CN101712752A - Hyperbranched polymer template material and application thereof in preparing organic nanoparticles - Google Patents
Hyperbranched polymer template material and application thereof in preparing organic nanoparticles Download PDFInfo
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- CN101712752A CN101712752A CN200910198214A CN200910198214A CN101712752A CN 101712752 A CN101712752 A CN 101712752A CN 200910198214 A CN200910198214 A CN 200910198214A CN 200910198214 A CN200910198214 A CN 200910198214A CN 101712752 A CN101712752 A CN 101712752A
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Abstract
The invention relates to a hyperbranched polymer template material and application thereof in preparing organic nanoparticles. The template material is prepared by the steps of carrying out the condensation polymerization on ABx type monomers to obtain a hydroxyl-terminated hyperbranched polyester, wherein, A stands for a carboxyl functional group, B stands for a hydroxyl functional group, and X is a natural number which is not less than 2; and then modifying the hydroxyl-terminated hyperbranched polyester by ionization to obtain a water-soluble hyperbranched polyester the internal cavity of which is lipophilic and the external of which is hydrophilic, wherein the water-soluble hyperbranched polyester can dissolve oil-soluble monomers, the molecular weight of the water-soluble hyperbranched polyester is 3000-7000 (the method for testing the molecular weight is gel permeation chromatography), and the number of the active terminal groups is 16-64.
Description
Technical field
The present invention relates to a kind of hyperbranched polymer template material and the application in the preparation organic nano particle thereof.
Background technology
Dendritic macromole and hyperbranched polymer are to utilize the characteristics of hyperbranched polymer molecule spheroid " there is cavity, outside fine and close inside " as the principle that template prepares nano material; act in the hyperbranched polymer spheroid internal cavities by space constraint and to hold the object nanoparticle; the performance template action; make nanoparticle be covered by the inside of hyperbranched polymer and be protected; can not condense, thereby obtain stable dispersion nanoparticle of uniform size.
Perignon N is " nano-reactor " with hyperbranched poly (amine monoamide), with NaBH
4Reduction AuCl
4～(removing～), the golden nanometer particle that obtains having good stability, its size is between 4～9nm.Bao etc. use NaBH by in the super branched polyurethane system
4The chemical reduction gold ion obtains the monodisperse gold nanometer particle of good stability.Mecking S etc. have obtained in hyperbranched Polyglycerine medium that form is regular, size is little, the palladium nanometer of narrowly distributing etc.Liu S H etc. are stablizer and template with the super branched polyurethane, have prepared nano Ag particles with ultraviolet light irradiation under the room temperature.That super branched polyurethane has played in the process of photoreduction is stable, the effect of dispersion and nano-reactor, and can effectively prevent the oxidation of nanometer silver.Usefulness hyperbranched poly silane such as Nechanicky M A are made presoma, by filter infiltration and high temperature ablation, make the silicon carbide α～SiC of 2 kinds of crystal formations and the composite particles of β～SiC.
The applied research of template action in the preparation of organic nano particle about dendritic macromole also has report.For example Newkome thinks, it is similar to micelle in nature that the possess hydrophilic property surface group has the dendritic macromole of hydrophobic inner layer again, is equivalent to a unimolecular micelle, and the space of its internal layer can be used as micromolecular containing space.Add oil-soluble monomer in the aqueous solution of this dendritic macromole, monomer can be embedded in the dendritic macromole, if add initiator, polymerization can take place in dendritic macromole monomer, is equivalent to micro-emulsion polymerization on the mechanism.Carry out because reaction is limited in the dendritic macromole, the size of the latex particle that obtains and shape can be limited by the dendritic macromole internal cavities.Finally obtain by the nanometer superpolymer latex or the high polymer alloy of dendritic macromole embedding.Because the constructional feature of dendritic macromole, this moment, dendritic macromole can be seen as the monomeric supramolecule of lipophilicity " sponge ", and what obtain is the monodisperse particle big or small, that shape is consistent, and was complete transparent solution system.And general micro-emulsion polymerization is because continuous nucleation is difficult to make monodispersed particle; And having that emulsifier content is too high, monomer content is crossed shortcomings such as low, these can both be prepared into to overcome with the dendritic macromole template.As usefulness surface groups such as Wege is monodisperse polymer particles such as the dendritic macromole of the carboxylate salt polystyrene that successfully prepared the dendritic macromole embedding, polymethylmethacrylate.
