CN109734833B - Short-side-chain anti-mud polycarboxylate superplasticizer and preparation method thereof - Google Patents
Short-side-chain anti-mud polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920005646 polycarboxylate Polymers 0.000 title claims description 18
- 239000008030 superplasticizer Substances 0.000 title claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002253 acid Substances 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 25
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 150000007519 polyprotic acids Polymers 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- 150000002148 esters Chemical class 0.000 claims description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 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 15
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 14
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- -1 acryloyl ethyl sulfobetaine Chemical compound 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
- 229940117986 sulfobetaine Drugs 0.000 claims description 9
- 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
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- 239000011976 maleic acid Substances 0.000 claims description 7
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 6
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 239000002211 L-ascorbic acid Substances 0.000 claims description 5
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000001530 fumaric acid Substances 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
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 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
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000000379 polymerizing effect Effects 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
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical class C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims 4
- 239000002734 clay mineral Substances 0.000 abstract description 9
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 7
- 229920000570 polyether Polymers 0.000 abstract description 7
- 239000004927 clay Substances 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000002687 intercalation Effects 0.000 abstract description 3
- 238000009830 intercalation Methods 0.000 abstract description 3
- 239000011229 interlayer Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical class C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 239000004568 cement Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound 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 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229910052901 montmorillonite Inorganic materials 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 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
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 231100000989 no adverse effect Toxicity 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- UNMYKPSSIFZORM-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)butane Chemical compound CCCCOCCOC=C UNMYKPSSIFZORM-UHFFFAOYSA-N 0.000 description 1
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- GCYHRYNSUGLLMA-UHFFFAOYSA-N 2-prop-2-enoxyethanol Chemical compound OCCOCC=C GCYHRYNSUGLLMA-UHFFFAOYSA-N 0.000 description 1
- IZUVGRMMRWJVKU-UHFFFAOYSA-N 3-ethoxycarbonylbut-3-enoic acid Chemical compound CCOC(=O)C(=C)CC(O)=O IZUVGRMMRWJVKU-UHFFFAOYSA-N 0.000 description 1
- VVAAYFMMXYRORI-UHFFFAOYSA-N 4-butoxy-2-methylidene-4-oxobutanoic acid Chemical compound CCCCOC(=O)CC(=C)C(O)=O VVAAYFMMXYRORI-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- OIYTYGOUZOARSH-UHFFFAOYSA-N 4-methoxy-2-methylidene-4-oxobutanoic acid Chemical compound COC(=O)CC(=C)C(O)=O OIYTYGOUZOARSH-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-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
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 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
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 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 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
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 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
- 238000012546 transfer Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a short-side-chain anti-mud polycarboxylic acid water reducing agent and a preparation method thereof. The micromolecule unsaturated vinyl ether with short side chains is adopted to replace the traditional polyether macromonomer, and the side chain structure is shorter, so that the polycarboxylic acid structure has higher charge density, the decrease of the spatial repulsive force caused by the short side chains can be compensated, the intercalation adsorption of the side chains on the clay interlayer structure can be reduced, and the tolerance of the polycarboxylic acid water reducing agent to clay minerals can be improved on the premise of ensuring the water reducing rate.
Description
Technical Field
The invention belongs to the technical field of concrete admixtures, and particularly relates to a short-side-chain anti-mud polycarboxylic acid water reducer and a preparation method thereof.
Background
In recent years, due to the large-scale development of capital construction projects, high-quality sandstone resources are gradually exhausted, but inferior materials such as sandstone resources with high mud content are often not suitable for a polycarboxylic acid water reducing agent in the use process, and a large amount of research is carried out by domestic and foreign research workers to solve the problem of adaptability of clay minerals and the polycarboxylic acid water reducing agent.
In the patent US 2017/028475Clay sensitive cement superplastifier, an anti-mud polycarboxylic acid water reducing agent is disclosed, styrene, dicarboxylic acid ring-opening maleic anhydride and ring-opening maleic anhydride half ester are copolymerized to prepare SMA copolymer, and then the SMA copolymer is esterified with MPEG-SMA, and researches show that the MPEG-SMA can reduce the negative effect of water-soluble bentonite on the water reducing agent. However, the preparation process of the MPEG-SMA needs to be finished in a dimethyl formamide solvent, and the reaction needs to be purified by ethane filtration after the reaction is finished, so that the method not only uses toxic dimethyl formamide, but also has the problems of troublesome production process, low efficiency and the like.
