CN105271900B - A kind of ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof - Google Patents
A kind of ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof Download PDFInfo
- Publication number
- CN105271900B CN105271900B CN201510666206.2A CN201510666206A CN105271900B CN 105271900 B CN105271900 B CN 105271900B CN 201510666206 A CN201510666206 A CN 201510666206A CN 105271900 B CN105271900 B CN 105271900B
- Authority
- CN
- China
- Prior art keywords
- reducing agent
- water
- ultra high
- early strength
- integer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims description 29
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 20
- 230000000694 effects Effects 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000003999 initiator Substances 0.000 claims description 35
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 34
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000012048 reactive intermediate Substances 0.000 claims description 22
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 19
- -1 sulfhydryl compound Chemical class 0.000 claims description 19
- 238000010792 warming Methods 0.000 claims description 17
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 15
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 15
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 14
- 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 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical class OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 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
- 238000000034 method Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- XFCCROJBZHEHMS-UHFFFAOYSA-N methoxymethane;phenol Chemical compound COC.OC1=CC=CC=C1 XFCCROJBZHEHMS-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 claims 1
- 239000000543 intermediate Substances 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 30
- 239000002689 soil Substances 0.000 abstract description 11
- 150000001768 cations Chemical class 0.000 abstract description 8
- 230000003335 steric effect Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000009830 intercalation Methods 0.000 abstract description 3
- 230000002687 intercalation Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- 238000009413 insulation Methods 0.000 description 14
- 229920005646 polycarboxylate Polymers 0.000 description 13
- 239000002245 particle Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000009835 boiling Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 239000003643 water by type Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 150000003926 acrylamides Chemical class 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 4
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical class OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 125000005395 methacrylic acid group Chemical class 0.000 description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 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 description 3
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical class CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 150000004808 allyl alcohols Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical class CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- CVEPFOUZABPRMK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;styrene Chemical compound CC(=C)C(O)=O.C=CC1=CC=CC=C1 CVEPFOUZABPRMK-UHFFFAOYSA-N 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical class NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- BFOCLBAICAUQTA-UHFFFAOYSA-N 2-methylpropane;prop-2-enamide Chemical compound CC(C)C.NC(=O)C=C BFOCLBAICAUQTA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 0 CCN(*)N(*)* Chemical compound CCN(*)N(*)* 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- LHTVMBMETNGEAN-UHFFFAOYSA-N pent-1-en-1-ol Chemical compound CCCC=CO LHTVMBMETNGEAN-UHFFFAOYSA-N 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N protonated dimethyl amine Natural products CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention provides a kind of ultra high early strength poly-carboxylic water-reducing agent, the ultra high early strength poly-carboxylic water-reducing agent is the compound shown in formula (I), the ultra high early strength poly-carboxylic water-reducing agent of the present invention is using surface-active macromonomer as Material synthesis, while the space steric effect of water-reducing agent is further improved, cation is introduced in the molecule, and cation has good anti-mud, so that the water-reducing rate of water-reducing agent is improved, resistance to mud and the adaptability to cement.There is more preferable tolerance to soil, even intercalation does not occur with soil.The cation of the ultra high early strength poly-carboxylic water-reducing agent of the present invention can suppress the expansion of soil, so as to reduce absorption of the soil to additive.The ultra high early strength poly-carboxylic water-reducing agent of the present invention can accelerate water and the change effect of cement, have super hardening effect.The ultra high early strength poly-carboxylic water-reducing agent of the present invention in normal concrete there is super hardening, resistance to mud to act on.
Description
Technical field
The present invention relates to a kind of water-reducing agent, and in particular to a kind of ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof.
Background technology
In recent years, the research of concrete admixture has tended to develop towards high-performance, pollution-free direction with production, concrete
Water-reducing agent is that application surface is most wide in concrete admixture, one kind of usage amount maximum., can in water-reducing agent incorporation fresh concrete
The flocculent structure of cement granules is destroyed, plays the role of disperse cement particles and hydrated cementitious particle, so as to discharge flocculation knot
Free water in structure, increases the mobility of concrete mix.PCEs water-reducing agents belong to anionic surfactant, mix water
In slurry body, adsorb in the cement particle surface with cation, and be dissociated into hydrophilic and oleophilic function organic anion base
Group.
Water-reducing agent molecular skeleton is made of main chain and more side chain.Contain more active group, and polarity on main chain
Relatively strong, by these active groups, main chain " can be anchored " on cement particle surface, and side chain has hydrophily, Ke Yishen
Exhibition in the liquid phase, so as to form larger three-dimensional adsorption structure in cement particle surface, produces space steric effect, so that water
Mud particle disperses and stablizes.Carboxylic acid ion makes the negative electrical charge on cement granules band produce electrostatic repulsion work between cement granules
With, and disperseing cement granules, contact of the increase cement granules with water, makes the abundant aquation of cement.In the mistake of disperse cement particles
Cheng Zhong, discharges the Free water that agglomerate is included, improves workability, reduce and mix water.
RCOO-With Ca2+Ionization forms complex compound, reduces the Ca in solution2+Concentration, delays Ca (OH)2Form knot
Crystalline substance, reduces the formation of C-H-S gels, has delayed the aquation of cement.
