CN104211409B - A kind of cyclodextrin graft copolymer type ceramic water reducing agent and preparation method thereof - Google Patents
A kind of cyclodextrin graft copolymer type ceramic water reducing agent and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to ceramic water reducing agent preparing technical field, disclose a kind of cyclodextrin graft copolymer type ceramic water reducing agent and preparation method thereof.Described water reducer is made up of cyclodextrin or cyclodextrin derivative, 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt, chain-transfer agent, initiator, chain terminator and deionized water.Due to the molecular structure that cyclodextrin is special, the water reducer prepared by the present invention has extraordinary diminishing and dispersion effect; Simultaneously described water reducer is amphoteric ion type polyelectrolyte, and its chemical and Heat stability is good, hydratability are by force and be not subject to solution ph impact; In addition, the water reducer prepared by the present invention also has the effect of enhancing to pottery.
Description
Technical field
The invention belongs to ceramic water reducing agent preparing technical field, be specifically related to a kind of cyclodextrin graft copolymer type ceramic water reducing agent and preparation method thereof.
Background technology
Ceramic additive is for meeting the common name of the auxiliary agent that processing requirement and performance need add in Ceramic production.Ceramic additive consumption aborning little (usually 0.5% ~ 2%), but effect is very large.The application of ceramic additive and the exploitation of various new additive agent has been become to an integral part of Development of Ceramic Industry.Ceramic additive can be divided into water reducer, softening agent, tamanori, wetting agent, defrother, sanitas, anti-sludging agent, mineralizer, other additives according to the function of ceramic additive.
Ceramic water reducing agent is as a kind of Application comparison ceramic additive widely, and major function is the electro kinetic potential of raising system thus improves the mobility of slurry, makes it when moisture content reduces, can keep again suitable mobility and suitable viscosity; Reduce the water content of green compact simultaneously, reducing the dry energy consumption with sintering of pottery, reducing production cost.Therefore, use excellent ceramic water reducing agent, can promote that Production of Ceramics is to the future development of high benefit, high quality, less energy-consumption.
According to the difference of the composition of ceramic water reducing agent, ceramic water reducing agent conventional in existing production can be divided into inorganic salt water reducer, organic molecule water reducer and polymeric superplasticizer.
Inorganic water reducer is generally the inorganic salt containing sodium ion, as water glass, tripoly phosphate sodium STPP, Sodium hexametaphosphate 99, sodium carbonate etc.Inorganic water reducer can ionize in water, plays a part to regulate electric charge.There is the shortcomings such as the mud stability difference that addition content is large, dispersion efficiency is low and obtained in inorganic ceramic water reducer.At present, the flourishing enterprise of external Production of Ceramics does not use the inorganic salt water reducer of one-component substantially.
Organic molecule water reducer, mainly low molecule organic electrolyte class water reducer and tensio-active agent water reducer, as Sodium salts humic acids, Trisodium Citrate, sodium ethylene diamine tetracetate (EDTA).The dispersion effect of this type of water reducer is better than inorganic water reducer, but price is relatively high, stability is not very good, and can to environment.
Polymeric superplasticizer is mainly water-soluble polymer, comprises complex polyelectrolyte particle and non-ionic type polymer.Polymer ceramic water reducer due to the position of hydrophobic group, hydrophilic group, size and quantity adjustable, molecular structure can be pectination, higly branched chain etc., and therefore polymer ceramic water reducer is to disperse particles surface coverage and encapsulating effect wants better, dispersion system is more stable, dispersion system adaptability is more extensive.Therefore, polymer ceramic water reducer will become the development trend of ceramic water reducing agent, and its synthesis and application also will become the focus of this area research gradually.Such as Davies etc. using molecular weight be the ammonium polyacrylate of 3500 as the water reducer of aluminum oxide, the viscosity drop of the alumina slurry of 83wt% can be made when suitable addition to 400mPas
-1left and right, viscosity reducing effect affects larger by concentration.The RAFT polymerization synthesis AMPS-MPEG multipolymer water reducer such as Bouhamed, and itself and random water reducer are contrasted, found that the absorption of segmented copolymer is also relevant with the length of block, the Zeta potential value simultaneously adding the slip of segmented copolymer is more negative, more easily reaches the state of balance and stability; The dispersion efficiency of block copolymer system is higher, and the impact simultaneously by medium ionic strength is also larger.But because industrial production cost is higher, polycarboxylic acid series polymer ceramic water reducer is mainly in conceptual phase.
