[go: up one dir, main page]

CN109705283B - Retarding polycarboxylate superplasticizer and preparation method thereof - Google Patents

Retarding polycarboxylate superplasticizer and preparation method thereof Download PDF

Info

Publication number
CN109705283B
CN109705283B CN201910031929.3A CN201910031929A CN109705283B CN 109705283 B CN109705283 B CN 109705283B CN 201910031929 A CN201910031929 A CN 201910031929A CN 109705283 B CN109705283 B CN 109705283B
Authority
CN
China
Prior art keywords
percent
acid
retarding
solution
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910031929.3A
Other languages
Chinese (zh)
Other versions
CN109705283A (en
Inventor
李芳�
杨秀芳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen Road & Bridge Sunstone Buidling Material Technology Co ltd
Original Assignee
Xiamen Road & Bridge Sunstone Buidling Material Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen Road & Bridge Sunstone Buidling Material Technology Co ltd filed Critical Xiamen Road & Bridge Sunstone Buidling Material Technology Co ltd
Priority to CN201910031929.3A priority Critical patent/CN109705283B/en
Publication of CN109705283A publication Critical patent/CN109705283A/en
Application granted granted Critical
Publication of CN109705283B publication Critical patent/CN109705283B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

The invention belongs to the field of water reducing agents, and particularly discloses a retarding polycarboxylate water reducing agent and a preparation method thereof. The retarding polycarboxylate superplasticizer is prepared from the following components in percentage by weight: 20 to 45 percent of unsaturated polyether, 2 to 6 percent of unsaturated acid, 0.9 to 10 percent of sodium p-styrene sulfonate, 0.5 to 2 percent of organic phosphoric acid, 0.2 to 1 percent of oxidant, 0.05 to 0.2 percent of reducing agent, 0.1 to 0.5 percent of chain transfer agent and the balance of water. The retarding polycarboxylate superplasticizer has high water reducing rate and good retarding effect, has good adaptability to different varieties of cement, and does not produce side effect due to different varieties of cement. In addition, the slow-setting polycarboxylate superplasticizer has a good anticorrosion effect, and the polycarboxylate superplasticizer cannot rot, delaminate, smell and the like due to overlong standing time in summer.

