cxtender /CH2\ ĩ CNHRNCO polyurethane Fig.2... Estes GM., Cooper SL.. Chang Y.J.P and Wilkes GL., Superstructure in Segmented Polyurethanes, J.. and Cooper SL., Exvivo interạctions and 8
Trang 1VNU JOURNAL OF SCIENCE, N a t, Sci., & Tech., T.XX1II NọỊ 2007
AMPHIPHILIC POLYURETHANES WITH A NOVEL PEG-
CONTAINING CHAIN EXTENDER
PART I: SYNTHESIS AND CHARACTERIZATION
Pham Ngoe Lan(1), Luu Van Boi(2)
{ì)P o lỵm er R esearch C enter, H a n o i U n iversity o f Technology
(2) D e p a rtm e n t o f C hem istry, College o f Science, V N U
1 I n tr o d u c tio n
P o ly u re th a n c s a r e block copolym ers com posed of a lte r n a tin g s h o rt h a rd seg m e n ts
an d long ílex ib le soft se g m e n ts t h a t a re th e rm o d y ĩiam ic a lly in co m p atib le a t th e
te m p e ra tu re of u se [1,2] P h a s e s e p a ra tio n of se g m e n te d p o ly u re th a n e s (SPU ) w ith a lim ited h a rd s e g m e n t c o n te n t re s u lts in h a rd s e g m e n t rich d o m ain s d isp e rse d in a
co n tin u o u s m a trix of th e so ft seg m e n ts [3] T h e h a rd d o m ain s a c t as p h y sical crosslink
p roviding th e po ly m er w ith m echanical s tre n g th w h ile th e soft m a trix co n trib u te s to
th e ela sto m e ric p ro p e rtie s [4,5] T h e m a in facto rs in A u en cin g th e h a rd d o m ain cohesion
a n d th e r e s u ltin g p h a s e s e p a ra tio n in clu d e h y d ro g en b o n d in g a n d c ry sta lliz a tio n [4]
S e v era l s tr a te g ie s h a v e b een proposed to íu r th e r im p ro v e th e su rface p ro p erties for p o ly u re th a n e s [5] In th is resp ect, p o ly eth y len e oxide rich su ría c e s t h a t non selectively re p e l p ro te in s a n d cells h av e b een p re p a re d a n d e v a lu a te d [6,7] In th e
p re s e n t w ork, a novel P E G -co n tain in g ch a in e x te n d e r w as sy n th e siz e d a n d th e
p o te n tia l u se of th is c h a in e x te n d e r for th e sy n th e sis o f se g m e n te d p o ly u re th a n e s w as
in v e stig a te d T h u s , a s e rie s of a m p h ip h ilic copolym ers w ith P E G sid e ch a in s of
d ifferen t MW w ere p re p a re d T h is artic le d escrib ed th e s y n th e s is a n d cheraical
c h a ra c te riz a tio n of b o th th e novel c h a in e x te n d e r a n d th e r e s u lta n t g rafted
p o ly u re th a n e s
2 E x p e rim e n ta l
2.1 M aterials
All so lv en ts w ere u se d a s received, excep t for p y rid in e (dried on C aH2) and
d ic h lo ro m e th a n e (d ried on P 20 5) Poly(TH F-CD ), a sp ecial p o ly e th e r p o ly carb o n ate diol
w ith MW 2000 a n d b a se d on Poly(TH F) w as o b ta in e d from BASF T h e a-hydroxy-cừ-
m eth o x y p o ly eth y len e glycols (M PEG ) w ere o b ta in e d from J a n s e n (MW 350), Acros (MW 550, 750, 1000) a n d P o ly m er L a b o ra to rie s (MW 1900) respectively Both
19
Trang 22 0 Pham N goe Lan, Luu Van Bo)i
Poly(TH F-C D ) a n d th e M P E G ’s w e re d rie d a t 6 0 °c for 6 h o u rs u n d e r re d u ced p r e s s u r e
im m e d ia te ly befo re u se H e x a m e th y le n e d iiso c y a n a te (H M D I), b u ta n e diol (BD).,
d ib u ty ltin d ia c e ta te (DBTDAc), d ie th a n o l a m in e (D EA ) a n d to sy lch lo rid e (TsCl) w e r e used a s received
