CN104262547A - Method for low-temperature synthesis of polycarboxylate water reducer by using isoamyl alcohol polyether - Google Patents
Method for low-temperature synthesis of polycarboxylate water reducer by using isoamyl alcohol polyether Download PDFInfo
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- CN104262547A CN104262547A CN201410487227.3A CN201410487227A CN104262547A CN 104262547 A CN104262547 A CN 104262547A CN 201410487227 A CN201410487227 A CN 201410487227A CN 104262547 A CN104262547 A CN 104262547A
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Abstract
The invention relates to a method for low-temperature synthesis of a polycarboxylate water reducer by using isoamyl alcohol polyether, belonging to the technical field of water reducer preparation. The method comprises the following steps: by adopting isoamyl alcohol polyether and acrylic acid as raw materials, firstly forming an isoamyl alcohol polyether solution by dissolving isoamyl alcohol polyether into deionized water under heating conditions, respectively dropwise adding an acrylic acid aqueous solution and a mixed solution of a mercaptan type water-soluble chain transfer agent and a free radical type initiating agent into the isoamyl alcohol polyether solution, adjusting the temperature of a system, then performing copolymerization, and adding an alkaline regulator to obtain a finished polycarboxylate water reducer. A technical scheme disclosed by the invention has the advantages of high monomer utilization rate, more effective components of the water reducer, low cost and the like.
Description
Technical field
The present invention relates to the method for a kind of prenol polyethers low temperature synthesis polycarboxylate water-reducer, belong to water reducer preparing technical field.
Background technology
Cement water reducing agent (also known as superplasticizer, Superlasticizer) refers under the condition that concrete workability, cement consumption are constant, can reduce mixing water content, improve the admixture of concrete strength; Water reducer hinders or destroys the flucculation structure of cement granules by surface-active action, complexing action, electrostatic repulsion forces etc., thus while saving cement consumption, can ensure concrete workability and intensity.The mechanism of action of cement water reducing agent is that the slowly-releasing gathering side chain by dispersion, lubrication, sterically hindered and grafting works.
Polycarboxylate water-reducer be continue wooden calcium be the ordinary water-reducing agent of representative and the third generation high-performance water reducing agent that grows up after being the high efficiency water reducing agent of representative with naphthalene.It is low that this kind of water reducer has volume, water-reducing rate is large, do not emanate, not bleeding, concrete slump property retention is good, with cement, adulterant and other admixture consistency good, strong and the super-durable concrete of superelevation can be made, the thermal insulation warming degree that effective reduction concrete is early stage, reduce the thermal cracking of mass concrete, degree of freedom in Molecular Structure Design is large, the potentiality realizing the high performance of water reducer are larger, synthesis does not adopt formaldehyde etc. environment to be had to the features such as the material of pollution, for promoting the use of large dosage hardened fly ashes, the industrial wastes such as slag provide technical guarantee.Thus domestic and international study hotspot is in recent years become.
The polymerization means of polycarboxylate water-reducer can adopt aqua-solution method or mass polymerization, and aqua-solution method is added to the water at monomer and conditioning agent, finally adds water soluble starter, react for some time cocoa at a certain temperature to final product.
CN102336845A discloses a kind of polycarboxylate water-reducer low temperature synthesis process, but a little item invention polyreaction is carried out in a solvent, finally also wants desolventizing, is not easy to suitability for industrialized production.CN201010246938 also discloses the technique of a kind of low temperature synthesis, what it was applied is redox system, the redox agent that this invention uses is persulphate, comprise wherein a kind of or its mixture of ammonium persulphate, Potassium Persulphate, Sodium Persulfate, reductive agent is wherein one or more the mixture of mercaptoethanol, mercaprol, Thiovanic acid, thiohydracrylic acid.This invents reduction system amount used is 1.5 ~ 6.0% of monomer, and material cost used is higher, and has certain toxicity.
Summary of the invention
In order to overcome, cost existing in the synthesis of conventional polycarboxylate water-reducer low temperature is high, toxicity large, need the problems such as solvent recuperation, the invention provides a kind of stability and high efficiency, without the need to adding solvent, having the method for the prenol polyethers low temperature synthesis polycarboxylate water-reducer compared with high water reducing rate.
