CN101648979B - Preparation method for low air bleeding lignosulphonate high-efficiency water reducing agent - Google Patents
Preparation method for low air bleeding lignosulphonate high-efficiency water reducing agent Download PDFInfo
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- CN101648979B CN101648979B CN200910112347.4A CN200910112347A CN101648979B CN 101648979 B CN101648979 B CN 101648979B CN 200910112347 A CN200910112347 A CN 200910112347A CN 101648979 B CN101648979 B CN 101648979B
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- lignosulphonate
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Abstract
The invention discloses a preparation method for a low air bleeding lignosulphonate high-efficiency water reducing agent, which adopts the following steps: under the alkali condition and the existance of a defoaming agent and an activating agent, carrying out the catalytic oxidation reaction o lignosulphonate water solution to ensure that part of molecular bonds are ruptured and recombined so as to improve the molecular weight; and then carrying out sulfonation reaction and introducing a sulfonic group to a molecular chain to improve the sulfonation degree. The preparation method has mild reaction, simple operation, no toxity and pollution and is safe to the environment; and the obtained products have stable performance and the advantages of small air bleeding amount, high water reducing rate and the like.
Description
Technical field
The present invention relates to a kind of preparation method of ligno-sulfate based plasticizer.
Background technology
Sulfonated lignin can improve the workability of fresh concrete as cement water reducing agent, and its wide material sources, cheap, therefore in concrete, apply very early, but there is long, the defect such as amount of air entrainment is large, water-reducing rate is low of slow setting time in it, seriously restricts its application.Sulfonated lignin be a kind of by phenmethyl propane derivative, be that hydrophobic grouping and sulfonic group, carboxyl, hydroxyl etc. are the anion surfactant of hydrophilic radical, its molecular structure and molecular weight distribution utmost point heterogeneity.And in sulfonated lignin, contain a large amount of reducing sugars, in the raising of concrete volume, can cause incoagulable phenomenon of concrete long time, cause engineering accident.Its amount of air entrainment of the sulfonated lignin of small molecules amount is large, easily causes the reduction of concrete strength in concrete application, therefore cannot be applied in high-strength concrete.The water-reducing rate of sulfonated lignin is on the low side in addition, generally as ordinary water-reducing agent, uses, and improves its water-reducing rate and has great importance to expanding its concrete practical application.In sulfonated lignin, contain multiple reactive group, there is reactive behavior, can be oxidized, sulfonation, condensation and alkylation etc., therefore can pass through chemical modification, improve the problem of itself existence.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of simple to operate, ligno-sulfate based plasticizer that water-reducing rate is high.
For achieving the above object, technical solution of the present invention is:
The preparation method who the invention provides a kind of ligno-sulfate based plasticizer, it comprises the following steps:
By mass parts, 100 parts of lignosulphonate solids and 66.7～150 parts of water are joined in reactor, be mixed with certain density solution; Add 0.5～0.8 part of defoamer and 0.2～0.4 part of activator, with appropriate sulphur acid for adjusting pH, be 8～10, be warming up to 50～70 ℃, add again 0.1～0.3 part of catalyzer and 1～5 part of oxygenant, react after 0.5～1 hour, in slow setting group in sulfonated lignin molecular structure and system, the slow setting group of reducing sugar all can be oxidized, owing to there is coupled reaction, reduced the content of low-molecular weight lignin sulfonate simultaneously; Add 12～20 parts of sulphonating agents, react 1～2 hour, sulfonated lignin can be introduced more sulfonic group in molecular structure, obtain low air bleeding lignosulphonate high-efficiency water reducing agent after cooling.
Described sulfonated lignin are a kind of in ammonium lignosulphonate, calcium lignin sulphonate, sodium lignosulfonate.
Described defoamer is a kind of in tributyl phosphate, dimethyl polysiloxane, polyoxyethylene polyoxypropylene glyceryl ether.
Described activator is a kind of in Amino Trimethylene Phosphonic Acid sodium, hexanediamine tetramethylene phosphonic acid sodium.