2.2 C h a r a c te r iz a tio n m e th o d s
1H -N M R sp ectroscopy
AU 'H -N M R sp ectro sco p y a n a ly s e s w e re re c o rd e d in d e u te r a te d chloroform on ai
B ru c k e r 360 M H z in s tr u m e n t T h e ch em ical s h ift w a s e x p re sse d in ppm re la tiv e tC)
te tra m th y l s ila n e a s in te r n a l S ta n d a rd
G P C a n a ly sis
G P C a n a ly s e s w e re p e rfo rra e d on 1% (w/v) so lu tio n in N M P T h e s ty ra g e l columru
(P olym er L a b o ra to rie s, 104-105 A°) w a s o p e ra te d a t 4 5 ° c a n d a flow r a t e of 1 m l/m in A
re íra c to m e te r w a s u s e d for d e te c tio n aríd th e d a ta a n a ly s is w a s d o n e w ith a W a te r s
D a ta M o d u le M 730 T h e r e la tiv e m o le c u la r w e ig h ts a n d th e p o ly d isp e rsity of t h e
s am p le s w e re c a lc u la te d u s in g a n a rro w m o le c u la r w e ig h t p o ly sty re n e Standard
c a lib ra tio n curve
F T -IR spectroscopy
F T -IR sp ectro sco p y w a s p e rfo rm e d on th in íĩlm a c a s t from a 1% (w/v) so lu tio n in
chloroform d ire c tly o n to K B r coins T h e s p e c tra w e re re c o rd e d on a P e rk in -E lm e r 1600
sp e c tro m e te r a n d w e re th e a v e ra g e of 16 sca n s a t a re so lu tio n of 4 c m '1
3 R e s u lts a n d d is c u s s ỉo n
8.1 S y n th e s is o f P E G -co n ta in in g Chain e x te n d e r Ax
S ta rtin g m a te ria ls u sed in clu d e a-hydroxy-a>-m ethoxypolyethylene glycols (MPEG)
of m o lecu lar w e ig h ts 350, 550, 750, 1000 a n d 1900
T h e d io l-te rm in a te d P E G m a c ro m e r Ax is e a sily p re p a re d v ia a tw o ste p re a c tio n
p ro c e d u re (F ig l) To a so lu tio n of M P E G in 25 m l of d ic h lo ro m e th a n e , 12 m l of d rie d
p y rid in e a n d 0.08 m m o les to sy lc h lo rid e w e re a d d e d in a p erio d of 20 m in u te s T h e
m ix tu re w a s r e a c te d o v e rn ig h t a t 4 ° c a n d s u b s e q u e n tly cooled to 0°c T h en , 20 ml of
c o n c e n tra te d HC1, 50 g ra m s o f ice a n d 20 m l d ic h lo ro m e th a n e w e re ad d ed T h e org an ic
p h se w as iso la te d a n d w a s h e d su ccessiv ely w ith a 3 M H C L so lu tio n , a s a tu r a te d N aC l
so lu tio n a n d a 5% N a H C 0 3 A fte r d ry in g on M g S 0 4 th e so lu tio n w as c o n c e n tra te d
u n d e r re d u c e d p r e s s u r e a n d p re c ip ita te d in h e x a n e T h e re s u ltin g a-hydroxy-co-toayl-
p o ly eth y len e oxide (M P E G -T s) w a s is o la te d by íìltr a tio n a n d d rie d u n d e r red u ced
p re s s u re a t room te m p e r a tu r e
V N U J o u r n a l o f S c ie n c e N a t Sc/ á T e c h , T X Q H N 0I , 2 0 0 7
Trang 3A m phiphilic poỉyurethancs wjth 21
CH3-(0C H 2C H 2^0H
o c - h y d r o x y - oJ> - m e t h y 1 - P E G
Tosylchloride
CH3-(0 C H 2C H 2 ^0 Ts
o c - m e t h y 1—c _ o - t o s y l - P E G
Pyridine DMAP
CH3-(OCH2CH2)-OTs + h n - ( c h 2c h 2oh)
o c - m e t h y l —o J> — t o s y l — P E G d i e t h a n o l a m i n e
CH3-fOCH2CH2) íi N-(CH2CH2OH)
A x ( w i t h X t h e M W o f t h e M P E G )
Fig.1 Synthesis o f the PEG-containing Chain extender Ax
Two m m oles o f M P E G -T s a n d a la rg e excess of D E A w e re re a c te d in b u lk for 4
