CN103881029B - The preparation method of short time without thermal source of sustained-release polycarboxylic high-performance slump retaining agent - Google Patents
The preparation method of short time without thermal source of sustained-release polycarboxylic high-performance slump retaining agent Download PDFInfo
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Abstract
The present invention relates to polycarboxylate water-reducer, be specifically related to the preparation method of short time without thermal source of a kind of sustained-release polycarboxylic high-performance slump retaining agent.The method comprises the following steps: add methyl allyl polyoxyethylene ether and water in container, after stirring at normal temperature 0.5h, then is added thereto to initiator and causes auxiliary agent, stirring at normal temperature 2min；It is simultaneously added dropwise acrylic acid, 2-(Acryloyloxy)ethanol and the mixed aqueous solution of 2 acrylamido 2 methyl propane sulfonic acids, chain-transferring agent aqueous solution, drip off in 1h simultaneously, being incubated 0.5h after dropping, use alkali liquor regulation pH value to 6～7, add water being diluted to solid content is 40%.Preparation technology of the present invention is simple, device simple, and whole course of reaction, without heating, saves the energy；Production cycle is only 2h, substantially increases production efficiency, applied widely, and the sustained-release polycarboxylic high-performance slump retaining agent of synthesis has the features such as volume is few, function of slump protection good, environmental friendliness.
Description
Technical field
The present invention relates to polycarboxylate water-reducer, be specifically related to the system of short time without thermal source of a kind of sustained-release polycarboxylic high-performance slump retaining agent
Preparation Method.
Background technology
China greatly develops capital construction at present, and commerical ready-mixed concrete is in great demand, and gathering as one of commerical ready-mixed concrete additive
The carboxylic acid water reducer market share is increasing.In the fierce market competition, water-reducing rate is high, protects effect of collapsing, the product of low cost
Competitive advantage will be had, the direction that this Ye Shige scientific research institution and enterprise are constantly pursued.
Poly carboxylic acid series water reducer, in preparation process, typically to select the most isoplastic monomer material of some bands, set according still further to molecule
The additive reaction water reducer by polymerizable construction unit synthesis predetermined structure with performance passed in principle by meter, it is possible to preferably solve coagulation
The problems such as soil diminishing, bleed, slow setting, bleeding.Generally by the monomer two or more containing carboxylic acid group and polyethylene oxide base, and contain
Some of sulfonic group, ester group or other group can be synthesized by free radicals copolymerization reaction by poly-monomer, and the molecule at polymer combined
Cheng Zhong, different monomers to condense together at random or regularly, molecular backbone and side chain introduce highly polar group such as carboxyl,
Sulfonic group, ester group, polyethylene oxide base etc., make molecule have comb-type structure, its superior function of its special structures shape.
But, the production technology of current polycarboxylate water-reducer is typically all at about 4 hours, carries out under 40～90 DEG C of temperature conditionss
Radical reaction synthesizes.By synthesizing without heat resource method, save the energy, also will greatly reduce production cost；Shorten reaction time,
Also production efficiency will be greatly improved.
Summary of the invention
It is an object of the invention to provide the preparation method of short time without thermal source of a kind of sustained-release polycarboxylic high-performance slump retaining agent, the method
With unsaturated polyoxyethylene ether, 2-(Acryloyloxy)ethanol as primary raw material, at a temperature of room temperature, the short time synthesizes one and has slow
Release the polycarboxylate water-reducer of high-thin arch dam performance, solve current Polyether polycarboxylic-acid water reducer and protect scarce capacity problem of collapsing.
The preparation method of short time without thermal source of sustained-release polycarboxylic high-performance slump retaining agent of the present invention, comprises the following steps:
(1) in container, methyl allyl polyoxyethylene ether and water, stirring at normal temperature 0.5h are added；
(2) in the solution that step (1) obtains, add initiator and cause auxiliary agent, stirring at normal temperature 2min；
(3) acrylic acid, 2-(Acryloyloxy)ethanol, 2-acrylamide-2-methylpro panesulfonic acid (AMPS) are dissolved in water, obtain third
Olefin(e) acid, 2-(Acryloyloxy)ethanol and the mixed aqueous solution of 2-acrylamide-2-methylpro panesulfonic acid；Chain-transferring agent is dissolved in water and obtains chain
Transfer agent aqueous solution；
(4) in the solution that step (2) obtains, it is simultaneously added dropwise acrylic acid, 2-(Acryloyloxy)ethanol and 2-acrylamido-2-first
The mixed aqueous solution of base propane sulfonic acid, chain-transferring agent aqueous solution, drip off in 1h simultaneously；
(5) being incubated 0.5h after dropping, use alkali liquor regulation pH value to 6～7, add water being diluted to solid content is 40% i.e.
