CN104129941A - Slump-retaining type polycarboxylic acid water reducing agent and preparation method thereof - Google Patents
Slump-retaining type polycarboxylic acid water reducing agent and preparation method thereof Download PDFInfo
- Publication number
- CN104129941A CN104129941A CN201410362628.6A CN201410362628A CN104129941A CN 104129941 A CN104129941 A CN 104129941A CN 201410362628 A CN201410362628 A CN 201410362628A CN 104129941 A CN104129941 A CN 104129941A
- Authority
- CN
- China
- Prior art keywords
- maleic anhydride
- water reducing
- reducing agent
- methyl
- acid water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a slump-retaining type polycarboxylic acid water reducing agent and a preparation method thereof. The preparation method comprises the steps: taking maleic anhydride and methoxy polyethylene glycol as raw materials, to obtain a monomethoxy polyethylene glycol maleate and dimethoxy polyethylene glycol maleate macromonomer mixture; taking maleic anhydride and methanol as raw materials, to obtain maleic anhydride dimethyl ester; adding a mixed aqueous solution of the macromonomer mixture, maleic anhydride dimethyl ester and 2-acrylamide-2-methyl propyl sodium sulfonate, simultaneously adding an initiator ammonium sulfate and a chain transfer agent mercaptoethanol, and carrying out heat preservation for 1 h at the temperature of 80-85 DEG C; rising the temperature to 95-100 DEG C, carrying out heat preservation for 2 h, and cooling; and adding sodium hydroxide to neutralize to the pH of 6-7, and thus obtaining the slump-retaining type polycarboxylic acid water reducing agent. The slump-retaining type polycarboxylic acid water reducing agent has the outstanding advantages of high water reducing rate, low mixing amount, wide cement adaptability, high slump-retaining performance, good enhancement effect and the like.
Description
Technical field
The technical field that the invention belongs to concrete admixture, is specifically related to a kind of collapse protective poly-carboxylic acid water reducing agent and preparation method thereof.
Background technology
Water reducer refers under concrete workability and cement consumption permanence condition, can reduce mixing water amount, improve concrete strength; Or under workability and intensity permanence condition, save the admixture of cement consumption.According to its development flow process, can be divided into three phases: the first-generation is to take the ordinary water-reducing agent that wooden calcium, wooden sodium is representative, and water-reducing rate is 6%～12%; The s-generation is to be the high efficiency water reducing agent of representative with naphthalene, and water-reducing rate is 15%～25%, but produce and use procedure in there is the problems such as formaldehyde pollution; The third generation is to take the high-performance water reducing agent that polycarboxylate is representative, has high water reducing rate (can reach 35%), volume few (0.2%～0.4%), and institute joins concrete and has the advantages such as high strength, environmental protection.
The method of synthesizing polycarboxylic acid dehydragent mainly contains three kinds at present: 1) reactive monomer copolymerization method: the advantage of property monomer copolymerization method is that the designability of Molecular Structure Design is good, the length of main chain and side chain can be controlled by the preparation of surface-active macromonomer and ratio and the reaction conditions of adjusting copolyreaction monomer.At present, conventional synthetic method mostly is this method both at home and abroad.Although this technique is simple, first will synthesize large monomer, separation and purification process is loaded down with trivial details, and cost is higher.2) functionalization method after polymerization: generally adopt the poly carboxylic acid of existing known molecular amount, carry out graft esterification with polyethers under the effect of catalyzer under comparatively high temps, obtain the multipolymer of pectination molecular structure.This method has advantages of that the additive methods such as technique is simple, production process clean environment firendly hardly match.This method is widely used in Europe.But kind and the specification of ready-made poly carboxylic acid product are limited, its composition and molecular weight adjustment are more difficult; The consistency of poly-acid and polyethers is bad, esterification actually operating difficulty; Meanwhile, in esterification reaction process, constantly there is water to generate, cause being separated.3) in-situ polymerization and grafting: method is to introduce side chain in main chain polymerization, using polyethers as the reaction medium of carboxylic-acid unsaturated monomer, gathers with esterification in one, overcome the bad problem of poly carboxylic acid and polyethers consistency.But molecular designing process is more difficult, main chain generally also can only be selected the monomer of carboxyl group, and this graft reaction is a reversible balanced reaction, and water existing a large amount of in reacting precursor system exist, and cause its graft(ing) degree not high, and process is difficult to control.At present, the synthesising reacting time of polycarboxylate water-reducer is 3～8h..
