CN102532558A - Preparation method of amido polycarboxylic water-reducing agent - Google Patents
Preparation method of amido polycarboxylic water-reducing agent Download PDFInfo
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Abstract
The invention relates to a preparation method of an amido polycarboxylic water-reducing agent. The preparation method comprises the following steps of: adopting a synthetic method with firstly polymerization and secondly functionalization, firstly forming a carboxylic polymer main chain, then carrying out grafting by amidation and esterification reaction with amino-terminated polyether and polyethylene glycol monoalkyl ether under certain temperature to introduce branched chains, and preparing the high-performance novel polycarboxylic water-reducing agent with jointed connection of the main chain and the branched chains by amide/imide bonds and ester bonds. According to the preparation method, the structure and the performance of the water-reducing agent are adjusted by molecular structure design, the reaction process is easy to control, the effect on environmental protection without pollution is achieved, the reaction conversion rate is high, the water reducing rate of a product is high, and under the conditions with low water-cement rate and low doping amount, the mortar doped with the amido polycarboxylic water-reducing agent has better fluidity compared with the common ester polycarboxylic water-reducing agent.
Description
Technical field
The present invention relates to technical field of concrete additives, specifically a kind of preparation method of acid amide type poly carboxylic acid series water reducer.
Background technology
Concrete admixture has indispensable effect in the construction work in modern times, and poly carboxylic acid series water reducer is one of staple product of New Building Materials mainstay industry as a kind of important concrete admixture.Poly carboxylic acid series water reducer not only can provide simple and easy to do construction technology, improve mechanical properties of concrete and nontoxic, environmental protection, pollution-free greatly.The poly carboxylic acid series water reducer product of promoting on the market now mainly is first-generation poly carboxylic acid series water reducer (methylacrylic acid/olefin(e) acid methyl terpolymer); S-generation poly carboxylic acid series water reducer (propenyl ether multipolymer); And to third generation poly carboxylic acid series water reducer (acid amides/imide-type) though existing now a spot of theoretical investigation does not also have industrialized product.
Patent CN 102101906 A have reported the preparation method of a kind of acid amides/imide-type high density polycarboxylate high performance water-reducing agent.This patent is earlier unsaturated acid anhydride and monobasic hydramine acylation reaction to be obtained acylate through the first step; Second step was that pol yalkylene glycol monoalkyl ether, unsaturated acid (acid anhydride) are carried out catalytic esterification; Obtain esterification products; The 3rd step be with acylate, esterification products, sulfonic acid class minor comonomer under the effect of initiator and copolymerization regulator, carry out free-radical polymerizedly then copolymerization product pH value being adjusted into 6～7, make poly carboxylic acid series water reducer.The water-reducing rate and the slump retaining of this water reducer are better; The water reducer that can prepare high density (70～80%) reduces transportation cost; But utilization unsaturated acid anhydride and monobasic hydramine carry out acylation reaction; Very difficult assurance does not have the generation of esterification, and the preparation process is comparatively complicated, and technique controlling difficulty is bigger.
Patent CN 102181020 A have reported the method for the synthetic high performance water reducing agent of polyocarboxy acid of amidation reactive monomer copolyreaction.This patent is (methyl) Acrylic Acid Monomer and an end to be contained amino methoxy polyoxyethylene base ether under catalyst action, prepare a kind of polymerisable monomer through amidate action, under the initiator effect, in the aqueous solution, makes poly carboxylic acid series water reducer with the basic soln neutralization after the copolymerization with (methyl) Acrylic Acid Monomer, chain transfer monomer again.Main side chain connects through amido linkage in this water reducer molecular structure, and water-reducing property is excellent, but prepares condition harshness in the polymerisable monomer process at amidate action, is difficult to control.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of acid amide type poly carboxylic acid series water reducer; The compound method of functionalization after the employing polymerization; Form carboxylic main polymer chain earlier, carry out grafting through amidation and esterification at a certain temperature with Amino Terminated polyether(ATPE), polyalkylene glycol monoalkyl ether then and introduce side chain.Main side chain is connected with ester bond through two kinds of chemical bond amido linkages in this water reducer molecular structure, can regulate the mol ratio of amido linkage and ester bond in the main side chain, has enriched the structure of water reducer, has given the water reducer particular performances.This water reducer has that synthesis technique is simple, transformation efficiency is high, Environmental Safety, water-reducing rate are high, under low water-cement ratio and low-dosage, have dispersiveness and degree of mobilization preferably.
