CN101624358A - Preparation method of sulfamate water reducing agent - Google Patents
Preparation method of sulfamate water reducing agent Download PDFInfo
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- CN101624358A CN101624358A CN 200910183847 CN200910183847A CN101624358A CN 101624358 A CN101624358 A CN 101624358A CN 200910183847 CN200910183847 CN 200910183847 CN 200910183847 A CN200910183847 A CN 200910183847A CN 101624358 A CN101624358 A CN 101624358A
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Abstract
The invention relates to a preparation method of a sulfamate water reducing agent, belonging to the technical filed of water reducing agent technique for concrete. In the preparation method, the sulfamate water reducing agent comprises the following materials by weight percent: 30-40% of sodium sulfanilate, 15.6-23.4% of hydroxybenzene, 15.8-23.5% of formaldehyde, 2.3-6.1% of sodium hydroxide and 13.1-36.3% of water, wherein the water and the sodium sulfanilate are added into a reaction kettle to be stirred till the temperature is increased to 30-40 DEG C, and then the hydroxybenzene is added into the reaction kettle; the pH value of a solution is measured by a pH meter after the hydroxybenzene is completely dissolved, the pH value is regulated to 7-9 by the sodium hydroxide so that the solution is in alkalescence; after the pH value is regulated, a formaldehyde solution is dripped into the solution, dripping speed is controlled to complete dripping within 1.5-2 hours, and the temperature is kept between 55 DEG C and 65 DEG C. When the formaldehyde solution is completely dripped, and the temperature is increased to 90-100 DEG C and kept for 2.5-3.5 hours to complete reaction; thus, the sulfamate water reducing agent is obtained.
Description
Technical field
The present invention relates to the concrete water reducer, relate in particular to a kind of preparation method of thionamic acid based water reducer.
Background technology
What at present, the high-strength high-performance concrete employing was maximum is poly carboxylic acid and sulfamate water reducer.Along with the raising of China's building level and civil building service requirements, high-strength high-performance concrete in its people building shared ratio also with increasing.Sulfamate water reducer is a kind of polymer condenses, comparing the molecular structure with comb type with naphthalene series high-efficiency water-reducing agent makes it have excellent dispersive ability in concrete, water-reducing rate height not only, concrete good fluidity, and concrete basic free of losses of the slump in 90～120 minutes.
This product can reduce water cement ratio significantly, improves the workability of concrete, improves the early strength of concrete, is that the Ministry of Construction first elects first-selected product in high-strength high-performance concrete.The NF-2 amido sulfoacid series high-efficiency water reducer meets " concrete admixture " (GB8076-2008) high efficiency water reducing agent acceptable end product standard.
The NF-2 high efficiency water reducing agent is that amino acid is non-bleed high efficiency water reducing agent, is synthesized by sulfanilate, phenol, formaldehyde, catalyzer condensation.It has intensive to disperse humidification to cement granules, the water-reducing rate height, and morning is strong and reinforced effects is remarkable.
The NF-2 high efficiency water reducing agent is mainly used in various important concrete workses such as Highrise buildings, railroad bridge, prestressed concrete member, high-strength prefabricated tubular pile.
At present in high efficiency water reducing agent, no matter use maximum naphthalene series high-efficiency water-reducing agents that remains domestic or abroad, and naphthalene series high-efficiency water-reducing agent complex manufacturing temperature requirement is high and environment is had serious pollution, is that production technique is an example with domestic naphthalene below, and its concrete technology is as follows: divide four-step reaction
The first step sulfonation reaction
To stir in NAPTHALENE FLAKES. (INDUSTRIAL GRADE and the vitriol oil input reactor, be warming up to 165 ℃ of reactor pressure and remain on 0.6～0.8MP, generate the α naphthene sulfonic acid when sulfonation temperature is low easily, the β naphthene sulfonic acid is as much as possible takes higher sulfonation temperature in order to guarantee to produce, and make reaction keep time enough, general reaction 2～3h, the β naphthene sulfonic acid can get more than 85% like this.For the α naphthene sulfonic acid that makes generation is converted into the β naphthene sulfonic acid as much as possible, reaction will be hydrolyzed after the sulfonation reaction.
