CN101069827A - Block dispersant and preparing method - Google Patents
Block dispersant and preparing method Download PDFInfo
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- CN101069827A CN101069827A CN200710038421.3A CN200710038421A CN101069827A CN 101069827 A CN101069827 A CN 101069827A CN 200710038421 A CN200710038421 A CN 200710038421A CN 101069827 A CN101069827 A CN 101069827A
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Abstract
The present invention relates to a block dispersing agent and its preparation method. Said dispersing agent possesses polyether/polyester block structure, so that its dispersion property can be greatly raised. Said invention also provides its structural general formula.
Description
Technical field
The present invention relates to macromolecular material and preparation method thereof, relate in particular to a kind of block dispersant and preparation method thereof.
Background technology
Polymer dispersant is generally amphiphilic structure.One end of its molecular structure is generally polar group, as carboxyl, sulfonic group, phosphate-based, sulfate group and various amido, quaternary ammonium salt base.These polar groups account for the 5-10% of dispersant molecule amount greatly, they can with treat dispersed solids particle surface strong bonded, be called anchoring group; The other end of dispersant is the polymer long-chain, must have good compatibility with decentralized medium, is called solvent chain.Solvent chain generally accounts for more than 90% of dispersant molecule amount.According to the difference of solvent chain, polymer dispersant mainly is divided into polyester-type and polyether-type at present.
The polyester-type dispersant generally be used for low polarity or middle polarity organic media (GB2056461 for example, GB2135804, CN1146371A).The polyether-type dispersant generally is used for water-based or strong polarizable medium (for example US4398955).During actual the use, when we found to use polyethers to make solvent chain merely in water-based or strong polarizable medium, the dispersion effect of dispersant was often unsatisfactory, and existing polyester-type dispersant can't use in such system at all.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of improvement dispersive property in order to overcome the defective that above-mentioned prior art exists, and that satisfies that solid particle disperses needs in water-based or opposed polarity organic media has block dispersant of polyether/polyester and preparation method thereof.
Purpose of the present invention can be achieved through the following technical solutions: a kind of block dispersant, it is characterized in that (1) this dispersant is because the initiator of solvent chain part and terminal agent different, and its structure comprises following general formula:
Wherein: R
1Be C
1～C
17Alkyl, R
2Be H or CH
3, R
3Be C
4～C
8The residue of dicarboxylic acid anhydride, m=1～50, n=1～50, p=1～500;
(2) when dispersant is the category-A structure (solvation chain for end carboxyl when ending), X=OM wherein, M is H
+, MH
4+Or Na
+, K
+Alkali metal ion, perhaps X=Y-Z, wherein Y is a bridged group, as-NH-,
-O-, Z are the residue of organic amine, organic amine salt or quaternary ammonium salt;
(3) when dispersant is the category-B structure when ending (solvation chain be terminal hydroxy group), wherein X is phosphate radical (ester), sulfate radical (ester), perhaps X=Q-Z, wherein Q is a bridged group, as
Z is the residue of organic amine, organic amine salt or quaternary ammonium salt.
Described initiator is the monohydroxy polyethers.
A kind of preparation method of block dispersant, usually be formed by connecting by solvent chain and anchoring group, it is characterized in that, described solvent chain is to be initiator with the monohydroxy polyethers, impel dicarboxylic acid anhydride and epoxides to replace open loop in the presence of catalyst, reaction obtains holding carboxyl or terminal hydroxy group block polymer, the general designation solvent chain, contain two groups that replace in its course of reaction, as:
Course of reaction is pressed I → II → I → II ... carry out, acid anhydrides is excessive in the reactant mixture, then obtains holding carboxyl polymer, with the dispersant that obtains the category-A structure after anchoring group is connected; Epoxides is excessive in the reactant mixture, finally obtains hydroxy-terminated polymer, with the dispersant that obtains the category-B structure after anchoring group is connected.
Adjustable factor is as follows in the building-up process:
(1) adopts mixed acid anhydride or hybrid ring oxidation thing, regulate between the different acid anhydrides simultaneously or the rate of charge between the different rings oxide, can change the structure and the polarity of solvent chain easily, the dispersant of final formation can be disperseed in the organic media of opposed polarity efficiently.Suitable dicarboxylic acid anhydride has maleic anhydride, succinyl oxide, phthalic anhydride, tetrabydrophthalic anhydride, chlorendic anhydride, PHT4; Suitable epoxides is oxirane, expoxy propane etc.
