CN109734833A - A kind of anti-chamotte mould polycarboxylate water-reducer of short-side chain and preparation method thereof - Google Patents
A kind of anti-chamotte mould polycarboxylate water-reducer of short-side chain and preparation method thereof Download PDFInfo
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- CN109734833A CN109734833A CN201811610837.2A CN201811610837A CN109734833A CN 109734833 A CN109734833 A CN 109734833A CN 201811610837 A CN201811610837 A CN 201811610837A CN 109734833 A CN109734833 A CN 109734833A
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- unsaturated
- side chain
- reducer
- short
- polycarboxylate water
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 40
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000002148 esters Chemical class 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 22
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 15
- 150000003384 small molecules Chemical class 0.000 claims abstract description 15
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 14
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 14
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical class C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 16
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 15
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 14
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- -1 sulfonic acid group Unsaturated glycine betaine Chemical class 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-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
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000002459 sustained effect Effects 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 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 2
- 239000012966 redox initiator Substances 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 239000004927 clay Substances 0.000 abstract description 11
- 239000002734 clay mineral Substances 0.000 abstract description 10
- 229920000570 polyether Polymers 0.000 abstract description 10
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 9
- 239000011229 interlayer Substances 0.000 abstract description 5
- 230000002687 intercalation Effects 0.000 abstract description 4
- 238000009830 intercalation Methods 0.000 abstract description 4
- 230000007423 decrease Effects 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000000178 monomer Substances 0.000 description 12
- 239000012452 mother liquor Substances 0.000 description 11
- 239000004568 cement Substances 0.000 description 10
- 230000003467 diminishing effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000003643 water by type Substances 0.000 description 10
- 150000007513 acids Chemical class 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 6
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- RTTAGBVNSDJDTE-UHFFFAOYSA-N 4-ethoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCOC(=O)CC(=C)C(O)=O RTTAGBVNSDJDTE-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 235000003642 hunger Nutrition 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- UNMYKPSSIFZORM-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)butane Chemical class CCCCOCCOC=C UNMYKPSSIFZORM-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical class OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- DYYFCJRYZVHEKQ-UHFFFAOYSA-N 3-butoxycarbonylbut-3-enoic acid Chemical class CCCCOC(=O)C(=C)CC(O)=O DYYFCJRYZVHEKQ-UHFFFAOYSA-N 0.000 description 1
- IZUVGRMMRWJVKU-UHFFFAOYSA-N 3-ethoxycarbonylbut-3-enoic acid Chemical class CCOC(=O)C(=C)CC(O)=O IZUVGRMMRWJVKU-UHFFFAOYSA-N 0.000 description 1
- KBFJHOCTSIMQKL-UHFFFAOYSA-N 3-methoxycarbonylbut-3-enoic acid Chemical class COC(=O)C(=C)CC(O)=O KBFJHOCTSIMQKL-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical class OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 206010020466 Hunger Diseases 0.000 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008030 superplasticizer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention discloses a kind of anti-chamotte mould polycarboxylate water-reducer of short-side chain and preparation method thereof, is polymerized in aqueous solution by small molecule unsaturated ethylene alkenyl ether, unsaturated polyacid/unsaturation multi-anhydride, unsaturation polyacid monoalkyl ester, the unsaturated glycine betaine containing sulfonic acid group.Traditional polyether macromonomer is replaced using the small molecule unsaturated ethylene alkenyl ether of short-side chain, since side-chain structure is shorter, so that polycarboxylic acid structure has bigger charge density, on the one hand the decline of steric repulsion caused by short-side chain can be made up, on the other hand the intercalation that side chain can be reduced in clay interlayer structure adsorbs, polycarboxylate water-reducer can be improved to the tolerance of clay mineral under the premise of guaranteeing water-reducing rate.
Description
Technical field
The invention belongs to technical field of concrete additives, and in particular to a kind of anti-chamotte mould polycarboxylate water-reducer of short-side chain and
Preparation method.
