CN100509867C - Preparation method for oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions - Google Patents
Preparation method for oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions Download PDFInfo
- Publication number
- CN100509867C CN100509867C CNB2007101161250A CN200710116125A CN100509867C CN 100509867 C CN100509867 C CN 100509867C CN B2007101161250 A CNB2007101161250 A CN B2007101161250A CN 200710116125 A CN200710116125 A CN 200710116125A CN 100509867 C CN100509867 C CN 100509867C
- Authority
- CN
- China
- Prior art keywords
- water
- preparation
- sorbitan monooleate
- ratio
- kerosene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention relates to a preparation method for polymeric reverse emulsion with hydroxamic acid structure, belonging to the water-soluble polymer synthesis technical field. The method copolymerizes AA-Na and AM in the reverse emulsion with KPS-TMEDA as the oxidation-reduction initiating system, leading to the smooth polymerization at normal temperature, and obtaining the water-soluble polymer with high molecular weight, and then under the strong alkalic condition, the method modifies the polymer with the hydroxylamine in the reverse emulsion, introduces the hydroxamic acid group and obtains a new polymer with good water solubility and temperature-resistance and salt-resistance. The latex is conveniently and high efficiently applied in the flocculation field as aluminium melting, waste water treatment, etc. and the powder products can be obtained after ethanol precipitation, drying and smashing, so the preparation method has broad application prospect in daily chemicals, oil field development and water treatment, etc.
Description
Technical field
The present invention relates to a kind of preparation method of oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions, belong to the water-soluble polymer synthesis technical field.
Background technology
In alumina producing, no matter be Bayer process or sintering process, or integrated process, all can produce a large amount of red muds, the settlement separate of red mud is important link of aluminium industry.If when using conventional negatively charged ion, positively charged ion and non-ionic polyacrylamide to handle, shortcomings such as consumption is big, floc sedimentation is little, mud-water separation weak effect are arranged all.Known oxygen oxime acid functional group is to transition metal, particularly iron has very strong avidity, and the surperficial ubiquity iron of most of mineral particle in the red mud, so the polyacrylamide modified product can stick to rapidly and securely on the red mud particle by the hydroxamic acid group, form bigger floc sedimentation, these floc sedimentations are more solid, it is broken that general stirring can not make it, thereby help reducing the turbidity of supernatant liquor, to this special absorption, even stirring once more can not smashed its floc sedimentation yet and be influenced turbidity.
The traditional preparation process method of oxygen-containing nitrolic acid structure polyalcohol normally adopts solution polymerization, use conventional initiator, there are many weak points in this preparation method, as the product solid content that makes is low, rate of polymerization is slow, poorly soluble, be not suitable for that low temperature uses and industrializing implementation difficulty etc.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of preparation method of oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions is provided, by adopting novel oxidation-reduction trigger system, utilize the oxygen-containing nitrolic acid structure polyalcohol latex products of the successful at ambient temperature synthetic macromolecule amount of antiphase emulsifiable method, can obtain powder product again through simple process.
Technical scheme of the present invention is as follows:
A kind of preparation method of oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions, adopt redox initiation system, select acrylamide (AM) and sodium acrylate (AA-Na) copolymerization in reversed-phase emulsion, aviation kerosene is an external phase, emulsifying agent is a polyoxyethylene octylphenol ether (OP 10) and the mixing of sorbitan monooleate (Span 80), water is disperse phase, reductive agent in the initiator system is Tetramethyl Ethylene Diamine (TMEDA), oxygenant is Potassium Persulphate (KPS), and oxygenant (KPS) is 1:0.7～1:1.3 with reductive agent (TMEDA) mol ratio.The polymer emulsion that obtains under alkaline condition and azanol reaction, is carried out modification, to introduce the hydroxamic acid group.Step is as follows:
One, polymerization
(1) oil phase
Polyoxyethylene nonylphenol ether 10 and Span 80 are dissolved in the kerosene, and OP 10 is 1:(6～11 with Span 80 mass ratioes), under agitation logical N
2Deoxygenation half an hour.The volume ratio of kerosene and water is 3:2～1:2, and with respect to the system cumulative volume, the dosage of Span 80 is 1.5～4.0gdL
-1
(2) water
Acrylamide (AM) and sodium acrylate (AA-Na) are by mass ratio (11～8): 1 mixes and is dissolved in the water gaging that feeds intake, acrylamide (AM) and sodium acrylate (AA-Na) are 1:(4～1 with the mass ratio of water), pH value to 6.5～9 of regulation system add reductive agent, logical N
2Deoxygenation half an hour.
