CN111019056A - Water-reducing bulk polymerization solid polycarboxylate superplasticizer and preparation method, use method and application thereof - Google Patents
Water-reducing bulk polymerization solid polycarboxylate superplasticizer and preparation method, use method and application thereof Download PDFInfo
- Publication number
- CN111019056A CN111019056A CN201911231415.9A CN201911231415A CN111019056A CN 111019056 A CN111019056 A CN 111019056A CN 201911231415 A CN201911231415 A CN 201911231415A CN 111019056 A CN111019056 A CN 111019056A
- Authority
- CN
- China
- Prior art keywords
- parts
- water
- weight
- solution
- sodium
- 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.)
- Pending
Links
- 239000007787 solid Substances 0.000 title claims abstract description 92
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 60
- 238000012662 bulk polymerization Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 28
- 229920000570 polyether Polymers 0.000 claims abstract description 28
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 10
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 8
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007800 oxidant agent Substances 0.000 claims abstract description 5
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 139
- 238000006116 polymerization reaction Methods 0.000 claims description 72
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 59
- 239000003638 chemical reducing agent Substances 0.000 claims description 59
- 238000003756 stirring Methods 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 45
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 44
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 40
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 35
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 35
- 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 34
- 239000002253 acid Substances 0.000 claims description 28
- 239000002994 raw material Substances 0.000 claims description 27
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 24
- 239000012263 liquid product Substances 0.000 claims description 24
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 24
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 24
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 24
- 239000004568 cement Substances 0.000 claims description 23
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 23
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 22
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 20
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 19
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 19
- 239000002211 L-ascorbic acid Substances 0.000 claims description 17
- 235000000069 L-ascorbic acid Nutrition 0.000 claims description 17
- 229960005070 ascorbic acid Drugs 0.000 claims description 17
- -1 E51 Chemical compound 0.000 claims description 15
- 239000004567 concrete Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 10
- 125000005394 methallyl group Chemical group 0.000 claims description 7
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 claims description 4
- 238000010276 construction Methods 0.000 claims description 4
- 238000005553 drilling Methods 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- USNWAMPROKAEIT-UHFFFAOYSA-N [Na].C(C=C)(=O)O Chemical compound [Na].C(C=C)(=O)O USNWAMPROKAEIT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000012719 thermal polymerization Methods 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 230000009967 tasteless effect Effects 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 22
- 230000009965 odorless effect Effects 0.000 description 14
- 239000000843 powder Substances 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 230000007613 environmental effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000005507 spraying Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 2
- 229910021205 NaH2PO2 Inorganic materials 0.000 description 2
- JDRJCBXXDRYVJC-UHFFFAOYSA-N OP(O)O.N.N.N Chemical compound OP(O)O.N.N.N JDRJCBXXDRYVJC-UHFFFAOYSA-N 0.000 description 2
- 239000005819 Potassium phosphonate Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- YXXXKCDYKKSZHL-UHFFFAOYSA-M dipotassium;dioxido(oxo)phosphanium Chemical compound [K+].[K+].[O-][P+]([O-])=O YXXXKCDYKKSZHL-UHFFFAOYSA-M 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 206010016807 Fluid retention Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical group [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The application relates to a water-reducing bulk polymerization solid polycarboxylate superplasticizer, which is used for preparing the water-reducing bulk polymerization solid polycarboxylate superplasticizer comprises the following components in parts by weight: unsaturated polyether, alkenyl unsaturated monomer, oxidant and phosphite or hypophosphite chain transfer agent. The application also relates to a preparation method, a using method and application of the water reducing bulk polymerization solid polycarboxylate superplasticizer. The bulk polymerization solid polycarboxylate superplasticizer is prepared from tasteless small materials, accords with the development trend of environment-friendly green chemistry, and has the advantages of simple preparation process, high water reducing rate and good slump retaining effect.
Description
Technical Field
The application relates to the technical field of building materials, concretely relates to water-reducing type body polymerization solid polycarboxylate water reducing agent who derives from odorless raw materials of environmental protection, the preparation method of water-reducing type body polymerization solid polycarboxylate water reducing agent who derives from odorless raw materials of environmental protection, the application method of water-reducing type body polymerization solid polycarboxylate water reducing agent who derives from odorless raw materials of environmental protection and the application of water-reducing type body polymerization solid polycarboxylate water reducing agent in the building engineering that requires height to concrete initial fluidity and slump retaining effect.
Background
With the development of the water reducing agent industry, the polycarboxylate water reducing agent gradually becomes one of the most used concrete admixtures. The polycarboxylic acid water reducing agent in the current market is mainly liquid with solid content of 30-50%, and the transportation cost is higher when the construction site is far away. The solid polycarboxylate superplasticizer can effectively solve the problem of transportation cost, and can be applied to the fields of dry powder mortar, high-strength grouting material, thermal insulation mortar, plastering mortar, ceramic bonding mortar and the like compared with a liquid polycarboxylate superplasticizer. However, the traditional high-temperature powder spraying process for preparing the solid polycarboxylic acid water reducing agent has high energy consumption and is easy to agglomerate. The addition of other components prevents caking and enhances flow of the powder, but reduces the amount of active ingredient in the powder.
The solid polycarboxylate superplasticizer prepared by bulk polymerization can effectively solve the problems of the liquid polycarboxylate superplasticizer and the high-temperature powder spraying process. On the one hand, however, the bulk polymerization process is difficult due to the absence of water or the very small amount of water in the reaction environment, and the obtained finished product has a poor effect and an application bottleneck compared with the same solid content of the water reducer mother liquor. On the other hand, the conventional small materials such as mercaptopropionic acid, thioglycolic acid, mercaptoethanol and the like have strong sulfide odor, and do not accord with the theme of green environmental protection.
For this reason, it is particularly urgent to develop a water-reducing bulk-polymerized solid polycarboxylic acid water reducing agent derived from environmentally friendly odorless raw materials.
Disclosure of Invention
The purpose of the present application is to overcome the defects of the prior art and provide a water-reducing bulk-polymerized solid polycarboxylic acid water reducer which is derived from environment-friendly odorless raw materials. Specifically, the water-reducing bulk polymerization solid polycarboxylic acid water reducing agent of the present application is prepared from environmentally-friendly odorless phosphite or hypophosphite chain transfer agent and other components. The tasteless environmental protection small material accords with the trend of green chemistry, can adopt the mode of bulk polymerization to synthesize solid polycarboxylate water reducing agent in the temperature range of relative broad, and the product has the characteristics that the water reducing rate is high, and the slump loss prevention effect is good. The water-reducing bulk polymerization solid polycarboxylate superplasticizer meets the requirement of reducing transportation cost, has the performance equivalent to that of the mother liquor of the common water-reducing polycarboxylate superplasticizer under the same mixing amount, and has slump retaining performance superior to that of the common water-reducing solid polycarboxylate superplasticizer within 1-2 hours. Effectively saves the cost, avoids the problems of high energy consumption and environmental pollution caused by the traditional high-temperature powder spraying process, and has good application prospect. The water-reducing bulk polymerization solid polycarboxylate superplasticizer disclosed by the application is simple in preparation process, convenient to operate, conventional and visible in raw materials, good in initial fluidity and good in slump retaining property, and has remarkable economic benefits, social benefits and environmental benefits.
The invention also aims to provide a preparation method of the water-reducing bulk polymerization solid polycarboxylate superplasticizer.
The application also aims to provide a use method of the water-reducing bulk polymerization solid polycarboxylate water reducer.
The application also aims to provide the application of the water-reducing bulk polymerization solid polycarboxylate superplasticizer in the building engineering.
