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T戌I ns ac 60l 1 sof" [ ' i aAi i n Uni ve r s i t y I SSN1006- 4982
pp254- 262
Vo1 .13
Aug.2007
No.4
Synt hesi s,Charact eri zat i on and i n vi t ro Degradat i on Propert i es of
Pol y(Pr opyl e ne Fumarat e- co- Pr opyl ene Sebac at e、 )Net wor ks Z HANG№( 张 娜) ,YANG De a n( 杨德安) ,CAI Z h o n g y u( 蔡仲雨 ) ,CHANG J u n bi a o( 常俊标) (1.S chol ofPha mmeeut i eal Sci ence andTe chnol ogy,Ti a nj i nUni v er s i t y,Ti anj i n 30 0072,Chi na;
2.S ch o o l o f Ma t e ia r l ci S e n c e nd a En g i n e e r i n g,Ti nj a i n Un iv e r s i y,Ti t  ̄j i n 3 0 0 0 7 2,Ch i na )
Abs t r ac t:Pol y(pr opyl ene f umar at e— co -pr opyl ene sebacat e)(P(PF_ co- PS))was cr ossl i nked wi t h N— vi nyI pyr r ol i done (N— VP)t o f cI r m net wor ks.I t was i nvest i gat ed as bi odegr adabl e bone cement.I n t hi s paper ,P(PF- co - PS)was synt hesi zed and char act er i zed by H— NMR。F - rI R and GPC.The ef —
f ect s of t he amount of sebacat e segment s i n P(PF_ co -PS)mai n chai ns and t he quant i t y of N— vi nyI pyr r ol i done on t he / n v i t r o degr adat i on of t he pol ymer net w or ks wer e exa m i ned.Cyl i ndr i caI speci —
mens wer e submer ged i n phosphat e bufer ed sal i ne (PBS)at 37 o C and t he pH val ue of PBS i s 7. 4 f 0r 1 0 weeks.The gr avi met r y and compr essi ve m echani caI pr oper t i es wer e t est ed over t he degr ada—
t i on per i d .Net o w or k s f or med by P(PF_ co -PS) 8020/ N— VP exhi bi t ed hi gher wei ght I OSS and bet t er me—
ch an i c aI pr oper t i es whe n co mpar d e wi t h p ol y( pr opy l en e f u mar a t e) / N— VP n et wor ks.Th e me cha ni c aI pr oper ti e s of P( PF- c -PS) o / N— VP c an be mai n t ai n ed f or a v e r y I on g t i me,e v en f or 7 0 da ys,t h e y i el d s t r engt h,f r act ur e st r engt h and co m pr essi ve mo d ul us ar e( 51. 78 ± 2. 01)MPa,( 52. 331 ± 1. 8 4) MPa and(957. 78 ± 24. 40)MPa,r espect i vel y.T h e r esul t s demons t r at e t ha t t he co m pr essi ve me— chani caI pr oper ti es and degr adat i on vel oci t y can be mo d ul at d by e t he m ount a of cr ossl i nki ng agent s and sebacat e s egment s al ong t he m ai n chai ns of copol ym er s.
Ke ywo rds:bi odegr adat i on;/ n v / t r o degr adat i on;pol yest er ;pol y(pr opyl ene f umar at e— co - pr opyl ene sebacat e);N— vi nyl pyr r ol i done ’ I’ he devel opment of bi odegr adabl e bone cement syst em py r r ol i done(N— VP)t o f or m t hr ee — di m en si on ne wor t ks j. has recei ved consi der abl e at t ent i on over t he past f ew year s. Degr aded s eg m ent s of PI) F ar e f umal 3c aci d a n d 1.2・pr op— One of t he most i r I r t aJ 1 t and at t ract ive f ami l i es i s bi d e— o yl ene gl ycol whi ch ar e bi ocompat i bl e a n d ca n b e el i mi nat ed ri car boxyl i c aci d cycl eL 3 -5j.r I 1 1 e net w or k of PPF/N— VP gr adabl e pol yest er s.They can be used a s bi omat er i l s a eaf - by t f ol d t o pr ovi de mechani cal supp o rt a n d mat ri x f or i ngr owt h has excel lent degr adabl e a n d me c hani ca l pr o pert i es. But
of new t iss ues… . Each est er gr oup al l ows t o degr ade vi a PPF ha s s ome shor t ages. esp e ci al l y when t he mol cu e la r est er hydr ol ysi s i nt o lcohol a n d a aci d whi ch ca n b e el i mi nat —
we i g h t i s ig h h ,i t il w e b v e y r is v c o u s nd a d i fi c ul t t o e b n— i
ed by pr ocess of met abol i sm . However. pr o pert y of ho— j ec t e d i nt o mou lds t o f o m a r c er t ai n s ha pe. Fi st r ly, t he mop ol ymer i s t oo si mpl e o s t at isf y n y a r equi r ement s of iss t ue c ossl r i nki ng r eact ion of PI ) F a n d N— VP f olowed t he m o cha—
engi neer i ng. Cop ol ymer wi h t t wo or t hr ee ki nds of mono— ni sm of radi ca l p ol m er y izat ion.
n t he p ol m er y ic sys t em
mer s has pr oper t i es of i t s di fer ent segment s a n d t he r at io i s t o vi scous,i t i s unf avor abl e t o heat r el ease n d a he aut t o-
n d cat a egor y of t hese s egment s ca n b e mo d ul at ed t o obt ai n accel emt i ve phenomen a w i1 1 b e obvi ous.Secondl y。 a vi s— cons mi xt ure i s ver y di iqcu f lt t o mi xed hom o geneousl y a n d
appr o pr i at e p ol ymer s.
he i si n de st r uct ure of net wor ks w i1 1 b e uneven. Po l y(pr opyl e ne f uma r a t e) (PI ) F)i s a l i nea r bi de— o t
n ma—
gr ada bl e p ol m er.r y I 1 1 e doubl e b o nds a long i s mai t n chain t er ia ls were compressed,t he s t r ess w i1 1 concent rat e on one ca n react w it h ot her ol ef ini c comp o unds, such a s N.v inyl par t n d des a t r oy t h e whol e st u ct r ure of mat er ia ls. Ac cept e d dat e: 2( XY / - 03-1 9.
ZHANG Na,b or n i n 19 76,f e ma l e,d oct or at e s t ude nt.
