CN104058751B - A kind of Ceramic manufacturing polyalcohol water reducing agent and synthetic method thereof - Google Patents
A kind of Ceramic manufacturing polyalcohol water reducing agent and synthetic method thereof Download PDFInfo
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- CN104058751B CN104058751B CN201410316056.8A CN201410316056A CN104058751B CN 104058751 B CN104058751 B CN 104058751B CN 201410316056 A CN201410316056 A CN 201410316056A CN 104058751 B CN104058751 B CN 104058751B
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Abstract
The present invention relates to a kind of Ceramic manufacturing polyalcohol water reducing agent and synthetic method thereof, it is characterized in that, first macromole unsaturated monomer and unsaturated acid copolymerization under radical initiator effect of long polyether chains will be contained, form the intermediate state polymkeric substance with certain molecular structure, then another part unsaturated acid and radical initiator is added, proceed polyreaction, be finally neutralized to neutrality, polyalcohol water reducing agent of the present invention can be obtained.This polyalcohol water reducing agent water-reducing rate is high, dispersion and plasticizing capacity strong, can be applicable to the technological processs such as the powder process of ceramic industry, injection forming, and coating, the dispersion of pigment and filler in ink.
Description
Technical field
The invention belongs to Ceramic manufacturing auxiliary agent field, be specifically related to a kind of Ceramic manufacturing polyalcohol water reducing agent and synthetic method thereof.
Background technology
Pottery is a resource industry, and China will consume the non-renewable mineral wealth such as a large amount of clays, gypsum every year, causes many tonerde storages significantly to reduce, some areas approach exhaustion.And pottery is also the industry that a high energy gamma source consumes, energy consumption accounts for 1/3rd of Production of Ceramics cost, will consume a large amount of electric energy and combustion gas every year.Therefore, reducing energy consumption, improving resource utilization is ceramic industry problem demanding prompt solution.
Water reducer applies maximum additives as in Ceramic manufacturing process, can not only reduce costs, and can also improve ceramic product performance further.If do not add water reducer, free water easily enters in clay particle, makes the Distance Shortened between particle, needs to add that a lot of water just can make base, glaze has mobility.Form hydrophobic structure and double electrical layers at surface of clay after adding water reducer, intergranular like this repulsive force increase, free water increase, thus improve the mobility of slip.Under the condition of equal amount of water, the mobility adding the slip of water reducer improves, and can improve the uniformity coefficient of particle, prevent sedimentation, and can shorten setting time, improves intensity, thus makes Production of Ceramics person obtain higher economic value added and social benefit.
Along with developing rapidly of ceramic industry, traditional ceramic additive oneself can not adaption demand.Countries in the world are all at active research and the new and effective ceramic water reducing agent of application.Polyalcohol water reducing agent adds in ceramic size, not only can significantly improve slip mobility and stability, can also reduce water ratio, and then reduces the production cost of pottery manufacture.Along with the development of ceramics, the production of high quality pottery more and more be unable to do without polyalcohol water reducing agent.Compared with developed countries, the overall study level of China's ceramic water reducing agent is not high, and existing polycarboxylate sodium and organic sulfonate all can not meet the needs in market.
For overcoming the above problems, the invention provides a kind of Ceramic manufacturing polyalcohol water reducing agent and synthetic method thereof.
Summary of the invention
The object of the invention is to provide a kind of high performance Ceramic manufacturing polyalcohol water reducing agent and synthetic method thereof.
To achieve these goals, technical solution of the present invention is, the polyalcohol water reducing agent prepared by radical polymerization, and its chemical structural formula is expressed as:
A is: Na, or K, or NH
4;
K, L, M, N are for repeating link units number: 20≤K≤60,2≤L≤10,5≤M≤20,30≤N≤300.
Above-mentioned polyalcohol water reducing agent and synthetic method thereof, it comprises the following steps:
1) radical polymerization, point low temperature causes technique and high temperature causes technique two kinds.
