Amphiphilic polyurethanes with a novel peg containing chain extender part 1 synthesis and characterization

VNU JOURNAL OF SCIENCE, N a t, Sci., & Tech., T.XX1II NọỊ 2007 AMPHIPHILIC POLYURETHANES WITH A NOVEL PEGCONTAINING CHAIN EXTENDER PART I: SYNTHESIS AND CHARACTERIZATION Pham Ngoe Lan(1), Luu Van Boi(2) {ì)P o lỵm er R esearch Center, H anoi U niversity o f Technology (2) D ep a rtm en t o f C hem istry, College o f Science, V N U I n tr o d u c tio n P o ly u re th a n c s a re block copolym ers com posed of a lte rn a tin g s h o rt h a rd segm ents and long ílexible soft seg m e n ts th a t a re th erm o d y ĩiam ically incom patible a t th e te m p e tu re of u se [1,2] P h a s e se p a tio n of seg m en ted p o ly u re th a n e s (SPU) w ith a lim ited h a rd seg m e n t c o n te n t re su lts in h a rd seg m e n t rich dom ains dispersed in a continuous m a trix of th e soft seg m en ts [3] T he h a rd d o m ains ac t as physical crosslink providing th e polym er w ith m echanical s tre n g th w hile th e soft m a trix co n trib u tes to th e elasto m eric p ro p e rtie s [4,5] T he m ain factors inA uencing th e h a rd dom ain cohesion an d th e re su ltin g p h a se se p a tio n include hydrogen b o nding an d cry stallizatio n [4] S ev eral s tra te g ie s h av e been proposed to íu rth e r im prove th e su rface p roperties for p o ly u re th a n es [5] In th is respect, polyethylene oxide rich su ríaces th a t non selectively rep el p ro te in s an d cells have been p re p a re d an d e v alu ated [6,7] In the p re se n t w ork, a novel P E G -co n taining ch ain e x te n d e r w as sy n th esized a n d th e p o ten tial use of th is c h ain e x te n d er for th e sy n th esis of segm ented p o ly u re th a n es w as in v estig ated T h u s, a se rie s of am phiphilic copolym ers w ith PEG side ch ain s of d ifferen t MW w ere p rep a re d T h is article described th e sy n th e sis an d cheraical ch ara c te riz a tio n of b oth th e novel chain e x te n d e r a n d th e r e s u lta n t grafted p o ly u reth a n es E x p e rim e n ta l 2.1 M aterials All so lv en ts w ere u sed as received, except for p y rid in e (dried on C aH 2) and dich lo ro m eth an e (dried on P 20 5) Poly(THF-CD), a special p o ly eth er polycarbonate diol w ith MW 2000 a n d b ased on Poly(THF) w as o b tain ed from BASF T he a-hydroxy-cừm ethoxypolyethylene glycols (M PEG) w ere o b tain ed from J a n s e n (MW350), Acros (MW550, 750, 1000) a n d P olym er L ab o rato ries (MW 1900) respectively Both 19 Pham N goe Lan, Luu Van Bo)i 20 Poly(TH F-CD ) a n d th e M P E G ’s w ere d rie d a t 60 °c for h o u rs u n d e r reduced p r e s s u r e im m ed iately before u se H e x a m e th y le n e d iiso c y a n a te (HM DI), 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 am in e (DEA) an d tosylchloride (TsCl) w e r e used a s received 2.2 C h a cteriza tio n m eth o d s 1H -N M R spectroscopy AU 'H -N M R sp ectro sco p y a n a ly se s w ere re c o rd ed in d e u te te d chloroform on B ru ck er 360 M H z in s tr u m e n t T h e chem ical sh ift w a s ex p ressed in ppm re la tiv e tC) te tra m th y l sila n e a s in te r n a l S ta n d ard G PC a n a ly sis G PC a n a ly s e s w ere p erfo rra ed on 1% (w/v) so lu tio n in N M P T h e sty g e l columru (Polym er L a b o to rie s, 104-105 A°) w as o p e te d a t °c an d a flow r a te of m l/m in A re íra c to m e te r w as u se