CN106366257B - A kind of muting sensitive induction reactance mud intersects branched chain type polycarboxylate water-reducer and preparation method thereof - Google Patents
A kind of muting sensitive induction reactance mud intersects branched chain type polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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- CN106366257B CN106366257B CN201610820591.6A CN201610820591A CN106366257B CN 106366257 B CN106366257 B CN 106366257B CN 201610820591 A CN201610820591 A CN 201610820591A CN 106366257 B CN106366257 B CN 106366257B
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 67
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 37
- 230000006698 induction Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 46
- -1 hydroxyl butyl vinyl Chemical group 0.000 claims abstract description 39
- 239000007864 aqueous solution Substances 0.000 claims abstract description 35
- 239000008367 deionised water Substances 0.000 claims abstract description 34
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 34
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 22
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 18
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 13
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract description 10
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract 4
- 239000000243 solution Substances 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 11
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 11
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 150000001409 amidines Chemical class 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 claims description 5
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical compound [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- VYBHLZOLHCQLHT-UHFFFAOYSA-N 1-(2-methylpropyl)-4,5-dihydroimidazole hydrochloride Chemical compound Cl.C(C(C)C)N1C=NCC1 VYBHLZOLHCQLHT-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical class OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 229920006395 saturated elastomer Polymers 0.000 claims 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000012986 chain transfer agent Substances 0.000 claims 1
- 150000002829 nitrogen Chemical class 0.000 claims 1
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 claims 1
- LUMVCLJFHCTMCV-UHFFFAOYSA-M potassium;hydroxide;hydrate Chemical compound O.[OH-].[K+] LUMVCLJFHCTMCV-UHFFFAOYSA-M 0.000 claims 1
- 229920000570 polyether Polymers 0.000 abstract description 30
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 11
- 125000005395 methacrylic acid group Chemical group 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000004568 cement Substances 0.000 description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- 101000908015 Homo sapiens Putative inactive carboxylesterase 4 Proteins 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 101710171243 Peroxidase 10 Proteins 0.000 description 2
- 102100023322 Putative inactive carboxylesterase 4 Human genes 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000003467 diminishing effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000004714 phosphonium salts Chemical group 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical class CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- YWDWYOALXURQPZ-CYBMUJFWSA-N 2-methyl-n-[3-[(6s)-2,3,5,6-tetrahydroimidazo[2,1-b][1,3]thiazol-6-yl]phenyl]propanamide Chemical compound CC(C)C(=O)NC1=CC=CC([C@@H]2N=C3SCCN3C2)=C1 YWDWYOALXURQPZ-CYBMUJFWSA-N 0.000 description 1
- GASMGDMKGYYAHY-UHFFFAOYSA-N 2-methylidenehexanamide Chemical compound CCCCC(=C)C(N)=O GASMGDMKGYYAHY-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229950000536 butamisole Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- PSXRWZBTVAZNSF-UHFFFAOYSA-N hydron;quinoline;chloride Chemical compound Cl.N1=CC=CC2=CC=CC=C21 PSXRWZBTVAZNSF-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C04B24/243—Phosphorus-containing polymers
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Detergent Compositions (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention discloses a kind of muting sensitive induction reactance mud to intersect branched chain type polycarboxylate water-reducer and preparation method thereof, and raw material is made of following component：4 hydroxyl butyl vinyl polyoxyethylene ethers, allyl polyethenoxy polyethers, methacrylic polyoxyethylene polyethers, isopentene group polyoxyethylene polyethers, unsaturated monocarboxylic acid, unsaturated carboxylate type monomer, dimethylaminoethyl acrylate methyl ammonia ethyl ester, dibutyl maleate, unsaturated both sexes quaternary alkylphosphonium salt, oxidant, the first reducing agent, azo-initiator, chain-transferring agent, appropriate potassium hydroxide aqueous solution, appropriate sodium hydrate aqueous solution and appropriate amount of deionized water.The side chain distribution of the polycarboxylate water-reducer of the present invention is more uniform, and guarantor is collapsed, and effect is good, and the volume of polycarboxylate water-reducer, which is changed, has excellent hyposensitivity energy.
Description
Technical field
The invention belongs to cement water reducing agent technical fields, and in particular to a kind of muting sensitive induction reactance mud intersects branched chain type polycarboxylic acids
Water-reducing agent and preparation method thereof.
Background technology
Poly carboxylic acid series water reducer has excellent dispersion performance, concrete can be made to reach preferable stream at low dosage
Dynamic property, is widely used in the engineerings such as highway, bridge, dam, tunnel, skyscraper.With the continuous development of polycarboxylic acids technology, gather
The water-reducing rate of carboxylic acid water reducer is continuously improved, although water-reducing rate raising can reduce the dosage of polycarboxylate water-reducer, reduces cost,
The sensibility of polycarboxylate water-reducer is also improved, is shown as in the construction process, the reasonable volume point drop of polycarboxylate water-reducer is a bit
Volume, can cause fresh concrete mobility not enough or loss is too fast, and reasonable volume point carries some volumes, then easily leads to concrete
Isolation, bleeding so that concrete production control difficulty increases, i.e., to volume sensitivity.
