CN101293954B - Carboxylation method of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer - Google Patents
Carboxylation method of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer Download PDFInfo
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- CN101293954B CN101293954B CN2008100385371A CN200810038537A CN101293954B CN 101293954 B CN101293954 B CN 101293954B CN 2008100385371 A CN2008100385371 A CN 2008100385371A CN 200810038537 A CN200810038537 A CN 200810038537A CN 101293954 B CN101293954 B CN 101293954B
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Abstract
The invention discloses a method for the carboxylation of a polyoxyethylene-polyoxypropylene-polyoxyethylene copolymer. The method comprises the following steps: allowing the addition reaction of an unsaturated nitrile compound and PEO-PPO-PEO block polymer in an aqueous solution in the presence of alkaline catalysts, hydrolyzing nitrile groups contained in the addition reaction product under alkaline or acidic conditions, extracting the crude product of carboxyl PEO-PPO-PEO block polymer from the hydrolysate by using organic solvents, and purifying by ether precipitation method to obtain a purified carboxyl PEO-PPO-PEO block polymer. The method has mild conditions and avoids the cleavage of ether bonds in PEO-PPO-PEO block polymer. Corresponding chemical bonds can be introduced to the original polymer structure during the carboxylation process as required so as to produce a modified product with uniform structure and stable performance. Furthermore, the method is suitable for mass preparation and industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of technical field of polymer materials, specifically, relate to a kind of polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer carbonylation process.
Background technology
Polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO) segmented copolymer is with hydrophilic PEO segment and hydrophobic PPO segment link macromolecular compound together with covalent linkage, it is the polymeric surface active agent of a class non-ionic type, trade(brand)name Pluronic (BASF AG) or Poloxamer (ICI company), as the polymer nonionogenic tenside, can be used as defoamer, emulsifying agent, emulsion splitter, lubricant, thickening material, washing composition and as makeup, the aspects such as additive of food and medicine, compare with low-molecular-weight surfactant, the PEO-PPO-PEO multipolymer has more superior performance, as extremely low micelle-forming concentration, the diversified amphipathic characteristic that diversified molecular chemistry is formed structure and caused thus, extremely low toxicity, excellent biological compatibility and albumen resistance etc., make them in wastewater treatment, the preparation of mesoporous material, bio-medical material, pharmaceutical carrier research, animal cell culture has broad application prospects with aspects such as biomacromolecule separate, can combine with insoluble drug as PEO-PPO-PEO multipolymer formed micella hydrophobic core in the aqueous solution, thereby reach the solvability that increases medicine, the effect of metabolic stability and body-internal-circulation time, the aqueous solution of PEO-PPO-PEO multipolymer also has unique temperature sensitive micellization and heat reversible gel characteristics, therefore can change intracellular medicine as pharmaceutical carrier and discharge mechanism, suppressing the medicine of medicine by hemato encephalic barrier or small intestine the time discharges, raising is to the bioavailability of brain administration and oral administration, can increase the multidrug resistant cancer cells to susceptibility of cancer therapy drug or the like, this makes things convenient for the production of pharmaceutical preparation for improving the particularly clinical adaptability of insoluble drug of medicine, transportation, use or the like has important value.
Yet this body structure of PEO-PPO-PEO multipolymer had the terminal hydroxy group activity very little, having limited its further expansion in a lot of fields uses, therefore to PEO-PPO-PEO multipolymer terminal hydroxy group modificationization, the preparation series derivates is necessary, one of them important method is that PEO-PPO-PEO is carboxylated, common hydroxyl carbonylation process can be divided into two big classes: the first kind is to introduce carboxyl by chemical reaction on hydroxyl, method commonly used is by hydroxyl and anhydride reaction, its deficiency is: reaction product contains ester bond, and ester bond easily is decomposed in human body, the transformation period of medicine-carried system in human body reduced, and this method requires to carry out in water-less environment, the special again easily suction of PEG, therefore extremely inconvenient and of a high price; Second class is that hydroxyl is converted into carboxyl, often utilizes the potassium permanganate oxidation hydroxyl to obtain carboxylated product, and this method reaction is more violent, usually can cause the fracture of ehter bond.