Described catalyzer is a kind of in Vanadium Pentoxide, Manganse Dioxide, ceric ammonium nitrate.
Described oxygenant is a kind of in potassium permanganate, hydrogen peroxide, ammonium persulphate.
Described sulphonating agent is a kind of in S-WAT, Sodium Pyrosulfite, thionamic acid, Sulphanilic Acid.
Adopt after such scheme, due in preparation process of the present invention, the catalytic oxidation of sulfonated lignin, can make the slow setting group (hydroxyl or ether) in molecular structure that oxidizing reaction occurs, and is oxidized to the carboxyl of little slow setting; In system, the slow setting group of reducing sugar also can be oxidized; Oxidizing reaction can also make sulfonated lignin molecular rupture, and the new free end of the chain of activity producing, under the effect of activator, can coupling form molecule long-chain, with this, improves the relative molecular weight of sulfonated lignin; In system, add defoamer, a large amount of bubble ends (small molecules amount sulfonated lignin) that can reduce the generation in oxidation reaction process are suspended in system top layer simultaneously, promote small molecules amount sulfonated lignin to participate in reaction.Catalyzed oxidation sulfonated lignin later, then pass through sulfonation reaction, in molecular chain, introduce sulfonic acid group, improve sulfonation degree, with this, improve its water-reducing rate.Therefore the present invention has the following advantages:
1, can improve the long problem of slow setting time of sulfonated lignin.
2, can reduce the amount of air entrainment of sulfonated lignin.
3, can improve the water-reducing rate of sulfonated lignin.
4, reaction conditions is gentle, simple to operate.
Embodiment
Embodiment 1
By mass parts, 100kg sodium lignosulfonate solid and 100kg water are joined in the reactor of 500L, be mixed with the solution of 50% concentration.Add 0.5kg tributyl phosphate and 0.2kg hexanediamine tetramethylene phosphonic acid sodium, with appropriate sulphur acid for adjusting pH, be 8, be warming up to 70 ℃, add again 0.2kg ceric ammonium nitrate and 5kg hydrogen peroxide, react after 0.5 hour, in slow setting group in sodium lignosulfonate molecular structure and system, the slow setting group of reducing sugar all can be oxidized, owing to there is coupled reaction, reduced the content of low-molecular weight lignin sulfonate simultaneously; Add 12kg thionamic acid, react 2 hours, sulfonated lignin can be introduced more sulfonic group in molecular structure, obtain low air bleeding lignosulphonate high-efficiency water reducing agent after cooling, and weight concentration is 53.95%.
Embodiment 2
By mass parts Ji，Jiang 100kg ammonium lignosulphonate's solid and 100kg water, join in the reactor of 500L, be mixed with the solution of 50% concentration.Add 0.7kg tributyl phosphate and 0.2kg hexanediamine tetramethylene phosphonic acid sodium, with appropriate sulphur acid for adjusting pH, be 9, be warming up to 50 ℃, add again 0.3kg Manganse Dioxide and 2kg potassium permanganate, react after 0.5 hour, in slow setting group in ammonium lignosulphonate's molecular structure and system, the slow setting group of reducing sugar all can be oxidized, owing to there is coupled reaction, reduced the content of low-molecular weight lignin sulfonate simultaneously; Add 16kg Sodium Pyrosulfite, react 1 hour, sulfonated lignin can be introduced more sulfonic group in molecular structure, obtain low air bleeding lignosulphonate high-efficiency water reducing agent after cooling, and weight concentration is 54.23%.
Embodiment 3
By mass parts, 100kg calcium lignin sulphonate solid and 100kg water are joined in the reactor of 500L, be mixed with the solution of 50% concentration.Add 0.8kg dimethyl polysiloxane and 0.4kg hexanediamine tetramethylene phosphonic acid sodium, with appropriate sulphur acid for adjusting pH, be 10, be warming up to 55 ℃, add again 0.2kg Vanadium Pentoxide and 4kg ammonium persulphate, react after 0.5 hour, in slow setting group in calcium lignin sulphonate molecular structure and system, the slow setting group of reducing sugar all can be oxidized, owing to there is coupled reaction, reduced the content of low-molecular weight lignin sulfonate simultaneously; Add 18kg S-WAT, react 2 hours, sulfonated lignin can be introduced more sulfonic group in molecular structure, obtain low air bleeding lignosulphonate high-efficiency water reducing agent after cooling, and weight concentration is 54.87%.