Bibliographical information is not seen in the research that is used for the preparation aspect of organic nano particle about hyperbranched polymer as yet.
Summary of the invention
Two (changing one into) of purpose of the present invention are to provide a kind of hyperbranched polymer template material.
Two of purpose of the present invention is to provide the preparation method of this mould material.
It is the method that template prepares organic nano particle with the hyperbranched polymer that three of purpose of the present invention is to provide a kind of.
Hyperbranched polymer is to utilize the characteristics of hyperbranched polymer molecule spheroid " there is cavity, outside fine and close inside " as the principle that template prepares nano material; act in the hyperbranched polymer spheroid internal cavities by space constraint and to hold the object nanoparticle; the performance template action; make nanoparticle be covered by the inside of hyperbranched polymer and be protected; can not condense, thereby obtain stable dispersion nanoparticle of uniform size.The present invention is the similarity on structure and performance according to hyperbranched polymer and dendritic macromole, by suitable Molecular Structure Design, obtains being applicable to the hyperbranched polymer of preparation organic nano particle, thereby prepares the polymer nano-particle of stable dispersion.
According to above-mentioned principle, the present invention adopts following technical scheme:
A kind of hyperbranched polymer template material is characterized in that this mould material is the superbrnaching end-hydroxy polyester that is generated through polycondensation by the monomer of ABx type, and wherein A represents that carboxyl functional group, B represent that hydroxy functional group, X represent the natural number more than or equal to 2; It is lipophilicity and outside hydrophilic water-soluble ultrabranching polyester that this superbrnaching end-hydroxy polyester obtains internal cavities through the ionization modification again, this water-soluble ultrabranching polyester has the ability of dissolving oil soluble monomers, its molecular weight is 3000～7000 (testing method of molecular weight is a gel permeation chromatography), and the active end group number is 16～64.
A kind ofly prepare above-mentioned hyperbranched polymer template material method, it is characterized in that the concrete steps of this method are:
A. the preparation of hyperbranched polymer template: the monomer by the ABx type generates superbrnaching end-hydroxy polyester through polycondensation, wherein A represents that carboxyl functional group, B represent that hydroxy functional group, X represent the natural number more than or equal to 2, molecular weight is 3000～7000, the testing method of molecular weight is a gel permeation chromatography, and the active end group number is 16～64;
B. the modification of hyperbranched polymer template: the acid anhydrides of step b gained superbrnaching end-hydroxy polyester and di-carboxylic acid formation is obtained end carboxyl super branched polyester through esterification, end carboxyl super branched polyester and ammoniacal liquor carry out ionising treatment, obtain the water-soluble ultrabranching polyester; The terminal hydroxy group quantity of superbrnaching end-hydroxy polyester is 1: 1 with the ratio of dicarboxylic acid anhydride molecule number; The mol ratio of ammoniacal liquor and dicarboxylic acid anhydride is 1: 1.
A kind of organic nanometer particle preparing process is a template with above-mentioned hyperbranched polymer, it is characterized in that the concrete steps of this method are:
A. above-mentioned water-soluble ultrabranching polyester is mixed with solid content and is 15～35% the aqueous solution, form template solution; After 0.15%～0.20wt% sodium bicarbonate of 0.15%～0.20% initiator of this aqueous solution of 30%～50% of reactant total mass, reactant total mass and reactant total mass mixed, stir and be warming up to backflow, form mixing solutions;
B. after the water-soluble ultrabranching polyester that the initiator of 0.15～0.20wt% of oil-soluble monomer, reactant total mass is dissolved in 30～50wt% of reactant total mass mixes, be added drop-wise in the step c gained mixing solutions, the control rate of addition dropwised at 2.5～3.5 hours, back flow reaction 30 minutes, obtain the transparent aqueous dispersion that has obvious blue light, be the aqueous dispersion of organic nano particle;
The quality sum that described reactant total mass is template solution, oil-soluble monomer and initiator, wherein the mass ratio of template solution and oil-soluble monomer is 80: (7～13), initiator amount are 1～5% of oil-soluble monomer quality.
