DSpace at VNU: Synthesis and characterization of Segmented polyurethanes based on polyethylene and polytetramethylene glycols (part I: Synthesis and characterization)

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So y Tech ĩ XIX N 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 POLYTKTKAM ETHYLENE GLYCOLS ( 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 nì N g o e L a n /W v///í7* lỉrs c u rc h ( \ ‘n ti'r t H a noi n iv c rs itv ( ) / Technology K S c h a c h t B io n ìa trrid ls P o lx n iịT ỉỉtn c a rc h G ro up , U n iv e rs ity o f G hent B v lg iu m In tro d u ctio n S egm onted p o ly u re th a n e s (SPU s) are m u lt ib lo c k - f- X “ Y “ J“ copolym ers w h ich 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 cop olym 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 ce s o f th (‘ suít and h ĩirđ SL»|ỊnuMitS' th e y u s u a lly segrate to fo rm an agrugated |).seiido-tw o-phase s tru c tu re s m o rp h o lo g ica l lw o -p h a se 111 SF>Us have good b io c o m p a tib ility structurc* and c o n se q u e n tly have due to the fo u n d exte nsive hiom ecỉical A p p lic a tio n s [2] The io n s h ip betvveun tiu* s trư c tu re s and p ro p e rtie s o f th e SPU 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* presen t the s tu d y on s y n th e s is and c h a c te riz a tio n ơf SPUs hnsed on m a cro d io ls (p o ly e th v le n e and p o ly te tra m e th y le n e g lyco ls), m e th y le n e 1.4l)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-butane cỉiol (H I))(c h a in exte n d e r) The rlĩec-ts o f m a cro d io ls th í‘i r m o lo c u la r 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 lynu*rs wi»re (lisrussed E xp erĩm en tal 2.1 M a t e r ia ls P o lve th ylo iu * and p o lv te m e th vlune glvcols selected fo r p re p a tio n ơf the p o ly u re th u n c s are listecl in th e ta b ỉe I Before use th e y w ere c a re íu lly d rie d bv azeotropic 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 ova l o f the solvent F ig u re 4(1 shows the IK sp e ctru m o f polyol PEG -2000 The 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 was d e te rm in e d hy r s t r r ií ì r í it ion of the m w ith acetic a n h y d rid e and subsequent titrim etric analysis ()f t h o c a rb o x y lic acid procedurc (BỊ 21 groups a c c o rd in g to the S tandard 22 P h a m Ngoe Lariy E S c h a c h t Table 1: P o lyd io ls fo r p re p a tio n o f SPU s Polyol M n '■» M n n th e s is (Itu ỉ c ì ì u r a v t c r ix a t in n of 2\ \ 1-hutaiu* tlio l (A M rii lì B ornem , lỉe lg iu m ) was d r ir d o v r r calc iu m h y d rid e for ‘J i l a y s ( I i s t i l l i - í l 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 | i u m ) a n d usecỉ w ith i)iit C u rtlu T p u n lii itm n D im r th y l !nrm;»m nlt* N =C = H =C=N-c o •N-CO- + HO OH o n N = c=0 O C -N < HO—□—OH (Chain extender) H H O I I II H( H D - - C - N t = > - N - C O V‘í OC-N-c n F ig u re : S ch e m a tic procedure 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 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 and th e m o le c u la r w e ig h t d is tr ib u tio n (d) is re la tiv e ly n a rro w The m a te ria ls o b ta in e d are 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 s Code Polyol tio Diiso- C h a in cyanate exte nd er Mw d P -l PEG-1000 + P TM O -2000 (1/1) MCDI BD 60027 20 PU-2 PEG-2000 + m i -2 0 (1/1) MCDI BD 70815 1.9 PU-3 PEG-4000 + PTM O -2000 (1/1) MCDI BD 61593 1.8 PƯ-4 PEG-2000 + IT M O -2 0 (2/1) MCDI BD 108533 2.1 PU-5 PEG-2000 + P TM O -2000 (1/2) MCDI BD 66242 2.0 S x n th e s is a n d c h a r a c te t'iz a tin n o/ 25 3,2 N M R s p e r tr a T h u stru ctu rc* ol thí* SPU 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 shovvs th t' N M K sp e ctru m o f p o ly u re th a n e PU-2 W i' can seu th a t the spect.rum show s rk * a rl\ ih t‘ peak at ổ = 1.6 ppm eo rru sp o n đ in # to |1-CH o f PTM O and íì Ị)c‘ak at ổ = ppni c o rre s p o n d in g to «-C H ’ P T M O and lM ííi F ig u re 3: 1M -N M R speetrum o f PU-2 (P E G -2000 + P T M O -200 (1/1)), Solvent: C h l o r o t o r m 3.3 I I i n a Ix s is F o r c o n ip a ris io n , fig u re 4a show s the IR sp e ctru m o f polyol P EG -2000 We can see c le a rlv