Embodiment 4
By mass parts, 100kg sodium lignosulfonate solid and 100kg water are joined in the reactor of 500L, be mixed with the solution of 50% concentration.Add 0.6kg polyoxyethylene polyoxypropylene glyceryl ether and 0.3kg Amino Trimethylene Phosphonic Acid sodium, with appropriate sulphur acid for adjusting pH, be 10, be warming up to 60 ℃, add again 0.1kg Vanadium Pentoxide and 1kg potassium permanganate, react after 1 hour, in slow setting group in sodium lignosulfonate molecular structure and system, the slow setting group of reducing sugar all can be oxidized, owing to there is coupled reaction, reduced the content of low-molecular weight lignin sulfonate simultaneously; Add 20kg Sulphanilic Acid, react 2 hours, sulfonated lignin can be introduced more sulfonic group in molecular structure, obtain low air bleeding lignosulphonate high-efficiency water reducing agent after cooling, and weight concentration is 54.10%.
Embodiment 5
By mass parts, 100kg sodium lignosulfonate solid and 150kg water are joined in the reactor of 500L, be mixed with the solution of 40% concentration.Add 0.7kg polyoxyethylene polyoxypropylene glyceryl ether and 0.3kg Amino Trimethylene Phosphonic Acid sodium, with appropriate sulphur acid for adjusting pH, be 9, be warming up to 60 ℃, add again 0.2kg Vanadium Pentoxide and 3kg potassium permanganate, react after 0.7 hour, in slow setting group in sodium lignosulfonate molecular structure and system, the slow setting group of reducing sugar all can be oxidized, owing to there is coupled reaction, reduced the content of low-molecular weight lignin sulfonate simultaneously; Add 15kg Sulphanilic Acid, react 1.5 hours, sulfonated lignin can be introduced more sulfonic group in molecular structure, obtain low air bleeding lignosulphonate high-efficiency water reducing agent after cooling, and weight concentration is 41.89%.
Embodiment 6
By mass parts, 100kg sodium lignosulfonate solid and 66.7kg water are joined in the reactor of 500L, be mixed with the solution of 60% concentration.Add 0.5kg polyoxyethylene polyoxypropylene glyceryl ether and 0.2kg Amino Trimethylene Phosphonic Acid sodium, with appropriate sulphur acid for adjusting pH, be 8, be warming up to 50 ℃, add again 0.1kg Vanadium Pentoxide and 2kg potassium permanganate, react after 0.5 hour, in slow setting group in sodium lignosulfonate molecular structure and system, the slow setting group of reducing sugar all can be oxidized, owing to there is coupled reaction, reduced the content of low-molecular weight lignin sulfonate simultaneously; Add 12kg Sulphanilic Acid, react 1 hour, sulfonated lignin can be introduced more sulfonic group in molecular structure, obtain low research work of air entrained type sulfonated lignin after cooling
High efficiency water reducing agent, weight concentration is 61.34%.
Embodiment 1 to embodiment 6 prepared low air bleeding lignosulphonate high-efficiency water reducing agent is tested.
Cement used is for building good fortune P.O 42.5R ordinary Portland cement, and sand is the medium sand of fineness modulus Mx=2.6, and stone is the rubble of particle diameter 5 ~ 31.5mm continuous grading.Water reducer volume is that 0.25%(is converted into solid masses calculating), according to GB8076-1997, measure.
Detected result is listed in table 1.
