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WO2017185218A1 - Procédé de préparation d'un film de polycaprolactone hydrophile - Google Patents

Procédé de préparation d'un film de polycaprolactone hydrophile Download PDF

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Publication number
WO2017185218A1
WO2017185218A1 PCT/CN2016/080180 CN2016080180W WO2017185218A1 WO 2017185218 A1 WO2017185218 A1 WO 2017185218A1 CN 2016080180 W CN2016080180 W CN 2016080180W WO 2017185218 A1 WO2017185218 A1 WO 2017185218A1
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Prior art keywords
polycaprolactone
reaction
solvent
hydrophilic
solution
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PCT/CN2016/080180
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English (en)
Chinese (zh)
Inventor
王海朋
李战雄
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Suzhou University
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Suzhou University
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Priority to PCT/CN2016/080180 priority Critical patent/WO2017185218A1/fr
Publication of WO2017185218A1 publication Critical patent/WO2017185218A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Definitions

  • the present invention relates to a method for preparing a hydrophilic polyester material, and more particularly to a method for preparing a polyethylene glycol grafted polycaprolactone hydrophilic film.
  • Polycaprolactone is a linear aliphatic polyester obtained by ring-opening polymerization of ⁇ -caprolactone monomer catalyzed by a metal organic compound such as tetraphenyltin. Excellent biodegradability, good biocompatibility, drug permeability and mechanical properties have been certified by the US FDA and have been widely studied and applied in the field of film applications.
  • the polycaprolactone (PCL) has a melting point of 59 to 64 ° C and a glass transition temperature of -60 ° C.
  • Its structural repeat unit has 5 non-polar methylene-CH 2 - and one polar ester group -COO-, ⁇ P-(C00CHCH 2 CH 2 CH 2 CH 2 CH 2 -)Pn, such a structure PCL has good flexibility and processability, and it has good biocompatibility.
  • polycaprolactone is used as a biomaterial. Due to the high hydrophobicity of polycaprolactone, its macromolecular backbone lacks reactive functional groups, thus causing it to be in organisms. The degradation rate is still not ideal, which limits the wide application of polycaprolactone in the biomedical field.
  • it is often used to copolymerize ⁇ -caprolactone monomer with other monomers, and a hydrophilic group is introduced into the copolymer to realize functional group modification of polycaprolactone, and the method has problems. It complicates the preparation process and makes the product quality control more difficult.
  • the present invention introduces a hydrophilic graft chain on a polycaprolactone macromolecular side group by a chemoselective method to obtain a graft-modified polycaprolactone.
  • the synthetic route is simple, the reaction conditions are mild and efficient, and the main chain structure of the polycaprolactone macromolecule is not destroyed, thereby obtaining a hydrophilic film material uniformly modified by the bulk of the polycaprolactone.
  • a method for preparing a hydrophilic polycaprolactone film comprising the following steps:
  • the amino alcohol is 2-amino-1-ethanol, 4-amino-1-butanol, 6-amino-1-hexanol, 8-amino-1-octanol or 10- Amino-1-nonanol;
  • the terminal hydroxyl polyethylene glycol is one of PEG100, PEG200, P EG400, PEG600, PEG1000, PEG 1200 ⁇ PEG 1600 ⁇ PEG2000;
  • the ether solvent is diethyl ether, tetrahydrofuran, 1 Any one or more mixed solvents of 4-dioxane;
  • the anti-solvent is any one or more of n-pentamidine, n-hexyl, n-glyoxime, n-octyl, and petroleum ether a mixed solvent;
  • the dilute acid is a hydrochloric acid solution or an acetic acid solution; and
  • the anhydrous carbonate is any one of potassium carbonate, sodium carbonate, sodium hydrogencarbonate
  • the mass ratio of the amino alcohol to the polycaprolactone is (1 to 10): (1) ⁇ 5) ;
  • step (2) the mass ratio of succinic anhydride, hydroxylated polycaprolactone, 4-dimethylaminopyridine, anhydrous carbonate is (1 ⁇ 15): (1 ⁇ 5) : ( 0.3-3) : (2 ⁇ 10);
  • step (3) the mass ratio of the terminal hydroxyl group polyethylene glycol, carboxylated polycaprolactone, hydrazine, ⁇ '-carbonyldiimidazole is (1.5 ⁇ 15) :( 0.2 ⁇ 3) : (0.5 ⁇ 5).