(2) change the consumption of initiator, can regulate the molecular weight of solvent chain.The number-average molecular weight Mn of solvent chain equals the gross weight (gram) of real reaction thing and the ratio of the molal quantity of initiator in theory.The actual molecular weight of solvent chain can be calculated by the acid number (Av) and the hydroxyl value (Hv) of assaying reaction system.Computing formula is: Mn=56100/ (Av+Hv).
(3) the solvent chain synthesis reaction temperature should be controlled between 110 ℃～130 ℃.Used catalyst can be tertiary amine or quaternary ammonium salt when synthetic, and as triethylamine, benzyltriethylammoinium chloride, TBAB, its consumption is 0.1～1.0% (wt%) of reaction-ure mixture.
(4) synthetic reaction can be carried out under normal pressure, and this moment, epoxides should add with the dropping mode; Synthetic reaction also can be pressurizeed and be carried out, and this moment, epoxides dropped in the reactor by rate of charge with other reactants.
(5) because being connected between solvent chain and the anchoring gene, in fact be exactly carboxyl or hydroxyl with polar group between be connected, its reaction condition is different with the difference of polar group, reacts but these reactions all are ripe classics.For example the reaction between terminal carboxyl polyester and primary amine or the secondary amine can be carried out between 120 ℃～160 ℃, and the extent of reaction can be judged according to the acid number of product, specifically not give unnecessary details among the present invention for this reason.Only be summarized as follows below with regard to connected mode between solvent chain and the anchoring group and corresponding product:
1) the end carboxyl polymer can directly use as dispersant, also can generate with NH with ammonia, alkali metal oxide or hydroxide effect
4 +Or alkali metal ion is (as Na
+, K
+) be the dispersant (A-1) of anchoring group;
2) the end carboxyl polymer can be that alcamines material (as the triethanolamine) reaction of tertiary amine forms with the organic amine with polyamine or amido also be the dispersant (A-2) of anchoring group, and it be the hyper-dispersant (A-3) of anchoring group that this dispersant can also further generate with amine salt or quaternary ammonium salt with alkylating reagents reactions such as acid (comprising mineral matter, organic acid) or sulfuric acid dialkyls;
3) hydroxy-terminated polymer can with inorganic anhydrides material (as P
2O
5Deng) to generate end group be the dispersant (B-1) of acid group or its ester in reaction; Also can be earlier and excessive polyisocyanates reaction, and then with polyamine or alcamines substance reaction, generation is the hyper-dispersant (B-2) of anchoring group with the organic amine, and it is the hyper-dispersant (B-3) of anchoring group that this dispersant also can further generate with amine salt or quaternary ammonium salt with acid or alkylating reagent reaction;
Above-mentioned said dispersant, its structural formula can be with following various description, and wherein swash is partly represented solvent chain;
Wherein: M is H
+, MH
4 +Or Na
+, K
+Alkali metal ion.
Wherein: a is O, and NH, or NR group, R are C
1～C
18Alkyl, b is C
1～C
18Alkyl, c, d are H or C
1～C
18Alkyl, the two can be identical, can also be different.-
Wherein: all with the explanation of (A-2), e is H or C for a, b, c
1～C
18Alkyl, F
-Be anion, as CH
3SO
4 -, Cl
-Deng.
Wherein: X be acid group or and ester, as phosphate radical (ester), sulfate radical (ester).
Wherein: all with the explanation of (A-2), G is C for a, b, c, d
1～C
18Alkyl, m=1～500.
Wherein: all with the explanation of (A-3), G, m are with the explanation of (B-2) for a, b, c, d, e, F.
Because solvent chain is the key factor that influences the dispersant serviceability, in order to guarantee that dispersant of the present invention can have good dispersion effect in water-based or opposed polarity organic media, the inventor by theory analysis after decision the solvent chain of polyether-type or polyester-type dispersant is improved.Imagination is an initiator with the monohydroxy polyethers, in the presence of catalyst, impel dicarboxylic acid anhydride and epoxides to carry out ring-opening reaction clocklike, make a kind of polyether/polyester block kind solvent chain, link to each other with anchoring group more under certain conditions then, form the said dispersant of the present invention.In addition, the present invention considers from being easy to industrialized angle, a kind of easy synthetic method is provided.