Chinese patent No. CN201810036393.X discloses a mud-resistant polycarboxylate water reducer and a preparation method thereof, wherein unsaturated halogen monomers, unsaturated carboxylic acid monomers, chain transfer agents and the like are prepared into a prepolymer solution, then N-vinyl pyrrolidone (NVP), unsaturated polyether monomers and a catalyst metal-organic complex are added into the prepolymer solution for reaction, insoluble substances are removed by filtration, and a solvent is removed by evaporation. However, the product needs to be separated and purified in the production process, and the problems of troublesome preparation, low efficiency and the like also exist.
Chinese CN 104446101A discloses a cation modified polycarboxylate water reducer, which is prepared by copolymerizing isopentenol polyoxyethylene ether, monounsaturated carboxylic acid and derivative monomers thereof, a cationic monomer and diunsaturated carboxylic acid and derivative monomers thereof under the action of an initiator and a chain transfer agent.
Chinese patent No. CN 103467670B discloses a mud-resistant polycarboxylic acid water reducing agent, which improves the mud resistance of the product by introducing quaternary ammonium salt groups into the molecular structure of polycarboxylic acid, firstly, epoxy bromopropane and tertiary amine compounds are used for preparing quaternary ammonium salt oligomers, and then, the quaternary ammonium salt oligomers, isopentenol polyoxyethylene ether, aminotrimethylene phosphonic acid and unsaturated carboxylic acid are copolymerized together through free radicals. However, the introduction of the phosphoric acid monomer in this method makes it difficult to control the molecular weight of the polymerization reaction, and the introduction of a large amount of the functional monomer greatly reduces the water-reducing ability.
The mud-resistant polycarboxylate superplasticizer is synthesized by different design ideas and methods, but conventional polyether or modified polyether monomers are used, and longer side chains can provide more excellent spatial repulsion force on one hand, but can increase the adsorption of clay minerals to polycarboxylic acid layers on the other hand, so that the design of mud resistance is not facilitated while the water reducing and dispersing capacity is improved. While the modification of the side chain structure has an adverse effect on the reactivity of the polyether monomer and is disadvantageous for increasing the conversion rate of the polymerization reaction. In addition, the above patents have problems of more or less complicated reaction process, need of separation and purification, etc. Therefore, it is necessary to develop a mud-resistant polycarboxylate superplasticizer with simple production process and excellent performance to solve the above problems.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a short-side-chain anti-mud polycarboxylate water reducer and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a short-side-chain anti-mud polycarboxylic acid water reducing agent which is prepared by polymerizing micromolecule unsaturated vinyl ether, unsaturated polybasic acid/unsaturated polybasic acid anhydride, unsaturated polybasic acid monoalkyl ester and unsaturated betaine containing a sulfonic acid group in an aqueous solution, wherein the mass ratio of the micromolecule unsaturated vinyl ether, the unsaturated polybasic acid/unsaturated polybasic acid anhydride, the unsaturated polybasic acid monoalkyl ester to the unsaturated betaine containing the sulfonic acid group is 100:60-120:30-60: 20-40.
According to the invention, the conventional polyether macromonomer is replaced by the micromolecule unsaturated vinyl ether with short side chains, and the side chain structure is shorter, so that the polycarboxylic acid structure has higher charge density, the reduction of the spatial repulsive force caused by the short side chains can be compensated, the intercalation adsorption of the side chains on the clay interlayer structure can be reduced, and the tolerance of the polycarboxylic acid water reducing agent to clay minerals can be improved on the premise of ensuring the water reducing rate.
The micromolecular unsaturated vinyl ether has the following molecular structure general formula:
wherein R is1Is H or C1-2Alkyl radical, R2Is C1-10An alkyl group.
The unsaturated polybasic acid/unsaturated polybasic anhydride is one or more of maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride.
Compared with the conventional monounsaturated acid such as acrylic acid, methacrylic acid and the like, the unsaturated polybasic acid/unsaturated polybasic anhydride can provide larger charge density for the main chain of the polycarboxylic acid structure.
The unsaturated polybasic acid monoalkyl ester is one or a combination of maleic acid monoalkyl ester and itaconic acid monoalkyl ester.