(1) low temperature causes technique, add the macromole unsaturated monomer containing long polyether chains and appropriate amount of deionized water in a kettle., be warming up to 30 ~ 50 DEG C of stirring and dissolving, add superoxol 1, slowly drip unsaturated carboxylic acid 1, xitix 1 and the chain-transfer agent aqueous solution simultaneously, control to drip unsaturated carboxylic acid in about 3 hours, within 3.5 hours, add xitix 1 aqueous solution, continue reaction 1 hour, obtain a kind of intermediate state polymkeric substance.Again in reactor, add superoxol 2, slowly drip unsaturated carboxylic acid 2 and xitix 2 aqueous solution simultaneously, control to drip unsaturated carboxylic acid in about 2 hours and add xitix 2 aqueous solution in 2,2.5 hours, continue to react 1-2 hour to obtain copolymerization product.
Its reaction raw materials proportioning is:
Be 1:3 ~ 1:6 containing the macromole unsaturated monomer of long polyether chains and the mol ratio of unsaturated acid 1;
Hydrogen peroxide 1 is 0.1 ~ 1.0% of the macromole unsaturated monomer quality containing long polyether chains;
Xitix 1 is 0.1 ~ 0.5% of the macromole unsaturated monomer quality containing long polyether chains;
Chain-transfer agent 1 is 0.2 ~ 1.0% of the macromole unsaturated monomer quality containing long polyether chains;
Be 1:15 ~ 1:60 containing the macromole unsaturated monomer of long polyether chains and the mol ratio of unsaturated acid 2;
Hydrogen peroxide 2 is 0.3 ~ 3.0% of the macromole unsaturated monomer quality containing long polyether chains;
Xitix 2 is 0.3 ~ 2.0% of the macromole unsaturated monomer quality containing long polyether chains.
(2) high temperature causes technique, add containing the macromole unsaturated monomer of long polyether chains, chain-transfer agent and appropriate amount of deionized water in a kettle., be warming up to 70 ~ 90 DEG C of stirring and dissolving, slowly drip unsaturated carboxylic acid 1 and ammonium persulphate 1 aqueous solution respectively, control to drip unsaturated carboxylic acid in about 3 hours, within 3.5 hours, add ammonium persulphate 1 aqueous solution, continue reaction 1 hour, obtain a kind of intermediate state polymkeric substance.Again in reactor, slowly drip unsaturated carboxylic acid 2 and ammonium persulphate 2 aqueous solution respectively, control to drip unsaturated carboxylic acid in about 2 hours and add ammonium persulphate 2 aqueous solution in 2,2.5 hours, continue reaction and obtain copolymerization product in 1 hour.
Its reaction raw materials proportioning is:
Be 1:3 ~ 1:6 containing the macromole unsaturated monomer of long polyether chains and the mol ratio of unsaturated acid 1;
Ammonium persulphate 1 is 0.5 ~ 2.0% of the macromole unsaturated monomer quality containing long polyether chains;
Chain-transfer agent 1 is 0.2 ~ 1.0% of the macromole unsaturated monomer quality containing long polyether chains;
Be 1:15 ~ 1:60 containing the macromole unsaturated monomer of long polyether chains and the mol ratio of unsaturated acid 2;
Ammonium persulphate 2 is 1.0 ~ 3.0% of macromole unsaturated monomer quality.
2) neutralizing treatment
After being cooled by gained copolymerization product, slowly add basic solution, as ammoniacal liquor or sodium hydroxide or potassium hydroxide solution are neutralized to pH value about 7, obtain poly carboxylic acid fluidizer.
The described macromole unsaturated monomer containing long polyether chains is allyl alcohol polyethenoxy ether or propyl alcohol polyoxyethylene polyoxypropylene copolyether or isopentenol polyoxyethylene ether or prenol polyoxyethylene polyoxypropylene copolyether; ;
Described unsaturated carboxylic acid is acrylic or methacrylic acid;
Described chain-transfer agent is Virahol or Thiovanic acid or thiohydracrylic acid or lauryl mercaptan.
