CN100560530C - A kind of concrete superplasticizer in amino carboxyl classes and synthetic method thereof - Google Patents
A kind of concrete superplasticizer in amino carboxyl classes and synthetic method thereof Download PDFInfo
- Publication number
- CN100560530C CN100560530C CNB2006101051218A CN200610105121A CN100560530C CN 100560530 C CN100560530 C CN 100560530C CN B2006101051218 A CNB2006101051218 A CN B2006101051218A CN 200610105121 A CN200610105121 A CN 200610105121A CN 100560530 C CN100560530 C CN 100560530C
- Authority
- CN
- China
- Prior art keywords
- concrete
- phenol
- classes
- water
- reaction
- 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.)
- Expired - Fee Related
Links
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a kind of concrete superplasticizer in amino carboxyl classes, this concrete superplasticizer in amino carboxyl classes cost is low, and the water-reducing rate height is good with cement adaptability.The invention also discloses the method and the application of synthetic this concrete superplasticizer in amino carboxyl classes, be reaction raw materials with the vitriol oil, phenylformic acid and phenol earlier, carry out sulfonation reaction, neutralize with sodium hydroxide, obtain sulfonated products, the mass ratio that carries out the polycondensation amount then is 65～80: 25～40; Described polycondensation reaction time is 6 ± 0.5h.Be converted to the described ammonia carboxylic of solid class new concrete high efficiency water reducing agent volume and be 0.35 of cement weight～0.6% o'clock, water-reducing rate is 20%～35%.Sulfamate high-effective water-reducing agent cost of the present invention is low, and the water-reducing rate height is good with cement adaptability, is easy to suitability for industrialized production.
Description
Technical field
The present invention relates to a kind of concrete high efficiency water reducing agent, relate in particular to a kind of concrete superplasticizer in amino carboxyl classes, the invention still further relates to the synthetic method of this concrete superplasticizer in amino carboxyl classes.
Technical background
Concrete high efficiency water reducing agent is as important composition in high-strength, the high performance concrete, and its effect is increasingly important.At present at home on the market, high efficiency water reducing agent mainly contains naphthalene system, melamine system, fatty family, sulfamate system and polycarboxylic acid series five big classes, wherein, the naphthalene series high-efficiency water-reducing agent share of market reaches more than 80%, and melamine system, fatty family and polycarboxylic acid series can not contend with it because of reasons such as price, performances.And sulfamate high-effective water-reducing agent is through in recent years researchdevelopment and market practice, accepted by the user because of advantages such as its cement adapts to, water-reducing rate height, slump-loss are little, not bleeds, and share of market increases gradually.
The grand grand condenses of introducing with amino-aryl sulfonic acid, phenol and formaldehyde that waits of the ancient bridge of Japan is as cement water reducing agent, found that it not only has stronger dispersive ability, more much better than than traditional water reducer aspect the maintenance concrete slump simultaneously, the research of sulfamate high-effective water-reducing agent from then on develops rapidly.
Furuhashi etc. introduce amino-aryl sulfonic acid-P-F condenses as cement dispersants, and this kind dispersion agent can improve the concrete slump greatly, especially are fit to pump concrete.The condenses of Kawamura usefulness bisphenol compound and alkylamino Phenylsulfonic acid, formaldehyde is as high efficiency water reducing agent, and water-reducing rate can reach 35% ~ 55% when this high efficiency water reducing agent was used in mortar, keeps good fluidity to surpass 1h.
Peace portion too youth waits the condenses of using Sulphanilic Acid, bisphenol S, phenylformic acid and formaldehyde as high efficiency water reducing agent.Ishitoku is used as cement dispersants with the condenses of trisphenol, Sulphanilic Acid, formaldehyde.The condenses of Tsuji phenol, aniline sulfonic acid, trimeric cyanamide and formaldehyde can improve concrete flowability as high efficiency water reducing agent.These water reducers all have high water reducing rate, and the may command concrete slump loss.