Find through literature search prior art, Iwasaki Keiji etc. are at " European patentapplication, Publication number:0206448 " (european patent application book, patent publication No.: 0206448) issued patents " Hemoglobin combined with a poly (alkylene oxide) " (oxyphorase links with polyoxy alkene), this patent proposes, use relatively mild Manganse Dioxide that hydroxyl oxidize is aldehyde radical, re-use hydrogen peroxide aldehyde radical is oxidized to carboxyl, its deficiency is: this method yield is very low, only has 30%.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of polyoxyethylene-poly-oxypropylene polyoxyethylene segmented copolymer carbonylation process is provided.The present invention is simple to operate, mild condition, cheap, transformation efficiency is high, and in the aqueous solution, helps obtaining the modified outcome of structure homogeneous, stable performance, and is suitable for a large amount of preparations and suitability for industrialized production.
The present invention is achieved by the following technical solutions, the present invention is reflected in the aqueous solution and carries out, under the basic catalyst effect, make unsaturated nitrile compounds and PEO-PPO-PEO segmented copolymer generation addition reaction, under alkalescence or acidic conditions, addition reaction product institute nitrile group-containing is hydrolyzed, with an organic solvent from hydrolysis reaction product liquid, extract and obtain carboxyl PEO-PPO-PEO segmented copolymer crude product, adopt the ether precipitator method to obtain the carboxyl PEO-PPO-PEO segmented copolymer of purifying at last.
The described ether precipitator method are to utilize the PEO-PPO-PEO segmented copolymer to be insoluble to the character of ethers, adopt contained oil-soluble impurities in the ether solvent dissolving crude product, thus the centrifugal method of removing the purified product that desolvates.
Totally three steps constituted the inventive method by two-step reaction and purifying:
The first step is dissolved in the PEO-PPO-PEO segmented copolymer in the water, adds the base catalysis agent solution while stirring, adds the unsaturated nitrile compounds then while stirring, and addition reaction finishes the back and adds sour adjust pH to neutral, obtains adduct through extraction.
Described PEO-PPO-PEO segmented copolymer, molecular formula is:
R′O(C
2H
4O)
x(C
3H
6O)
y(C
2H
4O)
zH
Structural formula:
The R ' here is-H ,-CH
3,-C
2H
5,-C
3H
7Deng group, wherein x, z are that 2-200, y are the integer of 15-100.
Described basic catalyst includes but not limited to alkaline matters such as sodium hydroxide, potassium hydroxide, calcium hydroxide and phosphoric acid one disodium hydrogen, is used alone or as a mixture, in order to catalytic addition reaction.
One of reactant of described addition reaction is the unsaturated nitrile compounds, includes but not limited to alkene nitrile compounds and alkynes nitrile compounds, the particularly vinyl cyanide of alkene nitrile.
Described addition reaction temperature is that the pH value is carried out under the condition of 7-14 at 0 ℃-50 ℃.
Described extraction, its method include but not limited to an organic solvent directly extractive reaction product liquid, remove the moisture content in the organic solvent, volatilize organic solvent; With an organic solvent extract residue after perhaps the moisture content in the addition reaction product solution being volatilized.
Described organic solvent includes but not limited to ester class, fat hydrocarbon, aromatic hydrocarbons, ketone, chlorinated hydrocarbon etc., and especially chlorinated hydrocarbon such as methylene dichloride, chloroform solvent is used alone or as a mixture.
Second step was dissolved in the reaction that is hydrolyzed in alkali lye or the acid solution with adduct, and reaction finishes the back sour water transfer of adding and separates reacting liquid pH value to acid, obtains crude product through extraction;
Described hydrolysis reaction is to carry out in the aqueous solution, and hydrolysis reaction can be 0 ℃-100 ℃ of temperature, and the pH value is carried out under the condition of 1-14.
Described hydrolysis reaction product liquid, the pH value is adjusted into 1-6.
Described extraction, its method include but not limited to an organic solvent extract the hydrolysis reaction product solution, remove the moisture content in the organic solvent, volatilize organic solvent; Or with an organic solvent extract residue after the moisture content in the hydrolysis reaction product solution volatilized.
Described organic solvent includes but not limited to ester class, fat hydrocarbon, aromatic hydrocarbons, ketone, chlorinated hydrocarbon etc., and especially chlorinated hydrocarbon such as methylene dichloride, chloroform solvent is used alone or as a mixture.
The 3rd step was settled out crude product with ether solvent and crude product vortex mixed, and centrifugal removing desolvated, and obtains the carboxyl PEO-PPO-PEO segmented copolymer of purifying after the vacuum-drying.