The invention has the advantages that:
Polyalcohol water reducing agent of the present invention has the advantages that water-reducing rate is high, plasticizing capacity is strong, adaptability is good, can be applicable to the technological processs such as the abrasive dust of ceramic industry, slurrying, idiosome be shaping, and coating, the dispersion of pigment and filler in ink.Powder dispersion can be promoted in ceramic abrasive dust, improve abrasive dust efficiency, conserve energy; The mobility that greatly can reduce water consumption in ceramic powder slurrying, promote the dispersion of powder, improve slurry, can save the energy needed for slurry drying simultaneously greatly; Water consumption, the intensity improving idiosome and ratio of briquetting can be reduced when idiosome is shaping, increase the density of pottery; The dispersion of pigment and filler can be promoted and prevent coagulation in coating, ink.
Embodiment
Illustrate content of the present invention further in conjunction with example, but the present invention is not only confined to following instance.
Example 1:
By molecular weight be 2000 allyl alcohol polyethenoxy ether 145kg, water 120kg add reactor, be heated to 30 DEG C and stir, after allyl alcohol polyethenoxy ether is dissolved completely, adding hydrogen peroxide (mass concentration 35%) 1.2kg.
Vinylformic acid 18kg and deionized water 20kg is added in No. 1 header tank, xitix 0.2kg, Virahol 1.0kg and deionized water 38kg is added in No. 2 header tanks, then solution in two header tanks is slowly added reactor simultaneously, control that liquid in No. 1 header tank adds for about 3 hours, liquid adds for about 3.5 hours in No. 2 header tanks.In No. 3 header tanks, add vinylformic acid 80kg, add xitix 0.5kg and deionized water 80kg to No. 4 header tanks.After liquid adds in No. 2 header tanks, continue constant temperature stirring reaction 1.0 hours, obtain a kind of intermediate state polymkeric substance.Then in reactor, add 1.5kg hydrogen peroxide (mass concentration 35%), open No. 3 and No. 4 header tank valves, slowly in reactor, add vinylformic acid and aqueous ascorbic acid, control that liquid in No. 3 header tanks adds for about 2 hours, liquid about 2.5 hours in No. 4 header tanks, add rear continuation isothermal reaction 2.0 hours, add ammonia neutralization after cooling and obtain 1# polyalcohol water reducing agent, its chemical structural formula is as follows:
1# poly carboxylic acid fluidizer is applied to alumina slurry preparation, the alumina slurry of addition 0.2%, water content 20%, measuring viscosity with rotational viscosimeter normal temperature is 200cP, is determined as 30s with coating-4 viscosity meter, flowing property is good, and static 24 hours of slurry is without demixing phenomenon.
Example 2:
By molecular weight be 2400 allyl alcohol polyethenoxy polyoxypropylene copolymeric ether 150kg, water 120kg add reactor, be heated to 30 DEG C and stir, after allyl alcohol polyethenoxy ether is dissolved completely, adding hydrogen peroxide (mass concentration 35%) 1.0kg.
Vinylformic acid 15kg and deionized water 20kg is added in No. 1 header tank, xitix 0.2kg, Virahol 1.0kg and deionized water 38kg is added in No. 2 header tanks, then solution in two header tanks is slowly added reactor simultaneously, control that liquid in No. 1 header tank adds for about 3 hours, liquid adds for about 3.5 hours in No. 2 header tanks.In No. 3 header tanks, add vinylformic acid 100kg, add xitix 0.4kg and deionized water 100kg to No. 4 header tanks.After liquid adds in No. 2 header tanks, continue constant temperature stirring reaction 1.0 hours, obtain a kind of intermediate state polymkeric substance.Then in reactor, add 1.2kg hydrogen peroxide (mass concentration 35%), open No. 3 and No. 4 header tank valves, slowly in reactor, add vinylformic acid and aqueous ascorbic acid, control that liquid in No. 3 header tanks adds for about 2 hours, liquid about 2.5 hours in No. 4 header tanks, add rear continuation isothermal reaction 2.0 hours, add ammonia neutralization after cooling and obtain 2# polyalcohol water reducing agent, its chemical structural formula is as follows:
2# poly carboxylic acid fluidizer is applied to alumina slurry preparation, the alumina slurry of addition 0.3%, water content 20%, measuring viscosity with rotational viscosimeter normal temperature is 160cP, is determined as 26s with coating-4 viscosity meter, flowing property is good, and static 24 hours of slurry is without demixing phenomenon.