Organic nano particle stability is measured: the aqueous dispersion and the ACRYLIC EMULSION of organic nano particle (are not added hyperbranched template modified aqueous solution, use OP-10 instead as emulsifying agent, other reactants are formed identical, the emulsion that adopts the conventional emulsion polymerization method to obtain) mixes with 3: 7～1: 1 weight ratio, centrifugal 5min under 3000rpm/min, precipitation promptly appears in ACRYLIC EMULSION 5min, and precipitation appears in hybrid dispersions 45min.
Advantage of the present invention: the hyper-branched polyester template adopts " one kettle way " preparation, and technology is simple, is fit to suitability for industrialized production.With the water-soluble ultrabranching polyester is that template prepares organic nano particle, and cost is low, and technological operation is simple, and the product dispersion stabilization that obtains is good.The organic nano particle that this method obtains is fit to be directly used in Application Areass such as tamanori, coating, polymeric membrane, also is suitable as the dispersion stabilizer of emulsion, has broad application prospects.
Description of drawings
The structure of the hyperbranched polymer that Fig. 1 prepares for embodiment one and the structure of the hyperbranched polymer after the modification thereof, wherein (a) is the structure of hyperbranched polymer; (b) be the structure of the hyperbranched polymer after the modification.
The nuclear magnetic spectrum of the hyperbranched polymer that Fig. 2 prepares for embodiment one.
The reaction formula and the structural formula of the hyperbranched polymer that Fig. 3 prepares for embodiment two.
The reaction formula and the structural formula of the hyperbranched polymer that Fig. 4 prepares for embodiment three.
Embodiment
The present invention will be further elaborated below by example.
Embodiment one:
(1) preparation of hyperbranched template A: 6.72g TriMethylolPropane(TMP) (TMP) is added in the there-necked flask, use the 100ml xylene soluble down at 100 ℃.After TriMethylolPropane(TMP) (TMP) dissolves fully, add 21.2g 2,2-dimethylol propionic acid (DMPA) and 0.2g tosic acid are warming up to 140 ℃, react about 2h; Be warming up to 150 ℃ and add 0.1g tosic acid reaction 0.5h, the water yield of measuring in the water trap generates the water yield near theory, cools to 140 ℃ and adds 42.4g 2, and 2-dimethylol propionic acid (DMPA), 100ml dimethylbenzene and 0.4g react about 2h to toluene sulphur; Be warming up to 150 ℃ and add 0.2g tosic acid reaction 0.5h, the water yield of measuring in the water trap generates the water yield near theory; Cool to 140 ℃ of adding 84.8g 2.2-dimethylol propionic acids (DMPA), the about 100ml of dimethylbenzene and 0.8g tosic acid and react about 2h; Be warming up to 150 ℃ and add 0.4g tosic acid reaction 0.5h, the water yield of measuring in the water trap generates the water yield near theory, and decompression removes and anhydrates and dimethylbenzene, if aquifer yield is too small, can adds and improve temperature of reaction or prolongation reaction times.React so repeatedly to design requirements, obtain the hyperbranched template of faint yellow thickness.The reaction formula of hyper-branched polyester A and structural formula see also Fig. 1, and nuclear magnetic resonance map is seen Fig. 2.
(2) modification of hyperbranched template A: above-mentioned reaction resulting polymers is got 21.4g, keep 85～95 ℃ of temperature, add 120ml acetone, the 14.5g maleic anhydride reacts 2h under the catalysis of 0.2g tin protochloride.Unnecessary acetone is removed in underpressure distillation.Cool to 40～70 ℃ and add 26ml ammoniacal liquor and 300ml deionized water, insulation 0.5h obtains light yellow transparent solution
(3) preparation of organic nano particle: get above-mentioned hyperbranched polymer modified solution 80ml, be divided into two parts of each 40ml, the hyperbranched polymer modified solution of getting 1 part of 40ml adds methyl methacrylate 12g and Diisopropyl azodicarboxylate 0.2g, and emulsify at a high speed 15min makes pre-emulsion.Get the hyperbranched polymer modified solution of 1 part of 40ml in addition, add Diisopropyl azodicarboxylate 0.2g and sodium bicarbonate 0.1g, join in the time of 65 ℃ to have and be equipped with in prolong, three mouthfuls of reaction flasks of mechanical stirrer 250ml, drip pre-emulsion with constant speed, the centre adds the deionized water 10ml of dissolving sodium bicarbonate 0.1g, about 1.5h drips off, and adds the deionized water 10ml of dissolving Diisopropyl azodicarboxylate 0.1g and sodium bicarbonate 0.1g then.Continue insulation reaction 0.5h, make monomer reaction complete.Cooling, discharging.Obtain the transparent aqueous dispersion that has obvious blue light.The model of producing through Beckman Coulter (U.S. Beckman Coulter Inc.) is that to obtain particle diameter be 90nm in Laser Particle Size Analyzer (laser particle size analyzer) test of LS 13 320.