*S u p p o r t d e b y ci S e n c e Co mmi s s i o n o fT i nj a m( NO. 0 4 31 8 6 01 1 ),Ou t s t a l 1 d i I 1 g Yo u n g ch S o l a r s ip h f r o m NS F C( NO. 3 01 2 5 4 3) 0 ,t h e Ba s i c Re - s e a r c h P r o j e c t ( NO. 2 0 0 2CC A01 6 5 0 0)o f t he MOS T nd a t he Na t u r a l ci S e n c e F o u n d at i o n o f Ti a n j i n( NO. 0 4 3 8 0 3 51 1). Cor r es ponden ce t o ZHANG Na,E- mai l: m gna t j u@ya ho o.c or n.c a. —
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ZH A NG N a e t a f : S y n t h e s i s,C h a r a c t e r i z a t i o n a n d i n v i t r o
Pr o p e r t i e s o fedy( Pr o #e i r e F u n mr a t e - o o - Pr o p y l e n e
y l e ne ly g c o 1 )wa s a d d e d t o f a c i l i t a t e s i t r r i n g.T he mi x t u r e s s ti r red f or a n ot her 12 h at r oom temp er at ur e.r nl e pr od. ( p r o p y l e n e f u ma r a t e - c o - p r o p y l e n e s e b a c a t e) 8 0 2 0[P(P F— wa s ext ract d w e it h met hyl ene ch lor ide f or t hree t i mes, c o - P S) 8 0 2 0]a nd p o l y( p r o p y l e n e f u ma r a t e — c o - p r o p y l e n e s e — uct wa w s a h d e wi h t wa t e r t w i c e ,a n d h t e n d r i e d w i h t a n h y d r o u s o s . b ac at e) 901 0 1 P( PF. co. PS)901 0 wer 1 e s y nt hes i z ed.r nl ei r I n t hi s paper, t wo ki nds of random cop el ymer s, p el y
net w o ̄ s wer e f ormed by usi ng N. vi nyl pyr rol i done as t he d i m u s ul f a t e o ve r ni h t.r g nl e ol s v ent wa s emove r d b y ot r a t or y
c ms shnki ng a ge nt L 4 j.The s t r uct ur e of P(PF. c o- PS)wa s e va por at i o n.Bi s (2- hy dr ox ypr op y1 )s e bac a t e wa s pur i ied f by charact er i ze d a n d t he mol ecul ar wei ght a n d p el ydi s er p si t y c ol umn it w h me t ha no l a nd me hyl t ene ch lor ide(wei ht g r a. i nde x(PI)o f P(PF. co. PS)we r e det er mi ne d .r nl e max i . t i o,5: 95).r nl e yi el d of bi s( 2- hydmxy pr o py1 )s eba ca t e i s mUl T I t emper at ure oft he cmss l i nki ng r eact i on duri ng net w or k a bo ut 56. 4% . Pr epa at r i o n of f uma r o yl c lor h ide a n d bi s(2.
hydmxy pr opy1 )r un.r a t e i s s i mi l r a t o bi s(2- hydmx y pr opy1 ) eba cat e. r n1 e t hi r d s t ep i s p ol y me iz r at io n. Bi s (2. he t wei ht g r a io o t f f uma r at e t o s ebac at e a nd a mount o f N. s VP,on he wei t ght l os s,wat er cont ent,s wel l ng i degr ee n d h a ydmxy pr opy1 )f umar at e nd a bi s( 2- hydmx ypr opy1 )s cba cat e t he change o f me chani cal prop e rt i es duri ng t he pr oces s o f wi h t a c e r t a i n we i ht g at r i o s a 80: 20 n d a 9 0: 1 0 wer e pl a ce d de gr a dat i on i n phos pha t e bufe r e d s a l i ne(PBS)wer e a ls o i n a t hr ee . ne ck la f sk t o s nt y hes i e z c o ol p y mer P(PF— c o. PS) exami ned.r nl e pH va lue ofPBS i s 7. 4 whi ch i s si mil r t a o 8 020 a nd P(PF_ c 0. PS) 901 0.Hydr o qui none wa s adde d s a a he i t n vi vo envi onment r o f human’ SL 6j r a di c a l i nhi bi or(1% o t f bi s(2- hy dr ox ypr opy 1 )f umar at e by we i ht). g r e act i on wa s he at d e at 1 70℃ a n d a t a pr es . 1 Experi m ent f or mat ion wa s exami ne d .The efect s of paramet er s,such a s
.
s ur e o f 1. 33 kPa(1 0 mmHg)u n de r a ni t r og e n a t mos pher e
1. 1 M at eri al s
or f 16 h t o obt ai n cop el ymer s.Af t er pol ymeri zat i on,prod-
s we e r di s ol s v d e i n me hyl t e ne c hl or ide.p et r ol e m u et he r Fumar i c aci d, sebaci c aci d, 1,2- propyl ene gl ycol, uct wa s adde d dropwi se t o pr eci pi at t e p ol ymer a n d r emove t he
N, N. di me hyl t f or ma mi de(DMF),anhy dr o us pot a ss i um c r. a
none i nhi bi t or.T h en t he p et r ol eu m et her wa s de. Donat e,sodi um ch lor ide,sodi m phosphat u e di basi c dodeca. hydroqui c n a t e d n a d h t e me h t y l e n e c l h o i r d e w s a r e mo v e d b y o r a t t o y r hydr at e, s odi m hydr u oxi de, s odi m phosphat u e monoba si c dehydr at e,phos phor ic aci d,hydroqui none a n d N,N— di me-
evap or at i on a t 60 ℃ f or 2 hL 8j.Pol ymer wa s dr i ed u n der
cul / / l q at room t emp er at ure f or 1 h.Fi g.1 shows t he pr o— t hy 1 . p- t o l ui di ne(DMPT)we e pu r r cha se d a n d us ed s r a e. va es s o f P( PF. c o. PS)s nt y hes i s. cei ved.Thi onyl chl or ide n d a N. 、1P wer e pur i ie f d by vacuu m c
3 Charact eri zat ion of pol ymers di s t i lat i on.Ben zo y l per o ide(BP)wa x s r e cr y s t ali z d f e r o m 1. ch lor of or m nd a me ha t no l n d a s t o r e d bel o w 1 0℃ . , nl e s t r uct ur e o f P(Pl F_ c o. PS)wa s c ha r a ct e iz r d by e H . n u c l e r a ma g n e t i c e r o s n n a c e ( H. N 豫 )a n d F o u r i e r 1. 2 Synt hes i s of PPF and P(PF. co-PS)
r ans onT f l i nf r a r e d (F1 7R)s ec p t r a. H. NMR n CDCh wa i s PPF wa s sy nt hesi z ed a n d charact er ized by he met t hods t of Pet er’ sL 川 .r nl e number of mol ecu la r wei ght a n d t he o bt ai ned o n a 500 MHz s pec t r o me t e r(v{ l r i n ,Sw a it z e r l nd) a
nd FI Ⅲ wa s o bt a i ne d on a Frs3 000 (B1 0. RAD,USA) pol ydi s per si t y i ndex of PPF t est d by gel e p er m eat ion chr om- a
p e c t r o me t e r u s i ng n e a t s a mp l e s.r nl e mo l cu e la r we i ht g nd a a t o gr a ph y(GPC)a 托 1 C r 7 1 Da a nd 1. 7,r es ec p iv t el y.P s ydi s pe r s i t y i ndex o f P(PF- c o- PS)wer e de t e r mi ne d by ( PF- c o= PS)wa s s nt y he s i z d t e hr oug h a t h r e e. s t ep r ea ct i on pol it h a di fe ent r ia l r ef r ct a o met e r de t ct e o r(A ent , pr o ce s s.Br ief ly,f ir s t ,s eba coyl c lo h ide r wa s pr ep a ̄ f r o m GPC w 1 1 0 0 S e i r e s ) , n a d c h r o m a t o g r a p h y c o l u m n( A g i l e n t , P L g e l sebaci 6aci d a n d hi t onyl ch lor ide whi l e t he mol arr at io of se. xed bed c ol umn。300 nl i n×7. 5 nl i n).r nl e ol s ve nt,t et . baci c aci d t o t hi onyl ch lor ide wa s 1:3.T h e mi xt ur e r ef luxe d mi r a h y d r f o u r a n w s a r u n t a 1 . 0 mU mi n n a d o p l y s t y r e n e s t a l 1 . at 7O ℃ f or about 2—- 3 hour s.DMF wa s u se d a s cat al yst. ar ds( 50-- - 1 00 0 00 Da)wer e us e d.r n1 e ol m cu e la r we i g ht Seba c oyl ch lor i de wa s puri ie f d by vacuu m di s ti lat i on u n der d nd PI o f P(PF. c o. PS)a l e s ho wn i n T£ I b. 1. ni t r o ge n pr o t ct e i o n.Sec ond,mo nomer ,bi s( 2- hyd mx ypr op- a 4 Cros aaf ldng r eact ion y 1 )s e ba cat e wa s pr epa r e d by he t me ho t d a s olo f ws:s eba. 1.