In addition, a large amount of case history and research shows that, with the water-reducing agents phase such as naphthalene system, melamine series and amido sulfoacid series
Than poly carboxylic acid series water reducer is more sensitive to the clay content of aggregate, is mainly shown as the diminishing dispersion energy of poly carboxylic acid series water reducer
Power degradation, guarantor's effect of collapsing are poor, lead to maturing strength reduction etc..Although it can be obtained by improving water-reducing agent volume
Alleviate, but be easy to cause the problems such as concrete coagulating time overlength is reduced with compressive strength rate, and greatly increase cost.
Invention content
It is an object of the invention to overcome prior art defect, a kind of muting sensitive induction reactance mud intersection branched chain type polycarboxylic acids is provided and is subtracted
Aqua.
Intersect the preparation side of branched chain type polycarboxylate water-reducer another object of the present invention is to provide above-mentioned muting sensitive induction reactance mud
Method.
Technical scheme is as follows：
A kind of muting sensitive induction reactance mud intersects branched chain type polycarboxylate water-reducer, and pH is 6.0~7.0, and solid content is 45~55%,
Its raw material is made of the component of following parts by weight：Molecular weight is 2000~5000 4- hydroxyl butyl vinyl polyoxyethylene ethers
(VPEG) 10~60 parts by weight, molecular weight be 500~3000 0~40 parts by weight of allyl polyethenoxy polyethers (APEG), point
Son amount be 500~3000 0~40 parts by weight of methacrylic polyoxyethylene polyethers (HPEG), molecular weight be 500~3000
0~40 parts by weight of isopentene group polyoxyethylene polyethers (TPEG), 6~10 parts by weight of unsaturated monocarboxylic acid, esters of unsaturated carboxylic acids
3~6 parts by weight of class monomer, 2~6 parts by weight of dimethylaminoethyl acrylate methyl ammonia ethyl ester, 2~6 parts by weight of dibutyl maleate, unsaturation
1~5 parts by weight of both sexes quaternary alkylphosphonium salt, 0.2~0.8 parts by weight of oxidant, 0.2~1.0 parts by weight of the first reducing agent, the second reducing agent
0.02~0.06 parts by weight, 0.2~0.6 parts by weight of chain-transferring agent, appropriate potassium hydroxide aqueous solution, appropriate sodium hydroxide is water-soluble
Liquid and appropriate amount of deionized water, wherein, unsaturated both sexes quaternary alkylphosphonium salt is triphenyl phosphorus and allyl bromide, bromoallylene with 1: 1.0~1.5 mole
Than being made in carbon tetrachloride by following reaction：
In a preferred embodiment of the invention, the preparation method of the unsaturated both sexes quaternary alkylphosphonium salt includes following step
Suddenly：
(1) 1: 1.0~1.5 triphenyl phosphorus and allyl bromide, bromoallylene are weighed in molar ratio；
(2) triphenyl phosphorus and appropriate carbon tetrachloride are mixed, fully dissolved；
(3) allyl bromide, bromoallylene is added dropwise with the speed of 1/2~5s of drop in the material obtained by step (2), is carried out during being added dropwise
Stirring is reacted simultaneously, and reaction temperature is kept for 40~50 DEG C, and the reaction time is 4~6h, obtains tan precipitate object；
(4) above-mentioned tan precipitate object is recrystallized with acetone, obtains recrystallized product；
(5) above-mentioned recrystallized product is dried in vacuo, obtains the powder of white, as described unsaturated both sexes quaternary phosphonium
Salt.
In a preferred embodiment of the invention, the unsaturated monocarboxylic acid is acrylic acid and/or metering system
Acid.
In a preferred embodiment of the invention, the unsaturated carboxylate type monomer is hydroxy-ethyl acrylate, first
In base hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, methyl acrylate and methyl methacrylate extremely
Few one kind.
In a preferred embodiment of the invention, the oxidant is hydrogen peroxide, sodium peroxydisulfate and ammonium persulfate
At least one of.
In a preferred embodiment of the invention, first reducing agent is sodium formaldehyde sulphoxylate, Br ü
ggolitTMAt least one of FF6 and sodium hypophosphite.
In a preferred embodiment of the invention, second reducing agent for two isobutyl imidazoline hydrochloride of azo,
Azo diisobutyl amidine hydrochloride, two N- hydroxyisobutyl amidines hydrate of azo, two N of azo, the hydration of N ' cyclobutyl isobutyl amidine
At least one of object and/or azo dimethyl N-2- hydroxyl butylacrylamides.
In a preferred embodiment of the invention, the chain-transferring agent is thioacetic acid, mercaptopropionic acid and sulfydryl second
At least one of alcohol.
Above-mentioned muting sensitive induction reactance mud intersects the preparation method of branched chain type polycarboxylate water-reducer, includes the following steps：
(1) each raw material components are weighed by weight；
(2) unsaturated monocarboxylic acid, chain-transferring agent are dissolved in 10~15 parts by weight of deionized water, and with appropriate hydroxide
Aqueous solutions of potassium adjusts pH to 5.5~6.0, obtains the first solution；First reducing agent is dissolved in 10~15 parts by weight of deionized water
Obtain the second solution；Unsaturated carboxylate type monomer, dibutyl maleate and dimethylaminoethyl acrylate methyl ammonia ethyl ester are dissolved in 6~10
Third solution is obtained in parts by weight of deionized water；
(3) by 4- hydroxyl butyl vinyl polyoxyethylene ethers (VPEG), allyl polyethenoxy polyethers (APEG), methyl alkene
Propyl polyoxyethylene polyethers (HPEG), isopentene group polyoxyethylene polyethers (TPEG) and unsaturated both sexes quaternary alkylphosphonium salt are dissolved in 80~90
In the deionized water of parts by weight, then it is sequentially added into 35~55% the first solution, appropriate sodium hydrate aqueous solution, the second reduction
Agent and oxidant, and adjust reaction temperature and reacted to 10~30 DEG C；
(4) while the first solution is added dropwise, in the material obtained by the second solution and third solution to step (3), 0.5~
It is added dropwise in 1.5h, 0.5~1.5h is kept the temperature after completion of dropwise addition；
(5) with the pH value of appropriate sodium hydrate aqueous solution regulating step (4) resulting material to 6.0~7.0 to get to described
Muting sensitive induction reactance mud intersects branched chain type polycarboxylate water-reducer.