In order to solve the above technical problem, the present application provides the following technical solutions.
In a first aspect, the present application provides a water-reducing bulk-polymeric solid polycarboxylate water reducer, characterized in that the raw materials for preparing the water-reducing bulk-polymeric solid polycarboxylate water reducer comprise the following components: an unsaturated polyether, an ethylenically unsaturated monomer, an oxidizing agent, and a phosphite or hypophosphite chain transfer agent;
the number average molecular weight of the unsaturated polyether is 2000-6000, and the unsaturated polyether is one or more of the following: methallyl polyoxyethylene ether, methyl allyl butyl polyoxyethylene ether or vinyl glycol ether polyoxyethylene ether;
the ethylenically unsaturated monomer is preferably one or more of the following: sodium acrylic acid and sodium methallyl sulfonate;
the oxidant is preferably one or more of the following: ammonium persulfate and hydrogen peroxide;
the phosphite or hypophosphite chain transfer agent is preferably one or more of the following: sodium hypophosphite, sodium phosphite, potassium hypophosphite, potassium phosphite, ammonium hypophosphite and ammonium phosphite.
In one embodiment, the hydrogen peroxide concentration in the hydrogen peroxide solution is conventional in the art, typically 30 wt%.
Sodium hypophosphite NaH2PO2Commonly known as sodium hypophosphite, sodium hypophosphite NaH2PO2·H2O is monohydrate of sodium hypophosphite, the Chinese characters are also named sodium hypophosphite and sodium dihydrogen hypophosphite, the sodium hypophosphite and the sodium hypophosphite are not distinguished and are the same, so the case of using the sodium hypophosphite in the text can also achieve the same effect by using the sodium hypophosphite.
In one embodiment of the first aspect, the raw materials for preparing the water-reducing bulk-polymerized solid polycarboxylic acid water reducer comprise the following components in parts by weight: 100 parts of unsaturated polyether, 4-25 parts of acrylic acid, 0-8 parts of sodium methallyl sulfonate, 0.0-3.0 parts of ammonium persulfate, 0.0-3.0 parts of hydrogen peroxide, 0.0-2.5 parts of L-ascorbic acid, 0.0-2.5 parts of E51, 0.0-2.5 parts of sodium formaldehyde sulfoxylate, 0.0-6.0 parts of sodium hypophosphite, 0.0-2.0 parts of sodium phosphite, 0.0-2.0 parts of ammonium hypophosphite, 0.0-2.0 parts of potassium hypophosphite and 0.0-6.0 parts of water, wherein the parts by weight of the ammonium persulfate and the hydrogen peroxide are not zero at the same time, and the parts by weight of the sodium hypophosphite, the sodium phosphite, the ammonium hypophosphite and the potassium hypophosphite are not zero at the same time.
In one embodiment of the first aspect, the acrylic acid is used in an amount of 12 to 22 parts;
the using amount of the sodium methallyl sulfonate is 0-5 parts;
the using amount of the ammonium persulfate is 0.5-2.5 parts;
the dosage of the hydrogen peroxide is 0.0-2.7 parts;
the dosage of the L-ascorbic acid is 0.1-2.5 parts;
the using amount of the E51 is 0.1-2.5 parts;
the dosage of the sodium formaldehyde sulfoxylate is 0.1-2.5 parts;
the dosage of the sodium hypophosphite is 1.0-4.0 parts;
the dosage of the sodium phosphite is 0.0-1.0 part;
the using amount of the ammonium hypophosphite is 0.0-1.0 part;
the dosage of the potassium hypophosphite is 0.0-1.0 part;
the amount of the water is 2.6-6.0 parts.
In one embodiment of the first aspect, the solid content of the water-reducing bulk-polymerized solid polycarboxylate superplasticizer is 94.5 wt% to 100 wt%, preferably 97.7 wt%.
In a second aspect, the present application provides a method for preparing a water-reducing bulk-polymerizing solid polycarboxylic acid water reducer according to the first aspect, characterized in that it comprises the steps of:
s1: melting the unsaturated polyether into liquid at the temperature of 50-90 ℃, and then mixing the liquid with the aqueous solution of the phosphite or hypophosphite chain transfer agent to obtain a mixture A;
s2: and adding an alkenyl unsaturated monomer into the mixture A, polymerizing for 60-330 minutes at the temperature of 50-90 ℃, continuing to perform thermal polymerization for 30-180 minutes at the temperature of 50-90 ℃, and cooling the obtained liquid product to obtain the water-reducing bulk polymerization solid polycarboxylic acid water reducer.
In one embodiment of the second aspect, the method comprises the steps of: under the condition of stirring, adding acrylic acid and sodium methallyl sulfonate which account for 10-50% of the amount of the acrylic acid into the mixture A, uniformly stirring, adding hydrogen peroxide, then dropwise adding the solution B, the solution C and the solution D, carrying out polymerization reaction, curing for a preset time period, and cooling a liquid product to obtain the water-reducing bulk polymerization solid polycarboxylic acid water reducer;
the mixture A is obtained by mixing unsaturated polyether, sodium hypophosphite, sodium phosphite, ammonium hypophosphite, potassium hypophosphite and anhydrous or trace water;
the solution B is obtained by mixing L-ascorbic acid, E51, sodium formaldehyde sulfoxylate and trace water;
the solution C is obtained by mixing ammonium persulfate and trace water;
the solution D is obtained from acrylic acid.
In one embodiment of the second aspect, the method comprises the steps of:
(1) mixing the mixture A: 100 parts by weight of unsaturated polyether, 0.0-6.0 parts by weight of sodium hypophosphite, 0.0-2.0 parts by weight of sodium phosphite, 0.0-2.0 parts by weight of ammonium hypophosphite, 0.0-2.0 parts by weight of potassium hypophosphite and 0.0-3.0 parts by weight of water, wherein 100 parts by weight of unsaturated polyether is put into a polymerization reaction kettle, heated to 50-90 ℃, and stirred to accelerate melting when the unsaturated polyether is in a molten state, 0.0-6.0 parts by weight of sodium hypophosphite, 0.0-2.0 parts by weight of sodium phosphite, 0.0-2.0 parts by weight of ammonium hypophosphite and 0.0-2.0 parts by weight of potassium hypophosphite which are dissolved by 0.0-3.0 parts by weight of water are put into the polymerization reaction kettle to be uniformly stirred and kept at the temperature of 50-90 ℃ for later use;
(2) adding 0.4-12.5 parts by weight of acrylic acid (accounting for 10% -50% of the amount of the acrylic acid) and 0-8 parts by weight of sodium methallyl sulfonate into the mixture A under the condition of stirring;
(3) adding acrylic acid and sodium methallyl sulfonate, stirring for 10 minutes, and adding 0.0-3.0 parts by weight of hydrogen peroxide into the mixture A;
(4) adding hydrogen peroxide, stirring for 5 minutes, dropwise adding the solution B, the solution C and the solution D into the mixture A, and simultaneously carrying out polymerization reaction at the temperature of 50-90 ℃; wherein the solution B is dripped off within 0-300 minutes, and the solution C is dripped off within 0-330 minutes; the solution D is dripped off within 60-300 minutes; the solution B comprises 0.0-2.5 parts by weight of L-ascorbic acid, 0.0-2.5 parts by weight of E51, 0.0-2.5 parts by weight of sodium formaldehyde sulfoxylate and 0.0-1.5 parts by weight of water, the solution C comprises 0.0-3.0 parts by weight of ammonium persulfate and 0.0-3.0 parts by weight of water, and the solution D comprises 2.0-22.5 parts by weight of acrylic acid; the total amount of the water in the mixture A, the solution B, the solution C and the solution D is 0.0-6.0 parts by weight;
(5) after the dropwise addition is finished, continuously preserving the heat at the temperature of 50-90 ℃ for carrying out polymerization reaction for 30-180 minutes;
(6) quickly pouring the liquid product after heat preservation onto aluminum foil paper, cooling and flaking, and naturally cooling and solidifying the liquid product;
wherein the total amount of the water in the mixture A, the solution B, the solution C and the solution D is 0.0-6.0 parts by weight.