Feng of Tsing-Hua University has modestly made sulfamate high-effective water-reducing agent AS with carrying out condensation reaction with aniline sulfonic acid, phenol and formaldehyde, and has studied the compound property of AS and naphthalene series high-efficiency water-reducing agent.The result shows: sulfamate high-effective water-reducing agent and naphthalene series high-efficiency water-reducing agent and different types of cement all have good consistency, and water-reducing rate is big, and concrete slump is little through time loss.
Chemical engineering institute of South China Science ﹠ Engineering University also sulfamate high-effective water-reducing agent is studied.They are by the assay optimization processing parameter, in the aqueous solution, add thermal polycondensation by Sulphanilic Acid, phenol and become sulfamate high-effective water-reducing agent ASP with formaldehyde, its water-reducing rate reaches more than 25%, and 2h is relative, and the degree of mobilization loss is little, and concrete crushing strength is greatly improved.But cost is higher and to the volume sensitivity, easily bleeding is emanated.
Take a broad view of the various sulfamate high-effective water-reducing agents of present research and development, ubiquity the problem of two aspects in actual applications, thereby influences wide popularization and application.The one, phenol in the raw material, Sodium sulfanilate price are expensive partially, cause this analog high efficiency water reducing agent product price height; The 2nd, responsive in the application process to addition ratio, if volume is low excessively, the cement particle can not fully disperse, concrete slump is less, if volume is excessive, the cement particle is too disperseed, the concrete water-retentivity is bad, the segregation excreting water phenomenon is serious, even slurry hardens and water sepn, thereby is difficult to grasp in construction.
At above-mentioned situation, the present invention adopts different production technique, different raw materials and proportioning, in the sulfamate high-effective water-reducing agent molecule, introduce carboxyl, develop the new and effective water reducer of ammonia carboxylic class, when having reduced product cost, also improved the performance of product significantly.
Summary of the invention
First technical problem that the present invention will solve is: a kind of concrete superplasticizer in amino carboxyl classes is provided, and this concrete superplasticizer in amino carboxyl classes cost is low, and the water-reducing rate height is good with cement adaptability.
Concrete superplasticizer in amino carboxyl classes expression formula of the present invention is:
In the formula: M represents Na
+
Second technical problem that the present invention will solve is: the synthetic method that a kind of concrete superplasticizer in amino carboxyl classes is provided.
For the technical scheme that solves the problems of the technologies described above technical solution problem of the present invention is: the synthetic method of this concrete superplasticizer in amino carboxyl classes is carried out in two steps:
The first step sulfonation reaction:
With the vitriol oil, phenylformic acid and phenol is reaction raw materials, carries out sulfonation reaction under 85～95 ℃, is the neutralization of 30% sodium hydroxide with concentration, transfers pH to 7～8, obtains sulfonated products, and its reaction formula is as follows:
In the formula: M represents Na+.
The mass ratio of phenylformic acid, phenol and the vitriol oil is 20～40: 55～75 in this sulfonation reaction: 100～115; The sulfonation reaction time is 2 ± 0.5h;
The reaction of second one-step polycondensation:
In the sulfonated products that the first step reaction makes, add entry, phenol, Sodium sulfanilate, transfer pH to 8～10 with solid sodium hydroxide on one side, slowly heat up on one side, when temperature rises to 75～85 ℃, begin constant temperature and at the uniform velocity drip formaldehyde, in 2 ± 0.5h, dropwise, continue to be warming up to 80～90 ℃, constant temperature carries out condensation reaction 4～6h, promptly obtains ammonia carboxylic class new concrete high efficiency water reducing agent:
In the formula: M represents Na+;
The raw materials quality ratio of this polycondensation is: the mass ratio of sulfonated products, Sodium sulfanilate, phenol and water is 60～70: 38～50: 25～40: 230～250, and the consumption of formaldehyde and the mass ratio of phenol usage are 65～80: 25～40; Described polycondensation reaction time is 6 ± 0.5h.
Preferred plan of the present invention is: the mass ratio of phenylformic acid, phenol and the vitriol oil in the described the first step sulfonation reaction is 25: 70: 105.The mass ratio of sulfonated products, Sodium sulfanilate, phenol and water in described second one-step polycondensation reaction is 65: 50: 30: 240.The consumption of formaldehyde and the mass ratio of phenol usage are 70: 30 in described second one-step polycondensation reaction.
