CN107129176A - A kind of synthetic method of modified sulfamate water reducer - Google Patents
A kind of synthetic method of modified sulfamate water reducer Download PDFInfo
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- CN107129176A CN107129176A CN201710108054.3A CN201710108054A CN107129176A CN 107129176 A CN107129176 A CN 107129176A CN 201710108054 A CN201710108054 A CN 201710108054A CN 107129176 A CN107129176 A CN 107129176A
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- water
- water reducer
- reactor
- melamine
- concrete
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- 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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Water reducer field is used the invention belongs to concrete, and in particular to a kind of synthetic method of modified sulfamate water reducer.The synthetic method includes：1) melamine methylolation；2) dissolving is neutralized, methylolation is condensed；3) strand is reset；Present invention preparation gained water reducer is good to mineral additive (flyash, miberal powder, silicon ash) conformability in concrete, can significantly improve the sensitiveness to water reducer volume in the water retention property of sulfamate water reducer, reduction concrete；The function of slump protection that the present invention prepares gained water reducer is excellent, the fluidity that binder materials is starched only basic free of losses in 4h, Mortar'S Flowability basic free of losses in 4h；Configuration commerical ready-mixed concrete, Cracking of High Flowing Concrete are used it for, with water-reducing rate height, strength enhancing significant advantage.
Description
Technical field
Water reducer field is used the invention belongs to concrete, and in particular to a kind of synthesis side of modified sulfamate water reducer
Method.
Background technology
With the development of concrete technology, concrete admixture has been an indispensable part, is to promote concrete
An important part for development.A kind of the use of most additive is cement water reducing agent in concrete admixture, is extremely important
Constituent.High efficiency water reducing agent occupies consequence with its preferable effect and function of slump protection, current domestic application
Comparing extensive high efficiency water reducing agent has：Polycarboxylic acid series high efficiency water reducing agent, lignosulfonates series high-efficiency water-reducing agent, naphthalene series high-efficiency subtract
Aqua, melamine superplasticizer and Amino-sulfonic Acid-based Water-reducer.
Wherein, sulfamate based water reducer is one of very important non-naphthalene water reducer.Sulfamate system is efficient
Water reducer has branch's many (or even netted), the design feature that hydrophobic group strand is short, polarity is stronger.Because branch is more, amino
Sulfonic acid sodium molecule is in vertical absorption typically in concrete particle surface, and this stereoeffect can make concrete in longer time
Interior its slump of holding and mobility；But the structure that hydrophobic group strand is short in molecule, polarity is stronger determines that it is applied to
Water retention property is poor during concrete, easy bleeding；And there is the noxious materials such as volatile phenol, formaldehyde, cost of material in raw material
Relatively partially expensive, production cost is higher.
The content of the invention
The present invention is in view of the shortcomings of the prior art, it is therefore intended that provide a kind of synthesis side of modified sulfamate water reducer
Method.
For achieving the above object, the technical solution adopted by the present invention is：
A kind of synthetic method of modified sulfamate water reducer, comprises the following steps：
(1) raw material is weighed：Sodium sulfanilate, phenol, sodium hydroxide, formalin, urea, water and melamine；
(2) melamine methylolation：Water, melamine, part formaldehyde are put into reactor A, 60 DEG C are warming up to,
After melamine is completely dissolved, continue to react 15 minutes, terminating reaction；
(3) dissolving is neutralized：By water, sodium sulfanilate, phenol input reactor B, stirring is warming up to 68~75 DEG C, so
After take sodium hydroxide to be dissolved in after water, be added to reactor B, continue to stir 15 minutes；
(4) methylolation is condensed：After the completion of question response kettle B stirring stirrings, formalin is added dropwise first quick and back slow thereto, controls
Formaldehyde time for adding processed is 1.5~2h, and keeping temperature is constant；After formalin is added dropwise to complete, sodium hydroxide is taken to be dissolved in after water
It is added in reactor B, rise temperature is incubated 4~5h to 90~98 DEG C；
(5) strand is reset：After reactor B methylolation condensation reaction terminates, 75~80 DEG C are cooled to, urine is added
Element, is incubated 1~2h, then solution in reactor A obtained by step (2) is added into reactor B, continues to react 2~3h, produces modified ammonia
Base sulfonate water reducer.