Description

Retarding polycarboxylate superplasticizer and preparation method thereof
Technical Field
The invention belongs to the field of water reducing agents, and particularly discloses a retarding polycarboxylate water reducing agent and a preparation method thereof.
Background
The retarding water reducer is an admixture with wide application range in concrete admixture, and has retarding and greatly reduced water consumption. As the basic construction development puts more and higher requirements on the performance of concrete, higher requirements on concrete admixtures are also put forward.
The high-performance polycarboxylate superplasticizer has the advantages of high water reducing rate, good cement dispersibility and small concrete slump loss. However, the polycarboxylate superplasticizers themselves have a relatively weak retarding effect, and the above-mentioned effect must be achieved by compounding with a retarder. Although the compounding technology can solve part of problems, the degree of solving the problems by compounding is limited, the original water reducing performance of the water reducing agent is sacrificed, and the cost is increased by additionally adding the retarder. In addition, the water reducing agent solution of the compound retarder can also have the phenomena of layering, precipitation, putrefaction, odor generation and the like, and the stability of the product performance is worried. Therefore, the development of a high-performance water reducing agent which has high water reducing rate, obvious retardation effect, stable product performance and ideal later reinforcing effect on concrete is urgently needed.
Disclosure of Invention
The invention aims to overcome the defects that the existing polycarboxylate superplasticizer cannot take water reducing and retarding into consideration and the performance of the polycarboxylate superplasticizer is influenced by compounding the existing polycarboxylate superplasticizer with the existing retarder, and provides the polycarboxylate superplasticizer which can take water reducing and retarding into consideration and a preparation method thereof.
The invention particularly provides a retarding polycarboxylate superplasticizer which is prepared from the following components in percentage by weight:
Figure GDA0003135068380000011
Figure GDA0003135068380000021
preferably, the retarding polycarboxylate superplasticizer is prepared from the following components in percentage by weight:
Figure GDA0003135068380000022
preferably, the unsaturated polyether is an isobutylene-based polyoxyethylene ether.
Preferably, the unsaturated polyether has a number average molecular weight of 600-3000, more preferably 2400-3000.
Preferably, the unsaturated acid is acrylic acid and/or methacrylic acid.
Preferably, the organophosphonic acid is hydroxyethylidene diphosphonic acid and/or aminotrimethylidene phosphonic acid.
Preferably, the oxidizing agent is potassium persulfate and/or ammonium persulfate.
Preferably, the reducing agent is ascorbic acid and/or tartaric acid.
Preferably, the chain transfer agent is thioglycolic acid and/or mercaptopropionic acid.
The invention also provides a preparation method of the retarding polycarboxylate superplasticizer, which comprises the following steps:
(1) preparing 45-55 wt% aqueous solution of sodium p-styrene sulfonate and unsaturated acid, and marking as a first solution, and preparing 3-10 wt% aqueous solution of reducing agent and chain transfer agent, and marking as a second solution;
(2) preparing the unsaturated polyether into an aqueous solution with the concentration of 35-45 wt%, adding the oxidant, then simultaneously dropwise adding the first solution and the second solution, adding the organic phosphoric acid after dropwise adding is finished, continuing to react for 0.5-2 h, and supplementing a certain amount of water after the reaction is finished to obtain a slow-setting polycarboxylic acid water reducer solution with the concentration of 40 wt%.
Preferably, the total time for dripping the first solution and the second solution is controlled within 2-3 h.
In addition, the invention also provides the retarding polycarboxylate superplasticizer prepared by the method.
The key point of the invention is that the unsaturated polyether, the unsaturated acid, the sodium p-styrene sulfonate and the organic phosphoric acid are used in a matching way according to specific dosage, especially the dosage of the sodium p-styrene sulfonate is increased, and the invention has the following beneficial effects:
(1) the retarding polycarboxylate superplasticizer has high water reducing rate and good retarding effect, has better adaptability with different varieties of cement, and does not generate side effect due to different varieties of cement;
(2) the slow-setting polycarboxylate superplasticizer has a good corrosion prevention effect, and can not be rotten, layered, smelly and the like due to overlong standing time in summer.
(3) The preparation process of the retarding polycarboxylate superplasticizer is simple, the reaction is carried out at normal temperature, the temperature in the whole process is not required to be controlled, the reaction time is short, the energy consumption is low, the safety coefficient is high, no pollution is caused, and the industrial production is easy to realize.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative of the invention and is not to be construed as limiting the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Raw materials: see table 1.
The preparation process comprises the following steps:
(1) preparing 50 wt% aqueous solution of sodium p-styrene sulfonate and unsaturated acid, and marking as a first solution, and preparing 5.5 wt% aqueous solution of reducing agent and chain transfer agent, and marking as a second solution;
(2) preparing unsaturated polyether into a 40wt% aqueous solution, adding an oxidant, then simultaneously dropwise adding the first solution and the second solution, controlling the total dropwise adding time to be 2-3 h, adding organic phosphoric acid after the dropwise adding is finished, and continuing to react for 1 h. After the reaction is finished, a certain amount of water is supplemented to obtain a retarding polycarboxylate superplasticizer solution with the concentration of 40 wt%.
Example 2
Raw materials: see table 1.
The preparation method is the same as that of example 1.
Example 3
Raw materials: see table 1.
The preparation method is the same as that of example 1.
Example 4
Raw materials: see table 1.
The preparation method is the same as that of example 1.
Example 5
Raw materials: see table 1.
The preparation method is the same as that of example 1.
Comparative example 1
Raw materials: the difference from example 2 is that the amount of sodium p-styrene sulfonate is reduced to 0.5 wt%, as shown in Table 1.
The preparation method is the same as that of example 1.
Comparative example 2
Raw materials: the difference from example 2 is that no organic phosphoric acid is added, as shown in Table 1.
The preparation method is the same as that of example 1.
TABLE 1 ingredient tables (unit: parts by weight) used in examples
Figure GDA0003135068380000041
Effect verification
(1) The net slurry fluidity of each of the examples and comparative examples at the same blending amount was measured by using the whelk p.o42.5 cement, the jianfu p.o42.5 cement and the minfu p.ii 42.5 cement. The test is carried out according to GB/T8077-2012 'concrete admixture homogeneity test method', the W/C is 2.9, the cement is 300g, the water is 87g, and the admixture mixing amount is the folded solid mixing amount. The test results are shown in Table 2.
TABLE 2 Net paste fluidity Performance results for different water reducer types
Figure GDA0003135068380000051
As can be seen from Table 2, the 1h cement paste fluidity loss of the retarding polycarboxylate water reducer in the example is smaller than that of the comparative example in different cements.
(2) Concrete test
The initial and final setting times of the concrete are tested by adopting Fujian cement and conch cement, and the test is carried out according to GB/T50080-2002 Standard of Performance test methods of concrete mixtures. The design label of the concrete is C30, the mix proportion of the concrete is that cement, water, sand, pebble, fly ash and mineral powder are 258, 170, 815, 996, 41 and 41 by weight, and the mixing amount of the water reducing agent is the mixing amount of the bending and fixing agent, calculated by the mass of the cement, the fly ash and the mineral powder. The test results are shown in Table 3.
TABLE 3 concrete setting time and compression strength meter (test temperature 20 deg.C)
Figure GDA0003135068380000061
The data in the table show that the retarding water reducer provided by the invention not only has higher water reducing rate, but also can prolong the setting time of concrete, and the compressive strength of the concrete in 7 days and 28 days can meet the construction requirements.
(4) The anticorrosion effect is as follows:
three samples of example 4, comparative example 1 and comparative example 2 were placed in numbers 1, respectively#、2#、3#Three stoppered tubes of (1) and stored in the laboratory (room temperature 30 ℃), and found 3 after one month#With slight floc, 1#、2#There was no change. Observed two months later, 3#With an odor and a pronounced floc precipitate, 1#And 2#The samples in these two tubes were unchanged. Therefore, the addition of the organic phosphoric acid can slow or prevent the deterioration and deterioration of the water reducing agent.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (8)