Summary of the invention
The object of the invention is the method that provides scientific and reasonable, utilize the more synthetic method of high-efficiency environment friendly, further improve the over-all properties of polycarboxylate water-reducer, reduce production costs, for further applying of polycarboxylate water-reducer, bring important economic benefit and social benefit.
For achieving the above object, adopt technical scheme as follows:
A collapse protective poly-carboxylic acid water reducing agent, its molecular weight, between 10000～60000, contains following repeated structural unit in molecular formula:
Wherein, m=6～23:n=10～60.
The preparation method of above-mentioned collapse protective poly-carboxylic acid water reducing agent, comprises the following steps:
1) take maleic anhydride and methoxy poly (ethylene glycol) as raw material, add catalyzer and stopper, control 80～120 ℃ of temperature, reaction times 10～15h obtains the mixture of toxilic acid mono methoxy polyethylene glycol ester and the large monomer of toxilic acid Varonic DM 55 ester;
2) take maleic anhydride and methyl alcohol as raw material, add and under catalyzer room temperature, react 2-3h and obtain maleic anhydride mono-methyl; Obtain maleic anhydride mono-methyl; Take gained maleic anhydride mono-methyl and methyl alcohol as raw material, add catalyzer at 80～120 ℃ of temperature, to react 2～3h and obtain the two methyl esters of maleic anhydride;
3) in 80～85 ℃ of environment, add temperature step 1) the large monomer mixture of gained, step 2) mixed aqueous solution of the two methyl esters of gained maleic anhydride, 2-acrylamide-2 methyl-propyl sodium sulfonate, add initiator ammonium sulfate and chain-transfer agent mercaptoethanol, at 80～85 ℃ of insulation 1h simultaneously; Temperature is elevated to 95～100 ℃ of insulation 2h, cooling; Add sodium hydroxide to neutralize pH=6-7 and prepare collapse protective poly-carboxylic acid water reducing agent.
Press such scheme, step 1) described middle maleic anhydride and methoxy poly (ethylene glycol) mol ratio be 1.1～1.8:1; Described catalyzer is tosic acid, and described stopper is cuprous chloride and Resorcinol.
Press such scheme, step 2) described in maleic anhydride and methyl alcohol mol ratio 1.05～1.1:1; Maleic anhydride mono-methyl and methyl alcohol mol ratio 1.05～1.1:1; Described catalyzer is the vitriol oil.
Press such scheme, step 3) described in mixed aqueous solution, step 1) the large monomer mixture of gained and step 2) mass ratio of the two methyl esters of gained maleic anhydride and 2-acrylamide-2 methyl-propyl sodium sulfonate is 3～11:1～5.5:1.
Press such scheme, step 3) in mixed aqueous solution, initiator and chain-transfer agent 2.5～3.5h add mix complete.
The synthetic target molecule process of the present invention is as follows:
The first step:
Second step:
The 3rd step:
Compare with existing most of polycarboxylate water-reducer, the present invention at least has following technical superiority:
Present method is solution polymerization, compares simpler, reasonable, easy to operate with the production technique of existing general retardant;
Collapse protective poly-carboxylic acid water reducing agent of the present invention has the outstanding advantages such as high water reducing rate, low-dosage, wide, the high function of slump protection of cement adaptability, reinforced effects be good.
Embodiment
Following examples are explaination technical scheme of the present invention further, but not as limiting the scope of the invention.
Collapse protective poly-carboxylic acid water reducing agent preparation process of the present invention is as follows:
Step 1) preparation of the mixture of large monomer: take maleic anhydride and methoxy poly (ethylene glycol) as raw material, add catalyzer and stopper, control 80～120 ℃ of temperature, reaction times 10～15h obtains the mixture of toxilic acid mono methoxy polyethylene glycol ester and the large monomer of toxilic acid Varonic DM 55 ester; Standby.
