VNU J O U R N A l OF SCIENCE N .i! . So y. Tech ĩ XIX N 4. 2003
S Y N T H E S I S A N D ( H :\R A C T E R IZ A T IO N O F S E G M K N T E D P O L Y U R K T H A N K S KASKI) O N P O L Y E T H Y L E N E A N D
P O L Y T K T K A M E T H Y L E N E G L Y C O L S
( P a r t I: S y n t h e s i s a n d c h a r a c t e r i z a t i o n )P h a nì N g o e L a n
/W v///í7* lỉrs c u rc h ( \ ‘n t i'r t H a noi ư n iv c rs itv ( ) / Technology K. S c h a c h t
B io n ìa tr r id ls P o lx n iịT ỉỉtn c a rc h G ro u p, U n iv e rs ity o f G he nt. B v lg iu m
1. In tr o d u c tio n
S e g m onted p o ly u re th a n e s (S P U s) are m u lt ib lo c k - f - X “ Y “ J“ co p olym e rs w h ic h ro n s is t o f th e rm o d v n a m ic a lly in c o m p a tib le segm ents. In these co p o lym e rs. X and Y are soft a n d harcl segm ent sequences re s p e c tiv e ly . D ue to th e th e rm o d y n a m ic d iííe rim c e s o f th (‘ suít and h ĩirđ SL»|ỊnuMitS' th e y u s u a lly se g ra te to fo rm an agrugated
|).seiido-tw o-phase s tru c tu re s 111. SF>Us have good b io c o m p a tib ility due to the m o rp h o lo g ic a l lw o -p h a se stru cturc* and c o n s e q u e n tly h a ve fo u n d e xte n sive hiom ecỉical A p p lic a tio n s [2].
T h e io n s h ip betvveun tiu* s trư c tu re s and p ro p e rtie s o f th e S PU s has been rx te n s iv e lv in v e s tiịỊỉite d |3. l,5 |.
In th is p a p c r \VI* p re se n t the s tu d y on s y n th e s is and c h a ra c te riz a tio n ơf SPUs hnsed on m a c ro d io ls (p o ly e th v le n e an d p o ly te tra m e th y le n e g ly c o ls ), m e th y le n e 1.4- l)i(c y c lo h e x v l is o c y a n a ti1) ( M I) C l) and 1,4 -bu tan e cỉiol (H I))(c h a in e x te n d e r). The rlĩec-ts o f m a c ro d io ls . th í ‘i r m o lo c u la r ra tio s on th e m o rp h o lo g y a n d p ro p e rtie s o f the re s u ltin g p o lyn u *rs wi»re (lisru ssed.
2. E x p e r ĩm e n ta l
2.1. M a t e r ia ls
P o lve th ylo iu * and p o lv te ra m e th vlune g lvco ls selected fo r p re p a ra tio n ơf the p o ly u re th u n c s are listecl in th e ta b ỉe I. B efore use th e y w e re c a r e íu lly d rie d bv aze otro pic c iis tilln tio n of thi* to lu e n e s o lu tio n and su b se q u e n t re m o va l o f the solvent. F ig u re 4(1 shows th e IK s p e c tru m o f p o lyo l PEG -2000.
T h e h y d ro x v l n u m b tT ()f p o lv o th e rd io ls fo r c a lc u la tio n o f m o le c u la r w e ig h ts w as d e te rm in e d hy r s t r r i í ì r í i t ion of th e m w ith a ce tic a n h y d rid e and subsequ ent t i t r i m e t r i c a n a l y s i s ()f t h o c a rb o x y lic a c i d gro u p s a c c o rd in g t o t h e S t a n d a r d p ro ce d u rc (BỊ.