Example 3:
By molecular weight be 2400 prenol polyoxyethylene polyoxypropylene copolyether 180kg, water 120kg add reactor, be heated to 30 DEG C and stir, after allyl alcohol polyethenoxy ether is dissolved completely, adding hydrogen peroxide (mass concentration 35%) 1.2kg.
Vinylformic acid 20kg and deionized water 20kg is added in No. 1 header tank, xitix 0.2kg, Thiovanic acid 0.5kg and deionized water 38kg is added in No. 2 header tanks, then solution in two header tanks is slowly added reactor simultaneously, control that liquid in No. 1 header tank adds for about 3 hours, liquid adds for about 3.5 hours in No. 2 header tanks.In No. 3 header tanks, add vinylformic acid 100kg, add xitix 0.5kg and deionized water 100kg to No. 4 header tanks.After liquid adds in No. 2 header tanks, continue constant temperature stirring reaction 1.0 hours, obtain a kind of intermediate state polymkeric substance.Then in reactor, add 1.5kg hydrogen peroxide (mass concentration 35%), open No. 3 and No. 4 header tank valves, slowly in reactor, add vinylformic acid and aqueous ascorbic acid, control that liquid in No. 3 header tanks adds for about 2 hours, liquid about 2.5 hours in No. 4 header tanks, add rear continuation isothermal reaction 2.0 hours, the neutralization of cooling back end hydrogenation sodium hydroxide solution obtains 3# polyalcohol water reducing agent, and its chemical structural formula is as follows:
3# poly carboxylic acid fluidizer is applied to alumina slurry preparation, the alumina slurry of addition 0.3%, water content 20%, measuring viscosity with rotational viscosimeter normal temperature is 150cP, is determined as 25s with coating-4 viscosity meter, flowing property is good, and static 24 hours of slurry is without demixing phenomenon.
Example 4:
By molecular weight be 2400 allyl alcohol polyethenoxy polyoxypropylene copolymeric ether 120kg, water 120kg, Virahol 1.5kg add reactor, be heated to 80 DEG C and stir, making allyl alcohol polyethenoxy ether completely molten.
Vinylformic acid 15kg and deionized water 20kg is added in No. 1 header tank, ammonium persulphate 3.0kg and deionized water 38kg is added in No. 2 header tanks, then solution in two header tanks is slowly added reactor simultaneously, control that liquid in No. 1 header tank adds for about 3 hours, liquid adds for about 3.5 hours in No. 2 header tanks.In No. 3 header tanks, add vinylformic acid 80kg, add ammonium persulphate 2.0kg and deionized water 100kg to No. 4 header tanks.After liquid adds in No. 2 header tanks, continue constant temperature stirring reaction 1.0 hours, obtain a kind of intermediate state polymkeric substance.Open No. 3 and No. 4 header tank valves, slowly in reactor, add vinylformic acid and ammonium persulfate aqueous solution, control that liquid in No. 3 header tanks adds for about 2 hours, liquid about 2.5 hours in No. 4 header tanks, add rear continuation isothermal reaction 1.0 hours, add ammonia neutralization after cooling and obtain 4# polyalcohol water reducing agent, its chemical structural formula is as follows:
4# poly carboxylic acid fluidizer is applied to alumina slurry preparation, the alumina slurry of addition 0.3%, water content 20%, measuring viscosity with rotational viscosimeter normal temperature is 220cP, is determined as 38s with coating-4 viscosity meter, flowing property is good, and static 24 hours of slurry is without demixing phenomenon.