In such scheme, the molecular weight of the modified sulfamate water reducer is 3000Da~10000Da.
In such scheme, the raw material is by mass percentage：Sodium sulfanilate 15~25%；Phenol 5~
10%；Sodium hydroxide 0.25~0.3%；Formalin 20~40%；Urea 0.5~1.5%；Water 20~40%；Melamine
10~25%, the mass fraction of the formalin is 37%.
In such scheme, the amount ratio of step (2) melamine and formaldehyde is 1:1.86.
In such scheme, the amount ratio of step (3) sodium hydroxide and step (4) described sodium hydroxide is 15:2.
Beneficial effects of the present invention：(1) present invention prepares gained water reducer to the mineral additive (fine coal in concrete
Ash, miberal powder, silicon ash) conformability is good, can significantly improve in the water retention property of sulfamate water reducer, reduction concrete to subtracting
The sensitiveness of aqua volume；(2) function of slump protection of present invention preparation gained water reducer is excellent, and the fluidity that binder materials is starched only exists
Basic free of losses in 4h, Mortar'S Flowability basic free of losses in 4h；Use it for configuration commerical ready-mixed concrete, large fluidity coagulation
Soil, with water-reducing rate height, strength enhancing significant advantage；(3) present invention improves side chain using the melamine and urea of low price
Length, reduces the production cost of sulfamate water reducer；And using in the synthesis of Absorption for Urea sulfamate water reducer
Free formaldehyde, it is possible to reduce the pollution to environment.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Embodiment 1
A kind of synthetic method of modified sulfamate water reducer, comprises the following steps：
(1) weight proportion of raw material is:Sodium sulfanilate 17.37%；Phenol 7.07%；Formaldehyde 21.9%；Hydrogen-oxygen
Change sodium 0.26%；Urea 1.56%；Melamine 14.6%；Water 37.24%；
(2) melamine methylolation：By 85g water, 97.4g melamines, 52.5g formaldehyde is put into reactor A, heating
To 60 DEG C, after melamine is completely dissolved, continue terminating reaction after reacting 15 minutes；
(3) dissolving is neutralized：Weigh 92.5g water, 115.6g sodium sulfanilates, 47g phenol input reactor stirring liter
Temperature is to 73 DEG C；1.5g sodium hydroxides are weighed to be dissolved in 20g water；Sodium hydroxide solution is added into reactor, 15min is stirred；
(4) methylolation is condensed：93.2g formalins (mass fraction of the formalin is 37%) are weighed, treat anti-
Answer after the completion of kettle B stirrings, formalin is added dropwise first quick and back slow thereto, it is 1.5h to control formaldehyde time for adding, and keeping temperature is not
Become, weigh 0.2g sodium hydroxides and be dissolved in 20ml water, after formalin is added dropwise to complete, add sodium hydroxide, raise temperature
To 95 DEG C, 4.5h is incubated；
(5) strand is reset：Weigh 10.35g urea to be dissolved in 30g water, question response kettle B methylolation condensation reaction
After end, 80 DEG C are cooled to, urea is added, 2h is incubated, then solution in reactor A obtained by step (2) is added into reactor B, after
Continuous reaction 2h, produces modified sulfamate water reducer.
Embodiment 2
A kind of synthetic method of modified sulfamate water reducer, comprises the following steps：
(1) weight proportion of raw material is:Sodium sulfanilate 18.9%；Phenol 9.1%；Formaldehyde 25.3%；Hydroxide
Sodium 0.33%；Urea 0.93%；Melamine 15.9%；Water 29.54%；
(2) melamine methylolation：By 80g water, 97.4g melamines, 52.5g formaldehyde is put into reactor A, heating
To 60 DEG C, after melamine is completely dissolved, continue terminating reaction after reacting 15 minutes；
(3) dissolving is neutralized：Weigh 87.5g water, 115.6g sodium sulfanilates, the input reactor stirring of 67.7g phenol
It is warming up to 73 DEG C；1.8g sodium hydroxides are weighed to be dissolved in 10g water；Sodium hydroxide solution is added into reactor, 15min is stirred；
(4) methylolation is condensed：102.5g formalins (mass fraction of the formalin is 37%) are weighed, treat anti-
Answer after the completion of kettle B stirring stirrings, formalin is added dropwise first quick and back slow thereto, it is 1.5h to control formaldehyde time for adding, keeps temperature
Degree is constant, weighs 0.24g sodium hydroxides and is dissolved in 20ml water, after formalin is added dropwise to complete, and adds sodium hydroxide, rise
Temperature is incubated 4.5h to 95 DEG C；
(5) strand is reset：Weigh 11.4g urea to be dissolved in 10g water, question response kettle B methylolation condensation reaction
After end, 80 DEG C are cooled to, urea is added, 2h is incubated, then solution in reactor A obtained by step (2) is added into reactor B, after
Continuous reaction 2h, produces modified sulfamate water reducer.
The properties of product that the embodiment of the present invention 1~2 prepares gained modified sulfamate water reducer are as follows：
(1) this product is brown liquid, and pH value is 8~9, and solid content is 30~31%.
(2) this product flowing degree of net paste of cement experiment in, the ratio of mud be 0.29 when, volume for cement quality 0.5~
When 0.6%, fluidity is 230~250.
(3) when this product quality proportioning is the cementitious material system of 0.7 part of cement and 0.3 part of flyash, the ratio of mud is
When 0.29, when volume is the 0.6~0.8% of cementitious material system quality, fluidity is 230~250.
(4) when this product quality proportioning is the cementitious material system of 0.5 part of cement and 0.5 part of miberal powder, the ratio of mud is 0.29
When, when volume is the 0.7~0.9% of cementitious material system quality, fluidity is 230~250.
(5) when this product quality proportioning is the cementitious material system of 0.95 part of cement and 0.05 part of miberal powder, the ratio of mud is
When 0.29, when volume is the 0.5~0.7% of cementitious material system quality, fluidity is 230~250.
(6) this product is in glue sand test, when controlling glue Mortar'S Flowability for 200 ± 5mm, and aqua volume is cement quality
0.8~1.2% when, the basic frees of losses of Mortar'S Flowability 4h, water reducing ratio of cement mortar be 18%~23% (as shown in table 1).
The slump the performance test results of table 1
(7) this product mixes this agent (ASP) in concrete test, compared to normal concrete, three days intensity of concrete
30~50% can be improved, seven days intensity, which can improve 25~50%, 28 days intensity, can improve 20~30%, compare
In naphthalene water reducer (NF), water reducer volume is lower, and early strength lifting is substantially (as shown in table 2, table 3).
The concrete proportioning of table 2
The testing concrete performance result of table 3
Obviously, above-described embodiment is only intended to clearly illustrate made example, and the not limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change or change therefore amplified
Move within still in the protection domain of the invention.
Claims (5)
1. a kind of synthetic method of modified sulfamate water reducer, it is characterised in that comprise the following steps：
（1）Weigh raw material：Sodium sulfanilate, phenol, sodium hydroxide, formalin, urea, water and melamine；
（2）Melamine methylolation：Water, melamine, part formaldehyde are put into reactor A, 60 DEG C is warming up to, treats three
After poly cyanamid is completely dissolved, continue to react 15 minutes, terminating reaction；
（3）Dissolving is neutralized：By water, sodium sulfanilate, phenol input reactor B, stirring is warming up to 68 ~ 75 DEG C, Ran Houqu
Sodium hydroxide is dissolved in after water, is added to reactor B, continues to stir 15 minutes；
（4）Methylolation is condensed：After the completion of reactor B stirring stirrings, formalin is added dropwise first quick and back slow thereto, formaldehyde is controlled
Time for adding is 1.5 ~ 2h, and keeping temperature is constant；After formalin is added dropwise to complete, takes sodium hydroxide to be dissolved in after water and be added to instead
Answer in kettle B, rise temperature is incubated 4 ~ 5h to 90 ~ 98 DEG C；
（5）Strand is reset：After reactor B methylolation condensation reaction terminates, 75 ~ 80 DEG C are cooled to, urea, insulation is added
1 ~ 2h, then by step（2）Solution adds reactor B in gained reactor A, continues to react 2 ~ 3h, produces modified sulfamate
Water reducer.
