CN103980437A - Polycarboxylic acid water reducing agent and preparation method thereof - Google Patents
Polycarboxylic acid water reducing agent and preparation method thereof Download PDFInfo
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- CN103980437A CN103980437A CN201410228501.5A CN201410228501A CN103980437A CN 103980437 A CN103980437 A CN 103980437A CN 201410228501 A CN201410228501 A CN 201410228501A CN 103980437 A CN103980437 A CN 103980437A
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- alcoxylates
- allyl group
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- fatty alcohol
- methacrylic acid
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Abstract
The invention discloses a polycarboxylic acid water reducing agent, the formula of which is as shown in the specification; R1 in the formula is a straight chain with 6 to 18 carbon atoms, and a branched alkyl; a is not less than 0 and not more than 30; b is not less than 0 and not more than 30; x is not less than 0 and not more than 30; y is not less than 0 and not more than 30, wherein a and b cannot be zero at the same time; x and y cannot be zero at the same time. The invention has the advantages of simple preparation process, mild reaction condition, controllable technological process, stable product performance and good water reducing effect.
Description
Technical field
The invention belongs to a kind of water reducer and preparation method, be specifically related to a kind of poly carboxylic acid series water reducer and preparation method thereof.
Technical background
Concrete mixes after water reducer, because Water-reducing Admixtures To Cements particle has sufficient dissemination, thereby improves concrete mobility, has strengthened its workability; In the situation that keeping original workability, can reduce water consumption, improve concrete intensity.Due to the application of water reducer, its water-reduction can reduce concrete water cement ratio greatly, thereby improves concrete intensity, like this, just can make the more concrete of high strength grade, the in the situation that of ad eundem, can reduce cement consumption, thereby reduce costs, increase economic efficiency.
In recent years, along with increasing and the fast development of high ferro of China building, the outstanding advantages such as polycarboxylate water-reducer is high with its water-reducing rate, concrete retentivity is good, was widely used in fields such as railway, traffic.On domestic market, poly carboxylic acid series water reducer is divided into two large classes substantially: a class is ether type, take the multipolymer that maleic anhydride and allyl polyglycol be formant; One class is ester type, the multipolymer that (methyl) vinylformic acid and methoxy poly (ethylene glycol) (methyl) acrylate of take is primary structure unit.The raw materials kind of water reducer is varied in the market, the modified polyether TPEG series that mainly contains MPEG series, APEG series and newly develop.But in above-mentioned two kinds of water reducer molecules, all do not contain chain alkyl, be difficult for reaching by changing carbon chain lengths the object of molecular designing.Adopting allyl group fatty alcohol-ether alcoxylates and allyl alcohol alcoxylates is that raw material and methacrylic acid carry out copolymerization and prepare poly carboxylic acid series water reducer, through retrieval, does not find to report.
Summary of the invention
The object of the present invention is to provide and a kind of polycarboxylate water-reducer is carried out to molecular designing, adopting allyl group fatty alcohol-ether alcoxylates and allyl alcohol alcoxylates is that raw material and methacrylic acid carry out copolymerization and prepare poly carboxylic acid series water reducer and preparation method thereof.
It is that raw material and methacrylic acid carry out copolymerization that present method adopts allyl group fatty alcohol-ether alcoxylates and allyl alcohol alcoxylates, by regulating the aliphatic chain length of allyl group fatty alcohol-ether alcoxylates and the polymerization degree of oxyethyl group or propoxy-, can realize polycarboxylate water-reducer is carried out to molecular designing, improve its application performance.
Reaction equation of the present invention is as follows:
R in formula
1for carbonatoms be 6-18 straight chain and branched-chain alkyl; 0≤a≤30; 0≤b≤30.0≤x≤30; 0≤y≤30, wherein a and b can not be zero simultaneously, x and y can not be zero simultaneously.
Polycarboxylate water-reducer provided by the invention, its molecular formula is as follows:
R in formula
1for carbonatoms be 6-18 straight chain and branched-chain alkyl; 0≤a≤30; 0≤b≤30; 0≤x≤30; 0≤y≤30, wherein a and b can not be zero simultaneously, x and y can not be zero simultaneously.
