CN111154045A - Ultralow-temperature polycarboxylate superplasticizer and synthesis method thereof - Google Patents
Ultralow-temperature polycarboxylate superplasticizer and synthesis method thereof Download PDFInfo
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 44
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 34
- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910001868 water Inorganic materials 0.000 claims abstract description 90
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000007800 oxidant agent Substances 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 191
- 238000003756 stirring Methods 0.000 claims description 103
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 49
- 230000003472 neutralizing effect Effects 0.000 claims description 47
- 238000002156 mixing Methods 0.000 claims description 40
- 238000007865 diluting Methods 0.000 claims description 33
- 239000003085 diluting agent Substances 0.000 claims description 26
- 238000006386 neutralization reaction Methods 0.000 claims description 22
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 14
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 9
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- 235000002906 tartaric acid Nutrition 0.000 claims description 7
- 239000011975 tartaric acid Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 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 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 5
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 claims description 4
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 description 10
- 239000004568 cement Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004576 sand Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- C08F4/40—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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an ultralow-temperature polycarboxylate superplasticizer and a synthesis method thereof, and solves the technical problems that in the prior art, a high-temperature method is adopted to synthesize the polycarboxylate superplasticizer, the reaction temperature is generally above 40 ℃, the energy consumption is high, and the cost is not easy to control. The preparation method comprises the following raw materials in parts by weight: f-1088275-300; 475.7-525.4 parts of water; 30-40.1 parts of acrylic acid; 0.5-1.7 parts of a reducing agent; 2.6-3.4 parts of an oxidant; 1.2-2 parts of a catalyst. The ultralow-temperature polycarboxylate superplasticizer and the synthesis method provided by the invention can be used for synthesizing the polycarboxylate superplasticizer at normal temperature, and can still be used for synthesizing the polycarboxylate superplasticizer even if the temperature is as low as 15 ℃, so that the energy consumption is greatly reduced, and the production cost is favorably reduced; and the synthesized polycarboxylate superplasticizer has excellent performance, and has almost no difference compared with the polycarboxylate superplasticizer produced at high temperature.
Description
Technical Field
The invention relates to a polycarboxylate superplasticizer, and particularly relates to an ultralow-temperature polycarboxylate superplasticizer and a synthesis method thereof.
Background
The polycarboxylate water reducing agent is a high-performance water reducing agent, and is a cement dispersing agent in the application of cement concrete. The method is widely applied to projects such as highways, bridges, dams, tunnels, high-rise buildings and the like.
In the prior art, a high-temperature method is generally adopted to synthesize the polycarboxylic acid water reducing agent, although the reaction time can be shortened, the reaction temperature is generally above 40 ℃, and the energy consumption is high, so that the cost is not favorably controlled.
The applicant has found that the prior art has at least the following technical problems:
in the prior art, a high-temperature method is adopted to synthesize the polycarboxylate superplasticizer, the reaction temperature is generally above 40 ℃, the energy consumption is high, and the cost is not easy to control.
Disclosure of Invention
The invention aims to provide an ultralow-temperature polycarboxylate superplasticizer and a synthesis method thereof, and aims to solve the technical problems that in the prior art, a high-temperature method is adopted to synthesize the polycarboxylate superplasticizer, the reaction temperature is generally above 40 ℃, the energy consumption is high, and the cost is not easy to control. The technical effects that can be produced by the preferred technical scheme in the technical schemes provided by the invention are described in detail in the following.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides an ultralow-temperature polycarboxylate superplasticizer which is prepared from the following raw materials in parts by weight:
further, the weight parts of the raw materials are respectively as follows:
further, the weight parts of the raw materials are respectively as follows:
further, the reducing agent is any one or more of VC, tartaric acid and sodium formaldehyde sulfoxylate.
Further, the oxidant is any one or more of hydrogen peroxide, ammonium persulfate and sodium hypophosphite.
Further, the catalyst is any one or more of mercaptoethanol, mercaptopropionic acid, methylpropanesulfonic acid, thioglycolic acid and mercaptopropionic acid.
Further, F-1088 is methyl allyl polyoxyethylene ether.