2. preparation method according to claim 1, it is characterised in that the molecular weight of the modified sulfamate water reducer
For 3000Da ~ 10000Da.
3. preparation method according to claim 1, it is characterised in that the raw material is by mass percentage：To amino
Benzene sulfonic acid sodium salt 15 ~ 25%；Phenol 5 ~ 10%；Sodium hydroxide 0.25 ~ 0.3%；Formalin 20 ~ 40%；Urea 0.5 ~ 1.5%；Water 20 ~
40%；Melamine 10 ~ 25%, the mass fraction of the formalin is 37%.
4. preparation method according to claim 1, it is characterised in that step（2）The consumption of the melamine and formaldehyde
Than for 1:1.86.
5. preparation method according to claim 1, it is characterised in that step（3）The sodium hydroxide and step（4）It is described
The amount ratio of sodium hydroxide is 15:2.
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| CN201710108054.3A CN107129176B (en) | 2017-02-27 | 2017-02-27 | A kind of synthetic method of modified sulfamate water reducer |
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| CN201710108054.3A CN107129176B (en) | 2017-02-27 | 2017-02-27 | A kind of synthetic method of modified sulfamate water reducer |
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| CN107129176A true CN107129176A (en) | 2017-09-05 |
| CN107129176B CN107129176B (en) | 2019-08-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109516727A (en) * | 2018-11-22 | 2019-03-26 | 盐城欣昌新型建材有限公司 | A kind of corrosion-resistant cement pipe pile of photovoltaic and preparation method thereof |
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|---|---|---|---|---|
| CN101723615A (en) * | 2009-12-18 | 2010-06-09 | 江苏特密斯混凝土外加剂有限公司 | Method for preparing novel sulfamic acid high-efficiency concrete water reducing agent |
| CN102267807A (en) * | 2011-05-11 | 2011-12-07 | 马清浩 | Modified melamine water reducer-containing cement-based grouting material and preparation method thereof |
| CN103965417A (en) * | 2013-12-28 | 2014-08-06 | 福清市永春混凝土外加剂有限公司 | Lignin sulfonate modified aminosulfonic acid series efficient water reducer and preparation method thereof |
| CN105819728A (en) * | 2016-03-10 | 2016-08-03 | 安徽鑫固环保股份有限公司 | Papermaking black liquor modified sulfamate high efficiency water reducer and preparation method thereof |
-
2017
- 2017-02-27 CN CN201710108054.3A patent/CN107129176B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101723615A (en) * | 2009-12-18 | 2010-06-09 | 江苏特密斯混凝土外加剂有限公司 | Method for preparing novel sulfamic acid high-efficiency concrete water reducing agent |
| CN102267807A (en) * | 2011-05-11 | 2011-12-07 | 马清浩 | Modified melamine water reducer-containing cement-based grouting material and preparation method thereof |
| CN103965417A (en) * | 2013-12-28 | 2014-08-06 | 福清市永春混凝土外加剂有限公司 | Lignin sulfonate modified aminosulfonic acid series efficient water reducer and preparation method thereof |
| CN105819728A (en) * | 2016-03-10 | 2016-08-03 | 安徽鑫固环保股份有限公司 | Papermaking black liquor modified sulfamate high efficiency water reducer and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109516727A (en) * | 2018-11-22 | 2019-03-26 | 盐城欣昌新型建材有限公司 | A kind of corrosion-resistant cement pipe pile of photovoltaic and preparation method thereof |
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| CN107129176B (en) | 2019-08-23 |
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Effective date of registration: 20201216 Address after: Room 8542, building 3, No. 112-118, Gaoyi Road, Baoshan District, Shanghai, 201900 Patentee after: Shanghai Yu Concrete Construction Technology Co.,Ltd. Address before: 430070 Hubei Province, Wuhan city Hongshan District Luoshi Road No. 122 Patentee before: WUHAN University OF TECHNOLOGY |
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