The dispersant that makes according to the method described above, when practical application, its optimum amount depends on the specific area (BET) of dispersed solid particle.Usual amounts can be at 0.5～5.Omg/M
2Choose in the scope, the optimum amount scope is 1.0～2.0mg/M
2When other factors is constant (certain as solid particle, solvent one is regularly), by investigating the variation relation of dispersion viscosity with dispersant dosage, can be in the hope of the use amount of optimum dispersant, when optimum amount, the viscosity of dispersion is minimum usually.In addition, when using dispersant of the present invention, should earlier dispersant be dissolved in decentralized medium, and then add solid particle and disperse (forming stable dispersion).Gained has the dispersant of polyether/polyester block structure, has improved dispersive property, can satisfy the needs that solid particle disperses in water-based or opposed polarity organic media.
The specific embodiment
Embodiment 1
In a 500ml four-hole boiling flask that has mechanical agitation, heating control apparatus, cooling and reflux device and a balance addition funnel, add poly-(epoxy ethane-epoxy propane) monomethyl ether 100 grams (0.2mol) (molecular structure of this monohydroxy polyethers is:
Embodiment 2
Make carboxyl polymer according to embodiment 1 identical method, then under 80 ℃, adding concentration is that (BASF AG produces 50% polyethyleneimine: amine aqueous solution, the trade mark is polymin P, molecular weight is about 50,000) 24.Og, dimethylbenzene 45ml, and after loading onto oil water separator (changing addition funnel), (dimethylbenzene and water azeotropic steamed in the course of reaction in 10 hours in heat temperature raising to 120 a ℃ reaction again, cooling back layering in oil water separator, water is directly emitted, and dimethylbenzene returns in the four-hole boiling flask and recycles), vacuumize at last except that removal xylene, obtain another dispersant of the present invention (have the category-A molecular structure, be called for short dispersant A-2).Record acid number Av=15.2.Degree according to the amidation process of the molecular weight of polymine and carboxyl calculates p=350.Because responseless part still keeps the molecular structure of dispersant A-1 in the reactant, therefore, dispersant A-2 is actually a kind of mixture that contains dispersant A-1.
Embodiment 3
Mechanical agitation is being housed, heating and temperature controlling device, cooling and reflux device in the 50Oml four-hole boiling flask of oil water separator, adds 370 gram (0.2mol) dispersant As-1, dimethylbenzene 40 grams, N, N-dimethyl-1,3-propane diamine 25.O gram, added thermal response 6 hours in 160 ℃, vacuumize and remove dimethylbenzene and unnecessary organic amine, must hold the tertiary amine groups polymer, be cooled to 50 ℃, add dimethyl suflfate 25.2 grams, system is warming up to 90 ℃ automatically, 95 ℃ of insulations 2 hours, must hold the quaternary ammonium salt base polymer, have the category-A molecular structure, be called for short dispersant A-3.
Embodiment 4
Get embodiment 1 resulting hydroxy-terminated polymer 350 grams (0.2mol), add the P of equivalent
2O
514.2 gram reacted 20 hours down at 90 ℃, must hold phosphate-based polymer, had the category-B molecular structure, was called for short dispersant B-1.
Embodiment 5
Get embodiment 1 resulting hydroxy-terminated polymer 175 grams (0.1mol), the toluene wiring solution-forming that adds same weight, the toluene di-isocyanate(TDI) (TDI) that adds 2.05 times of equivalents, be warming up to 80 ℃ of reactions two hours then, be cooled to room temperature, add 10.2 gram N, N-dimethyl-1, the 3-propane diamine obtains having the toluene solution of the dispersant of category-B molecular structure, abbreviates hyper-dispersant B-2 as.
Embodiment 6
In embodiment 5 resulting dispersant Bs-2, add 12.6 gram dimethyl suflfates, system will heat up automatically, keep 2hrs at 95 ℃, obtain having the dispersant of category-B molecular structure, abbreviate dispersant B-3 as.
