名古屋工業大学学術機関リポジトリ

Title
Author(s)
Synthesis of Polyesters Using an Organic Catalyst and Design
of Polyester-based Double Network Gels 有機触媒を用いた
ポリエステルの合成とポリエステルを基盤としたダブル
ネットワークゲルの設計
Tang, Tang
Citation
Issue Date
URL
2014-09-03
http://repo.lib.nitech.ac.jp/handle/123456789/22176
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タンタン
氏
名
TANG TANG
学位の種類
博士（工学）
学位記番号
博第963号
学位授与の日付
平成26年9月3日
学位授与の条件
学位規則第4条第1項該当課程博士
学位論文題冒
Syl］thesis of PolyeSters Using an Organic Catalyst and
Design of Polyester−based Double Network Gels
（有機触媒を用いたポリエステルの合成とポリエステルを基
盤としたダブルネットワークゲルの設計）
論文審査委員
山
主査
准教授
局
須
昭
則
教授
稲
井
嘉
人
教授
鈴
木
将
人
准教授
高
木
幸
治
教授
楊
小平（北京化工大学）
論文内容の要旨
Aliphatic polyesters， especially unsaturated polyesters， are now fascinating
because of their biodegradability and biocompatibility To sy斑hesize a∬phatic
polyesters via an environmen㌔f五endly method， meta1−f士ee catalyst is essentiaL
Moreover， how to enhallce the mechanical s加ngth of the polyesters in order to suit fbr
fUr血er apPlications is also still remained subj ect． In this decade， fbr the continuous
development of interpenetτat輌ng polymer networks（IPNs）， double network（DN）
concept was observed in some works．
Chapter 1：Tb synthesize polyesters and pehodic copolymers catalyzed by
nona且uorobutanesulfbnimide（Nf＞NH）， we perfb㎜ed ring−opening copolymerizations
of cyclic anhyd亘des with tetrahydrof泣an（THF）． At h輌gh temperature（100420°C）， the
cyclic anhyd亘des copolymerized with THF via ri1〕g−op頭ing to produce polyesters． At
low・temperatじre， ring−opening copolymerizations of the cyclic anhydrides wi也THF
produced poly（ester−ether）． When toluene（4 M）was used as a solvent， GAn reacted
with THF（urLit ratio：1：2）to produce periodic copolymers．
Chapteぞ2：We report herein the polycondensations‘of unsaturated cyclic
anhydrides with diols at moderate tempera勧res using the sub五imating organ輌c catalyst，
随NH， to sWthesize polyesters containing caH）on−carbon double bonds． We lnitially
synthesized isomerization−］＆ee unsaturated polyesters containing alternat輌ng maleate or
itaconate and 3−methy1−1，5−pe斑anediol units． Additionally， using copolyesters
containing maleate and itaconate units， we could selectively photo−crosshrd（the
exo−type double bonds of the itaconate units to a餓）rd unsaturated polyester gels・
Starting with these gels， we then isomerized the maleate un江c∫ぷdouble bonds to功η3
double bonds by a diethylamine−catalyzed oiぷイγαηぷisomerization． The swelhng
properties ofthe gels were fbund to depend on the initial maleate to fUmarate unit ratios
（degree ofisomerization）as well as the maleate to itaconate㎜it ratios．
Chapter 3：The Michael addition and UV二initiated radical polymedzation were
used to fabr輌cate a one−pot method fbr synthesis of polyester−based DN gels． The
unsaturated copolyesters contairlillg itaconate and maleate units were prepared via
polycolldensation under mild collditions． Then a double−network（DN）gel was
sWthes輌zed by two−stepS． After dissolved polyester， methyl methacrylate（MMA）and
UV二initiator in toluene， diamine was added into mixture． The first gel was prepaτed by
the catalyst−f≧ee selective cross−1inking of maleate double bonds with diamine at room
temperatuτe． Subsequ斑tbらthe first gel was irradiated㎜1der UV二1ight fbr 3 h． The
