CN112708063A - Reducing agent for improving monomer conversion rate, preparation method thereof and redox method for preparing polycarboxylic acid with high monomer conversion rate - Google Patents
Reducing agent for improving monomer conversion rate, preparation method thereof and redox method for preparing polycarboxylic acid with high monomer conversion rate Download PDFInfo
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 70
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 65
- 239000000178 monomer Substances 0.000 title claims abstract description 56
- 239000002253 acid Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 25
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 229920000570 polyether Polymers 0.000 claims abstract description 22
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 29
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical group OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 12
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 10
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 8
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 229940107700 pyruvic acid Drugs 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 4
- 238000004519 manufacturing process Methods 0.000 claims 3
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 5
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- 229920005646 polycarboxylate Polymers 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000008030 superplasticizer Substances 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 229920000151 polyglycol Polymers 0.000 description 3
- 239000010695 polyglycol Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- -1 3-methylbut-3-enyl Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013365 molecular weight analysis method Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011513 prestressed concrete Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 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
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of building additives, in particular to a reducing agent for improving monomer conversion rate, a preparation method thereof and an oxidation-reduction method for preparing polycarboxylic acid with high monomer conversion rate, wherein the reducing agent for improving monomer conversion rate comprises the following components: acid compounds, sodium hydroxide, sodium hydrosulfite and water; simultaneously provides a redox method for preparing polycarboxylic acid with high monomer conversion rate, which comprises the following steps: the polyether modified polyether is prepared by the copolymerization reaction of a polyether monomer, unsaturated carboxylic acid, a reducing agent, an oxidizing agent and a chain transfer agent. The reducing agent for improving the monomer conversion rate and the redox method for preparing the polycarboxylic acid with high monomer conversion rate provided by the invention adopt common and easily available raw materials to prepare a reducing agent solution with high reaction activity and low cost to realize free radical polymerization reaction, and realize polymerization reaction at low temperature through the polyether macromonomer with high reaction activity to obtain a product with high monomer conversion rate, and the reaction process is simple and the product performance is excellent.
Description
Technical Field
The invention relates to the technical field of building additives, in particular to a reducing agent for improving monomer conversion rate, a preparation method thereof and a redox method for preparing polycarboxylic acid with high monomer conversion rate.
Background
The polycarboxylate superplasticizer is a high-performance superplasticizer, and is widely applied to precast and cast-in-place concrete, reinforced concrete and prestressed concrete for engineering construction of high-speed railways, passenger dedicated lines, industrial and civil buildings, roads, bridges, ports and docks, airports and the like. For the synthesis of the polycarboxylic acid water reducing agent, the design of the molecular structure is crucial, wherein the molecular structure comprises a main chain group, a side chain density, a side chain length and the like, and the synthesis is generally carried out through a free radical solution polymerization reaction.
Free radical polymerization is a polymerization reaction initiated with a free radical, causing the propagation of a growing free radical. Many monomers are linked to form macromolecules by opening double bonds in the monomer molecules and performing repeated addition reactions between molecules. In free radical polymerization, the conversion and relative molecular mass change with time, chain extension reactions increase the degree of polymerization, and monomer conversion increases.
The prepared polycarboxylate superplasticizer with high conversion rate can improve the conversion of reaction monomers, improve effective substances in products, and further achieve the purposes of improving performance and reducing cost.
Therefore, the application number 202010336501.2 entitled "catalyst for improving the synthetic conversion rate of polycarboxylate superplasticizer and application thereof" discloses a catalyst for improving the synthetic conversion rate of polycarboxylate superplasticizer, the publication date is 8/4/2020, and comprises the following components in percentage by weight: 5-10% of initiating oxidant, 5-15% of VC, 0.5-1.5% of phosphoric acid, 10-20% of polyethylene glycol and 60-80% of deionized water, wherein the initiating oxidant is one or a mixture of more of ammonium persulfate, persulfuric acid, persulfate, hydrogen peroxide, tert-butyl hydroperoxide and dibenzoyl peroxide, the VC is used as a reducing agent, the initiating oxidant and the phosphoric acid are used as oxidizing agents, the synthetic conversion rate of the polycarboxylic acid water reducing agent can be effectively improved, and by adopting the redox system, when the using amount of the reducing agent is 0.2% of the mass of the polyether monomer and the reaction temperature is 55 ℃, the polycarboxylic acid water reducing agent with excellent performance can be prepared.