For achieving the above object, the technical scheme taked of the present invention is as follows:
A kind of method of prenol polyethers low temperature synthesis polycarboxylate water-reducer, with prenol polyethers, vinylformic acid is raw material, first prenol polyethers being dissolved in a heated condition formation mass concentration is in deionized water 20-60% prenol polyether solutions, the mixing solutions of acrylic acid aqueous solution (mass concentration 50-90%) and thio-alcohol water-soluble chain transfer agent and free radical type initiator is dripped respectively in this prenol polyether solutions, adjustment system temperature is 10-45 DEG C, carry out copolyreaction 4-12 hour, react complete and directly add alkaline conditioner adjustment system pH to 6-8 without the need to lowering the temperature, finished product polycarboxylate water-reducer can be obtained, wherein, prenol polyethers and acrylic acid mol ratio are that this mol ratio of 1:3-6(refers to the methacrylic polyether acid before being mixed with the aqueous solution and acrylic acid mol ratio), the duration that small molecule monomer acrylic acid aqueous solution drips in prenol polyether solutions is 2.5-6 hour, the mass concentration of the mixing solutions that thio-alcohol water-soluble chain transfer agent and free radical type initiator are formed is 20-60%, the addition of thio-alcohol water-soluble chain transfer agent is the 0.01-1% of raw material total mass, the mass concentration of radical initiator is the 0.02-10% of raw material total mass, and the dropping duration of radical initiator is 3-7 hour.
As preferably, further arrange as follows:
The molecular weight of described prenol polyethers is 500-5000.
Described thio-alcohol water-soluble chain transfer agent is the one in thiohydracrylic acid, Thiovanic acid or mercaptoethanol.
Described radical initiator is the one in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, hydrogen peroxide or L-AA.
Described alkaline conditioner is any one in sodium hydroxide and the aqueous solution, potassium hydroxide and the aqueous solution thereof, sodium carbonate and the aqueous solution thereof.
In described finished product polycarboxylate water-reducer, solid content is 10-50%, and its polymkeric substance is pectination molecule, and structure is:
, molecular weight is 5000-100000, and molecular skeleton is made up of main chain and side chain, and main chain is made up of acrylic polymerization, and side chain is made up of the alcohol ether chain of hydrophilic radical.
The present invention compared with prior art, has following outstanding advantages and positively effect:
1. in technical solution of the present invention, adopt prenol polyethers, vinylformic acid is as main raw material, then specific order of addition and addition manner is adopted to add radical initiator and thio-alcohol water-soluble chain transfer agent carries out copolyreaction, first by prenol polyethers, vinylformic acid and thio-alcohol water-soluble chain transfer agent and radical initiator are mixed with solution respectively, and control their respective interpolation concentration, addition manner, guarantee that copolyreaction temperature is 10-45 DEG C, the copolyreaction time is 4-12 hour, question response is abundant, after copolyreaction terminates, namely the pH value of system is adjusted to 6 ~ 8 with alkaline conditioner without the need to cooling, thus reach control tooth in polymkeric substance pectination density degree to reach good effect, adopt technique scheme integrated artistic of the present invention reasonable, simple to operate, reaction conditions is gentle.
2. in technique scheme, control the proportioning raw materials in reaction process, chain tra nsfer dosage amounts and copolyreaction temperature, the processing parameters such as time and condition, thus prepare the prerequisite of the polycarboxylate water-reducer of high water reducing rate at stability and high efficiency under, in reaction process outside deionizing water, without the need to using solvent, avoid the toxic action of organic solvent, also without the need to carrying out removal and the recovery of solvent, operation is easier, in whole reaction process, it is 0.01 ~ 1% that chain-transfer agent consumption enters, usage quantity in existing patent and existing document, cost reduces greatly, also the harm of chain-transfer agent to operator is controlled to a great extent.
3. macromonomer prenol polyethers and small molecule monomer vinylformic acid are polymerized, and regulate and control its proportioning raw materials, the polycarboxylate water-reducer that copolymerization is obtained is pectination molecule, molecular weight is 5000-100000, molecular skeleton is made up of main chain and side chain, main chain is made up of propenyl polymerization, side chain is made up of the alcohol ether chain of hydrophilic radical, molecular chain arrangement density is suitable for, when polymer molecule is attracted on cement granules, anionic polar group on main chain provides electrostatic repulsion, there is hydrophilic side chain can stretch in the liquid phase, thus form large three-dimensional adsorption structure generation space steric effect at particle surface, electrostatic repulsion and sterically hindered effect act synergistically, hinder and destroy the flucculation structure of cement granules, thus while saving cement consumption, ensure concrete workability and intensity, improve the integrated application performance of polycarboxylate water-reducer.
