CN101544757A - Amphiphilic polyanhydride polymer and preparation method thereof - Google Patents
Amphiphilic polyanhydride polymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an amphiphilic polyanhydride polymer. The above molecular formula is the general structure of the amphiphilic polyanhydride polymer, wherein a=3-6, b=2-9, x is the mole number of a diatomic fatty acid prepolymer, y is the mole number of a diatomic aromatic acid prepolymer, z is the mole number of a double-end carboxyl polyethyleneglycol prepolymer, x/y=50/50-90/10, and z/(x+y)=5/100-30/100. The invention further discloses a preparation method of the amphiphilic polyanhydride polymer, the diatomic fatty acids and diatomic aromatic acids are adopted to be carried out the melt co-polymerization with the double-end carboxyl polythyleneglycol. The polymer contains polyanhydride lyophobic fragments and polyethyleneglycol hydrophile fragments; and compared with the prior art, the invention improves the hydrophilicity of molecules, and has moderate hydrophobicity and slow degradation.
Description
Technical field
The present invention relates to a kind of polyanhydride polymer, particularly amphiphilic polyanhydride polymer.The preparation method who also relates to this amphiphilic polyanhydride polymer.
Background technology
Document " publication number is the Chinese patent of CN1544508 " discloses a kind of poly-acid anhydrides, and its general structure is:
X=11 in the formula～16, m is the mole number of dimeracid prepolymer, n is the mole number of saturated di-carboxylic acid prepolymer, m/n=1/30～1/3.The acid anhydrides molecule is to be formed by the aliphatic dibasic acid polycondensation but this birdss of the same feather flock together, and does not contain hydrophilic segment in the molecule, when being used to wrap up protein medicaments and making medicine carrying microballoons or nanometer ball, then can cause proteic non-covalent gathering, causes protein denaturation.
Summary of the invention
For the poly-acid anhydrides that overcomes prior art has lipophilicity, when being used to wrap up protein medicaments and making medicine carrying microballoons or nanometer ball, then can cause proteic non-covalent gathering, cause protein-denatured deficiency, the invention provides a kind of amphiphilic polyanhydride polymer, hydrophilic segment polyoxyethylene glycol (PEG) induces one in poly-acid anhydrides skeleton, can improve the wetting ability of molecule, solid support material used as preparation protein medicaments microballoon, can improve the stability of protein medicaments, avoid the pharmaceutical grade protein sex change, and molecular weight that can be by regulating hydrophilic block and (or) ratio between the hydrophilic/hydrophobic block comes the regulating medicine rate of release.
The present invention also provides the preparation method of this amphiphilic polyanhydride polymer.
The technical solution adopted for the present invention to solve the technical problems: a kind of amphiphilic polyanhydride polymer, its general structure is:
A=3 in the formula～16, b=2～9, x is the mole number of binary lipid acid prepolymer, and y is the mole number of binary aromatic acid prepolymer, and z is the mole number of both-end carboxy polyethylene glycol prepolymer, x/y=50/50～90/10, z/ (x+y)=5/100～30/100;
Described binary lipid acid prepolymer is any of pentanedioic acid (GA), hexanodioic acid (AA), pimelic acid (PA), suberic acid, nonane diacid, sebacic acid (SA), dodecanedioic acid, tetradecane diacid, Thapsic acid or octadecane diacid;
Described binary aromatic acid prepolymer is 1, two (to the carboxyl phenoxy group) propane (CPP), 1 of 3-, two (to the carboxyl phenoxy group) hexanes (CPH) of 6-, to the carboxyl phenylium, to the positive valeric acid of carboxyl phenoxy group or to any of carboxyl phenoxy group pelargonic acid;
Described both-end carboxy polyethylene glycol prepolymer is any of both-end carboxy polyethylene glycol 400, both-end carboxy polyethylene glycol 600, both-end carboxy polyethylene glycol 800, both-end carboxy polyethylene glycol 1000, both-end carboxy polyethylene glycol 2000, both-end carboxy polyethylene glycol 4000, both-end carboxy polyethylene glycol 6000 or both-end carboxy polyethylene glycol 8000.