Background technique
In recent years, due to the extensive development of infrastructure project, quality sand and stone resources is caused gradually to be exhausted, and to contain
Poor material for the high sand and stone resources of mud amount in use, often will appear and polycarboxylate water-reducer is unconformable asks
Topic, for the adaptability problem for solving clay mineral and polycarboxylate water-reducer, domestic and international research worker has carried out a large amount of research.
It is disclosed in patent US 2017/028475Clay insensitive concrete superplasticizer
A kind of anti-chamotte mould polycarboxylate water-reducer is made by styrene, dicarboxylic acids ring-opened maleic acid acid anhydride, ring-opened maleic acid acid anhydride half-ester copolymerization
Then SMA copolymer is esterified the MPEG-SMA to be formed with MPEG, by studies have shown that MPEG-SMA can reduce water-soluble swelling
Negative effect of the soil to water-reducing agent.But the preparation process of MPEG-SMA need to be completed in solvent dimethylformamide, and reaction terminates
It also needs to be filtered with ethane afterwards and purify, toxic dimethylformamide is not used only, and production process is also more troublesome, simultaneously
The problems such as there are low efficiencys.
Chinese CN201810036393.X patent discloses a kind of anti-chamotte mould polycarboxylate water-reducer and preparation method thereof, leads to
It crosses by obtained prepolymer solutions such as unsaturated halogen monomer, unsaturated carboxylic acid monomer, chain-transferring agents, then in prepolymer solution
N-vinyl pyrrolidone (NVP), unsaturated polyether monomer and catalyst metals-organic coordination compound reaction is added, is filtered to remove
Insoluble matter, subtract be evaporated off solvent be made, which introduces NVP unit in polyether lateral chain, makes polyether lateral chain molecular dimension
It is significantly increased, to improve side chain hydrated sheath thickness, and then improves the steric repulsion of side chain, while the increasing of side chain molecular dimension
Adding also makes it be difficult to be inserted into the layer structure of clay, has good diminishing and anti-mud effect.But product is in production process
In the problems such as needing separating-purifying, equally existing preparation troublesome and low efficiency.
Chinese 104446101 A patent of CN discloses a kind of cation-modified polycarboxylate water-reducer, by prenol
Polyoxyethylene ether, unitary unsaturated carboxylic acid and its derivatives monomer, cationic monomer and binary unsaturated carboxylic acid and its derivative
Object monomer is copolymerized under the action of initiator and chain-transferring agent, and product strand in cement slurry extends, tool
There is more excellent diminishing dispersion effect, but the application feature for showing highly resistance chamotte mould energy while diminishing dispersion is not implemented.
Chinese 103467670 B patent of CN discloses a kind of anti-chamotte mould polycarboxylate water-reducer, by polycarboxylic acids molecule
Quaternary ammonium salt group is introduced in structure to improve the anti-mud performance of product, prepares season with epoxy bromopropane and tertiary amine compounds first
Ammonium salt oligomer, then by quaternary ammonium salt oligomer and isoamyl alcohol polyoxyethylene ether, aminotrimethylenephosphonic acid, unsaturated carboxylic acid
It is made together by free-radical polymerized, which can be avoided in concrete aggregate clay content to poly carboxylic acid series water reducer
Adverse effect solves the problems, such as that concrete strength is relatively low.But the phosphorus acid monomer introduced in this method causes polymerization reaction to be difficult to control
Molecular weight processed, and a large amount of function monomers introduced make water reducing ability decline to a great extent.
Above-mentioned patent has synthesized anti-chamotte mould polycarboxylate water-reducer by different mentality of designing and method, but using conventional
On the one hand polyethers or modified polyether monomer, longer side chain can provide more excellent steric repulsion, can increase but then
Big clay mineral is unfavorable for the design of anti-mud performance to polycarboxylic acids Inter layer adsorption, while improving diminishing dispersibility instead.
And there is adverse effect to reactivity of the modification of side-chain structure to polyether monomer, it is not for improving polymerization conversion
Benefit.In addition, above-mentioned patent all more or less exists, reaction process is complicated, needs the problems such as separating-purifying.It is therefore desirable to open
Send out simple production process a kind of, the anti-chamotte mould polycarboxylate water-reducer that has excellent performance is to solve the above problems.