The beneficial effects of the invention are as follows：
1st, muting sensitive induction reactance mud of the invention intersects branched chain type polycarboxylate water-reducer and uses with high double bond retention rate, high activity
4- hydroxyl butyl vinyl polyoxyethylene ether polymeric monomers (VPEG), the polycarboxylate water-reducer side chain distribution of synthesis is more uniform,
Guarantor's effect of collapsing is good, has excellent hyposensitivity energy to the volume variation of polycarboxylate water-reducer, in addition with the alkene of different molecular weight
Propyl polyoxyethylene polyethers (APEG), methacrylic polyoxyethylene polyethers (HPEG) and isopentene group polyoxyethylene polyethers
(TPEG) copolymerization is as branch is intersected, and not only synthesis cost is relatively low, and the polycarboxylate water-reducer slump synthesized is kept
Property good, high sand, well adapting to property of stone with clay content can effectively improve the intensity of concrete.
2nd, preparation method of the invention introduces unsaturated both sexes quaternary alkylphosphonium salt and dibutyl maleate, season in the synthesis process
The activity for acting as inhibiting or reducing soil of microcosmic salt cation group side chain makes point so as to reduce absorption of the soil to water-reducing agent
Carboxylic acid ion and polyether lateral chain in minor structure play absorption cement and disperse the effect of cement respectively, are finally presented as anti-mud
Adaptability and hyposensitivity, and dibutyl maleate is introduced, this cross-linked structure can be right under the alkaline condition of water-cement system
Cement granules can be wrapped up preferably, improve dispersibility, and crosslinked structure has better anti-special adsorption, has good
Good anti-mud performance and guarantor is collapsed effect.
3rd, preparation method of the invention introduces unsaturated carboxylate type monomer in the synthesis process, and carboxylic acid esters group exists
Under alkaline condition, the carboxylic acid ion of water-reduction has been slowly released, has further ensured the diminishing of poly carboxylic acid series water reducer
Guarantor's effect of collapsing.
4th, the present invention is due to introducing undersaturated dimethylaminoethyl methacrylate, so as to change reaction polymeric monomer
Propyl polyoxyethylene polyethers (APEG), methacrylic polyoxyethylene polyethers (HPEG) and isopentene group polyoxyethylene polyethers
(TPEG) activity at low temperature improves the ratio of copolymerization so that polymer molecular weight is controllable, and with good water-reducing rate
And function of slump protection.
5th, preparation method of the invention uses low-temperature oxidation reduction initiating system, and the synthesis technology material dropping time is short,
Production efficiency is high, and polymerize in aqueous solution, pollution-free.
Specific embodiment
Technical scheme of the present invention is further detailed and described below by way of specific embodiment.
It is 1: 1.2 anti-that unsaturated both sexes quaternary alkylphosphonium salt in following embodiments, which is triphenyl phosphorus and allyl bromide, bromoallylene according to molar ratio,
It should be made, specific method is as follows：The triphenyl phosphorus of 20g and the carbon tetrachloride of 30g are added in 100mL three-necked flasks, magnetic force stirs
It mixes, is dissolved.Dissolving finishes, and (1 drop/2 seconds) 11.07g allyl bromide, bromoallylenes are added dropwise, magnetic agitation, reaction are carried out during being added dropwise
Temperature is kept for 45 DEG C, will have tan precipitate precipitation after reacting a period of time.After 4h, precipitated product is tied again with acetone
Crystalline substance, the product of recrystallization is dry in 80 DEG C of vacuum drying ovens, finally obtains the powder of white, as unsaturated both sexes quaternary alkylphosphonium salt.
Embodiment 1
(1) each raw material components are weighed by following parts by weight：4- hydroxyl butyl vinyl polyoxyethylene ether (VPEG molecular weight
2000) 30 parts by weight, allyl polyethenoxy polyethers (APEG molecular weight 500) 40 parts by weight, methacrylic polyoxyethylene gather
Ether (HPEG molecular weight 1000) 20 parts by weight, isopentene group polyoxyethylene polyethers (TPEG molecular weight 2400) 10 parts by weight, propylene
Sour 8 parts by weight, 6 parts by weight of hydroxy-ethyl acrylate, 2 parts by weight of dibutyl maleate, unsaturated 2 parts by weight of both sexes quaternary alkylphosphonium salt, first
2 parts by weight of base acrylic acid diformazan ammonia ethyl ester, hydrogen peroxidase 10 .5 parts by weight, Br ü ggolitTM0.7 parts by weight of FF6, azo two are different
0.04 parts by weight of Butamisole quinoline hydrochloride, 0.35 parts by weight of thioacetic acid, 4 weight of potassium hydroxide aqueous solution of 50% mass concentration
Part, 5 parts by weight of sodium hydrate aqueous solution of 32% mass concentration, remaining is deionized water, is adjusted to 50% solid content.
