CN1088592A - Compound sulfonated carbamide-resin and its production and use - Google Patents
Compound sulfonated carbamide-resin and its production and use Download PDFInfo
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- CN1088592A CN1088592A CN 93120430 CN93120430A CN1088592A CN 1088592 A CN1088592 A CN 1088592A CN 93120430 CN93120430 CN 93120430 CN 93120430 A CN93120430 A CN 93120430A CN 1088592 A CN1088592 A CN 1088592A
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- reaction
- sulfonated
- resin
- carbamide
- sulfonation
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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
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/30—Condensation polymers of aldehydes or ketones
- C04B24/307—Urea-formaldehyde condensation polymers
-
- 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
- C04B2103/32—Superplasticisers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Compound sulfonated carbamide-resin that is used as the concrete superplasticizer and preparation method thereof includes the macromolecular synthetic reaction under organic compounds and the common reaction of mineral compound.It is gone through successively under alkaline condition, is 1 by urea and formaldehyde mole ratio: the proportioning of (2.1～3) is reinforced, carries out hydroxymethylation; Be that 1: 1～5 proportioning adds each component of composite sulfonated dose successively by the mol ratio of urea and composite sulfonated dose again, carry out sulfonation reaction; Under acidic conditions, carry out condensation reaction then; At last under the condition of stable p H=7.5～8.0, carry out molecular rearrangement reaction and promptly get the concrete superplasticizer that every performance index meet or exceed the similar products at home and abroad standard, its consumption is few and to reduce reinforced effects remarkable, and can adapt to the pumping of flowing concrete continuity in producing, the needs that pipe send Technology.
Description
The present invention relates to macromolecule synthesising technology, specifically belong to the macromolecular synthetic reaction under the common reaction of organic compound and mineral compound.
The conventional concrete superplasticizer is the sulfonated melamine compound water soluble resin.At U.S. Pat pat 4,430,469 denominations of invention are thought the preparation method of at present state-of-the-art sulfonated melamine compound resin as the concrete superplasticizer for disclosing a kind of this area in " high dense low sticking water-soluble terpolycyantoamino-formaldehyde resin manufacturing processed ".Though this achievement is called as the important breakthrough in concrete technology field, its effect is also fine, has promoted the development of cement applications technology effectively, but the used prices of raw and semifnished materials costliness of this preparation method, be difficult to realize industrialization, be unfavorable for especially in Chinese widespread use.
The objective of the invention is to overcome the defective of background technology, it is cheap to create a kind of prices of raw and semifnished materials, concrete superplasticizer that production cost descends significantly and preparation method thereof.Developing China is still very backward concrete superplasticizer Application Areas at present, to quicken the progress of building construction technology.
The objective of the invention is to reach by following measure:
Make compound sulfonated carbamide-resin that the concrete superplasticizer uses and preparation method thereof, it is characterized in that going through successively hydroxymethylation, sulfonation reaction, condensation reaction and molecular rearrangement reaction, the reaction product compound sulfonated carbamide-resin of gained, its chemical structural formula is:
The step and the processing condition thereof of this method are:
The first step: hydroxymethylation
The chemical reaction skeleton symbol:
Carry out hydroxymethylation by proportioning input formaldehyde and urea under alkaline condition, its reaction product is a methylolurea.
Its processing condition are:
(1), the mol ratio of urea and formaldehyde is 1: (2.1～3.0);
(2), add PH stablizer trolamine or sodium hydroxide and make PH=7.5～11;
(3), temperature of reaction is 50 ℃～95 ℃;
(4), 1～2.5 hour reaction times;
(5), when free formaldehyde content reduce to≤1% the time, be considered as reaction and finish.
Second step: sulfonation reaction
The chemical reaction skeleton symbol
In the reaction product methylolurea of the first step, add composite sulfonated dose of each component successively by proportioning, in stable alkaline environment, carry out sulfonation reaction, its reaction product is the low molecule of sulfonated urea-formaldehyde.