A kind of preparation method of above-mentioned amphiphilic polyanhydride polymer is characterized in may further comprise the steps:
(a) in polyoxyethylene glycol, add Succinic anhydried or MALEIC ANHYDRIDE according to polyoxyethylene glycol: Succinic anhydried or MALEIC ANHYDRIDE=1:2～1:10 (mol ratio), adding 1%～5% (W/V) pyridine or 4-Dimethylamino pyridine again and make catalyzer, is solvent with chloroform or tetrahydrofuran (THF), reacts 12～72 hours down in 0～60 ℃, cooled and filtered, the underpressure distillation concentrated filtrate, after slowly be added drop-wise in anhydrous diethyl ether or sherwood oil or the hexanaphthene and precipitate, filter, drying promptly gets the both-end carboxy polyethylene glycol;
(b) with both-end carboxy polyethylene glycol and diacetyl oxide in molar ratio 1:2～1:5 be incorporated with in the container of nitrogen protection, 140～180 ℃ of back flow reaction 15～50 minutes, be cooled to 50～100 ℃, vacuum rotary steam is removed the part diacetyl oxide, and concentrated solution is placed down in 0 ℃ and spent the night, filter collecting precipitation, place anhydrous diethyl ether or sherwood oil or hexanaphthene to stir, remove a spot of diacetyl oxide residual solution, filter, drying promptly gets both-end carboxy polyethylene glycol prepolymer;
(c) with binary lipid acid and diacetyl oxide in molar ratio 1:2～1:5 be incorporated with in the container of nitrogen protection, 140～180 ℃ of back flow reaction 15～50 minutes, be cooled to 50～100 ℃, the diacetyl oxide that pressure reducing and steaming does not react completely, get white solid, be cooled to room temperature, add the dry toluene dissolving, the sealing cooling is separated out precipitation, suction filtration, with anhydrous diethyl ether or methyl ethyl ether or tetrahydrofuran (THF) washing, the gained solid changes in the Erlenmeyer flask, adds anhydrous diethyl ether or sherwood oil or hexanaphthene and soaks, and last suction filtration promptly gets binary lipid acid prepolymer;
(d) with binary aromatic acid and diacetyl oxide in molar ratio 1:2～1:5 be incorporated with in the container of nitrogen protection, 140～180 ℃ of back flow reaction 15～50 minutes, cooled and filtered, 50～100 ℃ of vacuum rotary steam filtrates, the concentrated solution recrystallization that spends the night, collecting precipitation also washs remaining diacetyl oxide with anhydrous diethyl ether or methyl ethyl ether or tetrahydrofuran (THF), product dissolves with DMF, add anhydrous diethyl ether or sherwood oil or hexanaphthene precipitation, place 0 ℃ of following recrystallization, filter collecting precipitation, with anhydrous diethyl ether or methyl ethyl ether or tetrahydrofuran (THF) washing, drying promptly gets binary aromatic acid prepolymer;
(e) binary lipid acid prepolymer, binary aromatic acid prepolymer 50/50～90/10 are added in molar ratio, both-end carboxy polyethylene glycol prepolymer is packed into by 5%～30% molar content in the polymerizing pipe, places silicone oil bath, induction stirring; Be warming up to 150～180 ℃, vacuum decompression to 30～50Pa, melt polymerization 1～2 hour, logical nitrogen was 10～30 seconds every 5～30 minutes, vacuumized again; Polymerization finishes, and cooling obtains solid product, with the methylene dichloride dissolving, filters, and with anhydrous diethyl ether or sherwood oil or hexanaphthene precipitation, filters, and drying promptly gets amphiphilic polyanhydride polymer.
The invention has the beneficial effects as follows: because the hydrophilic segment polyoxyethylene glycol (PEG) that in poly-acid anhydrides skeleton, induces one, improved the wetting ability of molecule, solid support material used as preparation protein medicaments microballoon, improved the stability of protein medicaments, avoided the pharmaceutical grade protein sex change, and molecular weight that can be by regulating hydrophilic block and (or) ratio between the hydrophilic/hydrophobic block comes the regulating medicine rate of release.
Below in conjunction with embodiment the present invention is elaborated.
