CN101619134A - Esterfying polycarboxylic acid type ceramic water-reducing agent and preparation method thereof - Google Patents
Esterfying polycarboxylic acid type ceramic water-reducing agent and preparation method thereof Download PDFInfo
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- CN101619134A CN101619134A CN200910041833A CN200910041833A CN101619134A CN 101619134 A CN101619134 A CN 101619134A CN 200910041833 A CN200910041833 A CN 200910041833A CN 200910041833 A CN200910041833 A CN 200910041833A CN 101619134 A CN101619134 A CN 101619134A
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Abstract
The invention relates to a ceramic water-reducing agent, in particular to an esterfying polycarboxylic acid type ceramic water-reducing agent and a preparation method thereof. The invention adopts the technical scheme as follows: carrying out polymerization reaction to obtain a high-polymer main chain, and introducing a certain proportion of functional group on the main chain through the esterification reaction to form a comb-pattern molecule structure so as to keep high water-reducing rate and not to cause obvious slow release, thereby an esterfying styrene maleic anhydride copolymer is obtained, the copolymer is prepared into solution by self or compounding with inorganic salts, and the solution can be used as the ceramic water-reducing agent. The method has easily-obtained materials, simple process, convenient operation as well as easy marketability and industrial production. The obtained water-reducing agent can obtain high polymer with the comb-pattern structure by esterfying styrene maleic anhydride. A polyether lateral chain has better hydrophilcity and can also play a steric exclusion role and remarkably improve the dispersing performance of the water-reducing agent to mud particles. The efficiency of the compounded water-reducing agent can be further improved.
Description
Technical field
The invention belongs to the preparation field of ceramic water reducing agent, be specifically related to a kind of esterfying polycarboxylic acid type ceramic water-reducing agent and preparation method thereof.
Background technology
Ceramic industry is a high energy consumption industry, and its energy more than 80% all is used to burn till and drying process.Therefore, the key technical problem that the sector faces be exactly in the control ceramic size add-on of water the least possible, and keep suitable flowability of mud and viscosity simultaneously.Ceramic water reducing agent is a kind of of ceramic additive, also claims liquefactent, dispersion agent, thinner or dispergator.Ceramic water reducing agent is the flowability that is used for improving glaze, makes it under the situation that moisture content reduces, and keeps the better manufacturability energy.Once, good water reducer can promote ceramic industry to develop to less energy-consumption, high quality, high benefit direction.
China's ceramic industry generally uses inorganic salts such as water glass, yellow soda ash, tripoly phosphate sodium STPP to be water reducer at present.Common ceramic water reducing agent is owing to be subjected to the influence of factors such as molecular structure, relative molecular mass, and its water-reducing effect is not good, and large usage quantity, has influenced size performance.Polymeric superplasticizer is because hydrophilic group, hydrophobic group position and adjustable size, and the molecular structure variation is therefore strong to disperse particles surface covered effect, and its dispersion system is easier to stablize, better mobile, but the inorganic relatively water reducer of cost wants high.The composite efficient water reducer more and more receives publicity, and its effect obviously is better than the water reducer of single component.
What polymer aspect research at present was more is polycarboxylic acids dehydragent.Poly carboxylic acid has very high dispersing property and good function of slump protection through suitable modification under low-dosage.Its preparation generally all is the synthetic earlier big monomer with polymerization activity, and the monomer with certain proportioning mixes direct employing solution polymerization and gets finished product then.The shortcoming of this mode is that difficulty is big, separate complex, and product stability is poor, is difficult for the marketization, and industrial cost's height.Therefore, seek a kind of suitable manner synthesis modification polyocarboxy acid type water reducer and compositely with inorganic salt be and reduce cost the effective way of increasing the benefit.
Summary of the invention
At the defective and the deficiency of prior art, purpose of the present invention at first provides a kind of preparation method of esterfying polycarboxylic acid type ceramic water-reducing agent.This method is raw materials used to be easy to get, and technology is simple, and is easy to operate, is easy to the marketization and industrial production.
The present invention also aims to provide a kind of ceramic water reducing agent of aforesaid method acquisition.
A further object of the present invention is that above-mentioned ceramic water reducing agent and inorganic salt is compound, and a kind of compound ceramic water reducing agent is provided, and its effect obviously is better than the water reducer of single component.
For achieving the above object, the present invention at first obtains high polymer main chain by polyreaction, introduces a certain proportion of functional group again on main chain, makes it have comb type molecular structure, to keep the water-reducing rate height and not cause obvious slowly-releasing.Rescreen and select inorganic salt, and carry out composite.Acquisition water-reducing effect the best, the scheme that cost is minimum.