Summary of the invention
For overcoming the shortcoming and defect of prior art, primary and foremost purpose of the present invention is to provide a kind of cyclodextrin graft copolymer type ceramic water reducing agent.
Another object of the present invention is to the preparation method that above-mentioned cyclodextrin graft copolymer type ceramic water reducing agent is provided.
Object of the present invention is achieved through the following technical solutions:
A kind of cyclodextrin graft copolymer type ceramic water reducing agent, is made up of cyclodextrin polymkeric substance, 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt (DMAPS), chain-transfer agent, initiator, chain terminator and deionized water; Described cyclodextrin polymkeric substance is cyclodextrin (CD) or cyclodextrin derivative.
Described cyclodextrin comprise in beta-cyclodextrin or alpha-cylodextrin more than one; Described cyclodextrin derivative be in hydroxypropyl cyclodextrin, quadrol-beta-cyclodextrin or glycidyl methacrylate-quadrol modified cyclodextrin (GMA-EDA-CD) more than one.
The mass ratio of described cyclodextrin polymkeric substance and 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt (DMAPS) is (0.2 ~ 2.0): 1.
Described chain-transfer agent is inorganic salts; Be preferably in inferior sodium phosphate or ortho phosphorous acid potassium more than one.
The quality of described chain-transfer agent is 2% ~ 5% of cyclodextrin polymkeric substance and 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt (DMAPS) total mass.
Described initiator is persulphate, is preferably ammonium persulphate.
The quality of described initiator is 0.5% ~ 3% of cyclodextrin polymkeric substance and 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt (DMAPS) total mass.
Described chain terminator is more than one in inferior sodium phosphate and ortho phosphorous acid potassium.
The quality of described chain terminator is 1% ~ 3% of cyclodextrin polymkeric substance and 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt (DMAPS) total mass.
The quality of described deionized water is 1.3 ~ 2.7 times of cyclodextrin polymkeric substance and 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt (DMAPS) total mass.
The preparation method of described cyclodextrin graft copolymer type ceramic water reducing agent, comprises the following steps:
(1) by cyclodextrin polymkeric substance, 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt (DMAPS), chain-transfer agent solution and portions of de-ionized water, stir lower mixing, obtain mixed solution I;
(2) under 70 ~ 90 DEG C of conditions, initiator solution is added drop-wise in mixed solution I, reacts 2 ~ 4 hours, obtain mixed solution II;
(3) in mixed solution II, add chain terminator solution, stop heating, cool under agitation, obtain polyocarboxy acid type high-efficiency ceramic water reducing agent and cyclodextrin graft copolymer type ceramic water reducing agent.
Chain-transfer agent solution described in step (1) adopts deionized water configuration, and its mass percent concentration is 1.5% ~ 7.5%.
The rotating speed stirred described in step (1) is 300 ~ 1000r/min.
Initiator solution described in step (2) adopts deionized water configuration, and its mass percent concentration is 0.9 ~ 8.3%;
The speed of the dropping described in step (2) is that 5 ~ 10s/ drips;
Chain terminator solution described in step (3) adopts deionized water configuration, and its mass percent concentration is 10%.
Cooling temperature described in step (3) is 15 ~ 30 DEG C;
The rotating speed stirred described in step (3) is 300 ~ 1000r/min.