The invention provides a low-temperature synthesis method of a poly-initiation polycarboxylate water reducer, which is disclosed in 'a low-temperature synthesis method of a poly-initiation polycarboxylate water reducer' with the application number of 201611004968.7, wherein the publication date of the low-temperature synthesis method is 5 months and 31 days in 2017. By compounding the multi-element initiator, the conversion rate of the product is greatly improved under the alternate combined action of the oxidant and the strong and weak reducing agents; the molecular mass distribution of the polycarboxylate superplasticizer is controlled by the dropping time, the initiator adding mode and the synthesis temperature, so that the water reducing rate and the slump retaining property are improved. The whole synthesis process of the invention does not need an external heating source, and the preparation process is simple and controllable, and has good product stability and strong adaptability.
Disclosure of Invention
In order to solve the problem of low monomer conversion rate in the prior polymerization reaction mentioned in the background art, the invention provides a reducing agent for improving the monomer conversion rate, which comprises the following components: acid compounds, sodium hydroxide, sodium hydrosulfite and water.
On the basis of the scheme, the carbonyl acid compound is glyoxylic acid or pyruvic acid.
On the basis of the scheme, the paint further comprises the following components in parts by mass:
the invention provides a preparation method of a reducing agent for improving monomer conversion rate, which comprises the following steps: mixing acid compound, sodium hydroxide and water, heating to 20-100 deg.C, adding sodium dithionite, and reacting.
The invention provides a redox method for preparing polycarboxylic acid with high monomer conversion rate, which comprises the following steps: the polyether is prepared by the copolymerization reaction of a polyether monomer, unsaturated carboxylic acid, a reducing agent, an oxidizing agent and a chain transfer agent;
wherein, the reducing agent adopts the reducing agent for improving the monomer conversion rate or the reducing agent prepared by the preparation method of the reducing agent for improving the monomer conversion rate.
On the basis of the scheme, the paint further comprises the following components in parts by mass:
on the basis of the scheme, the structural formula of the polyether monomer is as follows:
CH2＝CH-O-CH2CH2-O-(CH2CH2O)m-H；
wherein m is an integer, and m is not less than 20 and not more than 100.
On the basis of the scheme, the chain transfer agent is thioglycolic acid or mercaptopropionic acid.
On the basis of the above scheme, further, the unsaturated carboxylic acid is acrylic acid; the oxidant is hydrogen peroxide.
On the basis of the scheme, further, the temperature of the polymerization reaction is 5-35 ℃.
Compared with the prior art, the reducing agent for improving the monomer conversion rate, the preparation method thereof and the redox method for preparing the polycarboxylic acid with high monomer conversion rate have the following effects:
1. the free radical polymerization reaction is realized by adopting common and easily obtained raw materials to prepare reducing agent solution with high reaction activity and low cost.
2. Adopts polyether macromonomer with high reaction activity to realize polymerization reaction at low temperature and obtain a product with high monomer conversion rate.
3. The reaction process is simple, and the product performance is excellent.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a redox method for preparing polycarboxylic acid with high monomer conversion rate, which comprises the following steps in parts by mass:
a) adding 65-85 parts of acid compound, 100-150 parts of sodium hydroxide and 400 parts of water into a reactor, stirring for dissolving, heating to 20-100 ℃, slowly adding 150-200 parts of sodium hydrosulfite under stirring, continuing to react for 30-300min after the sodium hydrosulfite is added, and obtaining the reducing agent.
b) Adding 0.15-1.5 parts of reducing agent prepared in the step a) into 5-10 parts of water to prepare reducing agent solution; adding 5-10 parts of acrylic acid into 5-10 parts of water to prepare an acrylic acid solution; adding 0.1-1.0 part of chain transfer agent into 5-10 parts of water to prepare a chain transfer agent solution,
c) under stirring, adding 80-95 parts of polyether monomer, 0.25-2.5 parts of hydrogen peroxide and 50-100 parts of water into a reactor, and controlling the reaction temperature to be 5-35 ℃; respectively dripping acrylic acid solution, reducing agent solution and chain transfer agent solution for 30-60min, and continuously reacting for 60min after dripping is finished to obtain the product.