The preparation method of the maleic acid monoalkyl ester comprises the following steps: adding anhydrous C into a reaction vessel1-4Alcohol, adding maleic anhydride to react for 2-4h when the temperature rises to 50-60 ℃, and distilling the reaction product under reduced pressure to remove unreacted alcohol to obtain maleic acid monoalkyl ester; wherein maleic anhydride and C1-4The ratio of the amount of alcohol to the amount of alcohol is 1:1.2-1.5。
The maleic acid monoalkyl ester has the following molecular structure general formula:
the preparation process of the itaconic acid monoalkyl ester comprises the following steps: mixing itaconic acid and anhydrous C1-4Adding alcohol and benzoyl chloride into a reaction vessel, mixing, heating and stirring to 60-80 deg.C, continuously reacting for 2-4h, and distilling the reaction product under reduced pressure to remove excessive C1-4Alcohol, adding a recrystallization solvent, refluxing for 15-20min, naturally cooling, and filtering to collect crystals, namely the itaconic acid monoalkyl ester; wherein itaconic acid and anhydrous C1-4The mass ratio of the alcohol to the benzoyl chloride is 1:2-5:0.02-0.08, the recrystallization solvent is a mixed solvent of benzene and petroleum ether, and the volume ratio of the benzene to the petroleum ether is 1: 0.3-3.
The itaconic acid monoalkyl ester has the following molecular structure general formula:
wherein R is3And R4Are all C1-4An alkyl group.
Unsaturated polybasic acid monoalkyl ester is used as an auxiliary comonomer of micromolecule unsaturated vinyl ether, unsaturated polybasic acid/unsaturated polybasic acid anhydride and unsaturated betaine containing sulfonic acid group, so that 4 types of raw materials in a reaction system can be polymerized better; on the other hand, the unsaturated polybasic acid monoalkyl ester can provide carboxyl and ester groups for the main chain of the polycarboxylic acid, and has the water reducing and slump retaining properties.
The unsaturated betaine containing sulfonic acid group comprises one or two of acryloyl ethyl sulfobetaine (structural formula 4) and methacryloyl ethyl sulfobetaine (structural formula 5).
Unsaturated betaine containing sulfonic acid groups is used as a functional monomer, and the tail end of the molecular structure of the unsaturated betaine is provided with the sulfonic acid groups, so that the unsaturated betaine has good dispersing performance, and quaternary ammonium salt cations in the molecular structure can be adsorbed on the surface of clay minerals to play a role of a clay mineral stabilizer.
The invention also provides a preparation method of the short-side-chain anti-mud polycarboxylic acid water reducer, which comprises the following steps:
1) adding micromolecular unsaturated vinyl ether, unsaturated polybasic acid/unsaturated polybasic anhydride, unsaturated polybasic acid monoalkyl ester, unsaturated betaine containing sulfonic acid group and deionized water into a reaction container, and uniformly stirring at 10-50 ℃;
2) dripping an initiator solution and a molecular weight regulator solution into the mixed solution obtained in the step 1), wherein the initiator solution and the molecular weight regulator solution are both controlled to be dripped into a reaction container at a constant speed within 2-4 hours;
3) and after the dropwise addition is finished, adjusting the pH value of the reaction solution to 5-7 to obtain the short side chain anti-mud polycarboxylic acid water reducing agent.
The initiator is redox initiator, wherein the oxidant is one or more of hydrogen peroxide and ammonium persulfate, and the reducing agent is L-ascorbic acid and Mohr salt.
The molecular weight regulator is one or combination of thioglycolic acid, mercaptopropionic acid and mercaptoethanol.