Summary of the invention
In response to the problems existing in the prior art, the purpose of the present invention is to provide a kind of anti-chamotte mould polycarboxylate water-reducers of short-side chain
And preparation method thereof, traditional polyether macromonomer is replaced using the small molecule unsaturated ethylene alkenyl ether of short-side chain, due to side chain knot
Structure is shorter, so that polycarboxylic acid structure has bigger charge density, on the one hand can make up under steric repulsion caused by short-side chain
Drop, the intercalation that on the other hand can reduce side chain in clay interlayer structure adsorb, and can improve poly- under the premise of guaranteeing water-reducing rate
Tolerance of the carboxylic acid water reducer to clay mineral.
To achieve the above object, the technical solution adopted by the present invention is that:
The present invention provides a kind of anti-chamotte mould polycarboxylate water-reducer of short-side chain, by small molecule unsaturated ethylene alkenyl ether, unsaturation
Polyacid/unsaturation multi-anhydride, unsaturated polyacid monoalkyl ester, the unsaturated glycine betaine containing sulfonic acid group are in aqueous solution
It is polymerized, the small molecule unsaturated ethylene alkenyl ether, unsaturated polyacid/unsaturation multi-anhydride, unsaturated polyacid list
Arrcostab, unsaturated glycine betaine containing sulfonic acid group mass ratio be 100:60-120:30-60:20-40.
The present invention replaces traditional polyether macromonomer using the small molecule unsaturated ethylene alkenyl ether of short-side chain, due to side chain knot
Structure is shorter, so that polycarboxylic acid structure has bigger charge density, on the one hand can make up under steric repulsion caused by short-side chain
Drop, the intercalation that on the other hand can reduce side chain in clay interlayer structure adsorb, and can improve poly- under the premise of guaranteeing water-reducing rate
Tolerance of the carboxylic acid water reducer to clay mineral.
The small molecule unsaturated ethylene alkenyl ether has following general formula of molecular structure:
Wherein, R1For H or C1-2Alkyl, R2For C1-10Alkyl.
Unsaturated polyacid/unsaturation multi-anhydride is one of maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride
Or it is a variety of.
Unsaturation polyacid/unsaturation the multi-anhydride is compared to unitary insatiable hungers such as conventional acrylic acid and methacrylic acid
And acid, bigger charge density can be provided for polycarboxylic acid structure's main chain.
Unsaturated polyacid monoalkyl ester is one of maleic acid monoalkyl ester, itaconic acid monoalkyl ester or group
It closes.
The maleic acid monoalkyl ester the preparation method comprises the following steps: anhydrous C is added in the reaction vessel1-4Alcohol, to temperature liter
To 50-60 DEG C, maleic anhydride is added and reacts 2-4h, reaction product vacuum distillation is removed into unreacted alcohol to get maleic is arrived
Monoalkyl ester；Wherein maleic anhydride and C1-4The ratio between amount of substance of alcohol is 1:1.2-1.5.
The maleic acid monoalkyl ester has following general formula of molecular structure:
The preparation process of the itaconic acid monoalkyl ester are as follows: by itaconic acid, anhydrous C1-4Pure and mild chlorobenzoyl chloride is added to reaction
It is mixed in container, heating stirring removes excessive C to 60-80 DEG C of temperature, sustained response 2-4h, by reaction product vacuum distillation1-4
Then recrystallization solvent reflux 15-20min is added in alcohol, the crystal being collected by filtration after natural cooling is itaconic acid monoalkyl ester；
Wherein itaconic acid, anhydrous C1-4The ratio between amount of substance of pure and mild chlorobenzoyl chloride is 1:2-5:0.02-0.08, and recrystallization solvent is benzene
With petroleum ether mixed solvent, the volume ratio of the benzene and petroleum ether is 1:0.3-3.
The itaconic acid monoalkyl ester has following general formula of molecular structure:
Wherein, R3And R4It is C1-4Alkyl.
