CN105542162A - Method for synthesizing polypyrrole in oil solvent - Google Patents
Method for synthesizing polypyrrole in oil solvent Download PDFInfo
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- CN105542162A CN105542162A CN201610115359.2A CN201610115359A CN105542162A CN 105542162 A CN105542162 A CN 105542162A CN 201610115359 A CN201610115359 A CN 201610115359A CN 105542162 A CN105542162 A CN 105542162A
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- polypyrrole
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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- Pyrrole Compounds (AREA)
Abstract
The invention relates to a method for synthesizing polypyrrole in an oil solvent. The method comprises the following steps: sodium dodecyl sulfate, polyethylene glycol 6000, polyvinyl pyrrolidone, ethanol, butanol, peracetic acid, benzoyl peroxide, pyrrole monomer and the oil solvent are fully stirred under the condition of the room temperature or ice bath; the mixture is then subjected to ultrasonic, washing and drying, and a black polypyrrole product is obtained. According to the method, benzoyl peroxide is used as strong oxidant, and trichloromethane (isopropanol, cyclohexane, acetone, methylbenzene and the like) is used as the oil solvent. Therefore, polypyrrole polymers with the advantages of high purity, large yield, good stability, fast reaction, mild reaction conditions, high temperature resistance, good anti-pressure capacity, low cost input and the like can be prepared.
Description
Technical field
The invention belongs to the technical fields such as material, chemical industry, biology, ion detection, anti-corrosion of metal, particularly prepare in polypyrrole at chemical oxidization method.
Background technology
A kind of black powder solid of polypyrrole or black thin film shape solid, the difference of its pattern depends primarily on the difference of synthetic method, the polypyrrole of chemical oxidization method synthesis is mostly Powdered, and the polypyrrole of electrochemical process synthesis mostly is film like, polypyrrole is water insoluble, also most organic solvent is insoluble to, society, the scarcity of Energy resources, resource utilization is low, waste is large, the development of synthesizing new macromolecular material to society is increasingly important, the research of macromolecular material was once becoming the focus of social concerns, about the article of macromolecular material and patent also emerge in an endless stream, in the middle of the research of macromolecular material, polypyrrole material is acknowledged as one of macromolecular material of most Research Prospects.In the middle of existing research, polypyrrole material electric conductivity is good, environmental stability is good, on super capacitor material, obtains good application.The polypyrrole of film like is attached to metallic surface, and metal is hedged off from the outer world, and efficiently avoid the oxidation of metal.Polypyrrole is insoluble to oil-based solvent, by its parcel gel breaker, also has a wide range of applications in the middle of oil production.About the application of polypyrrole aspect is innumerable especially, so in order to obtain polypyrrole product, people study and have attempted various way (this place refers to that chemical oxidization method synthesizes), but the method for this research synthesis is all mainly concentrate in aqueous phase solvent, be difficult to play its advantage in oil-based solvent solvent, the report of simultaneously synthesizing polypyrrole in oil-based solvent is also very little, so it is significant to synthesize polypyrrole in oil-based solvent;
(1) ammonium persulphate method; In deionized water, add ammonium persulphate solid particulate, carry out mechanical stirring 1h, ammonium persulphate solid particulate is dissolved completely, and dropping acetic acid or hydrochloric acid control solution pH are 2-3, add a small amount of dispersion agent, play the effect disperseing and provide negatively charged ion, fast drop is through the pyrrole monomer (or ice bath) of refrigeration, and mechanical stirring 4-6h, pulls atrament out, ultrasonic, wash three times, 50 DEG C of vacuum-drying 24h, can obtain product.Ammonium persulphate is water-soluble, is difficult to play its advantage in oil-based solvent, although also can prepare polypyrrole in oil-based solvent, ammonium persulphate is wrapped in the middle of polypyrrole, and the polypyrrole purity obtained is extremely low.
(2) tri-chlorination iron processes; In deionized water, iron trichloride solid particulate is added, mechanical stirring 1h, liquor ferri trichloridi can fully be dissolved, dropping acetic acid or hydrochloric acid conditioning solution pH are 2-3, drip a small amount of dispersion agent, and fast drop is through the pyrrole monomer (or ice bath) of refrigeration, mechanical stirring 4-6h, pull atrament out, ultrasonic, wash three times, 50 DEG C of vacuum-drying 24h, can obtain product.Because iron trichloride is soluble in water, there is strong color interference, be unfavorable for the observation of colour-change in polypyrrole synthesis, and have the doping of iron ion in the middle of synthesis polypyrrole, the purity of polypyrrole is had a certain impact.