Compared with the prior art, the invention has the beneficial effects that:
(1) the micromolecule unsaturated vinyl ether with short side chains is adopted to replace the traditional polyether macromonomer, and the side chain structure is shorter, so that the polycarboxylic acid structure has higher charge density, the reduction of the spatial repulsive force caused by the short side chains can be compensated, the intercalation adsorption of the side chains on the clay interlayer structure can be reduced, and the tolerance of the polycarboxylic acid water reducer to clay minerals can be improved on the premise of ensuring the water reducing rate;
(2) compared with the conventional monounsaturated acids such as acrylic acid, methacrylic acid and the like, the unsaturated polybasic acid/unsaturated polybasic anhydride adopted can provide larger charge density for the main chain of the polycarboxylic acid structure;
(3) unsaturated polybasic acid monoalkyl ester is used as an auxiliary comonomer of micromolecule unsaturated vinyl ether, unsaturated polybasic acid/unsaturated polybasic acid anhydride and unsaturated betaine containing sulfonic acid group, so that 4 types of raw materials in a reaction system can be polymerized better; on the other hand, the unsaturated polybasic acid monoalkyl ester can provide carboxyl and ester groups for a polycarboxylic acid main chain, and has the water reducing and slump retaining performances;
(4) unsaturated betaine containing sulfonic acid groups is used as a functional monomer, and the tail end of the molecular structure of the unsaturated betaine is provided with the sulfonic acid groups, so that the unsaturated betaine has good dispersing performance, and quaternary ammonium salt cations in the molecular structure can be adsorbed on the surface of clay minerals to play a role of a clay mineral stabilizer.
(5) The short-side-chain mud-resistant polycarboxylate water reducer disclosed by the invention is subjected to free radical polymerization in an aqueous phase environment, has the characteristics of environmental friendliness and high efficiency compared with products needing to be polymerized in an organic phase, and has the advantage obviously higher than that of a common polycarboxylate water reducer under the condition that the mud content of a concrete raw material is higher.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
100 parts of 4-hydroxybutyl vinyl ether, 60 parts of fumaric acid, 60 parts of monomethyl maleate, 20 parts of acryloylethyl sulfobetaine and a plurality of deionized water are added into a reaction vessel and stirred uniformly at 30 ℃. Beginning to drop 2 parts of hydrogen peroxide, 0.5 part of L-ascorbic acid and 0.5 part of thioglycolic acid solution at a constant speed for 3 hours. After the dropwise addition is finished, NaOH solution is added to adjust the pH value to 5, and a plurality of deionized water is supplemented to adjust the solid content of the reaction solution to 40 percent, so that the anti-mud mother solution UC-CT1 is obtained.
The preparation method of the monomethyl maleate comprises the following steps: adding anhydrous maleic glycol into a reaction vessel, adding maleic anhydride to react for 3 hours when the temperature rises to 50-60 ℃, and distilling the reaction product under reduced pressure to remove unreacted alcohol to obtain monomethyl maleate; wherein the mass ratio of maleic anhydride and maleic glycol is 1: 1.2.
Example 2
100 parts of ethylene glycol butyl vinyl ether, 75 parts of maleic anhydride, 52 parts of monobutyl maleate, 25 parts of acryloyl ethyl sulfobetaine and a plurality of deionized water are added into a reaction vessel and stirred uniformly at 40 ℃. And (3) beginning to dropwise add 2 parts of ammonium persulfate, L-ascorbic acid and mercaptopropionic acid solution at a constant speed for 2.5 hours. After the dropwise addition is finished, adding a plurality of NaOH solutions to adjust the pH value to 5.5, and supplementing a plurality of deionized water to adjust the solid content of the reaction solution to 40 percent to obtain the anti-mud mother liquor UC-CT 2.
The preparation method of the maleic acid monobutyl ester comprises the following steps: adding anhydrous maleic glycol into a reaction vessel, adding maleic anhydride to react for 3 hours when the temperature rises to 50-60 ℃, and distilling the reaction product under reduced pressure to remove unreacted alcohol to obtain maleic acid monobutyl ester; wherein the mass ratio of maleic anhydride and maleic glycol is 1: 1.2.
Example 3
100 parts of diethylene glycol monovinyl ether, 90 parts of itaconic acid, 45 parts of itaconic acid monoethyl ester, 30 parts of methacryloyl ethyl sulfobetaine and a plurality of deionized water are added into a reaction vessel and stirred uniformly at 40 ℃. And (3) beginning to dropwise add ammonium persulfate, Mohr's salt and thioglycollic acid solution at a constant speed for 2 h. After the dropwise addition is finished, adding a plurality of NaOH solutions to adjust the pH value to 6, and supplementing a plurality of deionized water to adjust the solid content of the reaction solution to 40% to obtain the anti-mud mother solution UC-CT 3.