The 3rd technical problem that the present invention will solve is: concrete superplasticizer in amino carboxyl classes
Preferred plan of the present invention is: the mass ratio of phenylformic acid, phenol and the vitriol oil in the described the first step sulfonation reaction is 25: 70: 105.The mass ratio of sulfonated products, Sodium sulfanilate, phenol and water in described second one-step polycondensation reaction is 65: 50: 30: 240.The consumption of formaldehyde and the mass ratio of phenol usage are 70: 30 in described second one-step polycondensation reaction.
The 3rd technical problem that the present invention will solve is: the application of concrete superplasticizer in amino carboxyl classes, and the volume of concrete superplasticizer in amino carboxyl classes is counted 0.35 of cement weight～0.6% o'clock by solid, and water-reducing rate is 20%～35%.
The invention has the beneficial effects as follows:
The invention solves traditional sulfamate high-effective water-reducing agent and have the problem of two aspects: the one, phenol in the raw material, Sodium sulfanilate price are expensive partially, cause this analog high efficiency water reducing agent product price height; The 2nd, responsive in the application process to addition ratio, if volume is low excessively, the cement particle can not fully disperse, concrete slump is less, if volume is excessive, the cement particle is too disperseed, the concrete water-retentivity is bad, the segregation excreting water phenomenon is serious, even slurry hardens and water sepn, thereby is difficult to grasp in construction.Sulfamate high-effective water-reducing agent cost of the present invention is low, and the water-reducing rate height is good with cement adaptability, is easy to suitability for industrialized production.
The synthetic of ammonia carboxylic class new concrete high efficiency water reducing agent of the present invention is to utilize concentrated acid sulfonation phenol and benzoic mixture, be that reaction raw materials carries out polycondensation with sulfonated products, phenol, Sodium sulfanilate again, under the prerequisite that need not change traditional sulfamate based water reducer production technique, introduced-COOH and-the OH ion, not only can improve water-reducing rate, retarding performance and the cement adaptability of product, also reduce product cost significantly.Adopt the concrete of ammonia carboxylic class new concrete high efficiency water reducing agent of the present invention preparation, when water reducer volume (being converted to solid) for cement weight 0.35～0.6% the time, water-reducing rate can reach 25%～35%; Concrete 3d, 7d, 28 days compressive strength rates are respectively 130%～155%, 135%～171%, 125%～145%; High guarantor collapsed, and the concrete 2h slump is not lost substantially; Workability is good, and concrete pumping resistance is little, is convenient to carry; It is good that concrete surface does not have bleeding line, not bleed, Surface Quality of Concrete; Alkali content is low; Chloride ion-containing does not have corrosive nature to reinforcing bar; Frost resistance and anti-carbonization ability significantly improve than normal concrete; The adaptation of product is strong, is applicable to the cement of plurality of specifications, model, is suitable for especially that high-quality fly ash, the compatible preparation of slag isoreactivity adulterant are high-strength, high-durability, the contour performance concrete of self-compacting; Product performance are stable, are convenient to standing storage; Advantages such as product is nontoxic, does not contain formaldehyde, and is environmentally safe.
Description of drawings
Fig. 1 is a concrete superplasticizer in amino carboxyl classes synthetic method schema of the present invention.
Embodiment
The present invention adopts following technical proposals to realize:
The proportioning of each reactant is as follows among the following embodiment:
Proportioning raw materials in the sulfonation reaction is as follows:
Phenylformic acid: phenol: the vitriol oil: the mass ratio of liquid caustic soda (solids content 30%) is 30～35: 70～65.100～115: 185～190; Optimum quality ratio is 30: 70.110.190.
Proportioning raw materials in the polycondensation is as follows:
Sulfonated products (solids content about 60%): Sodium sulfanilate: phenol: the mass ratio of formaldehyde (solids content 37%) is 60～70: 40～50.25～35: 70～75; Optimum quality ratio is 65: 50.30: 75.