The objective of the invention is to realize like this:
A kind of preparation method of acid amide type poly carboxylic acid series water reducer is characterized in that comprising following two steps:
(1) synthetic carboxylic polymkeric substance: at first water is added in the reaction kettle; In reaction kettle, drip initiator solution, the chain-transfer agent aqueous solution and carboxylic monomer solution when being warmed up to 60 ℃～95 ℃ successively; The dropping time is 1～5 hour; Drip back insulation 0～5 hour, obtain carboxylic polymkeric substance;
(2) amidation and esterification: again Amino Terminated polyether(ATPE) monomer, polyalkylene glycol monoalkyl ether monomer are joined in the reaction kettle of step (1); Sealed reactor; 100 ℃～170 ℃ ,-0.03MPa～-0.10 Mpa condition under the reaction 0.5 hour～8 hours after; Be cooled to 20 ℃～80 ℃, regulate pH value to 4～10, obtain acid amide type poly carboxylic acid series water reducer of the present invention with alkaline solution.
Initiator described in the step (1) is one or more in hydrogen peroxide, ammonium persulphate, Sodium Persulfate, the Potassium Persulphate, and consumption is 0.5%～5.0% of step (a 1) total monomer weight.
Chain-transfer agent described in the step (1) is one or more in mercaptoethanol, Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, Virahol, Hypophosporous Acid, 50, sodium hypophosphite, the potassium hypophosphite, and consumption is 0.5%～10.0% of step (a 1) total monomer weight.
Carboxylic monomer described in the step (1) is that vinylformic acid is or/and methylacrylic acid.
The Amino Terminated polyether(ATPE) structural formula is shown in general formula (1) described in the step (2)
Wherein: R
1Identical or different, expression hydrogen, methyl or ethyl; R
2Alkyl or its mixture of expression hydrogen or 1-6 carbon atom; N representes the adduct number of oxyalkylene group, is the arbitrary number among the 5-100.
Amino Terminated polyether(ATPE) consumption described in the step (2) is 30.0%～90.0% of step (1) and step (a 2) total monomer weight.
Polyalkylene glycol monoalkyl ether described in the step (2) is one or more in poly glycol monomethyl ether, polyethyleneglycol ether, polyethyleneglycol propyl ether, the polyoxyethylene glycol monobutyl ether.
Polyalkylene glycol monoalkyl ether weight-average molecular weight is 400～5000 described in the step (2), and consumption is 5.0%～50.0% of step (1) and step (a 2) total monomer weight.
Alkali described in the step (2) is one or more in ammoniacal liquor, Pottasium Hydroxide, sodium hydroxide, the trolamine.
In the reaction process of carrying out step (2), can add catalyzer, to accelerate speed of reaction.Catalyzer is a kind of or any several kinds of mixtures in sulfuric acid, methylsulphonic acid, the tosic acid, and consumption is 0～5.0% of step (1) and step (a 2) total monomer weight.
In the reaction process of carrying out step (2), can add skimmer, to reduce the foam in the reaction process.Skimmer is one or both the mixture in polyethers, the silicone based skimmer, and consumption is 0～0.1% of step (1) and step (a 2) total monomer weight.
The water reducer of the present invention's preparation has following advantage:
(1) compound method of functionalization after the employing polymerization, success ester bond and amido linkage are connected on the main side chain of water reducer molecule reached the chemically composited of water reducer molecule aspect, is superior to the water reducer that simple ester bond or amido linkage connect.
(2) because the uniqueness of structure has given water reducer excellent performance, water-reducing rate is high, under low water-cement ratio and low-dosage, has dispersiveness and degree of mobilization preferably.
(3) reaction process is easy to control, safety and environmental protection, and cleanliness without any pollution, and also conversion rate of products is higher.
(4) product concentration can regulating and controlling, can prepare the high density product, and remote transportation can be saved a large amount of freight charges for product.
Embodiment
Further present invention is described through following examples, but the present invention is not produced any restriction.
Listed abbreviation below having used in an embodiment:
The Amino Terminated polyether(ATPE) monomer A; Structural formula is
, and wherein the addition mode of oxyethane and propylene oxide is random copolymerization;
The Amino Terminated polyether(ATPE) monomers B; Structural formula is
, and wherein the addition mode of oxyethane and propylene oxide is random copolymerization;
Amino Terminated polyether(ATPE) monomer C, structural formula are
.