c o yl c lo h r i de(1 e qui v.)i n met hyl e ne ch lo ide(1:1 r Vo 1 . ' F nd a P(PF. c o - PS)wer e c r os s l i nke d w it h a l i qui d i v n y l mo n o me r N — VP s a c o r s s l i n k i n g g a e n t .B P n a d D姗 ’ U l T l e r at i o)wa s a dde d d r o pwi s e t o a mi xt ur e of pr opy l e ne e us ed a s i ni iat t or n d a a c cel er at or espect r i vel y.I n or der g l yc o l( 3 e qu i v. )i n me hyl t ene ch lor ide(1: 2 Vol u me at r io wer nd a anhy dr o us pot a s s i m c u ar bo na t e(1. 5 eq 眦i v.)a t 0 ℃ t o e xami ne he t efe ct s of wei ht g at r io off uma r a t e t o eba s c at e n der a ni u t r ogen at mos pher eL 6j. r n1 e mi xt ure wa s st i rr ed t o quant i t y of N. 、1P on t he max imUl Tl t emp er at ure of t he wi h a t n over he ad mechani ca l s t i r r er t o f or m a vi s cous s l ur. crossl i nki ng r eact ion,wei ght l oss, equi l i br iu m wat er cont -
r y.Af t e r a ddi ng he t s eba co y l c lo h ide,add r it i ona l met hyl — ent, s weli ng degr ee, compr essi ve s ngt h at yi el d, con- essi ve st reng t h at f r act ure a n d compr ess i ve modu lus of e ne c lo h r i de( ha l f of he t v ol me u se u d t o is d ol s v e he t p r o p. pr -・
-—
—
255 ・ ・ - — —
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Tr ans a c t i ons o f Ti an  ̄n Uni v e r s i t y
Vo 1.13 No. 4 2007
net wor ks, f our f or mul at i ons composed of t hr ee pol ymer s
BP( 0. O1 g PP F)a n d DMVr( 1. 0 g PP F)we r e k e p t
wi t h t wo amount s of erossl i nki ng agent wer e desi gned.The
constant.
f our f or mul at i ons ar e present ed i n Tab.2.The amount s of
H。
几 … 昔
H。
c ・
O
0
H。
c 。
c 佃 、
Ret l ux
。H + s
/ 显 \ c
c。
c。
。
K 0, a 川
。
。
舯
。 。
0
0
O
O
H。 c。
c 。
A + B
/ L \ 。 H
。H
睾
1 . 3 3 ̄ a ( 1 0衄 H
H 。 。 人 O 人 O c
。 H
一PF. PS—忭 PF— , s Pn, FPF— S . r a ndom e ̄ l yme rP( PF- e  ̄- PS)
IF:pmpyl ene ̄l l l l l l l l l le se nef n;IS:pmpyl e ̄e sekl cat
隐 . 1 s y n
pr o c e s s o fl ' ( 1  ̄- c o - PS)
1抽 . 1 Mo l e c u l  ̄ we i 雩 a ndH o f p0 切岫e r s
呦
. 2 0
n硒 呜 ex per i me nt des i g, 1
11l e cr ossl i nki ng r eact i on was per for med 1 t 8 f ol l ows.N. wat er bat h.11l e t emper at ure WaS r ecorded ever y 15 S unt i l i t VP was di vi ded i nt o t wo pa ns.Hal foft he N. vP was mi xed dec r ea s e d t o 37 ℃ .
’ v i t h po l y mer s an d DⅫ P 1 r :t he ot her ha l f wa s mi x ed wi t h 1. 6 BP.Af t er st i r ri ng t o homogenei t y,t he t wo component s wer e
/n v i t r o degr adat i on Each eyl i ndri cal t est speci men of6 mm di amet erby 12
mi xe d t og et her a nd t he ina f l s ol ut i on was i n j e ct e d i nt o a e y. mm l eng t h was pl a ce d s ep ar a t e l y i n a t es t vi 8 1 a nd wa s i m- 1 i nd r i c al gl as s vi a l(6. 0 mm X 1 2 mm)a t r o om t e mpe r a- mers ed i n 10 mL phosphat e bufer ed s al i ne.r I1 l e PBS was t ure.Then t he gl ass vi 81 was pl aced i n 37 ℃ wat er bat h t o i ni t i at e t he cr ossl i nl dng r eact i on. Af t er 24 h cur i ng, t he speci mens wer e r emoved f r om t he vi 81 by breaki ng t he
对a s s.RodS wer e t he n c ut wi t h a di a mond s a w t o pr oduce t e s t c y l i nde r s wi t h a 6 mm di ame t e r and a 1 2 mm l e ngt h.
p r e p a r e d 1 t 8 f o l l o ws :d i s o d i u m h y d r o g e n p h o s ph a t e O. 2 I l L( 71. 6 g o f Na 2 I - [ P O4‘ 1 2H2 O p e r 1 0 0 0 mL)a n d 0. 2 n  ̄l /L s o di um di hy dr o ge n pho s phat e(31. 2 g of Nat t 2PO4‘ 2H' O pe r l 000 I I 1 L)i n 0. 9% s a l i ne s o l ut i o n wer e pr e.
r e d s e pa r at el y and t he n mi xe d i n a r a t i o o f77: 23(V_ 0 1 . Fi g. 2 i s t he cr o s s l i nl dng r e ac t i o n be t wee n P(Pl F_ co . PS) pa m e r a t i o).Na oH a nd H3 PO4 we r e us ed t o modu l a t e t he
a nd N. vP.