The invention provides a synthesis method of an ultralow-temperature polycarboxylate superplasticizer, which sequentially comprises the following steps:
(1) the raw materials were prepared as follows, respectively, as raw materials to be added directly to the flask, raw materials to be provided with the material A, raw materials to be provided with the material B, and raw materials to be provided with the neutralizing diluent:
① raw materials added directly to the flask:
f-1088, water and a part of acrylic acid;
or, F-1088, water, and an oxidizing agent;
② preparation of raw materials of A material:
part of acrylic acid, a catalyst, a reducing agent and water;
or all of acrylic acid, catalyst, reducing agent and water;
③ preparing raw materials of material B:
an oxidizing agent and water;
or a reducing agent and water;
④ preparing neutralizing diluent material comprising sodium hydroxide and water;
wherein, the oxidant is directly added into the flask or is prepared in the material B;
the reducing agent is configured in the material A or the material B;
adding a part of acrylic acid into a flask, and adding the rest part when preparing the material A; or all the acrylic acid is prepared in the material A;
(2) preparing a material A, a material B and a neutralization diluent:
① preparing material A, mixing the raw materials and stirring uniformly to obtain material A;
② preparing material B, mixing the raw materials and stirring to obtain material B;
③ preparing neutralizing and diluting material, mixing the materials for preparing neutralizing and diluting material, and stirring to obtain neutralizing and diluting material;
(3) adding F-1088 and water into a flask, and uniformly stirring;
(4) stopping heating when the temperature of the reaction liquid in the flask reaches 15-35 ℃, adding an oxidant, acrylic acid or a reducing agent into the flask under stirring, continuously stirring and reacting for 10 min;
(5) then, the material A is dripped under stirring, and the dripping time is 120-150 min;
(7) then, the material B is dropwise added under stirring, wherein the dropwise adding time is 180-200 min; then preserving the temperature of the reaction solution at the end of the dropwise adding, wherein the preserving time is 60-180 min;
(6) and finally, adding the neutralization diluent, and uniformly stirring to obtain the finished product of the ultralow-temperature polycarboxylate superplasticizer.
Based on the technical scheme, the embodiment of the invention can at least produce the following technical effects:
the ultralow-temperature polycarboxylate superplasticizer and the synthesis method provided by the invention can be used for synthesizing the polycarboxylate superplasticizer at normal temperature, and can still be used for synthesizing the polycarboxylate superplasticizer even if the temperature is as low as 15 ℃, so that the energy consumption is greatly reduced, and the production cost is favorably reduced; and the synthesized polycarboxylate superplasticizer has excellent performance, and has almost no difference compared with the polycarboxylate superplasticizer produced at high temperature.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
Example 1:
oxidizing agent: hydrogen peroxide is adopted;
reducing agent: VC is adopted;
catalyst: mercaptoethanol is used.
1.1 starting materials (as shown in table 1 below):
TABLE 1 example 1 raw materials (units of raw materials: g)
1.2 the preparation method comprises the following steps:
the method sequentially comprises the following steps:
(1) preparing according to the raw material proportion in the table 1:
① adding F-1088, water and hydrogen peroxide solution into the flask;
② preparing raw materials of material A, including acrylic acid, mercaptoethanol, VC and water;
③ neutralizing the diluted feedstock;
(2) preparing a material A and a neutralization diluent:
① preparing material A, mixing the raw materials and stirring uniformly to obtain material A;
② preparing neutralizing and diluting material, mixing the materials for preparing neutralizing and diluting material, and stirring to obtain neutralizing and diluting material;
(3) adding F-1088 and water into a flask, and heating the reaction solution in the flask to 35 ℃ in a water bath under stirring;
(4) stopping heating when the temperature of the reaction liquid in the flask reaches 35 ℃, adding hydrogen peroxide into the flask while stirring, continuously stirring and reacting for 10 min;
(5) then, dropwise adding the material A under stirring for 120min, and then keeping the temperature of the reaction solution at the end of dropwise adding for 180 min;
(6) and finally, adding the neutralization diluent, and uniformly stirring to obtain the finished product of the ultralow-temperature polycarboxylate superplasticizer.
Example 2:
oxidizing agent: hydrogen peroxide is adopted;
reducing agent: VC is adopted;
catalyst: mercaptopropionic acid was used.