d for d etec tio n aríd th e d a ta a n a ly s is w as done w ith a W a te rs D ata M odule M 730 T h e re la tiv e m o lecu lar w e ig h ts an d th e p o ly d isp ersity of t h e sam p les w ere c a lc u la te d u s in g a n a rro w m o le c u la r w eight p o ly sty ren e Standard c a lib ratio n curve F T -IR spectroscopy F T -IR sp ectro sco p y w as p erfo rm ed on th in íĩlm a c a st from a 1% (w/v) solution in chloroform d ire ctly o nto K B r coins T h e s p e c tra w e re recorded on a P e rk in -E lm e r 1600 sp ec tro m e te r a n d w ere th e a v e g e of 16 scan s a t a re so lu tio n of c m '1 R e su lts a n u rn a ỉ o f S cien c e , N a t.' Sci.,& T e c h ,T J Ũ Ũ II, N 0I , 0 Phain Ngoe Lan, Luu Van Bo)i 22 e th e r or d istilled w a te r an d d ried u n d e r red u ced p re ssu re P u riíĩc a tio n from low raolecular w eig h t p ro d u cts a n d c a ta ly s t w as p erfo rm ed by dissolving th e polym er i n chloroíbrm an d p re c ip ita tio n in h exane stepl o -0 C N R N H C - K - C H 2C H C H 2C H 20 ) r C K C H C H C H 2C H 20 /|r - CNHRNCO 90 N2Step2 CNHRNCO prepolymer + H C H 2C H 2N C H 2C H H I I Ãa i l Chain cxtender DMF DBTDAc 90° c / 3h N2- atm CNHRNCO /CH2\ ĩ c h polyurethane Fig.2 Synthesis of am phiphilic PEG-containing grafted polyurethane* 3.3 IR- spectra F igure show s th e IR sp ectru m of a p o ly u re th a n e (PU) o b tain ed T he typical fun ctio n al groups of th e P U a re show n clearly in th e sp ectru For exam ple, NHgroups absorb a t 1522.6 c m '\ 3377.9 cm '1 an d 3330.7 cm '1 T h e b a n d s a t 3377.9 cra'1 an d 3330.7 cm '1co rresp o n d to th e non-bonded a n d b o n d ed N H -groups respectively The V N U J o u r n a l o f S cien c e, N a t., Sci.,& T e c h , T X Q Ỉ Ì , N cJ, 2007 23 /Amphiphilic polyurethanes with p e a k s a t 1713.6 cm a n d 1719.7 cm belong to th e non-bonded an d bonded carbonyl g ro u p s resp ectiv ely T he e th e r groups a p p e a r a t 1040.4 c m V ery stro n g peak a t 1257.3 cm co rresp o n d s to th e C-O- group a d ja c e n t to carbonyl group P a rtia lly bonded N H - an d -C = 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 te d [8] rm m tn B M P Fig.3 IR spectrum o f a polyurethane 3.4 'H-NMR sp ectra and GPC analysis T he ty p ical 'H -N M R sp ectru m of a PU are show n in fig u re In th e spectrum N H -group (1) a p p e a rs a t a b o u t ppm T he CH2-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 CH2- group (3) gives stro n g p eak a t 1.8 ppm I t is seen t h a t th e o b ta in e d P U a re v ery well characterized Table su m m a riz e s th e h a rd segm ent co n ten ts an d m olecular 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 es Codes for sam p le s a re a s follows e.g PU-HTA550, w h ere H, T a n d 550 re p re s e n t HM DI, PT H F-C D a n d a ch ain e x ten d er w ith a P E G MW of 550 respectively T h e reíerence polym er PU -H T-B D w as sy n th esized vvith b u tan ed io l as 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 PEG side chain A iro d el compound PƯ -HT was also included T his was p rep ared by reacting HMDI and PTHFCD in e q u iv a le n t am o u n ts u n d e r th e sam e conditiona as for th e p re p a tio n of th e p o ly u re th a n es T h e w eig h t p ercen tag e of h a rd se g e n ts (wt% HS) w as calcu ỉated by com bining th e vveight of th e diisocyanate an d BD or th e non-PE G p a r t of th e PEGco n tain in g c h a in e x te n d