Step 2) preparation of the two methyl esters of maleic anhydride: take maleic anhydride and methyl alcohol as raw material, add and react 2-3h under catalyzer room temperature and obtain maleic anhydride mono-methyl; Obtain maleic anhydride mono-methyl; Take gained maleic anhydride mono-methyl and methyl alcohol as raw material, add catalyzer at 80～120 ℃ of temperature, to react 2～3h and obtain the two methyl esters of maleic anhydride; Standby.
Step 3) preparation of collapse protection type water reducer of the present invention: in 80～85 ℃ of environment, add temperature step 1) the large monomer mixture of gained, step 2) mixed aqueous solution of the two methyl esters of gained maleic anhydride, 2-acrylamide-2 methyl-propyl sodium sulfonate, add initiator ammonium sulfate and chain-transfer agent mercaptoethanol, at 80～85 ℃ of insulation 1h simultaneously; Temperature is elevated to 95～100 ℃ of insulation 2h, cooling; Add sodium hydroxide to neutralize pH=6-7 and prepare collapse protective poly-carboxylic acid water reducing agent.
Step 1) in, maleic anhydride and methoxy poly (ethylene glycol) mol ratio are 1.1～1.8:1; Catalyzer is tosic acid, and consumption is 2%～8% of total mass (maleic anhydride and methoxy poly (ethylene glycol)); Stopper is cuprous chloride and Resorcinol, and Resorcinol consumption is 0.5%～3% of maleic anhydride quality, and cuprous chloride consumption is 0.5%～1.5% of maleic anhydride quality.Reaction solvent is selected toluene, and its consumption is 50%～150% of raw material total mass.
Step 2) maleic anhydride and methyl alcohol mol ratio 1.05～1.1:1 in; Maleic anhydride mono-methyl and methyl alcohol mol ratio 1.05～1.1:1; Described catalyzer is the vitriol oil.
Step 3) in mixed aqueous solution, step 1) the large monomer mixture of gained and step 2) mass ratio of the two methyl esters of gained maleic anhydride and 2-acrylamide-2 methyl-propyl sodium sulfonate is 3～11:1～5.5:1.Initiator ammonium persulfate quality is step 2) the two methyl esters of gained maleic anhydride and 2-acrylamide-2 methyl-propyl sodium sulfonate monomer mass 1.8%～8%.Chain-transfer agent mercaptoethanol quality is step 2) the two methyl esters of gained maleic anhydride and 2-acrylamide-2 methyl-propyl sodium sulfonate monomer mass 0.1%～2%.
Wherein, step 3) in, mixed aqueous solution, initiator and chain-transfer agent slowly add reaction environment simultaneously, 2.5～3.5h add mix complete.
Embodiment proportioning is as shown in table 1, and its performance is as shown in table 2.
In experiment, cement used is the new P.O 42.5 of China, and concrete consumption is in Table 1.In table 2, " 0 " number embodiment water reducer used is commercially available 40% polycarboxylate water-reducer.Proportioning weighs according to C30 concrete material.Experimental technique reference: GB8076-2008 < < concrete admixture > >
By the analysis of table 2 experimental data, we can find, the collapse protective poly-carboxylic acid water reducing agent of preparing by the inventive method not only has higher water-reducing rate, lower volume, and the slump of concrete 2h is more than 210mm, more than 28d intensity can reach 46Mp, can be widely used in various concrete workses.
Table 1 embodiment material mixture ratio (wt%)
The maleic anhydride class cement water reducing agent performance evaluation that table 2 embodiment is synthetic
Claims (6)
1. a collapse protective poly-carboxylic acid water reducing agent, is characterized in that molecular weight is between 10000～60000, contains following repeated structural unit in molecular formula:
Wherein, m=6～23:n=10～60.