1. A preparation method of a retarding polycarboxylate superplasticizer is characterized by comprising the following steps:
(1) preparing 45-55 wt% aqueous solution of sodium p-styrene sulfonate and unsaturated acid, and marking as a first solution, and preparing 3-10 wt% aqueous solution of a reducing agent and a chain transfer agent, and marking as a second solution;
(2) preparing unsaturated polyether into an aqueous solution with the concentration of 35-45 wt%, adding an oxidant, then simultaneously dropwise adding the first solution and the second solution, adding organic phosphonic acid after dropwise adding is finished, continuing to react for 0.5-2 h, and supplementing a certain amount of water after the reaction is finished to obtain a retarding polycarboxylate water reducer solution with the concentration of 40 wt%;
the weight percentage of each raw material is as follows:
20 to 45 percent of unsaturated polyether;
2 to 6 percent of unsaturated acid;
4.1 to 10 percent of sodium p-styrene sulfonate;
0.5 to 2 percent of organic phosphonic acid;
0.2 to 1 percent of oxidant;
0.05 to 0.2 percent of reducing agent;
0.1 to 0.5 percent of chain transfer agent;
the balance of water;
the unsaturated polyether is isobutylene polyoxyethylene ether; the organic phosphonic acid is hydroxyethylidene diphosphonic acid and/or amino trimethylene phosphonic acid.
2. The preparation method of the slow-setting polycarboxylate water reducer according to claim 1, characterized in that the total time for dripping the first solution and the second solution is controlled within 2-3 h.
3. The preparation method of the retarding polycarboxylate water reducer according to claim 1, characterized in that the weight percentages of the raw materials are as follows:
25 to 35 percent of unsaturated polyether;
2.5 to 4 percent of unsaturated acid;
4.1 to 7 percent of sodium p-styrene sulfonate;
0.7 to 1.5 percent of organic phosphonic acid;
0.25 to 0.65 percent of oxidant;
0.06 percent to 0.15 percent of reducing agent;
0.1 to 0.4 percent of chain transfer agent;
the balance being water.
4. The method for preparing the retarding polycarboxylate water reducer according to any one of claims 1-3, wherein the number average molecular weight of the unsaturated polyether is 600-3000.
5. The preparation method of the slow-setting polycarboxylate water reducer as claimed in claim 4, wherein the number average molecular weight of the unsaturated polyether is 2400-3000.
6. The preparation method of the retarding polycarboxylate water reducer according to any one of claims 1-3, characterized in that the unsaturated acid is acrylic acid and/or methacrylic acid.
7. The preparation method of the retarding polycarboxylate water reducer according to any one of claims 1-3, characterized in that the oxidant is potassium persulfate and/or ammonium persulfate; the reducing agent is ascorbic acid and/or tartaric acid; the chain transfer agent is thioglycolic acid and/or mercaptopropionic acid.
8. The retarding polycarboxylate water reducer prepared by the method of any one of claims 1-7.
CN201910031929.3A 2019-01-14 2019-01-14 Retarding polycarboxylate superplasticizer and preparation method thereof Active CN109705283B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910031929.3A CN109705283B (en) 2019-01-14 2019-01-14 Retarding polycarboxylate superplasticizer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910031929.3A CN109705283B (en) 2019-01-14 2019-01-14 Retarding polycarboxylate superplasticizer and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109705283A CN109705283A (en) 2019-05-03
CN109705283B true CN109705283B (en) 2021-10-15