The molecular formula of described carboxyl PEO-PPO-PEO segmented copolymer is:
RO(C
2H
4O)
a(C
3H
6O)
b(C
2H
4O)
cMCOOH
Structural formula:
The R here is-C
2H
4COOH ,-H ,-CH
3,-C
2H
5,-C
3H
7Deng group, M is-(CH
2)
2-,-(CH
2)
3-wait group, wherein a, c are that 2-200, b are the integer of 15-100.
Described ether solvent includes but not limited to use ether, methyl ethyl ether, sherwood oil, phenyl ethyl ether, methyl-phenoxide, isopropyl ether, n-butyl ether etc.
The present invention has the following advantages:
1, simple to operate, cheap, preparation process does not need complicated plant and instrument, is suitable for a large amount of preparations and suitability for industrialized production;
2, mild condition, can not cause the fracture of ehter bond in the PEO-PPO-PEO segmented copolymer;
3, carboxylated process can be introduced the corresponding chemical key as required in the original copolymer structure, when making the PEO-PPO-PEO segmented copolymer be used for slowly-releasing, the target administration of organic synthesis, protein and polypeptide drugs modification, Polymer Synthesizing and medicine, help obtaining structure accurately, the modified outcome of stable performance.
Description of drawings
Fig. 1 is the infrared spectrogram of PEO-PPO-PEO segmented copolymer;
Fig. 2 is the adduct infrared spectrogram of PEO-PPO-PEO segmented copolymer and vinyl cyanide;
Fig. 3 is the carboxylated product infrared spectrogram of PEO-PPO-PEO segmented copolymer;
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Take by weighing 2g P123 type PEO-PPO-PEO segmented copolymer, to add an amount of 40% potassium hydroxide solution after the 30mL pure water stirring and dissolving while stirring, make reacting liquid temperature be maintained at 2 ± 0.5 ℃, Dropwise 5 mL vinyl cyanide while stirring, continue to stir (200rpm) reaction 24h, it is extremely neutral with the concentrated hydrochloric acid adjust pH that reaction finishes the back, use equal-volume dichloromethane extraction addition reaction product solution, add anhydrous sodium sulphate and place institute's water content in the absorption extraction liquid that spends the night, filter, filtrate volatilizes solvent through 50 ℃ of water-bath rotary evaporations, and vacuum-drying is spent the night and eliminated solvent, gets adduct;
Adduct is dissolved in the 20mL2M sodium hydroxide solution, 105 ℃ of oil bath back flow reaction 6h, reaction product solution is with concentrated hydrochloric acid adjust pH to 2, use equal-volume dichloromethane extraction addition reaction product solution, add anhydrous sodium sulphate and place institute's water content in the absorption extraction liquid that spends the night, filter, filtrate volatilizes solvent through 50 ℃ of water-bath rotary evaporations, vacuum-drying is spent the night and is eliminated solvent, gets crude product;
With equal-volume ether and crude product vortex mixed, the crude product precipitation is separated out, and centrifugal removing desolvated, and precipitation obtains the carboxylated PEO-PPO-PEO segmented copolymer of P123 type of purifying after 30 ℃ of vacuum-dryings are spent the night.
Getting former P123 segmented copolymer, adduct, carboxylated product, is dissolution with solvents with an amount of methylene dichloride respectively, pressing potassium bromide troche, and liquid is filmed, and measures infrared spectra (seeing accompanying drawing 1-3), and accompanying drawing 1 is the infrared spectrogram of PEO-PPO-PEO segmented copolymer; Accompanying drawing 2 is the adduct infrared spectrogram of PEO-PPO-PEO segmented copolymer and vinyl cyanide, and the infrared signature signal of the appearance-CN of 2251.48cm-1 place among the figure shows in the PEO-PPO-PEO structure to be introduced into-the CN group; Accompanying drawing 3 is the carboxylated product infrared spectrogram of PEO-PPO-PEO segmented copolymer, and the infrared signature signal of the appearance-COOH of 1738.00cm-1 place among the figure shows in the PEO-PPO-PEO structure to be introduced into-the COOH group that carboxylated product prepares successfully; There is no other group signal among Fig. 2,3 and occur, with the sodium hydroxide solution titration of demarcating, transformation efficiency is 100%.
