CN103145364A - Sulfoacid modified polycarboxylic superplasticizer and preparation method thereof - Google Patents
Sulfoacid modified polycarboxylic superplasticizer and preparation method thereof Download PDFInfo
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- CN103145364A CN103145364A CN 201310085730 CN201310085730A CN103145364A CN 103145364 A CN103145364 A CN 103145364A CN 201310085730 CN201310085730 CN 201310085730 CN 201310085730 A CN201310085730 A CN 201310085730A CN 103145364 A CN103145364 A CN 103145364A
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Abstract
The invention discloses and provides a sulfoacid modified polycarboxylic superplasticizer and a preparation method thereof. The method comprises the steps of firstly, carrying out polymerization reaction on polyethylene glycol allyl ether, sulfamic acid, concentrated sulfuric acid and hydroquinone taken as materials to obtain the sulfoacid modified polyethylene glycol allyl ether, carry out copolymerization on the obtained sulfoacid modified polyethylene glycol allyl ether, the polyethylene glycol allyl ether, unsaturated acid anhydride, a chain transfer agent, an initiator, unsaturated carboxylic acid, a reducing agent and water taken as materials to obtain a copolymerization product; and after cooling the copolymerization product, adding alkali compound to adjust the pH value to 7-8, thus obtaining the sulfoacid modified polycarboxylic superplasticizer. The sulfoacid structure seals polyether terminal hydroxy, so that the stability of polycarboxylic acid molecules can be improved; a polyether chain segment is prevented from degrading under an acidic condition or alkaline condition; the electronic effect of the polycarboxylic acid molecule sulfonic acid group is utilized at the same time; the strength and the stability of a hydration shell can be improved; and the mobility and the slump keeping performance of concrete are also improved.
Description
Technical field
The present invention relates to a kind of sulfonic group modified polycarboxylic acid super-plasticizer and preparation method thereof.
Background technology
At present, be not only high-strength to the high performance concrete requirement, and be more the super-long-term weather resistance of paying close attention to this structured material, possessed simultaneously closely knit, stable and good workability on high-strength basis.In the technical measures of preparation high performance concrete, except cement, aggregate are had higher requirement, most important feature also is in layoutprocedure to use ultrafine powder adulterant and chemical admixture, especially has efficient diminishing, suitably bleed and can reduce and prevent the high-performance superplasticizer of Slump Time losing of Large.Superplasticizer is again concrete admixture, refer to produce to have the chutable concrete that good workability (high workability, water-retentivity, cohesiveness) is more convenient for pouring into a mould, but do not reduce the additive of cement consumption and intensity, mainly refer to high efficiency water reducing agent that water-reducing rate is high and high-performance water reducing agent etc. in China.Polycarboxylic acid super-plasticizer with comb shaped structure due to have high water reducing rate, concrete slump through the time loss little, the advantage such as volume is low, become the focus of domestic and international admixture research and development.
In recent years, the construction of domestic large quantities of heavy construction, Line for Passenger Transportation, Hydraulic and Hydro-Power Engineering, and the rise of real estate, cause concrete raw material in short supply, cause thus the quality such as coarse aggregate, mineral adulterant, fine aggregate, cement to occur descending, add China's cement type various, Engineering Mixed Proportions is varied, tends to cause superplasticizer and concrete incompatible.Exist existing superplasticizer inferior suitability, unstable properties, remaining superplasticizer concentration reduce and too fastly cause concrete to collapse damaging too fast shortcoming.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, a kind of strength and stability that can improve hydration shell is provided, improves sulfonic group modified polycarboxylic acid super-plasticizer of concrete mobility and slump retaining and preparation method thereof.
The technical scheme that a kind of sulfonic group modified polycarboxylic acid super-plasticizer of the present invention adopts is: the chemical structural formula of described sulfonic group modified polycarboxylic acid super-plasticizer is:
Wherein, described a is the polymerization degree, 10≤a≤80;
Described L is the polymerization degree, 15≤L≤50;
Described M is the polymerization degree, 5≤M≤50;
Described N is the polymerization degree, 5≤N≤50;
Described P is the polymerization degree, 2≤P≤20;
Described Q is the polymerization degree, 2≤Q≤20.