(2) acrylic acid, thioacetic acid are dissolved in 15 parts by weight of deionized water, and with the potassium hydroxide of 50% mass concentration
Aqueous solution adjusts pH to 5.5~6.0, obtains the first solution；By Br ü ggolitTMFF6, which is dissolved in 15 parts by weight of deionized water, to be obtained
Second solution；Hydroxy-ethyl acrylate, dibutyl maleate and dimethylaminoethyl acrylate methyl ammonia ethyl ester are dissolved in 10 parts by weight deionizations
Third solution is obtained in water；
(3) 4- hydroxyl butyl vinyls polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in remaining deionized water,
It is sequentially added into 35% the first solution, the sodium hydrate aqueous solution of 32% mass concentration, two isobutyl imidazoline hydrochloric acid of azo again
Salt and hydrogen peroxide, and reaction temperature is adjusted to 10 DEG C；
(4) the first solution, in the material obtained by the second solution and third solution to step (3), three kinds of solution are added dropwise while
It is added dropwise in 1h, 1.5h is kept the temperature after completion of dropwise addition；
(5) heat preservation terminates, and pH value is adjusted as 6.0~7.0 to get to institute with the sodium hydrate aqueous solution of 32% mass concentration
It states muting sensitive induction reactance mud and intersects branched chain type polycarboxylate water-reducer PCE-1.
Embodiment 2
(1) each raw material components are weighed by following parts by weight：4- hydroxyl butyl vinyl polyoxyethylene ether (VPEG molecular weight
2400) 40 parts by weight, allyl polyethenoxy polyethers (APEG molecular weight 1000) 30 parts by weight, methacrylic polyoxyethylene gather
Ether (HPEG molecular weight 2000) 30 parts by weight, isopentene group polyoxyethylene polyethers (TPEG molecular weight 3000) 20 parts by weight, propylene
Sour 6 parts by weight, 3 parts by weight of hydroxyethyl methacrylate, 3 parts by weight of dibutyl maleate, unsaturated 1 weight of both sexes quaternary alkylphosphonium salt
Part, 3 parts by weight of dimethylaminoethyl acrylate methyl ammonia ethyl ester, 0.6 parts by weight of sodium peroxydisulfate, 0.8 parts by weight of sodium formaldehyde sulphoxylate, idol
0.02 parts by weight of nitrogen diisobutyl amidine hydrochloride, 0.4 parts by weight of mercaptopropionic acid, 50% mass concentration potassium hydroxide aqueous solution 2
Parts by weight, 6 parts by weight of sodium hydrate aqueous solution of 32% mass concentration, remaining is deionized water, is adjusted to 50% solid content.
(2) acrylic acid, mercaptopropionic acid are dissolved in 15 parts by weight of deionized water, and with the potassium hydroxide of 50% mass concentration
Aqueous solution adjusts pH to 5.5~6.0, obtains the first solution；Sodium formaldehyde sulphoxylate is dissolved in 15 parts by weight of deionized water
Obtain the second solution；Hydroxyethyl methacrylate, dibutyl maleate and dimethylaminoethyl acrylate methyl ammonia ethyl ester are dissolved in 10 weight
Third solution is obtained in part deionized water；
(3) 4- hydroxyl butyl vinyls polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in remaining deionized water,
It is sequentially added into 45% the first solution, the sodium hydrate aqueous solution of 32% mass concentration, azo diisobutyl amidine hydrochloride again
And sodium peroxydisulfate, and reaction temperature is adjusted to 15 DEG C；
(4) the first solution, in the material obtained by the second solution and third solution to step (3), three kinds of solution are added dropwise while
It is added dropwise in 0.5h, 1h is kept the temperature after completion of dropwise addition；
(5) heat preservation terminates, and pH value is adjusted as 6.0~7.0 to get to institute with the sodium hydrate aqueous solution of 32% mass concentration
It states muting sensitive induction reactance mud and intersects branched chain type polycarboxylate water-reducer PCE-2.
Embodiment 3
(1) each raw material components are weighed by following parts by weight：4- hydroxyl butyl vinyl polyoxyethylene ether (VPEG molecular weight
3000) 50 parts by weight, allyl polyethenoxy polyethers (APEG molecular weight 2000) 20 parts by weight, methacrylic polyoxyethylene gather
Ether (HPEG molecular weight 2400) 40 parts by weight, isopentene group polyoxyethylene polyethers (TPEG molecular weight 500) 5 parts by weight, methyl-prop
7 parts by weight of olefin(e) acid, 3 parts by weight of hydroxypropyl acrylate, 5 parts by weight of dibutyl maleate, unsaturated 3 parts by weight of both sexes quaternary alkylphosphonium salt,
4 parts by weight of dimethylaminoethyl acrylate methyl ammonia ethyl ester, 0.4 parts by weight of ammonium persulfate, Br ü ggolitTM0.7 parts by weight of FF6, azo two
0.06 parts by weight of N- hydroxyisobutyl amidines hydrate, 0.5 parts by weight of mercaptoethanol, 50% mass concentration potassium hydroxide aqueous solution
3 parts by weight, 4 parts by weight of sodium hydrate aqueous solution of 32% mass concentration, remaining is deionized water, is adjusted to 50% solid content.