Embodiment
End water and unsaturated alcohol polyethers is dropped in four-hole boiling flask, be stirred to after dissolving completely and add peroxide initiator, start the aqueous solution dripping vinylformic acid, chain-transfer agent and initiator, drip off after rear insulation slaking certain hour treats copolyreaction, add alkali lye and neutralize.The present embodiment water used is deionized water, and its add-on can be adjusted accordingly according to the solid content of the polycarboxylate water-reducer of required preparation; In polymeric system, solid content controls 10% ~ 50%, the polycarboxylate water-reducer best results of acquisition.
The present invention is not limited to following embodiment, when practical application, can require and use occasion according to the different performance of poly carboxylic acid series water reducer, select the differing temps in following embodiment, proportioning, or differing temps, the proportioning except following each embodiment, but all do not limit the scope of the invention in any form.
embodiment 1
In the four-hole boiling flask that band stirs, drop into 300 parts of prenol polyethers and 300 parts of water, be warming up to 10 DEG C, forming prenol polyether solutions to melting completely, adding 5 parts of H
2o
2(50%) H of and 82 parts of water configurations
2o
2the aqueous solution, stir after 10min, drip acrylic acid aqueous solution that 27 parts of vinylformic acid and 30 parts of water configures and the mixing solutions that 0.1 part of L-AA, 6 parts of Thiovanic acids and 71 parts of water configure respectively, the dropping duration of acrylic acid aqueous solution and mixing solutions is respectively 2.5 hours and 3 hours, drip rear insulation and carry out copolyreaction in 3 hours, after question response, add the aqueous sodium hydroxide solution of 28 part 30%, adjustment system pH=6.2, stir 10min, discharging obtains polycarboxylate water-reducer, wherein, and 5 parts of H
2o
2(50%) H of and 82 parts of water configurations
2o
2the aqueous solution, as reductive agent, forms initiator system with added 0.1 part of L-AA.
embodiment 2
In the four-hole boiling flask that band stirs, drop into 300 parts of prenol polyethers and 200 parts of water, be warming up to 25 DEG C, forming prenol polyether solutions to melting completely, adding 8 parts of H
2o
2(50%) H of and 82 parts of water configurations
2o
2the aqueous solution, after stirring 10min, drip acrylic acid aqueous solution that 40 parts of vinylformic acid and 5 parts of water configures and the mixing solutions that 1 part of L-AA, 0.2 part of thiohydracrylic acid and 194 parts of water configure respectively, the dropping duration of acrylic acid aqueous solution and mixing solutions is respectively 5 hours and 5.5 hours, drips rear insulation and carries out copolyreaction, after question response in 2 hours, add the aqueous sodium hydroxide solution of 42 part 30%, adjustment system pH=7.2, stir 10min, discharging obtains polycarboxylate water-reducer.
embodiment 3
In the four-hole boiling flask that band stirs, drop into 300 parts of prenol polyethers and 1200 parts of water, be warming up to 25 DEG C, forming prenol polyether solutions to melting completely, adding 8 parts of H
2o
2(50%) H of and 82 parts of water configurations
2o
2the aqueous solution, after stirring 10min, drip acrylic acid aqueous solution that 54 parts of vinylformic acid and 18 parts of water configures and the mixing solutions that 1 part of L-AA, 0.2 part of thiohydracrylic acid and 144 parts of water configure respectively, the dropping duration of acrylic acid aqueous solution and mixing solutions is respectively 6 hours and 7 hours, drips rear insulation and carries out copolyreaction, after question response in 1 hour, add the aqueous sodium hydroxide solution of 56 part 30%, adjustment system pH=6.8, stir 10min, discharging obtains polycarboxylate water-reducer.
embodiment 4
In the four-hole boiling flask that band stirs, drop into 300 parts of prenol polyethers and 200 parts of water, be warming up to 45 DEG C, prenol polyether solutions is formed to melting completely, add the ammonium persulphate of 17g, after stirring 5min, drip the acrylic acid aqueous solution that 40 parts of vinylformic acid and 5 parts of water are formed respectively, the mixing solutions that 1.7 parts of thiohydracrylic acids and 276 parts of water are formed, the time for adding of acrylic acid aqueous solution and mixing solutions is respectively 3 hours and 3.5 hours, drip rear insulation and carry out copolyreaction in 5 hours, after question response, add the aqueous sodium hydroxide solution of 42 part 30%, adjustment system pH=7.2, stir 10min, discharging obtains polycarboxylate water-reducer.