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P h a m Ngoe Lariy E. S c h a c h tTable 1:
P o ly d io ls fo r p re p a ra tio n o f S PU sPolyol M n '■» M n <w T m . UC Tg, “C
PEG-1000 1207 1100 40 • 70 (ve ry weak)
PEG -2000 2341 2070 55 •7Q (ve rv w eak)
PEG -4000 4280 4109 62 -
P TM O -2000 2186 1950 25 •30
(a): Determined via GPC
(b): D e te rm in e d v ia c h e m ic a l tit r a t io n
The m o le c u la r w e ig h ts o f th e p o ly d io ls w ere a lso v e riíìe d b y m eans o f gel p e rm e a tio n c h ro m a to g ra p h y (P L co lu m n s, 103A°, 7m m i. d., 60 cm le n g th , P o lym e r L a b o ra to rie s L td , S h ro p s h ire , Ư K. E lu e n t: c h lo ro fo rm . D iíT e re n tia l re fle c to m e tric d e te c tio n (M odel W a te rs 401, M illip o r e , M A , U S A). D a ta a n a ly s is o c cu rre d on a
Waters data module model
M 7 3 0 .Calibration was based on a peak
p o s itio n c a lib r a tio n cu rve e s ta b lis h e d u s in g p o ly s ty re n e s ta n d a rd s ( M illip o r e , M illío r d , M A ,USA).
D iis o c y a n a te (M D C I) (A ld ric h B o rn e m , B e lg iu m ) w as v a c u u m d is tille d and stored u n d e r d rie d c o n d itio n s in a re írig e ra to r p r io r to use. Th e IR s p e ctru m o f M D C I is show n in fỉg u r e 1
•1» »•*
F ig u re 1. IR s p e c tru m o f d iis o c y a n a te : M C D I
s>
n th e s is (Itu ỉ c ì ì u r a v t c r ix a t i n no
f. 2\ \1 .1-hutaiu* tlio l ( A M r ii lì. B o rn e m , lỉe lg iu m ) was d r ir d o v r r calc iu m h y d rid e fo r
‘J i l a y s . ( I i s t i l l i - í l 2 1 1 1 ( 1 s t o ỉ v d i m d t T m l r o ^ r n .
D i b u t v l t i n ( l i a t v t a t í * \v;i> u b t a i n e đ f r o n ì A l d r i r h ( l ỉ o r n r m , h r l |4i u m ) a n d usecỉ w i t h i ) i i t C u r t l u T p u n l i i . i t m n
D im r t h y l !nrm ;»m nlt* <DMK) (A líiric h lk 'ltfiu m ) was (iric d over C ỉìlriiim h y đ r id r r<>r 2 <I;ìv> iin d th i*n va cu u m d is t illr d .
2.2. C h a r a c t e r is a t io n m e th o d s
1R s ỊH T tra Wt*rr iv c o rd rd u s in g a P e rk in -E lrrH T M odel 1600 S p e r tro p h o to m i* trr
N M K s p c r tra VVIMV m o n l r d in I ) \ I S 0 ‘ (i„ u s in tf U *tra n u 'th v l s ila n i* (T M S ) as in to r n a ỉ s tíin d a rd s . on an Aspcct .'Ỉ000 s p e c tro p h o to m e to r.
T h e m o le c u la r vvei^hts and m o le c u la r vveight d is tr ib u tio n ()f th e p o lym ers YVI-n* d e te rm in e c i hy gvì ỊM /rm riitio n c h ro m a to g ra p h y (W a te rs associates. m odel 510) at 60 c . Tht* flo w ratt* o f t l ì r s o lv o n t. l-m e th y l- 2 - p v r r o lid in o n e (N M P ). was 1
m l.m in \ F o r c a lc u la tio n . m o nodispersed p o lystyreru* s ta n d a rd s vverc uscd.
DSC th o rm o ^ ra m s were recorđed on a P e rk in -E lm e r DSC' u n d e r n itro g e n p u rg in g (h c a tin g ra te l O C . m in 1, IVom -100°c to 1()0"C). Th e u n it was equipped w ith a d a ta P rocessing m odulo th a t allovvs s u h s tra c tio n o f th e b a c k g ro u n d and n o rm a liz a tio n fo r sa m p le vveight.