1. 5
^
n删
t emoel  ̄t Vme
r I 1 l e maxi mum t emper at ure of emss l i nki ng r eact ion was
pH va l ue.
t e s t v i a l s we r e mai nt ai ne d a t 37 ℃ and t he
PBS s olut i on was exeh ̄ ged ever y 12 h f or t he f irst t wo
s,da i l y f or t he nex t 1 2 days,t wi ce a wee k f o r t he ne xt de t e ml i ned by t he f ol l owi ng me t hod. I 1 1 e c r o s s l i nki ng mi x- day 2 w e e k s a n d we e k l y f o r t h e r e ma i n i n g 6 w e e k s . At 0, 2,7 , t ure was pl aced i n a ass t ube of 12 mm di amet er and 10 4,28,42,56 and 70 d,speci mens were r emoved t o un- cm lengt h,and a t her moeoupl e was i m ert ed t o hal f of t he 1 d e r g o me e h  ̄ e a l t e s t i n g a n d g r a v i me t r y a n a l y s i s . dept h of t he t ube.Then t he t ube was i mmersed i n a 37 ℃ ‘_。—
—
256 ‘ _ 。 — —
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Z HA NGNa e t n f : S y n t h e s / s, 删咖
H0
/、、
a n d/ a
如 脚 (
…
。
删 砌删 o D - 删
c
BP 37 ℃ DMPr
r yPF— c o - PS) / N— VP n et wo r ks 。
2 CI 1 D s s l i
r e
be t we e nP( PF- c o - PS)a ndN- VP
ine f d by drawi ng a l i ne par al l el t o t he sl ope def mi ng t he
1. 7 Gr av i me t r y锄翰l ys i s Degr adat i on of t he net works was det er mi ned by a
mo du lus.b eg inni ng a t 1. 0% s t r a i n.T he i nt e r s e ct ion of
hi s l i ne it w h t he s t r ess—st rai n curve i s r ecor de d a s t he con— gr a vi me t r y a na l ys i s . Be f o r e be gi nni ng t he de g r a dat ion, t pr essi ve st r engt h t a yi el d.Mechani ca l t est in g f or ever y sam— he wei t ght of e ach speci men wa s r ecorde d a s ,t hen t he
c yl i nd r i c a l s pe ci me n wa s pl ac d e i n PBS s o l ut io n(pH 7. 4) and st or ed i n a 37 o C envi ronment.At each t i me poi nt,t he
pl e gr o up wa s r un ive f t i mes(n=5). 1. 9 St at ist i c al anal ys i s
Da t a a l e e x pr es s d e s t a he(mea n 4 -s t a nda r d dev i a— io n). S at t is ic t l s a i g n i ic f nc a e wa s a ss es s e d u t i l i z ng i wa s wi p e d it w h f i l t e r p a p e r.Th e we i g h t 0 f山e we t s p e c me i n t speci m en wa s r emove d f rom PBS and wat er on t he s urf ace
i s
nnet t ’ s met hod w it h 95% co nf ide nc e i nt er va ls (P < .Af t er d ng at 3 7℃ f or 48 h n d a unde r va cuum t o Du
c o n s t a nt we i g h t ,t l 1 e we i g h t 0 f山e s p e c me i n wa s r e c o r de d s 0.05). a Wd.T h e we i g h t l o s s ,wa t e r c o n t e n t nd a s we l l i n g d e g r e e wer e ca lcul at ed wi h t t he f olowi ng equat i ons.
2. 1 Sy nt he s i s o f P( PF- c o- IS)
We i ht g l o s s: c 0 n t:
×1 0 0%
( 1)
×1 0 0%
P( PF- co - PS)wa s s y nt he s ze i d by a t hr e e— s ep t pr oce s s. I n t hi s met hod, t he i nt er medi te a m o no mer h is (2-
( 2) h y d r o x y p mp y 1 )s eb a c te a nd a b i s ( 2 一 h y d r o x y pr o p y 1 )f u ma r a e t wer e l i quid a n d t h e p ol ymer i zat ion i s hom o geneous phase
S we l ng i d e g r e e=
×1 0 0%
e ac t i on.t hus he t empe t at r ur e of ol p y me iz r at ion wa s 1 70 ℃ ( 3) r wh ich i s t he t emper at ure t hat t he end gr oup of i nt er m edi a
1. 8 M echani c al propert i es
wa s ct a ive d .I t i s l o wer han t he t empe t r a t ur e( 292℃ ,me l t —
l e me cha ni ca l pr ope r t i e s of PPF/ N— VP n d a P(PF- c o- i ns oi p nt of f u ma r i c ci a d)t ha t us i g n f u ma r i c a ci d,s eba c i c PS) / N— VP net wo ks r we e r de t e r mi ne d n der u co mpr es s i o n.A a c i d a nd 1, 2 一 p r o p y l e ne g l y c o l o t p ep r a r e P( PF - c o — PS)d i —
s ys t em me cha ni c al t es ing ma t chi ne (M350,Tes t ome t r i c, r e c d y.
UK)f olo we d he t gui de l i ne s s et i n AS
e n t } l e t e mp e at r u r e o f ol p y me r i z a t i o n i s ig h he r
F451- 95.Cy l i n— t ha n 250 ℃ .t he c on ig f ur at ion of f um ̄ c a ci d eg s ment i1 w 1
dr i cal s peci m ens wer e compr es sed i n a dr y st at e at a cr oss—
e b eve r r s e d o t c i s f o m r a nd t hi s per f o r ma nce wi l l afe ct de g— head speed of 1 r am/r ai n u nt i l f ai lur e wh il e t } l e st r ess ver sus r ada io t n a nd el i mi nat ion of net wo r ks v / v o be c aus e he t n— i
s t r d i n C L L r v e Wa s r e co r de d t hr oug hout he t e x per i ment. nl e t er m edi at e pr oduct oft r i car boxyl i c a ci d cycl e i s f t l mar l c ac— compr essi ve st rengt h at f ract ur e i s def ine d a s t he maxi l nunl id。but not mal ei c ci a d.On one ha n d,t he end gr oup of i n— st res s duri ng t he t est.11 1 e mo du lus of compr essi on i s de- t er medi at e m o nomer i s hydroxyl gr oup a nd t her ef or e he end t
f me d s a he t s l ope of he t i ni ia t l l i ne ar or p t i on o f he t s t r es s—
g r oup o f p ol y me r pr o duce d b y t he i n ono nl  ̄ r s i s hy dr o yl x
st rai n curve.And t he compr ess i ve s t r engt h at vi el d i s de— gr oup,t oo.Whi l e usi g f n umar i c ci a d,sebaci c aci d and 1, ...—
—
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Vo 1.1 3 No. 4 20 07
2 一 p r o p y l e n e g l y c o l p o l y me r i z e d di r e c ly,e t n d g r o u p s o f p o l y— mer s wer e mi xt ures of hydroxyl and earboxyl groups.So t he t hr ee—st ep met hod i s much easi er t o cont r ol t h e s t ruct ur es of pol ymers.On t he ot her hand,t hi s m e t ho d al s o avoi ds t h e
sel f - pol ymer i zat i on of aci ds or a lcohol s a n d makes t he pol ydi s per si t y i ndex l ower.