In one embodiment of the second aspect, in step (4), solution B is added dropwise to the polymerization reactor using a DHL-a constant flow pump;
in the step (4), the solution C is dripped into a polymerization reaction kettle by adopting a DHL-A constant flow pump;
in the step (4), the solution D is dripped into a polymerization reaction kettle by adopting a DHL-A constant flow pump;
in the steps (4) and (5), the temperature of the polymerization reaction is 60-80 ℃;
in the step (4), the dripping time of the solution B is 150-300 minutes;
the dropping time of the solution C is 120-270 minutes;
the dripping time of the solution D is 90-240 minutes;
in the step (4), there is no particular requirement for the stirring speed as long as the solution B, the solution C and the solution D can be uniformly mixed with the mixture a.
In a third aspect, the present application provides a method of using a water-reducing bulk polymeric solid polycarboxylate water reducer as described in the first aspect, said method comprising adding said water-reducing bulk polymeric solid polycarboxylate water reducer to a cement paste, said water-reducing bulk polymeric solid polycarboxylate water reducer preferably being added in an amount of 0.20% by weight of the cement; or the method comprises adding the water-reducing bulk polymerization solid polycarboxylate water reducer into concrete, wherein the addition amount of the water-reducing bulk polymerization solid polycarboxylate water reducer is preferably 0.50 wt% of the weight of cement.
In a fourth aspect, the present application provides the use of the water-reducing bulk-polymerizing solid polycarboxylate superplasticizer according to the first aspect in construction works requiring high initial fluidity and slump retaining effect of concrete, preferably including high-rise buildings, long-span bridges, marine drilling platforms, tunnels, dams or airports.
Compared with the prior art, the bulk polymerization solid polycarboxylic acid water reducer has the positive effects that (1) the bulk polymerization solid polycarboxylic acid water reducer is high in water reducing rate and good in slump retaining effect. It is colorless to light yellow solid, and the solid content is 94.5 wt% -100 wt%. When the addition amount of the bulk polymerization solid polycarboxylate superplasticizer in the cement paste is 0.20 percent of the weight of cement, the initial fluidity of the cement paste with the water-cement ratio of 0.29 can be 190-260 mm, and the fluidity can be kept at 120-245 mm in 1 hour. When the addition amount of the bulk polymerization solid polycarboxylic acid water reducing agent in the concrete is 0.50 percent of the weight of the cement, the initial slump of the fresh concrete is good, the expansion degree is large, the water reducing rate is high, the 1h slump and the expansion degree are well maintained, and the 2h slump and the expansion degree are also well maintained; can improve the water retention of the concrete, and is suitable for the building engineering with high requirements on the initial water reduction and slump retaining of the concrete.
(2) The bulk polymerization solid polycarboxylic acid water reducer has the advantages of conventional and visible raw materials, simple preparation method and process, convenient operation and contribution to large-scale industrial production.
(3) In the preparation method of the bulk polymerization solid polycarboxylic acid water reducing agent, phosphite or hypophosphite is used as a chain transfer agent, the small materials are tasteless and environment-friendly, and are beneficial to improving the reaction activity and improving the water reducing and slump retaining performances of the product, wherein the phosphite or hypophosphite can be one or more of sodium hypophosphite, sodium phosphite, potassium hypophosphite, potassium phosphite, ammonium hypophosphite and ammonium phosphite.
(4) The invention can be used for the production of additive production plants, and has the advantages of low raw material cost, good performance, one-step polymerization and the like; the bulk polymerization solid polycarboxylic acid water reducer can effectively solve the problem of transportation cost, can be applied to the fields of dry powder mortar, high-strength grouting material, heat-insulating mortar, plastering mortar, ceramic bonding mortar and the like, and simultaneously avoids the condition of low content of effective components caused by adding anti-caking components in the traditional high-temperature powder spraying process. The method is used for projects such as high-rise buildings, long-span bridges, ocean drilling platforms, tunnels, dams, airport constructions and the like with high requirements on initial water reduction and slump protection.
Detailed Description
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. Where applicable, the contents of any patent, patent application, or publication referred to in this application are incorporated herein by reference in their entirety and their equivalent family patents are also incorporated by reference, especially as they disclose definitions relating to synthetic techniques, products and process designs, polymers, comonomers, initiators or catalysts, and the like, in the art. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The numerical ranges in this application are approximations, and thus may include values outside of the ranges unless otherwise specified. A numerical range includes all numbers from the lower value to the upper value, in increments of 1 unit, provided that there is a separation of at least 2 units between any lower value and any higher value. For example, if a compositional, physical, or other property (e.g., molecular weight, melt index, etc.) is recited as 100 to 1000, it is intended that all individual values, e.g., 100, 101,102, etc., and all subranges, e.g., 100 to 166,155 to 170,198 to 200, etc., are explicitly recited. For ranges containing a numerical value less than 1 or containing a fraction greater than 1 (e.g., 1.1, 1.5, etc.), then 1 unit is considered appropriate to be 0.0001, 0.001, 0.01, or 0.1. For ranges containing single digit numbers less than 10 (e.g., 1 to 5), 1 unit is typically considered 0.1. These are merely specific examples of what is intended to be expressed and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application. It should also be noted that the terms "first," "second," and the like herein do not define a sequential order, but merely distinguish between different structures.
When used with respect to chemical compounds, the singular includes all isomeric forms and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively) unless expressly specified otherwise. In addition, unless explicitly stated otherwise, the use of the terms "a", "an" or "the" are intended to include the plural forms thereof.
The terms "comprising," "including," "having," and derivatives thereof do not exclude the presence of any other component, step or procedure, and are not intended to exclude the presence of other elements, steps or procedures not expressly disclosed herein. To the extent that any doubt is eliminated, all compositions herein containing, including, or having the term "comprise" may contain any additional additive, adjuvant, or compound, unless expressly stated otherwise. Rather, the term "consisting essentially of … …" excludes any other components, steps or processes from the scope of any of the terms hereinafter recited, except those necessary for performance. The term "consisting of … …" does not include any components, steps or processes not specifically described or listed. Unless explicitly stated otherwise, the term "or" refers to the listed individual members or any combination thereof.
In one embodiment, the application provides a water-reducing bulk polymerization solid polycarboxylate water reducer derived from environment-friendly odorless raw materials, which is prepared from the raw materials comprising the following components in parts by weight: 100 parts of unsaturated polyether, 4-25 parts of acrylic acid, 0-8 parts of sodium methallyl sulfonate, 0.0-3.0 parts of ammonium persulfate, 0.0-3.0 parts of hydrogen peroxide, 0.0-2.5 parts of L-ascorbic acid, 0.0-2.5 parts of E51 (the main components are sodium formaldehyde sulfoxylate and sodium carbonate which are purchased from Shanghai Enlossa chemical technology Co., Ltd.), 0.0-2.5 parts of sodium formaldehyde sulfoxylate, 0.0-6.0 parts of sodium hypophosphite, 0.0-2.0 parts of sodium phosphite, 0.0-2.0 parts of ammonium hypophosphite, 0.0-2.0 parts of potassium hypophosphite and 0.0-6.0 parts of water, wherein the unsaturated polyether is methyl allyl/methyl alkene butyl/vinyl glycol ether, and the number average molecular weight is 2000-6000.