2.3. P o ly m e r p r e p a r a t io n
S o lu tio n s o f p o ly d io i and (ỉiis o c y a n a te w ere p re p a re d s e p a ra te lv in 1)MF.
T h e c o n e e n tra tio n was a p p ro x im a to ly 15% (w /w ). A fo u r*n e cke d íla s k , equipped w ith a s t ir r e r , a n itr o g r iì in le t and o u tle t an d a th c rm o m e te r, w a s ch a rg e d w ith the diisocyanaU * s o lu tio n . T h e p o ly e th e rd io l s o lu tio n . c o n ta in in g 0.5 w t % o f c a ta ly s t ( d i b u t y l t i n d ia c e ta te ) based o n t h e w e i g h t « f t h e re a c ta n t, w a s a d d c d s l o w l y t o t h e (In s o c v a n n tr s o lu tio n T h e m o ln r r a tio N C O :O H was set to 2:1. T h í' re a c tio n was c a rrie d o u t at 90 r u n d e r n itro g e n p u rg e and vvas a llo w e d to proceed u n t il the th e o re tic a l is o c y a n a te c o n te n t was reached as d e te rm in e d hy th e d i-n -b u ty l a m in e
titration method |7]. Then the reaction mixture was cooled down to room
to m p e ra tu re a n d thí* (h a m e x te n d tT (B D ) was ndded s lo w ỉy . T h i' o v e ra ll N C O :O H r a tio was 1:1. T h e c h a in e x te n sio n rc a c tio n w as c a rrie d o u t at 90" c and c o n tin u e d u n til a ll N C O g ro u p s w ere reactod, as c o n firm e d by th e d is a p p e a ra n c e o f the IR a b s o rp tio n b iin đ at 2262 em T h e m ic tio n m ix tu re was th e n p r e c ip ila te d in w a te r and th e fin a l p o ly m e r VVÍÌS (Irie d u n d e r va cu u m a t 60° c . A fte r d r y in g it was re d isso lve d in T H F and re p re e ip itn te d in th e s o lv o n t m ix tu r e h e x a n e -e th e r (1/1).
T h e c o p o ly m e r p ro đ u e t was (Irie d u n d e r vacu um a t 6 0 °c at le a s t fo r 2 ciays.
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P h a m Ngoe L a n , E. S c h a c h t3 .1. S y n th e s is o f s e g m e n te d p o ly u r e th a n e s
S egm ented p o ly u re th a n e s (SPƯs) vvere s y n th e s iz e d by a tw o -s te p p o ly m e riz a tio n (F ig u re 2). P o lyo l íìrs t re a cte d w ith tw o e q u iv a le n ts o f thí*
d iis o c y a n a te . S u b s e q u e n t c h a in e xte n sio n w as o b ta in e d by re a c tio n vvith a n e q u iv a le n t a m o u n t ()f 1 ,4 -b u ta n e d io l. The íìn a l p o ly m e r w as p u rifie d p ro p e rly hv p re c ip ita tio n , v a c u u m d rie d an d th e n c h a ra c te riz e d . T h e m o le c u la r vveights o f th e SPUs d e te rm in e d bv G PC m e th o d and are lis te d in ta b le 2.
3. R e s u lts a n d d is c u s io n
2 0
= C = N - « = > N = C
= 0+ HO
O H0
=C=N-c
H o
•N-CO-
o n
O C - N < N = c=0
HO—□—OH (Chain extender)
H H O
I I II
H ( H D -
0- C - N t = > - N - C O 0
V ‘í
OC-N-c
n
F ig u re 2 : S c h e m a tic pro ce d u re o f segm ented p o ly u re th a n e fo rm a tio n
W c can see fro m th e ta b le 2 th a t a ll th e S P U s have q u ite h ig h m o le c u la r w e ig h ts an d th e m o le c u la r w e ig h t d is tr ib u tio n (d) is r e la tiv e ly n a rro w . The m a te ria ls o b ta in e d a re s tro n g ns vvill be show n in th e n e x t p u b lic a tio n .