2. 2 GPC
The mo l e cul a r we i ght nd a PI f o P( PF- eo- PS) 8020 nd a P(PF- co— PS)9 01 0 a r e s ho wn i n .1.T he mol ecul a r
( -CH 一,一CH )
we i ht g fP( o PF - c o — P S) s i s n o t h i 【 h( g 1 o we r t ha n 1 2 0 0 Da ), becaus e when appl i ed i n vi vo.pol ymer s a n d N— vP wi l l be er os sl i nked i n si t u a n d mol ded a s t he shape of bone de—
3 500
3000
2 500
2000
1 500
1 000
5oo
1 000
50o
Wavenumbedcm一
f ect s.T h i s r equi res t hat p ol m er y s shou l d have appr opr iat e
( a )Fr I R o f bi s ( 2一 hy dr ox y pr o py 1 )s e ba c at e
v i s c o s i t y.T he ef r o e r he t mo l e c la u r we i ht g o f ol p me y r s h o ld u n o t e b v e r y h i h g i n o r d e r o t k e 印g o o d lu f i d i y t nd a ma k e he t i n j e c t i o n p r o c e s s e a s i l y.I n a d it d i o n,p ol me y s w r it h h i 【 h g mo l e c u l r a we i ht g de g r a d e mo e d r i fi c lt u l y t ha n t ho e s it w h l o w mo l e c la u r we i ht g . 2. 3 FI ' 】 R
Fi g. 3(a)i s he t FHR s pe ct r um o f bi s( 2一 hydr o xyp mp— y 1 )s eb ae at e nd a Fi g. 3(b)i s he t F 1Ⅲ s peemma o fP( PF. c o— PS)8020.I n Fi g.3(a) t he i nt ens e OH s t r e t ch at 3 550 a m o f bi s(2一 hy dr ox ypr opy 1)s eba ea t e i s s t r ong e r ha t n he t s t r et ch a t 3 4 0 一3 550 a m一 ofP(PF- e o- PS)8020 i n Fi g. 3(b)b ec a us e b ef or e p ol me y r i z at i o n her t e
3 500
3000
a r e mo e h r ydr o xyl end gr o up s i n t he ol i g o mer o f bi s(2一
2 50o
2000
1 500
W avenumbedcm一
hy dr o x ypmpy 1 )s eba ea t e.Whe n t he p ol m er y wa s f o r med,
( b)gr l R o fP( PF- c 0一 PS) 8o 2o
he syst t em l ost much 1,2- propyl ene gl ycol end gr oups a n d
r ag. 3 FrIR s i e r ra of oUgome r and pol ymer
h e OH st t ret ch wa s weaker.
I n Fi g.3(a),t he C_ 一H s t r e t ch at 2 85( ) _ 一2 940 am~ due t o t he m e t hyl ene a n d met h yl of 1,2- propyl ene
ly g c o l e n d g r o u ps i s s t r o n g e r ,b u t i n Fi g. 3(b)C—H
of GPC ca n b e prove d by t he r esu lt her e.
2. 4
H- NM R
Fi g.4(a) i s t he H— NMR s pee t l ' ul n o f bi s(2一
st r et ch at 2 85( ) _ 一2 94 0 am一 i s weaker b e caus e of t he
e l i mi n a t i o n f o 1, 2 - p r o p y l e n e ly g c o l d u r i n g he t p r o c e s s f o
h ydr ox ypmp y1 )s eba e at e,Fi g. 4(b)i s t he H— N
s pec—
nl m f o P(PF. c o- PS)8020 a nd Fi g. 4(e)i s t he H— N ol p yeondensat i on.At t h e s ame t i me. t h e C— O st ret ch o f t
eet p nma fP(PF. o c 0一 PS) 901 0.I n Fi g. 4( a),t he eh emi c l a es t er onds b at 1 263 am~ of P(PF- co — ps)8o20 i n Fi g.3 s sh of 1. 22 x 10 i s at t ri but ed t o hydr ogen of met hvl (b)i s s t r ong er ha t n t ha t i n Fi g. 3( a).T hi s c ha ng e ca n e b r o u p o f l, 2 一 pr o p y l e n e ly g c o l ,wh i l e he t 3. 9 8 x 1 0 i s at t r i but ed t o mor e es t er b on s i d n p ol m er y t ha n i n bi s(2一 g hydr o x ypmpy 1)s eba e at e.T h e C— O s t r et c h ofes t er gr ou ps
hydr ogen o f met hi ne gr oup a n d t he 4. O
.16 x 10_6 i s
y d r o g e n o f et m hy l e n e g r o u p o f l,2 - p mp y l e n e g ly c o l r e— at 1 726 am~ i n Fi g. 3(a)i s wea ker ha t n ha t t i n Fi g. 3(b) h e caus b e t her e are mor e ear bonyl gr oups i n ol p ymer.I n Fi g.
3(b)we ca n ee s he t C— C s t r et c h o fP(PF. c 0 .Ps)8 020 at 1 646 am 一 a n d t he C— H st r et ch of doubl e bonds at 984
speet i vel y.T h e chemica l s hi f t of 2.41 x 10 i s hydr ogen of met hyl ene whi ch i s next t o t he ea rb o nyl group o f s eba— cat e.wh il e h e 1. t 62 x 10—0 n d a 1.34 x 10_o a re at t ri but d e
a m~ whi l e i n Fi g.3(a)t her e ar e no C- - C s t r et c h a nd
o t he hydr t ogen of 一a nd ) , .carbon at oms of ebacat s e.Com—
C_ 一 H st r et ch o f doubl e b o nd s . AⅡ t hes e ev idences show
pa r i ng Fi g. 4(a),4(b)a nd 4(e),t he hy dr oge n of do bl u e
ha t t bi s(2一 hy dr ox ypr o py 1)s ebae at e c ha ng e d t o p ol me y r.
o nds b a ppea r e d wi t h t he che mi ca l s hi f t o f6. 89× 1 0 a f t er
Bu t he t OH o f 1. 2 - p r o p y l e n e ly g c o l e n d g r o u p s nd a C— O st r et ch of est er gr oups di d not cha n ge mar kedl y b e caus e t he
mo l e c la u r we i ht g o f ol p me y r i s n o t v e y r ig h h .An d t h e es r lt u -
-
— -
—
258 . . . — —
ol p m er y i zat ion.T h e rat i o of met hyl ene hydr ogen of e bacat s e
eg s me n t t o me hy t l h y d r o g e n o f l, 2一 pr o p y l e n e g l y c 0 l s e gme n t ncr i ea se d af t er pol m er y izat ion becaus e t her e al e mor e s eba—
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Z H ANG Na e t a l : 5 yu l  ̄i s ,C h a r  ̄
a n d i n v i t r o De g r a d a t i o n P r o p e r t i e s o fPay( Pr o  ̄a e F u ma r a t e - c o - Pr op y l e n e’ i s 9 0: 1 0,whi l e t hat o f P( PF. co . PS) 8020 i s 80: 2 0.The r e. f o e r he t amou nt o fdou bl e o nds b o fP( Pl F_ co - PS)9 01 0 i s a l i t t l e mor e t han hat t f P( o PF. co . PS) 8020.1 ] h e da t a pr ov d e
。 H
。“
t I 1 e r esul t s o f FⅡR .
2. 5
] VI axi nl Ul ll t em perat ure Fi g. 5 s ho ws he t max i i nun l t e mpe r at u r e o f he t our f or f -
(
7
6
5
maxi l num t emperat ur e wa s afect d by t e he amou nt o f seba.