The technical scheme that the present invention specifically provides is as follows:
A kind of preparation method of esterfying polycarboxylic acid type ceramic water-reducing agent may further comprise the steps:
(1) preparation maleic anhydride solution, heating slowly drip the vinylbenzene that contains chain-transfer agent and initiator simultaneously, dripped at 1～2 hour, 60～100 ℃ of isothermal reactions 3～5 hours, the cooling suction filtration, dry Zelan 338;
(2) esterification: relative molecular mass is mixed with Zelan 338 at 100～1500 polyoxyethylene glycol or polyalkylene glycol monoalkyl ether, contained maleic anhydride mol ratio is (1～4) in polyoxyethylene glycol or polyalkylene glycol monoalkyl ether and the Zelan 338: 1, reacted 2～7 hours down at 100～150 ℃, obtain the esterification co-poly carboxylic acid;
(3) step (2) gained multipolymer is made into the aqueous solution, and transferring pH is that 7-8 is esterfying polycarboxylic acid type ceramic water-reducing agent.
In the step (1), gained Zelan 338 relative molecular mass is preferably 2000～20000, and its maleic anhydride molar content is preferably 10%～50%.
In the step (1), the mass concentration of maleic anhydride solution is preferably 2-20%, and solvent can be selected toluene or ethylene dichloride for use;
Maleic anhydride and cinnamic mol ratio preferably are controlled at 1: (0.5-5); More preferably 1: (1-3);
The add-on of initiator is preferably the 0.1-5% of reactant system quality, and more preferably 0.5, initiator can be selected benzoyl peroxide or dibenzoyl peroxide;
The add-on of chain-transfer agent is preferably the 0.1-5% of reactant system quality, more preferably 0.5%-1%, and chain-transfer agent can be Thiovanic acid, lauryl mercaptan or mercaptoethanol.
In the step (2), the alkyl in the described polyalkylene glycol monoalkyl ether is 1～4 carbon; Be reflected at N, carry out under the solvent existence condition of dinethylformamide.
The esterfying polycarboxylic acid type ceramic water-reducing agent that the present invention also provides method for preparing to obtain.
For further improving the performance of above-mentioned esterfying polycarboxylic acid type ceramic water-reducing agent, the invention provides a kind of esterification polyocarboxy acid type composite ceramic water reducing agent, with described esterfying polycarboxylic acid type ceramic water-reducing agent and inorganic salt are composite obtains, being used for composite inorganic salt can be any one or two kinds of above mixtures of carbonate, silicate and phosphoric acid salt.Composite ratio generally is that the mass ratio of esterification co-poly carboxylic acid and inorganic salt is 1: 5-5: 1, more preferably 1: 3-3: 1.
Above-mentioned esterfying polycarboxylic acid type ceramic water-reducing agent or composite ceramic water reducing agent mass concentration in use is generally 20%-60%.
Compared with prior art, the present invention has following advantage:
(1) the method raw material is easy to get, and technology is simple, and is easy to operate, is easy to the marketization and industrial production.
(2) styrene-maleic anhydride is carried out the polymer that esterification can obtain pectination.Polyether lateral chain wetting ability preferably can also play the steric exclusion effect, can obviously improve the dispersing property of water reducer to mud particles.
What (3) the present invention prepared can better bring into play water-reducing effect with inorganic salt are composite, is used for ceramic industry and has saved energy consumption, has reduced cost and has improved quality product.
Embodiment
Below in conjunction with embodiment, the present invention is done detailed description further, but implementation of the present invention is not limited thereto.
Embodiment 1:
Take by weighing the 96g maleic anhydride and add 800mL 1, in the 2-ethylene dichloride, be heated to 75 ℃ of dissolvings, add vinylbenzene 110g, benzoyl peroxide 5g, mercaptoethanol 2g is mixed in the separating funnel, splashes into there-necked flask.Drip off the back 80 ℃ of reactions 2 hours, elevated temperature to 95 ℃ reacted 2 hours again.After the cooling, add sherwood oil, suction filtration, dry Zelan 338, maleic anhydride content is a molar fraction 38%.
Poly glycol monomethyl ether is proportionally mixed in Zelan 338, and making the maleic anhydride mol ratio of poly glycol monomethyl ether in Zelan 338 is 1.5: 1, reacts 8 hours down at 120 ℃, obtains the esterification co-poly carboxylic acid.
Above-mentioned multipolymer is made into 30% aqueous solution, and regulating pH with sodium hydroxide is 7.5, separates and removes precipitation, obtains the light brown transparent liquid, i.e. the esterification modification polycarboxylic acid type ceramic water-reducing agent.