Polycarboxylate water-reducer (PCEs) with combed molecular structure usually by polyethoxy (PEO) side chain graft to it is cloudy from
Formed on the main chain of son, PEO side chains produce space steric effect between the cement granules of water phase are suspended in, by adjusting PCEs
Molecular structure, can achieve the purpose that different, as slump retaining is good, water-reducing rate is high, and cohesiveness is good, and resistance to mud is good etc., in addition low
Cost, it is pollution-free the advantages that, polycarboxylate water-reducer research become domestic and international concrete admixture research and development hot spot.
The primary raw material of poly carboxylic acid series water reducer has unsaturated acids, such as maleic anhydride, maleic acid and acrylic acid, metering system
Alkenyl material, poly styrene sulfonate or the esters such as the polymerizable carboxylic acid such as acid, polyalkenyl hydrocarbon, ether, alcohol and acrylates, ester,
Benzenediol, acrylamide etc., synthetic method generally have polymerisable monomer to be directly copolymerized, polymerize Post functionalization method, in-situ polymerization
With grafting etc..
Polymerisable monomer is directly copolymerized：This synthetic method usually first prepares the big list of pendant reactive with polymerization activity
Body (being usually methoxy polyethylene glycol methacrylate-styrene polymer), then the monomer of certain match ratio is mixed, directly adopt
Finished product is obtained with polymerisation in solution.This polymerization, technique is simple, but on condition that want the polymerizable surface-active macromonomer of synthesizing activity,
And the performance of surface-active macromonomer directly determines and affects the performance of final products polycarboxylate water-reducer.
The active polymeric monomer that China market is used to produce PCEs water-reducing agents at present mainly has：
MPEG：Poly glycol monomethyl ether
VPEG:4- hydroxy butyl vinyl ether polyoxyethylene ether
APEG：Allyl alcohol polyethenoxy ether
HPEG：Isobutene alcohol polyoxyethylene ether
TPEG：Isoamyl alcohol polyoxyethylene ether
APEG is bar-shaped rigid structure, high to cement adsorbance, and TPEG microstructures are star-shape polymers, have flexibility
Segment microstructure is few to cement adsorbance.
APEG is the primary raw material of synthesizing polycarboxylic acid high-performance water reducing agent, and the PCEs water-reducing agents of synthesis have dispersiveness
Well, the advantages that volume is low, and water-reducing rate is high, adaptability is good；Shortcoming is inferior suitability, and Slump Time losing of Large is big.HPEG with
TPEG is the water-reducing agent of raw material production, and water-reducing rate is not much different, but summer uses, and slump retaining gap is larger, and cement adaptability is slightly
Difference.Using the polycarboxylate water-reducer that TPEG is main material production, water-reducing rate is high, and slump retaining is good, strong to cement adaptability, production
Process equipment is simple, and by polycarboxylate water-reducer, manufacturer favors.But complexity due to China's concrete raw material and various
Property, especially when the soil content of sandstone is big, the slump-loss of concrete is big, the polycarboxylate water-reducer produced by TPEG,
Since even intercalation occurs for PEG side chains and soil, make its resistance to mud poor, can not meet the requirement of concrete construction performance.
The content of the invention
Provide a kind of ultra high early strength poly-carboxylic it is an object of the invention to overcome the shortcomings of the prior art part and subtract
Aqua and preparation method thereof, the water-reducing agent have cationic charge in the molecular structure, due to its unique both sexes structure and sky
Between steric effect so that it has unique dispersibility, and water-reducing rate is high, and slump-retaining good, resistance to soil is good.
To achieve the above object, the technical solution taken：A kind of ultra high early strength poly-carboxylic water-reducing agent, the poly- carboxylic of super hardening
Sour water-reducing agent is the compound shown in formula (I), and the structural formula of the compound shown in the formula (I) is as follows：
Wherein a is 1~80 integer, and b is 1~80 integer, and c is 1~50 integer；L is 1~50 integer；
A isR for H or
CH3；
B is
C is
M is R2、R3And R4Point
It is not C alone1-3Alkyl；X-For Cl-、Br-Or I-；M be 5~200 integer, n be 0~50 integer, z be 1~150 it is whole
Number.
The present invention provides the preparation method of ultra high early strength poly-carboxylic water-reducing agent described above, the described method includes following step
Suddenly：
By surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, HPEG,
One kind in VPEG and TPEG, one kind in acrylamide and 2- acrylamide-2-methyl propane sulfonics, water and molecular weight regulator
Mixing, is warming up to 85~95 DEG C, and initiator is added dropwise, and time for adding be 1~10h, is kept the temperature after being added dropwise, and soaking time is 1~
12h, is then cooled to 45~50 DEG C, adds sodium hydroxide solution and adjusts pH to 7.0-8.0, obtains ultra high early strength poly-carboxylic diminishing
Agent；
The surface-active macromonomer is the compound shown in formula (II), and the structural formula of the compound shown in the formula (II) is such as
Under：
Wherein R1For OrR2、R3And R4It is respectively C alone1-3Alkyl；X-
For Cl-、Br-Or I-；M is 5~200 integer, and n is 0~50 integer, and z is 1~150 integer.
Preferably, the m is 10~180 integer, and the n is 0~40 integer, and the z is 1~100 integer.More
Preferably, the m is 12~100 integer, and the n is 0~30 integer, and the z is 1~80 integer.
