CN101381421A - Azos thermal initiator, synthetic method and application thereof - Google Patents
Azos thermal initiator, synthetic method and application thereof Download PDFInfo
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- CN101381421A CN101381421A CNA2008102015434A CN200810201543A CN101381421A CN 101381421 A CN101381421 A CN 101381421A CN A2008102015434 A CNA2008102015434 A CN A2008102015434A CN 200810201543 A CN200810201543 A CN 200810201543A CN 101381421 A CN101381421 A CN 101381421A
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Abstract
The invention relates to an azo thermal initiator for use in preparation of a nano-sized spherical polyelectrolyte brush, a synthesis method and an application thereof. Firstly, azodiiso-alkylnitrile and diol are taken as raw materials to synthesize an intermediate azodiisoacid diol ester; and then the intermediate reacts with alkyl acrylyl chloride to obtain the novel azo thermal initiator with a C=C double bond as a terminal group. A novel azo thermal initiator both ends of which contain C=C double bonds can be obtained through the separation by a certain method. The thermal initiator can initiate the in-situ polymerization of monomers such as acrylic acid, 4-ethenyl-benzenesulfonic acid sodium salt and so on, on the surfaces of polystyrene milk globules to prepare the nano-sized spherical polyelectrolyte brush with controllable polyelectrolyte length and grafting density.
Description
Technical field
The present invention relates to thermal initiator and synthetic method thereof and application, more particularly, relate to azo class thermal initiator.
Background technology
Polymer brush is fixed on the solid surface by many polymer chains with an end and arranges densely and assembles.Because the structure that this brush is the same can greatly change surface property, as cementability, oilness, wettability, frictional property, biocompatibility etc., they have a wide range of applications in a lot of fields.The charged polymer brush that forms on nano level emulsion particle surface is called as nanometer spherical polyelectrolyte brush.Nanometer spherical polyelectrolyte brush not only has satisfactory stability and redispersible, and its size can inner gegenion concentration and the not considerable change with the change of outside atmosphere of pH value by external conditions (as temperature, pH value, ionic concn etc.) control.Therefore, they are carriers of ideal controllable nano-device and protein, enzyme, medicine, diagnosis group and catalyzer.
Present inventor in 1999 Germany adopted the light emulsion polymerization prepared first size brush at the polyacrylic acid brush and the polyvinylbenzenesulfonic acid sodium of 100～200 nanometers.But expensive and complicated ultraviolet reactor is difficult to realize suitability for industrialized production.For this reason, we design and adopt the thermal control method of emulsion polymerization to prepare nanometer spherical polyelectrolyte brush (seeing that name that the applicant submits on the same day is called the application for a patent for invention of " a kind of preparation method of spherical polyelectrolyte brush and application thereof ").And the key that realizes this method is the synthetic a kind of novel thermal initiator of design.
Summary of the invention
The objective of the invention is to that the synthetic a kind of efficiency of initiation height of design, suitable monomers are wide, initiation conditions is easily controlled, can be used for the azo class thermal initiator that the thermal control emulsion polymerisation process prepares nanometer spherical polyelectrolyte brush.
Azo class thermal initiator chemical structural formula provided by the invention is shown in following general formula I or the general formula III:
Wherein, Z
1Substituting group has the structure shown in the general formula I I:
Wherein, Z
2Substituent structure for general formula I V:
Wherein, R
1Be CH
3, CH
3CH
2, (CH
3)
2CHCH
2, R
2, R
3Be H, C
1～6Alkyl, C
1～6Alkoxyl group, R
4Be H, C
1～3Alkyl, n=1～3.
More specifically, the represented compound of above-mentioned general formula III can be azo two isopropylformic acids (vinylformic acid glycol ester) esters, azo diisoamyl acid (vinylformic acid glycol ester) ester, azo two isoamyl acetic acids (vinylformic acid glycol ester) ester, azo two isopropylformic acids (methacrylic acid glycol ester) ester, azo diisoamyl acid (methacrylic acid glycol ester) ester, azo two isoamyl acetic acids (methacrylic acid glycol ester) ester, azo two isopropylformic acids (vinylformic acid butanediol ester) ester, azo diisoamyl acid (vinylformic acid butanediol ester) ester, azo two isoamyl acetic acids (vinylformic acid butanediol ester) ester, azo two isopropylformic acids (methacrylic acid butanediol ester) ester, azo diisoamyl acid (methacrylic acid butanediol ester) ester or azo two isoamyl acetic acids (methacrylic acid butanediol ester) ester.