Embodiment 1
235.5g water is joined in the there-necked flask, start stirring, be warmed up to 75 ℃～77 ℃.Drip simultaneously by the 2.5g Potassium Persulphate and be dissolved in initiator solution that 30.0g water obtains, be dissolved in chain-transfer agent solution that 60.0g water obtains and be dissolved in the monomer solution that obtains in the 154.0g water by 400.0g vinylformic acid, 100.0g methylacrylic acid by the 18.0g Virahol; The dropping time is 3 hours; Be added dropwise to complete back insulation 2 hours, obtain carboxylic polymkeric substance.Be that 1000 poly glycol monomethyl ether joins in the above-mentioned there-necked flask with 1955.0g Amino Terminated polyether(ATPE) monomer A, 1000.0g molecular weight again; Heat up; 130 ℃～140 ℃ ,-0.07Mpa～-0.08Mpa conditioned response 2 hours, being cooled to 40 ℃, to add the 900.0g concentration be 20% sodium hydroxide, pH value of solution value to 8.5; Add 4560.8g water at last, obtain concentration and be 40% acid amide type poly carboxylic acid series water reducer.
Embodiment 2
235.5g water is joined in the there-necked flask, start stirring, be warmed up to 65 ℃～67 ℃.Drip simultaneously by the 12.0g ammonium persulphate and be dissolved in initiator solution that 30.0g water obtains, be dissolved in chain-transfer agent solution that 60.0g water obtains and be dissolved in the monomer solution that obtains in the 154.0g water by 300.0g vinylformic acid, 200.0g methylacrylic acid by the 6.0g Hypophosporous Acid, 50; The dropping time is 5 hours; Be added dropwise to complete back insulation 1 hour, obtain carboxylic polymkeric substance.Be that 400 polyethyleneglycol ether and 19.4g catalyzer tosic acid join in the above-mentioned there-necked flask with 2490.0g Amino Terminated polyether(ATPE) monomers B, 810.0g molecular weight again; Heat up; 110 ℃～120 ℃ ,-0.08Mpa～-0.09Mpa conditioned response 6 hours, being cooled to 50 ℃, to add the 560.0g concentration be 30% Pottasium Hydroxide, pH value of solution value to 7.0; Add 3559.4g water at last, obtain concentration and be 50% acid amide type poly carboxylic acid series water reducer.
Embodiment 3
235.5g water is joined in the there-necked flask, start stirring, be warmed up to 85 ℃～87 ℃.Drip simultaneously by the 9.0g hydrogen peroxide and be dissolved in initiator solution that 30.0g water obtains, be dissolved in chain-transfer agent solution that 60.0g water obtains and be dissolved in the monomer solution that obtains in the 154.0g water by 350.0g vinylformic acid, 150.0g methylacrylic acid by the 3.0g mercaptoethanol; The dropping time is 2 hours; Be added dropwise to complete back insulation 3 hours, obtain carboxylic polymkeric substance.Be that 2000 polyethyleneglycol propyl ether joins in the above-mentioned there-necked flask with 3000.0g Amino Terminated polyether(ATPE) monomer C, 500.0g molecular weight again; Heat up; 160 ℃～170 ℃ ,-0.03Mpa～-0.04Mpa conditioned response 7 hours, being cooled to 30 ℃, to add the 445.0g concentration be 40% trolamine, pH value of solution value to 6.5; Add 1528.7g water at last, obtain concentration and be 70% acid amide type poly carboxylic acid series water reducer.
Embodiment 4
235.5g water is joined in the there-necked flask, start stirring, be warmed up to 93 ℃～95 ℃.Drip simultaneously by the 20.0g Sodium Persulfate and be dissolved in initiator solution that 30.0g water obtains, be dissolved in chain-transfer agent solution that 60.0g water obtains and be dissolved in the monomer solution that obtains in the 154.0g water by 250.0g vinylformic acid, 250.0g methylacrylic acid by the 45.0g2-thiohydracrylic acid; The dropping time is 4 hours; Be added dropwise to complete back insulation 1 hour, obtain carboxylic polymkeric substance.Be that 2000 polyoxyethylene glycol monobutyl ether, 119.0g catalyst sulfuric acid and 1.4g polyethers skimmer join in the above-mentioned there-necked flask with 1420.0g Amino Terminated polyether(ATPE) monomer C, 1330.0g molecular weight again; Heat up; 120 ℃～130 ℃ ,-0.08Mpa～-0.09Mpa conditioned response 2 hours, being cooled to 40 ℃, to add the 710.0g concentration be 30% ammoniacal liquor, pH value of solution value to 7.5; Add 1935.3g water at last, obtain concentration and be 60% acid amide type poly carboxylic acid series water reducer.