The technical scheme that a kind of sulfonic group modified polycarboxylic acid super-plasticizer of the present invention adopts is: it comprises the following steps:
A, polyreaction: polyoxyethylene glycol allyl ethers, thionamic acid, the vitriol oil, Resorcinol are added reactor, be heated with stirring to 100-110 ℃ of afterreaction 2～3 hours, obtain sulfonic group modified polyoxyethylene glycol allyl ethers;
B, copolyreaction: with described sulfonic group modified polyoxyethylene glycol allyl ethers, polyoxyethylene glycol allyl ethers, unsaturated acid anhydride, chain-transfer agent, initiator and water, keep 70～85 ℃ of temperature, slowly drip again unsaturated carboxylic acid and reductive agent, dripped in 2-3 hour respectively, react stopped heating after 3-4 hour, obtain copolymerization product;
C, neutralizing treatment: after described copolymerization product is cooling, add basic cpd to regulate pH value 7～8, obtain sulfonic group modified polycarboxylic acid super-plasticizer.
Optimize, in step a, the mol ratio of described thionamic acid and described polyoxyethylene glycol allyl ethers is 1:1～1.2:1;
The described vitriol oil is 0.1～0.3% of described polyoxyethylene glycol allyl ethers quality;
Described Resorcinol is 0.05 ~ 0.1% of described polyoxyethylene glycol allyl ethers quality.
Optimize, in step b, the mol ratio of described sulfonic group modified polyoxyethylene glycol allyl ethers and described polyoxyethylene glycol allyl ethers is 1:1～1:5;
The total mole number of described sulfonic group modified polyoxyethylene glycol allyl ethers and described polyoxyethylene glycol allyl ethers and the ratio of described unsaturated carboxylic acid are 1:2～1:5;
The total mole number of described sulfonic group modified polyoxyethylene glycol allyl ethers and described polyoxyethylene glycol allyl ethers and the ratio of described unsaturated acid anhydride are 1:0.5～1:2; Described initiator (oxygenant) is 1～3% of described sulfonic group modified polyoxyethylene glycol allyl ethers, described polyoxyethylene glycol allyl ethers, described unsaturated carboxylic acid, described unsaturated acid anhydride total mass;
Described chain-transfer agent is 0.2～2% of described sulfonic group modified polyoxyethylene glycol allyl ethers, described polyoxyethylene glycol allyl ethers, described unsaturated carboxylic acid, described unsaturated acid anhydride total mass;
The add-on of described water is described sulfonic group modified polyoxyethylene glycol allyl ethers, described polyoxyethylene glycol allyl ethers, described unsaturated carboxylic acid, described unsaturated acid anhydride total mass 1～2 times.
Optimize, described basic cpd is sodium hydroxide and the aqueous solution or potassium hydroxide and the aqueous solution or ammoniacal liquor.
Optimize, described unsaturated carboxylic acid is acrylic or methacrylic acid, and described unsaturated acid anhydride is maleic anhydride.
Optimize, described initiator is ammonium persulphate or Potassium Persulphate or Sodium Persulfate.
Optimize, described reductive agent is sodium bisulfite or ferrous sulfate or Sulfothiorine.
Optimize, described chain-transfer agent is Virahol or Thiovanic acid or thiohydracrylic acid.
The invention has the beneficial effects as follows: the present invention is with sulfonic group structure sealing polyethers terminal hydroxy group, can improve the stability of poly carboxylic acid molecule, prevent that polyether segment from degrading under acidity or alkaline condition, utilize simultaneously the sulfonic electronic effect of poly carboxylic acid molecule, the strength and stability of hydration shell be can improve, concrete mobility and slump retaining improved.
Embodiment
Further illustrate content of the present invention in conjunction with example, but the present invention not only is confined to following instance.