Embodiment 7
Changing the initiator among the embodiment 1 into 500 gram (0.5mol) molecular weight is 1000 poly glycol monomethyl ether, the maleic anhydride input amount changes 245 grams (2.5mol) into, the preparation method of hydroxy polymer is with embodiment 1, drip expoxy propane down at 120 ℃, acid number Av=0 until the reaction system, vacuumize and remove remaining expoxy propane, get hydroxy-terminated polymer.Be cooled to 60 ℃ then, add 14.2 gram P again
2O
5, in 90 ℃ of reactions 20 hours, must hold phosphate-based polymer, have category-B molecular structure (m ≈ 22), be called for short dispersant B-4.
Above-mentioned dispersant effect is exemplified below:
(1) gets in the 191 type unsaturated polyester resins that 0.5g dispersant A-1 is dissolved in 49.5g, add 5OgAl (OH) then
3Fire-retardant filler (average grain diameter is 8 μ) stirs, and recording viscosity with NDJ-79 type viscosimeter is 1.6OPaS; If without dispersant,, add 5OgAl (OH) then only with 191 type unsaturated polyester resin 5Og
3Fire-retardant filler (average grain diameter is 8 μ) stirs, and recording viscosity with above-mentioned same viscosimeter is 3.5OPaS, not only viscosity height, and system instability, very fast generation Al (OH)
3Precipitation.If use the dispersant A-1 in the Chinese patent 96116371.2 instead, then viscosity is 2.10PaS.
(2) get 0.4g dispersant A-2, vinyl chloride-vinyl acetate-vinyl alcohol copolymer thing 1.06g after toluene-cyclohexanone-butanone mixed solvent (mixing by 2: 2: 6 volume ratios) 5.4g mixes, adds cobalt improved γ-Fe
2O
3Magnetic 8.Og, ground 2 hours with quick grinding dispersion machine, add polyurethane resin solution 12.1g then and (wherein contain polyurethane resin 1.06g, toluene-cyclohexanone-butanone mixed solvent 11.04g), ground again 2 hours, the magnetic paint viscosity of gained is 0.18PaS (used viscosimeter is the same, is omitted when narrating later on), and recording the squareness ratio that characterizes the magnetic dispersive property after the coating is 0.89; As the alkylbenzene APEO dispersant RE-610 that produces of the GAFC company that uses above-mentioned same amount, obtaining magnetic paint by above-mentioned identical proportioning and method of operating, its corresponding viscosity is 0.26paS, squareness ratio is 0.83; And for example by above-mentioned same consumption and proportioning and method, only dispersant changes patent GB2 into, 153,804 examples, 2 described dispersants, and the magnetic paint of acquisition, its viscosity is 0.25PaS, squareness ratio is 0.85.If use the dispersant A-2 in the Chinese patent 96116371.2 instead, then viscosity is 0.22 paS, and squareness ratio is 0.88.Therefore dispersant of the present invention all is better than prior art.
(3) get 1.0g dispersant A-3, in the ethanolic solution of adding 29g polyamide (concentration is 10%), add iron oxide yellow pigments 7Og again, ground 1.2 hours with grinding dispersion machine fast, obtain a kind of uniform and stable iron oxide yellow pigments and starch, its viscosity is 0.08PaS; If use patent GB2, disclosed dispersant in 153,804 examples 2 mixes according to above-mentioned identical proportioning, and grinds 2.O hour, reach qualified fineness after, recording viscosity is 0.15PaS, and the iron oxide yellow pigments of gained slurry is unstable, easily flocculation; If be made into coating with above-mentioned two kinds of iron oxide yellow slurries, the former gloss and degree of staining all are better than the latter, and this proves absolutely that dispersant A of the present invention-3 dispersion effect in polar solvent is better than prior art, so the wide industrial development prospect is arranged.
(4) change above-mentioned polyamide ethanolic solution into water-borne acrylic resin solution, dispersant changes B-4 into, and all the other are constant, and gained result and example 3 are similar.Illustrate that dispersant B-4 not only adapts to strong polar organic solvent, and in water-based system, have good adaptability.
(5) get 2.0g dispersant B-2, be dissolved in the acetone of 8Og, add carbon black (average grain diameter is 25nm) 2Og again, ground 2 hours with speed muller, it is 0.03PaS that the gained slurry records viscosity; And as if the dispersant B of using instead in the Chinese patent 96116371.2-2, then viscosity is 0.05PaS; Use GB2, the dispersant described in 153, the 804 patent examples 2, according to the slurry that above-mentioned identical proportioning and method grind to form, the viscosity that records is 0.2PaS, visible dispersant of the present invention has in intensive polar solvent than the better dispersion effect of existing technology.