The reaction of second one-step hydrolysis
The α naphthene sulfonic acid generates at low temperatures easily, in the higher easy hydrolysis of temperature nextpage.Therefore after sulfonation finishes, add water for cooling to 70 ℃ reaction 30～45 minutes, make in the many sulfonic acid of a part that generates in the sulfonation reaction, be removed after the naphthene sulfonic acid hydrolysis of α position, be beneficial to the polycondensation of β naphthalenesulfonate.
The 3rd step condensation reaction
Hydrolysis reaction begins to drip formaldehyde solution at 70 ± 5 ℃ after finishing, and the control rate of addition dropwises at 1.5～2h. and treat that formaldehyde all adds the back and is being warming up to 100～105 ℃ gradually, but can not surpass 110 ℃, behind insulation 2～3h, condensation reaction can be finished.
The 4th step neutralization reaction
The naphthalene sulfonic acidformaldehyde condensation product that generates is converted into sodium salt, neutralizes unnecessary sulfuric acid simultaneously.After being neutralized to pH value=8, promptly obtain naphthalene series high-efficiency water-reducing agent.
It is loaded down with trivial details to exist synthesis technique in the above-mentioned production method, the unmanageable problem of reaction conditions.
Summary of the invention
In order to overcome above-mentioned defective, the technical problem to be solved in the present invention is: at naphthalene water reducer complex manufacturing temperature requirement height and to environment serious pollution problems is arranged, a kind of preparation method of sulfamate water reducer is provided.
In order to overcome the defective that exists in the background technology, the technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of sulfamate water reducer, and the raw material weight proportioning is:
Sodium sulfanilate: 30～40%
Hydroxybenzene: 15.6～23.4%
Formaldehyde: 15.8～23.5%
Sodium hydroxide: 2.3～6.1%
Water: 13.1%～36.3%
Have following steps:
The first step dissolving neutralization
Water, Sodium sulfanilate dropped into to stir in the reactor drop into hydroxybenzene when being warming up to 30～40 ℃, the pH value of usefulness PH instrumentation solution is transferred to pH value between 7～9 with sodium hydroxide when hydroxybenzene dissolves fully after, makes solution be weakly alkaline.
The sulfonation condensation of second step
Begin to drip formaldehyde solution after mixing up pH value, the control rate of addition dropwises at 1.5～2h, maintains the temperature at 55～65 ℃.After formaldehyde solution dropwises, be warming up to 90～100 ℃, insulation 2.5～3.5h reaction finishes.
Among the present invention related correlated response as shown in the formula:
Best proportioning in the preparation process among the present invention is
Sodium sulfanilate: 40%
Hydroxybenzene: 15.6%
Formaldehyde: 23.5%
Sodium hydroxide: 4.5%
Water: 18.6%.
The molecular weight ranges of the sulfamate water reducer that the present invention makes is 3000～10000, and such water reducer molecular weight helps improving the water-reducing rate of water reducer, improves the performance of water reducer.
Beneficial effect: the present invention has shortened original preparation technology greatly, and the molecular weight size that can optimize the finished product constitutes, and has reduced production cost, has simplified production technique, easy control of reaction conditions; Can be used to dispose high-strength, high-performance pumping concrete, the gentle self-compacting that flows automatically mixes concrete etc.
Embodiment
The present invention is further detailed explanation with preferred embodiment in conjunction with the accompanying drawings now.These accompanying drawings are the synoptic diagram of simplification, basic structure of the present invention only is described in a schematic way, so it only show the formation relevant with the present invention.