Preferably, the surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride,
A kind of mole in a kind of and acrylamide and 2- acrylamide-2-methyl propane sulfonics in APEG, HPEG, VPEG and TPEG
Than for the surface-active macromonomer：One kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride：APEG、HPEG、VPEG
With one kind in TPEG：One kind=1.0~3.0 in acrylamide and 2- acrylamide-2-methyl propane sulfonics：1~6.0：1：
0.2~6.0.
Preferably, the molecular weight regulator is at least one of sulfhydryl compound and isopropanol, the molecular weight tune
The dosage of section agent is the surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG,
A kind of total mole number in a kind of and acrylamide and 2- acrylamide-2-methyl propane sulfonics in HPEG, VPEG and TPEG
0.005~5%.It is highly preferred that the molecular weight regulator for 3- mercaptopropionic acids, thioacetic acid, mercaptoethanol, sodium formaldehyde sulfoxylate and
At least one of isopropanol, the dosage of the molecular weight regulator are the surface-active macromonomer, methacrylic acid, acrylic acid,
1~3.5% of a kind of total mole number in a kind of and APEG, HPEG, VPEG and TPEG in itaconic acid and maleic anhydride.Most
Preferably, the dosage of the molecular weight regulator is the surface-active macromonomer, methacrylic acid, acrylic acid, itaconic acid and Malaysia
1.2~2.5% of a kind of total mole number in a kind of and APEG, HPEG, VPEG and TPEG in acid anhydrides.
Preferably, the time for adding of the initiator is 2~3h；The soaking time is 2~4h.
Preferably, the mass concentration of the sodium hydroxide solution is 30%；The initiator is potassium peroxydisulfate, persulfuric acid
One kind in ammonium, hydrogen peroxide and benzoyl peroxide, the dosage of the initiator are the surface-active macromonomer, methacrylic acid,
One kind in acrylic acid, itaconic acid and maleic anhydride, one kind and acrylamide and 2- third in APEG, HPEG, VPEG and TPEG
0.05%~5% of a kind of total mole number in acrylamide -2- methyl propane sulfonic acids.
Preferably, the cation quaternary ammonium salt PEO surface-active macromonomers are prepared by following methods：
(1) by one kind in allyl alcohol, isobutene alcohol, 4- hydroxy butyl vinyl ethers and prenol, ethylene oxide and ring
One kind in the mixture of oxidative ethane and propylene oxide, mixes with epoxyhalopropane, adds catalyst, is 80~150 in temperature
When reaction 2~10 is small under the conditions of DEG C, reactive intermediate is obtained；Its reaction equation is as follows：
(2) quarternary ammonium salt compound is mixed with polymerization inhibitor, the reactive intermediate for being slowly added to step (1) synthesis is in temperature
1~10h is reacted under the conditions of 10~80 DEG C, obtains the surface-active macromonomer；Its reaction equation is as follows：
The quarternary ammonium salt compound is N (R2R3R4), wherein R2、R3And R4It is respectively C alone1-3Alkyl.
Preferably, allyl alcohol in step (1) described in the step (1), isobutene alcohol, 4- hydroxy butyl vinyl ethers and different
One kind in the mixture of one kind in pentenol, ethylene oxide and ethylene oxide and propylene oxide, with rubbing for epoxyhalopropane
You are than being one kind in allyl alcohol, isobutene alcohol, 4- hydroxy butyl vinyl ethers and prenol：Ethylene oxide and ethylene oxide with
One kind in the mixture of propylene oxide：Epoxyhalopropane=1:5~250:1~150.
Preferably, the molar ratio of quarternary ammonium salt compound and reactive intermediate is 0.2 in the step (2):1~2:1.
Preferably, catalyst is sodium hydride or sodium in the step (1)；Polymerization inhibitor is hydroquinone in the step (2)
Or to methyl ether phenol, the dosage of the polymerization inhibitor is the 0.02%~0.08% of the reactive intermediate molal quantity.
The beneficial effects of the present invention are：The present invention provides a kind of ultra high early strength poly-carboxylic water-reducing agent, relative to existing skill
Art, its advantage are：
The present invention ultra high early strength poly-carboxylic water-reducing agent using cation quaternary ammonium salt PEO surface-active macromonomers as Material synthesis, into
While one step improves the space steric effect of water-reducing agent, cation is introduced in the molecule, and cation has good anti-mud,
So as to improve the water-reducing rate of water-reducing agent, resistance to mud and the adaptability to cement.There is more preferable tolerance to soil, with soil not
Generation connects intercalation.
The cation of the ultra high early strength poly-carboxylic water-reducing agent of the present invention can suppress the expansion of soil, so as to reduce soil to additional
The absorption of agent.When the ultra high early strength poly-carboxylic water-reducing agent of the present invention is added in cement slurry, the anionic charge absorption of main chain
In positively charged cement particle surface, and the positive charge of side chain end group is then adsorbed in negatively charged cement particle surface, point
Bulk cement particle.Since polyhydroxy and water are into hydrogen bond, the viscosity of cement slurry is added, improves the flowing of concrete mix
Property and cohesiveness.
The ultra high early strength poly-carboxylic water-reducing agent of the present invention can accelerate water and the change effect of cement, have super hardening effect.This hair
Bright ultra high early strength poly-carboxylic water-reducing agent has the effect of resistance to mud in normal concrete, in pipe pile body concrete, has super
Early strength function, it can be achieved that pile pile singly exempt from and it is double exempt from technique, without adding any active mineral admixture.
Embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
Embodiment 1
A kind of embodiment of the preparation method of surface-active macromonomer of the present invention：
1), the synthesis of reactive intermediate
5mol prenols, 5g sodium hydrides, 25mol ethylene oxide, and 5mol epoxy chlorine are injected in the autoclave of closing
Propane, stirring, 80 DEG C of reaction 10h, up to reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
1mol triethylamines and 0.001mol hydroquinones are added in flask, 10 DEG C is warming up to, is slowly added dropwise containing 5mol
The triethylamine solution of the reactive intermediate of step (1) synthesis, after being added dropwise, under the conditions of 10 DEG C, continues insulation reaction 10h,
Up to surface-active macromonomer.
Embodiment 2
A kind of embodiment of the preparation method of cation quaternary ammonium salt PEO surface-active macromonomers of the present invention：
1), the synthesis of reactive intermediate
5mol isobutene alcohols, 20g sodium hydrides, 500mol ethylene oxide, 250mol epoxies are injected in the autoclave of closing
Propane, and 750mol epoxy bromopropanes, stirring, 150 DEG C of reaction 2h, up to reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
3mol trimethylamines and 0.004mol hydroquinones are added in flask, 30 DEG C is warming up to, is slowly added dropwise containing 5mol
The trimethylamine solution of the reactive intermediate of step (1) synthesis, after being added dropwise, under the conditions of 30 DEG C, continues insulation reaction 10h,
Up to surface-active macromonomer.
Embodiment 3
A kind of embodiment of the preparation method of surface-active macromonomer of the present invention：
1), the synthesis of reactive intermediate
5mol allyl alcohols, 10g sodium hydrides, 1000mol ethylene oxide, and 400mol epoxies are injected in the autoclave of closing
Iodopropane, stirring, 100 DEG C of reaction 6h, up to reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
5mol tripropyl amine (TPA)s and 0.0015mol hydroquinones are added in flask, 50 DEG C is warming up to, is slowly added dropwise containing 5mol
The tripropyl amine (TPA) solution of the reactive intermediate of step (1) synthesis, after being added dropwise, under the conditions of 50 DEG C, continues insulation reaction 8h, i.e.,
Obtain surface-active macromonomer.
Embodiment 4
A kind of embodiment of the preparation method of surface-active macromonomer of the present invention：
1), the synthesis of reactive intermediate
The injection 5mol 4- hydroxy butyl vinyl ethers in the autoclave of closing, 10g sodium hydrides, 50mol ethylene oxide,
5mol propylene oxide and 500mol Epiiodohydrins, stirring, 120 DEG C of reaction 5h, up to reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
By 7mol N, N- dimethyl amines and 0.0005mol add in flask methyl ether phenol, are warming up to 70 DEG C, slowly
The N of the reactive intermediate containing 5mol steps (1) synthesis, N- dimethyl amine solution, after being added dropwise, in 70 DEG C of conditions is added dropwise
Under, continue insulation reaction 4h, up to surface-active macromonomer.
Embodiment 5
A kind of embodiment of the preparation method of surface-active macromonomer of the present invention：
1), the synthesis of reactive intermediate
The injection 5mol allyl alcohols in the autoclave of closing, 10g sodium, 900mol ethylene oxide, 150mol propylene oxide, and
150mol Epiiodohydrins, stirring, 120 DEG C of reaction 5h, up to reaction product reactive intermediate.
2) synthesis of surface-active macromonomer
By 10mol N, N- diethyl methyl amines and 0.002mol add in flask methyl ether phenol, are warming up to 80 DEG C, slowly
The N of the reactive intermediate containing 5mol steps (1) synthesis, N- diethyl methyl amine solution, after being added dropwise, in 80 DEG C of conditions is added dropwise
Under, continue insulation reaction 1h, up to surface-active macromonomer.
Embodiment 6
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water-reducing agent of the present invention：
In the 1000ml four-hole boiling flasks equipped with blender, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer, 1mol methacrylic acids, 1.0mol APEG, 0.2mol acrylamides and 400ml are gone described in 1mol embodiments 1
Ionized water, the molecular weight regulator are 3- mercaptopropionic acids, and the dosage of the molecular weight regulator is the surface-active macromonomer, first
The 0.005% of base acrylic acid, acrylamide and APEG total mole numbers, is warming up to 85 DEG C, the aqueous solution of initiator is added dropwise, described to draw
Hair agent is potassium peroxydisulfate, and the dosage of the initiator is always rubbed for the surface-active macromonomer, methacrylic acid, acrylamide and APEG
0.05%, time for adding 1h of your number, after being added dropwise, insulation reaction 1h, is cooled at 50 DEG C, adds mass concentration and is
30% NaOH solution, adjusts pH=7.0, up to ultra high early strength poly-carboxylic water-reducing agent.