As known by the technical knowledge, the present invention can be realized by other the embodiment not departing from its spirit or essential feature.Therefore, above-mentioned disclosed embodiment, with regard to each side, all just illustrates, is not only.Within the scope of the present invention all or be all included in the invention being equal to the change in scope of the present invention.
Claims (8)
1. a Ceramic manufacturing polyalcohol water reducing agent, is characterized in that: its chemical structure of general formula is expressed as:
Wherein, X is:
, or
;
R is H; R
1, R
2, R
3, R
4for H or CH
3;
A is: Na, or K, or NH
4;
K, L, M, N are for repeating link units number: 20≤K≤60,2≤L≤10,5≤M≤20,30≤N≤300.
2. the synthetic method of Ceramic manufacturing polyalcohol water reducing agent as claimed in claim 1, is characterized in that, is that radical polymerization low temperature causes technique, comprises:
(1) the macromole unsaturated monomer containing long polyether chains and appropriate amount of deionized water is added in a kettle., be warming up to 30 ~ 50 DEG C of stirring and dissolving, first time adds superoxol, slowly drip unsaturated carboxylic acid, xitix and the chain-transfer agent aqueous solution respectively simultaneously, first time controls to drip unsaturated carboxylic acid in about 3 hours, within 3.5 hours, add aqueous ascorbic acid, continue reaction 1 hour, obtain a kind of intermediate state polymkeric substance;
Second time adds superoxol in reactor, slowly drip unsaturated carboxylic acid and aqueous ascorbic acid respectively simultaneously, control to drip unsaturated carboxylic acid in about 2 hours, within 2.5 hours, add aqueous ascorbic acid, add rear continuation isothermal reaction and obtain copolymerization product in 1-2 hour;
(2) neutralizing treatment step:
After described copolymerization product cooling, slowly add basic solution and be neutralized to pH value about 7, obtain polyalcohol water reducing agent.
3. the synthetic method of Ceramic manufacturing polyalcohol water reducing agent as claimed in claim 2, is characterized in that, the reaction raw materials proportioning that described low temperature causes in technique is respectively:
The hydrogen peroxide that first time adds is 0.1 ~ 1.0% of the described macromole unsaturated monomer quality containing long polyether chains;
The described macromole unsaturated monomer containing long polyether chains is 1:3 ~ 1:6 with the mol ratio of the unsaturated carboxylic acid added for the first time;
The xitix that first time adds is 0.1 ~ 0.5% of the described macromole unsaturated monomer quality containing long polyether chains;
The chain-transfer agent that first time adds is 0.2 ~ 1.0% of the described macromole unsaturated monomer quality containing long polyether chains;
The described macromole unsaturated monomer containing long polyether chains is 1:15 ~ 1:60 with the mol ratio of the unsaturated carboxylic acid added for the second time; The hydrogen peroxide that second time adds is 0.3 ~ 3.0% of the described macromole unsaturated monomer quality containing long polyether chains;
The xitix that second time adds is 0.3 ~ 2.0% of the described macromole unsaturated monomer quality containing long polyether chains.
4. the synthetic method of Ceramic manufacturing polyalcohol water reducing agent as claimed in claim 1, is characterized in that, is that radical polymerization high temperature causes technique, comprises:
(1) add in a kettle. containing the macromole unsaturated monomer of long polyether chains, chain-transfer agent and appropriate amount of deionized water, be warming up to 70 ~ 90 DEG C of stirring and dissolving, first time slowly drips unsaturated carboxylic acid and ammonium persulfate aqueous solution respectively; Control to drip unsaturated carboxylic acid in about 3 hours, within 3.5 hours, add ammonium persulfate aqueous solution; Continue reaction 1 hour, obtain a kind of intermediate state polymkeric substance;
In reactor, slowly drip unsaturated carboxylic acid and ammonium persulfate aqueous solution respectively for the second time, control to drip unsaturated carboxylic acid in about 2 hours, within 2.5 hours, add ammonium persulfate aqueous solution, continue reaction and obtain copolymerization product in 1 hour;
(2) neutralizing treatment step:
After described copolymerization product cooling, slowly add basic solution and be neutralized to pH value about 7, obtain polyalcohol water reducing agent.