(4) organic nano particle stability is measured: the aqueous dispersion and the 60～70wt% ACRYLIC EMULSION that 30～40wt% are contained organic nano particle (do not add hyperbranched template modified aqueous solution, use OP-10 instead as emulsifying agent, other reactants are formed identical, the emulsion that adopts the conventional emulsion polymerization method to obtain) mixes, centrifugal 5min under 3000rpm/min, precipitation promptly appears in ACRYLIC EMULSION 5min, and precipitation appears in hybrid dispersions 45min.
Embodiment two:
(1) preparation of hyperbranched template B: in the four-hole boiling flask that reflux condensing tube, agitator, water trap, thermometer, logical nitrogen protection are housed; with 100 gram dimethylol propionic acid and little amount of catalyst tosic acid; 200 gram dimethylbenzene react 6～7h under reflux state; no longer including water in water trap distillates; temperature of reaction to 150～165 ℃ gradually raise; vacuumize further reaction 1～2h, remove remaining dimethylbenzene, obtain faint yellow superbrnaching end-hydroxy polyester B.The system acid number is lower than 20mgKOH/g.The reaction formula of hyper-branched polyester B and structural formula see also Fig. 3.
(2) modification of hyperbranched template B: in the four-hole boiling flask that reflux condensing tube, agitator, water trap, thermometer, logical nitrogen protection are housed, superbrnaching end-hydroxy polyester B100 gram, Succinic anhydried 75 grams and a small amount of tosic acid are dissolved in the dimethylbenzene; be heated to backflow; reaction 5～6h; no longer including water in water trap distillates; reaction terminating stops heating.Product is poured out, and cooling obtains faint yellow end carboxyl super branched polyester.
(3) preparation of organic nano particle: get above-mentioned hyperbranched polymer modified solution 80ml, be divided into two parts of each 40ml, the hyperbranched polymer modified solution of getting 1 part of 40ml adds methyl methacrylate 12g and Diisopropyl azodicarboxylate 0.2g, and emulsify at a high speed 15min makes pre-emulsion.Get the hyperbranched polymer modified solution of 1 part of 40ml in addition, add Diisopropyl azodicarboxylate 0.2g and sodium bicarbonate 0.1g, join in the time of 65 ℃ to have and be equipped with in prolong, three mouthfuls of reaction flasks of mechanical stirrer 250ml, drip pre-emulsion with constant speed, the centre adds the deionized water 10ml of dissolving sodium bicarbonate 0.1g, about 1.5h drips off, and adds the deionized water 10ml of dissolving Diisopropyl azodicarboxylate 0.1g and sodium bicarbonate 0.1g then.Continue insulation reaction 0.5h, make monomer reaction complete.Cooling, discharging.Obtain the transparent aqueous dispersion that has obvious blue light.The model of producing through Beckman Coulter (U.S. Beckman Coulter Inc.) is that to obtain particle diameter be 100nm in Laser Particle Size Analyzer (laser particle size analyzer) test of LS 13320.
(4) organic nano particle stability is measured: the aqueous dispersion and the 60～70wt% ACRYLIC EMULSION that 30～40wt% are contained organic nano particle (do not add hyperbranched template modified aqueous solution, use OP-10 instead as emulsifying agent, other reactants are formed identical, the emulsion that adopts the conventional emulsion polymerization method to obtain) mixes, centrifugal 5min under 3000rpm/min, precipitation promptly appears in ACRYLIC EMULSION 5min, and precipitation appears in hybrid dispersions 40min.