(2) methacrylic acid, mercaptoethanol are dissolved in 15 parts by weight of deionized water, and with the hydrogen-oxygen of 50% mass concentration
Change aqueous solutions of potassium and adjust pH to 5.5~6.0, obtain the first solution；By Br ü ggolitTMFF6 is dissolved in 15 parts by weight of deionized water
Obtain the second solution；Hydroxypropyl acrylate, dibutyl maleate and dimethylaminoethyl acrylate methyl ammonia ethyl ester are dissolved in 10 parts by weight
Third solution is obtained in ionized water；
(3) 4- hydroxyl butyl vinyls polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in remaining deionized water,
It is sequentially added into 40% the first solution, the sodium hydrate aqueous solution of 32% mass concentration, two N- hydroxyisobutyl amidines of azo again
Hydrate and ammonium persulfate, and reaction temperature is adjusted to 20 DEG C；
(4) the first solution, in the material obtained by the second solution and third solution to step (3), three kinds of solution are added dropwise while
It is added dropwise in 0.75h, 0.5h is kept the temperature after completion of dropwise addition；
(5) heat preservation terminates, and pH value is adjusted as 6.0~7.0 to get to institute with the sodium hydrate aqueous solution of 32% mass concentration
It states muting sensitive induction reactance mud and intersects branched chain type polycarboxylate water-reducer PCE-3.
Embodiment 4
(1) each raw material components are weighed by following parts by weight：4- hydroxyl butyl vinyl polyoxyethylene ether (VPEG molecular weight
4000) 60 parts by weight, allyl polyethenoxy polyethers (APEG molecular weight 3000) 10 parts by weight, methacrylic polyoxyethylene gather
Ether (HPEG molecular weight 3000) 10 parts by weight, isopentene group polyoxyethylene polyethers (TPEG molecular weight 1000) 40 parts by weight, methyl
9 parts by weight of acrylic acid, 5 parts by weight of methyl acrylate, 2 parts by weight of dibutyl maleate, unsaturated 4 parts by weight of both sexes quaternary alkylphosphonium salt,
5 parts by weight of dimethylaminoethyl acrylate methyl ammonia ethyl ester, hydrogen peroxidase 10 .7 parts by weight, 1.0 parts by weight of sodium hypophosphite, azo dimethyl N-
0.05 parts by weight of 2- hydroxyls butylacrylamide, 0.6 parts by weight of mercaptopropionic acid, 50% mass concentration 5 weight of potassium hydroxide aqueous solution
Part is measured, 5 parts by weight of sodium hydrate aqueous solution of 32% mass concentration, remaining is deionized water, is adjusted to 50% solid content.
(2) methacrylic acid, mercaptopropionic acid are dissolved in 15 parts by weight of deionized water, and with the hydrogen-oxygen of 50% mass concentration
Change aqueous solutions of potassium and adjust pH to 5.5~6.0, obtain the first solution；Sodium hypophosphite is dissolved in 15 parts by weight of deionized water and is obtained
Second solution；Methyl acrylate, dibutyl maleate and dimethylaminoethyl acrylate methyl ammonia ethyl ester are dissolved in 10 parts by weight of deionized water
In obtain third solution；
(3) 4- hydroxyl butyl vinyls polyoxyethylene ether, unsaturated both sexes quaternary alkylphosphonium salt are dissolved in remaining deionized water,
It is sequentially added into 55% the first solution, the sodium hydrate aqueous solution of 32% mass concentration, azo dimethyl N-2- hydroxyl butyl again
Acrylamide and hydrogen peroxide, and reaction temperature is adjusted to 30 DEG C；
(4) the first solution, in the material obtained by the second solution and third solution to step (3), three kinds of solution are added dropwise while
It is added dropwise in 1h, 0.75h is kept the temperature after completion of dropwise addition；
(5) heat preservation terminates, and pH value is adjusted as 6.0~7.0 to get to institute with the sodium hydrate aqueous solution of 32% mass concentration
It states muting sensitive induction reactance mud and intersects branched chain type polycarboxylate water-reducer PCE-4.
Embodiment 5
The muting sensitive induction reactance mud that Examples 1 to 4 is synthesized intersect branched chain type polycarboxylate water-reducer (PCE-1, PCE-2,
PCE-3 and PCE-4) and commercially available ethers polycarboxylic acid water reducing agent (PCE-0) carry out different addition quantity concrete performance compare, by adjusting
Water-reducing agent volume, according to GB/T50080-2011《Standard for test methods of properties of ordinary concrete mixture standard》, by fresh concrete
Divergence accomplishes 400 ± 10mm (volume a%) and 550 ± 10mm (volume b%) respectively, calculates its volume width ratio γ
(γ=b/a), γ is bigger, illustrates that water-reducing agent is more insensitive, and adaptability is better.