h o u rs a t 90°c A fte r th e a d d itio n of 10 m l of d istille d w a te r , th e re a c tio n m ix tu re w as cooled to room te m p e r a tu r e a n d th e form ed a m m o n iu m s a lt w as c o n v e rte d to its free
a m in e form w ith 10 ml of 0.5 M N aO H so lu tio n A fte r th e e x tra c tio n of th e m ix tu re
w ith d ic h lo ro m e th a n e , th e collected o rg a n ic p h a s e s w e re d rie d on M g S 0 4 a n d
co n c e n tra te d u n d e r re d u ced p re ss u re F u r th e r p u rific a tio n of th e c h a in e x te n d e r w as
v aried w ith th e M W of th e M PE G c h a in C h a in e x te n d e r A 1900, A 1000 (solid) an d A750, A550 w ere p u riíĩe d by p re c ip ita tio n in a la rg e ex cess d ie th y le th e r a t room
te m p e ra tu re a n d 0 ° c resp ectiv ely C h a in e x te n d e r A 350 (liq u id ) w a s e x tra c te d w ith 0.5
M N aO H so lu tio n All s tr u c tu r e s w ere v e riíĩe d u s in g 'H -N M R spectroscopy P e a k s positions 2.68 a n d 2.73 p p m c o rresp o n d to th e a -N a n d p - 0 m e th y le n e p ro to n s of th e
P E G a n d n o n -P E G p a r t of th e c h a in e x te n d e r re sp e c tiv e ly T h e in te g ra tio n s for b o th
p e a k s re la te to e a c h o th e r a s 1:2 in d ic a tin g c o rap lete co version
3.2 S y n th e sis o f th e a m p h ip h ilic P E G -co n ta in in g g r a fte d p o ly u r e th a n e s
T h e s e g m e n te d p o ly u re th a n e s w ere p r e p a re d b y a Standard tw o-8tep so lu tio n
p o ly m erizatio n in D M F (Fig.2) T h e c a ta ly s t u se d w as d ib u ty ltin d ia c e ta te (1%) a n d th e
to ta l c o n c e n tra tio n of th e re a c tio n m ix tu re w as a p p ro x im a te ly 15% (w/v) T h e tw o reactio n ste p s w e re c a rrie d o u t u n d e r a N 2 a tm o s p h e re a t 9 0 ° c a n d w ith s tirrin g , for 1
a n d 3 h o u rs resp e c tiv ely In th e f ir s t ste p , th e m acro d io l (P T H F -C D , M W 2000) w as
re acted w ith th e d iiso c y a n a te (H M D I) in a 1:2 m o la r ra tio T h e p re p o ly m e r th u s
ob tain ed w as s u b s e q u e n tly re a c te d w ith th e P E G -c o n ta in in g c h a in e x te n d e r in
e q u iv a le n t a m o u n ts T h e re s u ltin g p o ly m er w a s is o la te d by p re c ip ita tio n in d ie th y l
V.VÍ/ J o u r n a ỉ o f S c ie n c e , N a t.' S ci.,& T e c h ,T J Ũ Ũ II, N 0I , 2 0 0 7
Trang 422 Phain Ngoe Lan, Luu Van Bo)i
e th e r or d istille d w a te r a n d d ried u n d e r re d u c ed p re s s u re P u riíĩc a tio n from lo w raolecular w e ig h t p ro d u c ts a n d c a ta ly s t w a s p e rfo rm e d by d isso lv in g th e p o ly m er i n chloroíbrm a n d p re c ip ita tio n in h ex an e
-0 C N R N H C 0 - K - C H 2C H 2 C H 2C H 20 ) 7 r C 0 K C H 2 C H 2 C H 2 C H 20 /|r - CNHRNCO
3.3 IR- sp ectra
F igure 3 show s th e IR s p e c tru m of a p o ly u re th a n e (PU) o b tain ed T h e typical
fu n ctio n al g ro u p s of th e P U a r e show n cle a rly in th e s p e c tru ra F or ex am p le, NH- groups ab so rb a t 1522.6 c m '\ 3377.9 cm '1 a n d 33 3 0 7 c m '1 T h e b a n d s a t 3377.9 cra'1
a n d 3330.7 c m '1 c o rresp o n d to th e non-bonded a n d b o n d e d N H -g ro u p s resp ectiv ely The
stepl
0
o
90
N2-Step2
CNHRNCO
prepolymer
DMF DBTDAc
I
I Ã a i l
Chain
90° c / 3h
N2- atm.