2.1 starting materials (as shown in Table 2 below):
table 2 example 2 raw materials (units of each raw material: g)
2.2 the preparation method comprises the following steps:
the method sequentially comprises the following steps:
(1) preparing according to the raw material proportion in the table 1:
① raw materials F-1088, water and acrylic acid were added directly to the flask;
② preparing raw materials of material A, including acrylic acid, mercaptopropionic acid, VC and water;
③ preparing raw materials of material B, including hydrogen peroxide and water;
④ neutralizing the diluted feedstock;
(2) preparing a material A, a material B and a neutralization diluent:
① preparing material A, mixing the raw materials and stirring uniformly to obtain material A;
② preparing material B, mixing the raw materials and stirring to obtain material B;
③ preparing neutralizing and diluting material, mixing the materials for preparing neutralizing and diluting material, and stirring to obtain neutralizing and diluting material;
(3) adding F-1088 and water into a flask, and heating the reaction solution in the flask to 35 ℃ in a water bath under stirring;
(4) stopping heating when the temperature of the reaction liquid in the flask reaches 35 ℃, adding acrylic acid into the flask while stirring, continuously stirring and reacting for 10 min;
(5) then, the material A is dripped under stirring for 150min,
(5) dropwise adding the material B under stirring for 180min, and then keeping the temperature of the reaction solution at the end of dropwise adding for 60 min;
(6) and finally, adding the neutralization diluent, and uniformly stirring to obtain the finished product of the ultralow-temperature polycarboxylate superplasticizer.
Example 3:
oxidizing agent: hydrogen peroxide is adopted;
reducing agent: VC is adopted;
catalyst: mercaptoethanol is used.
3.1 starting materials (as shown in Table 3 below)
Table 3 example 3 raw materials (units of each raw material: g)
3.2 the preparation method comprises the following steps:
the method sequentially comprises the following steps:
(1) preparing according to the raw material proportion in the table 1:
① raw materials F-1088, water and acrylic acid were added directly to the flask;
② preparing raw materials of material A, including acrylic acid, mercaptoethanol, VC and water;
③ preparing raw materials of material B, including hydrogen peroxide and water;
④ neutralizing the diluted feedstock;
(2) preparing a material A, a material B and a neutralization diluent:
① preparing material A, mixing the raw materials and stirring uniformly to obtain material A;
② preparing material B, mixing the raw materials and stirring to obtain material B;
③ preparing neutralizing and diluting material, mixing the materials for preparing neutralizing and diluting material, and stirring to obtain neutralizing and diluting material;
(3) adding F-1088 and water into a flask, and heating the reaction solution in the flask to 35 ℃ in a water bath under stirring;
(4) stopping heating when the temperature of the reaction liquid in the flask reaches 35 ℃, adding acrylic acid into the flask while stirring, continuously stirring and reacting for 10 min;
(5) then, the material A is dripped under stirring for 150min,
(5) dropwise adding the material B under stirring for 180min, and then keeping the temperature of the reaction solution at the end of dropwise adding for 60 min;
(6) and finally, adding the neutralization diluent, and uniformly stirring to obtain the finished product of the ultralow-temperature polycarboxylate superplasticizer.
Example 4:
oxidizing agent: hydrogen peroxide is adopted;
reducing agent: VC is adopted;
catalyst: mercaptoethanol is used.
4.1 starting materials (as shown in Table 4 below):
table 4 example 4 materials (units of each material are: g)
4.2 the preparation method comprises the following steps:
the method sequentially comprises the following steps:
(1) preparing according to the raw material proportion in the table 1:
① raw materials F-1088, water and acrylic acid were added directly to the flask;
② preparing raw materials of material A, including acrylic acid, mercaptoethanol, VC and water;
③ preparing raw materials of material B, including hydrogen peroxide and water;
④ neutralizing the diluted feedstock;
(2) preparing a material A, a material B and a neutralization diluent:
① preparing material A, mixing the raw materials and stirring uniformly to obtain material A;
② preparing material B, mixing the raw materials and stirring to obtain material B;
③ preparing neutralizing and diluting material, mixing the materials for preparing neutralizing and diluting material, and stirring to obtain neutralizing and diluting material;
(3) adding F-1088 and water into a flask, and uniformly stirring;
(4) the temperature of the reaction liquid in the flask is 15 ℃ at normal temperature, acrylic acid is added into the flask under stirring, and the reaction is carried out for 10min under continuous stirring;
(5) then, the material A is dripped under stirring for 150min,
(5) dropwise adding the material B under stirring for 180min, and then keeping the temperature of the reaction solution at the end of dropwise adding for 60 min;
(6) and finally, adding the neutralization diluent, and uniformly stirring to obtain the finished product of the ultralow-temperature polycarboxylate superplasticizer.