Using Fujian good fortune cement (P.O 42.5R), concrete mix is：Cement 260kg/m3, flyash 80kg/m3, sand
790kg/m3, stone 1140kg/m3, water 170kg/m3, aggregate clay content is 1.5%, and acquired results are as shown in table 1：
1 embodiment performance comparison of table
It can be seen that from the above, its volume width ratio of commercially available ethers polycarboxylic acid water reducing agent γ is 1.41, and passes through reality
The polycarboxylate water-reducer of example synthesis is applied, volume width ratio γ is respectively 1.68,1.74,1.70 and 1.78, is greater than commercially available
Ethers polycarboxylic acid water reducing agent volume width ratio illustrates that the muting sensitive sense polycarboxylate water-reducer of embodiment synthesis changes less volume
It is sensitive.And in the case where aggregate clay content is 1.5%, reach identical divergence, commercially available ethers polycarboxylic acid water reducing agent is mixed
Amount is substantially higher compared with the polycarboxylate water-reducer volume that embodiment synthesizes, and is protected to collapse and wanted poor, illustrates that the muting sensitive sense of embodiment synthesis gathers
Carboxylic acid water reducer is preferable to adaptability for materials, and anti-mud effect is good.
Those of ordinary skill in the art remain able to it is found that when technical scheme of the present invention changes in following ranges
To same as the previously described embodiments or similar technique effect, protection scope of the present invention is still fallen within：
A kind of muting sensitive induction reactance mud intersects branched chain type polycarboxylate water-reducer, and pH is 6.0~7.0, and solid content is 45~55%,
Its raw material is made of the component of following parts by weight：Molecular weight is 2000~5000 4- hydroxyl butyl vinyl polyoxyethylene ethers
(VPEG) 10~60 parts by weight, molecular weight be 500~3000 0~40 parts by weight of allyl polyethenoxy polyethers (APEG), point
Son amount be 500~3000 0~40 parts by weight of methacrylic polyoxyethylene polyethers (HPEG), molecular weight be 500~3000
0~40 parts by weight of isopentene group polyoxyethylene polyethers (TPEG), 6~10 parts by weight of unsaturated monocarboxylic acid, esters of unsaturated carboxylic acids
3~6 parts by weight of class monomer, 2~6 parts by weight of dimethylaminoethyl acrylate methyl ammonia ethyl ester, 2~6 parts by weight of dibutyl maleate, unsaturation
1~5 parts by weight of both sexes quaternary alkylphosphonium salt, 0.2~0.8 parts by weight of oxidant, 0.2~1.0 parts by weight of the first reducing agent, the second reducing agent
0.02~0.06 parts by weight, 0.2~0.6 parts by weight of chain-transferring agent, appropriate potassium hydroxide aqueous solution, appropriate sodium hydroxide is water-soluble
Liquid and appropriate amount of deionized water, wherein, unsaturated both sexes quaternary alkylphosphonium salt is triphenyl phosphorus and allyl bromide, bromoallylene with 1: 1.0~1.5 mole
Than being made in carbon tetrachloride by following reaction：
The preparation method of the unsaturation both sexes quaternary alkylphosphonium salt includes the following steps：
(1) 1: 1.0~1.5 triphenyl phosphorus and allyl bromide, bromoallylene are weighed in molar ratio；
(2) triphenyl phosphorus and appropriate carbon tetrachloride are mixed, fully dissolved；
(3) allyl bromide, bromoallylene is added dropwise with the speed of 1/2~5s of drop in the material obtained by step (2), is carried out during being added dropwise
Stirring is reacted simultaneously, and reaction temperature is kept for 40~50 DEG C, and the reaction time is 4~6h, obtains tan precipitate object；
(4) above-mentioned tan precipitate object is recrystallized with acetone, obtains recrystallized product；
(5) above-mentioned recrystallized product is dried in vacuo, obtains the powder of white, as described unsaturated both sexes quaternary phosphonium
Salt.
The unsaturated monocarboxylic acid is acrylic acid and/or methacrylic acid.The unsaturated carboxylate type monomer is third
Olefin(e) acid hydroxyl ethyl ester, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxy propyl methacrylate, methyl acrylate and methyl-prop
At least one of e pioic acid methyl ester.The oxidant is at least one of hydrogen peroxide, sodium peroxydisulfate and ammonium persulfate.It is described
First reducing agent is sodium formaldehyde sulphoxylate, Br ü ggolitTMAt least one of FF6 and sodium hypophosphite.Second reduction
Agent is two isobutyl imidazoline hydrochloride of azo, azo diisobutyl amidine hydrochloride, two N- hydroxyisobutyl amidines hydrate of azo, idol
At least one of nitrogen two N, N ' cyclobutyl isobutyl amidine hydrate and/or azo dimethyl N-2- hydroxyl butylacrylamides.It is described
Chain-transferring agent is at least one of thioacetic acid, mercaptopropionic acid and mercaptoethanol.
Above-mentioned muting sensitive induction reactance mud intersects the preparation method of branched chain type polycarboxylate water-reducer, includes the following steps：
(1) each raw material components are weighed by weight；
(2) unsaturated monocarboxylic acid, chain-transferring agent are dissolved in 10~15 parts by weight of deionized water, and with appropriate hydroxide
Aqueous solutions of potassium adjusts pH to 5.5~6.0, obtains the first solution；First reducing agent is dissolved in 10~15 parts by weight of deionized water
Obtain the second solution；Unsaturated carboxylate type monomer, dibutyl maleate and dimethylaminoethyl acrylate methyl ammonia ethyl ester are dissolved in 6~10
Third solution is obtained in parts by weight of deionized water；
(3) by 4- hydroxyl butyl vinyl polyoxyethylene ethers (VPEG), allyl polyethenoxy polyethers (APEG), methyl alkene
Propyl polyoxyethylene polyethers (HPEG), isopentene group polyoxyethylene polyethers (TPEG) and unsaturated both sexes quaternary alkylphosphonium salt are dissolved in 80~90
In the deionized water of parts by weight, then it is sequentially added into 35~55% the first solution, appropriate sodium hydrate aqueous solution, the second reduction
Agent and oxidant, and adjust reaction temperature and reacted to 10~30 DEG C；
(4) while the first solution is added dropwise, in the material obtained by the second solution and third solution to step (3), 0.5~
It is added dropwise in 1.5h, 0.5~1.5h is kept the temperature after completion of dropwise addition；
(5) with the pH value of appropriate sodium hydrate aqueous solution regulating step (4) resulting material to 6.0~7.0 to get to described
Muting sensitive induction reactance mud intersects branched chain type polycarboxylate water-reducer.