(3) hydrogen peroxide method (or Peracetic Acid method); Add excess hydrogen peroxide (or Peracetic Acid) in deionized water; mechanical stirring makes hydrogen peroxide (or Peracetic Acid) fully dissolve in aqueous; nitrogen can be led to and do protection gas before dropping monomer; it is 2-3 (without the need to dripping hydrochloric acid or acetic acid in Peracetic Acid system) that dropping hydrochloric acid or acetic acid control pH value of solution; fast drop pyrrole monomer; till mechanical stirring black polypyrrole to be had generates; pull atrament out; ultrasonic; wash three times; 50 DEG C of vacuum-drying 24h, can obtain product.The polypyrrole length consuming time of the method synthesis, output is relatively low, and large-scale commercial production has certain limitation.
Above-mentioned several method can both prepare polypyrrole product, but the polypyrrole prepared is in the middle of aqueous phase solvent mostly, and the inorganic salt that adopt as oxygenant more, and the polypyrrole of above-mentioned several method synthesis is all that molecular weight is larger, the present invention adopts organo-peroxide and prepare polypyrrole in the middle of oil-based solvent, the polypyrrole speed of reaction that the present invention obtains is exceedingly fast, synthesize the polypyrrole of small-molecular-weight, when fast drop pyrrole monomer, observing color becomes blackish green immediately, explanation pyrrole monomer is oxidized, less than half hour, namely color becomes black, illustrate that polypyrrole product synthesizes, for making the monomer polymerization of reaction complete, continue mechanical stirring 4-6h.The polypyrrole of the present invention's synthesis has the advantages such as purity is high, speed of reaction is fast, production capacity is large, reaction conditions is gentle, product is easy to separation, high temperature resistant, stability is strong, anti-pressure ability is good, cost input is low.
Summary of the invention
The object of the invention is to the method proposing to synthesize polypyrrole in oil-based solvent.
Described method is fully stirred under room temperature or condition of ice bath sodium lauryl sulphate, polyethylene glycol 6000, polyvinylpyrrolidone, ethanol, butanols, Peracetic Acid, benzoyl peroxide, pyrrole monomer and oil-based solvent, then can obtain the polypyrrole product of black through ultrasonic, washing, drying.
Concrete steps are as follows;
(1) by sodium lauryl sulphate, polyethylene glycol 6000, polyvinylpyrrolidone, benzoyl peroxide adds in oil-based solvent, under room temperature condition (or ice bath), mechanical stirring makes polyethylene glycol 6000, sodium lauryl sulphate, polyvinylpyrrolidone and benzoyl peroxide fully dissolve.
(2) in above-mentioned solution, add butanols, ethanolic soln, drip a small amount of Peracetic Acid, regulator solution pH is 2-3 (pyrroles can be polymerized in acid condition), continues mechanical stirring, solution is mixed.
(3) after solution mixes, fast drop pyrrole monomer, solution becomes blackish green, reacts and becomes black less than solution half an hour, has illustrated that black polypyrrole generates, and for making to react completely, continuing mechanical stirring and reacting fully.
(4) left standstill by the resultant solution obtained, treat polypyrrole sedimentation layering, suck upper solution, ultrasonic, with deionized water wash, centrifugal 4-6 time of dehydrated alcohol, 50 DEG C of vacuum-dryings, can obtain the Powdered polypyrrole product of black.
In reaction system, by quality hundred ratio, each composition is: 0.18-0.3% sodium lauryl sulphate, 0.3-0.56% polyethylene glycol 6000,0.10-0.18% polyvinylpyrrolidone, 0.13-0.25% ethanol, 0.05-0.123% butanols, Peracetic Acid dripping quantity makes pH be 2-3,4.8-5.5% benzoyl peroxide, 2.5-3% pyrrole monomer, all the other are oil-based solvent, amount to 100%.
Preferred proportioning is: sodium lauryl sulphate 0.20%, polyethylene glycol 6000 0.35%, polyvinylpyrrolidone 0.10%, ethanol 0.15%, butanols 0.07%, Peracetic Acid dripping quantity makes pH be 2-3, benzoyl peroxide 5.0%, pyrrole monomer 2.5%, all the other are oil-based solvent.