Example 5:
oxidizing agent: hydrogen peroxide is adopted;
reducing agent: VC is adopted;
catalyst: mercaptoethanol is used.
5.1 starting materials (as shown in Table 5 below):
TABLE 5 example 5 raw materials (units of raw materials: g)
5.2 the preparation method comprises the following steps:
the method sequentially comprises the following steps:
(1) preparing according to the raw material proportion in the table 1:
① raw materials F-1088, water and acrylic acid were added directly to the flask;
② preparing raw materials of material A, including acrylic acid, mercaptoethanol, VC and water;
③ preparing raw materials of material B, including hydrogen peroxide and water;
④ neutralizing the diluted feedstock;
(2) preparing a material A, a material B and a neutralization diluent:
① preparing material A, mixing the raw materials and stirring uniformly to obtain material A;
② preparing material B, mixing the raw materials and stirring to obtain material B;
③ preparing neutralizing and diluting material, mixing the materials for preparing neutralizing and diluting material, and stirring to obtain neutralizing and diluting material;
(3) adding F-1088 and water into a flask, uniformly stirring, and heating the reaction solution in the flask to 35 ℃ in a water bath under the condition of stirring;
(4) the temperature of the reaction liquid in the flask is 35 ℃ at normal temperature, the heating is stopped, acrylic acid is added into the flask under stirring, and the reaction is carried out for 10min under continuous stirring;
(5) then, the material A is dripped under stirring for 150min,
(5) dropwise adding the material B under stirring for 180min, and then keeping the temperature of the reaction solution at the end of dropwise adding for 60 min;
(6) and finally, adding the neutralization diluent, and uniformly stirring to obtain the finished product of the ultralow-temperature polycarboxylate superplasticizer.
Example 6:
oxidizing agent: hydrogen peroxide is adopted;
reducing agent: VC is adopted;
catalyst: mercaptoethanol is used.
6.1 starting materials (as shown in Table 6 below):
TABLE 6 example 6 materials (units of each material are: g)
6.2 the preparation method comprises the following steps:
the method sequentially comprises the following steps:
(1) preparing according to the raw material proportion in the table 1:
① adding F-1088, water, acrylic acid and hydrogen peroxide into the flask;
② preparing raw materials of material A, including acrylic acid, mercaptoethanol, VC and water;
③ preparing raw materials of material B, including hydrogen peroxide and water;
④ neutralizing the diluted feedstock;
(2) preparing a material A, a material B and a neutralization diluent:
① preparing material A, mixing the raw materials and stirring uniformly to obtain material A;
② preparing material B, mixing the raw materials and stirring to obtain material B;
③ preparing neutralizing and diluting material, mixing the materials for preparing neutralizing and diluting material, and stirring to obtain neutralizing and diluting material;
(3) adding F-1088 and water into a flask, and uniformly stirring;
(4) the temperature of the reaction liquid in the flask is 35 ℃ at normal temperature, acrylic acid is added into the flask under stirring, and the reaction is carried out for 10min under continuous stirring;
(5) then, the material A is dropwise added under stirring, wherein the dropwise adding time is 150 min; meanwhile, after dropping the material A for 60min, adding hydrogen peroxide (prepared from the raw materials directly added into the flask) into the flask;
(6) then, dropwise adding the material B under stirring for 180 min; then preserving the temperature of the reaction solution at the end of the dropwise adding, wherein the preserving time is 60 min;
(7) and finally, adding the neutralization diluent, and uniformly stirring to obtain the finished product of the ultralow-temperature polycarboxylate superplasticizer.
Example 7:
oxidizing agent: adopting sodium hypophosphite, hydrogen peroxide and ammonium persulfate;
reducing agent: adopting a rongalite;
catalyst: methyl propane sulfonic acid is used.