Its processing condition are:
(1), the mol ratio of urea and composite sulfonated dose is 1: (1～5)
(2), composite sulfonated dose composition and mol ratio thereof:
Composite sulfonated dose by main sulphonating agent, help sulphonating agent and three kinds of components of sulfonation reaction promotor to be formed,
Main sulphonating agent is 10: 1 with helping the mol ratio of sulphonating agent,
The mol ratio that helps sulphonating agent and sulfonation promotor is 1: 1,
Main sulphonating agent is Sodium Pyrosulfite or sodium bisulfite,
Helping sulphonating agent is thionamic acid,
Sulfonation promotor is S-WAT;
(3), adjust pH value to a certain value between being stabilized in 9～13 with alkali;
(4), temperature of reaction is 75 ℃～100 ℃;
(5), 1.5～3 hours reaction times;
(6), when free methylol group content≤6%, be considered as reaction and finish;
The 3rd step: condensation reaction
The chemical reaction skeleton symbol:
Material dewaters in acidic conditions, and reaction is constantly carried out, and its molecular chain is increased.
Its processing condition are:
(1), add acid and transfer pH value to 0.5～4.5, and be stabilized in a certain value;
(2), 75 ℃～100 ℃ of setting-up point, and be stabilized in a certain value;
(3), the backflow condensation reaction time is 1～4 hour;
The 4th step: molecular rearrangement reaction
Its processing condition are:
(1), transfer pH value and add the PH stablizer, make PH=7.5～8.0 with alkali;
(2), the molecular rearrangement reaction temperature is 80 ℃～90 ℃;
(3), 1～3 hour molecular rearrangement reaction time, reach 500～1500 centipoises with viscosity and be as the criterion; Last cooling discharging.
By contriver's years of researches, repetition test has been grasped the set of dispense ratio of appropriate reaction conditions and appropriateness finally, synthesizes with sulfonation ultrapas formaldehyde resin performance and quite and traditionally thinks the sulfonated carbamide-resin that the sulfonation yield is very low.In order to further specify technological process of the present invention, exemplify following embodiment.
Embodiment one
The first step: hydroxymethylation
Get 5.51 moles 37% industrial formol earlier and put into the there-necked flask that spherical reflux exchanger, agitator, thermometer are housed.Use PH stablizer trolamine again, make whole system PH keep stable, i.e. PH=7.5.In weakly alkaline environment, slowly add 2 moles urea while stirring, be warming up to 90 ℃, under reflux state, reacted 0.5 hour then, the free sub-formaldehyde content of check≤1% o'clock is looked hydroxymethylation and is finished, and gets the reaction product methylolurea.
Second step: sulfonation reaction
In hydroxymethylation product methylolurea, add respectively 2 moles main sulphonating agent sodium bisulfite, 0.2 mole help sulphonating agent thionamic acid and three kinds of components of 0.2 mole of sulfonation promotor S-WAT, adjust pH value with sodium hydroxide again, to PH=12, temperature transfers to 80 ℃, and back flow reaction is 2 hours then, check free methylol group content≤6% o'clock, be considered as reaction and finish, getting the sulfonation reaction product is the low molecule of sulfonated urea-formaldehyde.
The 3rd step: condensation reaction
Add the 98% an amount of vitriol oil and transfer pH value in the low molecule of sulfonation reaction product sulfonated urea-formaldehyde, to PH=4, be incubated 80 ℃, the backflow condensation reaction makes material dewatering.
The 4th step: molecular rearrangement reaction
For the sulfonated urea-formaldehyde macromolecular structure is rearranged, the sodium hydroxide that adds an amount of 10N is adjusted pH value, add an amount of PH stablizer trolamine again, pH value is stabilized between 7.5～8.0, be incubated 80 ℃, during reaction 2.5 hours, reach 1000 centipoise postcooling dischargings to viscosity, being can be as the compound sulfonated carbamide-resin of concrete superplasticizer.