embodiment 5
In the four-hole boiling flask that band stirs, drop into 300 parts of prenol polyethers and 200 parts of water, be warming up to 45 DEG C, prenol polyether solutions is formed to melting completely, add the ammonium persulphate of 10g, after stirring 5min, drip acrylic acid aqueous solution and 1 part of Thiovanic acid that 40 parts of vinylformic acid and 5 parts of water formed respectively, the mixing solutions that 1 part of thiohydracrylic acid and 276 parts of water are formed, the time for adding of acrylic acid aqueous solution and mixing solutions is respectively 3 hours and 3.5 hours, drip rear insulation and carry out copolyreaction in 5 hours, after question response, add the aqueous sodium hydroxide solution of 43 part 30%, adjustment system pH=7.6, stir 10min, discharging obtains polycarboxylate water-reducer.
embodiment 6
In the four-hole boiling flask that band stirs, drop into 300 parts of prenol polyethers and 1200 parts of water, be warming up to 25 DEG C, forming prenol polyether solutions to melting completely, adding 8 parts of H
2o
2(50%) H that and 82 parts of water is formed
2o
2the aqueous solution, after stirring 10min, drip acrylic acid aqueous solution that 54 parts of vinylformic acid and 18 parts of water formed and the mixing solutions that 1 part of L-AA, 0.2 part of thiohydracrylic acid and 144 parts of water are formed respectively, the time for adding of acrylic acid aqueous solution and mixing solutions is respectively 6 hours and 7 hours, drips rear insulation and carries out copolyreaction, after question response in 1 hour, add the aqueous sodium carbonate of 28 part 30%, adjustment system pH to 6.5, stir 20min, discharging obtains polycarboxylate water-reducer.
comparative example
In the four-hole boiling flask that band stirs, drop into 300 parts of prenol polyethers and 300 parts of water, be warming up to 60 DEG C, forming prenol polyether solutions to melting completely, adding 10 parts of H
2o
2(50%) H that and 85 parts of water is formed
2o
2the aqueous solution, stir 10min, drip the mixing solutions of acrylic acid aqueous solution that 36 parts of vinylformic acid and 30 parts of water prepares and 1.5 parts of L-AAs, 10 parts of Thiovanic acids and 80 parts of water respectively, the time for adding of acrylic acid aqueous solution and mixing solutions is respectively 3 hours and 3.5 hours, drips rear insulation and carries out copolyreaction in 1 hour, after completion of the reaction, add the sodium hydroxide solution of 38 part 30%, adjustment pH=7.2, stir 10min, discharging obtains polycarboxylate water-reducer.
Table 1 is the contrast of slurry index only
。
The formation test result of the finished product polycarboxylate water-reducer obtained under the different embodiment of table 2
。
Aforesaid way of the present invention is adopted to carry out the preparation of polycarboxylate water-reducer, clean slurry is to the representational index of water reducer application performance most, the data of associative list 1, can find out, polycarboxylate water-reducer prepared by each embodiment and comparative example starches experimental evaluation only, under identical parameter, the initial paste flowing degree of the polycarboxylate water-reducer prepared by the present invention has more about 30mm than comparative example; Degree of mobilization various embodiments of the present invention after 60min are also better than comparative example all in various degree, therefore, after adopting technical solution of the present invention, at embodiment rational technology, simple to operate, reaction conditions is gentle, the application performance of comparative example can be reached when energy consumption is little, even more excellent.
Data in associative list 2 can be found out, the water reducer polymerization degree that the present invention produces all increases, thus improves the utilization ratio of monomer, also makes the effective ingredient of water reducer increase, is just conducive to application cost.
Above content is the further description done provided technical scheme in conjunction with the preferred embodiment of the present invention; can not assert that the present invention specifically implements to be confined to these explanations above-mentioned; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made, all should be considered as belonging to protection scope of the present invention.