姒
h …
.
mul at i ons dur i ng t he process of crossl i nki ng r eact i on.11 he
4
3
2
1
( a) H— NMR s pe c t r um o f bi s ( 2一 hy dr ox y pr o py 1 )s e ba ca t e
ml l l T l t e mper at ur e de cr ea s e d (F>s2>S1)be ca us e s eba- cat e seg m ent s decr ease d t he densi t y of dou bl e b o nds al ong n d a heat o f el p ymer i zaf i0n was r el ease d when cmssl i nki ng, so l ess amou nt s o f dou bl e b o nds, l ess he at r el ea se d a n d
g P
HO
Wi h t he amount t of sebacat e segment s i ncr easi ng,t he maxi-
he pol t ymer chai ns.Dou b le o nds wer b e op e ne d by i ni t i at or
Fr equency/10
I
cat e segment s i neopol m er y chai ns and t he a m ou nt of N_VP.
l ower maxi i nunl t emper at ure dur i ng t he pr oces s of cms sl i nk-
i j 、 o f . 『 / 0 r
i ng ea r c t i o n.Al ho t u h g wi h t t h p e i 暑甜 n c 盘 r e 昌 a s _i 昌j ng 昌胃 f苫 o N- VP.t he ma xi ml l m t e mp er at u r e i nc r ea s e d(s3>S2>S1),i t i s l o we r t ha n t hat of F.T h e r ea s on may be hat t t he dens i y o t f dou bl e
d
o nds b a long pol ymer mai n chai ns ha s much mor e efect t han
he t mo a nt u f o N. VP i n P(PF. c o. PS)net wo r k s. d
I. 8
7
.
6
5
4
3
2
l
Frequency/lO
( b ) H— NMR s p ec t r u m o f P( PF-c o -PS) 8020 g P
I H0
2.6 Gravi met ry anal ys i s Sampl es wer e i mmer se d i n PBS a n d t aken out t o t est
te h we i ht g l o s s ,wa t e r c o nt e n t nd a s we l l i n g d e g r e e a c c o r d i n g t o Eqs. (1),( 2)a nd( 3)pe r i odi c al l y. Fi g. 6 i s wei ht g . 1 os s o fnet wo r ks s a a f unct io n f o de gr a- 8
7
6
5
4
3
2
1
Frequency/lO
( c ) H・ NMR s p ec t r um o f P( PF—c o -PS ) 9 01 0
魄 . 4
H- NMR 叩 :
ofdi gl l me r and coI  ̄ yme rs
af d ion t i me.I t shows t hat addi ng sebacat e s eg m ent s i n pol y- me/ x 3 wi 1 1 i ncl '  ̄ase t he wei ght l oss.T h e l eason o f t hi s phe. nomenon i s t hat t her e ar e no dou bl e b o nds a long t he seg. ment s of sebacat e.
en cr ossl i nke d wi h N. t VP,segment s
o f s e ba c at e id d no t l i nk wi t h N. 、1 P by c a r bo n. ca r bon o nds b i ke f umamt e s eg m ent s. T h er ef or e when t he cyl i ndr i ca l cat e segment s i nt r oduced i n pol ymer.On t he ot her hand, l s p e c i me n a b s o r b e d w a t e r n a d s we l l d e u p ,t h e e s t e r o b n d s f o he t r at i o ofdoubl e bonds hydrogen t o met hyl hydr ogen ofP
e bac at e s we e r br o ke n y b hydr ol ys i s a nd much mor e s e ba- ( PF - c o - PS) 9 01 0 i s a l i t t l e b i g g e r t h a n t h a t o f P( P F- c o - P S) s cat e seg m ent s wer e l ost f rom net w orks.Thi s pr ocess makes 8 020 be ca us e whe n ol p me y r i z ed,t he we i g ht r at i o o f bi s(2- he we i ht g l os s f P( o PF_ co - PS) / N. VP i ncr e as e d.T he e r a r e h ydr o xy pr o py1 )f uma r a t e t o bi s(2- hydr o x ypr o py1 )se ba ca t e t mor e f umarat e s eg m ent s l i nke d wi h N_VP i t n PPF/N_VP -
-—
—
259 - 。 — —
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V .13 No.4 2007 逞 %0 _ 【 鼍 一
墨吉
∞
ne t wo r ks(f ( I 丌瑚l l a t i on F),a l t houg h es t e r b onds o f f uma r — at es were broken by hydrol ysi s,t he f umari c aci d r esi dues
we e r l i n ke d wi h p t ol y(N— v i nyl py r r o l i do ne).Af t e r 70 d, h e wei t ght l oss of f or mul at i on F i s t h e l east among t h e f our
f o mu r la t i o n s .Co mp a r i n g he t we i ht g l o s s e s f o S 1 a n d S 2. he t e r a l e mo e r s e b a c a t e s e g me n t s i n S 1,b u t he t we i ht g l o s s 0f S2 i s mor e t han S1., nl e r eas on o f t hi s phenomenon may be t he hydrophobi c chai n of s ebacat e weakene d t he i nt er ac— t i on b et w een wat er n d est a er o nds b of pol ymer net wor ks.S3
Degr adat i on t i me/ d
i s t he f o mu r la t i on it w h mor e N— VP n d a he t wei ht g l os s of S3 i s mor e t han t he ot her t hr ee f or mu lat i ons because t he ket one
ri g. 8 Swe ll i ng degr ee舔 a f l l l  ̄ on ofde gr ada ti on t i me
ca lb o nyl o f N— VP has b et t er abi l i t y of hydrophi l e. I t ca n v i t h S3.wat er cont ent a n d s weli ng degr ee i ncr ea se d w it h combi ne w it h mor e wat er, make t he br eak o f est er b o nds ’ he i ncr ea si ng o f t he amou nt of N—VP., nl e r eason m a e a s i l y nd a he t we i ht g l o s s f o n e wo t r k s i n c r e a s e s.Ac c o r d i n g t
y b e
hat when t he amou nt o f N. VP i ncr ea sed. t he net chai n o f t o he t da t a of wei ht g l os s.t he a mo unt s f o N— VP n d a s eb a— t w or k s produced by cr ossl i ki n ng r eact i on wa s l onger a n d c at e s eg ment s i n P(PF— c o- PS)a r e wo t mai n f a ct o r s t hat c n net a he mes t h si e of z net w or ks w i I b e great er.Thi s i s f avor abl e i n f l uenc e he t we i ht g l os s f o ne wor t ks. or f wat er ent er i ng i nt o net w or ks. 更 aI
昌0车∞
2. 7 M e chani cal prooert i es , nl e mechani ca l pr oper t i es o f net w or ks wer e t est d pe— e ri odi cal l y duri ng t he pr ocess of degr adat i on., nl e compr e s— si ve s t rengt hs at yi el d,compr e ssi ve st rengt h at f ract ure a n d
compr es si ve modu lus of t he f our f or m ul at i ons ale s hown i n Fi 帑 .9_一 11,r e spect i vel y. Fi g.9 shows t hat t he i ni t i l compr a e ssi ve st r engt h at Degr adat i on t ime/ d
Fi g. 6 W ei ght l os s as a hl net i on of degr adat ion t i me
y i e l d ofP(PF_ o o . I X 3) / N— VP ne wor t ks i s l o wer ha t n 唧 , N— VP net w or ks because i nt r oduci ng s of t s ebacat e s eg m ent s i n he mai t n chai ns o f PPF i ncr e ased pl st a i ci y o t f net w or k s.