The use of ceramic water reducing agent according to a conventional method.The esterfying polycarboxylic acid type ceramic water-reducing agent addition is 0.3wt%, and the water slurry mass ratio is that 0.3: 1 o'clock water-reducing rate reaches 37%.2h starches flow velocity only can reach 20.7 seconds, does not produce the glaze phenomenon that contracts.
Embodiment 2:
Remodeling co-poly carboxylic acid and yellow soda ash that embodiment 1 obtains are composite according to 1: 1 quality, obtain the composite ceramic water reducer.
The use of ceramic water reducing agent according to a conventional method.The addition of composite ceramic water reducing agent is 0.3wt%, and the water slurry mass ratio is 0.3: 1 o'clock, and water-reducing rate reaches 42%.2h starches flow velocity only can reach 18.9 seconds, does not produce the glaze phenomenon that contracts.
Embodiment 3:
Remodeling co-poly carboxylic acid that embodiment 1 obtains and water glass (Na
2SiO
39H
2O), yellow soda ash is composite according to 1: 1.5: 1.5 quality, obtains the composite ceramic water reducer.
The use of ceramic water reducing agent according to a conventional method.Composite ceramic water reducer, addition are 0.3wt%, and the water slurry mass ratio is 0.3: 1 o'clock, and water-reducing rate reaches 46%.2h starches flow velocity only can reach 17.2 seconds, does not produce the glaze phenomenon that contracts.
Embodiment 4:
This routine functional quality concentration is the toluene solution of 2% maleic anhydride, and maleic anhydride and cinnamic mol ratio are 1: 0.5, the ratio of other raw material such as embodiment 1.
Reaction conditions aspect, the condition of the first step polyreaction be 60 ℃ 4 hours, be increased to 100 ℃ of reactions 2 hours, second step, 110 ℃ of reactions 10 hours, all the other were same with embodiment 1 during esterification.
The Zelan 338 that obtains, maleic anhydride content are molar fraction 40%.
Obtain the esterification co-poly carboxylic acid.Be made into 40% aqueous solution, regulating pH with sodium hydroxide is 7.5, separates and removes precipitation, obtains the light brown transparent liquid, i.e. the esterification modification polycarboxylic acid type ceramic water-reducing agent.
The use of ceramic water reducing agent according to a conventional method.The ceramic water reducing agent addition is 0.3wt%, and the water slurry mass ratio is 0.3: 1 o'clock, and water-reducing rate reaches 40%.2h starches flow velocity only can reach 18.5 seconds, does not produce the glaze phenomenon that contracts.
Embodiment 5
This routine functional quality concentration is the toluene solution of 20% maleic anhydride, and maleic anhydride and cinnamic mol ratio are 1: 5, the ratio of other raw material such as embodiment 1.
Reaction conditions aspect, the condition of the first step polyreaction be 80 ℃ 2 hours, be increased to 95 ℃ of reactions 2 hours, second step, 100 ℃ of reactions 10 hours, all the other were same with embodiment 1 during esterification.
The Zelan 338 that obtains, maleic anhydride content are molar fraction 39%.
Obtain the esterification co-poly carboxylic acid.Be made into 50% aqueous solution, regulating pH with sodium hydroxide is 8, separates and removes precipitation, obtains the light brown transparent liquid, i.e. the esterification modification polycarboxylic acid type ceramic water-reducing agent.
The use of ceramic water reducing agent according to a conventional method.The ceramic water reducing agent addition is 0.3wt%, and the water slurry mass ratio is 0.3: 1 o'clock, and water-reducing rate reaches 35%.2h starches flow velocity only can reach 19.8 seconds, does not produce the glaze phenomenon that contracts.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1, a kind of preparation method of esterfying polycarboxylic acid type ceramic water-reducing agent may further comprise the steps:
(1) preparation maleic anhydride solution, heating slowly drip the vinylbenzene that contains chain-transfer agent and initiator simultaneously, dripped at 1～2 hour, 60～100 ℃ of isothermal reactions 3～5 hours, the cooling suction filtration, dry Zelan 338;
(2) esterification: relative molecular mass is mixed with Zelan 338 at 100～1500 polyoxyethylene glycol or polyalkylene glycol monoalkyl ether, contained maleic anhydride mol ratio is (1～4) in polyoxyethylene glycol or polyalkylene glycol monoalkyl ether and the Zelan 338: 1, reacted 2～10 hours down at 100～150 ℃, obtain the esterification co-poly carboxylic acid;
(3) step (2) gained multipolymer is made into the aqueous solution, and accent pH is 7-8, is esterfying polycarboxylic acid type ceramic water-reducing agent.
2, the preparation method of esterfying polycarboxylic acid type ceramic water-reducing agent according to claim 1, it is characterized in that: in the step (1), described Zelan 338 relative molecular mass is 2000～20000, and its maleic anhydride molar content is 10%～50%.