Wherein, the acid compound is one of glyoxylic acid or pyruvic acid;
the chemical structural formula of the polyether monomer is as follows:
CH2＝CH-O-CH2CH2-O-(CH2CH2O)m-H，
m is an integer, and m is more than or equal to 20 and less than or equal to 100;
the chain transfer agent is one of thioglycolic acid or mercaptopropionic acid;
the polyether monomer is preferably ethylene glycol monovinyl polyglycol ether.
The invention also provides the following examples and comparative examples:
TABLE 1 Reductant Components Table
In specific practice, the preparation of the reducing agent is provided as follows according to the contents of the table above:
reducing agent A
Adding 65 parts of glyoxylic acid, 135 parts of sodium hydroxide and 400 parts of water into a reactor, stirring for dissolving, heating to 20 ℃, slowly adding 150 parts of sodium hydrosulfite while stirring, and continuously reacting for 300min after the sodium hydrosulfite is added to obtain a reducing agent A with the mass concentration of 46.67%.
Reducing agent B
Adding 70 parts of pyruvic acid, 150 parts of sodium hydroxide and 400 parts of water into a reactor, stirring for dissolving, heating to 100 ℃, slowly adding 200 parts of sodium hydrosulfite under stirring, and continuously reacting for 30min after the sodium hydrosulfite is added to obtain a reducing agent B with the mass concentration of 51.22%.
Reducing agent C
a) Adding 85 parts of glyoxylic acid, 100 parts of sodium hydroxide and 400 parts of water into a reactor, stirring for dissolving, heating to 60 ℃, slowly adding 185 parts of sodium hydrosulfite while stirring, and continuously reacting for 130min after the sodium hydrosulfite is added to obtain a reducing agent C with the mass concentration of 48.05%.
Table 2 components of examples
The following examples are provided according to the above table:
example 1
Adding 0.15 part of the prepared reducing agent A into 5 parts of water to prepare a reducing agent solution; adding 10 parts of acrylic acid into 10 parts of water to prepare an acrylic acid solution; adding 1 part of thioglycolic acid into 5 parts of water to prepare a chain transfer agent solution;
under stirring, adding 95 parts of polyether monomer, 2.5 parts of hydrogen peroxide and 100 parts of water into a reactor, and controlling the reaction temperature to be 5 ℃; and respectively dropwise adding an acrylic acid solution, a reducing agent solution and a chain transfer agent solution for 30min, and continuously reacting for 60min after dropwise adding is finished to obtain the polycarboxylic acid polymer with the mass concentration of 46.42%.
Example 2
Adding 0.45 part of the prepared reducing agent B into 7 parts of water to prepare a reducing agent solution; adding 8 parts of acrylic acid into 8 parts of water to prepare an acrylic acid solution; adding 0.7 part of mercaptopropionic acid into 10 parts of water to prepare a chain transfer agent solution;
under stirring, adding 85 parts of polyether monomer, 2.0 parts of hydrogen peroxide and 50 parts of water into a reactor, and controlling the reaction temperature to be 10 ℃; and respectively dropwise adding an acrylic acid solution, a reducing agent solution and a chain transfer agent solution for 60min, and continuously reacting for 60min after dropwise adding is finished to obtain the 55.01 mass percent polycarboxylic acid polymer.
Example 3
Adding 0.85 part of the prepared reducing agent A into 7 parts of water to prepare a reducing agent solution; adding 5 parts of acrylic acid into 5 parts of water to prepare an acrylic acid solution; 0.4 part of thioglycolic acid is added into 7 parts of water to prepare a chain transfer agent solution;
under stirring, adding 90 parts of polyether monomer, 1.5 parts of hydrogen peroxide and 75 parts of water into a reactor, and controlling the reaction temperature to be 12 ℃; and respectively dropwise adding an acrylic acid solution, a reducing agent solution and a chain transfer agent solution for 30min, and continuously reacting for 60min after dropwise adding is finished to obtain the polycarboxylic acid polymer with the mass concentration of 50.20%.