Preparation method of the present invention comprises the following steps:
(1) in reactor, add water, allyl group fatty alcohol-ether alcoxylates, allyl alcohol alcoxylates and oxygenant, be heated with stirring to 30-70 ℃, wherein the mass ratio of allyl group fatty alcohol-ether alcoxylates and water is 1:1～3, the mass ratio of allyl group fatty alcohol-ether alcoxylates and allyl alcohol alcoxylates is 1:2～3, and oxygenant consumption is 0.1～2wt% of allyl group fatty alcohol-ether alcoxylates;
(2) by allyl group fatty alcohol-ether alcoxylates and methacrylic acid mol ratio, be 1:3～6, the mixed aqueous solution of methacrylic acid and reductive agent is added dropwise to reaction in step (1), time for adding is 2～3 hours, wherein the mass ratio of methacrylic acid and water is 1:1～3,0.1～2wt% that reductive agent consumption is methacrylic acid;
3) dropwise reaction finishes, and is incubated 1 hour, is down to below 25 ℃, adds alkaline solution to regulate pH value to neutral, and discharging, had both obtained described polycarboxylate water-reducer.
Oxygenant as above is a kind of in persulphate or hydrogen peroxide.
Reductive agent as above is a kind of in sodium bisulfite or Sodium Pyrosulfite.
Alkaline solution as above comprises a kind of in sodium hydroxide, potassium hydroxide, sodium carbonate or salt of wormwood, and its concentration is between 5～50wt%.
Advantage of the present invention is as follows:
1, in general water reducer molecule, all do not contain long-chain, the allyl group fatty alcohol-ether alcoxylates that the present invention can pass through to drop into different carbon chain is as raw material, obtain the polycarboxylate water-reducer of different carbon chain, can reach by changing the polymerization degree of carbon chain lengths and oxyethyl group or propoxy-molecule is designed, it is applied in dissimilar water reducer.
2, preparation technology of the present invention is simple, reaction conditions is gentle, and technological process is easy to control.
3, product performance are stable, and water-reducing effect is good, are applicable to the concrete technical requirements of modern high performance and construction requirement.
Embodiment
Embodiment 1:
In four-hole bottle, add 150 grams of deionized waters, 150 grams of allyl group hexanol Soxylat A 25-7s (30EO), 300 grams of allyl alcohol ethoxylates (30EO), 0.15 gram of Sodium Persulfate, be heated with stirring to 70 ℃, start to drip the aqueous solution of methacrylic acid and sodium bisulfite, 53 grams of (n allyl group hexanol Soxylat A 25-7s: n methacrylic acid=1:6) of methacrylic acid wherein, 0.05 gram of sodium bisulfite, 60 grams, water, after 2 hours, drip and finish, in 70 ℃ of insulations, after 1 hour, be cooled to 20 ℃, add the sodium hydroxide solution of 5wt% to regulate pH value to neutral, obtain following structure water reducer:
Embodiment 2:
In four-hole bottle, add 240 grams of deionized waters, 80 grams of allyl group stearyl alcohol polyethenoxy ethers (8EO), 240 grams of allyl alcohol segmented copolymers (9EO-5PO), 1.6 grams of Sodium Persulfates, be heated with stirring to 30 ℃, start to drip the aqueous solution of methacrylic acid and Sodium Pyrosulfite, 31 grams of (n allyl group stearyl alcohol polyethenoxy ethers: n methacrylic acid=1:3) of methacrylic acid wherein, 0.62 gram of Sodium Pyrosulfite, 93 grams, water, after 3 hours, drip and finish, in 30 ℃ of insulations, after 1 hour, be cooled to 20 ℃, add 50% potassium hydroxide solution to regulate pH value to neutrality, obtain following structure water reducer:
Embodiment 3:
In four-hole bottle, add 160 grams of deionized waters, 80 grams of allyl group lauryl alcohol ether ethoxylation propoxylation multipolymers (12EO-5PO), 180 grams of allyl alcohol propoxylated glycerines (12EO), 0.8 gram of Potassium Persulphate, be heated with stirring to 60 ℃, start to drip the aqueous solution of methacrylic acid and sodium bisulfite, wherein (n allyl group lauryl alcohol ether ethoxylation propoxylation is got polymers altogether: n methacrylic acid=1:5) for 20 grams of methacrylic acids, 0.2 gram of sodium bisulfite, 50 grams, water, after 2 hours, drip and finish, in 60 ℃ of insulations, after 1 hour, be cooled to 20 ℃, add 15% sodium carbonate solution to regulate pH value to neutrality, obtain following structure water reducer:
Embodiment 4:
In four-hole bottle, add 150 grams of deionized waters, 100 grams of allyl group isooctyl alcohol Soxylat A 25-7s (20EO), 250 grams of allyl alcohol ethoxylates (20EO), 1.5 grams of hydrogen peroxide, be heated with stirring to 50 ℃, start to drip the aqueous solution of methacrylic acid and pyrosulphite hydrogen sodium, 33 grams of (n allyl group isooctyl alcohol Soxylat A 25-7s: n methacrylic acid=1:4) of methacrylic acid wherein, 1 gram of sodium bisulfite, 70 grams, water, after 2.5 hours, drip and finish, in 50 ℃ of insulations, after 1 hour, be cooled to 20 ℃, add 25% sodium carbonate solution to regulate pH value to neutrality, obtain following structure water reducer:
The performance test results that above-described embodiment is prepared sample is as following table:
Concrete water-reducing ratio and compressive strength test are carried out with reference to GB8076-1997 < < concrete admixture > >.Allyl group ether type polycarboxylic acid series dehydragent PC-A is that common employing allyl polyglycol (APEG), maleic anhydride and methyl acrylate is the synthetic poly carboxylic acid series water reducer of monomer at present.