Whe n co mpr es s e d,P(PF_ c o- I X 5) /N— VPne wor t ks a l e e as i e r Fi g. 7 i s wat er cont ent a n d Fi g.8 i s s wel l ng degr i ee o f t o have p er manent def or mat i on t han Pl PF/N—VP net w or k s. net wor ks as a imct f i on of degr adat i on t i me r especti vel y.
i. e.a s ma l l er s t r es s ca n c ompr es s t he P(PF_ co - I X 5) / N— VP net wor ks t o t he y iel d p0i nt .But a f t e r b ei ng d egr a de d i n
P BS.t he c h ng a e f o y i e l d s t r e n g t h i s di fe en r t .Wl e i ht g l o s s f o he f t our f or mu lat i ons i s about 20% 一 30% af t er 70 d o f degr adat i on,but duri ng t he 70 d,t he compr essi ve s t rengt h
at yi e l d o f S1 a nd S2 i nc r e as e d. , nl e nl Kxi l nu l n y ie l d
s t r e n g t h o fS1 i s( 5 9. 5 6±2. 2 9)MP a( 4 2 d),hi he g rt ha n he t i ni t i l a va lue(( 28. 07±1. 92)
a,0 d)a nd S2’ s i s
( 55. 21士1. 7 4) a( 4 2 d) ,a ls o h i he g r ha t n he t i ni t i l a Degr adat ion t imeM
i g. F 7 W at er cont e nt舔 a f I 删
0n ofde gr adat ion ime t
en t he amou nt of N— VP i s he s t al 】 ,t he wat er o n— c t ent a n d sweli ng degr ee of net w orks decre ased it w h t h e i n—
va lue((1 6. 90±2. 4o) a,0 d)whi l e he t yi e l d s t r e ngt h f f o or mu lat i o n F de cr e as e d a n d t he nl Kx i l n ul n i s onl y
( 53. 12±7. 72) a( 7 d)dur i ng deg r a da t i o n,l o we rt ha n te h i ni t i l a ie y l d s t r eng t h(( 73. 75士9. 81)MPa,0 d). l "  ̄a son o ft hi s phenomenon i s t hat S1 a n d S2 l ost much mor e s of t sebacat e eg s m ent s duri ng he pr t ocess o f degr adat i on a n d
cr e as i ng f o s e bac a t e s eg m en s t n i P(PF- c o- PS).Mor e s e ba— t he s t r uc t u r e o f r es i d ua r y s hor t c hai n P(N— v i nyl pyr r ol i — cat e seg m ent s ca n i n cr ease t h e mesh si ze o f net w orks a n d
mor e wat er ent ered i nt o sp e ci mens,but her e t he h ̄dr opho— bi c f t mct i on f o ebacat s e i s mor e r emarka bl e.Compari ng S2 ・-
-—
—
260 ・ - - — —
do ne) i S de ns e.I t s us t ai ne d t he who l e s t r uc t ur e o f ne t — wor ks.Al hou t gh he t wei ht g l os es s f o S1 n d a S 2 at 42 d al e mor e t ha n F,t he r el at ive pr opor t i on o f r i gi d pyr rol e cycl es
如
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Z H A NG Na e t 0 f : S y n t  ̄/ s,C h a r a a z/ z a a ' o n a n d/ n v / t r o
o fP o l y(P , o  ̄
Fu ma r a t ec o - Pr 0 p y / e n e
f r act ure i ncr ease d duri ng t he pr oces s of degr ad at i on.For of P(PF- c o. - PS) / N. VP ne t wor ks i UC l  ̄a ¥ e d hi ghe r t ha n PPF/ at N. VP net works and when t he compressi ve st ress i s gr eat er. S3.much i nor e N— VP decr ease d t he f ract ure st r engt h a n d hi nk t hat he n t as0n i s t he 8ai ne s compr a ess i ve s t r engt h he t P(PF_ c o. PS) , N 、 1 P net wo ks r wi 1 1 hav e pe r ma nent de we t f ormat i on.Becaus e t her e was a part off umar at e r esi due st i l l
at y i e l d.
i n t he mat eri als aft er degr adat ion a n d t hese r esi dues i 1 ' 1 . cr eased t he pl ast ici t y of PPF/N VP net w or k s. sp e ci mens wi 1 1 have p e rmanent def or mat i on w h en t he compr essi ve
s t r es s i s s ma l l,i us t l i ke he t phe no men a o f P( PF’ c 0 PS) / N VP net w or ks bef or e degr adat i on.
Degr adat i on t i me/d
ri g. 1 0 Co mpr e s s i v e s t r e n gt h t a f r a c t ur e舔 a f l m ̄  ̄ol l o fde g - rl l d ̄ Ol l ime t 日dJ ,【 目 皇∞自
∞
箦
∞ ∞ ∞ ∞ 加 m O
Fi g.1l s hows t hat t he i ni t i l compr a essi ve modu lus of
net w orks w it h s of t s ebacat e s eg m ent s i s a l i t t l e l ower t han ri g. 9 Compr es s i ve s t re ngt h at yi 枷
舔 a f l mcl i Ol l ofde gr ada-
ion t f i m e
net w orks w it hout sebacat e s eg m ent s. But t he compr essi ve modul us of al l t he f our f or mu lat i on s i ncr ease d duri ng t he
pr oce s s of deg r ada io t n bec a us e h en w d egr a dat i o n,t he pr o p- Wi h t t he i ncr ea si ng of he t amount of N 、, P.t he i ni t i l o a r t i on o f P(N. VP)j r l ne wo t r k s j nc r e a se d nd a he t d di y t o f
wo t r ks i nc r e a s ed. compr es si ve s t r engt h at yi el d decr eased when compar i ng S3 ne wi h S2. t
n c o mpr es se d by s t r es s.net wo ks r
fi cul t t o def or m a n d t he compr essi ve modu lus i n en t he degr adat ion b e gi ns. t he compr essi ve ale di
eased.For f or m ul at ion S3.t her e ar e much mor e N vP i 1 , 1 st r engt h at yi el d of S3 i s st il l l ower t ha n t hat of S2.Mavbe cr w or ks.t he i ncr ease d val ue of compr essi ve modu lus i s not ncr i easi ng t he amou nt of N. VP n d i a nt r oduci ng sof t seh a cat e net egment s s i n pol ymer mai n chai n at t he sanl e t i me,t he mesh
v e r y h i h .Ma g y e b he t r e a s o n i s he t s a n l e s a y i e l d s t r e n g t h
a d f r ct a ur e s t r engt h t hat mor e N.VP makes t he st r uct ur e of si z e of net w or k i s t oo l arge a n d t he st r uct ure of net w or k i s n w orks t o spars e a n d t he r i gi di t y of S3 i s l ower t han t he t oo spar se.Duri ng t he process of degr adat i on, t he l oss of net her t hr ee f or mu l at i ons.T h us t he compr essi ve modu lus of sebacat e segment s of S3 i s much mor e t ha n al l t he ot her ot
3 d u in r g d e g r a d a i t o n i s l o we r t h a n o he t r s.Al ho t u h g he t t hr e e f or mu l at i o ns(Fi g. 6,wei g ht l OS S o f net wo r ks)a nd he t S ompr e s s i v e mo du lus f o P(PF- c o- PS) / N 、 , P ne t wo r ks i s a whol e net st r uct ure may b e des t r oye d a n d t he compr essi ve c l i t t l e l o we r h t n a P P F / N VP n e w t o k r s .t h e y c n a a l s o s a i t s f y s t r engt h at yi el d i s ver y l ow.