Oil-based solvent described in the present invention is trichloromethane, Virahol, hexanaphthene, acetone or toluene etc.
After fast drop pyrrole monomer, when there being oxygenant to exist in system, oxidizedly under the effect of oxygenant an electronics can be lost in an electroneutral polypyrrole monomer molecule, become radical cation, so latter two radical cation collides dication two polypyrrole be combined into containing two radical cations in system, and dication now generates one in electroneutral two polypyrroles through disproportionation in system.Electroneutral two polypyrroles can be combined with each other with the radical cation in system again the radical cation of generation three polypyrrole, generate trimerical polypyrrole, go round and begin again and finally generate the polypyrrole of long molecular chain through disproportionation,
Peracetic Acid is strong oxidizer, also there is strongly-acid, drip the object that other acid also can play regulator solution pH, but than other acid, dripping a small amount of Peracetic Acid just can the pH of regulation system effectively, and the strong oxidizing property of Peracetic Acid also can play promoter action to the polymerization of pyrrole monomer in addition.Being carried out in advance by pyrrole monomer refrigerating (3 DEG C) is because pyrrole monomer is unstable, and meet light heat chance oxygenant and easily react, the pyrrole monomer simultaneously after refrigeration is conducive to the polymerization of pyrrole monomer.The object adding sodium lauryl sulphate, polyethylene glycol 6000 and polyvinylpyrrolidone is to make the resultant of reaction to have good dispersiveness, the hydrophilic of tensio-active agent and lipophilic group is utilized just to change dispersiveness and the stability of solution, and adding of these negatively charged ion, on the one hand; Doping enters in the middle of polypyrrole, has carried out modification to a certain degree, be convenient to better production application, on the other hand to it; Due to the existence of a large amount of negatively charged ion, also the synthesis of polypyrrole is served to the effect of promotion.Because there being the existence of tensio-active agent in whipping process, foam being produced, dripping ethanol mainly in order to play the effect of froth breaking.Butanols add the effect serving good cosurfactant.
Innovative point of the present invention is, with traditional method ratio;
(1) advantages such as speed of reaction of the present invention is high, energy consumption is low, economic input is few, colour-change is obvious, be easy to observe, output high, good stability, small-molecular-weight.
(2) innovative point that the present invention is maximum is in oil-based solvent (trichloromethane, Virahol, hexanaphthene, acetone, toluene etc.), oiliness strong oxidizer (being not limited to benzoyl peroxide), can prepare polypyrrole product under the acidic conditions that normal temperature or low temperature have negatively charged ion to exist fast.Compensate for the defect that traditional method can only prepare polypyrrole in aqueous phase solvent and water-soluble strong oxidizer.
(3) simple, the preparation process convenient operation of present invention process, is applicable to scale operation and industrial application.
Because polypyrrole is both water insoluble, also most organic solvent is insoluble to, exactly because this advantage, so synthesis and large-scale application polypyrrole are also extremely have industry and economic worth in oil-based solvent, the method that the present invention synthesizes polypyrrole in oil-based solvent meets this industrial requirements, and the present invention has very large market application potential and high economic worth.
Accompanying drawing explanation
The TEM figure of the polypyrrole product of Fig. 1 a embodiment 2 formula preparation.
The TEM figure of the polypyrrole product that Fig. 1 b prepares.
The SEM figure of the polypyrrole product that Fig. 2 prepares.
Embodiment
Describe the present invention below in conjunction with specific embodiment, it should be noted that, protection scope of the present invention is not limited in following embodiment.
Illustrate: the medicine used in the present invention is commercially available prod or laboratory conventional medication.
The preparation of reaction soln; Sodium lauryl sulphate, polyethylene glycol 6000, polyvinylpyrrolidone, ethanol, a small amount of butanols, Peracetic Acid, benzoyl peroxide, pyrrole monomer and trichloromethane (Virahol, hexanaphthene, acetone, toluene etc.).
The process of reaction monomers; Lucifuge, cryopreservation (3 DEG C), to separate with strong acid, highly basic, strong oxidizer.
The preparation of Peracetic Acid; The content of preparation Peracetic Acid is 40%.
By changing the additive dripping different amounts in the present invention, keeping reaction conditions constant, comparing test, thus drawing best formula.