Embodiment two
The first step: hydroxymethylation
Get 500 moles 37% industrial formol earlier and put into the reactor that pipe bundle condenser, agitator, thermometer, heat exchange chuck are housed.Use PH stablizer sodium hydroxide again, make reacting system PH value keep stable, i.e. PH=10.In alkaline environment, add 200 moles urea while stirring, ℃ then about 1 hour of reaction under reflux state of heating in water bath to 60, promptly to be white in color muddy back 5～10 minutes of reaction product, this moment the reaction product methylolurea.
Second step: sulfonation reaction
In hydroxymethylation product methylolurea, add respectively 150 moles main sulphonating agent Sodium Pyrosulfite, 7.5 moles help sulphonating agent thionamic acid and three kinds of components of 7.5 moles of sulfonation promotor S-WATs, adjust pH value with sodium hydroxide again, to PH=10, be warming up to 95 ℃, back flow reaction is 1.5 hours then, check free methylol group content≤6%, sulfonation reaction finishes, and gets the low molecule of sulfonated urea-formaldehyde.
The 3rd step: condensation reaction
In the low molecule of sulfonated urea-formaldehyde, add an amount of sulfuric acid to transfer pH value, to PH=3.5,60 ℃ of temperature, material dewatering increases the reaction product molecular chain.
The 4th step: molecular rearrangement reaction
For the sulfonated urea-formaldehyde macromolecular structure is rearranged, this law adds proper amount of sodium hydroxide and transfers pH value, add an amount of PH stablizer trolamine again, make PH=7.5～8.0 of reaction system, temperature is 70 ℃, reacted 0.5 hour, and reached 900 centipoise postcooling dischargings to viscosity, being to be the compound sulfonated carbamide-resin of cement alkali aqua as the concrete superplasticizer.
Example three: purposes example
Take by weighing standard sand 750 grams, 425
#Cement 300 grams, tap water 125 grams, compound sulfonated carbamide-resin 3 grams that the present invention of 50% solids content is prepared, putting into agitator, mix and stirred 3 minutes, is 15% with jumping table test water-reducing rate, make a collection of sand oar sample again, surveying different age strengths, obtain the intensity rate compared with blank, is 100 in blank:
| The length of time | Compressive strength rate |
| Three days | 141 |
| Seven days | 132 |
| 28 days | 122 |
Technical scheme provided by the present invention and products thereof has the following advantages:
1, the prices of raw and semifnished materials that adopt are cheap, and the production cost of comparing the sulfonated melamine compound resin in the background technology descends significantly.
2, the property indices by the product quality of this law preparation meets or exceeds standard GB/T 8076-87, and meets or exceeds the property indices of the like product of main advanced country.
Following table is the comparison of the prepared product of the present invention with some relevant performance indications of advanced country:
3, the product of the present invention's preparation is longer stationary phase, namely reaches more than 1 year.
4, the product of the present invention's preparation can mix with any ratio with water, can adapt to the needs that pumping, pipe in the flowing concrete consecutive production send technology or early strength concrete to prepare, and has good general application prospect.
5, product addition in concrete production of the present invention preparation few (add cement consumption 0.5～1.2%), and that water-reducing effect and enhancing especially strengthen effect is remarkable.