Embodiment three
(1) preparation of hyperbranched template D: neopentyl glycol 10.5 grams, dimethylol propionic acid 402 grams and little amount of catalyst p-methyl benzenesulfonic acid are added in the four-hole reactor, add dimethylbenzene 200 grams simultaneously as reflux solvent.Then reactor is placed the oil bath of 140 ℃ of preset temperatures to heat, underpressure distillation removes solvent and water after the reaction 4h, and collecting reaction product obtains faint yellow superbrnaching end-hydroxy polyester D.The reaction formula of hyper-branched polyester D and structural formula see also Fig. 4.
(2) modification of hyperbranched template D: superbrnaching end-hydroxy polyester D 100 grams that obtain are dissolved in the pyridine, add diacetyl oxide 59 grams, stirring at room reaction 2 hours obtains end carboxyl super branched polyester.
(3) preparation of organic nano particle: get above-mentioned hyperbranched polymer modified solution 80ml, be divided into two parts of each 40ml, the hyperbranched polymer modified solution of getting 1 part of 40ml adds methyl methacrylate 12g and Diisopropyl azodicarboxylate 0.2g, and emulsify at a high speed 15min makes pre-emulsion.Get the hyperbranched polymer modified solution of 1 part of 40ml in addition, add Diisopropyl azodicarboxylate 0.2g and sodium bicarbonate 0.1g, join in the time of 65 ℃ to have and be equipped with in prolong, three mouthfuls of reaction flasks of mechanical stirrer 250ml, drip pre-emulsion with constant speed, the centre adds the deionized water 10ml of dissolving sodium bicarbonate 0.1g, about 1.5h drips off, and adds the deionized water 10ml of dissolving Diisopropyl azodicarboxylate 0.1g and sodium bicarbonate 0.1g then.Continue insulation reaction 0.5h, make monomer reaction complete.Cooling, discharging.Obtain the transparent aqueous dispersion that has obvious blue light.The model of producing through Beckman Coulter (U.S. Beckman Coulter Inc.) is that to obtain particle diameter be 120nm in Laser Particle Size Analyzer (laser particle size analyzer) test of LS 13 320.
(4) organic nano particle stability is measured: the aqueous dispersion and the 60～70wt% ACRYLIC EMULSION that 30～40wt% are contained organic nano particle (do not add hyperbranched template modified aqueous solution, use OP-10 instead as emulsifying agent, other reactants are formed identical, the emulsion that adopts the conventional emulsion polymerization method to obtain) mixes, centrifugal 5min under 3000rpm/min, precipitation promptly appears in ACRYLIC EMULSION 5min, and precipitation appears in hybrid dispersions 38min.
In the organic nano particle preparation process, replace Diisopropyl azodicarboxylate with ammonium persulphate, other conditions are identical with embodiment 1, obtain the aqueous dispersion that oyster white has obvious blue light, and particle diameter is 210nm.
Embodiment four: present embodiment and embodiment one are basic identical, and different is in the organic nano particle preparation process, and the consumption of methyl methacrylate is 10g, obtain the faint yellow aqueous dispersion that has obvious blue light, and particle diameter is 140nm.
Embodiment five: present embodiment and embodiment one are basic identical, and different is in the organic nano particle preparation process, and the consumption of methyl methacrylate is 8g, obtain the faint yellow aqueous dispersion that has obvious blue light, and particle diameter is 180nm.
Embodiment six: present embodiment and embodiment one are basic identical, and different is in the organic nano particle preparation process, and oil-soluble monomer is a methyl acrylate, and its consumption is 12g, obtain the faint yellow aqueous dispersion that has obvious blue light, and particle diameter is 100nm.
Embodiment seven: present embodiment and embodiment one are basic identical, and different is in the organic nano particle preparation process, and oil-soluble monomer is an ethyl propenoate, and its consumption is 12g, obtain the faint yellow aqueous dispersion that has obvious blue light, and particle diameter is 95nm.
Claims (3)
1. hyperbranched polymer template material is characterized in that this mould material is the superbrnaching end-hydroxy polyester that the monomer by the ABx type generates through polycondensation, and wherein A represents that carboxyl functional group, B represent that hydroxy functional group, X represent the natural number more than or equal to 2; It is lipophilicity and outside hydrophilic water-soluble ultrabranching polyester that this superbrnaching end-hydroxy polyester obtains internal cavities through the ionization modification again, this water-soluble ultrabranching polyester has the ability of dissolving oil soluble monomers, its molecular weight is 3000～7000, the testing method of molecular weight is a gel permeation chromatography, and the active end group number is 16～64.