cxtender
/CH2\
ĩ
CNHRNCO
polyurethane
Fig.2 Synthesis of am phiphilic PEG-containing grafted polyurethane*
V N U J o u r n a l o f S c ie n c e , N a t., S ci.,& T e c h , T X Q Ỉ Ì , N cJ, 20 0 7
Trang 5/Amphiphilic polyurethanes with 23
p e a k s a t 1713.6 cm 1 a n d 1719.7 cm 1 belong to th e n o n -b o n d ed a n d bonded carbonyl
g ro u p s resp ectiv ely T h e e th e r groups a p p e a r a t 1040.4 c m 1 V ery stro n g p e a k a t 1257.3 cm 1 c o rre sp o n d s to th e C-O- group a d ja c e n t to c a rb o n y l group P a rtia lly bonded
N H - a n d -C = 0 g ro u p s in P U possibly m ake it p a rtia lly p h a s e s e p a ra te d [8]
r m m tn B M P
Fig.3 IR spectrum o f a polyurethane
3.4 'H-NMR sp e c tr a and GPC an alysis
T h e ty p ic a l 'H -N M R s p e c tru m of a PU a re sh o w n in fig u re 4 In th e sp ectru m
N H -group (1) a p p e a rs a t a b o u t 8 ppm T he CH 2-group (2) a d ja c e n t to e th e r group
a p p e a rs a t a b o u t 4.2 ppm T h e o th e r CH 2- group (3) g ives stro n g p e a k a t 1.8 ppm I t is seen t h a t th e o b ta in e d P U a r e v e ry w ell c h aracterize d
Table 1 s u m m a riz e s th e h a r d seg m en t c o n te n ts a n d m o lecu lar w eight8 of th e
d iíĩe re n t a m p h ip h ilic p o ly u re th a n e s Codes for sa m p le s a r e a s follows e.g PU -H T- A550, w h e re H , T a n d 550 re p re s e n t HM DI, P T H F -C D a n d a c h a in e x te n d e r w ith a
P E G MW of 55 0 resp ectiv ely T h e reíeren ce po ly m er PU -H T -B D w as sy n th e siz e d vvith
b u ta n e d io l a s c h a in e x te n d e r a n d a s such it does n o t c o n ta in a P E G side ch ain A iro d e l compound PƯ -H T was also included T h is was p rep a red by reactin g HMDI and PTHF-
CD in e q u iv a le n t a m o u n ts u n d e r th e sam e con d itio n a a s for th e p r e p a ra tio n of th e
p o ly u re th a n e s T h e w e ig h t p e rc en tag e of h a rd s e g ra e n ts (wt% H S) w as c a lc u ỉa te d by com bining th e vveight of th e d iiso cy an a te a n d BD or th e n o n -P E G p a r t of th e PEG -
c o n ta in in g c h a in e x te n d e r Ax
Y N U J o u r n a i o f S c ie n c e N a t Sci.,& T e c h , T X Q H , N 0I , 2 0 0 7
Trang 624 Pham Ngoe Lan Luu V an Bo)i
Table 1 GPC analysis and 'H-NMR spectroscopy of the PEG containin g
grafted polyurethanes and a m odel com pound
extender
method)
d
As can be seen from the GPC d ata, all polym ers h av e su íĩĩcien tly high m o lecu lar
w eight and narrow polydispersity to provide polym er ỉilm s w ith good elasto m eric properties
C o n clu sio n
In th is article, th e sy n th esis an d ch arac teriza tio n of a new , PE G -containing chain extender Ax are described A series of am phiphilic P E G -grafted p o ly u reth an es w ith
d iíĩeren t PEG chain len g th w as subsequently p re p a re d and well ch aracterized by IR and 'H-NM R spectroscopy All polym ers containing th is new ch ain ex ten d er h a d high
m olecular w eights and n arro w polydispersity to provide polym er íĩlm s w ith good elastoraeric properties
V N Ư J o u r n a l o f S c ie n c e N a i., S c i A T e c h : T x a n N 01 2 0 0 7