Example 4
Adding 1.25 parts of the prepared reducing agent C into 8 parts of water to prepare a reducing agent solution; adding 6 parts of acrylic acid into 6 parts of water to prepare an acrylic acid solution; adding 0.3 part of mercaptopropionic acid into 7 parts of water to prepare a chain transfer agent solution;
under stirring, adding 80 parts of polyether monomer, 0.5 part of hydrogen peroxide and 65 parts of water into a reactor, and controlling the reaction temperature to be 15 ℃; and respectively dropwise adding an acrylic acid solution, a reducing agent solution and a chain transfer agent solution for 60min, and continuously reacting for 60min after dropwise adding is finished to obtain the polycarboxylic acid polymer with the mass concentration of 50.30%.
Example 5
Adding 1.50 parts of the prepared reducing agent C into 10 parts of water to prepare a reducing agent solution; adding 8 parts of acrylic acid into 8 parts of water to prepare an acrylic acid solution; 0.1 part of thioglycolic acid is added into 10 parts of water to prepare a chain transfer agent solution;
under stirring, adding 90 parts of polyether monomer, 0.25 part of hydrogen peroxide and 70 parts of water into a reactor, and controlling the reaction temperature to be 30 ℃; and respectively dropwise adding an acrylic acid solution, a reducing agent solution and a chain transfer agent solution for 30min, and continuously reacting for 60min after the dropwise adding is finished to obtain the 50.34 mass percent polycarboxylic acid polymer.
TABLE 3 comparative example Components Table
The comparative examples shown below are provided according to the above table:
comparative example 1
Adding 0.45 part of prepared ascorbic acid into 7 parts of water to prepare a reducing agent solution; adding 8 parts of acrylic acid into 8 parts of water to prepare an acrylic acid solution; adding 0.7 part of mercaptopropionic acid into 10 parts of water to prepare a chain transfer agent solution;
under stirring, adding 85 parts of polyether monomer, 2.0 parts of hydrogen peroxide and 50 parts of water into a reactor, and controlling the reaction temperature to be 10 ℃; and respectively dropwise adding an acrylic acid solution, a reducing agent solution and a chain transfer agent solution for 60min, and continuously reacting for 60min after dropwise adding is finished to obtain the 55.01 mass percent polycarboxylic acid polymer.
Comparative example 2
Adding 0.45 part of the prepared reducing agent B into 7 parts of water to prepare a reducing agent solution; adding 8 parts of acrylic acid into 8 parts of water to prepare an acrylic acid solution; adding 0.7 part of mercaptopropionic acid into 10 parts of water to prepare a chain transfer agent solution;
under stirring, adding 85 parts of 3-methylbut-3-enyl polyglycol ether and 2.0 parts of hydrogen peroxide into a reactor, adding 50 parts of water, and controlling the reaction temperature to be 10 ℃; and respectively dropwise adding an acrylic acid solution, a reducing agent solution and a chain transfer agent solution for 60min, and continuously reacting for 60min after dropwise adding is finished to obtain the 55.01 mass percent polycarboxylic acid polymer.
Comparative example 3
Adding 0.45 part of prepared ascorbic acid into 7 parts of water to prepare a reducing agent solution; adding 8 parts of acrylic acid into 8 parts of water to prepare an acrylic acid solution; adding 0.7 part of mercaptopropionic acid into 10 parts of water to prepare a chain transfer agent solution;
under stirring, adding 85 parts of 3-methylbut-3-enyl polyglycol ether and 2.0 parts of hydrogen peroxide into a reactor, adding 50 parts of water, and controlling the reaction temperature to be 10 ℃; and respectively dropwise adding an acrylic acid solution, a reducing agent solution and a chain transfer agent solution for 60min, and continuously reacting for 60min after dropwise adding is finished to obtain the 55.01 mass percent polycarboxylic acid polymer.
It should be noted that the specific parameters or some common reagents in the above embodiments are specific examples or preferred embodiments of the present invention, and are not limited thereto; those skilled in the art can adapt the same within the spirit and scope of the present invention.
The polycarboxylic acid polymers synthesized in the above examples 1 to 5 and comparative examples 1 to 3 were subjected to molecular weight analysis test using a gel chromatograph, and the product was subjected to a net slurry test according to GB/T8077-2012 "test method for homogeneity of concrete admixture", wherein 300g of cement, 87g of water, and 0.2% of polycarboxylic acid was added based on the mass of cement, and the cement was Fujian cement.