Using unsaturated polyacid monoalkyl ester as small molecule unsaturated ethylene alkenyl ether, unsaturated polyacid/unsaturation
The additional comonomer of multi-anhydride and the unsaturated glycine betaine containing sulfonic acid group can make 4 class raw materials in reaction system more preferable
Polymerization；On the other hand unsaturated polyacid monoalkyl ester can provide carboxyl and ester group for polycarboxylic acids main chain, have both diminishing with
Function of slump protection.
The unsaturated glycine betaine containing sulfonic acid group includes acryloyl ethyl sulfobetaines (structural formula 4) and methyl
One or both of acryloyl ethyl sulfobetaines (structural formula 5).
Using the unsaturated glycine betaine containing sulfonic acid group as functional form monomer, since its molecular structure end has sulfonic acid
Group, makes it have good dispersion performance, and the quaternary ammonium salt cationic in molecular structure can be adsorbed on clay mineral surface, play
The effect of clay mineral stabilizing agent.
The present invention also provides a kind of preparation methods of the anti-chamotte mould polycarboxylate water-reducer of short-side chain, comprising the following steps:
1) by small molecule unsaturated ethylene alkenyl ether, unsaturated polyacid/unsaturation multi-anhydride, unsaturated polyacid list alkane
Base ester, the unsaturated glycine betaine containing sulfonic acid group and deionized water are added in reaction vessel, are stirred under the conditions of 10-50 DEG C equal
It is even；
2) to mixed solution and dripping initiator solution obtained by step 1) and molecular-weight adjusting agent solution, initiator solution and
Molecular-weight adjusting agent solution is controlled at the uniform velocity to be added dropwise in reaction vessel in 2-4 hours；
3) after being added dropwise, reaction solution pH to 5-7 is adjusted, the anti-chamotte mould polycarboxylate water-reducer of the short-side chain is obtained.
The initiator uses redox initiator, and wherein oxidant is one of hydrogen peroxide, ammonium persulfate or more
Kind, reducing agent is L-AA, Mohr's salt.
Molecular weight regulator is one of thioacetic acid, mercaptopropionic acid, mercaptoethanol or combination.
Compared with prior art, the beneficial effects of the present invention are:
(1) traditional polyether macromonomer is replaced using the small molecule unsaturated ethylene alkenyl ether of short-side chain, due to side-chain structure
It is shorter, so that polycarboxylic acid structure has bigger charge density, the decline of steric repulsion caused by short-side chain on the one hand can be made up,
On the other hand the intercalation that side chain can be reduced in clay interlayer structure adsorbs, and can improve poly- carboxylic under the premise of guaranteeing water-reducing rate
Tolerance of the sour water-reducing agent to clay mineral；
(2) using unsaturated polyacid/unsaturation multi-anhydride, compared to unitary such as conventional acrylic acid and methacrylic acid
Unsaturated acids can provide bigger charge density for polycarboxylic acid structure's main chain；
(3) using unsaturated polyacid monoalkyl ester as small molecule unsaturated ethylene alkenyl ether, unsaturated polyacid/insatiable hunger
With multi-anhydride and the additional comonomer of the unsaturated glycine betaine containing sulfonic acid group, 4 class raw materials in reaction system can be made more
Good polymerization；On the other hand unsaturated polyacid monoalkyl ester can provide carboxyl and ester group for polycarboxylic acids main chain, have both diminishing
And function of slump protection；
(4) using the unsaturated glycine betaine containing sulfonic acid group as functional form monomer, since its molecular structure end has
Sulfonic acid group makes it have good dispersion performance, and the quaternary ammonium salt cationic in molecular structure can be adsorbed on clay mineral surface,
Play the role of clay mineral stabilizing agent.
(5) the anti-chamotte mould polycarboxylate water-reducer free radical polymerization under aqueous environment of short-side chain of the present invention compares one
The product that need to polymerize in organic phase a bit, have the characteristics that environmental protection, it is efficient, in the relatively high situation of concrete raw material clay content
Under, it is with the obvious advantage to be higher than common polycarboxylate water-reducer.
Specific embodiment
Technical solution of the present invention is clearly and completely described below, it is clear that described embodiment is only this hair
Bright a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
All other embodiment obtained under the conditions of creative work is made, shall fall within the protection scope of the present invention.