2. method for preparing hyperbranched polymer template material according to claim 1 is characterized in that the concrete steps of this method are:
A. the preparation of hyperbranched polymer template: the monomer by the ABx type generates superbrnaching end-hydroxy polyester through polycondensation, wherein A represents that carboxyl functional group, B represent that hydroxy functional group, X represent the natural number more than or equal to 2, molecular weight is 3000～7000, the testing method of molecular weight is a gel permeation chromatography, and the active end group number is 16～64;
B. the modification of hyperbranched polymer template: the acid anhydrides of step b gained superbrnaching end-hydroxy polyester and di-carboxylic acid formation is obtained end carboxyl super branched polyester through esterification, end carboxyl super branched polyester and ammoniacal liquor carry out ionising treatment, obtain the water-soluble ultrabranching polyester; The terminal hydroxy group quantity of superbrnaching end-hydroxy polyester is 1: 1 with the ratio of dicarboxylic acid anhydride molecule number; The mol ratio of ammoniacal liquor and dicarboxylic acid anhydride is 1: 1, obtains hyperbranched polymer template material.
3. an organic nanometer particle preparing process is a template with hyperbranched polymer template material according to claim 1, it is characterized in that the concrete steps of this method are:
A. above-mentioned water-soluble ultrabranching polyester is mixed with solid content and is 15～35% the aqueous solution, form template solution; After 0.15%～0.20wt% sodium bicarbonate of 0.15%～0.20% initiator of this aqueous solution of 30%～50% of reactant total mass, reactant total mass and reactant total mass mixed, stir and be warming up to backflow, form mixing solutions;
B. after the water-soluble ultrabranching polyester that the initiator of 0.15～0.20wt% of oil-soluble monomer, reactant total mass is dissolved in 30～50wt% of reactant total mass mixes, be added drop-wise in the step a gained mixing solutions, the control rate of addition dropwised at 2.5～3.5 hours, back flow reaction 30 minutes, obtain the transparent aqueous dispersion that has obvious blue light, be the aqueous dispersion of organic nano particle;
The quality sum that described reactant total mass is template solution, oil-soluble monomer and initiator, wherein the mass ratio of template solution and oil-soluble monomer is 80: (7～13), initiator amount are 1～5% of oil-soluble monomer quality.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788667A (en) * | 2015-04-03 | 2015-07-22 | 嘉兴学院 | 8-hydroxyquinoline terminated hyperbranched polyester rare earth complex as well as preparation method and application thereof |
| CN105646816A (en) * | 2016-01-27 | 2016-06-08 | 平顶山正植科技有限公司 | Preparing method for persistent viscosity waterborne polyurethane dispersoid |
| CN112480328A (en) * | 2020-12-03 | 2021-03-12 | 江苏富琪森新材料有限公司 | Hyperbranched acrylic acid secondary dispersion, preparation method and application thereof |
| CN117383862A (en) * | 2023-10-13 | 2024-01-12 | 长沙千巽新材料科技有限公司 | Air entraining agent regulator and preparation method and application thereof |
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2009
- 2009-11-03 CN CN200910198214A patent/CN101712752A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788667A (en) * | 2015-04-03 | 2015-07-22 | 嘉兴学院 | 8-hydroxyquinoline terminated hyperbranched polyester rare earth complex as well as preparation method and application thereof |
| CN105646816A (en) * | 2016-01-27 | 2016-06-08 | 平顶山正植科技有限公司 | Preparing method for persistent viscosity waterborne polyurethane dispersoid |
| CN105646816B (en) * | 2016-01-27 | 2018-07-24 | 平顶山正植科技有限公司 | A kind of preparation method for holding viscous aqueous dispersions of polyurethanes |
| CN112480328A (en) * | 2020-12-03 | 2021-03-12 | 江苏富琪森新材料有限公司 | Hyperbranched acrylic acid secondary dispersion, preparation method and application thereof |
| CN112480328B (en) * | 2020-12-03 | 2023-02-28 | 江苏富琪森新材料有限公司 | Hyperbranched acrylic acid secondary dispersion, preparation method and application thereof |
| CN117383862A (en) * | 2023-10-13 | 2024-01-12 | 长沙千巽新材料科技有限公司 | Air entraining agent regulator and preparation method and application thereof |
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Open date: 20100526 |