TABLE 4 test results of examples and comparative examples
As can be seen from the test results in Table 4, examples 1-5 synthesized according to the present invention are superior to the comparative examples in conversion and working performance;
compared with the comparative examples 1, 2 and 3, the embodiment 2 shows that compared with the common reducing agent, the reducing agent for improving the monomer conversion rate provided by the invention is adopted, so that the conversion rate is obviously improved in the process of preparing the polycarboxylic acid polymer, and the performance is also improved; meanwhile, the polyether macromonomer with high reactivity is matched to realize the polymerization reaction at low temperature, so that a product with high monomer conversion rate is obtained, and the performance of the prepared product is more excellent.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A reducing agent for increasing monomer conversion, comprising the following components: acid compounds, sodium hydroxide, sodium hydrosulfite and water.
2. The reducing agent for increasing monomer conversion according to claim 1, wherein: the acid compound is glyoxylic acid or pyruvic acid.
3. The reducing agent for improving monomer conversion according to claim 1, comprising the following components in parts by mass:
4. a method for preparing a reducing agent for improving monomer conversion, comprising the steps of: mixing acid compound, sodium hydroxide and water, heating to 20-100 deg.C, adding sodium dithionite, and reacting.
5. A redox process for preparing a high monomer conversion polycarboxylic acid comprising the steps of: the polyether is prepared by the copolymerization reaction of a polyether monomer, unsaturated carboxylic acid, a reducing agent, an oxidizing agent and a chain transfer agent;
wherein the reducing agent is the reducing agent for improving monomer conversion according to any one of claims 1 to 3, or the reducing agent prepared by the method for preparing the reducing agent for improving monomer conversion according to claim 4.
6. The redox process for preparing high monomer conversion polycarboxylic acid according to claim 5, characterized in that it comprises the following components in parts by mass:
7. the redox process of claim 5 or 6 for the preparation of high monomer conversion polycarboxylic acids characterized in that: the structural formula of the polyether monomer is as follows:
CH2＝CH-O-CH2CH2-O-(CH2CH2O)m-H；
wherein m is an integer, and m is not less than 20 and not more than 100.
8. The redox process of claim 5 or 6 for the preparation of high monomer conversion polycarboxylic acids characterized in that: the chain transfer agent is thioglycolic acid or mercaptopropionic acid.
9. The redox process of claim 5 or 6 for the preparation of high monomer conversion polycarboxylic acids characterized in that: the unsaturated carboxylic acid is acrylic acid; the oxidant is hydrogen peroxide.
10. The redox process for preparing high monomer conversion polycarboxylic acids according to claim 5 or 6, characterized in that the temperature of the polymerization reaction is 5-35 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011446522.6A CN112708063A (en) | 2020-12-08 | 2020-12-08 | Reducing agent for improving monomer conversion rate, preparation method thereof and redox method for preparing polycarboxylic acid with high monomer conversion rate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011446522.6A CN112708063A (en) | 2020-12-08 | 2020-12-08 | Reducing agent for improving monomer conversion rate, preparation method thereof and redox method for preparing polycarboxylic acid with high monomer conversion rate |
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Citations (3)
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| CN1237156A (en) * | 1997-10-02 | 1999-12-01 | L·布鲁克曼两合公司 | Sulphinic acid derivatives, method for producing them, and their use |
| CN109705282A (en) * | 2019-01-08 | 2019-05-03 | 山西佳维新材料股份有限公司 | A kind of preparation method of novel polyether synthesis superelevation water reducing type polycarboxylate water-reducer |
| CN110591015A (en) * | 2019-09-29 | 2019-12-20 | 贵州石博士科技有限公司 | Polycarboxylate superplasticizer and method for rapidly synthesizing same at normal temperature |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1237156A (en) * | 1997-10-02 | 1999-12-01 | L·布鲁克曼两合公司 | Sulphinic acid derivatives, method for producing them, and their use |
| CN109705282A (en) * | 2019-01-08 | 2019-05-03 | 山西佳维新材料股份有限公司 | A kind of preparation method of novel polyether synthesis superelevation water reducing type polycarboxylate water-reducer |
| CN110591015A (en) * | 2019-09-29 | 2019-12-20 | 贵州石博士科技有限公司 | Polycarboxylate superplasticizer and method for rapidly synthesizing same at normal temperature |
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Application publication date: 20210427 |