1, each raw material is taken respectively with following each side case;
Embodiment 1:0.20% sodium lauryl sulphate, 0.35% polyethylene glycol 6000,0.10% polyvinylpyrrolidone, 0.15% ethanol, 0.07% butanols, Peracetic Acid dripping quantity makes pH be 2-3,5.0% benzoyl peroxide, 2.5% pyrrole monomer, all the other are trichloromethane (Virahol, hexanaphthene, acetone, toluene etc.), amount to 100%.
Embodiment 2:0.25% sodium lauryl sulphate, 0.30% Macrogol 2000,0.14% polyvinylpyrrolidone, 0.13% ethanol, 0.05% butanols, Peracetic Acid dripping quantity makes pH be 2-3,5.5% benzoyl peroxide, 3% pyrrole monomer, all the other are trichloromethane (Virahol, hexanaphthene, acetone, toluene etc.), amount to 100%.
Embodiment 3:0.18% sodium lauryl sulphate, 0.35% polyethylene glycol 6000,0.12% polyvinylpyrrolidone, 0.15% ethanol, 0.07% butanols, Peracetic Acid dripping quantity makes pH be 2-3,5.0% benzoyl peroxide, 2.8% pyrrole monomer, all the other are trichloromethane (Virahol, hexanaphthene, acetone, toluene etc.), amount to 100%.
Embodiment 4:0.23% sodium lauryl sulphate, 0.32% polyethylene glycol 6000,0.10% polyvinylpyrrolidone, 0.16% ethanol, 0.06% butanols, Peracetic Acid dripping quantity makes pH be 2-3,5.0% benzoyl peroxide, 2.4% pyrrole monomer, all the other are trichloromethane (Virahol, hexanaphthene, acetone, toluene etc.), amount to 100%.
Embodiment 5:0.30% sodium lauryl sulphate, 0.56% polyethylene glycol 6000,0.18% polyvinylpyrrolidone, 0.25% ethanol, 0.08% butanols, Peracetic Acid dripping quantity makes pH be 2-3,4.8% benzoyl peroxide, 2.5% pyrrole monomer, all the other are trichloromethane (Virahol, hexanaphthene, acetone, toluene etc.), amount to 100%.
2, preparation technology;
Above-mentioned 5 kinds of embodiments are prepared 5 kinds of polypyrrole products respectively as follows, under sodium lauryl sulphate, polyethylene glycol 6000, polyvinylpyrrolidone, ethanol, butanols, Peracetic Acid, benzoyl peroxide, pyrrole monomer and trichloromethane (Virahol, hexanaphthene, acetone, toluene etc.) are placed in the there-necked flask room temperature of 100ml, (or ice bath) stirs 4-6 hour, ultrasonic, washing, dry, polypyrrole product can be obtained, as Fig. 1 b, Fig. 2 verify mutually, the polypyrrole product of synthesis, its pattern is mainly based on ball-type.
3, experiment conclusion;
The polypyrrole product of Tecnai12 transmission electron microscope to synthesis is adopted to analyze, the optimum proportioning sodium lauryl sulphate 0.20% drawing and synthesize polypyrrole is contrasted by Fig. 1 a and Fig. 1 b, polyethylene glycol 6000 0.35%, polyvinylpyrrolidone 0.10%, ethanol 0.15%, butanols 0.07%, Peracetic Acid dripping quantity makes pH be 2-3, benzoyl peroxide 5.0%, pyrrole monomer 2.5%, all the other are trichloromethane (Virahol, hexanaphthene, acetone, toluene etc.).Polypyrrole product has fast and effeciently been prepared in this invention, and the polypyrrole that this proportioning draws is dispersed better with stability, and output is large.The present invention is promoted, under the acidic conditions that oiliness strong oxidizer (being not limited to the benzoyl peroxide in the present invention) normal temperature of oil-based solvent or low temperature has negatively charged ion to exist can be dissolved in, also can prepare polypyrrole product fast.
Claims (5)
1. in oil-based solvent, synthesize the method for polypyrrole, it is characterized in that, sodium lauryl sulphate, polyethylene glycol 6000, polyvinylpyrrolidone, ethanol, butanols, Peracetic Acid, benzoyl peroxide, pyrrole monomer and oil-based solvent are fully stirred under room temperature or condition of ice bath, then through polypyrrole product that is ultrasonic, that wash, be drying to obtain black.