Family

ID=66261042

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910031929.3A Active CN109705283B (en) 2019-01-14 2019-01-14 Retarding polycarboxylate superplasticizer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109705283B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111187026B (en) * 2020-01-14 2022-02-18 云南森博混凝土外加剂有限公司 Machine-made sand wet-mixed mortar additive and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1289736A (en) * 1999-11-17 2001-04-04 武汉水利电力大学 High-efficiency water-reducing, retarding and plastic-retaining agent for concrete
CN103848944A (en) * 2013-05-14 2014-06-11 科之杰新材料集团有限公司 Preparation method of super-retarding type polycarboxylate superplasticizer
CN105254825A (en) * 2015-11-18 2016-01-20 科之杰新材料集团有限公司 Preparation method of esters retarding polycarboxylic acid slump retaining agent
CN106116232A (en) * 2016-06-24 2016-11-16 桂林华越环保科技有限公司 A kind of anti-freezing concrete water reducer
CN107987227A (en) * 2017-12-07 2018-05-04 科之杰新材料集团有限公司 A kind of preparation method of low hydration heat extra retarded set type polycarboxylate water-reducer

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5890840A (en) * 1995-12-08 1999-04-06 Carter, Jr.; Ernest E. In situ construction of containment vault under a radioactive or hazardous waste site
CN103183792B (en) * 2011-12-27 2015-04-29 山西黄腾化工有限公司 Preparation method of polycarboxylic water reducer
JP6832773B2 (en) * 2016-03-31 2021-02-24 株式会社日本触媒 Admixture material composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1289736A (en) * 1999-11-17 2001-04-04 武汉水利电力大学 High-efficiency water-reducing, retarding and plastic-retaining agent for concrete
CN103848944A (en) * 2013-05-14 2014-06-11 科之杰新材料集团有限公司 Preparation method of super-retarding type polycarboxylate superplasticizer
CN105254825A (en) * 2015-11-18 2016-01-20 科之杰新材料集团有限公司 Preparation method of esters retarding polycarboxylic acid slump retaining agent
CN106116232A (en) * 2016-06-24 2016-11-16 桂林华越环保科技有限公司 A kind of anti-freezing concrete water reducer
CN107987227A (en) * 2017-12-07 2018-05-04 科之杰新材料集团有限公司 A kind of preparation method of low hydration heat extra retarded set type polycarboxylate water-reducer

Also Published As

Publication number Publication date
CN109705283A (en) 2019-05-03

Similar Documents

Publication Publication Date Title
CN101952216B (en) additives for cement
CN104944824B (en) A kind of cement concrete early strength agent and early strength water-reducing agent
EP3027576B1 (en) Fast setting portland cement compositions with alkali metal citrates and phosphates with high early-age compressive strength and reduced shrinkage
EP4119519A1 (en) Strength enhancing admixture for low-carbon cementitious compositions
US6827776B1 (en) Method for accelerating setting of cement and the compositions produced therefrom
CN1087009C (en) Efficient water-reducing, slow-settling plasticizing agent of concrete
CN104774293B (en) A kind of anti-chamotte mould polycarboxylate water-reducer and preparation method thereof
CN104844047A (en) Composite antifreezing agent and antifreezing pumping agent
CN106866015A (en) A kind of β semi-hydrated gypsums retarder and preparation method thereof
CN118290062A (en) Nano hydrated calcium carbonate aluminate early strength agent and preparation method thereof
CN115180915B (en) High-performance concrete and preparation method thereof
CN109705283B (en) Retarding polycarboxylate superplasticizer and preparation method thereof
JP2020001966A (en) Mortar / concrete admixture, cement composition containing the same, mortar composition and concrete composition, and method for producing hardened mortar and hardened concrete
CN109021179B (en) Phosphonic acid-based polymer, preparation method thereof and phosphate mother liquor
US7867333B2 (en) Mortar compositions with base on ultra-fine clinker, refined sand and chemical additives
Sobolev et al. The development of high-strength mortars with improved thermal and acid resistance
JP2020128315A (en) Mortar/concrete admixture, cement composition/mortar composition/concrete composition including the admixture, and production method for mortar and concrete hardened materials
CN108219079B (en) Polycarboxylic acid water reducing agent, and preparation method and use method thereof
CN105152570B (en) A kind of liquid cement grinding additive and preparation method thereof
US6740155B1 (en) Method of delaying the set time of cement and the compositions produced therefrom
CN115819008B (en) High-activity low-shrinkage composite mineral admixture and preparation method thereof
Çallı et al. Use of boron compounds as grinding aids with alcohol amines and their effect on portland cement setting points
CN112062486B (en) Low-temperature cement and preparation method thereof
WO2023190108A1 (en) Cement admixture, and cement composition
CN110759660B (en) Additive for magnesium phosphate cement repair mortar and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant