CN106188455A - A kind of synthetic method of bisphenol A polyethenoxy ether modified sulfamate water reducer - Google Patents
A kind of synthetic method of bisphenol A polyethenoxy ether modified sulfamate water reducer Download PDFInfo
- Publication number
- CN106188455A CN106188455A CN201610585679.4A CN201610585679A CN106188455A CN 106188455 A CN106188455 A CN 106188455A CN 201610585679 A CN201610585679 A CN 201610585679A CN 106188455 A CN106188455 A CN 106188455A
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- Prior art keywords
- bisphenol
- polyethenoxy ether
- water reducer
- sulfamate water
- ether modified
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- 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
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
-
- 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
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses the synthetic method of a kind of bisphenol A polyethenoxy ether modified sulfamate water reducer, comprise the steps: 1. to put in reactor a certain proportion of phenol, bisphenol A polyethenoxy ether, sodium sulfanilate and deionized water, it is sufficiently stirred under room temperature state, makes reaction system transparent and homogeneous；2. it is warming up to 55 65 DEG C, with NaOH, reaction system is adjusted to alkaline state, control pH value 9.00 13.00；When being 3. continuously heating to 80 DEG C, remaining a constant speed and drip formalin in reaction system, time for adding is 24 hours, and keeping temperature during dropping is 80 90 DEG C；4. finally 80 100 DEG C of insulation reaction 35 hours, it is cooled to 40 DEG C and with bottom discharge and get final product.The modified sulfamate water reducer using this technique to prepare efficiently solves sulfamate water reducer when being used alone, the problem easily cause fresh concrete bleeding, hardening, it is greatly improved the popularity of products application, also shows, when the most directly using, the water-reducing rate that product is the highest.
Description
One, technical field
The invention belongs to high performance water-reducer technical field, be specifically related to a kind of bisphenol A polyethenoxy ether modified sulfamate and subtract
The synthetic method of water preparation.
Two, background technology
Sulfamate water reducer is a critically important class concrete high efficiency water reducing agent.Its molecular structure is single aromatic ring type, long
The short main chain of side chain, polarity is stronger.This water reducer has that water-reducing rate height, good dispersion, deferred action be relatively strong, little loss of slump
Etc. feature, production technology is simple, and Application comparison is extensive at home.But its volume is the most sensitive, diminishing easily occurs when volume is low
Rate is little, and the slump is little；Easily produce bleeding during volume height, affect the homogeneity of concrete.Easily make when being particularly used alone
The problem become fresh concrete bleeding, hardening, reduces the popularity of products application, is the most all compounding use.It is conventionally synthesized
The primary raw material of sulfamate high-effective water-reducing agent is phenol, sulfamic acid sodium and formaldehyde, therefore both at home and abroad at the modified ammonia of research
It is in the work that base sulfonate high efficiency water reducing agent aspect is done, main by introducing the 4th monomer in addition to above-mentioned three kinds of raw materials,
Molecular structure is modified.Patent publication No. is to mention introducing in CN104961375A containing carboxyl material such as salicylic acid etc., master
It is reduction of it to produce and use cost；Patent publication No. is the waste liquid mentioned in CN104844053A and use bisnaphthol, right
Molecular structure is modified, primarily to solve the emission problem of bisnaphthol waste liquid；Patent publication No. is
CN102432218A mentions sulfamate is modified, mainly also for reducing cost.
Three, summary of the invention
It is an object of the invention to provide the synthetic method of a kind of bisphenol A polyethenoxy ether modified sulfamate water reducer, use
Modified sulfamate water reducer prepared by this technique can efficiently solve the problems in existing product application.
For achieving the above object, the technical solution used in the present invention is: the method comprises the steps:
1. in reactor, put into a certain proportion of phenol, bisphenol A polyethenoxy ether, sodium sulfanilate and deionized water,
It is sufficiently stirred under room temperature state, makes reaction system transparent and homogeneous；
2. it is warming up to 55-65 DEG C, with NaOH, reaction system is adjusted to alkaline state, control pH value at 9.00-13.00；
When being 3. continuously heating to 80 DEG C, remaining a constant speed and drip formalin in reaction system, time for adding is 2-4 hour,
Temperature is kept to be 80-90 DEG C during dropping；
4. last 80-100 DEG C of insulation reaction 3-5 hour, it is cooled to 40 DEG C and with bottom discharge and get final product.
Above-mentioned bisphenol A polyethenoxy ether right for 6-40, preferred degree of polymerization is 8-14.
The pH value of above-mentioned reaction system controls at 9.50-10.50.