2. synthesize the method for polypyrrole in oil-based solvent according to claim 1, it is characterized in that, concrete steps are as follows:
(1) by sodium lauryl sulphate, polyethylene glycol 6000, polyvinylpyrrolidone, benzoyl peroxide adds in oil-based solvent, under room temperature or condition of ice bath, mechanical stirring makes polyethylene glycol 6000, sodium lauryl sulphate, polyvinylpyrrolidone and benzoyl peroxide fully dissolve
(2) in above-mentioned solution, add butanols, ethanolic soln, drip a small amount of Peracetic Acid, regulator solution pH is 2-3, continues mechanical stirring, solution is mixed;
(3) after solution mixes, fast drop pyrrole monomer, continues mechanical stirring and reacts fully,
(4) left standstill by the resultant solution obtained, treat polypyrrole sedimentation layering, suck upper solution, ultrasonic, with deionized water wash, centrifugal 4-6 time of dehydrated alcohol, 50 DEG C of vacuum-dryings, namely obtain the Powdered polypyrrole product of black.
3. synthesize the method for polypyrrole in oil-based solvent according to claims 1, it is characterized in that described oil-based solvent is any one in trichloromethane, Virahol, hexanaphthene, acetone or toluene.
4. synthesize the method for polypyrrole in oil-based solvent according to claims 1, it is characterized in that; In reaction system, by quality hundred ratio, each composition is: 0.18-0.3% sodium lauryl sulphate, 0.3-0.56% polyethylene glycol 6000,0.10-0.18% polyvinylpyrrolidone, 0.13-0.25% ethanol, 0.05-0.123% butanols, Peracetic Acid dripping quantity makes pH be 2-3,4.8-5.5% benzoyl peroxide, 2.5-3% pyrrole monomer, all the other are oil-based solvent, amount to 100%.
5. in oil-based solvent according to claims 4, synthesize the method for polypyrrole, it is characterized in that, the percentage ratio of sodium lauryl sulphate is 0.20%, and the percentage ratio of polyethylene glycol 6000 is 0.35%, and the percentage ratio of polyvinylpyrrolidone is 0.10%, the percentage ratio of ethanol is 0.15%, the percentage ratio of butanols is 0.07%, and Peracetic Acid dripping quantity makes pH be 2-3, and the percentage ratio of benzoyl peroxide is 5.0%, pyrrole monomer percentage ratio is 2.5%, and all the other are oil-based solvent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108193314A (en) * | 2018-01-22 | 2018-06-22 | 王家浩 | A kind of polypyrrole conductive fiber |
| CN114166911A (en) * | 2021-11-17 | 2022-03-11 | 大连民族大学 | Microfluidic-based marine metal ion detection system and preparation method of coating of electrochemical sensor |
| CN115286791A (en) * | 2022-08-16 | 2022-11-04 | 北方民族大学 | Inorganic salt @ polypyrrole nano capsule and preparation method and application thereof |
Citations (2)
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| CN102627958A (en) * | 2012-03-26 | 2012-08-08 | 扬州大学 | Efficient microcapsule gel breaker and preparation method thereof |
| CN105330826A (en) * | 2015-12-04 | 2016-02-17 | 扬州大学 | Method for synthesizing polypyrrole microcapsules |
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- 2016-03-01 CN CN201610115359.2A patent/CN105542162B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627958A (en) * | 2012-03-26 | 2012-08-08 | 扬州大学 | Efficient microcapsule gel breaker and preparation method thereof |
| CN105330826A (en) * | 2015-12-04 | 2016-02-17 | 扬州大学 | Method for synthesizing polypyrrole microcapsules |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108193314A (en) * | 2018-01-22 | 2018-06-22 | 王家浩 | A kind of polypyrrole conductive fiber |
| CN114166911A (en) * | 2021-11-17 | 2022-03-11 | 大连民族大学 | Microfluidic-based marine metal ion detection system and preparation method of coating of electrochemical sensor |
| CN114166911B (en) * | 2021-11-17 | 2023-12-12 | 大连民族大学 | Microfluidic-based ocean metal ion detection system and preparation method of coating of electrochemical sensor |
| CN115286791A (en) * | 2022-08-16 | 2022-11-04 | 北方民族大学 | Inorganic salt @ polypyrrole nano capsule and preparation method and application thereof |
| CN115286791B (en) * | 2022-08-16 | 2023-08-18 | 北方民族大学 | Inorganic salt@polypyrrole nano capsule and preparation method and application thereof |
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