Embodiment 5
235.5g water is joined in the there-necked flask, start stirring, be warmed up to 80 ℃～82 ℃.Drip simultaneously by the 15.0g hydrogen peroxide and be dissolved in initiator solution that 30.0g water obtains, be dissolved in chain-transfer agent solution that 60.0g water obtains and be dissolved in the monomer solution that obtains in the 154.0g water by 300.0g vinylformic acid, 200.0g methylacrylic acid by the 39.0g Thiovanic acid; The dropping time is 3 hours; Be added dropwise to complete back insulation 1 hour, obtain carboxylic polymkeric substance.Be that 1000 polyoxyethylene glycol monobutyl ether and 2.2g silicone antifoam agent join in the above-mentioned there-necked flask with 1245.0g Amino Terminated polyether(ATPE) monomer A, 1575.0g molecular weight again; Heat up; 150 ℃～160 ℃ ,-0.07Mpa～-0.08Mpa conditioned response 5 hours, being cooled to 30 ℃, to add the 530.0g concentration be 40% sodium hydroxide, pH value of solution value to 8.0; Add 1178.9g water at last, obtain concentration and be 70% acid amide type poly carboxylic acid series water reducer.
Implement performance: carry out the test of mortar experimental performance as comparative sample, employing 612g Wan An cement P.O 42.5,1307.3g standard sand by embodiment 1 to embodiment 5 prepared acid amide type poly carboxylic acid series water reducer with on the market ester class water reducer.
Table 1 product of the present invention and normal ester class water reducer contrast at the mortar application performance
The result can find out that under low water-cement ratio and low-dosage, the mortar ratio normal ester class water reducer product of mixing product of the present invention has better degree of mobilization from table.
Claims (1)
1. the preparation method of an acid amide type poly carboxylic acid series water reducer is characterized in that this method may further comprise the steps:
(1) synthetic carboxylic polymkeric substance: at first water is added in the reaction kettle; In reaction kettle, drip initiator solution, the chain-transfer agent aqueous solution and carboxylic monomer solution when being warmed up to 60 ℃～95 ℃ successively; The dropping time is 1～5 hour; Drip back insulation 0～5 hour, obtain carboxylic polymkeric substance;
(2) amidation and esterification: again Amino Terminated polyether(ATPE) monomer, polyalkylene glycol monoalkyl ether monomer are joined in the reaction kettle of step (1); Sealed reactor; 100 ℃～170 ℃ ,-0.03MPa～-0.10 Mpa condition under the reaction 0.5 hour～8 hours after; Be cooled to 20 ℃～80 ℃, regulate pH value to 4～10, obtain described acid amide type poly carboxylic acid series water reducer with alkaline solution; Wherein:
Initiator described in the step (1) is one or more in hydrogen peroxide, ammonium persulphate, Sodium Persulfate, the Potassium Persulphate, and consumption is 0.5%～5.0% of step (a 1) total monomer weight;
Chain-transfer agent described in the step (1) is one or more in mercaptoethanol, Thiovanic acid, 2 mercaptopropionic acid, 3-thiohydracrylic acid, Virahol, Hypophosporous Acid, 50, sodium hypophosphite, the potassium hypophosphite, and consumption is 0.5%～10.0% of step (a 1) total monomer weight;
Carboxylic monomer described in the step (1) is that vinylformic acid is or/and methylacrylic acid;
The Amino Terminated polyether(ATPE) structural formula is shown in general formula (1) described in the step (2)
Wherein: R
1Identical or different, expression hydrogen, methyl or ethyl; R
2Alkyl or its mixture of expression hydrogen or 1-6 carbon atom; N representes the adduct number of oxyalkylene group, is the arbitrary number among the 5-100;
Amino Terminated polyether(ATPE) consumption described in the step (2) is 30.0%～90.0% of step (1) and step (a 2) total monomer weight;
Polyalkylene glycol monoalkyl ether described in the step (2) is one or more in poly glycol monomethyl ether, polyethyleneglycol ether, polyethyleneglycol propyl ether, the polyoxyethylene glycol monobutyl ether;
Polyalkylene glycol monoalkyl ether weight-average molecular weight is 400～5000 described in the step (2), and consumption is 5.0%～50.0% of step (1) and step (a 2) total monomer weight;