Temperature and insulation reaction temperature is kept to be 90-95 DEG C during above-mentioned dropping formaldehyde.
Above-mentioned phenol: bisphenol A polyethenoxy ether: sodium sulfanilate: deionized water=1:0.02-0.2:0.4-0.8:
7.8-31, aforementioned proportion is mol ratio.
In above-mentioned formalin, formaldehyde mass fraction is 30%-50%；Phenol: formalin=1:0.6-1.5, aforementioned proportion
For mass ratio.
Above-mentioned phenol: sodium hydroxide=1:0.1-0.15, aforementioned proportion is mol ratio.
The modified sulfamate water reducer using this technique to prepare efficiently solve its when being used alone, easily cause
Fresh concrete bleeding, the problem hardened, be greatly improved the popularity of products application, also shows when the most directly using
The water-reducing rate that product is the highest.
Present invention have the advantage that
(1) by introducing the 4th monomeric bisphenol A polyoxyethylene ether, asking of sulfamate water reducer volume sensitivity is solved
Topic, improves product and uses the tolerance of volume.
(2) by introducing the 4th monomeric bisphenol A polyoxyethylene ether, solve and hold when sulfamate water reducer is used alone
The problem easily cause fresh concrete bleeding, hardening, is greatly improved the popularity of products application, when the most directly using also
Show the water-reducing rate that product is the highest.
(3) by introducing the 4th monomeric bisphenol A polyoxyethylene ether, make that formaldehyde react more fully, reduce formaldehyde and exist
Residual quantity in product, it is achieved that the greenization of product.
Four, detailed description of the invention
Embodiment 1:
Phenol 107.3g, bisphenol A polyethenoxy (10) ether 25.8g, sodium sulfanilate 161.4g is put in 2L reactor
With deionized water 506.4g, stir 20 minutes under room temperature state, in reactor, be rendered as colourless transparent liquid.Reactor adds
Heat, is warming up to 55 DEG C, adds NaOH pressed powder 11.1g, reaction system is adjusted to alkaline state, the most instead in reactor
The pH value answering system is 10.15.Continue to heat up when temperature reaches 80 DEG C, keep 1.5g/min at the uniform velocity to drip in reaction system
Formalin, drips formaldehyde 188.9g in 2 hours, keeps temperature to be 80-90 DEG C during dropping.Last 88-90 DEG C of guarantor
Temperature reaction 3 hours, is cooled to 40 DEG C of dischargings, and product solid content is 37%.
Embodiment 2:
Phenol 107.3g, bisphenol A polyethenoxy (15) ether 62.3g, sodium sulfanilate 207.8g is put in 2L reactor
With deionized water 438.8g, stir 30 minutes under room temperature state, in reactor, be rendered as colourless transparent liquid.Reactor adds
Heat, is warming up to 60 DEG C, adds NaOH pressed powder 15.9g, reaction system is adjusted to alkaline state, the most instead in reactor
The pH value answering system is 10.95.Continue to heat up when temperature reaches 80 DEG C, keep 1.5g/min at the uniform velocity to drip in reaction system
Formalin, drips formaldehyde 243.2g in 2.5 hours, keeps temperature to be 80-90 DEG C during dropping.Last at 88-90 DEG C
Insulation reaction 3.5 hours, is cooled to 40 DEG C of dischargings, and product solid content is 50%.
Embodiment 3:
In 2L reactor, put into phenol 98g, bisphenol A polyethenoxy (9) ether 21.7g, sodium sulfanilate 132.1g and go
Ionized water 164g, stirs 20 minutes under room temperature state, is rendered as colourless transparent liquid in reactor.Reactor heats, and heats up
To 55 DEG C, in reactor, add NaOH pressed powder 4.9g, reaction system is adjusted to alkaline state, now reaction system
PH value is 10.28.Continue to heat up when temperature reaches 80 DEG C, keep 1g/min at the uniform velocity to drip formaldehyde in reaction system water-soluble
Liquid, drips formalin 119.8g in 2 hours, keeps temperature to be 80-90 DEG C during dropping.Last 88-90 DEG C of insulation
Reacting 3 hours, be cooled to 40 DEG C of dischargings, product solid content is 45%.