Embodiment one:
Be that 2000 polyoxyethylene glycol allyl ethers 200.0g, thionamic acid 9.7g, the vitriol oil (98%) 0.4g, Resorcinol 0.1g add in there-necked flask with molecular weight, be heated with stirring to 110 ℃, reacted 2 hours, and coolingly obtained sulfonic group modified polyoxyethylene glycol allyl ethers.
previous step is reacted the sulfonic group modified polyoxyethylene glycol allyl ethers that obtains, polyoxyethylene glycol allyl ethers 200.0g, Virahol 8g, maleic anhydride 9.8g, ammonium persulphate 12g, water 300g adds in reactor, be heated with stirring to 80 ℃ of dissolvings, drip respectively acrylic acid aqueous solution (containing vinylformic acid 43.2g and water 106.8g) and sodium sulfite solution (containing sodium bisulfite 11g and water 139g), acrylic acid aqueous solution was approximately added in 3 hours, sodium sulfite solution approximately added in 3.5 hours, add rear insulation reaction 1 hour, cooling, sodium hydroxide with mass concentration 40% is neutralized to pH value 7, thin up is to massfraction 40%, obtain sulfonic group modified polycarboxylic acid super-plasticizer.
Embodiment two:
Be that 2000 polyoxyethylene glycol allyl ethers 200.0g, thionamic acid 9.7g, the vitriol oil (98%) 0.4g, Resorcinol 0.1g add in there-necked flask with molecular weight, be heated with stirring to 110 ℃, reacted 2 hours, and coolingly obtained sulfonic group modified polyoxyethylene glycol allyl ethers.
previous step is reacted the sulfonic group modified polyoxyethylene glycol allyl ethers that obtains, polyoxyethylene glycol allyl ethers 200.0g, Virahol 8g, maleic anhydride 19.6g, ammonium persulphate 12g, water 300g adds in reactor, be heated with stirring to 80 ℃ of dissolvings, drip respectively acrylic acid aqueous solution (containing vinylformic acid 36.0g and water 114.0g) and sodium sulfite solution (containing sodium bisulfite 11g and water 139g), acrylic acid aqueous solution was approximately added in 3 hours, sodium sulfite solution approximately added in 3.5 hours, add rear insulation reaction 1 hour, cooling, sodium hydroxide with mass concentration 40% is neutralized to pH value 7, thin up is to massfraction 40%, obtain sulfonic group modified polycarboxylic acid super-plasticizer.
Embodiment three:
Be that 2000 polyoxyethylene glycol allyl ethers 200.0g, thionamic acid 10.7g, the vitriol oil (98%) 0.6g, Resorcinol 0.2g add in there-necked flask with molecular weight, be heated with stirring to 110 ℃, reacted 2 hours, and coolingly obtained sulfonic group modified polyoxyethylene glycol allyl ethers.
previous step is reacted the sulfonic group modified polyoxyethylene glycol allyl ethers that obtains, polyoxyethylene glycol allyl ethers 100.0g, Virahol 6g, maleic anhydride 7.4g, ammonium persulphate 9g, water 250g adds in reactor, be heated with stirring to 80 ℃ of dissolvings, drip respectively acrylic acid aqueous solution (containing vinylformic acid 32.4g and water 87.6g) and sodium sulfite solution (containing sodium bisulfite 8.3g and water 111.7g), acrylic acid aqueous solution was approximately added in 3 hours, sodium sulfite solution approximately added in 3.5 hours, add rear insulation reaction 1.5 hours, cooling, sodium hydroxide with mass concentration 40% is neutralized to pH value 7, thin up is to massfraction 40%, obtain sulfonic group modified polycarboxylic acid super-plasticizer.
Embodiment four:
Be that 2000 polyoxyethylene glycol allyl ethers 200.0g, thionamic acid 10.7g, the vitriol oil (98%) 0.6g, Resorcinol 0.2g add in there-necked flask with molecular weight, be heated with stirring to 110 ℃, reacted 2 hours, and coolingly obtained sulfonic group modified polyoxyethylene glycol allyl ethers.
previous step is reacted the sulfonic group modified polyoxyethylene glycol allyl ethers that obtains, polyoxyethylene glycol allyl ethers 100.0g, Virahol 6g, maleic anhydride 14.7g, ammonium persulphate 9g, water 250g adds in reactor, be heated with stirring to 80 ℃ of dissolvings, drip respectively acrylic acid aqueous solution (containing vinylformic acid 27.0g and water 93.0g) and sodium sulfite solution (containing sodium bisulfite 8.3g and water 111.7g), acrylic acid aqueous solution was approximately added in 3 hours, sodium sulfite solution approximately added in 3.5 hours, add rear insulation reaction 1.5 hours, cooling, sodium hydroxide with mass concentration 40% is neutralized to pH value 7, thin up is to massfraction 40%, obtain sulfonic group modified polycarboxylic acid super-plasticizer.
