CN112142923A - Preparation method of polycarboxylate superplasticizer macromonomer suitable for normal-temperature polymerization - Google Patents
Preparation method of polycarboxylate superplasticizer macromonomer suitable for normal-temperature polymerization Download PDFInfo
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 34
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 26
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 229920000570 polyether Polymers 0.000 claims abstract description 22
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 18
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000003638 chemical reducing agent Substances 0.000 claims description 35
- -1 hydroxybutyl Chemical group 0.000 claims description 9
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims 2
- 125000005394 methallyl group Chemical group 0.000 claims 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 230000000977 initiatory effect Effects 0.000 abstract description 13
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 13
- 239000000178 monomer Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 16
- 239000002253 acid Substances 0.000 description 15
- 239000004568 cement Substances 0.000 description 11
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012966 redox initiator Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- AOAGVPIEEAAAOL-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;hydrogen peroxide Chemical compound OO.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O AOAGVPIEEAAAOL-RXSVEWSESA-N 0.000 description 1
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- 230000005526 G1 to G0 transition Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—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
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/08—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of alkali metals
- C08F4/083—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of alkali metals an alkali metal bound to oxygen
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention provides a preparation method of a polycarboxylate superplasticizer macromonomer suitable for normal-temperature polymerization, which comprises the following steps: nitrate is added in the preparation process of the conventional polycarboxylate superplasticizer macromonomer, so that the polycarboxylate superplasticizer macromonomer is fully and uniformly dispersed. The preparation process of the polycarboxylate superplasticizer is a process of carrying out free radical polymerization through double bonds in a polyether macromonomer structure and bonds in a micromolecular monomer structure such as acrylic acid and methacrylic acid, wherein the free radical polymerization is a reaction of chain initiation, chain transfer and chain termination.
Description
Technical Field
The invention relates to the field of chemistry, in particular to a preparation method of a polycarboxylate superplasticizer macromonomer suitable for normal-temperature polymerization.
Background
The polycarboxylic acid water reducing agent is a third generation high-performance concrete water reducing agent developed after a common water reducing agent represented by lignin and a naphthalene high-performance water reducing agent, and is widely favored by the concrete engineering industry with high water reducing rate and good slump retentivity.
The preparation process of the polycarboxylate superplasticizer is related to the production efficiency and the performance of the obtained water reducer, so the preparation process is always a key topic for developing the polycarboxylate superplasticizer. At present, the production of polycarboxylic acid water reducing agents is mainly based on free radical polymerization. Specifically, radical polymerization includes chain initiation, chain propagation, and chain transfer, and in the chain initiation reaction, the primary radical endothermic reaction requires high activation energy and slow reaction. Therefore, in the free radical polymerization, the initiation of the polymerization reaction is a main factor related to the temperature of the preparation process of the polycarboxylic acid water reducing agent. The polyether macromonomer has large intermolecular steric hindrance, so that higher activation energy is required, and therefore, the macromonomer participating in the reaction needs high activation energy when preparing the polycarboxylic acid water reducing agent, so that a high-efficiency initiation system is required. For this reason, the initiation of the polymerization reaction is conventionally effected by high temperatures. However, with the stricter requirements on energy conservation and environmental protection, the high-temperature method with high energy consumption is restricted, and in addition, the high-temperature method has the problems of large equipment investment, long production period and the like. Therefore, the production of polycarboxylic acid water reducing agent by high temperature method is less and less.
With the search of those skilled in the art, the synthesis process of polycarboxylic acid has been shifted from high temperature (above 60 ℃) polymerization systems to medium temperature (35-60 ℃) or even normal temperature (15-35 ℃). Many patents, such as CN105254822B, CN101928114B, CN104371076B, CN104788629B, CN104356314A, CN107652404A, CN105418856B, CN105542092B, etc., report polycarboxylic acid initiation systems at normal temperature. However, these systems are all realized by redox initiation systems using peroxides and persulfates as oxidizing agents, reducing low-valent sulfates and ascorbic acid as reducing agents, i.e., several peroxides or several reducing substances are needed to act synergistically to improve initiation efficiency, so that the number of raw materials involved is increased, and the complexity of the process is increased.
In summary, there is a need for a method for preparing a macromonomer of a polycarboxylic acid water reducing agent suitable for normal temperature polymerization, which is suitable for a common initiation system, and enables small and micro enterprises with weak technical strength to develop normal temperature process production, so that the process for synthesizing the polycarboxylic acid water reducing agent at normal temperature is popularized.
Disclosure of Invention
In order to solve the problems, the invention provides the following technical scheme:
a preparation method of a polycarboxylate superplasticizer macromonomer suitable for normal temperature polymerization comprises the following steps:
nitrate is added in the preparation process of the conventional polycarboxylate superplasticizer macromonomer, so that the polycarboxylate superplasticizer macromonomer is fully and uniformly dispersed.