2. the preparation method of collapse protective poly-carboxylic acid water reducing agent claimed in claim 1, is characterized in that comprising the following steps:
1) take maleic anhydride and methoxy poly (ethylene glycol) as raw material, add catalyzer and stopper, control 80～120 ℃ of temperature, reaction times 10～15h obtains the mixture of toxilic acid mono methoxy polyethylene glycol ester and the large monomer of toxilic acid Varonic DM 55 ester;
2) take maleic anhydride and methyl alcohol as raw material, add and under catalyzer room temperature, react 2-3h and obtain maleic anhydride mono-methyl; Obtain maleic anhydride mono-methyl; Take gained maleic anhydride mono-methyl and methyl alcohol as raw material, add catalyzer at 80～120 ℃ of temperature, to react 2～3h and obtain the two methyl esters of maleic anhydride;
3) in 80～85 ℃ of environment, add temperature step 1) the large monomer mixture of gained, step 2) mixed aqueous solution of the two methyl esters of gained maleic anhydride, 2-acrylamide-2 methyl-propyl sodium sulfonate, add initiator ammonium sulfate and chain-transfer agent mercaptoethanol, at 80～85 ℃ of insulation 1h simultaneously; Temperature is elevated to 95～100 ℃ of insulation 2h, cooling; Add sodium hydroxide to neutralize pH=6-7 and prepare collapse protective poly-carboxylic acid water reducing agent.
3. the preparation method of collapse protective poly-carboxylic acid water reducing agent as claimed in claim 2, is characterized in that step 1) described middle maleic anhydride and methoxy poly (ethylene glycol) mol ratio be 1.1～1.8:1; Described catalyzer is tosic acid, and described stopper is cuprous chloride and Resorcinol.
4. the preparation method of collapse protective poly-carboxylic acid water reducing agent as claimed in claim 2, is characterized in that step 2) described in maleic anhydride and methyl alcohol mol ratio 1.05～1.1:1; Maleic anhydride mono-methyl and methyl alcohol mol ratio 1.05～1.1:1; Described catalyzer is the vitriol oil.
5. the preparation method of collapse protective poly-carboxylic acid water reducing agent as claimed in claim 2, it is characterized in that step 3) described in mixed aqueous solution, step 1) the large monomer mixture of gained and step 2) mass ratio of the two methyl esters of gained maleic anhydride and 2-acrylamide-2 methyl-propyl sodium sulfonate is 3～11:1～5.5:1.
6. the preparation method of collapse protective poly-carboxylic acid water reducing agent as claimed in claim 2, is characterized in that step 3) in mixed aqueous solution, initiator and chain-transfer agent 2.5～3.5h add mix complete.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410362628.6A CN104129941A (en) | 2014-07-28 | 2014-07-28 | Slump-retaining type polycarboxylic acid water reducing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410362628.6A CN104129941A (en) | 2014-07-28 | 2014-07-28 | Slump-retaining type polycarboxylic acid water reducing agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104129941A true CN104129941A (en) | 2014-11-05 |
Family
ID=51802850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410362628.6A Pending CN104129941A (en) | 2014-07-28 | 2014-07-28 | Slump-retaining type polycarboxylic acid water reducing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104129941A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188558A (en) * | 2016-07-17 | 2016-12-07 | 北京工业大学 | The method preparing cement water reducing agent for monomer with p styrene sulfonic acid salt |
| CN111560092A (en) * | 2020-05-14 | 2020-08-21 | 中建材料技术研究成都有限公司 | Phenolic aldehyde modified mud-resistant polycarboxylate superplasticizer and preparation method thereof |
| CN112645630A (en) * | 2020-12-19 | 2021-04-13 | 厦门宏发先科新型建材有限公司 | Fluorine-containing early-strength polycarboxylate superplasticizer, preparation method thereof and early-strength concrete |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792960A (en) * | 2005-11-24 | 2006-06-28 | 武汉理工大学 | Maleic acid anhydride series concrete water-reducing agent and preparation process thereof |
| CN101792282A (en) * | 2010-03-26 | 2010-08-04 | 山西大学 | Polycarboxylate water reducing agent and preparation method thereof |
| CN103553409A (en) * | 2013-11-01 | 2014-02-05 | 长沙加美乐素化工有限公司 | High-performance polycarboxylate superplasticizer synthetized by low temperature method, and preparation method thereof |
-
2014