Embodiment 1:
30g phenylformic acid, 70g phenol and the 110g vitriol oil are put into reaction vessel, be warming up to 85 ℃, carry out sulfonation reaction 2h, the sodium hydroxide solution with 30% is neutralized to pH value 7～8, gets the sulfonation reaction product.In another reactor, add sulfonation reaction product 65g, Sodium sulfanilate 50g, phenol 30g and water 240g, be warming up to 80 ℃, with the sodium hydroxide adjust pH is 8～9, stir 15min, at the uniform velocity drip formaldehyde 75g, 2h left and right sides formaldehyde dropwises, and 80 ℃ of 6h of constant temperature carry out condensation reaction, obtains ammonia carboxylic class new concrete high efficiency water reducing agent of the present invention.
Embodiment 2:
40g phenylformic acid, 60g phenol and the 110g vitriol oil are put into reaction vessel, be warming up to 85 ℃, carry out sulfonation reaction 2h, the sodium hydroxide solution with 30% is neutralized to pH value 7～8, gets the sulfonation reaction product.In another reactor, add sulfonation reaction product 70g, Sodium sulfanilate 42g, phenol 30g and water 240g, be warming up to 85 ℃, with the sodium hydroxide adjust pH is 8～9, stir 15min, at the uniform velocity drip formaldehyde 72g, 2h left and right sides formaldehyde dropwises, and 85 ℃ of 6h of constant temperature carry out condensation reaction, obtains ammonia carboxylic class new concrete high efficiency water reducing agent of the present invention.
Claims (6)
1, a kind of method of ammonia-carboxylic acids concrete high efficiency water reducing agent is characterized in that, the synthetic method of this concrete superplasticizer in amino carboxyl classes is carried out in two steps:
The first step, sulfonation reaction:
1) be reaction raw materials with the vitriol oil, phenylformic acid and phenol, wherein, the mass ratio of phenylformic acid, phenol and the vitriol oil is 20～40: 55～75: 100～115, under 85～95 ℃, carry out sulfonation reaction, and the sulfonation reaction time is 2 ± 0.5h; Reaction formula is as follows:
2) be the neutralization of 30% sodium hydroxide with concentration, transfer pH to 7～8, obtain sulfonated products, reaction formula is as follows:
Second step, polycondensation:
Entry, phenol, Sodium sulfanilate will be added in the sulfonated products that make, transfer pH to 8～10 with sodium hydroxide on one side, slowly heat up on one side, when temperature rises to 75～85 ℃, begin constant temperature and at the uniform velocity drip formaldehyde, in 2 ± 0.5h, dropwise, continue to be warming up to 80～90 ℃, constant temperature carries out condensation reaction 4～6h, promptly obtains concrete superplasticizer in amino carboxyl classes; Its reaction formula is as follows:
In the formula: M represents Na+;
The raw materials quality ratio of this polycondensation is: the mass ratio of sulfonated products, Sodium sulfanilate, phenol and water is 60～70: 38～50: 25～40: 230～250, and the consumption of formaldehyde and the mass ratio of phenol usage are 65～80: 25～40.
2, the method for ammonia-carboxylic acids concrete high efficiency water reducing agent as claimed in claim 1: it is characterized in that: the mass ratio of phenylformic acid, phenol and the vitriol oil in the described the first step sulfonation reaction is 25: 70: 105.
3, the method for ammonia-carboxylic acids concrete high efficiency water reducing agent as claimed in claim 1: it is characterized in that: the mass ratio of sulfonated products, Sodium sulfanilate, phenol and water in described second one-step polycondensation reaction is 65: 50: 30: 240.
4, the method for ammonia-carboxylic acids concrete high efficiency water reducing agent as claimed in claim 1: it is characterized in that: the consumption of formaldehyde and the mass ratio of phenol usage are 70: 30 in described second one-step polycondensation reaction.
5, the concrete superplasticizer in amino carboxyl classes of the described method preparation of claim 1.