Specifically, the preparation method of the polycarboxylate superplasticizer macromonomer suitable for normal-temperature polymerization comprises the following steps: polymerizing an initiator containing double bonds with ethylene oxide or propylene oxide, vacuumizing to remove redundant ethylene oxide or propylene oxide after polymerization is finished to obtain a conventional polycarboxylate superplasticizer macromonomer, adding nitrate into the reaction kettle, and uniformly stirring to obtain the polycarboxylate superplasticizer macromonomer suitable for normal-temperature polymerization. The initiator containing double bonds may be methallyl alcohol, allyl alcohol, isopentenol, vinyl hydroxybutyl ether or phenol, etc.
Preferably, the mass percentage concentration of the nitrate is 10-200 ppm.
The polycarboxylate superplasticizer macromonomer is allyl polyether, methyl allyl polyether, isoamylol polyether, hydroxybutyl polyether or phenol polyether.
The polycarboxylate water reducing agent macromonomer is polycarboxylate water reducing agent polyether macromonomer, and the polyether is polyoxyethylene ether, polyoxypropylene ether, ethylene oxide and propylene oxide random polyether or ethylene oxide and propylene oxide block polyether.
The nitrate is one or more of sodium nitrate, potassium nitrate and ammonium nitrate.
The principle of the invention is as follows: the preparation process of the polycarboxylate water reducing agent is a process of carrying out free radical polymerization through double bonds in a polyether macromonomer structure and bonds in a micromolecular monomer structure such as acrylic acid and methacrylic acid, the free radical polymerization is a reaction of chain initiation, chain transfer and chain termination, nitrate has oxidability under the acidic condition of a reaction system, increases the oxidation-reduction initiation system to generate free radicals, and promotes the free radical polymerization, so that the current situation that the free radical product is promoted by heating in the traditional process is changed. The conventional hydrogen peroxide-ascorbic acid can be used as an initiating system.
Drawings
FIG. 1 is a temperature profile of reaction temperature and reaction time for groups 1-8 reactions in examples of the present invention.
Detailed Description
In order to make the technical means, characteristics and effects of the invention easy to understand, the invention is further described below with reference to the specific embodiments.
The embodiment provides a preparation method of a polycarboxylate superplasticizer macromonomer suitable for normal-temperature polymerization, which comprises the following steps:
polymerizing an initiator containing double bonds with ethylene oxide or propylene oxide under the action of a catalyst under a certain temperature condition, vacuumizing to remove redundant ethylene oxide or propylene oxide after polymerization is finished to obtain a conventional polycarboxylate water reducer macromonomer, adding nitrate into a reaction kettle, uniformly stirring to obtain the polycarboxylate water reducer macromonomer suitable for normal-temperature polymerization, and then transferring the polycarboxylate water reducer macromonomer into a slicing machine or a granulating machine for granulation.
The following are the performance tests of the polycarboxylate superplasticizer macromonomer prepared by the method of this example:
(1) temperature rise of reaction
Radical polymerization is an exothermic reaction and the temperature rise is the maximum temperature occurring during the reaction minus the initial temperature before addition of the initiator.
(2) Monomer conversion test
The monomer conversion rate is measured by using a gel chromatograph, 0.85g of a water reducing agent sample to be measured with the solid content of 40% is accurately weighed, the water reducing agent sample is dissolved in 6.0ml of distilled water, 0.1g/ml of sodium nitrate solution is used as a mobile phase, a gel porous filling agent is used as a stationary phase, and the monomer conversion rate is measured.
(3) Viscosity measurement
The viscosity of the copolymers is determined by reference to the standard GB 265 kinematic viscometer. The specific experimental method is shown in the specification of 4.2.5 viscosity measurement.
(4) Cement paste fluidity test
The fluidity of the cement paste is tested according to GB/T8077-. Pouring cement, water and water reducing agent into a stirring pot, stirring at low speed for 2min, stopping stirring for 15s, and then stirring at high speed for 2 min. And (4) quickly injecting the mixed cement paste into a conical test mold, and scraping by using a scraper. The conical test mold was lifted in the vertical direction and expressed in mm as the maximum diameter of the cement paste flowing freely over the glass plane for 30 s. Wherein the mixing amount of the water reducing agent is 0.23 percent of the mass of the cement, the water cement ratio is 0.29, and the temperature is 20 +/-1 ℃ during the test.
The specific experimental method comprises the following steps:
adding a polyacid water reducer ether polymaleic allyl Alcohol Polyoxyethylene Ether (APEG) and small monomer acrylic acid with a molar ratio of 1:3.5 and a proper amount of deionized water (the mass concentration of water is 60%) into a three-neck flask provided with a thermometer and a stirrer, and starting an electric stirrer to uniformly mix and dissolve the raw materials; dropping initiator solution for about 1 h; after the initiator solution is dripped, stirring and reacting for 3 hours to finish the polymerization reaction; and (3) adjusting the pH value to about 7 by using a 30% sodium hydroxide solution to obtain the corresponding polycarboxylic acid water reducer with the concentration of 40%.