Trang 7A m phiphilic polyurcthanes vvith 25
1 Estes GM., Cooper SL and Tobolsky AV., J Macromol.Sci., C4 (1970, 313-320.
2 Li Y., Yang LH Ma D and Chu B., J Poỉym Sci., Part B: Polymer physics, 31 (1993), 853-867.
3 Chang Y.J.P and Wilkes GL., Superstructure in Segmented Polyurethanes, J Polym Sci.:
Polym Phys Ed., 13 (1975), 455-476.
4 Chang AL and Thomas EL.f A C S Adv Chem., 176 (1979), 31-39.
5 Lelah MD., Grasel TG., Pierce JA and Cooper SL., Exvivo interạctions and 8urface
property relationships of polyurethanes, J Biomed Mater Res., 20 (1986) 433-468.
6 Cooper SL and Tobolsky AV., Properties of linear elastomeric polyurethanes, J Appl
Polym Sci., 10 (1966) 1837-1844.
7 T akahara A., T ashita J., Kajiyama T and Takayanagi M., Blood compatibility and microphase separatéd stru ctu re of segmented poly(urethane urea) with various soft
segment componemts, Rept Progr Polym Phys Japan, 25 (1982) 841-844.
8 Pham Ngoe Lan, Corneilỉie s , Schacht E., Davies M and Shard A., Synthesis and characterization of segmented polyurethanes based on amphiphilic polyether diol,
Biomaterừils, 17 (1996) 2273-2279.
TẠP CHÍ KHOA HỌC ĐHQGHN, KHTN & CN, T.XXII1 Số 1, 2007
POLYURETAN AMPHIPHILIC VỚI HỢP CHAT N ố i DÀI MẠCH
CHỨA POLYETYLEN GLYCOL
PHẨN I: TỔNG HỢP VÀ ĐẶC TRƯNG TÍNH CHẤT
Phạm Ngọc Lân(1), Lưu Văn Bôi(S)
(X)T ru n g tâ m N g h iên cứu V ật liệu Polyme, Trường Đ ại học Bách khoa H à N ội
mK hoa Hóa học, Trường Đại học Khoa học T ự nhiên, Đ H Q G H N
Bài báo trìn h bày vể n ghiên cứu tổng hợp và đặc trư n g tín h c h ấ t của m ột loại
ch ất nối dài m ạch mới Ax C h ấ t nối dài m ạch loại mối n à y được dừng để tổng hợp một
s ố p o ly u re ta n g h ép P E G có độ d à i m ạch P E G th a y đổi (từ 350 đ ế n 1900 Da) Đ ã sử dụng m acrodiol PTH F-C D là m ột polyete diol đặc b iệt với độ p h â n cực tă n g dần do có
m ặt m ột lượng nhỏ nhóm cacbonat để tổng hợp các polyuretan T ấ t cả sản phẩm polyuretan th u được có khối lượng p h ân tử k h á cao và độ đa p h â n tá n tương đốì thếp Cấu trú c polyme được xác định b ằn g phương p háp phổ hồng ngoại và cộng hưởng từ h ạ t
n h ân proton
T ừ k h ó a : P o ly u re ta n g h ép PEG, c h ấ t nối d à i m ạ ch , k h ố i lượng p h â n tử, độ đ a
p h â n tán.
V N U J o u r r ư tlo f S cien c e N a i : S c i i T e c h T - V a n N o ], 2 0 0 7