  • the reaction temperature is 40 to 90 ° C, the reaction time is l ⁇ 24h; in the step (2), the reaction temperature is 50 to 90 ° C, the reaction time is l ⁇ 12h; In the step (3), the reaction temperature is 25 to 65 ° C, and the reaction time is 1 to 24 hours.
  • the step (1) to the step (3) further includes a purification step, specifically:
  • the alcohol solvent is any one of ethanol, methanol, and isopropyl alcohol or a mixed solvent of one or more.
  • m is an integer of 1 to 1000
  • n is an integer of 0 to 1000
  • y is an integer of 100 to 2000.
  • Polycaprolactone is a kind of linear aliphatic polyester obtained by ring-opening polymerization of ⁇ -caprolactone monomer catalyzed by a metal organic compound (such as tetraphenyltin).
  • the initiator structural unit is present at the terminal, and the present invention does not limit the type of the initiator.
  • the initiator unit in the polycaprolactone does not affect the technical effect of the present invention.
  • the present invention utilizes an amino alcohol-functionalized polycaprolactone for the first time to prepare a side chain hydroxylated polycaprolactone, and then introduces a carboxyl group into a side chain of a hydroxylated polycaprolactone by using succinic anhydride, and then clicks Chemically, polyethylene glycol (PEG) is grafted to the hydroxylated polycaprolactone backbone to obtain PCL-g-PEG, which is then spin-coated to prepare a hydrophilic polycaprolactone film.
  • PEG polyethylene glycol
  • the hydrophilic polycaprolactone disclosed by the invention has strong hydrophilicity, and the preparation method of the public cockroach can effectively regulate the grafting density and the graft chain length of the polycaprolactone, and the preparation property is excellent. Hydrophilic graft modified polycaprolactone.
  • the hydrophilic modification of the present invention is to modify the bulk of the polycaprolactone, and all the polycaprolactone macromolecules in the obtained modified material have been grafted with polyethylene glycol; Hydrophilic modification of the surface of polycaprolactone material The difference is that the modified polycaprolactone also changes from hydrophobic to hydrophilic, and an unexpected technical effect is obtained.
  • reaction solution was poured into 20 g of n-hexane, and PCL of grafted PEG-400 was precipitated by an anti-solvent method, and filtered to obtain a white solid, using ethanol and deionized water. (Volume ratio 1:1) Wash the mixed solution 4 times, use 100 g each time, then wash it 4 times with deionized water, use 300 g each time, put the obtained product into a vacuum oven, and bake at 37 °C. Osmium, a polycaprolactone grafted with PEG-400, called PCL-g-PEG.
  • the hydrophilic polycaprolactone is dissolved in 1,4-dioxane, formulated into a 20% mass concentration solution, and spin-coated on a spin coater at 2000 rpm to obtain hydrophilicity.
  • Polycaprolactone film Through the static contact angle test, the static contact angle of the polycaprolactone (PCL) film is as high as 95°, and the static contact angle of the obtained PCL-g-PEG film is obtained after grafting polyethylene glycol (PEG) onto the P CL main chain. It is 38°, which indicates that the hydrophilic property of polycaprolactone (PCL) is remarkably improved by grafting a polyethylene glycol having a hydrophilic effect of a polyether segment.
  • 6-Amino-1-hexanol was reacted in a closed system for 8 hours.
  • the reaction solution was poured into 60 g of n-heptane, and the hydroxyl-activated polycaprolactone was precipitated by an anti-solvent method, and filtered to obtain a white solid, which was washed three times with ethanol, 200 g each time, and deionized again.
  • the water was washed 3 times, 500 g each time, and then the product was placed in a vacuum oven and baked at 37 ° C for 24 hours to obtain a hydroxylated polycaprolactone.
  • reaction solution was poured into 25 g of n-heptane, and PCL of grafted PEG-600 was precipitated by an anti-solvent method, and filtered to obtain a white solid, which was mixed with ethanol and deionized water (v/v, 1: 1). Wash 4 times, use 100 g each time, wash 4 times with deionized water, use 300 g each time, put the obtained product into a vacuum oven, and bake at 37 ° C for 24 hours to obtain grafted PEG-600. Polycaprolactone.
  • hydrophilic polycaprolactone is dissolved in 1,4-dioxane, formulated into a 10% by mass solution, and spin-coated on a spin coater at 4000 rpm to obtain hydrophilicity.
  • Polycaprolactone film The static contact angle of the grafted PEG-600 polycaprolactone PCL-g-PEG film was tested by static contact angle to be 3 ⁇ .
  • ⁇ , ⁇ '-carbonyldiimidazole (CDI) and 60 g of dehydrogenated tetrahydrofuran (THF) were dissolved at room temperature.
  • dehydrogenated tetrahydrofuran (THF) 60 g was dissolved at room temperature.
  • 7.2 g of PEG-400 was dissolved in 40 g of dehydrogenated tetrahydrofuran (THF), and added dropwise to a three-necked flask through a constant temperature and constant pressure funnel, and the addition was completed in 1.5 hours at 35 ° C. Reaction for 8 hours.
  • reaction solution was poured into 30 g of petroleum ether, and PCL of grafted PEG-400 was precipitated by an anti-solvent method, and filtered to obtain a white solid, which was washed with a mixed solution of methanol and deionized water (v/v, 1: 1). 4 times, use 200 g each time, then wash 4 times with deionized water, use 300 g each time, put the obtained product into a vacuum oven, and bake at 37 ° C for 24 hours to obtain the graft of grafted PEG-400.
  • Caprolactone is poured into 30 g of petroleum ether, and PCL of grafted PEG-400 was precipitated by an anti-solvent method, and filtered to obtain a white solid, which was washed with a mixed solution of methanol and deionized water (v/v, 1: 1). 4 times, use 200 g each time, then wash 4 times with deionized water, use 300 g each time, put the obtained product into a vacuum oven
  • hydrophilic polycaprolactone is dissolved in 1,4-dioxane, formulated into a 20% mass concentration solution, and spin-coated on a spin coater at 2000 rpm to obtain hydrophilicity.
  • Polycaprolactone film The static contact angle of the grafted polycaprolactone PCL-g-PEG film was measured by static contact angle to be 36°.
  • 6-Amino-1-hexanol was reacted in a closed system for 8 hours.
  • the reaction solution was poured into 80 g of n-hexane, and the hydroxyl-activated polycaprolactone was precipitated by an anti-solvent method, and filtered to obtain a white solid, which was washed three times with ethanol, 200 g each time, and then deionized.
  • the water was washed 3 times, 400 g each time, and then the product was placed in a vacuum oven and baked at 37 ° C for 24 hours to obtain hydroxylated polycaprolactone.
  • reaction solution was poured into 60 g of hexamethylene ruthenium, and PCL of grafted PEG-800 was precipitated by an anti-solvent method, and filtered to obtain a white solid, which was washed with a mixed solution of ethanol and deionized water (v/v, 1:1). 4 times, 300 per use
  • the mixture was baked at ° C for 24 hours to obtain a polycaprolactone grafted with PEG-800.
  • hydrophilic polycaprolactone was dissolved in 1,4-dioxane, formulated into a 20% mass concentration solution, and spin-coated on a spin coater at 2000 rpm to obtain hydrophilicity. Polycaprolactone film.
  • the static contact angle of the grafted PEG-S00 polycaprolactone PCL-g-PEG film was measured by static contact angle to be 32°.
  • DMAP 4-dimethylaminopyridine
  • 20 g of anhydrous potassium carbonate and 150 g of dehydrogenated tetrahydrofuran (THF) were dissolved by stirring at 60 ° C, and 10 g of theylated polycaprolactone was dissolved in 200 g of tetrahydrofuran.
  • THF dehydrogenated tetrahydrofuran
  • reaction solution was poured into 160 g of petroleum ether, and PCL of grafted PEG-400 was precipitated by anti-solvent method, and filtered to obtain a white solid, which was washed with a mixed solution of ethanol and deionized water (v/v, 1: 1). 4 times, use 300 g each time, then wash 4 times with deionized water, use 600 g each time, put the obtained product into a vacuum oven, and bake at 37 ° C for 24 hours to obtain the graft of grafted PEG-400.
  • Caprolactone is poured into 160 g of petroleum ether, and PCL of grafted PEG-400 was precipitated by anti-solvent method, and filtered to obtain a white solid, which was washed with a mixed solution of ethanol and deionized water (v/v, 1: 1). 4 times, use 300 g each time, then wash 4 times with deionized water, use 600 g each time, put the obtained product into a vacuum oven, and bake at
  • hydrophilic polycaprolactone was dissolved in 1,4-dioxane, formulated into a 20% mass concentration solution, and spin-coated on a spin coater at 2000 rpm to obtain hydrophilicity.
  • Polycaprolactone film The static contact angle of the polycaprolactone PCL-g-PEG film was measured by a static contact angle of 36°.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

La présente invention concerne un procédé de préparation d'un film de polycaprolactone hydrophile, le procédé comprenant les étapes consistant à : introduire un groupe oxime dans un groupe pendant polycaprolactone ; soumettre un anhydride succinique à une estérification avec un groupe hydroxyle dans un groupe oxime latéral de manière à obtenir une polycaprolactone carboxylée ; puis faire réagir un polyéthylène glycol hydroxy terminal avec un carboxyle, et à greffer le polyéthylène glycol sur une chaîne latérale de polycaprolactone de manière à obtenir une polycaprolactone hydrophile ; et préparer un film de polycaprolactone hydrophile en utilisant un revêtement en solution. Selon la présente invention, l'intérieur d'un corps de matériau à base de polycaprolactone à modification hydrophile passe également du statut hydrophobe à hydrophile, ce qui permet d'obtenir un produit modifié ayant un taux de greffe élevé et un caractère hydrophile élevé. Par ailleurs, le procédé de préparation décrit dans la présente invention présente les avantages de conditions réactionnelles douces, de procédés de préparation simples et d'une forte capacité de contrôle, et est approprié pour la production industrielle.
PCT/CN2016/080180 2016-04-25 2016-04-25 Procédé de préparation d'un film de polycaprolactone hydrophile Ceased WO2017185218A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5932686A (en) * 1996-10-18 1999-08-03 Ems-Inventa Ag Adhesion promoter for a polyamid-compounds
WO2002053610A1 (fr) * 2000-12-29 2002-07-11 Kimberly-Clark Worldwide, Inc. Compositions biodegradables modifiees et leur procede de fabrication par extrusion reactive
CN102276817A (zh) * 2011-04-22 2011-12-14 武汉大学 树状接枝聚己内酯
CN104520343A (zh) * 2012-08-09 2015-04-15 阿肯马法国公司 基于pla的聚合物组合物
CN105754122A (zh) * 2016-04-25 2016-07-13 苏州大学张家港工业技术研究院 一种亲水性聚己内酯薄膜的制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5932686A (en) * 1996-10-18 1999-08-03 Ems-Inventa Ag Adhesion promoter for a polyamid-compounds
WO2002053610A1 (fr) * 2000-12-29 2002-07-11 Kimberly-Clark Worldwide, Inc. Compositions biodegradables modifiees et leur procede de fabrication par extrusion reactive
CN102276817A (zh) * 2011-04-22 2011-12-14 武汉大学 树状接枝聚己内酯
CN104520343A (zh) * 2012-08-09 2015-04-15 阿肯马法国公司 基于pla的聚合物组合物
CN105754122A (zh) * 2016-04-25 2016-07-13 苏州大学张家港工业技术研究院 一种亲水性聚己内酯薄膜的制备方法

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