The polycarboxylate superplasticizer macromonomer of the patent selects allyl alcohol polyoxyethylene ether, and the added nitrate is shown in the following table
| Experiment number | Kind of monomer | NaNO in monomer3Content (ppm) | KNO in monomer3Content (ppm) |
| 1 | |
0 | 0 |
| 2 | |
10 | 0 |
| 3 | APEG | 100 | 0 |
| 4 | APEG | 200 | 0 |
| 5 | |
0 | 10 |
| 6 | |
0 | 100 |
| 7 | |
0 | 200 |
| 8 | |
50 | 50 |
The polyether macromonomer is used for preparing the polycarboxylic acid water reducing agent according to a specific experimental method. The following tests were performed on the above polycarboxylic acid water reducing agent:
test 1 reactivity test
The synthesis of the water reducing agent is free radical polymerization reaction, belongs to exothermic reaction, and records the temperature of 1-8 groups of reaction processes respectively, wherein the experimental results are shown in figure 1:
as can be seen from FIG. 1, after the addition of nitrate, the reaction has a significant temperature rise, as indicated by the free radical polymerization, in the experimental groups 2-6 compared to group 1. The possible reason of the mechanism is that the reaction system contains acrylic acid, the concentration of hydrogen ions in the solution is gradually increased, nitrate ions with symmetrical structures are influenced by hydrogen ions with higher polarization in the solution, the stability of the nitrate ions is smaller and smaller, and the nitrate ions are changed from non-oxidizing to stronger oxidizing. Thereby achieving the purpose of increasing the capability of generating free radicals by a redox initiation system and promoting the generation of free radical polymerization. And the viscosity indexes of the obtained water reducing agent are as follows:
chemical index of polycarboxylic acid water reducing agent
From the above table, it can be seen that experimental group 1 is relatively strong in acidity, indicating the presence of unreacted acrylic acid, and small in viscosity indicating that polymerization is not complete, further indicating that the presence of nitrate in the product can promote radical polymerization.
Test 2 monomer conversion test
Gel chromatography analysis was performed on each of the above experimental groups, yielding the following results:
monomer conversion rate of polycarboxylic acid water reducing agent
As can be seen from the above, the scheme can obviously increase the monomer conversion rate
Test 3. Cement paste test
The polycarboxylic acid water reducing agent has good dispersing performance and is reflected in good fluidity of cement paste and less loss in application. The application performance of the polycarboxylate superplasticizer in the experimental group is tested in concrete, and the result is as follows:
the cement paste fluidity test is carried out according to the relevant standards specified in the concrete admixture homogeneity test method GB/T8077-2012.
Test results of cement paste test
From the test results in the table above, it can be seen that the water reducing agent product obtained by normal temperature polymerization has high initial net slurry fluidity and good net slurry fluidity retention after 2 hours of time under the condition of containing nitrate. The reaction is better along with the increase of the dosage, which shows that the viscosity is high, and the net pulp retention rate is improved.
The allyl alcohol polyoxyethylene ether can also polymerize under the condition of large initiator amount, and the table shows that the polymerization degree of the macromonomer is lower and the reaction is relatively mild in the same reaction time compared with the macromonomer of the invention. Therefore, the macromonomer prepared by the method has high activity, is suitable for synthesizing the water reducing agent by a normal-temperature process, and can reduce the dosage of an initiation system and the process time so as to reduce the production cost.
Claims (6)
1. A preparation method of a polycarboxylate superplasticizer macromonomer suitable for normal temperature polymerization is characterized by comprising the following steps:
nitrate is added in the preparation process of the conventional polycarboxylate superplasticizer macromonomer, so that the polycarboxylate superplasticizer macromonomer is fully and uniformly dispersed.
2. The preparation method according to claim 1, which specifically comprises:
polymerizing an initiator containing double bonds with ethylene oxide or propylene oxide, vacuumizing to remove redundant ethylene oxide or propylene oxide after polymerization is finished to obtain a conventional polycarboxylate superplasticizer macromonomer, adding nitrate into the reaction kettle, and uniformly stirring to obtain the polycarboxylate superplasticizer macromonomer suitable for normal-temperature polymerization.
3. The preparation method of claim 1 or 2, wherein the conventional polycarboxylate superplasticizer macromonomer is allyl polyether, methallyl polyether, prenol polyether, hydroxybutyl polyether or phenol polyether.
4. The preparation method according to claim 3, wherein the conventional polycarboxylate water reducer macromonomer is polycarboxylate water reducer polyether macromonomer, and the polyether is in the form of polyoxyethylene ether, polyoxypropylene ether, ethylene oxide propylene oxide random polyether or ethylene oxide propylene oxide block polyether.
5. The production method according to claim 1 or 2, wherein the nitrate is present in a concentration of 10 to 200ppm by mass.
6. The preparation method according to claim 5, wherein the nitrate is one or more of sodium nitrate, potassium nitrate and ammonium nitrate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102585089A (en) * | 2011-01-07 | 2012-07-18 | 上海浦泰化工有限公司 | Cationic polyacrylamide polymer, method for preparing same and application thereof |
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