e r Ax Y N U J o u rn a i o f S c ie n c e N a t Sci.,& T ec h , T X Q H , N 0I , 0 Pham Ngoe Lan Luu Van Bo)i 24 Table GPC analysis and 'H-NMR spectroscopy of the PEG containing grafted polyurethanes and a m odel com pound Polymer PU-HT-BD PU-HT-A350 PU-HT-A550 PU-HT-A750 PU-HT-A1000 PU-HT-A1900 PU-HT Chain extender BD A350 A550 A750 A1000 A1900 - wt% HS 18.3 12.6 14.3 13.2 12.7 10.0 7.9 Mn (GPC method) 75,300 69,000 51,200 26,200 36,500 47,400 67,200 d 1.4 1.8 1.7 1.8 1.5 1.4 1.5 As can be seen from the GPC data, all polym ers have suíĩĩciently high m olecular w eight and narrow polydispersity to provide polym er ỉilm s w ith good elastom eric properties C o n clu sio n In th is article, the synthesis an d characterizatio n of a new, PE G -containing chain extender Ax are described A series of am phiphilic P E G -grafted polyurethanes w ith diíĩerent PEG chain length w as subsequently p rep a red and well characterized by IR and 'H-NM R spectroscopy All polym ers containing th is new chain extender had high m olecular w eights and narrow 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 cien c e N a i., S c i A T e c h : T x a n N 01 2007 25 A m phiphilic polyurcthanes vvith REFEREN CES , Estes GM., Cooper SL and Tobolsky AV., J Macromol.Sci., C4 (1970, 313-320 Li Y., Yang LH Ma D and Chu B., J Poỉym Sci., Part B: Polymer physics, 31 (1993), 853-867 Chang Y.J.P and Wilkes GL., Superstructure in Segmented Polyurethanes, J Polym Sci.: Polym Phys Ed., 13 (1975), 455-476 Chang AL and Thomas EL.f AC S Adv Chem., 176 (1979), 31-39 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 Cooper SL and Tobolsky AV., Properties of linear elastomeric polyurethanes, J Appl Polym Sci., 10 (1966) 1837-1844 Takahara A., T ashita J., Kajiyama T and Takayanagi M., Blood compatibility microphase separatéd structure of segmented poly(urethane urea) with various segment componemts, Rept Progr Polym Phys Japan, 25 (1982) 841-844 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 and soft 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)Trung tâm N ghiên cứu Vật liệu Polyme, Trường Đ ại học Bách khoa H N ội mKhoa Hóa học, Trường Đại học Khoa học T ự nhiên, Đ H Q G H N Bài báo trìn h bày vể nghiên cứu tổng hợp đặc trư n g tín h ch ất loại ch ất nối dài m ạch Ax C h ấ t nối dài m ạch loại mối dừng để tổng hợp số p o ly u re ta n ghép P E G có độ d i m ạch PE G th a y đổi (từ 350 đ ến 1900 Da) Đ ã sử dụng macrodiol PTHF-CD m ột polyete diol đặc biệt với độ p h ân cực tăn g dần có m ặt m ột lượng nhỏ nhóm cacbonat để tổng hợp polyuretan T ất sản phẩm polyuretan th u có khối lượng phân tử kh cao độ đa p h ân tá n tương đốì thếp Cấu trú c polyme xác định phương pháp phổ hồng ngoại cộng hưởng từ h t n h ân proton T k h ó a : P o lyu reta n ghép PEG, ch ấ t nối d i m ạch, k h ố i lượng p h â n tử, độ đa p h â n tán V N U J o u r r tlo f Scien ce N a i : S ci i T e ch T - V a n N o ], 0 ... PU-HT Chain extender BD A3 50 A5 50 A7 50 A1 000 A1 900 - wt% HS 18 .3 12 .6 14 .3 13 .2 12 .7 10 .0 7.9 Mn (GPC method) 75,300 69,000 51, 200 26,200 36,500 47,400 67,200 d 1. 4 1. 8 1. 7 1. 8 1. 5 1. 4 1. 5 As can... polyurethanes, J Biomed Mater Res., 20 (19 86) 433-468 Cooper SL and Tobolsky AV., Properties of linear elastomeric polyurethanes, J Appl Polym Sci., 10 (19 66) 18 37 -18 44 Takahara A. , T ashita J., Kajiyama... 8 41- 844 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 (19 96) 2273-2279