Embodiment
It is specific as follows that the present invention prepares the synthetic line that gathers acid anhydrides:
A=3 in the formula～16, b=2～9, x is the mole number of binary lipid acid prepolymer, and y is the mole number of binary aromatic acid prepolymer, and z is the mole number of both-end carboxy polyethylene glycol prepolymer, x/y=50/50～90/10, z/ (x+y)=5/100～30/100.
Embodiment 1: taking polyethylene glycol 400 1:2 in molar ratio adds Succinic anhydried, and the chloroform dissolving adds 1% (W/V) pyridine again, reacts 72 hours down in 0 ℃.Cooled and filtered, the underpressure distillation concentrated filtrate, after slowly be added drop-wise in the anhydrous diethyl ether and precipitate, filter, drying promptly obtains both-end carboxy polyethylene glycol 400.With hexanodioic acid and diacetyl oxide in molar ratio 1:2 be incorporated with in the container of nitrogen protection, 140 ℃ of back flow reaction 50 minutes are cooled to 50 ℃; the diacetyl oxide that pressure reducing and steaming does not react completely; get white solid, the back adds the dry toluene dissolving, and sealing is cooled off; separate out a large amount of precipitations; suction filtration, with the anhydrous diethyl ether washing, the gained solid changes in the Erlenmeyer flask; add sherwood oil and soak, last suction filtration promptly gets the hexanodioic acid prepolymer.With 1; two (to the carboxyl phenoxy group) propane of 3-and diacetyl oxide 1:2 in molar ratio are incorporated with in the container of nitrogen protection; 140 ℃ of back flow reaction 50 minutes; cooled and filtered, 50 ℃ of vacuum rotary steam filtrates, the concentrated solution recrystallization that spends the night; collecting precipitation also washs remaining diacetyl oxide with anhydrous diethyl ether; product dissolves with DMF, adds petroleum ether precipitation, places 0 ℃ of following recrystallization.Filter collecting precipitation, with the anhydrous diethyl ether washing, drying promptly obtains 1, two (to the carboxyl phenoxy group) the propane prepolymers of 3-.With both-end carboxy polyethylene glycol 400 and diacetyl oxide in molar ratio 1:2 be incorporated with in the container of nitrogen protection; 140 ℃ of back flow reaction 50 minutes; be cooled to 50 ℃, vacuum rotary steam is removed the part diacetyl oxide, and concentrated solution is placed down in 0 ℃ and spent the night; filter collecting precipitation; place anhydrous diethyl ether to stir, remove a spot of diacetyl oxide residual solution, filter; drying promptly gets both-end carboxy polyethylene glycol 400 prepolymers.At diameter 2cm, add hexanodioic acid prepolymer 1.8 grams, 1 in the polymerizing pipe of long 20cm, two (to the carboxyl phenoxy group) propane prepolymer 0.2 grams of 3-, both-end carboxy polyethylene glycol 400 prepolymers 0.1 gram place silicone oil bath, induction stirring.Be warming up to 150 ℃, vacuum decompression is to 30Pa, melt polymerization 1 hour, and logical nitrogen was 10 seconds every 5 minutes, vacuumized again.Polymerization finishes, cool off faint yellow solid, with methylene dichloride dissolving, the G4 sand core funnel filters, petroleum ether precipitation, precipitation is washed after drying with ether, must slightly yellowy pulverulent solids.
After testing, to prepare productive rate be 90% to present embodiment.Synthetic similar as stated above the carrying out of other different prepolymer quality proportionings.Prepare protein microsphere with this poly-acid anhydrides, microspherulite diameter 1～3 μ m, encapsulation rate 80%～95%, external drug release time 3 days is to not waiting in 1 week.