Embodiment five:
Be that 2000 polyoxyethylene glycol allyl ethers 200.0g, thionamic acid 11.6g, the vitriol oil (98%) 0.4g, Resorcinol 0.2g add in there-necked flask with molecular weight, be heated with stirring to 110 ℃, reacted 2 hours, and coolingly obtained sulfonic group modified polyoxyethylene glycol allyl ethers.
previous step is reacted the sulfonic group modified polyoxyethylene glycol allyl ethers that obtains, polyoxyethylene glycol allyl ethers 400.0g, Virahol 12g, maleic anhydride 14.8g, ammonium persulphate 18g, water 500g adds in reactor, be heated with stirring to 80 ℃ of dissolvings, drip respectively methacrylic aqueous acid (containing vinylformic acid 77.4g and water 72.6g) and sodium sulfite solution (containing sodium bisulfite 16.6g and water 133.4g), the methacrylic aqueous acid was approximately added in 3 hours, sodium sulfite solution approximately added in 3.5 hours, add rear insulation reaction 2 hours, cooling, sodium hydroxide with mass concentration 40% is neutralized to pH value 7, thin up is to massfraction 40%, obtain sulfonic group modified polycarboxylic acid super-plasticizer.
Embodiment six:
Be that 2000 polyoxyethylene glycol allyl ethers 200.0g, thionamic acid 11.6g, the vitriol oil (98%) 0.4g, Resorcinol 0.2g add in there-necked flask with molecular weight, be heated with stirring to 110 ℃, reacted 2 hours, and coolingly obtained sulfonic group modified polyoxyethylene glycol allyl ethers.
previous step is reacted the sulfonic group modified polyoxyethylene glycol allyl ethers that obtains, polyoxyethylene glycol allyl ethers 400.0g, Virahol 12g, maleic anhydride 7.4g, ammonium persulphate 18g, water 500g adds in reactor, be heated with stirring to 80 ℃ of dissolvings, drip respectively methacrylic aqueous acid (containing vinylformic acid 103.2g and water 46.8g) and sodium sulfite solution (containing sodium bisulfite 16.6g and water 133.4g), the methacrylic aqueous acid was approximately added in 3 hours, sodium sulfite solution approximately added in 3.5 hours, add rear insulation reaction 2 hours, cooling, sodium hydroxide with mass concentration 40% is neutralized to pH value 7, thin up is to massfraction 40%, obtain sulfonic group modified polycarboxylic acid super-plasticizer.
Application example
Sulfonic group modified polycarboxylic acid super-plasticizer product of the present invention is carried out cement paste test by existing national standard, and when volume is 0.2% of cement quality, each performance test results is as follows:
Claims (9)
1. sulfonic group modified polycarboxylic acid super-plasticizer, it is characterized in that: the chemical structural formula of described sulfonic group modified polycarboxylic acid super-plasticizer is:
Wherein, described a is the polymerization degree, 10≤a≤80;
Described L is the polymerization degree, 15≤L≤50;
Described M is the polymerization degree, 5≤M≤50;
Described N is the polymerization degree, 5≤N≤50;
Described P is the polymerization degree, 2≤P≤20;
Described Q is the polymerization degree, 2≤Q≤20.
2. the preparation method of a sulfonic group modified polycarboxylic acid super-plasticizer as claimed in claim 1, it is characterized in that: it comprises the following steps:
A, polyreaction: polyoxyethylene glycol allyl ethers, thionamic acid, the vitriol oil, Resorcinol are added reactor, be heated with stirring to 100-110 ℃ of afterreaction 2～3 hours, obtain sulfonic group modified polyoxyethylene glycol allyl ethers;
B, copolyreaction: with described sulfonic group modified polyoxyethylene glycol allyl ethers, polyoxyethylene glycol allyl ethers, unsaturated acid anhydride, chain-transfer agent, initiator and water, keep 70～85 ℃ of temperature, slowly drip again unsaturated carboxylic acid and reductive agent, dripped in 3-4 hour respectively, react stopped heating after 2-3 hour, obtain copolymerization product;
C, neutralizing treatment: after described copolymerization product is cooling, add basic cpd to regulate pH value 7～8, obtain sulfonic group modified polycarboxylic acid super-plasticizer.