Embodiment 1
By 100 parts of 4- hydroxy butyl vinyl ethers, 60 parts of fumaric acid, 60 parts of monomethyl cis-butenedioic acids and 20 parts of acryloyl second
Base sulfobetaines and several deionized waters are added in reaction vessel, are stirred evenly at 30 DEG C.Start at the uniform velocity to be added dropwise 2 parts pairs
Oxygen water, 0.5 part of L-AA and 0.5 part of mercaptoacetic acid solution, time for adding 3h.After being added dropwise, add NaOH solution
PH to 5 is adjusted, several deionized waters is supplemented and adjusts the solid containing to 40% of reaction solution, obtain anti-chamotte mould mother liquor UC-CT1.
The monomethyl cis-butenedioic acid the preparation method comprises the following steps: anhydrous cis-butenediol is added in the reaction vessel, to temperature
Degree rises to 50-60 DEG C, and maleic anhydride is added and reacts 3h, and reaction product vacuum distillation is removed unreacted alcohol to get to along fourth
Enedioic acid mono-methyl；Wherein the ratio between amount of substance of maleic anhydride and cis-butenediol is 1:1.2.
Embodiment 2
By 100 parts of ethylene glycol butyl vinyl ethers, 75 parts of maleic anhydrides, 52 parts of Kunshun butene two acid mono-character esters and 25 part third
Alkene acyl ethyl sulfobetaines and several deionized waters are added in reaction vessel, are stirred evenly at 40 DEG C.Start at the uniform velocity to drip
Add 2 parts of ammonium persulfates, L-AA and mercaptopropionic acid, time for adding 2.5h.After being added dropwise, add several NaOH
Solution adjusts pH to 5.5, supplements several deionized waters and adjusts the solid containing to 40% of reaction solution, obtains anti-chamotte mould mother liquor UC-CT2.
The Kunshun butene two acid mono-character ester the preparation method comprises the following steps: anhydrous cis-butenediol is added in the reaction vessel, to temperature
Degree rises to 50-60 DEG C, and maleic anhydride is added and reacts 3h, and reaction product vacuum distillation is removed unreacted alcohol to get to along fourth
Enedioic acid mono-n-butylester；Wherein the ratio between amount of substance of maleic anhydride and cis-butenediol is 1:1.2.
Embodiment 3
By 100 parts of diethylene glycol monovinyl base ethers, 90 parts of itaconic acids, 45 parts of ethyl itaconates and 30 parts of methacryls
Ethyl sulfobetaines and several deionized waters are added in reaction vessel, are stirred evenly at 40 DEG C.Start at the uniform velocity to be added dropwise
Ammonium sulfate, Mohr's salt and mercaptoacetic acid solution, time for adding 2h.After being added dropwise, add several NaOH solutions adjust pH to
6, it supplements several deionized waters and adjusts the solid containing to 40% of reaction solution, obtain anti-chamotte mould mother liquor UC-CT3.
The preparation process of the ethyl itaconate are as follows: by itaconic acid, anhydrous C1-4Pure and mild chlorobenzoyl chloride, which is added to reaction, to be held
It is mixed in device, heating stirring to temperature 70 C, sustained response 3h, reaction product vacuum distillation is removed into excessive C1-4Alcohol, then
Recrystallization solvent reflux 15-20min is added, the crystal being collected by filtration after natural cooling is ethyl itaconate；Its underpants' health
Sour, anhydrous C1-4The ratio between amount of substance of pure and mild chlorobenzoyl chloride is 1:4:0.05, and recrystallization solvent is that benzene and petroleum ether mixing are molten
The volume ratio of agent, the benzene and petroleum ether is 1:2.
Embodiment 4
By 100 parts of ethylene glycol vinyl ethers, 105 parts of itaconic anhydrides, 38 parts of monomethyl itaconates and 35 parts of methacryls
Ethyl sulfobetaines and several deionized waters are added in reaction vessel, are stirred evenly at 40 DEG C.Start at the uniform velocity to be added dropwise
Hydrogen peroxide, Mohr's salt and mercaptopropionic acid, time for adding 4h.After being added dropwise, add several NaOH solutions adjust pH to
6.5, it supplements several deionized waters and adjusts the solid containing to 40% of reaction solution, obtain anti-chamotte mould mother liquor UC-CT4.