(6) get 0.4g dispersant B-3, vinyl chloride-vinyl acetate-vinyl alcohol copolymer thing 1.06g, toluene-cyclohexanone-butanone (by 2: 2: 6 volume ratio preparation) mixed solvent 5.84g, cobalt improved ultra-fine γ-Fe
2O
3Magnetic 8.Og, place quick grinding dispersion machine to disperse 2 hours, and then adding polyurethane solutions 12.1g (wherein contains polyurethane resin 1.06g, toluene-cyclohexanone-butanone mixed solvent 11.04g), grind again and disperseed 2 hours, gained magnetic paint viscosity is 0.19PaS, and recording the squareness ratio that characterizes the magnetic dispersive property after the coating is 0.90; As use the RE-610 dispersant of prior art, and to disperse according to above-mentioned same proportioning and method, the viscosity of gained magnetic paint is 0.26PaS, and squareness ratio is 0.83, and visible dispersant of the present invention is better than prior art.
(7) get the dispersant B-1 of 0.7g, dimethylbenzene cyclohexanone mixed solvent (mixing) 18g by 1: 1 volume ratio, hydroxyl acrylic resin 2.Og wiring solution-forming adds TiO again
2Pigment 80g was disperseing 2 hours in the grinding dispersion machine fast, and the viscosity of gained graining paste is 0.25PaS; If use the GB2 of same amount, 153, the dispersant of describing in the 804 patent examples 2, disperse after the same method, the viscosity of gained graining paste is 0.42PaS, if change dispersant into described in the WO0121298 patent of same amount dispersant, the viscosity of gained graining paste is 0.48PaS, and visible dispersant of the present invention is better than prior art.
(8) in 100 gram water-and acrylate resin solutions, add the dispersant B-4 of 2.0g, titanium dioxide 200 grams were disperseing 2 hours in the grinding dispersion machine fast, and the viscosity of gained graining paste is 0.3PaS, places and does not see obvious layering after 2 months; If use the polyether-type dispersant of describing in the US4398955 patent example 1 of same amount, to disperse after the same method, the viscosity of gained graining paste is 0.9PaS, places layering just to occur after three days, visible dispersant of the present invention is better than prior art.
Claims (10)
1. a block dispersant is characterized in that, (1) this dispersant is because the initiator of solvent chain part and terminal agent different, and its structure comprises following general formula:
Wherein: R
1Be C
1～C
17Alkyl, R
2Be H or CH
3, R
3Be C
4～C
8The residue of dicarboxylic acid anhydride, m=1～50, n=1～50, p=1～500;
(2) when dispersant is the category-A structure (solvation chain for end carboxyl when ending), X=OM wherein, M is H
+, MH
4+Or Na
+, K
+Alkali metal ion, perhaps X=Y-Z, wherein Y is a bridged group, as-NH-,
,-O-, Z are the residue of organic amine, organic amine salt or quaternary ammonium salt;
(3) when dispersant is the category-B structure when ending (solvation chain be terminal hydroxy group), wherein X is phosphate radical (ester), sulfate radical (ester), perhaps X=Q-Z, wherein Q is a bridged group, as
Z is the residue of organic amine, organic amine salt or quaternary ammonium salt.
2. a kind of block dispersant according to claim 1 is characterized in that, described initiator is the monohydroxy polyethers.
3. the preparation method of a block dispersant, usually be formed by connecting by solvent chain and anchoring group, it is characterized in that, described solvent chain is to be initiator with the monohydroxy polyethers, impel dicarboxylic acid anhydride and epoxides to replace open loop in the presence of catalyst, reaction obtains holding carboxyl or terminal hydroxy group block polymer, the general designation solvent chain, contain two groups that replace in its course of reaction, as:
Course of reaction is pressed I → II → I → II ... carry out, acid anhydrides is excessive in the reactant mixture, then obtains holding carboxyl polymer, with the dispersant that obtains the category-A structure after anchoring group is connected; Epoxides is excessive in the reactant mixture, finally obtains hydroxy-terminated polymer, with the dispersant that obtains the category-B structure after anchoring group is connected.