Claims (5)
1. a poly carboxylic acid series water reducer, is characterized in that its molecular formula is as follows:
R in formula
1for carbonatoms be 6-18 straight chain and branched-chain alkyl; 0≤a≤30; 0≤b≤30; 0≤x≤30; 0≤y≤30, wherein a and b can not be zero simultaneously, x and y can not be zero simultaneously.
2. the preparation method of a kind of poly carboxylic acid series water reducer as claimed in claim 1, is characterized in that comprising the following steps:
(1) in reactor, add water, allyl group fatty alcohol-ether alcoxylates, allyl alcohol alcoxylates and oxygenant, be heated with stirring to 30-70 ℃, wherein the mass ratio of allyl group fatty alcohol-ether alcoxylates and water is 1:1～3, the mass ratio of allyl group fatty alcohol-ether alcoxylates and allyl alcohol alcoxylates is 1:2～3, and oxygenant consumption is 0.1～2wt% of allyl group fatty alcohol-ether alcoxylates;
(2) by allyl group fatty alcohol-ether alcoxylates and methacrylic acid mol ratio, be 1:3～6, the mixed aqueous solution of methacrylic acid and reductive agent is added dropwise to reaction in step (1), time for adding is 2～3 hours, wherein the mass ratio of methacrylic acid and water is 1:1～3,0.1～2wt% that reductive agent consumption is methacrylic acid;
(3) dropwise reaction finishes, and is incubated 1 hour, is down to below 25 ℃, adds alkaline solution to regulate pH value to neutral, and discharging, had both obtained described polycarboxylate water-reducer.
3. the preparation method of a kind of poly carboxylic acid series water reducer as claimed in claim 2, is characterized in that described oxygenant is a kind of in persulphate or hydrogen peroxide.
4. the preparation method of a kind of poly carboxylic acid series water reducer as claimed in claim 2, is characterized in that described reductive agent is a kind of in sodium bisulfite or Sodium Pyrosulfite.
5. the preparation method of a kind of poly carboxylic acid series water reducer as claimed in claim 2, is characterized in that described alkaline solution comprises a kind of in sodium hydroxide, potassium hydroxide, sodium carbonate or salt of wormwood, and its concentration is between 5～50wt%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109535341A (en) * | 2018-11-16 | 2019-03-29 | 中交二航武汉港湾新材料有限公司 | Hydrophobically modified viscosity reduction type polycarboxylate water-reducer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199298A (en) * | 2011-03-23 | 2011-09-28 | 中国日用化学工业研究院 | Preparation method for polycarboxylic acid series comb-shaped surface active agent |
| CN102503221A (en) * | 2011-08-12 | 2012-06-20 | 周绍春 | Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof |
| CN102585194A (en) * | 2011-12-14 | 2012-07-18 | 中国日用化学工业研究院 | Method for synthesizing allyl fatty alcohol-polyoxyethylene ether or allyl alkylphenol ethoxylate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102199298A (en) * | 2011-03-23 | 2011-09-28 | 中国日用化学工业研究院 | Preparation method for polycarboxylic acid series comb-shaped surface active agent |
| CN102503221A (en) * | 2011-08-12 | 2012-06-20 | 周绍春 | Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof |
| CN102585194A (en) * | 2011-12-14 | 2012-07-18 | 中国日用化学工业研究院 | Method for synthesizing allyl fatty alcohol-polyoxyethylene ether or allyl alkylphenol ethoxylate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109535341A (en) * | 2018-11-16 | 2019-03-29 | 中交二航武汉港湾新材料有限公司 | Hydrophobically modified viscosity reduction type polycarboxylate water-reducer and preparation method thereof |
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