Mechanism of the present invention is:
Water joins in clay, can be adsorbed by clay particle.The combining form of water and clay particle mainly contains two kinds: one is mortise water, i.e. the water layer of the regular arrangement of clay particle surface; A kind of is loose Bound moisture, i.e. irregular alignment water layer.In addition, due to hydration, aquation positively charged ion meeting adsorbed water molecule, this is water existence form main in clay.Simultaneously due to pedesis, the particle in ceramic size system is always ceaselessly moving, and constantly mutually collides between particle.Owing to there is Van der Waals force and electrostatic attraction between particle, particle can be assembled mutually and form coacervate.Coated free water in a large number in these coacervates, thus ceramic slurry system viscosity is raised, cause Production of Ceramics processing difficulties.
Gu in water-dispersion system, due to the existence of clay particle ion surface electric charge, under the effect of electrostatic attraction, must attract to wait the counterions (or gegenion) of electricity to be looped around around solid, and gegenion in solution because of thermal motion be disperse state distribution in the solution, fitly can not arrange in one plane, thus form so-called double electrical layers (diffusion layer near outside the adsorption layer of particle and adsorption layer) and Zeta potential.So-called double electrical layers is made up of adsorption layer and diffusion layer, and namely internal layer one deck gegenion near particle surface proper alignment, is called adsorption layer; Skin is diffusion layer, namely gegenion both by electrostatic attraction effect close to interface, again by random thermal motion impact and to Medium Diffusion.The face that adsorption layer contacts with diffusion layer phase is called slip plane, and the difference of slipping plane place current potential and solution built-in potential is called zeta current potential.This two layer charges thickness increases, and interparticle repulsive forces increases, and the easy relatively sliding of particle, not easily coheres coagulation because of collision, so just can improve stability and the mobility of mud.
On the other hand sterically hindered repulsion produces by between the tensio-active agent being coated on ceramic grain surface, when ceramic particle is close to each other, steric restriction effect can be produced between absorption polymeric superplasticizer in its surface, make mutually to assemble between particle to become difficulty, dispersion system is tended towards stability.The present invention introduces sterically hindered larger cyclodextrin in the polymer, makes dispersion effect of the present invention better.
Owing to introducing carboxylate radical and macromonomer on Inventive polymers, can form hydrogen bond with clay particles surface, and the Van der Waals force of macromonomer and surface of clay is stronger, the present invention has higher enhancement to biscuit of ceramics.
The present invention, relative to prior art, has following advantage and effect:
1, the present invention is by cyclodextrin and derivatives graft thereof on high polymer main chain, and due to the molecular structure that cyclodextrin is special, the present invention, relative to inorganic salts ceramic water reducing agent, has higher diminishing and dispersion effect;
2, the present invention is amphoteric ion type polyelectrolyte, and its chemical and Heat stability is good, hydratability are by force and be not subject to solution ph impact;
3, the present invention has obvious reinforced effects to biscuit of ceramics, adding of polyocarboxy acid type high-efficiency ceramic water reducing agent prepared by the present invention, can reduce the use of ceramics reinforcing agent;
4, reaction conditions of the present invention is gentle, and synthesis technique is simple, is easy to realize suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) take the alpha-cylodextrin (α-CD) of 4g and 3-(2-methylacryoyloxyethyl dimethylin) the propanesulfonic acid salt (DMAPS) of 20g, and join in there-necked flask; Take 1.1g inferior sodium phosphate and be dissolved in 20.00g water, obtaining ortho phosphorous acid sodium water solution; Ortho phosphorous acid sodium water solution and 10g deionized water are joined in above-mentioned there-necked flask, stirs (rotating speed is 1000r/min) mixing, obtain mixed solution I;
(2) 0.72g ammonium persulphate is dissolved in 8.00g deionized water, obtains ammonium persulfate aqueous solution; Under 90 DEG C of conditions, ammonium persulfate aqueous solution is dropwise dripped initiation reaction in (the speed 5s/ of dropping drips) to mixed solution I, react 2 hours, obtain mixed solution II;
(3) by the ortho phosphorous acid sodium water solution of 4.8g10wt% (wherein, the consumption of deionized water is 4.32g) join in mixed solution II, under agitation be cooled to room temperature (rotating speed of stirring is 1000r/min), obtain cyclodextrin graft copolymer type ceramic water reducing agent; In whole system, the content of deionized water is 42.32g, is 1.76 times of alpha-cylodextrin (α-CD) and 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt (DMAPS) total mass.