(3) press profit phase volume ratio 3:2～1:2, above-mentioned water is added dropwise in the oil phase slowly, stir fast, be convenient to system emulsification while dripping.
(4) treat that above-mentioned system emulsification adds oxygenant Potassium Persulphate (KPS) in the back well, with respect to the system cumulative volume, the KPS dosage is 1.5～6.5mmolL
-1, 15～60 ℃ of temperature, the pH value of polymerization system is 6.5～12, polymerization reaction time 1～20h, the stopping of reaction gets homogeneous thickness oyster white and stablizes glue.
Two, modification
The homogeneous thickness oyster white that above-mentioned steps one is made is stablized glue and is handled, and step is as follows:
(1) oil phase
Polyoxyethylene nonylphenol ether 10 and Span 80 are dissolved in the kerosene, and OP 10 is 1:(6～11 with Span 80 mass ratioes), with respect to kerosene, the dosage of Span 80 is 16.0～35.0gdL
-1
(2) water
Water-soluble (oxammonium hydrochloride is 1～1:2) with the quality ratio with oxammonium hydrochloride, sodium hydroxide is water-soluble, and (sodium hydroxide is 1～1:2) with the quality ratio, again two solution are mixed slowly that (two solution qualities are than being 1:0.5～1:1.5), guarantee that heat release is too inviolent, control reaction temperature is below 60 ℃.
(3) the homogeneous thickness oyster white that makes by polymerization procedure is stablized the volume ratio 1:1～4:1 that makes in glue and the modification procedure (1), above-mentioned oil phase is added dropwise to slowly stablizes in the glue, again the water that makes in the above-mentioned modification procedure (2) is added dropwise to slowly and stablizes in the glue, stir fast while dripping, be convenient to system emulsification.
(4) treat that above-mentioned system emulsification is good after, reduce stirring velocity, 50～90 ℃ of control reaction temperature, pH value 8～14, modified-reaction time 2～20h, the stopping of reaction, must homogeneous thickness breast stable yellow emulsion slightly.
The latex products of above-mentioned hydroxamic acid type polymkeric substance can directly be used, and also can go out solid with ethanol sedimentation, drying, pulverize the powdery product of hydroxamic acid type polymkeric substance.
In above-mentioned inverse emulsion polymerization system, total monomer concentration (with respect to the system cumulative volume) is 20～50gdL
-1, be preferably 27～35gdL
-1Relative two kinds of monomeric total mass numbers, the quality feed ratio of monomer sodium acrylate (AA-Na) is 1～50%, the best is 5～25%; Monomer acrylamide (AM) quality feed ratio is 1～99%, and the best is 80～95%.
Reductive agent Tetramethyl Ethylene Diamine (TMEDA) in the above-mentioned polymerization initiation system is 1:(0.9～1.1 with the mole proportioning of oxygenant Potassium Persulphate (KPS) the best);
Above-mentioned polymerization oxidation agent Potassium Persulphate (KPS) is with respect to the system cumulative volume, and dosage the best is 1.5～6.5mmolL
-1
The volume ratio of kerosene and water the best is 1:1～2:3 in the above-mentioned polymerized emulsion system; With respect to the system cumulative volume, the optimal addn of emulsifying agent Span 80 is 1.8～2.3gdL
-1OP 10 is 1:(9～11 with Span 80 optimum quality ratios).