Use azo class thermal initiator provided by the invention to prepare nanometer spherical polyelectrolyte brush, with the particle diameter of each stage emulsion particle in the method test emulsion polymerization process of dynamic light scattering.The particle diameter of polystyrene spheres is generally at 50～100nm, and the particle diameter of spherical polyelectrolyte brush is at 80～250nm, brush from examine the surface to the controllable thickness of outer built in 10～200nm scope.
The synthetic method of azo class thermal initiator provided by the invention mainly comprises following two steps:
(1) preparation of intermediate
In the container that organic solvent such as tetrahydrofuran (THF), benzene,toluene,xylene equal solvent are housed, add the binary primary alconol, as ethylene glycol, butyleneglycol, isobutyl-glycol etc., and the recrystallization azo compound of purifying, as Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile) etc.Under churned mechanically situation, feed the exsiccant hydrogen chloride gas lentamente continuously.0～15 ℃ of temperature of reaction, 10～24 hours reaction times.When reaction finished, reactant became white viscous liquid.The molar ratio of control binary primary alconol and azo compound is 1:50 to 1:10, preferably 1:20 to 1:10.If reactive ratio is too high, then forms the oligopolymer of the two easily, and can not get small molecule monomer.Add few ice cubes in white thick liquid, vigorous stirring 1～2 hour makes it fully be hydrolyzed to ester.
Divide the sub-cloud dope with separating funnel, collect the upper strata organic layer; With saturated nacl aqueous solution washing 3～5 times, with saturated sodium bicarbonate solution washing 3～5 times, add anhydrous magnesium sulfate drying more then; Way with underpressure distillation is removed organic solvent; At last, add amount of methanol, separate out a spot of white oligopolymer, can obtain described intermediate behind the pressure reducing and steaming methyl alcohol.
Through proton nmr spectra detection compound structure, confirm that the gained compound is the azo analog derivative intermediate that end group has hydroxyl.
(2) by the intermediate preparation thermal initiator
By the intermediate preparation thermal initiator several different methods is arranged, as follows:
Method one:
The acyl chlorides, azo analog derivative intermediate and the adding of a certain amount of exsiccant organic solvent that end group are contained two keys are equipped with in the container of magnetic agitation, acyl chlorides can be acrylate chloride, methacrylic chloride etc., the molar ratio of acyl chlorides and intermediate is 1:2 to 1:3, and organic solvent can be acetone, benzene, chloroform, methylene dichloride etc.Slowly drip the exsiccant pyridine then, the dropping process is cooled off with ice-water bath, and the molar ratio of acyl chlorides and pyridine is 1:1 to 1:3.After dropwising, sealed vessel at room temperature reacted three days.
Method two:
In the container of magnetic agitation is housed, the exsiccant pyridine is slowly splashed into the acyl chlorides that end group contains two keys, the molar ratio of acyl chlorides and pyridine is 1:1 to 1:3.The dropping process is cooled off with ice-water bath, adds a certain amount of exsiccant organic solvent then, accelerates to stir, and it is uniformly dispersed.Slowly drip azo analog derivative intermediate then, equally with the ice-water bath cooling, the molar ratio of acyl chlorides and azo analog derivative intermediate is 1:2 to 1:3 in the dropping process.After dropwising, sealed vessel at room temperature reacted three days.
Method three:
In the container of magnetic agitation is housed, the exsiccant pyridine is slowly splashed into the acyl chlorides that end group contains two keys, the molar ratio of acyl chlorides and pyridine is 1:1 to 1:3.The dropping process is cooled off with ice-water bath, adds a certain amount of exsiccant organic solvent then, accelerates to stir, and it is uniformly dispersed.Slowly drip azo analog derivative intermediate then, equally with the ice-water bath cooling, the molar ratio of acyl chlorides and azo analog derivative intermediate is 1:2 to 1:3 in the dropping process.After dropwising, sealed vessel is warming up to 30～40 ℃, reacts 15～24 hours.
Method one is identical to the post-treating method of method three: 1, remove by filter pyridinium salt; 2, organic solvent is removed in underpressure distillation; 3, add the benzene,toluene,xylene lysate; 4, with saturated nacl aqueous solution washing 3～5 times; 5, use anhydrous magnesium sulfate drying.Thick product separates with silica gel column chromatography purifies, and the final product yield is 5～15%, purity 90～98%.