Embodiment 5
By 100 parts of allyl hydroxyethyl ethers, 120 parts of fumaric acid, 30 parts of monobutyl itaconates and 40 parts of methacryl second
Base sulfobetaines and several deionized waters are added in reaction vessel, are stirred evenly at 40 DEG C.Start at the uniform velocity to be added dropwise double
Oxygen water, L-AA and mercaptoacetic acid solution, time for adding 3.5h.After being added dropwise, several NaOH solutions is added to adjust
PH to 7 supplements several deionized waters and adjusts the solid containing to 40% of reaction solution, obtains anti-chamotte mould mother liquor UC-CT5.
Implementation result
Flowing degree of net paste of cement test is carried out by GB/T 8077-2012 " Methods for testing uniformity of concrete admixture ".Examination
Testing with cement is Ge Zhou Ba PO42.5 cement, and clay is montmorillonite.
Concrete test is carried out by GB/T 50080-2002 " Standard for test methods of properties of ordinary concrete mixture ".
Comparative example 1 selects the conventional diminishing mother liquor UC-WR of Wuhan You Cheng Science and Technology Ltd. production, solid content 40%.
1. flowing degree of net paste of cement is tested
Cement 570g, montmorillonite 30g, water 174g, water-reducing agent is based on the solid volume of folding.It is de- that illiteracy is not incorporated into blank group Blank
Native (i.e. cement 600g, water 174g), and the conventional diminishing mother liquor UC- that water-reducing agent uses You Cheng Science and Technology Ltd. in Wuhan to produce
WR。
1. flowing degree of net paste of cement of table
Data in analytical table 1 are compared using conventional diminishing mother liquor (Blank and comparative example 1), interior in cement to mix 5% illiteracy
After de- soil, net slurry mobility sharply declines (initial flow degree is down to 128mm from 276mm), and the UC-CT1 in incorporation embodiment is extremely
After UC-CT5 mother liquor, net slurry initial flow degree is improved much compared to comparative example 1, and have it is good through when mobile performance.
The above result shows that anti-chamotte mould polycarboxylate water-reducer of the present invention has good anti-mud compared to conventional structure polycarboxylic acids
Energy.
2. testing concrete performance
By match ratio cement 270kg/m3, miberal powder 50kg/m3, flyash 60kg/m3, sand 770kg/m3, great Shi 800kg/m3、
Gravelstone 260kg/m3, water 150kg/m3Concrete test is carried out, wherein sand clay content 8%, it is 0.15% that polycarboxylic acids, which rolls over solid volume,.
Concrete test the results are shown in Table 2.
2. concrete test result of table
From the point of view of the concrete test result of table 2, in identical volume and match ratio condition, high stone material containing silt particle is used
Under conditions of, UC-CT1 to UC-CT5 mother liquor is compared to UC-WR with more preferably diminishing and function of slump protection, the clay being excellent in are resistance to
By property, furthermore from the point of view of compression strength result, had no adverse effect using UC-CT1 to intensity of the UC-CT5 mother liquor to concrete.
In summary from the point of view of test result, 5 kinds of mother liquors of embodiment all have good clay tolerance, and to coagulation
The intensity of soil is without negative effect.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (10)
1. a kind of anti-chamotte mould polycarboxylate water-reducer of short-side chain, which is characterized in that more by small molecule unsaturated ethylene alkenyl ether, unsaturation
First acid/unsaturated multi-anhydride, unsaturated polyacid monoalkyl ester, the unsaturated glycine betaine containing sulfonic acid group gather in aqueous solution
It closes, the small molecule unsaturated ethylene alkenyl ether, unsaturated polyacid/unsaturation multi-anhydride, unsaturated polyacid list alkane
Base ester, unsaturated glycine betaine containing sulfonic acid group mass ratio be 100:60-120:30-60:20-40.
