Block copolymers of lactones and poly(propylene fumarate)

A kind of technology of propylene glycol fumarate and block copolymer, applied in the field of preparation and functionalization of the polymer

Pending Publication Date: 2019-06-28
THE UNIVERSITY OF AKRON
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The main disadvantage of using PPF polymers in these systems is that any excess DEF (i.e. any DEF that does not actually crosslink the PPF polymer chains) must be removed before the printed structures can be used in biological systems

Method used

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  • Block copolymers of lactones and poly(propylene fumarate)
  • Block copolymers of lactones and poly(propylene fumarate)
  • Block copolymers of lactones and poly(propylene fumarate)

Examples

Experimental program
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Effect test

no. 1 example

[0182] The ROCOP synthesis of δVL and εCL was also studied, followed by the ROCOP of MAn and PO. Use Mg again (BHT) 2 (THF) 2 As a catalyst and BnOH as an initiator, δVL and εCL were copolymerized in toluene at a concentration of 2M at 80°C for 24 hours. 1 The H NMR spectrum showed that in addition to MAn and PO, δVL and εCL were equally incorporated into the polymer chain. by 13 C NMR spectroscopy analysis of the carbonyl binary resonance peak shows a sequence-like block, where δVL and εCL are randomly incorporated into the first block, and MAn and PO are alternately incorporated into the second block. DOSY NMR spectroscopy confirmed the existence of a single diffusive polymer species.

[0183] Thermal analysis using differential scanning calorimetry (DSC) reveals a wide range of properties. (See Figure 21-28 ). As expected, the polymer containing the aliphatic lactone block has a melting temperature higher than room temperature and a crystallization temperature higher than 0...

Embodiment 1

[0197] Synthesis of ε-heptanolide and γ-methyl-ε-caprolactone

[0198] The single-neck round bottom flask containing 250 mL of dichloromethane was cooled in an ice bath, and then 223 mmol of 2-methylcyclohexanone or 4-methylcyclohexanone and 275 mmol of m-chloroperoxybenzoic acid were added. After refluxing for 3 days, the reaction mixture was cooled in an ice bath, filtered with Celite, and used 10% Na 2 S 2 O 3 Solution, saturated Na 2 CO 3 Solution and brine wash. Then use MgSO 4 The organic layer was dried and filtered, and then the solvent was removed by rotary evaporation. The two products were dried overnight on calcium hydride and distilled under vacuum before use.

[0199] ε-Heptanolide :

[0200] by 1 H NMR (300MHz, 303K, CDCl 3 ) Confirm the presence of ε-heptanolide: δ = 4.44 (m, CH 2 (CH 3 )O), 2.64(m,C(=O)CH 2 ), 1.73(m,CH 2 CH(CH 3 )), 1.42(m,CH 2 CH 2 CH(CH 3 )).

[0201] γ-methyl-ε-caprolactone :

[0202] by 1 H NMR (300MHz, 303K, CDCl 3 ) Confirm the presence of γ...

Embodiment 2

[0204] Synthesis of θ-propargyl-ε-nonanolactone

[0205] 30.0mL cyclohexanone (28.4g, 289mmol), 28.5mL pyrrolidine (24.7g, 347mmol) and 55.0mg p-toluenesulfonic acid monohydrate (0.289mmol) were dissolved in 60mL toluene in a round bottom flask. The bottom flask is equipped with a Dean-Stark device and a reflux condenser. The solution was stirred at 150°C for 16 hours. The resulting solution was washed and cooled to room temperature, washed with water and brine, and then washed with MgSO 4 Dry and remove the solvent under reduced pressure. The product was purified by vacuum fractional distillation (31.4 g, boiling point 107-114°C) to obtain a pale yellow oil. Then it was dissolved in dry MeCN in a double-necked round bottom flask equipped with a reflux condenser, and then 26.8 mL of propargyl bromide (80% toluene solution, 37.0 g, 249 mmol) was added dropwise to the solution. in. The reaction was stirred overnight under reflux, then cooled to room temperature, and then the so...

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Abstract

In various embodiments, the present invention provides well-defined biodegradable poly(lactone-b-propylene fumarate) diblock and triblock polymers formed using a novel one-pot, scalable ring-opening block-order copolymerization (ROBOCOP) technique that utilizes magnesium 2,6-di-tert-butyl-4-methylphenoxide (Mg(BHT)2(THF)2) to "switch" from the ROP of cyclic esters to the ROCOP of maleic anhydride(MAn) and propylene oxide (PO) to produce PPF based block copolymers for application in additive manufacturing and patient specific regenerative medicine. These block copolymers are fully resorbable and can be photochemically crosslinked in a number of applications, including 3D printing. By adding the lactone block to the PPF polymer, the viscosity of the resulting block copolymer at working temperatures can be precisely controlled and the quantity of the reactive diluent in printable resins can be reduced or eliminated.

Description

[0001] Cross references to related applications [0002] This application requires the U.S. Provisional Patent Application Serial No. 62 / 500,777 filed on May 3, 2017 entitled "Post 3D Printing Functionalized Polymer Scaffold for Enhanced Biological Activity", filed on May 22, 2017 U.S. Provisional Patent Application Serial No. 62 / 509,340 named "functionalized poly(propylene fumarate) polymer and its preparation method", filed on August 7, 2017, named "well-defined synthesis and characterization of poly (Propylene fumarate) and poly(ethylene glycol) block copolymer" U.S. Provisional Patent Application Serial No. 62 / 541,889, filed on September 22, 2017 under the name "Poly(propylene fumarate) U.S. Provisional Patent Application Serial No. 62 / 561,722 and the applicant’s filed on February 2, 2018 entitled "Functionalized poly(fumaric acid) prepared by ring-opening polymerization using magnesium catalyst All of these documents are incorporated herein by reference in their entirety. [...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08G69/14C08G75/14C08G81/00
CPCC08G63/91C08G63/08C08G63/52C08G63/682C08G63/685C08G63/83
Inventor M·贝克J·威尔逊S·皮特森
Owner THE UNIVERSITY OF AKRON
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