It should be noted that in the present application, the amount of sodium formaldehyde sulfoxylate (also known as a sodium formaldehyde sulfoxylate) does not include the amount of sodium formaldehyde sulfoxylate in E51.
It should be noted that in the present application, the amount of water does not include the amount of water in the hydrogen peroxide.
In the present invention, the methallyl/methylen butyl/vinyl glycol ether polyoxyethylene ether is a commercially available product, preferably provided by Shanghai Dongdong chemical Co., Ltd. The molecular weight of the unsaturated polyether is preferably 2400-3000. The unsaturated polyether forms a side chain in the polymerization process to generate steric hindrance effect, prevent the cement particles from coagulating and keep the dispersibility. Unsaturated polyether can be polymerized with acrylic acid, sodium methallyl sulfonate and the like to introduce carboxyl and sulfonic group. Ammonium persulfate, hydrogen peroxide and L-ascorbic acid, E51 and sodium formaldehyde sulfoxylate form a redox system, and are used as an initiator to enable each monomer to participate in polymerization reaction. And sodium hypophosphite, sodium phosphite, ammonium hypophosphite and potassium hypophosphite are used as chain transfer agents to control the molecular weight of the synthesized water reducing agent.
Wherein the concentration of hydrogen peroxide in the hydrogen peroxide is conventional in the field, and is generally 30 wt%.
Wherein, the amount of the acrylic acid is preferably 12 to 22 parts. The amount of the sodium methallyl sulfonate is preferably 0 to 5 parts. The amount of ammonium persulfate is preferably 0.5 to 2.5 parts. The dosage of the hydrogen peroxide is preferably 0.0-3.0 parts. The L-ascorbic acid is preferably used in an amount of 0.0 to 2.5 parts. The amount of E51 is preferably 0.0-2.5 parts. The amount of the sodium formaldehyde sulfoxylate is preferably 0.0 to 2.5 parts. The amount of sodium hypophosphite is preferably 1.0-4.0 parts. The amount of the sodium phosphite is preferably 0.0 to 2.0 parts. The amount of ammonium hypophosphite is preferably 0.0-1.0 part. The amount of potassium hypophosphite is preferably 0.0 to 1.0 part. The amount of water is preferably 2.6 to 6.0 parts. The above parts are all parts by weight.
In the invention, the solid content of the water-reducing bulk polymerization solid polycarboxylate superplasticizer derived from the environment-friendly odorless raw material is preferably 94.5-97.7 wt%, and more preferably 97.7 wt%.
It should be noted that, in the present application, the amount of water included in the hydrogen peroxide is calculated when the solid content of the water-reducing bulk-polymerizing solid polycarboxylate superplasticizer is calculated.
The invention also provides a preparation method of the water-reducing bulk polymerization solid polycarboxylate superplasticizer from the environment-friendly odorless raw material, which comprises the following steps: under the condition of stirring, adding acrylic acid and sodium methallyl sulfonate which account for 10-50% of the amount of the acrylic acid into the mixture A, uniformly stirring, adding hydrogen peroxide, then dropwise adding the solution B, the solution C and the solution D, carrying out polymerization reaction, curing for a preset time period, quickly pouring a liquid product subjected to heat preservation onto aluminum foil paper, cooling and flaking, and naturally cooling and solidifying the liquid product to obtain a water-reducing bulk polymerization solid polycarboxylic acid water reducer with the solid content of 94.5-100 wt%, wherein the water-reducing bulk polymerization solid polycarboxylic acid water reducer is derived from an environment-friendly odorless raw material;
the mixture A is obtained by mixing unsaturated polyether, sodium hypophosphite, sodium phosphite, ammonium hypophosphite, potassium hypophosphite and anhydrous or trace water;
the solution B is obtained by mixing L-ascorbic acid, E51, sodium formaldehyde sulfoxylate and trace water;
the solution C is obtained by mixing ammonium persulfate and trace water;
the solution D is obtained from acrylic acid.
In the present application, the term "trace amount of water" means an amount of water less than or equal to 3.0 grams.
Preferably, the preparation method of the water-reducing bulk polymerization solid polycarboxylate superplasticizer from environment-friendly odorless raw materials comprises the following steps:
(1) mixing the mixture A: 100 parts by weight of unsaturated polyether, 0.0-6.0 parts by weight of sodium hypophosphite, 0.0-2.0 parts by weight of sodium phosphite, 0.0-2.0 parts by weight of ammonium hypophosphite, 0.0-2.0 parts by weight of potassium hypophosphite and 0.0-3.0 parts by weight of water, wherein 100 parts by weight of unsaturated polyether is put into a polymerization reaction kettle, heated to 50-90 ℃, and stirred to accelerate melting when the unsaturated polyether is in a molten state, 0.0-6.0 parts by weight of sodium hypophosphite, 0.0-2.0 parts by weight of sodium phosphite, 0.0-2.0 parts by weight of ammonium hypophosphite and 0.0-2.0 parts by weight of potassium hypophosphite which are dissolved by 0.0-3.0 parts by weight of water are put into the polymerization reaction kettle to be uniformly stirred and kept at the temperature of 50-90 ℃ for later use;
(2) adding 0.4-12.5 parts by weight of acrylic acid (accounting for 10% -50% of the amount of the acrylic acid) and 0-8 parts by weight of sodium methallyl sulfonate into the mixture A under the condition of stirring;
(3) adding acrylic acid and sodium methallyl sulfonate, stirring for 10 minutes, and adding 0.0-3.0 parts by weight of hydrogen peroxide into the mixture A;
(4) adding hydrogen peroxide, stirring for 5 minutes, dropwise adding the solution B, the solution C and the solution D into the mixture A, and simultaneously carrying out polymerization reaction at the temperature of 50-90 ℃; wherein the solution B is dripped off within 0-300 minutes, and the solution C is dripped off within 0-330 minutes; the solution D is dripped off within 60-300 minutes; the solution B comprises 0.0-2.5 parts by weight of L-ascorbic acid, 0.0-2.5 parts by weight of E51, 0.0-2.5 parts by weight of sodium formaldehyde sulfoxylate and 0.0-1.5 parts by weight of water, the solution C comprises 0.0-3.0 parts by weight of ammonium persulfate and 0.0-3.0 parts by weight of water, and the solution D comprises 2.0-22.5 parts by weight of acrylic acid; the total amount of the water in the mixture A, the solution B, the solution C and the solution D is 0.0-6.0 parts by weight;
(5) after the dropwise addition is finished, continuously preserving the heat at the temperature of 50-90 ℃ for carrying out polymerization reaction for 30-180 minutes;
(6) quickly pouring the liquid product after heat preservation onto aluminum foil paper, cooling and flaking, and naturally cooling and solidifying the liquid product;
wherein, the total amount of the water in the mixture A, the solution B, the solution C and the solution D is preferably 2.6 to 6.0 parts by weight.
In the step (4), the solution B is preferably dropwise added into a polymerization reaction kettle by adopting a DHL-A constant flow pump.
In the step (4), the solution C is preferably dripped into the polymerization reaction kettle by adopting a DHL-A constant flow pump.
In the step (4), the solution D is preferably dropwise added into a polymerization reaction kettle by adopting a DHL-A constant flow pump.
In the steps (4) and (5), the polymerization temperature is preferably 60 ℃ to 80 ℃.
In the step (4), the dropping time of the solution B is preferably 150 to 300 minutes. The dropping time of the solution C is preferably 120 to 270 minutes. The dropping time of the solution D is preferably 90 to 240 minutes.