7.1 starting materials (as shown in Table 7 below):
table 7 example 7 materials (units of each material are: g)
7.2 the preparation method comprises the following steps:
the method sequentially comprises the following steps:
(1) preparing according to the raw material proportion in the table 1:
① adding F-1088, water, sodium hypophosphite, hydrogen peroxide and ammonium persulfate;
② preparing raw materials of material A, including acrylic acid, methyl propanesulfonic acid and water;
③ preparing raw materials of material B, namely sodium formaldehyde sulfoxylate and water;
④ neutralizing the diluted feedstock;
(2) preparing a material A and a material B:
① preparing material A, mixing the raw materials and stirring uniformly to obtain material A;
② preparing material B, mixing the raw materials and stirring to obtain material B;
(3) adding F-1088 and water into a flask, and uniformly stirring;
(4) the temperature of the reaction liquid in the flask is 21 ℃ at normal temperature, sodium hypophosphite and hydrogen peroxide are added into the flask together under stirring, and the mixture is continuously stirred and reacts for 5 min; aims to firstly generate oxidation-reduction reaction so as to improve the temperature of a reaction kettle and increase an activation system;
(5) then, the material A is dropwise added under stirring, and the dropwise adding time is 180 min; meanwhile, after dropping the material A for 60min, adding ammonium persulfate into the flask;
(5) dropwise adding the material B under stirring for 200min, and then keeping the temperature of the reaction solution at the end of dropwise adding for 60 min;
(6) and finally, adding the neutralized and diluted raw material (water), and uniformly stirring to obtain the finished product of the ultralow-temperature polycarboxylate superplasticizer.
Example 8:
oxidizing agent: hydrogen peroxide is adopted;
reducing agent: tartaric acid is adopted;
catalyst: mercaptoethanol is used.
8.1 starting materials (as shown in Table 8 below):
table 8 example 8 materials (units of each material are: g)
8.2 the preparation method comprises the following steps:
the method sequentially comprises the following steps:
(1) preparing according to the raw material proportion in the table 1:
① raw materials F-1088, water and acrylic acid were added directly to the flask;
② preparing raw materials of material A, including acrylic acid, thioglycolic acid, tartaric acid and water;
③ preparing raw materials of material B, including hydrogen peroxide and water;
④ neutralizing the diluted feedstock;
(2) preparing a material A, a material B and a neutralization diluent:
① preparing material A, mixing the raw materials and stirring uniformly to obtain material A;
② preparing material B, mixing the raw materials and stirring to obtain material B;
③ preparing neutralizing and diluting material, mixing the materials for preparing neutralizing and diluting material, and stirring to obtain neutralizing and diluting material;
(3) adding F-1088 and water into a flask, and uniformly stirring;
(4) adding acrylic acid into a flask under stirring at normal temperature, continuously stirring and reacting for 10 min;
(5) then, the material A is dripped under stirring, the temperature of the material A when dripping is started is 23.5 ℃, the dripping time of the material A is 150min,
(5) dropwise adding the material B under stirring for 180min, and then keeping the temperature of the reaction solution at the end of dropwise adding for 60 min;
(6) and finally, adding the neutralization diluent, and uniformly stirring to obtain the finished product of the ultralow-temperature polycarboxylate superplasticizer.
Example 9:
oxidizing agent: hydrogen peroxide is adopted;
reducing agent: tartaric acid is adopted;
catalyst: mercaptoethanol is used.