Embodiment 2
Take by weighing 2g F127 type PEO-PPO-PEO segmented copolymer, to add an amount of 50% potassium hydroxide solution behind the 20mL pure water ultrasonic dissolution while stirring, make reacting liquid temperature be maintained at 0 ± 0.5 ℃, drip the 2mL vinyl cyanide while stirring, continue to stir (100rpm) reaction 48h, it is extremely neutral with the concentrated hydrochloric acid adjust pH that reaction finishes the back, use equal-volume dichloromethane extraction addition reaction product solution, add anhydrous sodium sulphate and place institute's water content in the absorption extraction liquid that spends the night, filter, filtrate volatilizes solvent through 40 ℃ of water-bath rotary evaporations, and vacuum-drying is spent the night and eliminated solvent, gets adduct;
Adduct is dissolved in the 40mL1M potassium hydroxide solution, 105 ℃ of oil bath back flow reaction 7h, reaction product solution is with concentrated hydrochloric acid adjust pH to 4, use equal-volume dichloromethane extraction addition reaction product solution, add anhydrous sodium sulphate and place institute's water content in the absorption extraction liquid that spends the night, filter, filtrate volatilizes solvent through 40 ℃ of water-bath rotary evaporations, vacuum-drying is spent the night and is eliminated solvent, gets crude product;
With equal-volume sherwood oil and crude product vortex mixed, the crude product precipitation is separated out, and centrifugal removing desolvated, and precipitation obtains the carboxylated PEO-PPO-PEO segmented copolymer of F127 type of purifying after 50 ℃ of vacuum-dryings are spent the night.
Embodiment 3
Take by weighing 2g P123 type PEO-PPO-PEO segmented copolymer, to add an amount of 20% potassium hydroxide solution after the 20mL pure water stirring and dissolving while stirring, make reacting liquid temperature be maintained at 4 ± 0.5 ℃, Dropwise 5 mL vinyl cyanide while stirring, continue to stir (200rpm) reaction 24h, it is extremely neutral with the concentrated hydrochloric acid adjust pH that reaction finishes the back, 60 ℃ of water-bath rotary evaporations volatilize solvent, 40 ℃ of vacuum-dryings are spent the night, add the chloroform extraction residue, filter, filtrate volatilizes solvent through 50 ℃ of water-bath rotary evaporations, vacuum-drying is spent the night and is eliminated solvent, gets adduct;
Adduct is dissolved in the 20mL2M sodium hydroxide solution, 200rpm stirring reaction 7d, reaction product solution is with concentrated hydrochloric acid adjust pH to 3,60 ℃ of water-bath rotary evaporations volatilize solvent, and 40 ℃ of vacuum-dryings are spent the night, add-on chloroform extraction residue, filter, filtrate volatilizes solvent through 50 ℃ of water-bath rotary evaporations, and vacuum-drying is spent the night and eliminated solvent, gets crude product;
With equal-volume methyl ethyl ether and crude product vortex mixed, the crude product precipitation is separated out, and centrifugal removing desolvated, and precipitation obtains the carboxylated PEO-PPO-PEO segmented copolymer of P123 type of purifying after 30 ℃ of vacuum-dryings are spent the night.
Embodiment 4
Take by weighing 2g F68 type PEO-PPO-PEO segmented copolymer, to add an amount of 40% potassium hydroxide solution after the 15mL pure water stirring and dissolving while stirring, make reacting liquid temperature be maintained at 1 ± 0.5 ℃, drip the 8mL vinyl cyanide while stirring, continue to stir (200rpm) reaction 24h, it is extremely neutral with the concentrated hydrochloric acid adjust pH that reaction finishes the back, use equal-volume dichloromethane extraction addition reaction product solution, add anhydrous sodium sulphate and place institute's water content in the absorption extraction liquid that spends the night, filter, filtrate volatilizes solvent through 50 ℃ of water-bath rotary evaporations, and vacuum-drying is spent the night and eliminated solvent, gets adduct;
Adduct is dissolved in the 40mL5M sulphuric acid soln, back flow reaction 6h, use equal-volume dichloromethane extraction addition reaction product solution, add anhydrous sodium sulphate and place institute's water content in the absorption extraction liquid that spends the night, filter, filtrate volatilizes solvent through 50 ℃ of water-bath rotary evaporations, and vacuum-drying is spent the night and eliminated solvent, gets crude product;
With equal-volume sherwood oil and crude product vortex mixed, the crude product precipitation is separated out, and centrifugal removing desolvated, and precipitation obtains the carboxylated PEO-PPO-PEO segmented copolymer of F68 type of purifying after 40 ℃ of vacuum-dryings are spent the night.