- 2014-07-28 CN CN201410362628.6A patent/CN104129941A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1792960A (en) * | 2005-11-24 | 2006-06-28 | 武汉理工大学 | Maleic acid anhydride series concrete water-reducing agent and preparation process thereof |
| CN101792282A (en) * | 2010-03-26 | 2010-08-04 | 山西大学 | Polycarboxylate water reducing agent and preparation method thereof |
| CN103553409A (en) * | 2013-11-01 | 2014-02-05 | 长沙加美乐素化工有限公司 | High-performance polycarboxylate superplasticizer synthetized by low temperature method, and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188558A (en) * | 2016-07-17 | 2016-12-07 | 北京工业大学 | The method preparing cement water reducing agent for monomer with p styrene sulfonic acid salt |
| CN106188558B (en) * | 2016-07-17 | 2018-12-25 | 北京工业大学 | The method for preparing cement water reducing agent as monomer using p styrene sulfonic acid salt |
| CN111560092A (en) * | 2020-05-14 | 2020-08-21 | 中建材料技术研究成都有限公司 | Phenolic aldehyde modified mud-resistant polycarboxylate superplasticizer and preparation method thereof |
| CN111560092B (en) * | 2020-05-14 | 2022-04-19 | 中建西部建设建材科学研究院有限公司 | Phenolic aldehyde modified mud-resistant polycarboxylate superplasticizer and preparation method thereof |
| CN112645630A (en) * | 2020-12-19 | 2021-04-13 | 厦门宏发先科新型建材有限公司 | Fluorine-containing early-strength polycarboxylate superplasticizer, preparation method thereof and early-strength concrete |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103450411B (en) | A kind of preparation method of high-slump-retentionpolycarboxylate polycarboxylate water reducer | |
| CN101333092B (en) | Cement concrete superplasticizer and method for preparing same | |
| CN103183788B (en) | The preparation method of polycarboxylic acid concrete slump retaining agent | |
| CN103613308B (en) | Water-reducing polycarboxylic concrete slump retaining agent and preparation method thereof | |
| CN1330600C (en) | Maleic acid anhydride series concrete water-reducing agent and preparation process thereof | |
| CN101508536B (en) | modified aliphatic water reducing agent and preparation method | |
| CN104140503A (en) | Method for synthesizing high-water-reduction high-slump-retaining high-performance polycarboxylate water reducer at normal temperature | |
| CN103396031B (en) | A kind of carboxylic acid water reducer and preparation method thereof | |
| CN103965416B (en) | Component high-early strength type polycarboxylic acids dehydragent and preparation method thereof | |
| CN102268121A (en) | Polycarboxylic acid water reducer with high water-reducing rate and high slump constant holding capacity, and its synthetic method and use method | |
| CN109337024B (en) | Preparation method of retarding polycarboxylate superplasticizer | |
| CN105601843A (en) | Early-strength ethers polycarboxylic acid water reducing agent and preparation method thereof | |
| CN103011680A (en) | Sulfate-resistant organosilicone modified polycarboxylic superplasticizer and preparation method thereof | |
| CN102603223A (en) | Polycarboxylic acid water reducer with solid raw materials and preparing process of the polycarboxylic acid water reducer | |
| CN105111383A (en) | Process for preparing high-performance polycarboxylic acid type water-reducing agent by combined macromonomers at normal temperature | |
| CN107337769B (en) | Slump-retaining type polycarboxylate superplasticizer and preparation method thereof | |
| CN103613307B (en) | Slump type polycarboxylate superplasticizer and preparation method thereof | |
| CN103965460A (en) | Polycarboxylate-type water reducing agent | |
| CN103693881A (en) | Polycarboxylic acid water reducer, application and preparation method of polycarboxylic acid water reducer | |
| CN102491709A (en) | Cement-based polymer water-proof mortar and preparation method thereof | |
| CN103497285A (en) | Method for preparing efficient polycarboxylate graft copolymer super plasticizer through microwave-assisting method | |
| CN104710310B (en) | O-maleoyl lactate ester compound and preparation method thereof and the application in polycarboxylate water-reducer synthesizes | |
| CN102503221B (en) | Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof | |
| CN104193215A (en) | Ternary block macromonomer graft copolymerization high-property polycarboxylic acid water-reducing agent and preparation method thereof | |
| CN104129941A (en) | Slump-retaining type polycarboxylic acid water reducing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141105 |
|
| RJ01 | Rejection of invention patent application after publication |