Can.
Wherein, optimal technical scheme is as follows:
The mass ratio of the methyl allyl polyoxyethylene ether described in step (1) and water is 1～1.1:1.
Initiator described in step (2) is Ammonium persulfate. or potassium peroxydisulfate.
The auxiliary agent that causes described in step (2) is one or more in sodium sulfite, sodium formaldehyde sulfoxylate or vitamin C.Described
The chemical name of sodium formaldehyde sulfoxylate be two hydration sodium bisulphite formaldehydes or two water sodium formaldehyde sulphoxylates.
Initiator described in step (2) and the mass ratio 1:0.2～0.4 of initiation auxiliary agent, methyl allyl polyoxyethylene ether and initiation
The mass ratio 1:0.01～0.015 of agent.
Acrylic acid described in step (3), 2-(Acryloyloxy)ethanol and the mixed aqueous solution of 2-acrylamide-2-methylpro panesulfonic acid
Mass percent concentration be 40～60%
Chain-transferring agent described in step (3) is one or more in TGA, mercaptopropionic acid or isopropanol, chain-transferring agent
The mass percent concentration of aqueous solution is 1～20%.
Methyl allyl polyoxyethylene ether and acrylic acid mass ratio 1:0.05～0.1, acrylic acid and the mass ratio of 2-(Acryloyloxy)ethanol
1:1～1.4, the mass ratio 1:0.1～0.3 of acrylic acid and 2-acrylamide-2-methylpro panesulfonic acid, acrylic acid and the quality of chain-transferring agent
Than 1:0.1～0.3.
The sodium hydroxide solution that alkali liquor is 30wt.% described in step (5).
The present invention utilizes initiation auxiliary agent to improve initiator decomposition rate at normal temperatures, by adjusting oxidant in redox system
With reducing agent consumption, each monomer ratio determines concrete synthetic schemes.
Beneficial effects of the present invention is as follows:
Preparation technology of the present invention is simple, device simple, and whole course of reaction, without heating, saves the energy；Production cycle is only 2h,
Substantially increasing production efficiency, applied widely, the sustained-release polycarboxylic high-performance slump retaining agent of synthesis has that volume is few, slump retaining
The features such as energy is good, environmental friendliness.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
In the 1000m1 there-necked flask of band muff, input molecule amount is the methyl allyl polyoxyethylene ether 330.5g of 2400,
Add 330g water, stir 0.5h；After methyl allyl polyoxyethylene ether all dissolves, put into 3.5g Ammonium persulfate. and 0.8g
Sodium sulfite, is sufficiently stirred for 2min；It is simultaneously added dropwise containing 20g acrylic acid, 21g 2-(Acryloyloxy)ethanol, 2.3gAMPS and 50g
The mixed liquor of water and 2.1g TGA and the mixed liquor of 80g water；1h drips off simultaneously, is incubated 0.5h after dropping；Add
Certain lye pH adjustment is to 6～7, and add certain water to be diluted to solid content be 40%.
Embodiment 2
In the 1000m1 there-necked flask of band muff, input molecule amount is the methyl allyl polyoxyethylene ether 330.5g of 2400,
Add 330g water, stir 0.5h；After methyl allyl polyoxyethylene ether all dissolves, put into 3.7g Ammonium persulfate. and 0.5g
Sodium sulfite and 0.4g vitamin C, be sufficiently stirred for 2min；Be simultaneously added dropwise containing 19g acrylic acid, 22g 2-(Acryloyloxy)ethanol,
The mixed liquor of 2.5gAMPS and 50g water and 2.6g TGA and the mixed liquor of 80g water；1h drips off simultaneously, drips complete
Rear insulation 0.5h；Add certain lye pH adjustment to 6～7, and add certain water to be diluted to solid content be 40%.
Embodiment 3
In the 1000m1 there-necked flask of band muff, input molecule amount is the methyl allyl polyoxyethylene ether 330.5g of 2400,
Add 330g water, stir 0.5h；After methyl allyl polyoxyethylene ether all dissolves, put into 3.2g Ammonium persulfate. and 0.83g
Sodium formaldehyde sulfoxylate, is sufficiently stirred for 2min；It is simultaneously added dropwise containing 19.5g acrylic acid, 20.5g 2-(Acryloyloxy)ethanol, 2.1gAMPS and 50g
The mixed liquor of water and 2.2g TGA and the mixed liquor of 80g water；1h drips off simultaneously, is incubated 0.5h after dropping；Add
Certain lye pH adjustment is to 6～7, and add certain water to be diluted to solid content be 40%.