9.1 starting materials (as shown in Table 9 below):
TABLE 9 example 9 raw materials (units of raw materials: g)
9.2 the preparation method comprises the following steps:
the method sequentially comprises the following steps:
(1) preparing according to the raw material proportion in the table 1:
① raw materials F-1088, water and acrylic acid were added directly to the flask;
② preparing raw materials of material A, including acrylic acid, thioglycolic acid, tartaric acid and water;
③ preparing raw materials of material B, including hydrogen peroxide and water;
④ neutralizing the diluted feedstock;
(2) preparing a material A, a material B and a neutralization diluent:
① preparing material A, mixing the raw materials and stirring uniformly to obtain material A;
② preparing material B, mixing the raw materials and stirring to obtain material B;
③ preparing neutralizing and diluting material, mixing the materials for preparing neutralizing and diluting material, and stirring to obtain neutralizing and diluting material;
(3) adding F-1088 and water into a flask, and uniformly stirring;
(4) adding acrylic acid into a flask under stirring at normal temperature, continuously stirring and reacting for 10 min;
(5) then, the material A is dripped under stirring, the temperature of the material A when dripping is started is 13 ℃, the dripping time of the material A is 150min,
(5) dropwise adding the material B under stirring for 180min, and then keeping the temperature of the reaction solution at the end of dropwise adding for 60 min;
(6) and finally, adding the neutralization diluent, and uniformly stirring to obtain the finished product of the ultralow-temperature polycarboxylate superplasticizer.
Comparative example:
oxidizing agent: ammonium persulfate is adopted;
reducing agent: VC is adopted;
catalyst: mercaptopropionic acid was used.
10.1 starting materials (as shown in table 10 below):
TABLE 10 comparative example materials (each raw material unit is: g)
10.2 the preparation method comprises the following steps:
the method sequentially comprises the following steps:
(1) preparing according to the raw material proportion in the table 1:
① raw materials F-1088, water and acrylic acid were added directly to the flask;
② preparing raw materials of material A, including acrylic acid, mercaptopropionic acid, tartaric acid and water;
③ preparing raw materials of material B, including hydrogen peroxide and water;
④ neutralizing the diluted feedstock;
(2) preparing a material A, a material B and a neutralization diluent:
① preparing material A, mixing the raw materials and stirring uniformly to obtain material A;
② preparing material B, mixing the raw materials and stirring to obtain material B;
③ preparing neutralizing and diluting material, mixing the materials for preparing neutralizing and diluting material, and stirring to obtain neutralizing and diluting material;
(3) adding F-1088, water and acrylic acid to a flask, stirring and heating to 50 ℃;
(5) heating to 50 deg.C, adding material A dropwise under stirring for 150min,
(5) dropwise adding the material B under stirring for 180min, and then keeping the temperature of the reaction solution at the end of dropwise adding for 60 min;
(6) and (3) cooling to below 40 ℃ after heat preservation, finally adding a neutralization diluent, and uniformly stirring to obtain the finished product of the ultralow-temperature polycarboxylate superplasticizer.
Experimental example:
1. the water reducing rate was determined according to the relevant regulations of GB8076-2008 "concrete Admixture". The water reducing rate of examples 1 to 9 and comparative examples was measured by using the same amount. Wherein the reference cement is 300 g, the water is 87 g, and the mixing amount of the water reducing agent is 0.09% of the glue material; the reference comparative example used 300 grams of reference cement and 105 grams of water.
2. The fluidity of the mortar is 450 g of standard cement, 1350 g of standard sand, 165 g of water (the water reducing rate is reduced by 26.5%) and the mixing amount of the water reducing agent is 1% (the breaking strength is 18%), namely 4.5 g according to GB/T8077-2012 'test method for homogeneity of concrete admixture'; the reference comparative example used 450 g of reference cement, 225 g of water and 1350 g of standard sand.
3. The concrete mixing proportion adopts the standard of railway CRCC certification, the 15L concrete mixing proportion is 4.95 kg of benchmark cement, 10.55 kg of high-quality river sand, 6.89 kg of small stone, 10.32 kg of large stone, 2.9 kg of water (the water content of the river sand and the stone is less than or equal to 0.5 percent, so the water content is not calculated any more), the mixing amount of the water reducing agent is 1 percent, namely 49.5 g (the bending strength is 18 percent, the mixing amount of the air entraining agent is 0.05 percent), and the size of the concrete test model is 150 multiplied by 150 mm.
4. According to the slump test method, referring to GB/T50080-2016 standard of common concrete mixture performance test method, a test block is poured after slump is measured, and pouring is carried out at one time, namely, the test block is pounded. The baseline contained no water reduction.
The results of the experiment are shown in table 1 below:
as can be seen from Table 1: the ultra-low temperature polycarboxylate water reducers synthesized in examples 1 to 9 (normal temperature synthesis) were excellent in performance, and were almost not different from the polycarboxylate water reducers synthesized at high temperature in comparative examples.