The preparation process of the monoethyl itaconate comprises the following steps: mixing itaconic acid and anhydrous C1-4Adding alcohol and benzoyl chloride into a reaction vessel, mixing, heating and stirring to 70 ℃, continuously reacting for 3h, and distilling the reaction product under reduced pressure to remove excessive C1-4Adding alcohol, adding a recrystallization solvent, refluxing for 15-20min, naturally cooling, and filtering to collect crystals, namely the monoethyl itaconate; wherein itaconic acidAnhydrous C1-4The mass ratio of the alcohol to the benzoyl chloride is 1:4:0.05, the recrystallization solvent is a mixed solvent of benzene and petroleum ether, and the volume ratio of the benzene to the petroleum ether is 1: 2.
Example 4
100 parts of ethylene glycol vinyl ether, 105 parts of itaconic anhydride, 38 parts of monomethyl itaconate, 35 parts of methacryloyl ethyl sulfobetaine and a plurality of deionized water are added into a reaction vessel and stirred uniformly at 40 ℃. Beginning to dropwise add hydrogen peroxide solution, Mohr salt and mercaptopropionic acid solution at a constant speed for 4 h. After the dropwise addition is finished, adding a plurality of NaOH solutions to adjust the pH value to 6.5, and supplementing a plurality of deionized water to adjust the solid content of the reaction solution to 40 percent to obtain the anti-mud mother liquor UC-CT 4.
Example 5
100 parts of allyl hydroxyethyl ether, 120 parts of fumaric acid, 30 parts of monobutyl itaconate, 40 parts of methacryloylethyl sulfobetaine and a plurality of deionized water are added into a reaction vessel and stirred uniformly at 40 ℃. Beginning to drop hydrogen peroxide, L-ascorbic acid and thioglycollic acid solution at a constant speed for 3.5 h. After the dropwise addition is finished, adding a plurality of NaOH solutions to adjust the pH value to 7, and supplementing a plurality of deionized water to adjust the solid content of the reaction solution to 40% to obtain the anti-mud mother solution UC-CT 5.
Effects of the implementation
The cement paste fluidity test is carried out according to GB/T8077-2012 'concrete admixture homogeneity test method'. The cement used in the test was Portland dam P.O 42.5 cement, and the clay was montmorillonite.
The concrete test is carried out according to GB/T50080-2002 ordinary concrete mixture performance test method.
Comparative example 1A conventional water-reducing mother liquor UC-WR produced by Wuhan Youchi science and technology Limited was used, and the solid content was 40%.
1. Cement paste fluidity test
570g of cement, 30g of montmorillonite, 174g of water and a water reducing agent in terms of solid-solid admixture. Montmorillonite (i.e., 600g of cement and 174g of water) is not added into Blank group Blank, and the water reducing agent is conventional water reducing mother liquor UC-WR produced by Wuhan Youcheng science and technology limited.
TABLE 1 Cement paste fluidity
Analyzing the data in the table 1, comparing with the conventional water-reducing mother liquor (Blank and comparative example 1), the fluidity of the clean slurry is reduced sharply (the initial fluidity is reduced from 276mm to 128mm) after 5% of montmorillonite is doped in the cement, and the initial fluidity of the clean slurry is improved greatly compared with that of the comparative example 1 after the UC-CT1 to UC-CT5 mother liquors are doped in the examples, and the clean slurry has good flow performance over time. The results show that the mud-resistant polycarboxylic acid water reducer has good mud resistance compared with polycarboxylic acid with a conventional structure.
2. Testing of concrete Properties
Cement 270kg/m according to the mixing proportion350kg/m of mineral powder360kg/m of fly ash3770kg/m of sand3800kg/m of large stone3260kg/m of small stones3150kg/m of water3The concrete test was carried out, wherein the sand content was 8% and the polycarboxylic acid content was 0.15%. The concrete test results are shown in table 2.
TABLE 2 concrete test results
From the concrete test results in Table 2, the mother liquor from UC-CT1 to UC-CT5 has better water reducing and slump retaining performances than UC-WR under the conditions of the same doping amount and mixing proportion and the use of high mud-containing sandstone materials, shows excellent clay tolerance, and in addition, the mother liquor from UC-CT1 to UC-CT5 has no adverse effect on the strength of concrete from the result of compressive strength.