Alkali described in the step (2) is a kind of or any several kinds of mixtures in ammoniacal liquor, Pottasium Hydroxide, sodium hydroxide, the trolamine.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103930454A (en) * | 2011-11-11 | 2014-07-16 | 罗门哈斯公司 | Small particle size hypophosphite telomers of unsaturated carboxylic acids |
| CN104003644A (en) * | 2013-06-21 | 2014-08-27 | 温州威力助剂有限公司 | Production process of polycarboxylic acid water-reducing agent |
| CN104231183A (en) * | 2014-09-23 | 2014-12-24 | 江苏奥莱特新材料有限公司 | Preparation method for polycarboxylate-type water reducer |
| CN105418857A (en) * | 2015-12-31 | 2016-03-23 | 江苏苏博特新材料股份有限公司 | Preparation method and application of polycarboxylate water reducer containing phosphate group |
| CN107151294A (en) * | 2017-06-08 | 2017-09-12 | 中建材中岩科技有限公司 | Early-strength polycarboxylate superplasticizer and its preparation method and application |
| CN104311752B (en) * | 2014-10-10 | 2017-09-22 | 科之杰新材料集团有限公司 | A kind of polycarboxylate water-reducer and preparation method thereof |
| CN108912279A (en) * | 2018-08-13 | 2018-11-30 | 山东轻工职业学院 | High-adaptability highly branched chain amide imine poly carboxylic acid series water reducer and preparation method thereof |
| CN109503774A (en) * | 2018-11-28 | 2019-03-22 | 南京友西科技股份有限公司 | A kind of polycarboxylate water-reducer that temperature sensitivity is small |
| CN109535342A (en) * | 2018-11-23 | 2019-03-29 | 上海东大化学有限公司 | A kind of amides poly carboxylic acid series water reducer and its preparation and application |
| CN113354782A (en) * | 2020-04-27 | 2021-09-07 | 武汉优城科技有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
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| US20020002218A1 (en) * | 2000-03-29 | 2002-01-03 | Ulf Velten | Polymers for cement dispersing admixtures |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103930454A (en) * | 2011-11-11 | 2014-07-16 | 罗门哈斯公司 | Small particle size hypophosphite telomers of unsaturated carboxylic acids |
| CN103930454B (en) * | 2011-11-11 | 2017-05-24 | 罗门哈斯公司 | Small particle size hypophosphite telomers of unsaturated carboxylic acids |
| CN104003644A (en) * | 2013-06-21 | 2014-08-27 | 温州威力助剂有限公司 | Production process of polycarboxylic acid water-reducing agent |
| CN104231183A (en) * | 2014-09-23 | 2014-12-24 | 江苏奥莱特新材料有限公司 | Preparation method for polycarboxylate-type water reducer |
| CN104311752B (en) * | 2014-10-10 | 2017-09-22 | 科之杰新材料集团有限公司 | A kind of polycarboxylate water-reducer and preparation method thereof |
| CN105418857A (en) * | 2015-12-31 | 2016-03-23 | 江苏苏博特新材料股份有限公司 | Preparation method and application of polycarboxylate water reducer containing phosphate group |
| CN105418857B (en) * | 2015-12-31 | 2017-10-10 | 江苏苏博特新材料股份有限公司 | The preparation method and application of the polycarboxylate water-reducer of phosphoric acid ester group |
| CN107151294A (en) * | 2017-06-08 | 2017-09-12 | 中建材中岩科技有限公司 | Early-strength polycarboxylate superplasticizer and its preparation method and application |
| CN107151294B (en) * | 2017-06-08 | 2020-03-24 | 中建材中岩科技有限公司 | Early-strength polycarboxylate superplasticizer and preparation method and application thereof |
| CN108912279A (en) * | 2018-08-13 | 2018-11-30 | 山东轻工职业学院 | High-adaptability highly branched chain amide imine poly carboxylic acid series water reducer and preparation method thereof |
| CN109535342A (en) * | 2018-11-23 | 2019-03-29 | 上海东大化学有限公司 | A kind of amides poly carboxylic acid series water reducer and its preparation and application |
| CN109503774A (en) * | 2018-11-28 | 2019-03-22 | 南京友西科技股份有限公司 | A kind of polycarboxylate water-reducer that temperature sensitivity is small |
| CN109503774B (en) * | 2018-11-28 | 2019-08-27 | 南京友西科技股份有限公司 | A kind of polycarboxylate water-reducer that temperature sensitivity is small |
| CN113354782A (en) * | 2020-04-27 | 2021-09-07 | 武汉优城科技有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN113354782B (en) * | 2020-04-27 | 2022-08-02 | 武汉优城科技有限公司 | Shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
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Application publication date: 20120704 |