Method four:
Azo analog derivative intermediate and the adding of no water sodium hydroxide are equipped with in the container of magnetic agitation, and the molar ratio of intermediate and sodium hydroxide is 1:1 to 1:1.5, is stirred to the generation faint yellow solid.Add certain amount of organic solvent then, as benzene, toluene, tetrahydrofuran (THF), chloroform etc.Add the acyl chlorides that end group contains two keys fast, the molar ratio of acyl chlorides and intermediate is 1:2 to 1:3.After adding acyl chlorides, sealed vessel at room temperature reacted 3 days.
Method five:
Azo analog derivative intermediate and the adding of no water sodium hydroxide are equipped with in the container of magnetic agitation, and the molar ratio of intermediate and sodium hydroxide is 1:1 to 1:1.5, is stirred to the generation faint yellow solid.Add certain amount of organic solvent then, as benzene, toluene, tetrahydrofuran (THF), chloroform etc.Add the acyl chlorides that end group contains two keys fast, the molar ratio of acyl chlorides and intermediate is 1:2 to 1:3.After adding acyl chlorides, sealed vessel is warming up to 30～40 ℃, reacts 24～36 hours.
Method four is identical to the post-treating method of method five: 1, solids removed by filtration precipitation; 2, organic solvent is removed in underpressure distillation; 3, add the benzene,toluene,xylene lysate; 4, use anhydrous magnesium sulfate drying.Thick product separates with silica gel column chromatography purifies, and the final product yield is 15～30%, purity 90～98%.
Being applied to of above-mentioned azo class thermal initiator prepares the polymer dielectric brush, concrete grammar is: above-mentioned azo class thermal initiator is grafted on micro polymer milk-globule surface, then at a certain temperature, original position causes electrolyte monomer, as vinylformic acid, methacrylic acid, sodium p styrene sulfonate, thereby become intensive polymer dielectric brush at described micro polymer milk-globule surface aggregate.
Thermal initiator provided by the invention has following advantage: the one, and percentage of grafting height: because carbon-carbon double bond is all contained at the two ends of thermal initiator, when being grafted to polystyrene micro emulsion ball surface, it can all be grafted on polystyrene micro emulsion ball surface with the form two ends of covalent linkage.The end group of general light trigger then only contains a carbon-carbon double bond, can only an end be grafted on the surface of polystyrene micro emulsion ball; The 2nd, the efficiency of initiation height: because thermal initiator is to be grafted on the polystyrene spheres surface with two ends, a thermal initiator molecule can generate two living radicals on the polystyrene spheres surface after decomposes.Therefore, its efficiency of initiation is the twice of light trigger in theory; The 3rd, initiation conditions is simple: the initiation of thermal initiator does not need complicated ultraviolet reactor, and only need be controlled at certain temperature can the trigger monomer polymerization.The 4th, trigger rate is controlled.Can control the trigger rate of thermal initiator by the height of control kick off temperature.
Embodiment
The present invention further specifies the present invention with the following example, but protection scope of the present invention is not limited to embodiment.Can make many other variation and modifications in the case of without departing from the spirit and scope of protection of the present invention to those skilled in the art, still be included in the scope of protecting in claims.
Embodiment 1 end group has azo analog derivative intermediate synthetic of hydroxyl
With 150ml benzene, 150ml ethylene glycol, and the 22g Diisopropyl azodicarboxylate is put into the 500ml flask.Under churned mechanically situation, feed the exsiccant hydrogen chloride gas lentamente continuously, reacted 10 hours down at 5 ℃.When reaction finished, reactant became white viscous liquid.Add the 15g ice cube in white thick liquid, vigorous stirring 2 hours makes its abundant hydrolysis.
Divide the sub-cloud dope with separating funnel, collect upper strata benzene layer; Divide 3 washings with the 1200ml saturated nacl aqueous solution then, divide 3 washings with the 900ml saturated sodium bicarbonate solution again, add anhydrous magnesium sulfate drying; The pressure reducing and steaming solvent benzol adds 20ml methyl alcohol again, separates out a spot of white oligopolymer.Can obtain the 35.8g intermediate behind the pressure reducing and steaming methyl alcohol, through gas chromatographic detection, purity is 98%.