Temperature the best is 20～35 ℃ in the above-mentioned polymerization procedure (4), promptly just can successful initiated polymerization under the room temperature situation.
Time is according to the difference of conditions such as monomer ratio in the polymeric system and concentration, initiator concentration, polymer temperature in the above-mentioned polymerization procedure (4), the complete required time of polymerization is also different, can be 1～20h, if feed intake by above-mentioned top condition, best polymerization time is 3～6h.
PH value the best of above-mentioned polymerization system is 6.5～8.
In above-mentioned modified system, azanol concentration (with respect to the system cumulative volume) is 7～25gdL
-1, the best is 10～15gdL
-1Sodium hydroxide/oxammonium hydrochloride optimum quality ratio is (0.85～1.1): 1.
The volume ratio of kerosene and emulsion the best is 1:(2～3 in the above-mentioned modified system); With respect to kerosene, the optimal addn of emulsifying agent Span 80 is 18.0～25.0gdL
-1, OP10 and Span 80 optimum quality ratios are 1:(9～11).
Temperature the best is 65～80 ℃ in the above-mentioned modification procedure (4).
The difference of conditions such as the molecular weight of the polymkeric substance that the time obtains according to polymerization in the above-mentioned modification procedure (4), degree of hydrolysis, polymer architecture, the complete required time of modification is also different, can be 2～20h, if feed intake by above-mentioned top condition, best modification time is 4～7h.
PH value the best of above-mentioned modified system is 11～13.
Kerosene and sodium acrylate selected among the preparation method of oxygen-containing nitrolic acid structure polyalcohol of the present invention are preferably as follows treatment process:
(1) processing of kerosene
Aviation kerosene with more than the activated carbon adsorption 4h, is filtered,, and then get final product with distilled water wash with the NaOH solution washing.
(2) preparation of AA-Na
Vinylformic acid with more than the activated carbon adsorption 4h, is filtered; NaOH is dissolved in the methyl alcohol, to saturated; Vinylformic acid is joined lentamente in the methanol solution of NaOH, constantly stir, soda acid is fully neutralized, be reflected under the low temperature-4～4 ℃ and carry out, the mass ratio of soda acid is 0.9～1.0.The reaction finish after, the suction filtration reaction solution, the solid that obtains is the head product of AA-Na, then with methyl alcohol with these head product washed twice, can obtain meeting the AA-Na raw material of production requirement.
Excellent results of the present invention is as follows:
1. raw material is easy to get, low price.
2. the synthetic polymkeric substance has the hydroxamic acid structure, has salt tolerance preferably, can be used for multiple flocculation place.
3. inverse emulsion polymerization, rate of polymerization is fast, and the polymer molecule quality height of preparation.
4. owing to adopted the new multicomponent oxidation-reduction trigger system, at room temperature can obtain the high-molecular weight water-soluble polymers by successful initiated polymerization, and the monomer conversion height.
5. Zhi Bei latex can directly be used, and is convenient efficient; Also available dehydrated alcohol precipitation, drying and crushing get powder product, and the recyclable utilization again of organic solvent.
Above-mentioned many characteristics show that the present invention is suitable for suitability for industrialized production, and are with a wide range of applications.
Embodiment
The present invention will be further described below in conjunction with specific embodiment, but protection domain of the present invention is not limited only to this.
Monomer and modification used in the following example are reinforced: acrylamide (AM), analytical pure, Tianjin section close europeanized reagent development centre; Vinylformic acid (AA), chemical pure, Tianjin section close europeanized reagent development centre; Sodium hydroxide, analytical pure, Tianjin extensively becomes chemical reagent company limited; Oxammonium hydrochloride, technical grade.
In the following example in the used multicomponent oxide reduction initiating system: Potassium Persulphate (KPS, oxygenant), analytical pure, four-way chemical plant, Tianjin; Tetramethyl Ethylene Diamine (TMEDA, reductive agent), analytical pure, chemical reagent work advances in Shanghai.