T able 2:
M o le c u la r w e ig h ts o f S P U sCode . Polyol ra tio D iiso-
cyan ate
C h a in e xte n d e r
M w d
P ư -l PEG -1000 + P TM O -2000 (1/1) M C D I BD 60027 2 0
PU-2 PEG-2000 + m i 0 -2 0 0 0 (1/1) M C D I BD 70815 1.9
PU-3 PEG -4000 + PTM O -2000 (1/1) M C D I BD 61593 1.8
PƯ-4 PEG -2000 + IT M O -2 0 0 0 (2/1) M C D I BD 108533 2.1
PU-5 PEG -2000 + P T M O -200 0 (1/2) M C D I BD 66242 2.0
S x n th e s is a n d c h a r a c t e t 'iz a t in n
o/. 25
3,2. N M R s p e r tr a
T h u stru c tu rc * ol thí* S PU s o b ta in e d was c o n firm e d bv p ro to n N M R spectra.
F ỉg u rc 3 shovvs th t' N M K s p e c tru m o f p o ly u re th a n e PU-2. W i' can seu th a t the spe ct.rum show s r k * a r l\ ih t ‘ peak at ổ = 1.6 ppm e o rru s p o n đ in # to |1-CH o f P TM O and íì Ị)c‘ak at ổ = 1 ppni c o rre s p o n d in g to « -C H . oí’ P T M O and lM ííi.
F ig u re 3: 1 M -N M R spe etru m o f PU-2 (P E G -2000 + P T M O -2 0 0 0 (1/1)),
Sol vent : C h l o r o t o r m
3.3. I I i ơ n a Ix s is
F o r c o n ip a ris io n , fig u re 4a show s the IR s p e c tru m o f p o lyo l P E G -2000. We can see c le a rlv th e c h a ra c te ris tic a b s o rp tio n band o f th e O H -g ro u p a t ‘3447.9 cm 1 w h ich was a lm o s t d is a p p e a re d in p o lv u re th a n e fo rm a tio n and th e e th e r g ro u p a t 1119.5 cm Bv p o lv u re th a n e fo rm in g , th e N C O g ro u p o f d iis o c y a n a tc d is a p p e a re d (2262.0 cm -1) (see fig u r e /) , b u t th e re ap pea red tw o new c h a ra c te ris tic group s: the N H - group at 3323.1 cm 1 a n d c = 0 g ro u p a t 1712.8 cm 1 (F ig u re 4b).
T h o p o lv u re th a n e s are segm ented co p o lym e rs c o n ta in in g íle x ib le p o ly e th e r segm onts an d h a rd segm onts o f isoeyanate m oeties. In th e h a rd seg m en ts o f the SPUs. h v d ro g e n honds ơccur due to th e in te ra c tio n o f h yd ro g e n a to m s o f N H -g ro u p s w ith c a rb o n y l groups. In th e p o ly e th e r p o ly u re th a n e co p o lym e rs, th e N H groups form hydrogíM ì bonds w ith th e c = 0 group s o f th e u re th a n e lin k a g e s m a k in g the harđ seg m en ts gootl packoci co n se q u e n tly th e c o p o ly m e r w e ll phase se p a ra te d . A t the sam e tin u ỉ th e h yd rog en bonds can occur due to th e in te ra c tio n b ctw e e n th e N U groups and th e oxvgen ato m s o f th e soft se g m e n t e th e r group s. In th is case the co p o lym e r becomes k ầss phase se p a ra te d . I t is
known
fro m th e lit e r a t u r e IH, 9| th a t th e IR a b s o rp tio n o f th e N H - and c = 0 g ro u p s <free and bonded) in th e SPƯs occurs in the fo Ilo w in g range:26 P h a m N goe L a n
,
E. S c h a c h tN H - (H *bon de d)
-► 3200 - 3350 cm
-N H - (H -fre e ) - > 3360 - 3500 cm
- c =0
(H -b o n d e d ) --- —► 1700 - 1714 cm- c =0
(H -fre e ) --- 1715 - 1740 cmAs w t‘ can see fro m th e fig u re 4b th a t the PƯ-5 is q i ite w e ll phase sep ara ted . The same good phase s e p a ra tio n can also be seen in th e o th e r S P U s in v e s tig a te d in th is vvork. T h e q u e s tio n c o n c e rn in g phase s e p a ra tio n o f th e S P U s w ill be discussed in m ore d e ta ils in th e p a rt II.