Performance test: the use of cyclodextrin graft copolymer type ceramic water reducing agent according to a conventional method.
The water-reducing property of cyclodextrin graft copolymer type ceramic water reducing agent has flowed required flowing time with ceramic slurry respectively and has represented in the painting filled-4 glasss.This tests blank used is Foshan standard recipe soil, and the addition of water reducer is the 0.3wt% of ceramic batch, and the slip water ratio obtained is 30wt%, is designated as slip I.Initial slip flowing time is 39.22s.
The reinforced effects of cyclodextrin graft copolymer type ceramic water reducing agent is by injecting above-mentioned slip I to " cuboid-type " grinding tool (the long 35cm of grinding tool, wide 2.5cm have the little trilateral that two inside in the middle of grinding tool) is inner, shaping.By the cracking situation of biscuit after certain hour (comprise whether ftracture, ftracture length), compare the reinforced effects of water reducer.Biscuit after the above-mentioned slip I of test discovery is shaping did not ftracture after 5 hours, the long 5.1cm of crackle after 12h.Add under similarity condition the slip of the tripoly phosphate sodium STPP of equal in quality mark shaping after, ftracture after 0.5 hour, the long 5.20cm of crackle after 5 hours.
Embodiment 2
(1) take beta-cyclodextrin (β-CD) and 5g3-(2-methylacryoyloxyethyl dimethylin) the propanesulfonic acid salt (DMAPS) of 10g, and join in there-necked flask; Take 0.3g inferior sodium phosphate to be dissolved in 20.00g water, obtain ortho phosphorous acid sodium water solution; Ortho phosphorous acid sodium water solution and 10g water are joined in above-mentioned there-necked flask, stirs (rotating speed is 300r/min) mixing, obtain mixed solution I;
(2) 0.075g ammonium persulphate is dissolved in 8.00g water, obtains ammonium persulfate solution; Under 70 DEG C of conditions, the speed that ammonium persulfate aqueous solution drips with 10s/ is dropwise added drop-wise to initiation reaction in mixed solution I, reacts 2 hours, obtain mixed solution II;
(3) the ortho phosphorous acid sodium water solution of 1.5g10wt% is joined in mixed solution II, be under agitation cooled to room temperature (rotating speed of stirring is 300r/min), obtain cyclodextrin graft copolymer type ceramic water reducing agent; The consumption of whole system deionized water is 39.35g, is 2.62 times of alpha-cylodextrin (α-CD) and 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt (DMAPS) total mass.
Performance test: the use of cyclodextrin graft copolymer type ceramic water reducing agent according to a conventional method.
The water-reducing property of cyclodextrin graft copolymer type ceramic water reducing agent has flowed required flowing time with ceramic slurry respectively and has represented in the painting filled-4 glasss.This tests blank used is Foshan standard recipe soil, and the addition of water reducer is the 0.3wt% of ceramic batch, and the slip water ratio obtained is 30wt%, is designated as slip I.Initial slip flowing time is 50.37s.
The reinforced effects of cyclodextrin graft copolymer type ceramic water reducing agent is by injecting above-mentioned slip I to " cuboid-type " grinding tool (the long 35cm of grinding tool, wide 2.5cm have the little trilateral that two inside in the middle of grinding tool) is inner, shaping.By the cracking situation of biscuit after certain hour (comprise whether ftracture, ftracture length), compare the reinforced effects of water reducer.Biscuit after the above-mentioned slip I of test discovery is shaping did not ftracture after 5 hours, the long 6.2cm of crackle after 12h.Add under similarity condition the slip of the tripoly phosphate sodium STPP of equal in quality mark shaping after, ftracture after 0.5 hour, the long 5.20cm of crackle after 5 hours.