Embodiment 7
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water-reducing agent of the present invention：
In the 1000ml four-hole boiling flasks equipped with blender, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer, 2.5mol acrylic acid, 1mol HPEG, 1mol 2- acrylamide-2-methyl propane sulfonics described in 2mol embodiments 2
With 600ml deionized waters, the molecular weight regulator is thioacetic acid, and the dosage of the molecular weight regulator is big for the activity
Monomer, acrylic acid, the 5% of 2- acrylamide-2-methyl propane sulfonics and HPEG total mole numbers, are warming up to 95 DEG C, and initiator is added dropwise
Aqueous solution, the initiator is ammonium persulfate, and the dosage of the initiator is the surface-active macromonomer, acrylic acid, 2- propylene
The 5% of acid amides -2- methyl propane sulfonic acids and HPEG total mole numbers, time for adding 10h, after being added dropwise, insulation reaction 12h, drop
At warm to 45 DEG C, the NaOH solution that mass concentration is 30% is added, pH=8.0 is adjusted, up to ultra high early strength poly-carboxylic water-reducing agent.
Embodiment 8
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water-reducing agent of the present invention：
In the 1000ml four-hole boiling flasks equipped with blender, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer, 6mol acrylic acid, 1mol TPEG, 6mol acrylamides and 500ml deionized waters, institute described in 3mol embodiments 3
It is mercaptoethanol to state molecular weight regulator, and the dosage of the molecular weight regulator is the surface-active macromonomer, acrylic acid, acryloyl
The 1% of amine and TPEG total mole numbers, is warming up to 90 DEG C, and the aqueous solution of initiator is added dropwise, and the initiator is matter benzoyl peroxide first
Acyl, the dosage of the initiator are the 0.1% of the surface-active macromonomer, acrylic acid, acrylamide and TPEG total mole numbers, are added dropwise
Time is 5h, and after being added dropwise, insulation reaction 6h, is cooled at 50 DEG C, adds the NaOH solution that mass concentration is 30%, adjusts
PH=7.5, up to ultra high early strength poly-carboxylic water-reducing agent.
Embodiment 9
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water-reducing agent of the present invention：
In the 1000ml four-hole boiling flasks equipped with blender, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer, 1.2mol methacrylic acids, 1.0mol VPEG, 0.6mol2- acrylamide -2- first described in 2mol embodiments 4
Base propane sulfonic acid and 400ml deionized waters, the molecular weight regulator are isopropanol, and the dosage of the molecular weight regulator is described
Surface-active macromonomer, methacrylic acid, the 3.5% of 2- acrylamide-2-methyl propane sulfonics and VPEG total mole numbers, are warming up to 85
DEG C, the aqueous solution of initiator is added dropwise, the initiator is hydrogen peroxide, and the dosage of the initiator is the surface-active macromonomer, first
3%, time for adding 2h of base acrylic acid, 2- acrylamide-2-methyl propane sulfonics and VPEG total mole numbers, after being added dropwise,
Insulation reaction 2h, is cooled at 50 DEG C, adds the NaOH solution that mass concentration is 30%, adjusts pH=7.0, gather up to super hardening
Carboxylic acid water reducer.
Embodiment 10
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water-reducing agent of the present invention：
In the 1000ml four-hole boiling flasks equipped with blender, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer, 2.5mol acrylic acid, 1mol HPEG, 2mol acrylamides and 600ml deionized waters described in 2mol embodiments 5,
The molecular weight regulator is sodium formaldehyde sulfoxylate, and the dosage of the molecular weight regulator is the surface-active macromonomer, acrylic acid, acryloyl
The 1.2% of amine and HPEG total mole numbers, is warming up to 95 DEG C, is added dropwise the aqueous solution of initiator, and the initiator is ammonium persulfate, institute
The dosage for stating initiator is the 2% of the surface-active macromonomer, acrylic acid, acrylamide and HPEG total mole numbers, and time for adding is
3h, after being added dropwise, insulation reaction 4h, is cooled at 45 DEG C, adds the NaOH solution that mass concentration is 30%, adjusts pH=
8.0, up to ultra high early strength poly-carboxylic water-reducing agent.
Embodiment 11
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water-reducing agent of the present invention：
In the 1000ml four-hole boiling flasks equipped with blender, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer described in 1mol embodiments 1,4mol acrylic acid, 1mol TPEG, 4mol 2- acrylamide-2-methyl propane sulfonics and
500ml deionized waters, the molecular weight regulator are mercaptoethanol, and the dosage of the molecular weight regulator is big single for the activity
Body, acrylic acid, the 2.5% of 2- acrylamide-2-methyl propane sulfonics and TPEG total mole numbers, are warming up to 90 DEG C, and initiator is added dropwise
Aqueous solution, the initiator is benzoyl peroxide, and the dosage of the initiator is the surface-active macromonomer, acrylic acid, 2-
The 1% of acrylamide-2-methyl propane sulfonic and TPEG total mole numbers, time for adding 7h, after being added dropwise, insulation reaction 8h,
It is cooled at 50 DEG C, adds the NaOH solution that mass concentration is 30%, pH=7.5 is adjusted, up to ultra high early strength poly-carboxylic water-reducing agent.
Embodiment 12
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water-reducing agent of the present invention：
In the 1000ml four-hole boiling flasks equipped with blender, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer, 1mol methacrylic acids, 1.0mol APEG, 1mol acrylamides and 400ml described in 1mol embodiments 2 go from
Sub- water, the molecular weight regulator are 3- mercaptopropionic acids, and the dosage of the molecular weight regulator is the surface-active macromonomer, methyl
The 2% of acrylic acid, acrylamide and APEG total mole numbers, is warming up to 85 DEG C, the aqueous solution of initiator is added dropwise, the initiator is
Potassium peroxydisulfate, the dosage of the initiator is the surface-active macromonomer, methacrylic acid, acrylamide and APEG total mole numbers
1.5%, time for adding 9h, after being added dropwise, insulation reaction 10h, is cooled at 50 DEG C, and it is 30% to add mass concentration
NaOH solution, adjusts pH=7.0, up to ultra high early strength poly-carboxylic water-reducing agent.