Embodiment 2 is by the intermediate preparation thermal initiator
4.0ml methacrylic chloride, 6.0g intermediate and the adding of 50ml benzene are equipped with in the container of magnetic agitation.Slowly drip the 3.6ml pyridine then, the dropping process is cooled off with ice-water bath.After dropwising, sealed vessel at room temperature reacted three days.
Remove by filter pyridinium salt, divide 3 washings, use anhydrous magnesium sulfate drying again with saturated nacl aqueous solution 900ml.Thick product separates with silica gel column chromatography purifies the mixed solvent of eluent benzene: acetone=2:1 (volume ratio).Finally obtain the 0.9g product, purity 96%.
Embodiment 3 is by the intermediate preparation thermal initiator
In the container of magnetic agitation is housed, the 4.8ml pyridine is slowly splashed into the 5.6ml methacrylic chloride, the dropping process is cooled off with ice-water bath.Add 43ml acetone then, accelerate to stir, the pyridinium salt of generation is uniformly dispersed.Slowly drip the 8.7g intermediate then, in the dropping process, cool off with ice-water bath equally.After dropwising, sealed vessel at room temperature reacted three days.
Remove by filter pyridinium salt, pressure reducing and steaming acetone adds 50ml benzene again and makes solvent.Divide 3 washings with saturated nacl aqueous solution 900ml, use anhydrous magnesium sulfate drying again.Thick product separates with silica gel column chromatography purifies the mixed solvent of eluent benzene: acetone=2:1 (volume ratio).Finally obtain the 1.5g product, purity 95%.
Embodiment 4 is by the intermediate preparation thermal initiator
In the container of magnetic agitation is housed, the 4.8ml pyridine is slowly splashed into the 5.6ml methacrylic chloride, the dropping process is cooled off with ice-water bath.Add 43ml acetone then, accelerate to stir, the pyridinium salt of generation is uniformly dispersed.Slowly drip the 8.7g intermediate then, in the dropping process, cool off with ice-water bath equally.After dropwising, sealed vessel is warming up to 35 ℃, reacts 18 hours.
Remove by filter pyridinium salt, pressure reducing and steaming acetone is made solvent adding 50ml benzene.Divide 3 washings with saturated nacl aqueous solution 900ml, use anhydrous magnesium sulfate drying again.Thick product separates with silica gel column chromatography purifies the mixed solvent of eluent benzene: acetone=2:1 (volume ratio).Finally obtain the 1.7g product, purity 94%.
Embodiment 5 is by the intermediate preparation thermal initiator
8.8g intermediate and 2.6g are not had water sodium hydroxide add and be equipped with in the container of magnetic agitation, be stirred to the generation faint yellow solid.Add 150ml toluene then.Add the 10.0g acrylate chloride fast.After adding acyl chlorides, sealed vessel at room temperature reacted 3 days.
The solids removed by filtration precipitation, toluene is removed in underpressure distillation, uses anhydrous magnesium sulfate drying then.Thick product separates with silica gel column chromatography purifies the mixed solvent of eluent benzene: acetone=2:1 (volume ratio).Finally obtain the 3.3g product, purity 92%.
Embodiment 6 is by the intermediate preparation thermal initiator
8.8g intermediate and 2.6g are not had water sodium hydroxide add and be equipped with in the container of magnetic agitation, be stirred to the generation faint yellow solid.Add 150ml toluene then.Add the 10.0g acrylate chloride fast.After adding acyl chlorides, sealed vessel is warming up to 40 ℃, reacts 18 hours.
The solids removed by filtration precipitation, toluene is removed in underpressure distillation, uses anhydrous magnesium sulfate drying then.Thick product separates with silica gel column chromatography purifies the mixed solvent of eluent benzene: acetone=2:1 (volume ratio).Finally obtain the 3.0g product, purity 93%.
Claims (8)
1, a kind of azo class thermal initiator is characterized in that, shown in the following general formula I of structure:
Wherein, R
1Be CH
3, CH
3CH
2, (CH
3)
2CHCH
2, Z
1Substituting group has the structure shown in the general formula I I;
Wherein, R
2, R
3Be H, C
1～6Alkyl, C
1～6Alkoxyl group, n=1～3.
2, a kind of azo class thermal initiator is characterized in that, shown in the following general formula III of structure:
Wherein, R
1Be CH
3, CH
3CH
2, (CH
3)
2CHCH
2, Z
2Substituting group has the structure shown in the general formula I V;
Wherein, R
2, R
3Be H, C
1～6Alkyl, C
1～6Alkoxyl group, R
4Be H, C
1～3Alkyl, n=1～3.
