Embodiment 5 is the performance test of high workability esters polycarboxylate water-reducer made from embodiment 1~4.
Embodiment 1~4 is synthesized to obtained high workability esters polycarboxylate water-reducer and standard type polycarboxylate water-reducer
(HPWR-S), using standard cement, volume is 0.15% (folding solid part) of glue material quality, according to GB8076-2008《Concrete
Additive》, test its concrete water-reducing ratio, the slump and gradual loss.Concrete mix is：Water 165Kg, cement 360Kg,
River sand 470Kg, Machine-made Sand 300Kg, stone 1020Kg, it is as shown in the table for acquired results.
The embodiment performance comparison of table 1：
It is described above, only it is present pre-ferred embodiments, any limitation not is done to the technical scope of the present invention, it is all
It is any simple modification, equivalent variations and the modification made according to the technical spirit of the present invention to above example, each falls within this
In the protection domain of inventive technique scheme.
Claims (6)
1. a kind of preparation method of high workability esters polycarboxylate water-reducer, it is characterised in that comprise the following steps：
1) in parts by mass, by 100 parts of acrylic acid, 2~10 parts of unsaturated phosphates, 2~8 parts of methacryloxypropyl ethene front threes
Ammonium chloride and 50 parts of water mix dissolving and in being reacted at 15 DEG C -35 DEG C, sequentially add 0.5~1.0 part of oxidant and 0.3
~2.0 parts of aided initiatings, then be added dropwise by 10~20 parts of acrylic acid, 0.5~2.0 part of chain-transferring agent, 0.1~1.0 part of reducing agent and
The mixed liquor of 50 parts of water formation and in 0.5~1.0 hour completion of dropping, follow-up continuation of insurance temperature is obtained in block copolymer for 0.5 hour
Mesosome, wherein the molecular weight of the block copolymer intermediate is 5000-20000；Described unsaturated phosphate is acryloyl
Oxygen ethyl phosphonic acid ester, acryloxypropyl phosphate, acryloyl-oxy Hydroxypropyl phosphate ester, methylacryoyloxyethyl phosphate,
The combination of one or both of methacryloxypropyl phosphate or methacryloxypropyl Hydroxypropyl phosphate ester；
2) in parts by mass, by 100 parts of poly glycol monomethyl ethers, 10~60 parts of steps 1) obtained by block copolymer intermediate
And the mixing of 0.15~2 part of catalyst, be warming up to 80 DEG C~100 DEG C, stir and vacuumize simultaneously make its 0.01MPa~
React 4~5 hours, after question response terminates, cool to less than 60 DEG C under 0.04MPa vacuum, add 10~30 parts of matter
Amount concentration obtains the high workability esters polycarboxylate water-reducer for 30% sodium hydroxide neutralization；Described catalyst is solid
Body super acids SO4 2-/TiO2/La3+、SO4 2-/TiO2/Sm3+、S2O8 2-/ZrO2One of which or two kinds of combinations.
2. a kind of preparation method of high workability esters polycarboxylate water-reducer according to claim 1, it is characterised in that：Step
It is rapid 1) in, described oxidant for one or both of hydrogen peroxide, ammonium persulfate, sodium peroxydisulfate combination.
3. a kind of preparation method of high workability esters polycarboxylate water-reducer according to claim 1, it is characterised in that：Step
It is rapid 1) in, described aided initiating for one or both of iron ammonium sulfate, ferrous sulfate, tetramethyl ammonium chloride combination.
4. a kind of preparation method of high workability esters polycarboxylate water-reducer according to claim 1, it is characterised in that：Step
It is rapid 1) in, described chain-transferring agent is mercaptoethanol, TGA, 3- mercaptopropionic acids, lauryl mercaptan, thioglycerin, thio apple
The combination of one or both of acid.
5. a kind of preparation method of high workability esters polycarboxylate water-reducer according to claim 1, it is characterised in that：Step
It is rapid 1) in, described reducing agent for one or both of L-AA, sodium formaldehyde sulphoxylate, sodium hydrogensulfite group
Close.
6. a kind of preparation method of high workability esters polycarboxylate water-reducer according to claim 1, it is characterised in that：Institute
The poly glycol monomethyl ether stated be molecular weight be 600,1200,2200,3000 poly glycol monomethyl ether in any one or
Two kinds of combination.
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| CN105837768B (en) * | 2016-05-11 | 2018-03-09 | 合肥工业大学 | A kind of preparation method of polyphosphate water reducer |
| CN106008593B (en) * | 2016-05-26 | 2019-04-05 | 广东复特新型材料科技有限公司 | It is a kind of for producing the unsaturated phosphate ester of high collapse protection type poly carboxylic acid series water reducer |
| CN108250343B (en) * | 2016-12-28 | 2020-06-26 | 江苏苏博特新材料股份有限公司 | Compound, air-entraining copolymer, preparation method thereof and application of air-entraining copolymer as concrete rheology modifier |
| MY186638A (en) * | 2018-12-24 | 2021-08-02 | Kzj New Mat Group Co Ltd | Method of preparing block slow releasing concrete admixture |
| CN109679108A (en) * | 2018-12-26 | 2019-04-26 | 浙江建研科之杰新材料有限公司 | A kind of preparation method of high water-retaining type polycarboxylate water-reducer |
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| CN102936109A (en) * | 2011-12-08 | 2013-02-20 | 江苏奥莱特新材料有限公司 | Polycarboxylic acid water reducing agent, preparation method and application thereof |
| CN103450411B (en) * | 2013-08-28 | 2015-08-19 | 科之杰新材料集团有限公司 | A kind of preparation method of high-slump-retentionpolycarboxylate polycarboxylate water reducer |
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