Embodiment 13
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water-reducing agent of the present invention：
In the 1000ml four-hole boiling flasks equipped with blender, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer described in 3mol embodiments 3,3mol acrylic acid, 1mol HPEG, 3mol 2- acrylamide-2-methyl propane sulfonics and
600ml deionized waters, the molecular weight regulator are thioacetic acid, and the dosage of the molecular weight regulator is big single for the activity
Body, acrylic acid, the 0.1% of 2- acrylamide-2-methyl propane sulfonics and HPEG total mole numbers, are warming up to 95 DEG C, and initiator is added dropwise
Aqueous solution, the initiator is ammonium persulfate, and the dosage of the initiator is the surface-active macromonomer, acrylic acid, 2- propylene
The 0.5% of acid amides -2- methyl propane sulfonic acids and HPEG total mole numbers, time for adding 3h, after being added dropwise, insulation reaction 4h, drop
At warm to 45 DEG C, the NaOH solution that mass concentration is 30% is added, pH=8.0 is adjusted, up to ultra high early strength poly-carboxylic water-reducing agent.
Embodiment 14
A kind of embodiment of the preparation method of ultra high early strength poly-carboxylic water-reducing agent of the present invention：
In the 1000ml four-hole boiling flasks equipped with blender, thermometer and reflux condensing tube, addition molecular weight regulator,
Surface-active macromonomer, 6mol acrylic acid, 1mol TPEG, 6mol acrylamides and 500ml deionized waters, institute described in 1mol embodiments 4
It is mercaptoethanol to state molecular weight regulator, and the dosage of the molecular weight regulator is the surface-active macromonomer, acrylic acid, acryloyl
The 0.01% of amine and TPEG total mole numbers, is warming up to 90 DEG C, and the aqueous solution of initiator is added dropwise, and the initiator is benzoyl peroxide first
Acyl, the dosage of the initiator is the surface-active macromonomer, the 4% of acrylic acid, acrylamide and TPEG total mole numbers, during dropwise addition
Between be 1h, after being added dropwise, insulation reaction 12h, is cooled at 50 DEG C, add mass concentration be 30% NaOH solution, adjust
PH=7.5, up to ultra high early strength poly-carboxylic water-reducing agent.
Embodiment 15：Practical application technique effect of the ultra high early strength poly-carboxylic water-reducing agent of the present invention in concrete
Concrete is prepared using the ultra high early strength poly-carboxylic water-reducing agent synthesized in the embodiment of the present invention 6~14, is gathered with common
As a comparison, common polycarboxylate water-reducer is the polycarboxylate water-reducer without cation quaternary ammonium salt to carboxylic acid water reducer.Survey first
Determine the water-reducing rate of the ultra high early strength poly-carboxylic water-reducing agent and common polycarboxylate water-reducer synthesized in the embodiment of the present invention 6~14,
Then concrete is prepared by following proportioning, measures the performances such as setting time and the maturing strength development of concrete.
The match ratio of normal concrete is as follows：
Cement：Flyash：Miberal powder：River sand：Rubble：Water：Common polycarboxylate water-reducer=200：90：60：800：1080：
165：8.5；
The match ratio of concrete is as follows made from 6~14 ultra high early strength poly-carboxylic water-reducing agent of the embodiment of the present invention：
Cement：Flyash：Miberal powder：River sand：Rubble：Water：Polycarboxylate water-reducer=200 of the present invention：9：60：800：1080：
165：7.0.
The coagulation prepared by 6~14 ultra high early strength poly-carboxylic water-reducing agent of the embodiment of the present invention and common polycarboxylate water-reducer
Native effect is compared as follows：
It can be seen from the above that the ultra high early strength poly-carboxylic water-reducing agent of the present invention is used in concrete, with common polycarboxylate water-reducer
Compare, have more preferable dispersiveness to cement slurry, water-reducing rate improves, simultaneously because the cation of side chain is adsorbed with suppression to clay
Make and use, thus this product has good resistance to mud effect；There is super hardening effect at the same time, cement hydrationization can be promoted to react,
Strength development to maturing plays a driving role.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of scope is protected, although being explained in detail with reference to preferred embodiment to the present invention, those of ordinary skill in the art should
Understand, can be to technical scheme technical scheme is modified or replaced equivalently, without departing from the essence of technical solution of the present invention
And scope.