3, according to the described azo class of claim 2 thermal initiator, it is characterized in that the compound that described general formula III is represented is: azo two isopropylformic acids (vinylformic acid glycol ester) ester, azo diisoamyl acid (vinylformic acid glycol ester) ester, azo two isoamyl acetic acids (vinylformic acid glycol ester) ester, azo two isopropylformic acids (methacrylic acid glycol ester) ester, azo diisoamyl acid (methacrylic acid glycol ester) ester, azo two isoamyl acetic acids (methacrylic acid glycol ester) ester, azo two isopropylformic acids (vinylformic acid butanediol ester) ester, azo diisoamyl acid (vinylformic acid butanediol ester) ester, azo two isoamyl acetic acids (vinylformic acid butanediol ester) ester, azo two isopropylformic acids (methacrylic acid butanediol ester) ester, azo diisoamyl acid (methacrylic acid butanediol ester) ester or azo two isoamyl acetic acids (methacrylic acid butanediol ester) ester.
4, the synthetic method of the described azo class of claim 1 or claim 2 thermal initiator is characterized in that, comprises following two steps:
(1) preparation of intermediate:
In the container of organic solvent is housed, add the azo compound that binary primary alconol and recrystallization were purified; Under churned mechanically situation, feed the exsiccant hydrogen chloride gas lentamente continuously; Temperature of reaction is 0～15 ℃, and the reaction times is 10～24 hours; Wherein, the molar ratio of described binary primary alconol and described azo compound is 1:10～1:50;
Divide the sub-cloud dope with separating funnel after reaction is finished, collect the upper strata organic layer; With saturated nacl aqueous solution washing 3～5 times, wash 3～5 times with saturated sodium bicarbonate solution more then, drying, organic solvent is removed in underpressure distillation; At last, add amount of methanol, separate out white oligopolymer, promptly obtain intermediate behind the pressure reducing and steaming methyl alcohol;
(2) by intermediate preparation azo class thermal initiator:
The described azo class of the described intermediate preparation thermal initiator that is obtained by step (1) is selected from one of following five kinds of methods:
Method one: end group is contained the acyl chlorides of two keys, described intermediate and the adding of a certain amount of exsiccant organic solvent be equipped with in the container of magnetic agitation, the molar ratio of acyl chlorides and described intermediate is 1:2～1:3; Slowly drip pyridine then, the dropping process is cooled off with ice-water bath, and the molar ratio of acyl chlorides and pyridine is 1:1～1:3; Dropwise the back sealed vessel, at room temperature reacted 3 days, product is described azo class thermal initiator;
Method two: in the container of magnetic agitation is housed, pyridine is slowly splashed into the acyl chlorides that end group contains two keys, the molar ratio of acyl chlorides and pyridine is 1:1～1:3; The dropping process is cooled off with ice-water bath, adds certain amount of organic solvent then, accelerates to stir, and it is uniformly dispersed; Slowly drip described intermediate then, equally with the ice-water bath cooling, the molar ratio of acyl chlorides and described intermediate is 1:2～1:3 in the dropping process; After dropwising, sealed vessel at room temperature reacted 3 days, and product is described azo class thermal initiator;
Method three: in the container of magnetic agitation is housed, pyridine is slowly splashed into the acyl chlorides that end group contains two keys, the molar ratio of acyl chlorides and pyridine is 1:1～1:3; The dropping process is cooled off with ice-water bath, adds certain amount of organic solvent then, accelerates to stir, and it is uniformly dispersed; Slowly drip described intermediate then, equally with the ice-water bath cooling, the molar ratio of acyl chlorides and described intermediate is 1:2 to 1:3 in the dropping process; After dropwising, sealed vessel is warming up to 30～40 ℃, reacts 15～24 hours, and product is described azo class thermal initiator;
Method four: described intermediate and the adding of no water sodium hydroxide are equipped with in the container of magnetic agitation, and the molar ratio of described intermediate and sodium hydroxide is 1:1～1:1.5, is stirred to the generation faint yellow solid; Add certain amount of organic solvent then, add the acyl chlorides that end group contains two keys fast, the molar ratio of acyl chlorides and intermediate is 1:2～1:3; After adding acyl chlorides, sealed vessel at room temperature reacted 3 days, and product is described azo class thermal initiator;
Method five: described intermediate and the adding of no water sodium hydroxide are equipped with in the container of magnetic agitation, and the molar ratio of described intermediate and sodium hydroxide is 1:1～1:1.5, is stirred to the generation faint yellow solid; Add certain amount of organic solvent then, add the acyl chlorides that end group contains two keys fast, the molar ratio of acyl chlorides and described intermediate is 1:2 to 1:3; After adding acyl chlorides, sealed vessel is warming up to 30～40 ℃, reacts 24～36 hours, and product is described azo class thermal initiator.
