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Synthesis, propagation kinetics, and...

The University of Southern Mississippi.

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Synthesis, propagation kinetics, and characterization of D,L-lactide-based polyols and polyurethanes therefrom.

Record Type:	Language materials, printed : Monograph/item
Title/Author:	Synthesis, propagation kinetics, and characterization of D,L-lactide-based polyols and polyurethanes therefrom./
Author:	Moravek, Scott Joseph.
Description:	130 p.
Notes:	Adviser: Robson F. Storey.
Contained By:	Dissertation Abstracts International70-02B.
Subject:	Chemistry, Polymer. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3346545
ISBN:	9781109013481

Synthesis, propagation kinetics, and characterization of D,L-lactide-based polyols and polyurethanes therefrom.
Moravek, Scott Joseph.

Synthesis, propagation kinetics, and characterization of D,L-lactide-based polyols and polyurethanes therefrom. - 130 p.

Adviser: Robson F. Storey.

Thesis (Ph.D.)--The University of Southern Mississippi, 2008.

In order to expand the usefulness of degradable polyesters, degradable polyurethanes were synthesized using a mixed polyol system including poly(D,L-lactide-co-glycolide) (PLGA), a well-known degradable polyester. Two isocyanate systems, methyl 2,6-diisocyantocaproate (LDI) and dicyclohexylmethane-4,4'-diisocyanate(H12MDI), were studied in order to achieve optimal physical and thermal properties of the thermoplastic polyurethane (TPU) while maintaining degradablity. The LDI based systems had excellent physical properties as well as thermal properties that may make them suitable for biomedical devices. The H12MDI based TPUs also had excellent physical properties as well as a higher melting temperature.

ISBN: 9781109013481Subjects--Topical Terms:

1018428
Chemistry, Polymer.

Synthesis, propagation kinetics, and characterization of D,L-lactide-based polyols and polyurethanes therefrom.
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020 $a 9781109013481
035 $a (UMI)AAI3346545
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040 $a UMI $c UMI
100 1 $a Moravek, Scott Joseph. $3 1018512
245 1 0 $a Synthesis, propagation kinetics, and characterization of D,L-lactide-based polyols and polyurethanes therefrom.
300 $a 130 p.
500 $a Adviser: Robson F. Storey.
500 $a Source: Dissertation Abstracts International, Volume: 70-02, Section: B, page: 1063.
502 $a Thesis (Ph.D.)--The University of Southern Mississippi, 2008.
520 $a In order to expand the usefulness of degradable polyesters, degradable polyurethanes were synthesized using a mixed polyol system including poly(D,L-lactide-co-glycolide) (PLGA), a well-known degradable polyester. Two isocyanate systems, methyl 2,6-diisocyantocaproate (LDI) and dicyclohexylmethane-4,4'-diisocyanate(H12MDI), were studied in order to achieve optimal physical and thermal properties of the thermoplastic polyurethane (TPU) while maintaining degradablity. The LDI based systems had excellent physical properties as well as thermal properties that may make them suitable for biomedical devices. The H12MDI based TPUs also had excellent physical properties as well as a higher melting temperature.
520 $a The aforementioned TPUs were synthesized in small batches. Another method of TPU polymerization was also developed. A reactive extrusion method was developed using a co-rotating twin screw extruder. This system was designed to emulate commercial processes, but on a smaller scale. This method proved to be very successful for synthesizing high molecular weight TPUs.
520 $a In order to better understand the urethane forming isocyanate/alcohol reaction, a model system was design based on the polymerization conditions of the TPU synthesis. 1-Butanol and 2-butanol served as the representative primary and secondary alcohol respectively. Three different catalysts were investigated to determine the effect on the rate of the reaction; dibutyl tindilaurate, tin (II) 2-ethylhexanoate (SnOct), and triethylamine. The reaction of each alcohol with H12MDI was monitored by real-time transmission FTIR, utilizing a temperature controlled flow cell connected to an external reactor. The isocyanate peak at 2256 cm-1 was monitored and second order kinetic plots were generated. The rate constant of each urethane-forming reaction was determined.
520 $a Ring-opening polymerization kinetics of D,L-lactide in refluxing tetrahydrofuran were investigated using a number alcohol/SnOct initiating systems. The alcohols used to initiate polymerization were of varying architecture, with functionalities of one to four, to study the effects of that architecture on the rate of polymerization. The polymerization reaction was monitored by following the 1240 cm -1 C-O-C asymmetric stretch and 933 cm-1 ring breathing mode of D,L-lactide in real-time using ATR-FTIR spectroscopy. First order kinetic plots were generated and apparent rate constants, kapp, were determined for each system.
520 $a The kinetics of D,L-lactide/epsilon-caprolactone copolymerization were also investigated, using two different methods of copolymerization. First, a conventional copolymerization was conducted where both monomers were polymerized in one reactor such that the monomer sequencing was controlled only by monomer reactivities. The second method was a two-pot synthesis where epsilon-caprolactone was polymerized and used as a macroinitiator for D,L-lactide. The goal of this alternate copolymerization method is to reduce the overall time required to achieve high conversion of both monomers.
590 $a School code: 0211.
650 4 $a Chemistry, Polymer. $3 1018428
690 $a 0495
710 2 $a The University of Southern Mississippi. $3 1018511
773 0 $t Dissertation Abstracts International $g 70-02B.
790 $a 0211
790 1 0 $a Storey, Robson F., $e advisor
791 $a Ph.D.
792 $a 2008
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3346545