Claims (10)
1. a kind of ultra high early strength poly-carboxylic water-reducing agent, it is characterised in that the ultra high early strength poly-carboxylic water-reducing agent is the change shown in formula (I)
Compound, the structural formula of the compound shown in the formula (I) are as follows：
Wherein a isInteger, b isInteger, c isInteger；L isInteger；
A isR is H or CH3；
B is
C is
M is
R2、R3And R4Point
It is not C alone1‐3Alkyl；X‐For Cl‐、Br‐Or I‐；M isInteger, n isInteger, z is's
Integer；
The preparation method of the ultra high early strength poly-carboxylic water-reducing agent, comprises the following steps：
By surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, HPEG, VPEG and
One kind in TPEG, one kind in acrylamide and 2- acrylamide-2-methyl propane sulfonics, water and molecular weight regulator mixing,
85~95 DEG C are warming up to, initiator is added dropwise, time for adding is 1~10h, is kept the temperature after being added dropwise, and soaking time is 1~12h, so
After be cooled to 45~50 DEG C, add sodium hydroxide solution and adjust pH to 7.0-8.0, obtain ultra high early strength poly-carboxylic water-reducing agent；
The surface-active macromonomer is the compound shown in formula (II), and the structural formula of the compound shown in the formula (II) is as follows：
Wherein R1For H2C=CH-O-CH2CH2CH2CH2-、H2C=CHCH2-、 R2、R3And R4It is respectively C alone1‐3Alkyl；X‐For Cl‐、Br‐Or I‐；
M isInteger, n isInteger, z isInteger.
A kind of 2. preparation method of ultra high early strength poly-carboxylic water-reducing agent as claimed in claim 1, it is characterised in that the method bag
Include following steps：
By surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, HPEG, VPEG and
One kind in TPEG, one kind in acrylamide and 2- acrylamide-2-methyl propane sulfonics, water and molecular weight regulator mixing,
85~95 DEG C are warming up to, initiator is added dropwise, time for adding is 1~10h, is kept the temperature after being added dropwise, and soaking time is 1~12h, so
After be cooled to 45~50 DEG C, add sodium hydroxide solution and adjust pH to 7.0-8.0, obtain ultra high early strength poly-carboxylic water-reducing agent；
The surface-active macromonomer is the compound shown in formula (II), and the structural formula of the compound shown in the formula (II) is as follows：
Wherein R1For H2C=CH-O-CH2CH2CH2CH2-、H2C=CHCH2-、 R2、R3And R4It is respectively C alone1‐3Alkyl；X‐For Cl‐、Br‐Or I‐；
M isInteger, n isInteger, z isInteger.
3. preparation method according to claim 2, it is characterised in that the surface-active macromonomer, methacrylic acid, propylene
One kind in acid, itaconic acid and maleic anhydride, one kind and acrylamide and 2- acryloyls in APEG, HPEG, VPEG and TPEG
A kind of molar ratio in amine -2- methyl propane sulfonic acids is the surface-active macromonomer：Methacrylic acid, acrylic acid, itaconic acid and horse
Carry out one kind in acid anhydrides：One kind in APEG, HPEG, VPEG and TPEG：Acrylamide and 2- acrylamide-2-methyl propane sulfonics
In one kind=1.0~3.0：1~6.0：1：0.2~6.0.
4. preparation method according to claim 2, it is characterised in that the molecular weight regulator is sulfhydryl compound and different
At least one of propyl alcohol, the dosage of the molecular weight regulator are the surface-active macromonomer, methacrylic acid, acrylic acid, clothing
One kind in health acid and maleic anhydride, one kind and acrylamide and 2- acrylamides -2- in APEG, HPEG, VPEG and TPEG
0.005~5% of a kind of total mole number in methyl propane sulfonic acid.
5. preparation method according to claim 2, it is characterised in that the time for adding of the initiator is 2~3h；It is described
Soaking time is 2~4h.
6. preparation method according to claim 2, it is characterised in that the mass concentration of the sodium hydroxide solution is
30%；The initiator is one kind in potassium peroxydisulfate, ammonium persulfate, hydrogen peroxide and benzoyl peroxide, the initiator
Dosage is the surface-active macromonomer, one kind in methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, APEG, HPEG,
A kind of total mole number in a kind of and acrylamide and 2- acrylamide-2-methyl propane sulfonics in VPEG and TPEG
0.05%~5%.
7. preparation method according to claim 2, it is characterised in that the surface-active macromonomer by following methods prepare and
Into：
(1) by one kind in allyl alcohol, isobutene alcohol, 4- hydroxy butyl vinyl ethers and prenol, ethylene oxide and epoxy second
One kind in the mixture of alkane and propylene oxide, mixes with epoxyhalopropane, adds catalyst, is 80~150 DEG C of bars in temperature
When reaction 2~10 is small under part, reactive intermediate is obtained；
(2) quarternary ammonium salt compound is mixed with polymerization inhibitor, be slowly added to the reactive intermediate of step (1) synthesis temperature for 10~
1~10h is reacted under the conditions of 80 DEG C, obtains the surface-active macromonomer；
The quarternary ammonium salt compound is N (R2R3R4), wherein R2、R3And R4It is respectively C alone1‐3Alkyl.
8. preparation method according to claim 7, it is characterised in that allyl alcohol, isobutene alcohol, 4- in the step (1)
One in the mixture of one kind in hydroxy butyl vinyl ether and prenol, ethylene oxide and ethylene oxide and propylene oxide
Kind, the molar ratio with epoxyhalopropane is one kind in allyl alcohol, isobutene alcohol, 4- hydroxy butyl vinyl ethers and prenol：
One kind in the mixture of ethylene oxide and ethylene oxide and propylene oxide：
9. preparation method according to claim 7, it is characterised in that quarternary ammonium salt compound and activity in the step (2)
The molar ratio of intermediate is 0.2:1~2:1.