Embodiment 3
(1) take 3-(2-methylacryoyloxyethyl dimethylin) the propanesulfonic acid salt (DMAPS) of 8g hydroxypropyl cyclodextrin and 20g and join in there-necked flask; Take 1.1g ortho phosphorous acid potassium to be dissolved in 20.00g water, obtain ortho phosphorous acid aqueous solutions of potassium; Ortho phosphorous acid aqueous solutions of potassium and 15g water are joined in above-mentioned there-necked flask, stirs (rotating speed is 500r/min) mixing, obtain mixed solution I.
(2) 0.45g ammonium persulphate is dissolved in 8.00g water, obtains ammonium persulfate aqueous solution; Under 80 DEG C of conditions, the speed that this ammonium persulfate aqueous solution drips with 6s/ is dropwise added drop-wise to initiation reaction in mixed solution I, reacts 4 hours, obtain mixed solution II.
(3) the ortho phosphorous acid sodium water solution of 5.8g10wt% is joined in mixed solution II, stop heating, be cooled to room temperature (rotating speed of stirring is 500r/min) under agitation, obtain cyclodextrin graft copolymer type ceramic water reducing agent; In whole system, the consumption of deionized water is 48.22g, is 1.72 times of alpha-cylodextrin (α-CD) and 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt (DMAPS) total mass.
Performance test: the use of cyclodextrin graft copolymer type ceramic water reducing agent according to a conventional method.
The water-reducing property of cyclodextrin graft copolymer type ceramic water reducing agent has flowed required flowing time with ceramic slurry respectively and has represented in the painting filled-4 glasss.This tests blank used is Foshan standard recipe soil, and the addition of water reducer is the 0.3wt% of ceramic batch, and the slip water ratio obtained is 30wt%, is designated as slip I.Initial slip flowing time is 28.81s.
The reinforced effects of cyclodextrin graft copolymer type ceramic water reducing agent is by injecting above-mentioned slip I to " cuboid-type " grinding tool (the long 35cm of grinding tool, wide 2.5cm have the little trilateral that two inside in the middle of grinding tool) is inner, shaping.By the cracking situation of biscuit after certain hour (comprise whether ftracture, ftracture length), compare the reinforced effects of water reducer.Biscuit after the above-mentioned slip I of test discovery is shaping did not ftracture after 5 hours, the long 6.1cm of crackle after 12 hours.Add under similarity condition the slip of the tripoly phosphate sodium STPP of equal in quality mark shaping after, ftracture after 0.5 hour, the long 5.20cm of crackle after 5 hours.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (8)
1. a cyclodextrin graft copolymer type ceramic water reducing agent, is characterized in that: be that raw material is prepared from by cyclodextrin polymkeric substance, 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt, chain-transfer agent, initiator, chain terminator and deionized water; Described cyclodextrin polymkeric substance is cyclodextrin or cyclodextrin derivative;
The mass ratio of described cyclodextrin polymkeric substance and 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt is (0.2 ~ 2.0): 1;
The quality of described chain-transfer agent is 2% ~ 5% of cyclodextrin polymkeric substance and 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt total mass;
The quality of described initiator is 0.5% ~ 3% of cyclodextrin polymkeric substance and 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt total mass;
The quality of described chain terminator is 1% ~ 3% of cyclodextrin polymkeric substance and 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt total mass;
Described cyclodextrin comprise in beta-cyclodextrin or alpha-cylodextrin more than one; Described cyclodextrin derivative be in hydroxypropyl cyclodextrin, quadrol-beta-cyclodextrin or GMA-EDA-CD more than one, described GMA-EDA-CD is glycidyl methacrylate-quadrol modified cyclodextrin.
2. cyclodextrin graft copolymer type ceramic water reducing agent according to claim 1, is characterized in that: described chain-transfer agent is inorganic salts; Described initiator is persulphate; Described chain terminator is more than one in inferior sodium phosphate or ortho phosphorous acid potassium.
3. cyclodextrin graft copolymer type ceramic water reducing agent according to claim 2, is characterized in that: described chain-transfer agent is more than one in inferior sodium phosphate or ortho phosphorous acid potassium; Described initiator is ammonium persulphate.