In the step (4), there is no particular requirement for the stirring speed as long as the solution B, the solution C and the solution D can be uniformly mixed with the mixture a.
The invention also provides a use method of the water-reducing bulk polymerization solid polycarboxylate superplasticizer prepared from the environment-friendly odorless raw material, which comprises the following steps: adding the bulk polymerization solid polycarboxylic acid water reducing agent into the cement paste, wherein the addition amount of the bulk polymerization solid polycarboxylic acid water reducing agent is 0.20 wt% of the weight of cement; or the following steps: and adding the bulk polymerization solid polycarboxylate superplasticizer into concrete, wherein the addition amount of the bulk polymerization solid polycarboxylate superplasticizer is 0.50 wt% of the weight of cement.
The water-reducing bulk polymerization solid polycarboxylate water reducer derived from the environment-friendly tasteless raw materials is suitable for building engineering with high requirements on initial fluidity and slump retaining effect of concrete, such as high-rise buildings, large-span bridges, ocean drilling platforms, tunnels, dams or airports.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The raw materials used in the present invention are commercially available.
Examples
The present application is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
(1) Preparation before polymerization:
preparation of mixture A: weighing 100 parts by weight of methyl allyl polyoxyethylene ether with the average molecular weight of 2000, putting the methyl allyl polyoxyethylene ether into a polymerization reaction kettle, heating the polymerization reaction kettle to 50 ℃, starting stirring to accelerate melting when the polymerization reaction kettle is in a molten state, adding 1.0 part by weight of sodium phosphite, 0.3 part by weight of ammonium hypophosphite and 0.3 part by weight of potassium hypophosphite when the polymerization reaction kettle is completely molten into liquid, uniformly stirring, and keeping the temperature at 50 ℃ for later use;
preparation of solution B: weighing 0.5 part by weight of L-ascorbic acid, 1.0 part by weight of E51, 0.9 part by weight of sodium formaldehyde sulfoxylate and 1.2 parts by weight of water, and uniformly stirring for dropwise adding;
preparation of solution D: weighing 12.5 parts by weight of acrylic acid for dropwise adding;
(2) polymerization: starting stirring a polymerization reaction kettle which is added with the mixture A in the step (1), adding 12.5 parts by weight of acrylic acid and 2 parts by weight of sodium methallyl sulfonate when the temperature is stabilized at 50 ℃, uniformly stirring for 10 minutes, continuing stirring for 5 minutes after adding 1.5 parts by weight of hydrogen peroxide, simultaneously dropwise adding the solution B and the solution D, controlling the dropwise adding speed, finishing dropping the solution B in 90 minutes, and finishing dropping the solution D in 60 minutes; after the dropwise addition is finished, continuing the thermal insulation polymerization reaction for 180 minutes;
(3) tabletting: and (3) quickly pouring the liquid product after heat preservation onto the aluminum foil paper, cooling and flaking, and naturally cooling and solidifying the liquid product to obtain the water reducing type bulk polymerization solid polycarboxylic acid water reducing agent derived from the environment-friendly tasteless raw material according to the embodiment 1.
Example 2
(1) Preparation before polymerization:
preparation of mixture A: weighing 100 parts by weight of methallyl polyoxyethylene ether with the average molecular weight of 2400, putting the methallyl polyoxyethylene ether into a polymerization reaction kettle, heating to 60 ℃, starting stirring when the methallyl polyoxyethylene ether is in a molten state, accelerating melting, adding 1.5 parts by weight of sodium hypophosphite and 0.8 part by weight of water when the methallyl polyoxyethylene ether is completely melted into liquid, uniformly stirring, and keeping the temperature at 60 ℃ for later use;
preparation of solution B: weighing 2.5 parts by weight of E51, 0.1 part by weight of sodium formaldehyde sulfoxylate and 1.3 parts by weight of water, and uniformly stirring for dropwise adding;
preparation of solution C: weighing 0.5 part by weight of ammonium persulfate and 0.5 part by weight of water, and uniformly stirring for dropwise adding;
preparation of solution D: weighing 18.7 parts by weight of acrylic acid for dropwise adding;
(2) polymerization: starting stirring a polymerization reaction kettle which is added with the mixture A in the step (1), adding 3.3 parts by weight of acrylic acid when the temperature is stabilized at 60 ℃, uniformly stirring, stirring for 10 minutes, adding 3.0 parts of hydrogen peroxide, continuing stirring for 5 minutes, simultaneously dropwise adding the solution B, the solution C and the solution D, controlling the dropwise adding speed, finishing dropping the solution B in 180 minutes, finishing dropping the solution C in 150 minutes, and finishing dropping the solution D in 120 minutes; after the dropwise addition is finished, the polymerization reaction is continued for 120 minutes under heat preservation;
(3) tabletting: and (3) quickly pouring the liquid product after heat preservation onto the aluminum foil paper, cooling and flaking, and naturally cooling and solidifying the liquid product to obtain the water reducing type bulk polymerization solid polycarboxylic acid water reducing agent derived from the environment-friendly tasteless raw material according to the embodiment 2.
Example 3
(1) Preparation before polymerization:
preparation of mixture A: weighing 100 parts by weight of methylen butyl polyoxyethylene ether with the average molecular weight of 2400, putting the methylen butyl polyoxyethylene ether into a polymerization reaction kettle, heating to 65 ℃, starting stirring when the methylen butyl polyoxyethylene ether is in a molten state, accelerating melting, adding 2.5 parts by weight of sodium hypophosphite and 1.5 parts by weight of water when the methylen butyl polyoxyethylene ether is completely molten into liquid, uniformly stirring, and keeping the temperature at 65 ℃ for later use;
preparation of solution B: weighing 0.4 part by weight of L-ascorbic acid, 0.5 part by weight of E51 and 0.4 part by weight of water, uniformly stirring, and preparing for dropwise adding;
preparation of solution C: weighing 1.0 part by weight of ammonium persulfate and 1.0 part by weight of water, and uniformly stirring for dropwise adding;
preparation of solution D: weighing 14.4 parts by weight of acrylic acid for dropwise adding;
(2) polymerization: starting stirring in a polymerization reaction kettle which is added with the mixture A in the step (1), adding 3.6 parts by weight of acrylic acid and 1 part by weight of sodium methallyl sulfonate when the temperature is stabilized at 65 ℃, uniformly stirring for 10 minutes, simultaneously dropwise adding the solution B, the solution C and the solution D, controlling the dropwise adding speed, finishing the dropwise adding of the solution B in 270 minutes, finishing the dropwise adding of the solution C in 240 minutes, and finishing the dropwise adding of the solution D in 210 minutes; after the dropwise addition is finished, the polymerization reaction is continued for 60 minutes under heat preservation;
(3) tabletting: and (3) quickly pouring the liquid product after heat preservation onto the aluminum foil paper, cooling and flaking, and naturally cooling and solidifying the liquid product to obtain the water reducing bulk polymerization solid polycarboxylic acid water reducing agent derived from the environment-friendly odorless raw material according to the embodiment 3.