obtained hydrophobic polyester／poly（MMA）DN gel containing amino group w輌th high
mecha磁cal str斑gth showed shape recovery property． To expand the application of this
method， a poly（ester−co−ether）／polyacrylamide DN hyd壬ogel was also synthesized．
論文審査結果の要旨
Aliphatic polyesters， especially unsa加rated polyester号， are now fascinating beca撃se of their
biodegradability and biocompatibility」Tb synthesize aliphatic polyesters via an envirollment−f貢endly
method， metal一丘ee catalyst is esse1ユtial． Moreover， how to enhance the mechanical strellgth of the
po玉yesters in order to suit fbr fUrther apPlications is also stiU relTla祖ed su句ect・In this decade， fbr the
colltinuous devebpment of interpelleぬtillg polymer networks（IPNs）， double network（DN）concept
was observed in some works．
Chapter 1： Tb sylユthesize poiyesters and pe百odic copolymers catalyzed by
nonafluorobutanesulfbllimide （Nf5NH）， he perfbnlled τi119−opelling copolymerizations of、cyc▲ic
anhydrides with tetrahydrofaran（THF）． At high temperature（10◎−120°C）ジthe cyclic a品ydrides
copolymel元zed with THF via rmg−opelling to produce polyesters． At low temperature， ring−openilユg
copolymerizatiolls of the cyclic anhydrides with THF produced poly（ester−ether）． When toluelle（4 M）
was used as a solv斑t， GAn reacted with THF（ullit ratio：1：2）to produce periodic copoly1〕ユers．
Ch叩ter 2：We report herein the polycondellsations ofullsaturated cyclic allhydrides with diols at
moderate tempera白res ushlg the sublimatillg organic catalyst， NfぷH， to synthesize polyesters
contaillhlg carbo1卜carbon double bonds．｝le initiaUy syllthes｛ze（l isomerization−｛ヤee ullsaturated
polyes缶rs contaillillg a▲temating maleate or itaconate alld 3−tγ｝ethyl−1，5−pe就allediol ullits． Additl◎11ally，
using copolyesters contai1加g maleate alld itaconate ullits， he could selectively photo−crossllnk the
exo−type double bonds of the itacollate units to affbrd unsaturated polyester gels． Starthlg w輌th these
gels， we th斑 isomerized the maleate u1〕it c∫3 double bollds to 〃・α12ぷ double bonds by a
die也ylamme−catalyzed c匡3イ1・α123 isomerizatio11． The swellillg properties of the gels were fbwld to
dep斑d oll the irlitial lnaleate to釦marate unit ratios（deg塾◆㈱of isomerizatiol1）as well as the maieate to
itaCOIlate un輌t ratios．
Chapter 3：The Michael addition alld UV・l illitiated radical polymerizatioll were used to｛hbricate
one−pot method fbr syr曲esis of polyester−based DN gels． The u三1saturated copolyesters co耐ainill
itacollate alld maleate ullits were prepared via polyco1、dellsa鍼011 ullder mild collditiolls． The韮1
double−network（DN）gel was sy耐hes▲zed by two−steps． A負er dissolved polyester， methyl methacrylat
（MMA）alld UV−in柱iator in toluene， diamille was added短to！nixture． The盲rst gel was prepared by th
catalyst−fピee selective cross−1輌nkillg of maleate double bonds wlth diarnille at rooln temperature．
Subsequentl鵠 the first gel was irradiated under U∼㌦Hght fbr 3 h． The obtained hydrophobi
polyes撤／poly（MMA）DN gel containing alnino group witll high mechanical strength showed shap
recOvery property．丑）expand the applicat輌on ofthis method， a poly（esteτ一co−e翫e1’）／polyacrylamide D
hydrogel was also s》哩ユthesized・・
The results are summa亘zed in three papers with peer rev輌ew and are valuable fbr the Ph D． thesis．

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