Embodiment one
Composition of raw materials (weight ratio) is:
Sodium sulfanilate: 30%
Hydroxybenzene: 23.4%
Formaldehyde: 15.8%
Sodium hydroxide: 6.1%
Water: 24.7%
Specific operation process:
The first step dissolving neutralization
Water, Sodium sulfanilate dropped into to stir in the reactor drop into hydroxybenzene when being warming up to 30 ℃, the pH value of usefulness PH instrumentation solution is transferred to pH value between 8 with sodium hydroxide when hydroxybenzene dissolves fully after, makes solution be weakly alkaline.
The sulfonation condensation of second step
Begin to drip formaldehyde solution after mixing up pH value, the control rate of addition dropwises at 1.5～2h, maintains the temperature at 65 ℃.After formaldehyde solution dropwises, be warming up to 90 ℃, insulation 2.5h reaction finishes, and obtains sulfamate water reducer.
Embodiment two:
Composition of raw materials (weight ratio) is:
Sodium sulfanilate: 34.6%
Hydroxybenzene: 17.5%
Formaldehyde: 16.8%
Sodium hydroxide: 4.5%
Water: 16.6%
Specific operation process:
The first step dissolving neutralization
Water, Sodium sulfanilate dropped into to stir in the reactor drop into hydroxybenzene when being warming up to 40 ℃, the pH value of usefulness PH instrumentation solution is transferred to pH value between 9 with sodium hydroxide when hydroxybenzene dissolves fully after, makes solution be weakly alkaline.
The sulfonation condensation of second step
Begin to drip formaldehyde solution after mixing up pH value, the control rate of addition dropwises at 2h, maintains the temperature at 65 ℃.After formaldehyde solution dropwises, be warming up to 100 ℃, insulation 3.5h reaction finishes, and obtains sulfamate water reducer.
Embodiment two:
Composition of raw materials (weight ratio) is:
Sodium sulfanilate: 40%
Hydroxybenzene: 15.6%
Formaldehyde: 23.5%
Sodium hydroxide: 4.5%
Water: 18.6%
Specific operation process:
The first step dissolving neutralization
Water, Sodium sulfanilate dropped into to stir in the reactor drop into hydroxybenzene when being warming up to 40 ℃, the pH value of usefulness PH instrumentation solution is transferred to pH value between 7～9 with sodium hydroxide when hydroxybenzene dissolves fully after, makes solution be weakly alkaline.
The sulfonation condensation of second step
Begin to drip formaldehyde solution after mixing up pH value, the control rate of addition dropwises at 2h, maintains the temperature at 65 ℃.After formaldehyde solution dropwises, be warming up to 100 ℃, insulation 3.5h reaction finishes, and obtains sulfamate water reducer.
It is as follows that the present invention makes product performance:
1. this product is brown liquid pH value 8-9 solid content 30-34%
2. this product volume in gelling material is an aqua 1.0-2.5% water-reducing rate 18%～30%, is the preparation commerical ready-mixed concrete, the concrete ideal material of high flowability.
3. add this agent when temperature 20 is spent, 1 day intensity of concrete improves 170-200%, and intensity improved 50-100% in 3 days, and intensity improved 40-80% in 7 days, under the low slump situation, can reach 100% of design strength in 2-5 days.
4. after mixing this product, concrete slump-loss is little, basic free of losses in two hours.
5. mix this agent and can improve freeze proof, the anti-charing, anticorrosive of concrete.Suppress performances such as alkali.And not chloride ion-containing, ammonia, etc. objectionable impurities, pollution-free to room air, to the harm of reinforcing bar non-corroding, belong to Green Product.
6. mix this agent and can adjust concrete final setting time just.
7. this product all has good adaptability to five big cement.Technique effect is slightly adjusted because of the difference of cement type.
NF-2 sulfamate high-effective water-reducing agent and naphthalene system (FDN) contrast the influence of concrete strength:
Concrete kind water reducer volume compressive strength rate %
3 days 7 days 28 days
0 100 100 100
Mix FDN concrete 0.5 151 136 125
Mix amino concrete 0.5 142 143 128
National standard 0.5 130 125 120
With above-mentioned foundation desirable embodiment of the present invention is enlightenment, and by above-mentioned description, the related work personnel can carry out various change and modification fully in the scope that does not depart from this invention technological thought.The technical scope of this invention is not limited to the content on the specification sheets, must determine its technical scope according to the claim scope.