In view of the above test results, all 5 of the mother liquors of the examples had good clay resistance and had no adverse effect on the strength of the concrete.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The short-side-chain mud-resistant polycarboxylate water reducer is characterized by being prepared by polymerizing micromolecule unsaturated vinyl ether, unsaturated polybasic acid/unsaturated polybasic acid anhydride, unsaturated polybasic acid monoalkyl ester and unsaturated betaine containing sulfonic acid groups in an aqueous solution, wherein the mass ratio of the micromolecule unsaturated vinyl ether, the unsaturated polybasic acid/unsaturated polybasic acid anhydride, the unsaturated polybasic acid monoalkyl ester to the unsaturated betaine containing the sulfonic acid groups is 100:60-120:30-60: 20-40.
2. The short-side-chain mud-resistant polycarboxylate superplasticizer according to claim 1, characterized in that: the unsaturated polybasic acid/unsaturated polybasic anhydride is one or more of maleic anhydride, fumaric acid, itaconic acid and itaconic anhydride.
3. The short-side-chain mud-resistant polycarboxylate superplasticizer according to claim 1, characterized in that: the unsaturated polybasic acid monoalkyl ester is one or a combination of maleic acid monoalkyl ester and itaconic acid monoalkyl ester.
4. The short-side-chain mud-resistant polycarboxylate superplasticizer according to claim 3, being characterized in that: the preparation method of the maleic acid monoalkyl ester comprises the following steps: adding anhydrous C into a reaction vessel1-4Alcohol, adding maleic anhydride to react for 2-4h when the temperature rises to 50-60 ℃, and distilling the reaction product under reduced pressure to remove unreacted alcohol to obtain maleic acid monoalkyl ester; wherein maleic anhydride and C1-4The mass ratio of the alcohol is 1: 1.2-1.5.
5. The short-side-chain mud-resistant polycarboxylate superplasticizer according to claim 3, being characterized in that: the preparation process of the itaconic acid monoalkyl ester comprises the following steps: mixing itaconic acid and anhydrous C1-4Adding alcohol and benzoyl chloride into a reaction vessel, mixing, heating and stirring to 60-80 deg.C, continuously reacting for 2-4h, and distilling the reaction product under reduced pressure to remove excessive C1-4Alcohol, adding a recrystallization solvent, refluxing for 15-20min, naturally cooling, and filtering to collect crystals, namely the itaconic acid monoalkyl ester; wherein itaconic acid and anhydrous C1-4The mass ratio of the alcohol to the benzoyl chloride is 1:2-5:0.02-0.08, the recrystallization solvent is a mixed solvent of benzene and petroleum ether, and the volume ratio of the benzene to the petroleum ether is 1: 0.3-3.
6. The short-side-chain mud-resistant polycarboxylate superplasticizer according to claim 1, characterized in that: the unsaturated betaine containing sulfonic acid group comprises one or a combination of acryloyl ethyl sulfobetaine and methacryloyl ethyl sulfobetaine.
7. The preparation method of the short-side-chain anti-mud polycarboxylate superplasticizer according to any one of claims 1 to 6, characterized by comprising the following steps:
1) adding micromolecular unsaturated vinyl ether, unsaturated polybasic acid/unsaturated polybasic anhydride, unsaturated polybasic acid monoalkyl ester, unsaturated betaine containing sulfonic acid group and deionized water into a reaction container, and uniformly stirring at 10-50 ℃;
2) dripping an initiator solution and a molecular weight regulator solution into the mixed solution obtained in the step 1), wherein the initiator solution and the molecular weight regulator solution are both controlled to be dripped into a reaction container at a constant speed within 2-4 hours;
3) and after the dropwise addition is finished, adjusting the pH value of the reaction solution to 5-7 to obtain the short side chain anti-mud polycarboxylic acid water reducing agent.
8. The preparation method of the short-side-chain anti-mud polycarboxylate superplasticizer according to claim 7, characterized by comprising the following steps: the initiator is redox initiator, wherein the oxidant is one or more of hydrogen peroxide and ammonium persulfate, and the reducing agent is one or more of L-ascorbic acid and Mohr salt.
9. The preparation method of the short-side-chain anti-mud polycarboxylate superplasticizer according to claim 7, characterized by comprising the following steps: the molecular weight regulator is one or combination of thioglycolic acid, mercaptopropionic acid and mercaptoethanol.
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