6, the application of concrete superplasticizer in amino carboxyl classes in concrete of claim 1 preparation is characterized in that, the volume of described concrete superplasticizer in amino carboxyl classes is counted 0.35 of cement weight～0.6% o'clock by solid, and water-reducing rate is 20%～35%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101051218A CN100560530C (en) | 2006-12-05 | 2006-12-05 | A kind of concrete superplasticizer in amino carboxyl classes and synthetic method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101051218A CN100560530C (en) | 2006-12-05 | 2006-12-05 | A kind of concrete superplasticizer in amino carboxyl classes and synthetic method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101003424A CN101003424A (en) | 2007-07-25 |
| CN100560530C true CN100560530C (en) | 2009-11-18 |
Family
ID=38702860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101051218A Expired - Fee Related CN100560530C (en) | 2006-12-05 | 2006-12-05 | A kind of concrete superplasticizer in amino carboxyl classes and synthetic method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100560530C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121805B (en) * | 2013-01-30 | 2014-11-05 | 李惠民 | High-performance concrete anti-cracking high efficiency water reducing agent |
| CN106277905A (en) * | 2016-08-08 | 2017-01-04 | 合肥永佳新材料科技有限公司 | A kind of concrete high-performance gas tracting subtractive agent and preparation method thereof |
| CN106277914A (en) * | 2016-08-08 | 2017-01-04 | 合肥永佳新材料科技有限公司 | A kind of anti-freezing concrete water reducer and preparation method thereof |
| CN116924746A (en) * | 2023-09-13 | 2023-10-24 | 邢台天泉商品混凝土有限责任公司 | Preparation process of high-performance anti-cracking concrete |
-
2006
- 2006-12-05 CN CNB2006101051218A patent/CN100560530C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101003424A (en) | 2007-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101508536B (en) | modified aliphatic water reducing agent and preparation method | |
| CN109081629B (en) | Chlorine-free enhanced slump retaining cement grinding aid and preparation method thereof | |
| CN100560530C (en) | A kind of concrete superplasticizer in amino carboxyl classes and synthetic method thereof | |
| CN103964731B (en) | A kind of polycarboxylate water-reducer and preparation method thereof | |
| CN101531479A (en) | Method for preparing low cost aliphatic high efficiency water reducing agent | |
| CN103951304A (en) | Concrete reinforcing agent as well as preparation method and application thereof | |
| EP2709964A1 (en) | Process for preparing additive for cementitious materials, additive and mixture comprising additive | |
| CN100357213C (en) | High performance water-reducing agent of sulfanilate-sulfonated acetone-formaldehyde condensate and process for making same | |
| CN102276184A (en) | Retarding and water reducing agent for occlusal pile of subway drilling | |
| CN111116839A (en) | High slump loss resistant mud resistant polycarboxylate superplasticizer mother solution as well as preparation method and application thereof | |
| CN1686907A (en) | Bricks and mortar made from fly ash and preparation method | |
| CN1821150A (en) | Process for preparing poly carboxylic acid modified fatty water-reducing agent | |
| CN102875049A (en) | High sulfonation degree aliphatic water reducing agent and preparation method thereof | |
| CN102503216A (en) | Method for synthesizing universal polycarboxylic water reducer | |
| CN1800075A (en) | Simplified method for preparing low alkaline naphthalene series concrete water reducing agent | |
| CN101774779B (en) | Comb-shaped low-slump concrete plastic-reserving agent with poly-sulphoacid structure | |
| CN102086105B (en) | Modified naphthalene water reducer and preparation method thereof | |
| CN102173634B (en) | Modified aliphatic high-efficiency water reducing agent | |
| CN102249589A (en) | Method for preparing lignosulfonate high-efficiency water reducing agent under promoting action of ultrasonic waves | |
| CN103012222A (en) | Method for preparing naphthalene-based high efficient water reducing agent | |
| CN1559963A (en) | Sulfamate as high performance reducing water agent for building and preparing proces thereof | |
| CN102452806A (en) | Novel melamine water reducer and preparation method | |
| CN1095450C (en) | Active agent for fly ash concrete | |
| CN104310842A (en) | Building water reduction agent | |
| CN103159425A (en) | Synthesis method of modified naphthalene water-reducing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091118 Termination date: 20111205 |