F ig u re 4. IR s p e c tru m ơf p o ly o l (4a) and p o ly u re th a n e P U -5 (4b)
S x n th e s is a n d c h a r a c t e r i z a t i o n tỉf.. 27
4. C o n c lu s io n
In th is s tu d y . thi* s y n th e s is and c h a ra c te riz a tio n o f p o ly u th y lu n e and p o lyte t ra n ic t h v lr n c tflv ro l lỉỉise d SPUs w ere described. T h iĩ s tr u c tu r e ()f th e SPUs o h ta iiu ‘(l w as c o n lìrm c d hy tlìi* N M K and IR sp e ctra . I t VVHS shovvn th a i th e selected s r u s to r th is s tiiílv híicl ( Ịiiilc goođ pha.se s e p a ra tio n .
R e fe re n c *o s
1 C o o p e r S L . . T o b o l s k y A V . e/. A p p l. P o lvm . S c i 1 0 ( 1 9 6 6 ) , 1 8 3 7 * 1 8 4 5 .
2 Leiah M I) . Cooper SL . Polyurethanes ỉn medicine, Boca Raton, K I/ CRC Press (1986) 3 T a kỉih a rn A . Tashita J Kajiynm a T-. Takayanngi M . M acknight w Polvmer,
26( 1985) 978 996
4 Hwanp Lin s . Tsay s Cooper SL . Pohmer, 25(1984). 947*952.
1* N Lán. C orn eillie s . Schacht K . Davies M and Shard A . Bìomateriữls, 17(1996) 2273-2280.
6 Su ri'n son WR.. ra m p b e ll TW Preperatiưe Methods o f Polymers Chemistry, New York, Interscienre, 1961
7 MaltH* KJ.. David 1)J., In David DJ, Staley HB., eds., A n a ly tic a l Chemistry o f Polvurcthane. N rw York: Wiley, 86*90.
8. Tanaka T . Yokoyama T . Yamaguchi Y., J. Polym. Sci. Part A ì, 1986, 0(1968) 2137- 2152.
9 Jin-L on # Hong, L illy n C l\, Chien JCW., Polymer, 33, 3247-3351 (1992).
TAP CHI K H O A H OC Đ H Q G H N , K H TN & CN, T .X iX . N04, 2003_________
TÓNCỈ h ợ p v à k h a o s á t t ỉ n h c h ấ t c ủ a c á c p o l y u r e t a n p h á n đ o ạ n
( P h ẩ n 1: T ô n g h ợ p v à k h ả o s á t t í n h c h â t ) P h ạ m N g ọ c L ã n
T ru n g tá m ng hiên cứu p o lym e, Đ ạ i học Bach khoa H a N ộ i
E. S c h a c h t
T ậ p đoàn nghiên cứu vát liệ u po lym e s in h học. D ạ i học G h e n t. B i
Bài báo để cập vế n g h iê n cứu và khả o sá t tín h c h ấ t của các p o ly u re ta n phân đoạn trô n cơ sỏ p o ly e ty le n g ỉy c o l và p o ly te tra m e ty le n g ly c o l. Đà sử d ụ n g phương pháp phố hồng ngoại (IR ) và cộng hưởng từ h ạ t nh â n p ro to n (1 H -N M R ) để xác đ ịn h cấu trú c củ a các p o ly u re ta n th u được. Đã n g h iê n cứu ả n h hưởng của các m a cro d io l và tỷ lệ m ol của c h ú n g lô n h ìn h th á i học và tín h c h ấ t của sản p h ẩ m p o ly u re ta n .
Từ khó a: m a c rn d io l. p o ly u re ta n phân đoạn, tá ch pha.