Used emulsifying agent in the following example: Span 80, chemical pure, and Tianjin extensively becomes chemical reagent company limited; OP 10, chemical pure, and Tianjin extensively becomes chemical reagent company limited.
Used other raw materials in the following example: aviation kerosene; Gac, Tianjin ComeOn chemical industry industry and trade company limited; Anhydrous methanol, analytical pure, Dihua worker company limited is won in Tianjin; Dehydrated alcohol, analytical pure, the huge industry chemical industry in Jinan, Shandong company limited.
The preparation of embodiment 1. sodium acrylates (AA-Na)
Take by weighing 23.7g sodium hydroxide, pour in the there-necked flask of the 400mL that prolong, constant pressure funnel and electronic stirring are housed, put into 0 ℃ constant temperature ice-water bath then, add the 100g anhydrous methanol, start stirring.With vinylformic acid with more than the charcoal absorption 4h, filter, treat that sodium hydroxide in the methyl alcohol dissolves fully after, the vinylformic acid that takes by weighing after 41.4g filters is poured constant pressure funnel into, splash in the there-necked flask slowly, 0.5h drip off, reaction finishes, and pours B into and filters, after anhydrous methanol flushing three times, put into 50 ℃ the dry 24h of vacuum drying oven, obtain white powder product 50.3g, productive rate 〉=93.1%.
The preparation of embodiment 2. oxygen-containing nitrolic acid structure polyalcohols
Polymeric part: oil phase: measure 40mL kerosene, take by weighing to join after 2.0g Span 80 and 0.2g OP10 dissolve stirring is housed, condenser in the four-hole bottle of logical nitrogen pipe and dropping funnel, stirs down logical N
2Deoxygenation half an hour.Water: take by weighing 27.0gAM and 3.3g AA-Na and be dissolved in the 60mL water, add 0.6mL (0.15molL then
-1) TMEDA, logical N
2Deoxygenation half an hour.Under the situation of high-speed stirring (rotating speed 〉=1100r/min), water is added dropwise to oil phase slowly, 30～60min dropwises, add KPS 0.033g (being dissolved in 2mL water) at last, after stirring 20min fast mixing speed is transferred to about 300r/min, and change over to simultaneously in 30 ℃ of waters bath with thermostatic control and react 5h, homogeneous thickness oyster white latex.
Modification part: oil phase: measure 40mL kerosene, take by weighing 10.0g Span 80 and 1.2g OP10 the dissolving after join in the dropping funnel, (rotating speed 〉=1100r/min), oil phase is added dropwise in the emulsion lentamente, 30min dropwises under the situation of high-speed stirring.Water: take by weighing the 20g oxammonium hydrochloride and be dissolved in the 30g water, 20g sodium hydroxide is dissolved in the 30g water, two solution are slowly mixed, constantly stir, treat to join in the dropping funnel behind the resolution of precipitate, (rotating speed 〉=1100r/min), water is added dropwise in the emulsion lentamente, 30min dropwises under the situation of high-speed stirring.After fast stirring 20min mixing speed is transferred to about 300r/min, and changes over to simultaneously in 70 ℃ of waters bath with thermostatic control and react 5h, the slightly yellowy latex of homogeneous thickness.Obtain ampholyte copolymer powder-like product 25.3g, limiting viscosity 8.4dLg through dehydrated alcohol precipitation, washing, drying, pulverizing
-1, settling time 31.7s (undertaken by 8.1 regulation among the GB 12005.1 by the mensuration of limiting viscosity; The result of limiting viscosity represents to be undertaken by 9.1 regulation among the GB 12005.1).
Settling time is measured: the preparation mass ratio is 0.1% sample; In 110mL mining site simulated solution, add the 8g red mud, stir 0.5h down in 90 ℃; Add 98mL red mud simulated solution in 100mL tool plug graduated cylinder, the frequency compounding 1min by positive 30 times of per minute (just be 2 times) adds the 2.2mL sample again, after positive 30 times, leave standstill and start stopwatch simultaneously, the record floc sedimentation drops to the time at 60mL scale place, is the settling time.