FI-IR and the physico-chemical property of the poly-acid anhydrides P (AA-CPP-PEG400) of table one
Embodiment 2: taking polyethylene glycol 1000 1:4 in molar ratio adds Succinic anhydried, and the chloroform dissolving adds 5% (W/V) pyridine again, reacts 12 hours down in 60 ℃.Cooled and filtered, the underpressure distillation concentrated filtrate, after slowly be added drop-wise in the anhydrous diethyl ether and precipitate, filter, drying promptly obtains both-end carboxy polyethylene glycol 1000.With sebacic acid and diacetyl oxide in molar ratio 1:2 be incorporated with in the container of nitrogen protection, 180 ℃ of back flow reaction 15 minutes are cooled to 100 ℃; the diacetyl oxide that pressure reducing and steaming does not react completely; get white solid, the back adds the dry toluene dissolving, and sealing is cooled off; separate out a large amount of precipitations; suction filtration, with the anhydrous diethyl ether washing, the gained solid changes in the Erlenmeyer flask; add sherwood oil and soak, last suction filtration promptly gets the sebacic acid prepolymer.With 1; two (to the carboxyl phenoxy group) hexanes of 6-and diacetyl oxide 1:2 in molar ratio are incorporated with in the container of nitrogen protection; 180 ℃ of back flow reaction 15 minutes; cooled and filtered, 100 ℃ of vacuum rotary steam filtrates, the concentrated solution recrystallization that spends the night; collecting precipitation also washs remaining diacetyl oxide with anhydrous diethyl ether; product dissolves with DMF, adds petroleum ether precipitation, places 0 ℃ of following recrystallization.Filter collecting precipitation, with the anhydrous diethyl ether washing, drying promptly obtains 1, two (to the carboxyl phenoxy group) the hexane prepolymers of 6-.With both-end carboxy polyethylene glycol 1000 and diacetyl oxide in molar ratio 1:2 be incorporated with in the container of nitrogen protection; 180 ℃ of back flow reaction 15 minutes; be cooled to 100 ℃, vacuum rotary steam is removed the part diacetyl oxide, and concentrated solution is placed down in 0 ℃ and spent the night; filter collecting precipitation; place anhydrous diethyl ether to stir, remove a spot of diacetyl oxide residual solution, filter; drying promptly gets both-end carboxy polyethylene glycol 1000 prepolymers.At diameter 2cm, add sebacic acid prepolymer 1.6 grams, 1 in the polymerizing pipe of long 20cm, two (to the carboxyl phenoxy group) hexane prepolymer 0.4 grams of 6-, both-end carboxy polyethylene glycol 1000 prepolymers 0.2 gram place silicone oil bath, induction stirring.Be warming up to 180 ℃, vacuum decompression is to 50Pa, melt polymerization 2 hours, and logical nitrogen was 30 seconds every 30 minutes, vacuumized again.Polymerization finishes, cool off faint yellow solid, with methylene dichloride dissolving, the G4 sand core funnel filters, petroleum ether precipitation, precipitation is washed after drying with ether, must slightly yellowy pulverulent solids.
After testing, present embodiment prepares productive rate 92%.Synthetic similar as stated above the carrying out of other different prepolymer quality proportionings.Prepare protein microsphere with this poly-acid anhydrides, microspherulite diameter 1～3 μ m, encapsulation rate 80%～95%, external drug release time 3 days is to not waiting in 1 week.
FI-IR and the physico-chemical property of table dimerization acid anhydrides P (SA-CPH-PEG1000)
Embodiment 3: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to Polyethylene Glycol-600, and hexanodioic acid is changed to pentanedioic acid.After testing, present embodiment prepares productive rate 90%.
Embodiment 4: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to polyoxyethylene glycol 800, and hexanodioic acid is changed to pimelic acid.After testing, present embodiment prepares productive rate 88%.
Embodiment 5: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to Macrogol 2000, and hexanodioic acid is changed to suberic acid.After testing, present embodiment prepares productive rate 86%.
Embodiment 6: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to Macrogol 4000, and hexanodioic acid is changed to dodecanedioic acid.After testing, present embodiment prepares productive rate 85%.
Embodiment 7: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to polyethylene glycol 6000, and hexanodioic acid is changed to tetradecane diacid.After testing, present embodiment prepares productive rate 86%.
Embodiment 8: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to polyoxyethylene glycol 8000, and hexanodioic acid is changed to Thapsic acid.After testing, present embodiment prepares productive rate 87%.
Embodiment 9: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to cetomacrogol 1000, and hexanodioic acid is changed to octadecane diacid.After testing, present embodiment prepares productive rate 92%.