TABLE 1 results of the experiment
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention.
Claims (8)
1. An ultra-low temperature polycarboxylate water reducing agent which is characterized in that: the preparation method comprises the following raw materials in parts by weight:
f-1088275-300 parts;
475.7-525.4 parts of water;
30-40.1 parts of acrylic acid;
0.5-1.7 parts of a reducing agent;
2.6-6.8 parts of an oxidant;
1.2-2 parts of a catalyst.
2. The ultra-low temperature polycarboxylate water reducer of claim 1 is characterized in that: the weight parts of the raw materials are respectively as follows:
300 portions of F-1088280;
504-520.7 parts of water;
40.1 parts of acrylic acid;
0.5-1 part of reducing agent;
2.6-5.4 parts of an oxidant;
and 2 parts of a catalyst.
3. The ultra-low temperature polycarboxylate water reducer of claim 2, which is characterized in that: the weight parts of the raw materials are respectively as follows:
f-1088300 parts;
520.7 parts of water;
40.1 parts of acrylic acid;
0.5 part of a reducing agent;
2.7 parts of an oxidizing agent;
and 2 parts of a catalyst.
4. The ultra-low temperature polycarboxylate water reducer according to any one of the claims 1-3, characterized in that: the reducing agent is any one or more of VC, tartaric acid and sodium formaldehyde sulfoxylate.
5. The ultra-low temperature polycarboxylate water reducer according to any one of the claims 1-3, characterized in that: the oxidant is any one or more of hydrogen peroxide, ammonium persulfate and sodium hypophosphite.
6. The ultra-low temperature polycarboxylate water reducer according to any one of the claims 1-3, characterized in that: the catalyst is any one or more of mercaptoethanol, mercaptopropionic acid, methylpropanesulfonic acid, thioglycolic acid and mercaptopropionic acid.
7. The ultra-low temperature polycarboxylate water reducer according to any one of the claims 1-3, characterized in that: and F-1088 is methyl allyl polyoxyethylene ether.
8. The synthesis method of the ultra-low temperature polycarboxylate superplasticizer according to any one of claims 1 to 7, characterized by comprising the following steps: the method sequentially comprises the following steps:
(1) the raw materials were prepared as follows, respectively, as raw materials to be added directly to the flask, raw materials to be provided with the material A, raw materials to be provided with the material B, and raw materials to be provided with the neutralizing diluent:
① raw materials added directly to the flask:
f-1088, water and a part of acrylic acid;
or, F-1088, water, and an oxidizing agent;
② preparation of raw materials of A material:
part of acrylic acid, a catalyst, a reducing agent and water;
or all of acrylic acid, catalyst, reducing agent and water;
③ preparing raw materials of material B:
an oxidizing agent and water;
or a reducing agent and water;
④ preparing neutralizing diluent material comprising sodium hydroxide and water;
wherein, the oxidant is directly added into the flask or is prepared in the material B;
the reducing agent is configured in the material A or the material B;
adding a part of acrylic acid into a flask, and adding the rest part when preparing the material A; or all the acrylic acid is prepared in the material A;
(2) preparing a material A, a material B and a neutralization diluent:
① preparing material A, mixing the raw materials and stirring uniformly to obtain material A;
② preparing material B, mixing the raw materials and stirring to obtain material B;
③ preparing neutralizing and diluting material, mixing the materials for preparing neutralizing and diluting material, and stirring to obtain neutralizing and diluting material;
(3) adding F-1088 and water into a flask, and uniformly stirring;
(4) stopping heating when the temperature of the reaction liquid in the flask reaches 13-35 ℃, adding an oxidant, acrylic acid or a reducing agent into the flask under stirring, continuously stirring and reacting for 10 min;
(5) then, the material A is dripped under stirring, and the dripping time is 120-150 min;
(7) then, the material B is dropwise added under stirring, wherein the dropwise adding time is 180-200 min; then preserving the temperature of the reaction solution at the end of the dropwise adding, wherein the preserving time is 60-180 min;
(6) and finally, adding the neutralization diluent, and uniformly stirring to obtain the finished product of the ultralow-temperature polycarboxylate superplasticizer.
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