Example 4
(1) Preparation before polymerization:
preparation of mixture A: weighing 100 parts by weight of methyl allyl butyl polyoxyethylene ether with the average molecular weight of 2800, putting the methyl allyl butyl polyoxyethylene ether into a polymerization reaction kettle, heating the polymerization reaction kettle to 70 ℃, starting stirring to accelerate melting when the polymerization reaction kettle is in a molten state, adding 1.0 part by weight of sodium hypophosphite, 2.0 parts by weight of sodium phosphite, 1.0 part by weight of ammonium hypophosphite, 1.0 part by weight of potassium hypophosphite and 1.8 parts by weight of water when the polymerization reaction kettle is completely molten into liquid, uniformly stirring, and keeping the temperature at 70 ℃ for later use;
preparation of solution B: weighing 0.1 part by weight of L-ascorbic acid, 2.5 parts by weight of sodium formaldehyde sulfoxylate and 1.0 part by weight of water, and uniformly stirring for dropwise adding;
preparation of solution C: weighing 1.5 parts by weight of ammonium persulfate and 1.5 parts by weight of water, and uniformly stirring for dropwise adding;
preparation of solution D: weighing 11.2 parts by weight of acrylic acid for dropwise adding;
(2) polymerization: starting stirring in a polymerization reaction kettle which is added with the mixture A in the step (1), adding 4.8 parts by weight of acrylic acid and 3 parts by weight of sodium methallyl sulfonate when the temperature is stabilized at 70 ℃, uniformly stirring for 10 minutes, continuing stirring for 5 minutes after adding 2.7 parts by weight of hydrogen peroxide, simultaneously dropwise adding the solution B, the solution C and the solution D, controlling the dropwise adding speed, finishing dropping the solution B in 300 minutes, finishing dropping the solution C in 270 minutes, and finishing dropping the solution D in 240 minutes; after the dropwise addition is finished, the polymerization reaction is continued for 90 minutes under heat preservation;
(3) tabletting: and (3) quickly pouring the liquid product after heat preservation onto the aluminum foil paper, cooling and flaking, and naturally cooling and solidifying the liquid product to obtain the water reducing type bulk polymerization solid polycarboxylic acid water reducing agent derived from the environment-friendly tasteless raw material according to the embodiment 4.
Example 5
(1) Preparation before polymerization:
preparation of mixture A: weighing 100 parts by weight of polyoxyethylene vinyl ether with the average molecular weight of 3000, putting the polyoxyethylene vinyl ether into a polymerization reaction kettle, heating the polymerization reaction kettle to 80 ℃, starting stirring when the polyoxyethylene vinyl ether is in a molten state, accelerating melting, adding 4.0 parts by weight of sodium hypophosphite and 2.0 parts by weight of water when the polyoxyethylene vinyl ether is completely melted into liquid, uniformly stirring, and keeping the temperature of 80 ℃ for later use;
preparation of solution B: weighing 2.5 parts by weight of L-ascorbic acid, 0.1 part by weight of E51, 0.3 part by weight of sodium formaldehyde sulfoxylate and 1.5 parts by weight of water, and uniformly stirring for dropwise adding;
preparation of solution C: weighing 2.5 parts by weight of ammonium persulfate and 2.5 parts by weight of water, and uniformly stirring for dropwise adding;
preparation of solution D: weighing 7.2 parts by weight of acrylic acid for dropwise adding;
(2) polymerization: starting stirring in a polymerization reaction kettle which is added with the mixture A in the step (1), adding 4.8 parts by weight of acrylic acid and 5 parts by weight of sodium methallyl sulfonate when the temperature is stable at 80 ℃, uniformly stirring for 10 minutes, continuing stirring for 5 minutes after adding 2.0 parts by weight of hydrogen peroxide, simultaneously dropwise adding the solution B, the solution C and the solution D, controlling the dropwise adding speed, finishing dropping the solution B in 150 minutes, finishing dropping the solution C in 120 minutes, and finishing dropping the solution D in 90 minutes; after the dropwise addition is finished, the polymerization reaction is continued for 30 minutes under heat preservation;
(3) tabletting: and (3) quickly pouring the liquid product after heat preservation onto the aluminum foil paper, cooling and flaking, and naturally cooling and solidifying the liquid product to obtain the water reducing type bulk polymerization solid polycarboxylic acid water reducing agent derived from the environment-friendly odorless raw material according to the embodiment 5.
Example 6
(1) Preparation before polymerization:
preparation of mixture A: weighing 100 parts by weight of polyoxyethylene vinyl ether with the average molecular weight of 6000, putting the polyoxyethylene vinyl ether into a polymerization reaction kettle, heating the polymerization reaction kettle to 90 ℃, starting stirring to accelerate melting when the polyoxyethylene vinyl ether is in a molten state, adding 6.0 parts by weight of sodium hypophosphite, 0.3 part by weight of sodium phosphite, 2.0 parts by weight of ammonium hypophosphite, 2.0 parts by weight of potassium hypophosphite and 3.0 parts by weight of water when the polyoxyethylene vinyl ether is completely melted into liquid, uniformly stirring, and keeping the mixture at 90 ℃ for later use;
preparation of solution C: weighing 3.0 parts by weight of ammonium persulfate and 3.0 parts by weight of water, and uniformly stirring for dropwise adding;
preparation of solution D: weighing 3.6 parts by weight of acrylic acid for dropwise adding;
(2) polymerization: starting stirring in a polymerization reaction kettle which is added with the mixture A in the step (1), adding 0.4 weight part of acrylic acid and 8 weight parts of sodium methallyl sulfonate when the temperature is stabilized at 90 ℃, uniformly stirring, stirring for 10 minutes, simultaneously dropwise adding the solution C and the solution D, controlling the dropwise adding speed, finishing the dropwise adding of the solution C in 330 minutes, and finishing the dropwise adding of the solution D in 300 minutes; after the dropwise addition is finished, the polymerization reaction is continued for 60 minutes under heat preservation;
(3) tabletting: and (3) quickly pouring the liquid product after heat preservation onto the aluminum foil paper, cooling and flaking, and naturally cooling and solidifying the liquid product to obtain the water reducing type bulk polymerization solid polycarboxylic acid water reducing agent derived from the environment-friendly tasteless raw material according to the embodiment 6.
Effects of the embodiment
The water-reducing bulk polymerization solid polycarboxylate water reducer prepared by adopting tasteless environmental-friendly small materials in example 1 is added into the cement paste, the addition amount is 0.20 percent of the weight of cement, the initial fluidity of the cement paste with the water-cement ratio of 0.29 can reach 240mm, and the fluidity can be maintained at 215mm in 1 hour. The cement slump constant powder is added into concrete, wherein the addition amount is 0.50% of the weight of cement, the initial slump is 165mm, the initial expansion degree is 500mm, the 1-hour slump is 160mm, the 1-hour expansion degree is 470mm, the 2-hour slump is 120mm, and the 2-hour expansion degree is 230 mm.
According to the method and steps of examples 2-6, the water-reducing bulk polymerization solid polycarboxylate water reducer is synthesized according to the formula shown in table 1, and the obtained water-reducing bulk polymerization solid polycarboxylate water reducer is added into cement paste and concrete according to the same adding amount shown in table 1, and the performance data of the obtained cement paste and concrete are also shown in table 1. Wherein, the comparative sample 1 is a commercial conventional polycarboxylate superplasticizer mother liquor TJ-188 with the solid content of 40%, and the comparative sample 2 is a water-reducing bulk polymerization solid polycarboxylate superplasticizer synthesized by adopting a common chain transfer agent mercaptopropionic acid according to a corresponding formula in the table 1.
TABLE 1 comparison of the feedstock, experimental conditions, and performance data for examples 1-6 with comparative samples at 0.40 wt% loading
The embodiments described above are intended to facilitate the understanding and appreciation of the application by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the embodiments herein, and those skilled in the art who have the benefit of this disclosure will appreciate that many modifications and variations are possible within the scope of the present application without departing from the scope and spirit of the present application.