Table 1 performance test results
Claims (4)
1. a preparation method for low air bleeding lignosulphonate high-efficiency water reducing agent, is characterized in that comprising the following steps: by mass parts, 100 parts of lignosulphonate solids and 66.7～150 parts of water are joined in reactor, be mixed with certain density solution; 0.2～0.4 part of activator, is 8～10 with appropriate sulphur acid for adjusting pH, is warming up to 50～70 ℃, then adds 0.1～0.3 part of catalyzer and 1～5 part of oxygenant, reacts after 0.5～1 hour; Add 12～20 parts of sulphonating agents, react 1～2 hour, sulfonated lignin can be introduced more sulfonic group in molecular structure, obtain low air bleeding lignosulphonate high-efficiency water reducing agent after cooling; Described activator is a kind of in Amino Trimethylene Phosphonic Acid sodium, hexanediamine tetramethylene phosphonic acid sodium; Described catalyzer is a kind of in Vanadium Pentoxide, Manganse Dioxide, ceric ammonium nitrate; Described oxygenant is a kind of in potassium permanganate, hydrogen peroxide, ammonium persulphate; Described sulphonating agent is a kind of in S-WAT, Sodium Pyrosulfite, thionamic acid, Sulphanilic Acid.
2. the preparation method of a kind of low air bleeding lignosulphonate high-efficiency water reducing agent according to claim 1, is characterized in that: when adding activator, add 0.5～0.8 part of defoamer.
3. the preparation method of a kind of low air bleeding lignosulphonate high-efficiency water reducing agent according to claim 1, is characterized in that: described sulfonated lignin are a kind of in ammonium lignosulphonate, calcium lignin sulphonate, sodium lignosulfonate.
4. the preparation method of a kind of low air bleeding lignosulphonate high-efficiency water reducing agent according to claim 2, is characterized in that: described defoamer is a kind of in tributyl phosphate, dimethyl polysiloxane, polyoxyethylene polyoxypropylene glyceryl ether.
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| CN102001841B (en) * | 2010-11-08 | 2012-05-30 | 福州大学 | Preparation method of zymolytic lignin modified water reducing agent |
| CN102627673A (en) * | 2012-03-23 | 2012-08-08 | 辽宁岩砂晶建材有限公司 | Method for sulfomethylation of lignin degradation |
| CN103739227A (en) * | 2013-12-19 | 2014-04-23 | 柳州正菱集团有限公司 | Concrete pumping agent |
| CN105271886A (en) * | 2015-10-16 | 2016-01-27 | 江苏名和集团有限公司 | Modified lignosulfonate superplasticizer and preparation method thereof |
| CN107010866A (en) * | 2017-03-31 | 2017-08-04 | 鹤山市超牌碳酸钙有限公司 | A kind of height lignosulfonate sulfonate water reducer and preparation method thereof |
| CN111138109A (en) * | 2019-12-26 | 2020-05-12 | 新疆大学 | Cotton stalk lignin-based air entraining agent and preparation method and application thereof |
| CN111362611A (en) * | 2020-04-16 | 2020-07-03 | 贵州宝维新材料科技有限公司 | Concrete water reducing agent and preparation method and application thereof |
| CN113321440A (en) * | 2021-07-06 | 2021-08-31 | 四川宇砼建材有限公司 | Modified lignosulfonate water reducing agent and preparation method thereof |
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| US20020065400A1 (en) * | 2000-04-06 | 2002-05-30 | Mikhail Raskin | Resin material and method of producing same |
| CN1730425A (en) * | 2004-08-04 | 2006-02-08 | 黄波 | Concrete additive of herb lignosulfonate |
| CN101147480B (en) * | 2007-09-13 | 2010-08-11 | 华南理工大学 | Modified lignosulfonate pesticide dispersing agent and its preparation method |
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Inventor after: Gui Miaomiao Inventor after: Fang Yunhui Inventor after: Ma Xiuxing Inventor after: Yu Feiyu Inventor after: Guo Xinqi Inventor after: Wen Qingru Inventor after: Jiang Zhuojun Inventor after: Wang Yingying Inventor after: Lin Tianxing Inventor before: Fang Yunhui Inventor before: Ma Xiuxing Inventor before: Yu Feiyu Inventor before: Guo Xinqi Inventor before: Wen Qingru Inventor before: Jiang Zhuojun Inventor before: Wang Yingying Inventor before: Lin Tianxing |
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