Embodiment 4:
In 2L reactor put into phenol 115g, bisphenol A polyethenoxy (12) ether 55.8g, sodium sulfanilate 183.1g and
Deionized water 402g, stirs 20 minutes under room temperature state, is rendered as colourless transparent liquid in reactor.Reactor heats, and rises
Temperature, to 55 DEG C, adds NaOH pressed powder 6.1g in reactor, reaction system is adjusted to alkaline state, now reaction system
PH value be 10.44.Continue to heat up when temperature reaches 80 DEG C, keep 1g/min at the uniform velocity to drip formaldehyde in reaction system water-soluble
Liquid, 1 hour 56 points drip formaldehyde 106g, during dropping keep temperature be 80-90 DEG C.Last in 88-90 DEG C of insulation reaction 3
Hour, it being cooled to 40 DEG C of dischargings, product solid content is 48%.
Embodiment 5:
In 2L reactor put into phenol 106g, bisphenol A polyethenoxy (11) ether 142.4g, sodium sulfanilate 110.1g and
Deionized water 341.3g, stirs 20 minutes under room temperature state, is rendered as colourless transparent liquid in reactor.Reactor heats,
It is warming up to 55 DEG C, in reactor, adds NaOH pressed powder 6.2g, reaction system is adjusted to alkaline state, now reactant
The pH value of system is 10.38.Continue to heat up when temperature reaches 80 DEG C, keep 1.1g/min at the uniform velocity to drip formaldehyde in reaction system
Aqueous solution, drips formaldehyde 132g in 2 hours, keeps temperature to be 80-90 DEG C during dropping.Last in 88-90 DEG C of insulation reaction 3
Hour, it being cooled to 40 DEG C of dischargings, product solid content is 49%.
Claims (10)
1. a synthetic method for bisphenol A polyethenoxy ether modified sulfamate water reducer, comprises the steps:
1. in reactor, put into a certain proportion of phenol, bisphenol A polyethenoxy ether, sodium sulfanilate and deionized water,
It is sufficiently stirred under room temperature state, makes reaction system transparent and homogeneous；
2. it is warming up to 55-65 DEG C, with NaOH, reaction system is adjusted to alkaline state, control pH value at 9.00-13.00；
When being 3. continuously heating to 80 DEG C, remaining a constant speed and drip formalin in reaction system, time for adding is 2-4 hour,
Temperature is kept to be 80-90 DEG C during dropping；
4. last 80-100 DEG C of insulation reaction 3-5 hour, it is cooled to 40 DEG C and with bottom discharge and get final product.
The synthetic method of a kind of bisphenol A polyethenoxy ether modified sulfamate water reducer the most according to claim 1, its
Feature is: described bisphenol A polyethenoxy ether right for 6-40.
The synthesis side of a kind of bisphenol A polyethenoxy ether modified sulfamate water reducer the most according to claim 1 and 2
Method, is characterized in that: described bisphenol A polyethenoxy ether right for 8-14.
The synthesis side of a kind of bisphenol A polyethenoxy ether modified sulfamate water reducer the most according to claim 1 and 2
Method, is characterized in that: the pH value of described reaction system controls at 9.50-10.50.
The synthesis side of a kind of bisphenol A polyethenoxy ether modified sulfamate water reducer the most according to claim 1 and 2
Method, is characterized in that: keep temperature and insulation reaction temperature to be 90-95 DEG C during described dropping formaldehyde.
The synthesis side of a kind of bisphenol A polyethenoxy ether modified sulfamate water reducer the most according to claim 1 and 2
Method, is characterized in that: described phenol: bisphenol A polyethenoxy ether: sodium sulfanilate: deionized water=1:0.02-0.2:0.4-
0.8:7.8-31, aforementioned proportion is mol ratio.
The synthesis side of a kind of bisphenol A polyethenoxy ether modified sulfamate water reducer the most according to claim 1 and 2
Method, is characterized in that: in described formalin, formaldehyde mass fraction is 30%-50%.
The synthesis side of a kind of bisphenol A polyethenoxy ether modified sulfamate water reducer the most according to claim 1 and 2
Method, is characterized in that: described phenol: formalin=1:0.6-1.5, and aforementioned proportion is mass ratio.
The synthesis side of a kind of bisphenol A polyethenoxy ether modified sulfamate water reducer the most according to claim 1 and 2
Method, is characterized in that: described phenol: sodium hydroxide=1:0.1-0.15, and aforementioned proportion is mol ratio.