th e c h a c te ris tic a b s o rp tio n band o f the O H -g ro u p a t ‘3447.9 cm 1w hich was a lm o st d isa 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 isa p p e a re d (2262.0 cm-1) (see fig u re /), b u t th e re appeared tw o new c h a c te ris tic groups: the N H group at 3323.1 cm a n d c = g ro u p a t 1712.8 cm (F ig u re 4b) T h o p o lv u re th a n e s are segm ented copolym ers c o n ta in in g íle x ib le p o ly e th e r segm onts and h a rd segm onts o f isoeyanate m oeties In th e h a rd segm ents o f the SPUs h vd ro g e n honds ơccur due to th e in te c tio n o f hyd rog en ato m s o f N H -g ro u p s w ith c a rb o n y l groups In the p o ly e th e r p o ly u re th a n e cop olym e rs, th e N H groups form hydrogíMì bonds w ith the c = groups o f th e u re th a n e lin k a g e s m a k in g the harđ segm ents gootl packoci co n se q u e n tly the co p o lym e r w e ll phase separated A t the same tin u ỉ th e hydrogen bonds can occur due to th e in te c tio n bctw een th e NU groups and th e oxvgen atom s o f th e soft segm ent e th e r groups In th is case the cop olym e r becomes k ầss phase separated I t is known fro m th e lite r a tu r e IH, 9| th a t the IR a b s o rp tio n o f th e N H - and c = groups 3200 - 3350 cm 3360 - 3500 cm - c =0 (H -b ond ed ) - —► 1700 - 1714 cm - c =0 (H -fre e ) - 1715 - 1740 cm As w t‘ can see fro m the 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 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 stio n co n ce rn in g phase se p a 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 IR sp e ctru m ơf p o ly o l (4a) and p o ly u re th a n e P U -5 (4b) S xn th e sis a n d c h a r a c t e r iz a t io n tỉf 27 C o n c lu s io n In th is stu d y thi* syn th e sis and c h a c te riz a tio n o f p o ly u th y lu n e and po lytet n ic t h v lrn c tflv ro l lỉỉised SPUs w ere described T h iĩ s tru c tu re ()f the SPUs o h ta iiu ‘(l w as c o n lìrm c d hy tlìi* N M K and IR spectra It VVHS shovvn th a i th e selected s r u s to r th is s tiiílv híicl ( Ịiiilc goođ pha.se se p a tio n R e fe re n c*o s C o o p e r S L T o b o l s k y A V e/ A p pl P olvm S ci Leiah M I) Cooper SL Polyurethanes ỉn medicine, Boca Raton, K I/ CRC Press (1986) T a kỉih arn A Tashita J 26( 1985) 978 996 Hwanp Lin s Tsay s 10(1966), 1837*1845 Kajiynma T- Takayanngi M M acknight w Polvmer, Cooper SL Pohmer, 25(1984) 947*952 1* N Lán C orneillie s Schacht K Davies M and Shard A Bìomateriữls, 17(1996) 2273-2280 Su ri'n son WR m p b e ll TW Interscienre, 1961 Preperatiưe Methods o f Polymers Chemistry, New York, 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 Tanaka T Yokoyama T Yamaguchi Y., J Polym Sci Part A ì, 1986, 0(1968) 21372152 Jin-Lon# Hong, L illy n C l\, Chien JCW., Polymer, 33, 3247-3351 (1992) TAP CHI K H O A HOC Đ H Q G H N , K HTN & CN, T.XiX N04, 2003 _ TÓNCỈ h ợ p v k h a o s t t ỉ n h c h ấ t c ủ a c c p o l y u r e t a n p h n đ o n ( P h ẩ n 1: T ô n g h ợ p v k h ả o s t t í n h c h â t ) P hạm N gọc L ã n T ru n g tá m nghiên cứu polym e , Đ i học Bach khoa H a N ộ i E S c h a c h t T ập đoàn nghiên cứu vát liệ u polym e s in h học D i học G he nt B i Bài báo để cập vế nghiên cứu khảo sát tín h c h ấ t p o ly u re ta n phân đoạn trô n sỏ p o ly e ty le n g ỉy c o l 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 ) cộng hưởng từ hạ t nhân p ro to n (1 H -N M R ) để xác đ ịn h cấu trú c p o ly u re ta n th u Đã n g h iê n cứu ả n h hưởng m acrodiol tỷ lệ m ol ch ú n g lơn h ìn h th i học tín h c h ấ t sản p h ẩ m p o ly u re ta n Từ khóa: m a crn d io l p o ly u re ta n phân đoạn, tách pha  ... rs 401, M illip o r e , M A , U SA) D a ta a n a ly s is o ccu rre d on a Waters data module model M 30 Calibration was based on a peak p o sitio n c a lib tio n curve e s ta b lis h e d u s in... hydrogen bonds can occur due to th e in te c tio n bctw een th e NU groups and th e oxvgen atom s o f th e soft segm ent e th e r groups In th is case the cop olym e r becomes k ầss phase separated... rge and vvas a llo w e d to proceed u n til the th e o re tic a l iso cya n a te co n te n t was reached as d e te rm in e d hy th e d i-n -b u ty l am ine titration method |7] Then the reaction