Embodiment 3. is as described in the embodiment 2, and different is that the monomeric charge ratio changes AM 30.0g, AA-Na 4.0g, oxammonium hydrochloride 22.5g, sodium hydroxide 23.0g into, obtains ampholyte copolymer powder product 26.1g, and limiting viscosity is 8.7dLg
-1, settling time 29.5s.
Embodiment 4. is as described in the embodiment 2, and different is that the monomeric charge ratio changes AM 30.0g, AA-Na 4.0g, oxammonium hydrochloride 22.5g, sodium hydroxide 24.0g into, obtains ampholyte copolymer powder product 26.3g, and limiting viscosity is 9.8dLg
-1, settling time 27.3s.
Embodiment 5. is as described in the embodiment 2, and different is that the monomeric charge ratio changes into outside AM 27.0g, the AA-Na 8.0g, obtains ampholyte copolymer powder product 23.7g, and limiting viscosity is 6.2dLg
-1, settling time 37.6s.
Claims (6)
1. the preparation method of an oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions, it is characterized in that, adopt redox initiation system, select sodium acrylate and acrylamide monomer copolymerization in reversed-phase emulsion, kerosene is external phase, and sorbitan monooleate and polyoxyethylene octylphenol ether are compound emulsifying agent, water is disperse phase, reductive agent in the initiator system is a Tetramethyl Ethylene Diamine, and oxygenant is a Potassium Persulphate, and oxygenant and reductive agent mol ratio are 1:0.7～1:1.3; Step is as follows:
One, polymerization
(1) oil phase
Emulsifying agent polyoxyethylene octylphenol ether and sorbitan monooleate are dissolved in the kerosene, and polyoxyethylene octylphenol ether and sorbitan monooleate mass ratio are 1:6～1:11, under agitation logical N
2Deoxygenation half an hour, with respect to the system cumulative volume, the dosage of sorbitan monooleate is 1.5～4.0gdL
-1
(2) water
Acrylamide and sodium acrylate are dissolved in the water gaging that feeds intake by mass ratio 11:1～8:1 mixing, and the gross weight of acrylamide and sodium acrylate and the mass ratio of water are 1:4～1:1, and pH value to 6.5～9 of regulation system add reductive agent, logical N
2Deoxygenation half an hour;
(3) press profit phase volume ratio 3:2～1:2, above-mentioned water is added dropwise in the oil phase slowly, stir fast, be convenient to system emulsification while dripping;
(4) treat that above-mentioned system emulsification adds the oxygenant Potassium Persulphate in the back well, with respect to the system cumulative volume, the Potassium Persulphate dosage is 1.5～6.5mmolL
-1, 15～60 ℃ of temperature, the pH value of polymerization system is 6.5～12, polymerization reaction time 1～20h, the stopping of reaction gets homogeneous thickness oyster white and stablizes glue;
Two, modification
The homogeneous thickness oyster white that above-mentioned steps one is made is stablized glue and is carried out modification and handle, and step is as follows:
(1) oil phase
Emulsifying agent polyoxyethylene octylphenol ether and sorbitan monooleate are dissolved in the kerosene, and polyoxyethylene octylphenol ether and sorbitan monooleate mass ratio are 1:6～1:11, and with respect to kerosene, the dosage of sorbitan monooleate is 16.0～35.0gdL
-1
(2) water
Oxammonium hydrochloride is water-soluble, and oxammonium hydrochloride is 1:1～1:2 with the quality ratio, and sodium hydroxide is water-soluble, sodium hydroxide is 1:1～1:2 with the quality ratio, two solution are slowly mixed, two solution qualities are than being 1:0.5～1:1.5 again, and control reaction temperature is below 60 ℃;
(3) the homogeneous thickness oyster white that makes by polymerization procedure is stablized the oil phase volume ratio 1:1～4:1 that makes in glue and the modification procedure (1), above-mentioned oil phase is added dropwise to slowly stablizes in the glue, again the water that makes in the above-mentioned modification procedure (2) is added dropwise to slowly and stablizes in the glue, stir fast while dripping, be convenient to system emulsification;
(4) treat that above-mentioned system emulsification is good after, reduce stirring velocity, 50～90 ℃ of control reaction temperature, pH value 8～14, modified-reaction time 2～20h, the stopping of reaction, must homogeneous thickness breast stable yellow emulsion slightly.