Embodiment 5
Take by weighing 2g P123 type PEO-PPO-PEO segmented copolymer, to add an amount of 40% potassium hydroxide solution after the 15mL pure water stirring and dissolving while stirring, make reacting liquid temperature be maintained at 0 ± 0.5 ℃, Dropwise 5 mL vinyl cyanide while stirring, continue to stir (200rpm) reaction 24h, it is extremely neutral with the concentrated hydrochloric acid adjust pH that reaction finishes the back, use equal-volume dichloromethane extraction addition reaction product solution, add anhydrous sodium sulphate and place institute's water content in the absorption extraction liquid that spends the night, filter, filtrate volatilizes solvent through 50 ℃ of water-bath rotary evaporations, and vacuum-drying is spent the night and eliminated solvent, gets adduct;
Adduct is dissolved in 40mL4M sulfuric acid, the 4M hydrochloric acid mixed acid solution, back flow reaction 6h, use equal-volume dichloromethane extraction addition reaction product solution, add anhydrous sodium sulphate and place institute's water content in the absorption extraction liquid that spends the night, filter, filtrate volatilizes solvent through 50 ℃ of water-bath rotary evaporations, and vacuum-drying is spent the night and eliminated solvent, gets crude product;
With equal-volume sherwood oil and crude product vortex mixed, the crude product precipitation is separated out, and centrifugal removing desolvated, and precipitation obtains the carboxylated PEO-PPO-PEO segmented copolymer of P123 type of purifying after 40 ℃ of vacuum-dryings are spent the night.
Embodiment 6
Take by weighing 2g P123 type PEO-PPO-PEO segmented copolymer, to add an amount of 20% potassium hydroxide solution after the 20mL pure water stirring and dissolving while stirring, make reacting liquid temperature be maintained at 4 ± 0.5 ℃, Dropwise 5 mL vinyl cyanide while stirring, continue to stir (200rpm) reaction 24h, it is extremely neutral with the concentrated hydrochloric acid adjust pH that reaction finishes the back, 60 ℃ of water-bath rotary evaporations volatilize solvent, 40 ℃ of vacuum-dryings are spent the night, add-on trichloromethane dissolved residue filters, and filtrate volatilizes solvent through 50 ℃ of water-bath rotary evaporations, vacuum-drying is spent the night and is eliminated solvent, gets adduct;
Adduct is dissolved in 40mL4M sulfuric acid, in the 4M hydrochloric acid mixed acid solution, back flow reaction 2h, use equal-volume dichloromethane extraction addition reaction product solution, add anhydrous sodium sulphate and place institute's water content in the absorption extraction liquid that spends the night, filter, filtrate volatilizes solvent through 50 ℃ of water-bath rotary evaporations, vacuum-drying is spent the night and is eliminated solvent, product is dissolved in the 20mL2M sodium hydroxide solution, 105 ℃ of oil bath back flow reaction 2h, reaction product solution uses equal-volume dichloromethane extraction addition reaction product solution with concentrated hydrochloric acid adjust pH to 4, adds anhydrous sodium sulphate and places institute's water content in the absorption extraction liquid that spends the night, filter, filtrate volatilizes solvent through 50 ℃ of water-bath rotary evaporations, and vacuum-drying is spent the night and eliminated solvent, gets crude product;
With equal-volume sherwood oil and crude product vortex mixed, the crude product precipitation is separated out, and centrifugal removing desolvated, and precipitation obtains the carboxylated PEO-PPO-PEO segmented copolymer of P123 type of purifying after 50 ℃ of vacuum-dryings are spent the night.
Above embodiment is arranged as can be seen, the present invention: 1, be reflected in the aqueous solution and carry out; 2, under the basic catalyst effect, make unsaturated nitrile compounds and PEO-PPO-PEO segmented copolymer generation addition reaction; 3, prepare carboxyl PEO-PPO-PEO segmented copolymer by hydrolysis to itrile group in the adduct; 4, adopt the ether precipitator method to obtain the carboxyl PEO-PPO-PEO segmented copolymer of purifying.Mild condition of the present invention, can not cause the fracture of ehter bond in the PEO-PPO-PEO segmented copolymer, carboxylated process can be introduced the corresponding chemical key as required in the original copolymer structure, when making the PEO-PPO-PEO segmented copolymer be used for slowly-releasing, the target administration of organic synthesis, protein and polypeptide drugs modification, Polymer Synthesizing and medicine, help obtaining the modified outcome of structure homogeneous, stable performance, and be suitable for a large amount of preparations and suitability for industrialized production.