The foregoing is only a preferred embodiment of the present invention, therefore cannot limit the range that the present invention is implemented according to this, i.e.,
According to the equivalent changes and modifications that the scope of the claims of the present invention and description are made, all should still belong in the range of the present invention covers.
Claims (9)
1. a kind of muting sensitive induction reactance mud intersects branched chain type polycarboxylate water-reducer, it is characterised in that：Its pH is 6.0~7.0, and solid content is
45~55%, raw material is made of the component of following parts by weight：The 4- hydroxy butyl vinyl ethers that molecular weight is 2000~5000 gather
10~40 parts by weight of allyl polyethenoxy ether that 10~60 parts by weight of ethylene oxide ether, molecular weight are 500~3000, molecular weight are
500~3,000 10~40 parts by weight of methyl allyl polyoxyethylene ether, the isopentene group polyoxy second that molecular weight is 500~3000
5~40 parts by weight of alkene ether, 6~10 parts by weight of unsaturated monocarboxylic acid, 3~6 parts by weight of unsaturated carboxylate type monomer, methyl-prop
2~6 parts by weight of olefin(e) acid diformazan ammonia ethyl ester, 2~6 parts by weight of dibutyl maleate, unsaturated 1~5 parts by weight of both sexes quaternary alkylphosphonium salt, oxygen
0.2~0.8 parts by weight of agent, 0.2~1.0 parts by weight of the first reducing agent, 0.02~0.06 parts by weight of azo-initiator, chain turn
0.2~0.6 parts by weight of agent, appropriate potassium hydroxide aqueous solution, appropriate sodium hydrate aqueous solution and appropriate amount of deionized water are moved, wherein,
Unsaturated both sexes quaternary alkylphosphonium salt is that triphenyl phosphorus and allyl bromide, bromoallylene are pressed as follows instead with 1: 1.0~1.5 molar ratio in carbon tetrachloride
It should be made：
2. a kind of muting sensitive induction reactance mud as described in claim 1 intersects branched chain type polycarboxylate water-reducer, it is characterised in that：It is described not
The preparation method of saturation both sexes quaternary alkylphosphonium salt includes the following steps：
(1) 1: 1.0~1.5 triphenyl phosphorus and allyl bromide, bromoallylene are weighed in molar ratio；
(2) triphenyl phosphorus and appropriate carbon tetrachloride are mixed, fully dissolved；
(3) allyl bromide, bromoallylene is added dropwise with the speed of 1/2~5s of drop in the material obtained by step (2), is carried out simultaneously during being added dropwise
Stirring is reacted, and reaction temperature is kept for 40~50 DEG C, and the reaction time is 4~6h, obtains tan precipitate object；
(4) above-mentioned tan precipitate object is recrystallized with acetone, obtains recrystallized product；
(5) above-mentioned recrystallized product is dried in vacuo, obtains the powder of white, as described unsaturated both sexes quaternary alkylphosphonium salt.
3. a kind of muting sensitive induction reactance mud as described in claim 1 intersects branched chain type polycarboxylate water-reducer, it is characterised in that：It is described not
Saturated monocarboxylic acid is acrylic acid and/or methacrylic acid.
4. a kind of muting sensitive induction reactance mud as described in claim 1 intersects branched chain type polycarboxylate water-reducer, it is characterised in that：It is described not
Saturated carboxylic acid esters monomer is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, methacrylic acid hydroxypropyl
At least one of ester, methyl acrylate and methyl methacrylate.
5. a kind of muting sensitive induction reactance mud as described in claim 1 intersects branched chain type polycarboxylate water-reducer, it is characterised in that：The oxygen
Agent is at least one of hydrogen peroxide, sodium peroxydisulfate and ammonium persulfate.
6. a kind of muting sensitive induction reactance mud as described in claim 1 intersects branched chain type polycarboxylate water-reducer, it is characterised in that：Described
One reducing agent is at least one of sodium formaldehyde sulphoxylate, Bruggolite FF6 and sodium hypophosphite.
7. a kind of muting sensitive induction reactance mud as described in claim 1 intersects branched chain type polycarboxylate water-reducer, it is characterised in that：The idol
Nitrogen class initiator is two isobutyl imidazoline hydrochloride of azo, azo diisobutyl amidine hydrochloride, two N- hydroxyisobutyl amidines of azo
In hydrate, azo two N, N ' cyclobutyl isobutyl amidine hydrate and/or azo dimethyl N-2- hydroxyl butylacrylamides at least
It is a kind of.
8. a kind of muting sensitive induction reactance mud as described in claim 1 intersects branched chain type polycarboxylate water-reducer, it is characterised in that：The chain
Transfer agent is at least one of thioacetic acid, mercaptopropionic acid and mercaptoethanol.