2. the preparation method of oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions as claimed in claim 1 is characterized in that, in the polymerization system, with respect to the system cumulative volume, total monomer is 20～50gdL in the reversed-phase emulsion copolymerization
-1Relative two kinds of monomeric total mass numbers, wherein monomer sodium acrylate quality feed ratio is 1～50%, monomer acrylamide quality feed ratio is 1～99%; In the modified system, with respect to the system cumulative volume, azanol concentration is for being 7～25gdL
-1, sodium hydroxide and quality of oxammonium hydrochloride feed ratio are 0.85:1～1.1:1.
3. the preparation method of oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions as claimed in claim 1 is characterized in that, in the described polymerization system, the volume ratio of kerosene and water is 1:1～2:3; With respect to the system cumulative volume, the add-on of emulsifying agent sorbitan monooleate is 1.8～2.3gdL
-1Polyoxyethylene octylphenol ether and sorbitan monooleate mass ratio are 1:9～1:11.
4. the preparation method of oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions as claimed in claim 1 is characterized in that, in the described modified system, the volume ratio of kerosene and emulsion is 1:2～1:3; With respect to kerosene, the add-on of emulsifying agent sorbitan monooleate is 18.0～25.0gdL-1, and polyoxyethylene octylphenol ether and sorbitan monooleate mass ratio are 1:9～1:11.
5. the preparation method of oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions as claimed in claim 1 is characterized in that, temperature is 20～35 ℃ in the described polymerization procedure (4); Temperature is 65～80 ℃ in the modification procedure (4).
6. the preparation method of oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions as claimed in claim 1 is characterized in that, the pH value of described polymerization system is 6.5～8; The pH value of modified system is 11～13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101161250A CN100509867C (en) | 2007-12-07 | 2007-12-07 | Preparation method for oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101161250A CN100509867C (en) | 2007-12-07 | 2007-12-07 | Preparation method for oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101220104A CN101220104A (en) | 2008-07-16 |
| CN100509867C true CN100509867C (en) | 2009-07-08 |
Family
ID=39630202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101161250A Expired - Fee Related CN100509867C (en) | 2007-12-07 | 2007-12-07 | Preparation method for oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100509867C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103524757B (en) * | 2012-07-04 | 2016-03-30 | 中国中化股份有限公司 | A kind of preparation method of hydroxamic acid modified polyacrylamide emulsion flocculant |
| CN103242489A (en) * | 2013-05-20 | 2013-08-14 | 安徽天润化学工业股份有限公司 | Preparation method of settling separation agent for red mud in aluminium ores |
| CN106632802B (en) * | 2016-12-09 | 2019-03-05 | 安徽天润化学工业股份有限公司 | A kind of preparation method of aluminium ore flocculating agent for red mud precipitation |
| CN107043439A (en) * | 2017-03-30 | 2017-08-15 | 山东诺尔生物科技有限公司 | A kind of preparation method of aluminium ore dedicated separation agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5124421A (en) * | 1989-12-20 | 1992-06-23 | Ceskoslovenska Akademie Ved | Hydrolytically degradable hydrophilic gels and the method for preparation thereof |
| US6395260B1 (en) * | 1999-07-08 | 2002-05-28 | Haarmann & Reimer Gmbh | Topical cosmetic compositions comprising benzaldoximes |
| CN1803870A (en) * | 2006-01-11 | 2006-07-19 | 浙江大学 | PH sensitive solution polyacrylic acyloxy oxo acetate and its synthesis method |
-
2007