Claims (11)
1. carboxylation method of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer is characterized in that may further comprise the steps:
The first step is dissolved in the PEO-PPO-PEO segmented copolymer in the water, adds the base catalysis agent solution while stirring, adds vinyl cyanide then while stirring, and addition reaction finishes the back and adds sour adjust pH to neutral, obtains adduct through extraction;
Described addition reaction temperature is to carry out under 0 ℃-4 ℃ condition;
Second step was dissolved in the reaction that is hydrolyzed in alkali lye or the acid solution with adduct, and reaction finishes the back sour water transfer of adding and separates reacting liquid pH value to acid, obtains crude product through extraction;
The 3rd step was settled out crude product with ether solvent and crude product vortex mixed, and centrifugal removing desolvated, and obtains the carboxyl PEO-PPO-PEO segmented copolymer of purifying after the vacuum-drying;
The molecular formula of described carboxylated PEO-PPO-PEO segmented copolymer:
RO(C
2H
4O)
a(C
3H
6O)
b(C
2H
4O)
cMCOOH
Structural formula is:
The R here is-C
2H
4COOH ,-H ,-CH
3,-C
2H
5,-C
3H
7Group, M are-(CH
2)
2-,-(CH
2)
3-group, wherein a, c are that 2-200, b are the integer of 15-100.
2. carboxylation method of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer as claimed in claim 1 is characterized in that, described PEO-PPO-PEO segmented copolymer, and molecular formula is:
R′O(C
2H
4O)
x(C
3H
6O)
y(C
2H
4O)
zH
Structural formula:
The R ' here is-H ,-CH
3,-C
2H
5,-C
3H
7Group, wherein x, z are that 2-200, y are the integer of 15-100.
3. carboxylation method of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer as claimed in claim 1 is characterized in that, described basic catalyst is sodium hydroxide, potassium hydroxide, calcium hydroxide and phosphoric acid one disodium hydrogen, is used alone or as a mixture.
4. carboxylation method of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer as claimed in claim 1 is characterized in that, described addition reaction is to carry out under the condition of pH value at 7-14.
5. carboxylation method of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer as claimed in claim 1, it is characterized in that, the extraction of described addition reaction product, its method is: with an organic solvent direct extractive reaction product liquid, remove the moisture content in the organic solvent, volatilize organic solvent; With an organic solvent extract residue after perhaps the moisture content in the addition reaction product solution being volatilized.
6. carboxylation method of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer as claimed in claim 5 is characterized in that, described organic solvent comprises ester class, fat hydrocarbon, aromatic hydrocarbons, ketone, chlorinated hydrocarbon, is used alone or as a mixture.
7. as claim 5 or 6 described carboxylation method of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer, it is characterized in that described organic solvent is methylene dichloride, chloroform, is used alone or as a mixture.
8. carboxylation method of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer as claimed in claim 1, it is characterized in that described hydrolysis reaction is to carry out in the aqueous solution, hydrolysis reaction is 0 ℃-100 ℃ of temperature, the pH value is carried out under the condition of 1-14, and hydrolysis reaction product liquid pH value is adjusted into 1-6.
9. carboxylation method of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer as claimed in claim 1, it is characterized in that, the extraction of described hydrolysis reaction product, its method comprises and with an organic solvent extracts the hydrolysis reaction product solution, remove the moisture content in the organic solvent, volatilize organic solvent; Or with an organic solvent extract residue after the moisture content in the hydrolysis reaction product solution volatilized.
10. carboxylation method of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer as claimed in claim 9 is characterized in that, described organic solvent comprises ester class, fat hydrocarbon, aromatic hydrocarbons, ketone, chlorinated hydrocarbon, is used alone or as a mixture.
11. carboxylation method of polyoxyethylene-poly-oxypropylene polyoxyethylene copolymer as claimed in claim 1 is characterized in that, described ether solvent, a kind of in ether, methyl ethyl ether, sherwood oil, phenyl ethyl ether, methyl-phenoxide, isopropyl ether, the n-butyl ether.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0206448B1 (en) * | 1985-06-19 | 1990-11-14 | Ajinomoto Co., Inc. | Hemoglobin combined with a poly(alkylene oxide) |
| CN1511920A (en) * | 2002-12-27 | 2004-07-14 | 山东师范大学 | Novel crude oil drag reduction and viscosity reducing agent |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0206448B1 (en) * | 1985-06-19 | 1990-11-14 | Ajinomoto Co., Inc. | Hemoglobin combined with a poly(alkylene oxide) |
| CN1511920A (en) * | 2002-12-27 | 2004-07-14 | 山东师范大学 | Novel crude oil drag reduction and viscosity reducing agent |
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