9. a kind of muting sensitive induction reactance mud as described in any claim in claim 1 to 8 intersects branched chain type polycarboxylate water-reducer
Preparation method, it is characterised in that：Include the following steps：
(1) each raw material components are weighed by weight；
(2) unsaturated monocarboxylic acid, chain-transferring agent are dissolved in 10~15 parts by weight of deionized water, and with appropriate potassium hydroxide water
Solution adjusts pH to 5.5~6.0, obtains the first solution；First reducing agent is dissolved in 10~15 parts by weight of deionized water and is obtained
Second solution；Unsaturated carboxylate type monomer, dibutyl maleate and dimethylaminoethyl acrylate methyl ammonia ethyl ester are dissolved in 6~10 weight
Third solution is obtained in part deionized water；
(3) by 4- hydroxy butyl vinyl ethers polyoxyethylene ether, allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, different
Pentenyl polyoxyethylene ether and unsaturated both sexes quaternary alkylphosphonium salt are dissolved in the deionized water of 80~90 parts by weight, then be sequentially added into 35
~55% the first solution, appropriate sodium hydrate aqueous solution, azo-initiator and oxidant, and adjust reaction temperature to 10~
30 DEG C are reacted；
(4) while the first solution is added dropwise, in the material obtained by the second solution and third solution to step (3), in 0.5~1.5h
It is inside added dropwise, 0.5~1.5h is kept the temperature after completion of dropwise addition；
(5) with the pH value of appropriate sodium hydrate aqueous solution regulating step (4) resulting material to 6.0~7.0 to get to the muting sensitive
Induction reactance mud intersects branched chain type polycarboxylate water-reducer.
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| CN106977129A (en) * | 2017-04-10 | 2017-07-25 | 河北润砼新材料科技有限公司 | Anti- mud collapse protective poly-carboxylic acid high efficiency water reducing agent and preparation method thereof |
| CN107603110B (en) * | 2017-10-31 | 2020-12-29 | 安徽森普新型材料发展有限公司 | Branched chain type mud-inhibiting polycarboxylate superplasticizer, and preparation method and application thereof |
| CN109111552A (en) * | 2018-07-27 | 2019-01-01 | 刘翠芬 | A kind of both sexes polycarboxylate water-reducer and preparation method thereof of pair of reinforcing bar non-corroding effect |
| CN109306038A (en) * | 2018-10-10 | 2019-02-05 | 安徽瑞和新材料有限公司 | A kind of extra retarded set type poly carboxylic acid series water reducer and its preparation method and application |
| CN110330600B (en) * | 2019-05-29 | 2022-04-22 | 科之杰新材料集团有限公司 | Low-sensitivity wet-mixed mortar plasticizer and preparation method thereof |
| CN112707667B (en) * | 2020-06-22 | 2022-08-26 | 科之杰新材料集团有限公司 | Low-sensitivity water reducing agent and preparation method thereof |
| CN113072668A (en) * | 2021-03-17 | 2021-07-06 | Sika技术股份公司 | Copolymers useful for maintaining high slump flow of mineral binder compositions, their preparation and use |
| CN113527592B (en) * | 2021-07-30 | 2022-07-19 | 连云港石化有限公司 | Polycarboxylic acid water reducer for gypsum-based self-leveling mortar and preparation method and use method thereof |
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| CN103554384A (en) * | 2013-10-26 | 2014-02-05 | 贵阳绿洲苑建材有限公司 | Phosphino-containing polycarboxylate water-reducing agent and preparation method thereof |
| CN103848944A (en) * | 2013-05-14 | 2014-06-11 | 科之杰新材料集团有限公司 | Preparation method of super-retarding type polycarboxylate superplasticizer |
| CN104177557A (en) * | 2014-08-22 | 2014-12-03 | 科之杰新材料集团有限公司 | Low-temperature preparation method of high-adaptability ether polycarboxylic acid water reducer |
| CN105236806A (en) * | 2015-10-22 | 2016-01-13 | 石家庄市长安育才建材有限公司 | Phosphoric-acid-base modified polycarboxylic-acid water reducer with high adaptability and preparation method thereof |
| CN105271893A (en) * | 2015-10-23 | 2016-01-27 | 上海三瑞高分子材料股份有限公司 | Slump-retaining water reducer and preparation method thereof |
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| ES2437842T3 (en) * | 2004-07-15 | 2014-01-14 | Kao Corporation | Phosphoric ester polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103848944A (en) * | 2013-05-14 | 2014-06-11 | 科之杰新材料集团有限公司 | Preparation method of super-retarding type polycarboxylate superplasticizer |
| CN103554384A (en) * | 2013-10-26 | 2014-02-05 | 贵阳绿洲苑建材有限公司 | Phosphino-containing polycarboxylate water-reducing agent and preparation method thereof |
| CN104177557A (en) * | 2014-08-22 | 2014-12-03 | 科之杰新材料集团有限公司 | Low-temperature preparation method of high-adaptability ether polycarboxylic acid water reducer |
| CN105236806A (en) * | 2015-10-22 | 2016-01-13 | 石家庄市长安育才建材有限公司 | Phosphoric-acid-base modified polycarboxylic-acid water reducer with high adaptability and preparation method thereof |
| CN105271893A (en) * | 2015-10-23 | 2016-01-27 | 上海三瑞高分子材料股份有限公司 | Slump-retaining water reducer and preparation method thereof |
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