- 2007-12-07 CN CNB2007101161250A patent/CN100509867C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5124421A (en) * | 1989-12-20 | 1992-06-23 | Ceskoslovenska Akademie Ved | Hydrolytically degradable hydrophilic gels and the method for preparation thereof |
| US6395260B1 (en) * | 1999-07-08 | 2002-05-28 | Haarmann & Reimer Gmbh | Topical cosmetic compositions comprising benzaldoximes |
| CN1803870A (en) * | 2006-01-11 | 2006-07-19 | 浙江大学 | PH sensitive solution polyacrylic acyloxy oxo acetate and its synthesis method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101220104A (en) | 2008-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100347209C (en) | Inverse emulsion process of preparing amphoteric polymer | |
| CN104556331B (en) | PAC (polyaluminium chloride)-modified sodium alginate inorganic-organic composite flocculant and preparation method thereof | |
| CN101885526B (en) | Ternary composite type flocculant, preparation and application | |
| CN104085971B (en) | Compound cationic flocculant and preparation method thereof | |
| CN101298347B (en) | Covalent bond type inorganic organic composite flocculant, preparation process and use thereof | |
| CN100509867C (en) | Preparation method for oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions | |
| CN100534917C (en) | Composite emulsion breaking scavenging agnet and preparation method thereof | |
| CN105924534B (en) | A kind of preparation method of modified starch heavy metal chelating agent | |
| CN103881006A (en) | Polymerization method of anion modified polyacrylamide inverse emulsion having high solid content and high molecular weight | |
| CN105199036A (en) | Ammonium acrylate/acrylamide copolymerized emulsion flocculant and preparation method thereof | |
| CN104828918A (en) | Inorganic-organic covalent hybrid flocculant and preparation method thereof | |
| CN104130630A (en) | Biomass environment-friendly water-based color paste and preparation method thereof | |
| CN109336239A (en) | A kind of preparation method of high solubility starch graft modification cationic flocculant | |
| CN102701387A (en) | Titanium tetrachloride-poly dimethyl diallyl ammonium chloride inorganic-organic compound flocculant and preparation method thereof | |
| CN105218758B (en) | Containing nanometer Fe (OH)3The preparation method of graft acrylamide copolymer flocculant | |
| CN101591415B (en) | Iso-hydroxamic modified polyacrylamide and preparation method thereof | |
| CN106915810A (en) | A kind of high efficiency composition flocculant and its preparation method and application | |
| CN104163887A (en) | Hydrophobically associating dimethyl diallyl ammonium chloride cation flocculating agent and preparation method thereof | |
| CN1051366A (en) | Dimethylacryl ammonium chloride-acrylamide copolymer | |
| CN103232146B (en) | Method for preparing modified flocculant of sodium alga acid | |
| CN102060950A (en) | Method for preparing homopolymer and copolymer of dimethyl diallyl ammonium chloride | |
| CN103964554A (en) | Polymeric titanium sulfate-PDMDAAC (poly dimethyl diallyl ammonium chloride) composite coagulant as well as preparation and application methods thereof | |
| CN104926991B (en) | A kind of preparation method of drilling fluid amphoteric ion copolymer | |
| CN103073676B (en) | A kind of preparation method of terpolymer anti-phase emulsion | |
| CN101708880A (en) | Novel environment friendly water treatment flocculant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Dongying Nuoer Chemical Co., Ltd. Assignor: Shandong University Contract record no.: 2010370000194 Denomination of invention: Preparation method for oxygen-containing nitrolic acid structure polyalcohol inphase opposition emulsions Granted publication date: 20090708 License type: Exclusive License Open date: 20080716 Record date: 20100428 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090708 Termination date: 20141207 |
|
| EXPY | Termination of patent right or utility model |