5. the synthetic method of Ceramic manufacturing polyalcohol water reducing agent as claimed in claim 4, it is characterized in that, described reaction raw materials proportioning is:
The chain-transfer agent that first time adds is 0.2 ~ 1.0% of the described macromole unsaturated monomer quality containing long polyether chains;
The described macromole unsaturated monomer containing long polyether chains is 1:3 ~ 1:6 with the mol ratio of the unsaturated carboxylic acid added for the first time;
The ammonium persulphate that first time adds is 0.5 ~ 2.0% of the described macromole unsaturated monomer quality containing long polyether chains;
The described macromole unsaturated monomer containing long polyether chains is 1:15 ~ 1:60 with the mol ratio of the unsaturated carboxylic acid added for the second time;
The ammonium persulphate that second time adds is 1.0 ~ 3.0% of the described macromole unsaturated monomer quality containing long polyether chains.
6., as the synthetic method of Ceramic manufacturing polyalcohol water reducing agent as described in any one in claim 2-5, it is characterized in that:
The described macromole unsaturated monomer containing long polyether chains is allyl alcohol polyethenoxy ether or propyl alcohol polyoxyethylene polyoxypropylene copolyether or isopentenol polyoxyethylene ether or prenol polyoxyethylene polyoxypropylene copolyether;
Described unsaturated carboxylic acid is acrylic or methacrylic acid;
Described chain-transfer agent is Virahol or Thiovanic acid or thiohydracrylic acid or lauryl mercaptan.
7. the synthetic method of Ceramic manufacturing polyalcohol water reducing agent according to any one of claim 2-5, is characterized in that, the basic solution in described neutralizing treatment step is ammoniacal liquor or sodium hydroxide or potassium hydroxide solution.
8. the synthetic method of Ceramic manufacturing polyalcohol water reducing agent as claimed in claim 6, is characterized in that, the basic solution in described neutralizing treatment step is ammoniacal liquor or sodium hydroxide or potassium hydroxide solution.
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| CN104910315A (en) * | 2015-07-14 | 2015-09-16 | 唐山市龙亿科技开发有限公司 | Method for preparing polycarboxylate-type ceramic dispersant by use of normal temperature method |
| CN106496442B (en) * | 2016-10-27 | 2018-11-06 | 湖南大学 | A kind of high-efficiency water-reducing agent of poly-carboxylic acid and preparation method thereof |
| CN109503776A (en) * | 2018-12-03 | 2019-03-22 | 广东科隆智谷新材料股份有限公司 | A kind of preparation method of polyocarboxy acid type ceramic dispersants |
| CN112851373A (en) * | 2021-02-01 | 2021-05-28 | 湖北工业大学 | High-dispersity ceramic water reducing agent and preparation method thereof |
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| CN101538134A (en) * | 2009-04-14 | 2009-09-23 | 大连市建筑科学研究设计院股份有限公司 | Polyether class polycarboxylic acid high-efficiency water reducing agent and preparation method thereof |
| CN103159899A (en) * | 2012-12-21 | 2013-06-19 | 新疆德蓝股份有限公司 | Preparing method for polycarboxylate water reducing agent |
| CN103183788A (en) * | 2011-12-27 | 2013-07-03 | 山西黄腾化工有限公司 | Preparation method for polycarboxylic acid type concrete slump-retaining agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101538134A (en) * | 2009-04-14 | 2009-09-23 | 大连市建筑科学研究设计院股份有限公司 | Polyether class polycarboxylic acid high-efficiency water reducing agent and preparation method thereof |
| CN103183788A (en) * | 2011-12-27 | 2013-07-03 | 山西黄腾化工有限公司 | Preparation method for polycarboxylic acid type concrete slump-retaining agent |
| CN103159899A (en) * | 2012-12-21 | 2013-06-19 | 新疆德蓝股份有限公司 | Preparing method for polycarboxylate water reducing agent |
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