Claims (10)
1. The water reducing bulk polymerization solid polycarboxylate superplasticizer is characterized in that raw materials for preparing the water reducing bulk polymerization solid polycarboxylate superplasticizer comprise the following components: an unsaturated polyether, an ethylenically unsaturated monomer, an oxidizing agent, and a phosphite or hypophosphite chain transfer agent;
the number average molecular weight of the unsaturated polyether is 2000-6000, and the unsaturated polyether is one or more of the following: methallyl polyoxyethylene ether, methyl allyl butyl polyoxyethylene ether or vinyl glycol ether polyoxyethylene ether;
the ethylenically unsaturated monomer is preferably one or more of the following: sodium acrylic acid and sodium methallyl sulfonate;
the oxidant is preferably one or more of the following: ammonium persulfate and hydrogen peroxide;
the phosphite or hypophosphite chain transfer agent is preferably one or more of the following: sodium hypophosphite, sodium phosphite, ammonium hypophosphite and potassium hypophosphite.
2. The water-reducing bulk-polymeric solid polycarboxylate superplasticizer according to claim 1, wherein the raw materials for preparing said water-reducing bulk-polymeric solid polycarboxylate superplasticizer comprise the following components in parts by weight: 100 parts of unsaturated polyether, 4-25 parts of acrylic acid, 0-8 parts of sodium methallyl sulfonate, 0.0-3.0 parts of ammonium persulfate, 0.0-3.0 parts of hydrogen peroxide, 0.0-2.5 parts of L-ascorbic acid, 0.0-2.5 parts of E51, 0.0-2.5 parts of sodium formaldehyde sulfoxylate, 0.0-6.0 parts of sodium hypophosphite, 0.0-2.0 parts of sodium phosphite, 0.0-2.0 parts of ammonium hypophosphite, 0.0-2.0 parts of potassium hypophosphite and 0.0-6.0 parts of water, wherein the parts by weight of the ammonium persulfate and the hydrogen peroxide are not zero at the same time, and the parts by weight of the sodium hypophosphite, the sodium phosphite, the ammonium hypophosphite and the potassium hypophosphite are not zero at the same time.
3. The water reducing bulk polymeric solid polycarboxylic acid water reducer according to claim 2, wherein said acrylic acid is used in an amount of 12 to 22 parts;
the using amount of the sodium methallyl sulfonate is 0-5 parts;
the using amount of the ammonium persulfate is 0.5-2.5 parts;
the dosage of the hydrogen peroxide is 0.0-2.7 parts;
the dosage of the L-ascorbic acid is 0.1-2.5 parts;
the using amount of the E51 is 0.1-2.5 parts;
the dosage of the sodium formaldehyde sulfoxylate is 0.1-2.5 parts;
the dosage of the sodium hypophosphite is 1.0-4.0 parts;
the dosage of the sodium phosphite is 0.0-1.0 part;
the using amount of the ammonium hypophosphite is 0.0-1.0 part;
the dosage of the potassium hypophosphite is 0.0-1.0 part;
the amount of the water is 2.6-6.0 parts.
4. A water-reducing bulk polymeric solid polycarboxylate water reducer according to any of the claims 1-3, characterized in that said water-reducing bulk polymeric solid polycarboxylate water reducer has a solid content of 94.5-100 wt%, preferably 97.7 wt%.
5. A method for preparing a water-reducing bulk polymeric solid polycarboxylate water reducer according to claim 1, characterized in that it comprises the steps of:
s1: melting the unsaturated polyether into liquid at the temperature of 50-90 ℃, and then mixing the liquid with the aqueous solution of the phosphite or hypophosphite chain transfer agent to obtain a mixture A;
s2: and adding an alkenyl unsaturated monomer into the mixture A, polymerizing for 60-330 minutes at the temperature of 50-90 ℃, continuing to perform thermal polymerization for 30-180 minutes at the temperature of 50-90 ℃, and cooling the obtained liquid product to obtain the water-reducing bulk polymerization solid polycarboxylic acid water reducer.
6. A process for the preparation of a water-reducing bulk polymeric solid polycarboxylate water reducer according to claim 2 or 3, characterized in that it comprises the steps of: under the condition of stirring, adding acrylic acid and sodium methallyl sulfonate which account for 10-50% of the amount of the acrylic acid into the mixture A, uniformly stirring, adding hydrogen peroxide, then dropwise adding the solution B, the solution C and the solution D, carrying out polymerization reaction, curing for a preset time period, and cooling a liquid product to obtain the water-reducing bulk polymerization solid polycarboxylic acid water reducer;
the mixture A is obtained by mixing unsaturated polyether, sodium hypophosphite, sodium phosphite, ammonium hypophosphite, potassium hypophosphite and anhydrous or trace water;
the solution B is obtained by mixing L-ascorbic acid, E51, sodium formaldehyde sulfoxylate and trace water;
the solution C is obtained by mixing ammonium persulfate and trace water;
the solution D is obtained from acrylic acid.
7. The method of claim 6, wherein the method comprises the steps of:
(1) mixing the mixture A: 100 parts by weight of unsaturated polyether, 0.0-6.0 parts by weight of sodium hypophosphite, 0.0-2.0 parts by weight of sodium phosphite, 0.0-2.0 parts by weight of ammonium hypophosphite, 0.0-2.0 parts by weight of potassium hypophosphite and 0.0-3.0 parts by weight of water, wherein 100 parts by weight of unsaturated polyether is put into a polymerization reaction kettle, heated to 50-90 ℃, and stirred to accelerate melting when the unsaturated polyether is in a molten state, 0.0-6.0 parts by weight of sodium hypophosphite, 0.0-2.0 parts by weight of sodium phosphite, 0.0-2.0 parts by weight of ammonium hypophosphite and 0.0-2.0 parts by weight of potassium hypophosphite which are dissolved by 0.0-3.0 parts by weight of water are put into the polymerization reaction kettle to be uniformly stirred and kept at the temperature of 50-90 ℃ for later use;
(2) adding 0.4-12.5 parts by weight of acrylic acid (accounting for 10% -50% of the amount of the acrylic acid) and 0-8 parts by weight of sodium methallyl sulfonate into the mixture A under the condition of stirring;
(3) adding acrylic acid and sodium methallyl sulfonate, stirring for 10 minutes, and adding 0.0-3.0 parts by weight of hydrogen peroxide into the mixture A;
(4) adding hydrogen peroxide, stirring for 5 minutes, dropwise adding the solution B, the solution C and the solution D into the mixture A, and simultaneously carrying out polymerization reaction at the temperature of 50-90 ℃; wherein the solution B is dripped off within 0-300 minutes, and the solution C is dripped off within 0-330 minutes; the solution D is dripped off within 60-300 minutes; the solution B comprises 0.0-2.5 parts by weight of L-ascorbic acid, 0.0-2.5 parts by weight of E51, 0.0-2.5 parts by weight of sodium formaldehyde sulfoxylate and 0.0-1.5 parts by weight of water, the solution C comprises 0.0-3.0 parts by weight of ammonium persulfate and 0.0-3.0 parts by weight of water, and the solution D comprises 2.0-22.5 parts by weight of acrylic acid; the total amount of the water in the mixture A, the solution B, the solution C and the solution D is 0.0-6.0 parts by weight;
(5) after the dropwise addition is finished, continuously preserving the heat at the temperature of 50-90 ℃ for carrying out polymerization reaction for 30-180 minutes;
(6) quickly pouring the liquid product after heat preservation onto aluminum foil paper, cooling and flaking, and naturally cooling and solidifying the liquid product;
wherein the total amount of the water in the mixture A, the solution B, the solution C and the solution D is 0.0-6.0 parts by weight.