Embodiment 4
In the 1000m1 there-necked flask of band muff, input molecule amount is the methyl allyl polyoxyethylene ether 330.5g of 2400,
Add 330g water, stir 0.5h；After methyl allyl polyoxyethylene ether all dissolves, put into 3.8g potassium peroxydisulfate and 0.8g
Sodium formaldehyde sulfoxylate, is sufficiently stirred for 2min；It is simultaneously added dropwise containing 20g acrylic acid, 23g 2-(Acryloyloxy)ethanol, 2.6gAMPS and 50g water
Mixed liquor and 5.3g isopropanol and the mixed liquor of 80g water；1h drips off simultaneously, is incubated 0.5h after dropping；Add certain
Lye pH adjustment to 6～7, and add certain water to be diluted to solid content be 40%.
Embodiment 5
In the 1000m1 there-necked flask of band muff, input molecule amount is the methyl allyl polyoxyethylene ether 330.5g of 2400,
Add 330g water, stir 0.5h；After methyl allyl polyoxyethylene ether all dissolves, put into 3.8g potassium peroxydisulfate and 0.6g
Sodium sulfite and 0.2 sodium formaldehyde sulfoxylate, be sufficiently stirred for 2min；Be simultaneously added dropwise containing 19g acrylic acid, 23.5g 2-(Acryloyloxy)ethanol, 2
The mixed liquor of gAMPS and 50g water and 2g mercaptopropionic acid and 1.1g isopropanol and the mixed liquor of 80g water；1h drips off simultaneously,
0.5h it is incubated after dropping；Add certain lye pH adjustment to 6～7, and add certain water to be diluted to solid content be 40%.
Embodiment 6
In the 1000m1 there-necked flask of band muff, input molecule amount is the methyl allyl polyoxyethylene ether 330.5g of 2400,
Add 330g water, stir 0.5h, after methyl allyl polyoxyethylene ether all dissolves, put into 3.9g potassium peroxydisulfate and 0.5g
Sodium sulfite and 0.45g vitamin C, be sufficiently stirred for 2min；Be simultaneously added dropwise containing 18g acrylic acid, 24g 2-(Acryloyloxy)ethanol,
The mixed liquor of 2.8gAMPS and 50g water and 2g TGA and 1.5g isopropanol and the mixed liquor of 80g water；1h drips simultaneously
Complete, it is incubated 0.5h after dropping；Add certain lye pH adjustment to 6～7, and add certain water and be diluted to solid content and be
40%.
The sustained-release polycarboxylic high-performance slump retaining agent of above 6 embodiments synthesis is carried out tests below respectively, and contrast product is city
Sell slump retaining agent BKS-103.
Test 1: cement paste is tested
This experiment cement is mountain aluminum P O 42.5.
Cement 300g, slump retaining agent and water 87g altogether, specific experiment result is as shown in table 1:
Table 1 cement paste experimental result table
As it can be seen from table 1 the sustained-release polycarboxylic high-performance slump retaining agent paste flowing degree later stage of the present invention all increases by a fairly big margin,
There is the flowing degree of net paste of cement holding capacity of excellence.
Test 2: the product of the present invention contrasts with the concrete test of contrast product
This experiment cement is mountain aluminum P O 42.5, grain fineness number modulus 2.5～2.8, and stone 5～25mm continuous grading, flyash is
GB II level, breeze is S95 level.Fit quality ratio is for water: cement: sand: stone: flyash: breeze=175:200:762:1052:96:80.
Concrete performance experimental result is as shown in table 2 below:
Table 2 concrete performance experimental result
From table 2 it can be seen that the sustained-release polycarboxylic high-performance slump retaining agent of the present invention has longer slump holding capacity, collapse
Degree of falling through time lose hardly, concrete strength is high, excellent combination property, and product cost is high.