5, the synthetic method of azo class thermal initiator according to claim 3, it is characterized in that, described organic solvent is tetrahydrofuran (THF), benzene, toluene or dimethylbenzene, described binary primary alconol is ethylene glycol, butyleneglycol or isobutyl-glycol, described azo compound is Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) or 2,2'-Azobis(2,4-dimethylvaleronitrile), and described acyl chlorides is acrylate chloride or methacrylic chloride.
6, the synthetic method of azo class thermal initiator according to claim 4 is characterized in that, the molar ratio of described binary primary alconol and described azo compound is 1:10～1:20.
7, the application of the described azo class of claim 1 or claim 2 thermal initiator is characterized in that, described azo class thermal initiator is used to prepare the polymer dielectric brush.
8, the application of azo class thermal initiator according to claim 7, it is characterized in that, described azo class thermal initiator is grafted on micro polymer milk-globule surface, then at a certain temperature, original position causes electrolyte monomer, as vinylformic acid, methacrylic acid, sodium p styrene sulfonate, thereby become intensive polymer dielectric brush at described micro polymer milk-globule surface aggregate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193989A (en) * | 2013-02-28 | 2013-07-10 | 北京科技大学 | Preparation method of light/pH-sensitive amphiphilic azobenzene polymer micelles |
| US9269986B2 (en) | 2011-11-25 | 2016-02-23 | Samsung Electronics Co., Ltd. | Electrolyte composition, gel polymer electrolyte, and lithium battery including the gel polymer electrolyte |
| CN106147320A (en) * | 2016-09-13 | 2016-11-23 | 广西南宁智翠科技咨询有限公司 | A kind of novel environment friendly emulsion paint |
| CN106147330A (en) * | 2016-09-13 | 2016-11-23 | 广西南宁智翠科技咨询有限公司 | A kind of environment friendly emulsion paint |
| CN106147321A (en) * | 2016-09-13 | 2016-11-23 | 广西南宁智翠科技咨询有限公司 | A kind of environment-friendly novel emulsion paint |
| CN106147331A (en) * | 2016-09-13 | 2016-11-23 | 广西南宁智翠科技咨询有限公司 | A kind of high-performance emulsion paint |
| CN106221332A (en) * | 2016-09-13 | 2016-12-14 | 广西南宁智翠科技咨询有限公司 | A kind of environment-friendly and high-performance emulsion paint |
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2008
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9269986B2 (en) | 2011-11-25 | 2016-02-23 | Samsung Electronics Co., Ltd. | Electrolyte composition, gel polymer electrolyte, and lithium battery including the gel polymer electrolyte |
| CN103193989A (en) * | 2013-02-28 | 2013-07-10 | 北京科技大学 | Preparation method of light/pH-sensitive amphiphilic azobenzene polymer micelles |
| CN103193989B (en) * | 2013-02-28 | 2014-10-15 | 北京科技大学 | Preparation method of light/pH-sensitive amphiphilic azobenzene polymer micelles |
| CN106147320A (en) * | 2016-09-13 | 2016-11-23 | 广西南宁智翠科技咨询有限公司 | A kind of novel environment friendly emulsion paint |
| CN106147330A (en) * | 2016-09-13 | 2016-11-23 | 广西南宁智翠科技咨询有限公司 | A kind of environment friendly emulsion paint |
| CN106147321A (en) * | 2016-09-13 | 2016-11-23 | 广西南宁智翠科技咨询有限公司 | A kind of environment-friendly novel emulsion paint |
| CN106147331A (en) * | 2016-09-13 | 2016-11-23 | 广西南宁智翠科技咨询有限公司 | A kind of high-performance emulsion paint |
| CN106221332A (en) * | 2016-09-13 | 2016-12-14 | 广西南宁智翠科技咨询有限公司 | A kind of environment-friendly and high-performance emulsion paint |
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