8. The method of claim 7, wherein in step (4), solution B is added dropwise to the polymerization reactor using a DHL-A constant flow pump;
in the step (4), the solution C is dripped into a polymerization reaction kettle by adopting a DHL-A constant flow pump;
in the step (4), the solution D is dripped into a polymerization reaction kettle by adopting a DHL-A constant flow pump;
in the steps (4) and (5), the temperature of the polymerization reaction is 60-80 ℃;
in the step (4), the dripping time of the solution B is 150-300 minutes;
the dropping time of the solution C is 120-270 minutes;
the dripping time of the solution D is 90-240 minutes;
in the step (4), there is no particular requirement for the stirring speed as long as the solution B, the solution C and the solution D can be uniformly mixed with the mixture a.
9. The method of using a water-reducing bulk polymeric solid polycarboxylate water reducer as described in any of the claims 1-3, said method comprising adding said water-reducing bulk polymeric solid polycarboxylate water reducer to a cement paste, preferably in an amount of 0.20% by weight of cement; or the method comprises adding the water-reducing bulk polymerization solid polycarboxylate water reducer into concrete, wherein the addition amount of the water-reducing bulk polymerization solid polycarboxylate water reducer is preferably 0.50 wt% of the weight of cement.
10. Use of the water-reducing bulk polymeric solid polycarboxylate water reducer as defined in any one of the claims 1-3 for construction work requiring high initial concrete fluidity and slump retention, preferably including high-rise buildings, long-span bridges, marine drilling platforms, tunnels, dams or airports.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911231415.9A CN111019056A (en) | 2019-12-05 | 2019-12-05 | Water-reducing bulk polymerization solid polycarboxylate superplasticizer and preparation method, use method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911231415.9A CN111019056A (en) | 2019-12-05 | 2019-12-05 | Water-reducing bulk polymerization solid polycarboxylate superplasticizer and preparation method, use method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111019056A true CN111019056A (en) | 2020-04-17 |
Family
ID=70204266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911231415.9A Pending CN111019056A (en) | 2019-12-05 | 2019-12-05 | Water-reducing bulk polymerization solid polycarboxylate superplasticizer and preparation method, use method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111019056A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851879A (en) * | 2021-01-11 | 2021-05-28 | 科之杰新材料集团(贵州)有限公司 | Polycarboxylate superplasticizer for concrete and preparation method thereof |
| CN112920345A (en) * | 2021-02-23 | 2021-06-08 | 厦门路桥翔通建材科技有限公司 | Preparation method of cement-based building material auxiliary water reducing agent |
| CN117164274A (en) * | 2023-11-03 | 2023-12-05 | 四川蜀道建筑科技有限公司 | Water reducer for mass concrete, preparation method and concrete |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017490A (en) * | 2015-07-14 | 2015-11-04 | 唐山市龙亿科技开发有限公司 | Method for preparing polycarboxylate superplasticizer by nonaqueous technique |
| CN106220791A (en) * | 2016-07-10 | 2016-12-14 | 安徽中铁工程材料科技有限公司 | The polycarboxylate water-reducer of a kind of phosphorous acidic group and preparation method |
| CN109021182A (en) * | 2018-08-30 | 2018-12-18 | 上海东大化学有限公司 | Polycarboxylate water-reducer and its preparation method and application from environment-friendly tasteless raw material |
-
2019
- 2019-12-05 CN CN201911231415.9A patent/CN111019056A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017490A (en) * | 2015-07-14 | 2015-11-04 | 唐山市龙亿科技开发有限公司 | Method for preparing polycarboxylate superplasticizer by nonaqueous technique |
| CN106220791A (en) * | 2016-07-10 | 2016-12-14 | 安徽中铁工程材料科技有限公司 | The polycarboxylate water-reducer of a kind of phosphorous acidic group and preparation method |
| CN109021182A (en) * | 2018-08-30 | 2018-12-18 | 上海东大化学有限公司 | Polycarboxylate water-reducer and its preparation method and application from environment-friendly tasteless raw material |
Non-Patent Citations (1)
| Title |
|---|
| 混凝土外加剂及其应用技术论坛编: "《聚羧酸系高性能减水剂及其应用技术新进展》", 31 March 2019, 北京理工大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112851879A (en) * | 2021-01-11 | 2021-05-28 | 科之杰新材料集团(贵州)有限公司 | Polycarboxylate superplasticizer for concrete and preparation method thereof |
| CN112920345A (en) * | 2021-02-23 | 2021-06-08 | 厦门路桥翔通建材科技有限公司 | Preparation method of cement-based building material auxiliary water reducing agent |
| CN117164274A (en) * | 2023-11-03 | 2023-12-05 | 四川蜀道建筑科技有限公司 | Water reducer for mass concrete, preparation method and concrete |
| CN117164274B (en) * | 2023-11-03 | 2024-01-05 | 四川蜀道建筑科技有限公司 | Water reducer for mass concrete, preparation method and concrete |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102849978B (en) | Sustained-release polycarboxylic high-performance water reducing agent and preparation method thereof | |
| CN102503226B (en) | High slump retaining type polycarboxylic acid water reducing agent with sustained-release effect and preparation method thereof | |
| CN111019056A (en) | Water-reducing bulk polymerization solid polycarboxylate superplasticizer and preparation method, use method and application thereof | |
| CN109021182B (en) | Polycarboxylate superplasticizer from environment-friendly odorless raw materials and preparation method and application thereof | |
| CN104030595B (en) | Compound concrete admixture with early strength and water reduction functions, and preparation method and application thereof | |
| CN114195421A (en) | Preparation method of polycarboxylic acid admixture for machine-made sand concrete | |
| CN110028632A (en) | Anti- chamotte mould polycarboxylate water-reducer of high water reduction and preparation method thereof | |
| CN109369860A (en) | It is sustained controllable type polycarboxylate superplasticizer mother liquor and preparation method thereof | |
| CN110963732A (en) | Environment-friendly alkali-free liquid accelerator and normal-temperature preparation method thereof | |
| CN109776021A (en) | A kind of low entraining type clear-water concrete additive and preparation method thereof | |
| CN104371074A (en) | Low-temperature high-concentration polycarboxylic acid water reducing agent and preparation method thereof | |
| CN108070059B (en) | High-workability polycarboxylic acid water reducing agent, and preparation method and use method thereof | |
| CN107954627B (en) | Composite concrete retarder and preparation method thereof | |
| CN109704619B (en) | Sulfamate high-efficiency water reducing agent and preparation process thereof | |
| CN108558261B (en) | Additive for inhibiting assembled concrete bleeding and preparation method thereof | |
| CN106243288A (en) | A kind of concrete slump retaining agent and preparation method thereof | |
| CN107759742A (en) | A kind of polycarboxylate water-reducer and preparation method thereof and application method | |
| US7671115B2 (en) | Method for enhancing water-repellency treatment of mineral hydraulic binder compositions and compositions obtainable by said method and their uses | |
| CN108892756B (en) | Preparation method of high-adaptability polycarboxylate superplasticizer based on 3000-molecular-weight polyether | |
| CN108219079B (en) | Polycarboxylic acid water reducing agent, and preparation method and use method thereof | |
| CN109021179B (en) | Phosphonic acid-based polymer, preparation method thereof and phosphate mother liquor | |
| CN105060759A (en) | Preparation method of slow-release polycarboxylate superplasticizer | |
| CN109721271A (en) | A kind of self-compaction high workability concrete polycarboxylate superplasticizer composition | |
| CN108395138A (en) | A kind of accelerator for cement slurry | |
| CN109336447B (en) | Stable slump retaining agent and preparation and use methods thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200417 |