Claims (3)
1, a kind of preparation method of sulfamate water reducer is characterized in that the raw material weight proportioning is:
Sodium sulfanilate: 30～40%
Hydroxybenzene: 15.6～23.4%
Formaldehyde: 15.8～23.5%
Sodium hydroxide: 2.3～6.1%
Water: 13.1%～36.3%
Have following steps:
The first step dissolving neutralization
Water, Sodium sulfanilate dropped into to stir in the reactor drop into hydroxybenzene when being warming up to 30～40 ℃, the pH value of usefulness PH instrumentation solution is transferred to pH value between 7～9 with sodium hydroxide when hydroxybenzene dissolves fully after, makes solution be weakly alkaline.
The sulfonation condensation of second step
Begin to drip formaldehyde solution after mixing up pH value, the control rate of addition dropwises at 1.5～2h, maintains the temperature at 55～65 ℃.After formaldehyde solution dropwises, be warming up to 90～100 ℃, insulation 2.5～3.5h reaction finishes, and makes sulfamate water reducer.
2, the preparation method of sulfamate water reducer as claimed in claim 1 is characterized in that:
The optimum weight proportioning of raw material is:
Sodium sulfanilate: 40%
Hydroxybenzene: 15.6%
Formaldehyde: 23.5%
Sodium hydroxide 4.5%
Water 18.6%.
3, as claimed in claim 1, it is characterized in that: the molecular weight of described sulfamate water reducer is 3000～10000.
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| CN 200910183847 CN101624358B (en) | 2009-08-03 | 2009-08-03 | Preparation method of sulfamate water reducing agent |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824128A (en) * | 2010-04-16 | 2010-09-08 | 南京瑞迪高新技术公司 | Beta-naphthol produced waste liquid modified amido sulfoacid series high-efficiency water reducer and preparation method thereof |
| CN101823854A (en) * | 2010-04-20 | 2010-09-08 | 江苏汇迪建材有限公司 | Method for preparing cellulose sulfamate water reducer |
| CN102504160A (en) * | 2011-10-31 | 2012-06-20 | 天津市职业大学 | Method for preparing concrete superplasticizer by utilizing synthesized aspirin waste liquor |
| CN102617829A (en) * | 2012-03-29 | 2012-08-01 | 重庆融极环保工程有限公司 | Phosphorous-containing flame retardant epoxy waterborne self-emulsifying curing agent and application thereof |
| CN104844053A (en) * | 2015-04-28 | 2015-08-19 | 萧县沃德化工科技有限公司 | Modified sulfamate efficient water reducer and preparation method thereof |
| CN105503004A (en) * | 2015-12-15 | 2016-04-20 | 中国农业大学烟台研究院 | Method for preparing water reducing agent through leather solid waste |
| CN106279597A (en) * | 2016-08-08 | 2017-01-04 | 合肥永佳新材料科技有限公司 | A kind of modified amido sulfoacid water reducer and preparation method thereof |
| CN106317357A (en) * | 2016-08-24 | 2017-01-11 | 安徽鑫固环保股份有限公司 | High-efficiency water-reducing agent of modified amino benzene sulfonic acid series of G sulfonic acid producing wastewater |
| CN108911559A (en) * | 2018-07-27 | 2018-11-30 | 科之杰新材料集团有限公司 | A kind of preparation method of modified sulfamate water reducer |
| CN109928657A (en) * | 2019-05-05 | 2019-06-25 | 杭州临安引力外加剂有限公司 | A kind of high performance sulfamate water reducer and preparation method thereof |
| CN113548827A (en) * | 2021-07-31 | 2021-10-26 | 广东科隆智谷新材料股份有限公司 | Preservative for concrete admixture and preparation method thereof |