3. the preparation method of a kind of sulfonic group modified polycarboxylic acid super-plasticizer according to claim 2 is characterized in that: in step a,
The mol ratio of described thionamic acid and described polyoxyethylene glycol allyl ethers is 1:1～1.2:1;
The described vitriol oil is 0.1～0.3% of described polyoxyethylene glycol allyl ethers quality;
Described Resorcinol is 0.05 ~ 0.1% of described polyoxyethylene glycol allyl ethers quality.
4. the preparation method of a kind of sulfonic group modified polycarboxylic acid super-plasticizer according to claim 2 is characterized in that: in step b,
The mol ratio of described sulfonic group modified polyoxyethylene glycol allyl ethers and described polyoxyethylene glycol allyl ethers is 1:1～1:5;
The total mole number of described sulfonic group modified polyoxyethylene glycol allyl ethers and described polyoxyethylene glycol allyl ethers and the ratio of described unsaturated carboxylic acid are 1:2～1:5;
The total mole number of described sulfonic group modified polyoxyethylene glycol allyl ethers and described polyoxyethylene glycol allyl ethers and the ratio of described unsaturated acid anhydride are 1:0.5～1:2; Described initiator (oxygenant) is 1～3% of described sulfonic group modified polyoxyethylene glycol allyl ethers, described polyoxyethylene glycol allyl ethers, described unsaturated carboxylic acid, described unsaturated acid anhydride total mass;
Described chain-transfer agent is 0.2～2% of described sulfonic group modified polyoxyethylene glycol allyl ethers, described polyoxyethylene glycol allyl ethers, described unsaturated carboxylic acid, described unsaturated acid anhydride total mass;
The add-on of described water is described sulfonic group modified polyoxyethylene glycol allyl ethers, described polyoxyethylene glycol allyl ethers, described unsaturated carboxylic acid, described unsaturated acid anhydride total mass 1～2 times.
5. the preparation method of a kind of sulfonic group modified polycarboxylic acid super-plasticizer according to claim 2, it is characterized in that: described basic cpd is sodium hydroxide and the aqueous solution or potassium hydroxide and the aqueous solution or ammoniacal liquor.
6. the preparation method of a kind of sulfonic group modified polycarboxylic acid super-plasticizer according to claim 2 is characterized in that: described unsaturated carboxylic acid is acrylic or methacrylic acid, and described unsaturated acid anhydride is maleic anhydride.
7. the preparation method of a kind of sulfonic group modified polycarboxylic acid super-plasticizer according to claim 2, it is characterized in that: described initiator is ammonium persulphate or Potassium Persulphate or Sodium Persulfate.
8. the preparation method of a kind of sulfonic group modified polycarboxylic acid super-plasticizer according to claim 2, it is characterized in that: described reductive agent is sodium bisulfite or ferrous sulfate or Sulfothiorine.
9. the preparation method of a kind of sulfonic group modified polycarboxylic acid super-plasticizer according to claim 2, it is characterized in that: described chain-transfer agent is Virahol or Thiovanic acid or thiohydracrylic acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273180A (en) * | 2015-11-03 | 2016-01-27 | 上海台界化工有限公司 | Synthesis method of unsaturated polyoxyethylene ether derivative and product of unsaturated polyoxyethylene ether derivative |
| CN108517026A (en) * | 2018-03-29 | 2018-09-11 | 福建三凯建筑材料有限公司 | A kind of polycarboxylate water-reducer |
-
2013
- 2013-03-18 CN CN 201310085730 patent/CN103145364A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105273180A (en) * | 2015-11-03 | 2016-01-27 | 上海台界化工有限公司 | Synthesis method of unsaturated polyoxyethylene ether derivative and product of unsaturated polyoxyethylene ether derivative |
| CN105273180B (en) * | 2015-11-03 | 2018-03-13 | 上海台界化工有限公司 | A kind of synthetic method of unsaturated polyoxyethylene ether derivant and products thereof |
| CN108517026A (en) * | 2018-03-29 | 2018-09-11 | 福建三凯建筑材料有限公司 | A kind of polycarboxylate water-reducer |
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Application publication date: 20130612 |