Claims (6)
1. the method for a prenol polyethers low temperature synthesis polycarboxylate water-reducer, it is characterized in that: with prenol polyethers, vinylformic acid is raw material, first prenol polyethers being dissolved in a heated condition formation mass concentration is in deionized water 20-60% prenol polyether solutions, the mixing solutions of acrylic acid aqueous solution and thio-alcohol water-soluble chain transfer agent and free radical type initiator is dripped respectively in this prenol polyether solutions, adjustment system temperature is 10-45 DEG C, carry out copolyreaction 4-12 hour, react complete and directly add alkaline conditioner adjustment system pH to 6-8 without the need to lowering the temperature, finished product polycarboxylate water-reducer can be obtained, wherein, prenol polyethers and acrylic acid mol ratio are 1:3-6, the dropping duration of the acrylic acid aqueous solution of small molecule monomer is 2.5-6 hour, the mass concentration of the mixing solutions that thio-alcohol water-soluble chain transfer agent and free radical type initiator are formed is 20-60%, the addition of thio-alcohol water-soluble chain transfer agent is the 0.01-1% of raw material total mass, the mass concentration of radical initiator is the 0.02-10% of raw material total mass, and the dropping duration of radical initiator is 3-7 hour.
2. the method for a kind of prenol polyethers low temperature synthesis polycarboxylate water-reducer as claimed in claim 1, is characterized in that: the molecular weight of described prenol polyethers is 500-5000.
3. the method for a kind of prenol polyethers low temperature synthesis polycarboxylate water-reducer as claimed in claim 1, is characterized in that: described thio-alcohol water-soluble chain transfer agent is the one in thiohydracrylic acid, Thiovanic acid or mercaptoethanol.
4. the method for a kind of prenol polyethers low temperature synthesis polycarboxylate water-reducer as claimed in claim 1, is characterized in that: described radical initiator is one in ammonium persulphate, Sodium Persulfate, Potassium Persulphate, hydrogen peroxide or L-AA or its mixture.
5. the method for a kind of prenol polyethers low temperature synthesis polycarboxylate water-reducer as claimed in claim 1, is characterized in that: described alkaline conditioner is any one in sodium hydroxide and the aqueous solution, potassium hydroxide and the aqueous solution thereof, sodium carbonate and the aqueous solution thereof.
6. the method for a kind of prenol polyethers low temperature synthesis polycarboxylate water-reducer as claimed in claim 1, it is characterized in that: in described finished product polycarboxylate water-reducer, solid content is 10-50%, its polymkeric substance is pectination molecule, molecular weight is 5000-100000, molecular skeleton is made up of main chain and side chain, main chain is made up of acrylic polymerization, and side chain is made up of the alcohol ether chain of hydrophilic radical.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153375A (en) * | 2015-09-21 | 2015-12-16 | 华南理工大学 | Method for synthesizing polycarboxylate superplasticizer through RAFT method |
| CN105175658A (en) * | 2015-10-28 | 2015-12-23 | 武汉理工大学 | Method of preparing comb block polycarboxylate superplasticizer bonding modified silica fume |
| CN113336875A (en) * | 2021-06-10 | 2021-09-03 | 武汉新绿博恩科技有限公司 | Application of isopropanol cleaning waste liquid treatment liquid |
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| CN102936109A (en) * | 2011-12-08 | 2013-02-20 | 江苏奥莱特新材料有限公司 | Polycarboxylic acid water reducing agent, preparation method and application thereof |
| CN103275279A (en) * | 2013-06-08 | 2013-09-04 | 武汉江北创新科技有限公司 | Method for producing polycarboxylate superplasticizer through one-off batch charging at normal temperature |
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2014
- 2014-09-23 CN CN201410487227.3A patent/CN104262547A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000185953A (en) * | 1998-12-24 | 2000-07-04 | Takemoto Oil & Fat Co Ltd | Dispersant for cement and cement formulation |
| CN102936109A (en) * | 2011-12-08 | 2013-02-20 | 江苏奥莱特新材料有限公司 | Polycarboxylic acid water reducing agent, preparation method and application thereof |
| CN103275279A (en) * | 2013-06-08 | 2013-09-04 | 武汉江北创新科技有限公司 | Method for producing polycarboxylate superplasticizer through one-off batch charging at normal temperature |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153375A (en) * | 2015-09-21 | 2015-12-16 | 华南理工大学 | Method for synthesizing polycarboxylate superplasticizer through RAFT method |
| CN105175658A (en) * | 2015-10-28 | 2015-12-23 | 武汉理工大学 | Method of preparing comb block polycarboxylate superplasticizer bonding modified silica fume |
| CN113336875A (en) * | 2021-06-10 | 2021-09-03 | 武汉新绿博恩科技有限公司 | Application of isopropanol cleaning waste liquid treatment liquid |
| CN113336875B (en) * | 2021-06-10 | 2022-04-19 | 武汉新绿博恩科技有限公司 | Application of isopropanol cleaning waste liquid treatment liquid |
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Application publication date: 20150107 |