| CN113563233A (en) * | 2021-08-13 | 2021-10-29 | 石家庄市长安育才建材有限公司 | Anti-carbonization concrete reinforcing agent and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101050081B (en) * | 2006-04-07 | 2010-10-06 | 中交武汉港湾工程设计研究院有限公司 | High performance water reducing agent in new type comb shaped molecular structure |
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2009
- 2009-08-03 CN CN 200910183847 patent/CN101624358B/en not_active Expired - Fee Related
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824128A (en) * | 2010-04-16 | 2010-09-08 | 南京瑞迪高新技术公司 | Beta-naphthol produced waste liquid modified amido sulfoacid series high-efficiency water reducer and preparation method thereof |
| CN101824128B (en) * | 2010-04-16 | 2011-11-23 | 南京瑞迪高新技术公司 | Beta-naphthol produced waste liquid modified amido sulfoacid series high-efficiency water reducer and preparation method thereof |
| CN101823854A (en) * | 2010-04-20 | 2010-09-08 | 江苏汇迪建材有限公司 | Method for preparing cellulose sulfamate water reducer |
| CN102504160A (en) * | 2011-10-31 | 2012-06-20 | 天津市职业大学 | Method for preparing concrete superplasticizer by utilizing synthesized aspirin waste liquor |
| CN102504160B (en) * | 2011-10-31 | 2013-02-13 | 天津市职业大学 | Method for preparing concrete superplasticizer by utilizing synthesized aspirin waste liquor |
| CN102617829A (en) * | 2012-03-29 | 2012-08-01 | 重庆融极环保工程有限公司 | Phosphorous-containing flame retardant epoxy waterborne self-emulsifying curing agent and application thereof |
| CN104844053A (en) * | 2015-04-28 | 2015-08-19 | 萧县沃德化工科技有限公司 | Modified sulfamate efficient water reducer and preparation method thereof |
| CN105503004A (en) * | 2015-12-15 | 2016-04-20 | 中国农业大学烟台研究院 | Method for preparing water reducing agent through leather solid waste |
| CN106279597A (en) * | 2016-08-08 | 2017-01-04 | 合肥永佳新材料科技有限公司 | A kind of modified amido sulfoacid water reducer and preparation method thereof |
| CN106317357A (en) * | 2016-08-24 | 2017-01-11 | 安徽鑫固环保股份有限公司 | High-efficiency water-reducing agent of modified amino benzene sulfonic acid series of G sulfonic acid producing wastewater |
| CN106317357B (en) * | 2016-08-24 | 2018-09-28 | 安徽鑫固环保股份有限公司 | A kind of waste liquid modified aminobenzenesulfonic acid series high-efficiency water-reducing agent of G sulfonic acid production |
| CN108911559A (en) * | 2018-07-27 | 2018-11-30 | 科之杰新材料集团有限公司 | A kind of preparation method of modified sulfamate water reducer |
| CN109928657A (en) * | 2019-05-05 | 2019-06-25 | 杭州临安引力外加剂有限公司 | A kind of high performance sulfamate water reducer and preparation method thereof |
| CN113548827A (en) * | 2021-07-31 | 2021-10-26 | 广东科隆智谷新材料股份有限公司 | Preservative for concrete admixture and preparation method thereof |
| CN113563233A (en) * | 2021-08-13 | 2021-10-29 | 石家庄市长安育才建材有限公司 | Anti-carbonization concrete reinforcing agent and preparation method thereof |
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Owner name: JIANGSU HUDI BUILDING MATERIALS CO., LTD. Free format text: FORMER OWNER: CHANGZHOU HUIDI BUILDING MATERIALS CO., LTD. Effective date: 20121105 |
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Effective date of registration: 20121105 Address after: 213176 Industrial Zone, Lijia Town, Wujin District, Jiangsu, Changzhou Applicant after: Jiangsu Huidi Building Materials Co., Ltd. Address before: 213176 Industrial Zone, Lijia Town, Wujin District, Jiangsu, Changzhou Applicant before: Changzhou Huidi Building Materials Co., Ltd. |
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