Embodiment 10: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to cetomacrogol 1000, and hexanodioic acid is changed to sebacic acid.After testing, present embodiment prepares productive rate 91%.
Embodiment 11: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to Macrogol 2000, and 1, two (to the carboxyl phenoxy group) propane of 3-are changed to 1, two (to the carboxyl phenoxy group) hexanes of 6-.After testing, present embodiment prepares productive rate 90%.
Embodiment 12: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to Macrogol 2000, and 1, two (to the carboxyl phenoxy group) propane of 3-are changed to the carboxyl phenylium.After testing, present embodiment prepares productive rate 93%.
Embodiment 13: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to Macrogol 2000, and 1, two (to the carboxyl phenoxy group) propane of 3-are changed to the positive valeric acid of carboxyl phenoxy group.After testing, present embodiment prepares productive rate 89%.
Embodiment 14: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to Macrogol 2000, and 1, two (to the carboxyl phenoxy group) propane of 3-are changed to carboxyl phenoxy group pelargonic acid.After testing, present embodiment prepares productive rate 92%.
Embodiment 15: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to Macrogol 4000, and hexanodioic acid is changed to sebacic acid, and 1, two (to the carboxyl phenoxy group) propane of 3-are changed to the carboxyl phenylium.After testing, present embodiment prepares productive rate 91%.
Embodiment 16: the preparation method is with embodiment 1, and wherein poly(oxyethylene glycol) 400 is changed to Macrogol 4000, and hexanodioic acid is changed to dodecanedioic acid, and 1, two (to the carboxyl phenoxy group) propane of 3-are changed to carboxyl phenoxy group pelargonic acid.After testing, present embodiment prepares productive rate 88%.
In addition, to the various combination matchings in various reactant consumptions interval, in the temperature of reaction interval, time interval has carried out test many times between the pressure zone, all obtained the equally good effect with above-mentioned embodiment.
Claims (2)
1, a kind of amphiphilic polyanhydride polymer, its general structure is:
A=3 in the formula～16, b=2～9, x is the mole number of binary lipid acid prepolymer, and y is the mole number of binary aromatic acid prepolymer, and z is the mole number of both-end carboxy polyethylene glycol prepolymer, x/y=50/50～90/10, z/ (x+y)=5/100～30/100;
Described binary lipid acid prepolymer is any of pentanedioic acid (GA), hexanodioic acid (AA), pimelic acid (PA), suberic acid, nonane diacid, sebacic acid (SA), dodecanedioic acid, tetradecane diacid, Thapsic acid or octadecane diacid;
Described binary aromatic acid prepolymer is 1, two (to the carboxyl phenoxy group) propane (CPP), 1 of 3-, two (to the carboxyl phenoxy group) hexanes (CPH) of 6-, to the carboxyl phenylium, to the positive valeric acid of carboxyl phenoxy group or to any of carboxyl phenoxy group pelargonic acid;
Described both-end carboxy polyethylene glycol prepolymer is any of both-end carboxy polyethylene glycol 400, both-end carboxy polyethylene glycol 600, both-end carboxy polyethylene glycol 800, both-end carboxy polyethylene glycol 1000, both-end carboxy polyethylene glycol 2000, both-end carboxy polyethylene glycol 4000, both-end carboxy polyethylene glycol 6000 or both-end carboxy polyethylene glycol 8000.
2, the preparation method of the described amphiphilic polyanhydride polymer of a kind of claim 1 is characterized in that may further comprise the steps:
(a) in polyoxyethylene glycol, add Succinic anhydried or MALEIC ANHYDRIDE according to polyoxyethylene glycol: Succinic anhydried or MALEIC ANHYDRIDE=1:2～1:10 (mol ratio), add 1%～5% (W/V) pyridine or 4-Dimethylamino pyridine again and make catalyzer, with chloroform or tetrahydrofuran (THF) is solvent, reacted 12～72 hours down in 0～60 ℃, cooled and filtered, the underpressure distillation concentrated filtrate, after slowly be added drop-wise in anhydrous diethyl ether or sherwood oil or the hexanaphthene and precipitate, filter, drying promptly gets the both-end carboxy polyethylene glycol;
(b) with both-end carboxy polyethylene glycol and diacetyl oxide in molar ratio 1; 2～1:5 is incorporated with in the container of nitrogen protection, 140～180 ℃ of back flow reaction 15～50 minutes, be cooled to 50～100 ℃, vacuum rotary steam is removed the part diacetyl oxide, and concentrated solution is placed down in 0 ℃ and spent the night, filter collecting precipitation, place anhydrous diethyl ether or sherwood oil or hexanaphthene to stir, remove a spot of diacetyl oxide residual solution, filter, drying promptly gets both-end carboxy polyethylene glycol prepolymer;
(c) with binary lipid acid and diacetyl oxide in molar ratio 1:2～1:5 be incorporated with in the container of nitrogen protection, 140～180 ℃ of back flow reaction 15～50 minutes, be cooled to 50～100 ℃, the diacetyl oxide that pressure reducing and steaming does not react completely, get white solid, be cooled to room temperature, add the dry toluene dissolving, the sealing cooling is separated out precipitation, suction filtration, with anhydrous diethyl ether or methyl ethyl ether or tetrahydrofuran (THF) washing, the gained solid changes in the Erlenmeyer flask, adds anhydrous diethyl ether or sherwood oil or hexanaphthene and soaks, and last suction filtration promptly gets binary lipid acid prepolymer;
(d) with binary aromatic acid and diacetyl oxide in molar ratio 1:2～1:5 be incorporated with in the container of nitrogen protection, 140～180 ℃ of back flow reaction 15～50 minutes, cooled and filtered, 50～100 ℃ of vacuum rotary steam filtrates, the concentrated solution recrystallization that spends the night, collecting precipitation also washs remaining diacetyl oxide with anhydrous diethyl ether or methyl ethyl ether or tetrahydrofuran (THF), product dissolves with DMF, add anhydrous diethyl ether or sherwood oil or hexanaphthene precipitation, place 0 ℃ of following recrystallization, filter collecting precipitation, with anhydrous diethyl ether or methyl ethyl ether or tetrahydrofuran (THF) washing, drying promptly gets binary aromatic acid prepolymer;
(e) binary lipid acid prepolymer, binary aromatic acid prepolymer 50/50～90/10 are added in molar ratio, both-end carboxy polyethylene glycol prepolymer is packed into by 5%～30% molar content in the polymerizing pipe, places silicone oil bath, induction stirring; Be warming up to 150～180 ℃, vacuum decompression to 30～50Pa, melt polymerization 1～2 hour, logical nitrogen was 10～30 seconds every 5～30 minutes, vacuumized again; Polymerization finishes, and cooling obtains solid product, with the methylene dichloride dissolving, filters, and with anhydrous diethyl ether or sherwood oil or hexanaphthene precipitation, filters, and drying promptly gets amphiphilic polyanhydride polymer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566922A (en) * | 2016-03-07 | 2016-05-11 | 山东理工大学 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol |
| CN105647198A (en) * | 2016-03-16 | 2016-06-08 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol membrane by using polycaprolactone and P(CPP-SA)-polyvinylpyrrolidone |
| CN109180928A (en) * | 2018-09-14 | 2019-01-11 | 湖北工业大学 | A kind of preparation method of the polyethylene glycol of high-purity mono carboxylic sealing end |
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2009
- 2009-04-20 CN CN200910022104A patent/CN101544757A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566922A (en) * | 2016-03-07 | 2016-05-11 | 山东理工大学 | Method for improving water resistance and compliance of polyvinyl alcohol film with poly trimethylene carbonate and P (CPP-SA)-polyethylene glycol |
| CN105647198A (en) * | 2016-03-16 | 2016-06-08 | 山东理工大学 | Method for improving water resistance and flexibility of polyvinyl alcohol membrane by using polycaprolactone and P(CPP-SA)-polyvinylpyrrolidone |
| CN109180928A (en) * | 2018-09-14 | 2019-01-11 | 湖北工业大学 | A kind of preparation method of the polyethylene glycol of high-purity mono carboxylic sealing end |
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