Claims (7)
1. the preparation method of short time without thermal source of a sustained-release polycarboxylic high-performance slump retaining agent, it is characterised in that: include following step
Rapid:
(1) in container, methyl allyl polyoxyethylene ether and water, stirring at normal temperature 0.5h are added；
(2) in the solution that step (1) obtains, add initiator and cause auxiliary agent, stirring at normal temperature 2min；
(3) acrylic acid, 2-(Acryloyloxy)ethanol, 2-acrylamide-2-methylpro panesulfonic acid are dissolved in water, obtain acrylic acid, propylene
Acid hydroxyl ethyl ester and the mixed aqueous solution of 2-acrylamide-2-methylpro panesulfonic acid；Chain-transferring agent is dissolved in water, and to obtain chain-transferring agent water-soluble
Liquid；
(4) in the solution that step (2) obtains, it is simultaneously added dropwise acrylic acid, 2-(Acryloyloxy)ethanol and 2-acrylamido-2-first
The mixed aqueous solution of base propane sulfonic acid, chain-transferring agent aqueous solution, drip off in 1h simultaneously；
(5) being incubated 0.5h after dropping, use alkali liquor regulation pH value to 6～7, add water being diluted to solid content is 40% i.e.
Can；
Initiator described in step (2) is Ammonium persulfate. or potassium peroxydisulfate；
The auxiliary agent that causes described in step (2) is one or more in sodium sulfite, sodium formaldehyde sulfoxylate or vitamin C；
Chain-transferring agent described in step (3) is one or more in TGA, mercaptopropionic acid or isopropanol.
Preparation method the most according to claim 1, it is characterised in that: the methacrylic polyoxy described in step (1)
The mass ratio of vinyl Ether and water is 1～1.1:1.
Preparation method the most according to claim 1, it is characterised in that: the initiator described in step (2) and initiation help
The mass ratio 1:0.2～0.4 of agent, the mass ratio 1:0.01～0.015 of methyl allyl polyoxyethylene ether and initiator.
Preparation method the most according to claim 1, it is characterised in that: the acrylic acid described in step (3), acrylic acid
The mass percent concentration of the mixed aqueous solution of hydroxyl ethyl ester and 2-acrylamide-2-methylpro panesulfonic acid is 40～60%.
Preparation method the most according to claim 1, it is characterised in that: the mass percent concentration of chain-transferring agent aqueous solution is
1～20%.
Preparation method the most according to claim 1, it is characterised in that: methyl allyl polyoxyethylene ether and acrylic acid matter
Amount ratio 1:0.05～0.1, the mass ratio 1:1～1.4 of acrylic acid and 2-(Acryloyloxy)ethanol, acrylic acid and 2-acrylamido-2-methyl-prop
The mass ratio 1:0.1～0.3 of sulfonic acid, the mass ratio 1:0.1～0.3 of acrylic acid and chain-transferring agent.
Preparation method the most according to claim 1, it is characterised in that: the alkali liquor described in step (5) is 30wt.%'s
Sodium hydroxide solution.
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| CN105754044A (en) * | 2014-12-17 | 2016-07-13 | 中建西部建设股份有限公司 | Polycarboxylic acid-type retarder for wet-mixed mortar and synthetic method thereof |
| CN104692700B (en) * | 2015-02-11 | 2016-09-28 | 四川恒泽建材有限公司 | Xu puts collapse protective poly-carboxylic acid high-performance water reducing agent and preparation method thereof |
| CN105293981B (en) * | 2015-10-29 | 2018-04-24 | 中国建筑材料科学研究总院 | Slump retention agent and preparation method thereof |
| CN105884979B (en) * | 2016-04-08 | 2019-01-25 | 湖南铭煌科技发展有限公司 | The normal temperature preparation method of sustained-release polycarboxylic slump retaining agent |
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| CN107445505A (en) * | 2017-08-24 | 2017-12-08 | 重庆三圣实业股份有限公司 | A kind of muting sensitive sense polycarboxylate water-reducer and preparation method thereof |
| CN109265622A (en) * | 2018-08-02 | 2019-01-25 | 四川恒泽建材有限公司 | A kind of no heat source high-performance controlled-release polycarboxylic acid water reducing agent and preparation method thereof |
| CN110577621A (en) * | 2019-10-14 | 2019-12-17 | 山东申鑫建材科技有限公司 | Synthetic method of polycarboxylic acid water-reducing slump-retaining comprehensive mother liquor |
| CN111499409A (en) * | 2020-04-24 | 2020-08-07 | 湖南加美乐素新材料股份有限公司 | Precast concrete bone exposing agent for fabricated building and preparation method thereof |
| CN114380957B (en) * | 2022-01-21 | 2023-08-25 | 太原市天鼎恒砼外加剂科技发展有限公司 | High-performance ultra-slow-release slump retaining agent and preparation method thereof |
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