3, the preparation method of esterfying polycarboxylic acid type ceramic water-reducing agent according to claim 1 is characterized in that: in the step (1), the mass concentration of described maleic anhydride solution is 2-20%.
4, the preparation method of esterfying polycarboxylic acid type ceramic water-reducing agent according to claim 1 is characterized in that: in the step (1), the solvent of described maleic anhydride solution is toluene or ethylene dichloride.
5, the preparation method of esterfying polycarboxylic acid type ceramic water-reducing agent according to claim 1 is characterized in that: in the step (1), described maleic anhydride and cinnamic mol ratio are 1: (0.5-5).
6, the preparation method of esterfying polycarboxylic acid type ceramic water-reducing agent according to claim 1, it is characterized in that: in the step (1), described initiator is benzoyl peroxide or dibenzoyl peroxide, and the add-on of described initiator is the 0.1-5% of reactant system quality; Described chain-transfer agent is Thiovanic acid, lauryl mercaptan or mercaptoethanol, and the add-on of described chain-transfer agent is the 0.1-5% of reactant system quality.
7, the preparation method of esterfying polycarboxylic acid type ceramic water-reducing agent according to claim 1 is characterized in that: in the step (2), the alkyl in the described polyalkylene glycol monoalkyl ether is C
1-4Alkyl; Described reaction is at N, and dinethylformamide carries out under existing.
8, a kind of esterfying polycarboxylic acid type ceramic water-reducing agent is characterized in that: prepared by each described method among the claim 1-7.
9, a kind of esterification polyocarboxy acid type composite ceramic water reducing agent, it is characterized in that: be that the composite back of the esterification co-poly carboxylic acid that will prepare in each described method among the claim 1-7 and inorganic salt is water-soluble, accent pH is 7-8, promptly obtains esterification polyocarboxy acid type composite ceramic water reducing agent.
10, according to the described esterification polyocarboxy acid type of claim 9 composite ceramic water reducing agent, it is characterized in that: the composite mass ratio of described esterification co-poly carboxylic acid and inorganic salt is 1: 5-5: 1; Described inorganic salt are any one or two kinds of above mixtures in carbonate, silicate and the phosphoric acid salt.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584093A (en) * | 2012-02-28 | 2012-07-18 | 昆明理工大学 | Main chain carboxy-density-adjustable high-efficiency polycarboxylic acid water reducing agent |
| CN104861101A (en) * | 2015-05-18 | 2015-08-26 | 真彩文具股份有限公司 | Water-soluble dispersing agent for gel ink and preparation method of water-soluble dispersing agent |
| CN108299650A (en) * | 2017-12-26 | 2018-07-20 | 苏州弗克技术股份有限公司 | A kind of grouting agent polycarboxylate water-reducer and preparation method thereof |
| CN115321873A (en) * | 2022-08-11 | 2022-11-11 | 广州奕邦汇科技有限公司 | Inorganic modified polycarboxylate ceramic water reducer and preparation method thereof |
| CN116789456A (en) * | 2023-07-10 | 2023-09-22 | 佛山市奥林万达新型建材有限公司 | Ceramic dispergator and preparation method thereof |
-
2009
- 2009-08-12 CN CN200910041833A patent/CN101619134A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584093A (en) * | 2012-02-28 | 2012-07-18 | 昆明理工大学 | Main chain carboxy-density-adjustable high-efficiency polycarboxylic acid water reducing agent |
| CN104861101A (en) * | 2015-05-18 | 2015-08-26 | 真彩文具股份有限公司 | Water-soluble dispersing agent for gel ink and preparation method of water-soluble dispersing agent |
| CN104861101B (en) * | 2015-05-18 | 2017-10-27 | 真彩文具股份有限公司 | Neutral writing ink water soluble dispersing agent and preparation method thereof |
| CN108299650A (en) * | 2017-12-26 | 2018-07-20 | 苏州弗克技术股份有限公司 | A kind of grouting agent polycarboxylate water-reducer and preparation method thereof |
| CN115321873A (en) * | 2022-08-11 | 2022-11-11 | 广州奕邦汇科技有限公司 | Inorganic modified polycarboxylate ceramic water reducer and preparation method thereof |
| CN116789456A (en) * | 2023-07-10 | 2023-09-22 | 佛山市奥林万达新型建材有限公司 | Ceramic dispergator and preparation method thereof |
| CN116789456B (en) * | 2023-07-10 | 2024-04-19 | 佛山市奥林万达新型建材有限公司 | Ceramic dispergator and preparation method thereof |
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Open date: 20100106 |