10. preparation method according to claim 7, it is characterised in that in the step (1) catalyst for sodium hydride or
Sodium；For polymerization inhibitor for hydroquinone or to methyl ether phenol, the dosage of the polymerization inhibitor is the reactive intermediate in the step (2)
The 0.02%~0.08% of molal quantity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510666206.2A CN105271900B (en) | 2015-10-14 | 2015-10-14 | A kind of ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510666206.2A CN105271900B (en) | 2015-10-14 | 2015-10-14 | A kind of ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105271900A CN105271900A (en) | 2016-01-27 |
| CN105271900B true CN105271900B (en) | 2018-04-20 |
Family
ID=55141824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510666206.2A Active CN105271900B (en) | 2015-10-14 | 2015-10-14 | A kind of ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105271900B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108752538A (en) * | 2018-06-28 | 2018-11-06 | 江苏百瑞吉新材料有限公司 | A kind of high overlength of system containing mud guarantor is collapsed concrete tailored version poly carboxylic acid series water reducer |
| US12227457B2 (en) * | 2018-10-29 | 2025-02-18 | Universiteit Gent | Admixture for a cementitious material to influence the rheology properties of the cementitious material |
| CN109734847B (en) * | 2018-12-25 | 2022-01-11 | 河北红墙新材料有限公司 | Viscosity reduction type polycarboxylate superplasticizer containing three viscosity reduction functional groups, and preparation method and application thereof |
| CN109734833B (en) * | 2018-12-27 | 2021-09-10 | 武汉优城科技有限公司 | Short-side-chain anti-mud polycarboxylate superplasticizer and preparation method thereof |
| CN109776722A (en) * | 2019-02-11 | 2019-05-21 | 山东理工大学 | Ternary graft copolymer and its preparation method and application |
| WO2020208951A1 (en) | 2019-04-11 | 2020-10-15 | 株式会社クラレ | Polymer, oxygen absorber using same, and curable composition |
| CN112708044B (en) * | 2019-12-23 | 2022-07-05 | 科之杰新材料集团有限公司 | Ether anti-mud type super-early-strength polycarboxylate superplasticizer and preparation method thereof |
| WO2021149738A1 (en) * | 2020-01-21 | 2021-07-29 | 株式会社クラレ | Curable composition, cured article using same, and method for producing cured article |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467670B (en) * | 2013-08-27 | 2015-07-08 | 南京瑞迪高新技术有限公司 | Preparation method of anti-mud polycarboxylic water reducer |
| CN104628967B (en) * | 2013-11-11 | 2017-07-28 | 辽宁奥克化学股份有限公司 | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN103992442B (en) * | 2014-04-30 | 2016-08-24 | 广东红墙新材料股份有限公司 | A kind of preparation method and application of negative and positive both sexes polycarboxylate water-reducer |
-
2015
- 2015-10-14 CN CN201510666206.2A patent/CN105271900B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105271900A (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105271900B (en) | A kind of ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof | |
| CN105199032B (en) | A kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof | |
| CN109021181A (en) | A kind of poly carboxylic acid series water reducer and preparation method thereof for having both viscosity reduction and protecting function of collapsing | |
| CN103992442B (en) | A kind of preparation method and application of negative and positive both sexes polycarboxylate water-reducer | |
| CN107586366B (en) | Modified polycarboxylate superplasticizer and preparation method thereof | |
| CN103613306B (en) | A kind of poly carboxylic acid series water reducer containing hyperbranched polyamine-ester structure and preparation method thereof | |
| CN104177562B (en) | Slow-release high-adaptability polyester polycarboxylic acid water-reducing agent and preparation method and application thereof | |
| CN104119482A (en) | Mud-resistant polycarboxylic acid water-reducing agent and preparation method thereof | |
| CN108794700A (en) | A kind of carboxylic acid group polymer and preparation method thereof and sustained-release polycarboxylic water reducer | |
| CN105294949B (en) | A kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof | |
| CN108047396A (en) | A kind of anti-chamotte mould polycarboxylate water-reducer of polycation and preparation method thereof | |
| CN111592272A (en) | Polycarboxylate superplasticizer for machine-made sand concrete prestressed component and preparation method thereof | |
| CN104479084A (en) | Polycarboxylate based anti-mud agent and preparation method thereof | |
| CN105440224B (en) | Purposes of the cation quaternary ammonium salt polycarboxylate water-reducer in ceramics are prepared | |
| CN104961373A (en) | Slump loss resistant type polycarboxylic water reducer and preparation method thereof | |
| CN106366257A (en) | Low-sensitivity anti-mud crossed branched chain type polycarboxylate superplasticizer and preparation method thereof | |
| CN105199060B (en) | A kind of ultra high early strength poly-carboxylic water reducer and preparation method thereof | |
| CN108218284B (en) | Concrete water reducing agent composition | |
| CN105199094B (en) | A kind of reactive intermediate and surface-active macromonomer | |
| CN105271902B (en) | A kind of ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof | |
| CN102503221A (en) | Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof | |
| CN112672985A (en) | Comb polymers as blocking additives for swelling clays | |
| CN106380551A (en) | Low-sensitivity anti-mud polycarboxylic acid water reducing agent and preparation method thereof | |
| CN104371075B (en) | A kind of preparation method of the polycarboxylate water-reducer of room temperature synthesis | |
| CN105330795B (en) | A kind of ultra high early strength poly-carboxylic water-reducing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |