Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

A kind of hydrophobic polycaprolactone and preparation method thereof

A technology of polycaprolactone and hydrophobic type, which is applied in the field of hydrophobic polycaprolactone and its preparation, can solve the problems of difficult unsaturated monomer modification, poor carbon-bromine bond activity, low liquid repellency, etc., and achieve molecular weight High, narrow molecular weight distribution, the effect of avoiding degradation

Active Publication Date: 2019-10-29
SUZHOU UNIV
View PDF7 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

This method has the following defects in the polymerization process: (1) affected by the macromolecular chain, the activity of the carbon-bromine bond (C-Br) at the end of the polycaprolactone chain is poor, and it is difficult to effectively initiate the polymerization of unsaturated monomers to realize the improvement. (2) Since the block-modified polycaprolactone of the fluorine-containing monomer is hydrophobic and has very low polarity, it is difficult to dissolve in conventional organic solvents, and it may be precipitated from the conventional organic solvent system in the early stage of the block polymerization reaction
In addition, fluorine-containing materials can endow the polymer with excellent liquid repellency and low surface energy and low polarity, so it is not conducive to biosorption and degradation

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • A kind of hydrophobic polycaprolactone and preparation method thereof
  • A kind of hydrophobic polycaprolactone and preparation method thereof
  • A kind of hydrophobic polycaprolactone and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0064] (1) Polycaprolactone terminal hydroxylation

[0065] Dissolve 50.0g of PCL with a molecular weight of 80,000 in 500g of 1,4-dioxane at 37°C. Under nitrogen protection, add 51g of 6-amino-1-hexanol and react for 8h. After the reaction was completed, the reaction solution was slowly added into 1000 g of absolute ethanol which was continuously stirred, and a solid was precipitated. After filtration, the filter cake was washed with absolute ethanol (100 g x 3 times), and dried in vacuum at 37° C. for 24 hours to obtain 39.6 g of the product with a yield of 79.2%. The molecular weight of the product was measured to be 69800.

[0066] (2) Polycaprolactone terminal carboxylation

[0067] Add 25.0 g of hydroxyl-terminated polycaprolactone (PCL-OH) and 28.5 g of succinic anhydride prepared above into 500 g of 1,4-dioxane. After stirring and dissolving, add 9.85g anhydrous potassium carbonate (K 2 CO 3 ) and 8.70g 4-dimethylaminopyridine (DMAP), reacted at room temperature f...

Embodiment 2

[0075] (1) Polycaprolactone terminal hydroxylation

[0076] Dissolve 50.0g of PCL with a molecular weight of 80,000 in 520g of 1,4-dioxane at 37°C, and add 49g of 6-amino-1-hexanol under nitrogen protection, and react for 12 hours. After the reaction was completed, the reaction solution was slowly added into 1050 g of absolute ethanol which was constantly stirred, and a solid was precipitated. After filtration, the filter cake was washed with absolute ethanol 100g × 3 times, and dried in vacuum at 37°C for 24h to obtain 37.9g ​​of the product with a yield of 75.8%. The molecular weight of the product was measured to be 67500.

[0077] (2) Polycaprolactone terminal carboxylation

[0078] Add 25.0 g of hydroxyl-terminated polycaprolactone (PCL-OH) and 29.2 g of succinic anhydride prepared above to 510 g of 1,4-dioxane. After stirring and dissolving, add 9.88g anhydrous potassium carbonate (K 2 CO 3) and 8.75g 4-dimethylaminopyridine (DMAP), reacted at room temperature for 4...

Embodiment 3

[0086] (1) The operation steps of polycaprolactone terminal hydroxylation and polycaprolactone terminal carboxylation are the same as in Example 1.

[0087] (2) Preparation of hydroxyl-terminated poly(1H,1H,2H,2H-tridecafluorooctyl acrylate) by ATRP method

[0088] Dissolve 418ug of ethylene glycol bromoisobutyrate and 620ug of pentamethyldiethylenetriamine (PMDETA) in 60g of 2-butanone, after dissolving, add 0.6g of cuprous bromide, under nitrogen protection at 40°C The reaction was stirred for 15 minutes to obtain a catalyst. Add 65.6g of 1H,1H,2H,2H-tridecafluorooctyl acrylate (TFOA), heat to 80°C, and react for 6 hours. After the reaction was completed, 360g THF and 120g benzotrifluoride were added and passed through a neutral alumina (200-300 mesh) column to obtain a pale yellow clear solution. The solution was evaporated under reduced pressure at 65°C to remove the solvent, then the crude product was added to 1050g of anhydrous methanol, and a solid was precipitated, f...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

PropertyMeasurementUnit
melting pointaaaaaaaaaa
glass transition temperatureaaaaaaaaaa
Login to View More

Abstract

The invention discloses a hydrophobic polycaprolactone and a preparation method thereof: react polycaprolactone with an amino alcohol compound to prepare hydroxyl-terminated polycaprolactone; react hydroxyl-terminated polycaprolactone with an acid anhydride to prepare carboxyl-terminated polycaprolactone Polycaprolactone; reacting ethylene glycol bromoisobutyrate with fluorine-containing alkyl acrylate to prepare hydroxyl-terminated fluorine-containing polyacrylate; reacting carboxyl-terminated polycaprolactone with hydroxyl-terminated fluorine-containing polyacrylate, Preparation of hydrophobic polycaprolactone. The molecular weight of the hydrophobic segment of the product of the invention is controllable, the molecular weight distribution is narrow, and the fluorine content and hydrophobicity are controllable. When preparing the hydrophobic polycaprolactone, the end group activated fluorine-containing polymer is pre-prepared to obtain a fluorine-containing polymerization product in a homogeneous system, which is easy to control the degree of polymerization. It solves the problem that it is difficult to generate fluoropolymer chain directly at the PCL chain end in situ due to the change of solubility. The product is prepared by direct condensation of active carboxyl-containing PCL and active hydroxyl-containing organic fluorine polymer under mild reaction conditions, which avoids the degradation of PCL.

Description

technical field [0001] The invention relates to a polymer modification technology, in particular to a hydrophobic polycaprolactone and a preparation method thereof. Background technique [0002] Poly-caprolactone (poly-caprolactone, PCL) is a kind of linear aliphatic polyester obtained by ring-opening polymerization of ω-caprolactone monomer under the catalysis of metal organic compounds (such as tetraphenyltin). Degradability, good biocompatibility, drug permeability and mechanical properties have been certified by the US FDA, and have been extensively researched and applied in the field of film applications. Polycaprolactone (PCL) has a melting point of 59-64°C and a glass transition temperature of -60°C. Its structural repeat unit has 5 non-polar methylene-CH 2 - and a polar ester group -COO-, ie -(COOCHCH 2 CH 2 CH 2 CH 2 CH 2 -)Pn, this structure makes PCL have good flexibility and processability, and this material has good biocompatibility. [0003] At present,...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): C08G81/02C08G63/91C08J5/18
CPCC08G63/912C08G81/027
Inventor 李战雄李武龙王海朋
Owner SUZHOU UNIV
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products