The synthesis side of a kind of bisphenol A polyethenoxy ether modified sulfamate water reducer the most according to claim 1 and 2
Method, is characterized in that: described under room temperature state mixing time be 20-30 minute.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610585679.4A CN106188455B (en) | 2016-07-25 | 2016-07-25 | A kind of synthetic method of bisphenol A polyethenoxy ether modified sulfamate water reducer |
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| CN201610585679.4A CN106188455B (en) | 2016-07-25 | 2016-07-25 | A kind of synthetic method of bisphenol A polyethenoxy ether modified sulfamate water reducer |
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| CN106188455B CN106188455B (en) | 2018-01-30 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107722207A (en) * | 2017-09-21 | 2018-02-23 | 广东科隆智谷新材料股份有限公司 | The preparation method of sulfamate water reducer |
| CN108250447A (en) * | 2016-12-28 | 2018-07-06 | 江苏苏博特新材料股份有限公司 | Polyether modified amino sulfonate high efficiency water reducing agent, preparation method and application |
| CN114230731A (en) * | 2022-02-24 | 2022-03-25 | 天津冶建特种材料有限公司 | Modified polycarboxylate superplasticizer and preparation method thereof |
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| GB2236533A (en) * | 1989-09-01 | 1991-04-10 | Sanyo Kokusaku Pulp Co | Bisphenol condensates |
| EP0308915B1 (en) * | 1987-09-25 | 1993-08-18 | Fujisawa Pharmaceutical Co., Ltd. | Aminoarylsulfonic acid-phenol-formaldehyde condensate and concrete admixture comprising the same |
| CN101293757A (en) * | 2008-06-17 | 2008-10-29 | 武汉理工大学 | Polyether modification type sulfamate water reducing agent and preparation method |
| CN102115520A (en) * | 2011-01-04 | 2011-07-06 | 福州大学 | Alkali lignin-phenol-sodium sulfanilate-formaldehyde polycondensate and preparation method thereof |
| CN102211912A (en) * | 2011-04-08 | 2011-10-12 | 马清浩 | Cement-based grouting material containing sulfamate water reducing agent and preparation method thereof |
| CN102504151A (en) * | 2011-10-17 | 2012-06-20 | 山东宏艺科技股份有限公司 | Sulfonate water reducer and preparation method thereof |
| CN103121805A (en) * | 2013-01-30 | 2013-05-29 | 李惠民 | High-performance concrete anti-cracking high efficiency water reducing agent |
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2016
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|---|---|---|---|---|
| EP0308915B1 (en) * | 1987-09-25 | 1993-08-18 | Fujisawa Pharmaceutical Co., Ltd. | Aminoarylsulfonic acid-phenol-formaldehyde condensate and concrete admixture comprising the same |
| GB2236533A (en) * | 1989-09-01 | 1991-04-10 | Sanyo Kokusaku Pulp Co | Bisphenol condensates |
| CN101293757A (en) * | 2008-06-17 | 2008-10-29 | 武汉理工大学 | Polyether modification type sulfamate water reducing agent and preparation method |
| CN102115520A (en) * | 2011-01-04 | 2011-07-06 | 福州大学 | Alkali lignin-phenol-sodium sulfanilate-formaldehyde polycondensate and preparation method thereof |
| CN102211912A (en) * | 2011-04-08 | 2011-10-12 | 马清浩 | Cement-based grouting material containing sulfamate water reducing agent and preparation method thereof |
| CN102504151A (en) * | 2011-10-17 | 2012-06-20 | 山东宏艺科技股份有限公司 | Sulfonate water reducer and preparation method thereof |
| CN103121805A (en) * | 2013-01-30 | 2013-05-29 | 李惠民 | High-performance concrete anti-cracking high efficiency water reducing agent |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250447A (en) * | 2016-12-28 | 2018-07-06 | 江苏苏博特新材料股份有限公司 | Polyether modified amino sulfonate high efficiency water reducing agent, preparation method and application |
| CN108250447B (en) * | 2016-12-28 | 2020-12-29 | 江苏苏博特新材料股份有限公司 | Polyether modified sulfamate high-efficiency water reducing agent, and preparation method and application thereof |
| CN107722207A (en) * | 2017-09-21 | 2018-02-23 | 广东科隆智谷新材料股份有限公司 | The preparation method of sulfamate water reducer |
| CN107722207B (en) * | 2017-09-21 | 2020-06-19 | 广东科隆智谷新材料股份有限公司 | Preparation method of sulfamate water reducer |
| CN114230731A (en) * | 2022-02-24 | 2022-03-25 | 天津冶建特种材料有限公司 | Modified polycarboxylate superplasticizer and preparation method thereof |
| CN114230731B (en) * | 2022-02-24 | 2022-05-03 | 天津冶建特种材料有限公司 | Modified polycarboxylate superplasticizer and preparation method thereof |
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| CN106188455B (en) | 2018-01-30 |
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