2. the anti-chamotte mould polycarboxylate water-reducer of a kind of short-side chain according to claim 1, it is characterised in that: the small molecule is not
Unsaturated ethylene base ether has following general formula of molecular structure:
Wherein, R1For H or C1-2Alkyl, R2For C1-10Alkyl.
3. the anti-chamotte mould polycarboxylate water-reducer of a kind of short-side chain according to claim 1, it is characterised in that: unsaturated polynary
Acid/unsaturated multi-anhydride is one of maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride or a variety of.
4. the anti-chamotte mould polycarboxylate water-reducer of a kind of short-side chain according to claim 1, it is characterised in that: unsaturated polyacid
Monoalkyl ester is one of maleic acid monoalkyl ester, itaconic acid monoalkyl ester or combination.
5. the anti-chamotte mould polycarboxylate water-reducer of a kind of short-side chain according to claim 4, it is characterised in that: the maleic two
Sour monoalkyl ester the preparation method comprises the following steps: anhydrous C is added in the reaction vessel1-4Alcohol rises to 50-60 DEG C to temperature, maleic acid is added
Reaction product vacuum distillation is removed unreacted alcohol to get maleic acid monoalkyl ester is arrived by anhydride reactant 2-4h；Wherein Malaysia
Acid anhydrides and C1-4The ratio between amount of substance of alcohol is 1:1.2-1.5.
6. the anti-chamotte mould polycarboxylate water-reducer of a kind of short-side chain according to claim 4, it is characterised in that: the itaconic acid list
The preparation process of Arrcostab are as follows: by itaconic acid, anhydrous C1-4Pure and mild chlorobenzoyl chloride, which is added in reaction vessel, to be mixed, heating stirring
To 60-80 DEG C of temperature, sustained response 2-4h, reaction product vacuum distillation is removed into excessive C1-4Then it is molten that recrystallization is added in alcohol
Agent flows back 15-20min, and the crystal being collected by filtration after natural cooling is itaconic acid monoalkyl ester；Wherein itaconic acid, anhydrous C1-4
The ratio between amount of substance of pure and mild chlorobenzoyl chloride is 1:2-5:0.02-0.08, and recrystallization solvent is benzene and petroleum ether mixed solvent, institute
The volume ratio for stating benzene and petroleum ether is 1:0.3-3.
7. the anti-chamotte mould polycarboxylate water-reducer of a kind of short-side chain according to claim 1, it is characterised in that: containing sulfonic acid group
Unsaturated glycine betaine includes one of acryloyl ethyl sulfobetaines and methacryloylethyl sulfobetaines or combination.
8. a kind of described in any item preparation methods of the anti-chamotte mould polycarboxylate water-reducer of short-side chain of claim 1-7, feature exist
In, comprising the following steps:
1) by small molecule unsaturated ethylene alkenyl ether, unsaturated polyacid/unsaturation multi-anhydride, unsaturated polyacid monoalkyl
Ester, the unsaturated glycine betaine containing sulfonic acid group and deionized water are added in reaction vessel, are stirred under the conditions of 10-50 DEG C equal
It is even；
2) to mixed solution and dripping initiator solution obtained by step 1) and molecular-weight adjusting agent solution, initiator solution and molecule
Amount adjusting agent solution is controlled at the uniform velocity to be added dropwise in reaction vessel in 2-4 hours；
3) after being added dropwise, reaction solution pH to 5-7 is adjusted, the anti-chamotte mould polycarboxylate water-reducer of the short-side chain is obtained.
9. a kind of preparation method of the anti-chamotte mould polycarboxylate water-reducer of short-side chain according to claim 8, it is characterised in that: institute
Initiator is stated using redox initiator, wherein oxidant is one of hydrogen peroxide, ammonium persulfate or a variety of, and reducing agent is
One of L-AA, Mohr's salt are a variety of.
10. a kind of preparation method of the anti-chamotte mould polycarboxylate water-reducer of short-side chain according to claim 8, it is characterised in that:
Molecular weight regulator is one of thioacetic acid, mercaptopropionic acid, mercaptoethanol or combination.
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