4, the preparation method of a kind of block dispersant according to claim 3 is characterized in that, described end carboxyl polymer can be directly as dispersant; Also can further react, generate with NH with ammonia, alkali metal hydroxide or alkali metal oxide
4 +Or Na
+, K
+The class alkali metal ion is the dispersant of anchoring group, and can also form with the organic amine with polyamine or hydramine reaction is the dispersant of anchoring group, and can be the dispersant of anchoring group with acid or alkylating reagent reaction generation with amine salt or quaternary ammonium salt further.
5, the preparation method of a kind of block dispersant according to claim 3, it is characterized in that, described hydroxy-terminated polymer can be earlier and excessive polyisocyanates reaction, and then to generate with the organic amine with polyamine or alcamines substance reaction be the dispersant of anchoring group, also can be further with acid or the alkylating reagent reaction generates amine salt or quaternary ammonium salt is the dispersant of anchoring group; It is the dispersant of anchoring group that hydroxy-terminated polymer also can directly generate with acid group or its ester with inorganic anhydrides substance reaction.
6, the preparation method of a kind of block dispersant according to claim 3, it is characterized in that described catalyst comprises tertiary amine or quaternary ammonium salt, as triethylamine, benzyltriethylammoinium chloride, TBAB, its consumption is 0.1～1.0wt% of reaction-ure mixture.
7, the preparation method of a kind of block dispersant according to claim 3 is characterized in that, described dicarboxylic acid anhydride comprises maleic anhydride, succinyl oxide, phthalic anhydride, tetrabydrophthalic anhydride, chlorendic anhydride, PHT4.
8, the preparation method of a kind of block dispersant according to claim 3 is characterized in that, described epoxides is oxirane, expoxy propane;
9, the preparation method of a kind of block dispersant according to claim 3 is characterized in that, the ring-opening reaction of described solvent chain is controlled in 110～130 ℃ of scopes carries out.
10, the preparation method of a kind of block dispersant according to claim 3 is characterized in that, the ring-opening reaction of described solvent chain can be carried out at normal pressure, also can pressurize and carry out.
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|---|---|---|---|
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Family
ID=38897339
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626989A (en) * | 2013-05-20 | 2014-03-12 | 华东理工大学 | Preparation method for polyphosphoester viscosity-reducing dispersant for inorganic flame-retardant unsaturated resin |
| CN104193985A (en) * | 2014-09-09 | 2014-12-10 | 江苏苏博特新材料股份有限公司 | Preparation method of esterified macromer for polycarboxylate water-reducer |
| CN112457764A (en) * | 2020-10-30 | 2021-03-09 | 中山市鑫峰光固化材料有限公司 | Ultraviolet curing coating without thickening and preparation method thereof |
| CN113754080A (en) * | 2021-09-09 | 2021-12-07 | 常州中南化工有限公司 | Coal gasification ash water dispersant and application thereof |
| CN113831520A (en) * | 2021-11-12 | 2021-12-24 | 山东国瓷康立泰新材料科技有限公司 | Polyamine grafted polyether-polyester segmented copolymer dispersant, and preparation method and application thereof |
-
2007
- 2007-03-23 CN CN200710038421.3A patent/CN101069827A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626989A (en) * | 2013-05-20 | 2014-03-12 | 华东理工大学 | Preparation method for polyphosphoester viscosity-reducing dispersant for inorganic flame-retardant unsaturated resin |
| CN104193985A (en) * | 2014-09-09 | 2014-12-10 | 江苏苏博特新材料股份有限公司 | Preparation method of esterified macromer for polycarboxylate water-reducer |
| CN112457764A (en) * | 2020-10-30 | 2021-03-09 | 中山市鑫峰光固化材料有限公司 | Ultraviolet curing coating without thickening and preparation method thereof |
| CN112457764B (en) * | 2020-10-30 | 2022-08-09 | 中山市鑫峰光固化材料有限公司 | Ultraviolet curing coating without thickening and preparation method thereof |
| CN113754080A (en) * | 2021-09-09 | 2021-12-07 | 常州中南化工有限公司 | Coal gasification ash water dispersant and application thereof |
| CN113831520A (en) * | 2021-11-12 | 2021-12-24 | 山东国瓷康立泰新材料科技有限公司 | Polyamine grafted polyether-polyester segmented copolymer dispersant, and preparation method and application thereof |
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Open date: 20071114 |