4. cyclodextrin graft copolymer type ceramic water reducing agent according to claim 1, is characterized in that: the quality of described deionized water is 1.3 ~ 2.7 times of cyclodextrin polymkeric substance and 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt total mass.
5. the preparation method of cyclodextrin graft copolymer type ceramic water reducing agent according to claim 1, is characterized in that: comprise the following steps:
(1) by cyclodextrin polymkeric substance, 3-(2-methylacryoyloxyethyl dimethylin) propanesulfonic acid salt, chain-transfer agent solution and portions of de-ionized water, stir lower mixing, obtain mixed solution I;
(2) under 70 ~ 90 DEG C of conditions, initiator solution is added drop-wise in mixed solution I, reacts 2 ~ 4 hours, obtain mixed solution II;
(3) in mixed solution II, add chain terminator solution, stop heating, cool under agitation, obtain polyocarboxy acid type high-efficiency ceramic water reducing agent and cyclodextrin graft copolymer type ceramic water reducing agent;
Chain-transfer agent solution, initiator solution and chain terminator solution are all adopt the configuration of another part deionized water to form.
6. the preparation method of cyclodextrin graft copolymer type ceramic water reducing agent according to claim 5, is characterized in that:
Described in step (1), chain-transfer agent solution quality percentage concentration is 1.5% ~ 7.5%;
Initiator solution mass percent concentration described in step (2) is 0.9 ~ 8.3%;
Described in step (3), chain terminator solution mass percent concentration is 10%.
7. the preparation method of cyclodextrin graft copolymer type ceramic water reducing agent according to claim 5, is characterized in that: the speed of the dropping described in step (2) is that 5 ~ 10s/ drips.
8. the preparation method of cyclodextrin graft copolymer type ceramic water reducing agent according to claim 5, is characterized in that:
The rotating speed stirred described in step (1) is 300 ~ 1000r/min;
Cooling temperature described in step (3) is 15 ~ 30 DEG C; The rotating speed stirred described in step (3) is 300 ~ 1000r/min.
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| CN105777142B (en) * | 2016-03-09 | 2019-01-11 | 韶关市合众化工有限公司 | A kind of high-efficiency ceramic green body reinforcing agent and preparation method and application |
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| CN102229479A (en) * | 2011-04-19 | 2011-11-02 | 广东红墙新材料股份有限公司 | Water-retaining polycarboxylic acid type water reducer containing beta-cyclodextrin, preparation method thereof and usage method thereof |
| CN103923275A (en) * | 2014-03-18 | 2014-07-16 | 深圳大学 | Amphoteric betaine polycarboxylic acid water reducing agent and preparation method thereof |
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| CN102229479A (en) * | 2011-04-19 | 2011-11-02 | 广东红墙新材料股份有限公司 | Water-retaining polycarboxylic acid type water reducer containing beta-cyclodextrin, preparation method thereof and usage method thereof |
| CN103923275A (en) * | 2014-03-18 | 2014-07-16 | 深圳大学 | Amphoteric betaine polycarboxylic acid water reducing agent and preparation method thereof |
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Effective date of registration: 20200610 Address after: 512400 No.3 comprehensive building, Ping'an 1st Road, industrial transfer park, Dalingshan (Nanxiong), Dongguan, Nanxiong City, Shaoguan City, Guangdong Province Co-patentee after: CAS GUANGZHOU CHEMISTRY Co.,Ltd. Patentee after: Guoke Guanghua (Nanxiong) New Materials Research Institute Co.,Ltd. Address before: 512400 Guangdong city of Shaoguan province Nanxiong City Abas Industrial Park (Guangdong Nanxiong fine chemical base) Co-patentee before: CAS GUANGZHOU CHEMISTRY Co.,Ltd. Patentee before: NANXIONG MATERIAL PRODUCTION BASE OF CHINESE ACADEMY OF SCIENCES GUANGZHOU CHEMICAL Co.,Ltd. |
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