Claims (3)
1, a kind of compound sulfonated carbamide-resin is characterized in that, it is a reaction product compound sulfonated carbamide-resin of going through hydroxymethylation, sulfonation reaction, condensation reaction and molecular rearrangement reaction gained successively, and its chemical structural formula is:
2, a kind of preparation method of compound sulfonated carbamide-resin is characterized in that, the step and the processing condition thereof of this method are as follows:
Step 1: hydroxymethylation
Carry out hydroxymethylation by proportioning input formaldehyde and urea under alkaline condition, get methylolurea, its processing condition are:
(1), the mol ratio of urea and formaldehyde is 1: (2.1～3.0),
(2), add PH stablizer trolamine or sodium hydroxide makes PH=7.5～11,
(3), 50 ℃～95 ℃ of temperature of reaction,
(4), 1～2.5 hour reaction times,
(5), when free formaldehyde content reduce to≤1% the time, be considered as reaction and finish;
Step 2: sulfonation reaction
In the reaction product methylolurea of the first step, add composite sulfonated dose of each component successively by proportioning, in stable alkaline environment, carry out sulfonation reaction, get the low molecule of sulfonated urea-formaldehyde, its processing condition are:
(1), the mol ratio of urea and composite sulfonated dose is: 1: (1～5),
(2), composite sulfonated dose composition and mol ratio thereof:
Composite sulfonated dose by main sulphonating agent, help sulphonating agent and three kinds of components of sulfonation reaction promotor to be formed,
Main sulphonating agent is 10: 1 with helping the mol ratio of sulphonating agent,
Help the mol ratio of sulphonating agent and sulfonation promotor: 1: 1,
Main sulphonating agent is Sodium Pyrosulfite or sodium bisulfite, and helping the sulphur agent is thionamic acid,
Sulfonation promotor is S-WAT,
(3), adjust pH value to a certain value between being stabilized in 9～13, with alkali
(4), 75 ℃～100 ℃ of temperature of reaction,
(5), 1.5～3 hours reaction times,
(6), when free methylol group content≤6%, be considered as reaction and finish;
Step 3: condensation reaction
Material dewaters in acidic conditions, and its molecular linkage is increased, and its processing condition are:
(1), add acid and transfer pH value to 0.5～4.5, and be stabilized in a certain value,
(2), 75 ℃～100 ℃ of setting-up point, and be stabilized in a certain value,
(3), the backflow condensation reaction time is 1～4 hour;
Step 4: molecular rearrangement reaction
Carry out molecular rearrangement reaction under stable alkaline environment, its processing condition are:
(1), transfer pH value and add the pH value stablizer, make PH=7.5～8.0 with alkali,
(2), 80 ℃～90 ℃ of molecular rearrangement reaction temperature,
(3), 1～3 hour molecular rearrangement reaction time, reaching 500～1500 centipoises with viscosity is the discharging standard.
3, a kind of compound sulfonated carbamide-resin is characterized in that compound sulfonated carbamide-resin makes the concrete superplasticizer and use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93120430 CN1088592A (en) | 1993-12-13 | 1993-12-13 | Compound sulfonated carbamide-resin and its production and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93120430 CN1088592A (en) | 1993-12-13 | 1993-12-13 | Compound sulfonated carbamide-resin and its production and use |
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| Publication Number | Publication Date |
|---|---|
| CN1088592A true CN1088592A (en) | 1994-06-29 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 93120430 Pending CN1088592A (en) | 1993-12-13 | 1993-12-13 | Compound sulfonated carbamide-resin and its production and use |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001023450A1 (en) * | 1999-09-29 | 2001-04-05 | Skw Polymers Gmbh | Sulfonated condensation products which are stabile in storage, method for the production thereof, and their use |
| CN1318468C (en) * | 2001-10-15 | 2007-05-30 | 中国林业科学研究院林产化学工业研究所 | Sulfonated urea-formaldehyde multifunctional soil improving agent and its preparation method |
| CN113105597A (en) * | 2021-04-06 | 2021-07-13 | 杭州邦利建材有限公司 | Preparation process of aliphatic water reducer |
-
1993
- 1993-12-13 CN CN 93120430 patent/CN1088592A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001023450A1 (en) * | 1999-09-29 | 2001-04-05 | Skw Polymers Gmbh | Sulfonated condensation products which are stabile in storage, method for the production thereof, and their use |
| US6864344B1 (en) | 1999-09-29 | 2005-03-08 | Skw Polymers Gmbh | Sulfonated condensation products which are stabile in storage, method for the production thereof, and their use |
| CN1318468C (en) * | 2001-10-15 | 2007-05-30 | 中国林业科学研究院林产化学工业研究所 | Sulfonated urea-formaldehyde multifunctional soil improving agent and its preparation method |
| CN113105597A (en) * | 2021-04-06 | 2021-07-13 | 杭州邦利建材有限公司 | Preparation process of aliphatic water reducer |
| CN113105597B (en) * | 2021-04-06 | 2022-11-29 | 杭州邦利建材有限公司 | Preparation process of aliphatic water reducer |
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