Fr o m hes t e es r lt u s of iel y d s t r engt h,t he met ho d o f i n creasi ng he amou t nt of N vP i n order t o i ncr ease t he cor n
he t r equi eme r nt s o f r e pl ac i ng t r a be cu la bo ne (5 一l 00 MPl a).
pr es s i v e s t r engt h at y ie l d i s l i mi t d .I e n cr ea si ng he t amo nt u of N. VP l l make t he mesh si ze of net w or ks t oo l rge a a n d he st t r uct ure of net w or ks t oo sparse
en t he compr ess i ve
s t r e s s i s s ma l l,net wor ks w i I h a ve p er ma ne nt de f or mat io n
nd a he t ie y l d s t r e ngt h i1 w 1 e b de cr ea s ed. Fi g.10 shows t hat t he cha n gi ng t rends of compr essi ve
s t r eng t h a t f r ac t ur e of P( PF- co - PS) , N— VP i s ve r y s i mi l r a t o
he t cha nge o f yi e l d s re t ngt h.I nt r o duc i ng s of t eba s cat e eg— s ment s decrease d t he i ni t i l f a ract ure st rengt h. Dur i ng t he Degradat ion ti me/d
deg r ada t i o n,l o s s of mo r e s of t eg s me nt s i ncr e as d e he t ng id  ̄ 一 t v of net w or ks a n d t he abi l i t y of w it hst andi ng compressi ve st r ess i ncreased.The r esu lt i s t hat t he compr essi ve st rengt h
ri g.11 Compres s i ve mot hl hl s 躯 a f umc don o f de gr a _ _ ̄" dt l on t i m e ・--—
—
261 ・ - - — —
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Tr an s a c t i on s o f T i an j i n Uni v e r s i t y
V o1.1 3 No. 4 2007 Acknowl edgement s h e T aut hor s ha t nk Dr.J oh n Rei ne r f or ss a i s t a nc e i n pr e —
I n or der t o i mpr ove t he model l i ng and bi odegr adabl e pari ng h e manus t cr ipt and Dr.W ang Zheng f or h e hel t p wi h t he di s cus si ons. pr ope r t i es of PPF,P(PF- c c ’ _ PS)was s y nt hes i z e d by s t e p t
pol ymeri z at i on.Duri ng t h e process of pr epar at i on,t h e i n—
t e r medi a s of bi s(2一 hydr o x ypmpy 1)f t ma ar a t e a nd bi s(2一 i nn l erM D,Yaz ems l 6M J eta1.Sy nt hes i s ofbi o— He S,Ti hydr o x ypmpy 1)s eb ac at e wer e us e d.Co ol p y mer s pr epar e d [1] by hi t s met ho d have r egul ar s t ruct ure a n d t he end groups of
d e g r a da b l e po l y(pr o p y l e ne f uma r a t e)ne t wor ks wi h p t o l y
cop ol ymers ar e a ll hydroxyl groups.1hi s met ho d al s o avoi ds
( pr o p y l e n e f uma r a t e) 一 di ac r yl me n l a c r o nl  ̄r s a s c os r s l i n ki ng
h e ser t f-pol ymer i zat i on of f l uI  ̄ c aci d,sebaci c aci d or 1,
agent s a nd char act er i z at ion of t hei r degr adat ion pr oduct s
2一pmpyl ene gl ycol n d t a he PI i s l ower.The chai n st ruct ures
o f P(PF— c o— PS)8020 a nd P(PF— co — PS)9o1 O wer e cha r a c— t eri zed by H—NMR a n d FIⅢ
spect ra a n d t h e mol ecul r a
wei ght n d a P1 wer e det ermi ned by GPC.r I 1 1 e r at i o of f umar— at e s egment s t o sebacat e seg m ent s i n t he mai n chai n of co—
ol p m er y ca n be mo du lat ed by t he rat i o of i nt er medi a b ef or e ol p m er y izat i on.
l J ].Po l yme r,2 001,42( 3):1 251 —1 26 0.
[ 2] L e wa n dr owski K U, Gr es ser J D, Wi se D L
.
Bi or esor babl e bone gr af t subs t i t udes of di fer ent o st eocon— duct i vi ies: A hi t s t ol ogi c eva lul at i 0n of o st eoi nt egr at i on of
po l y( p r o py l e n e g l y c o l - f umar i c ac i d) 一 b a s e d c e me n t i mp l nt a s
i n r a sE t J ].Bi omo  ̄r / a/ s,20 00,21( 8):75 7—7 64. [ 3] Lee K Y,Mooney D J.Hydr ogel s f or t is s ue engi neer i ng l JJ.Ch e mi c al Re v i e ws,2 001,1 01( 7):1 8 6 ~1 8 79.
PPF-a nd Pf PF- c o- PS)一 ba se d p ol m er y ne t wo r ks wer e [ 4] Ho fma n A S.Hyd r o g e l s f o r b i o me di c a l a p pl i c a io t n s[ J]. s nt y hesi z ed by radi ca l p ol m er y iz at i on.Dur ing he cmssl t i nk—
Ad v an c e d D De l i er v y Re y i e w¥,2 O0 2,43(1):3 —1 2.
la n dr el l i L, I mnf i 5] Ca i ng pr o ce s s,廿 1 e max i l nun l t emper at ur e of P(PF. c0 一 PS) 一 [
B,Mahncor ico M et f a1.Pr epara—
based net w or ks i s l ower t han t h at of PPF-based net w or ks.
t i on a n d c har act er iz at ion of composi t es base d on bi odegr ad—
he T P(PF— co - PS) /N一 、 1 P net wo r ks e xhi bi t ed wel 1. mat c he d
bl a e ol p y me r s or f i n v i v o a p pl i c a t i o n[ J].Po l y me r,20 00,
e cha m nica l a n d gravi met ry pr opert i es wi h PPF/N.VP net t —
41(22):8027— 8o33.
er S J,I Gm P,Yas ko A W et a1.Cms s hnki ng char ac— [ 6] Pet wor ks duri ng t he pr ocess of i n vi t ro degr adat ion i n phos— t e is f ic t s f o n a i n j e c t a bl e p o l y( pr o p y l e ne f u ma r a t e) / l・ f - t r i c l・ a -
phat e bu fer e d s li a ne(pH 7. 4)when he t co ndi t i ons o f o— p l ymeri zat i on a n d t he amount of cmss li nki ng agent ar e t he
s a l T l e ea ch o he t r.Se bac at e s eg ment s i n P(PF- co — l o S)mai n
c h a i ns i n c ea r s e d he t h y d r o p h o b i c p mp or t i e s nd a he t we i ht g
ci um phosphat e pas t e a n d mecha ni ca l pr oper t i es o f t he cr ss o l i nke d c ompos i t e f or us e as a bi ode gr adabl e b o ne ce—
me n t [ J].J ou ma/o fBi o me di c al Ma t e r i a l s Re s e ar c h,1 9 99, 4 4( 3):31 4—321.
l oss of net wor ks.But t he mechani ca l pmp or t i es can b e ma—
K, Mi kos A G . Pr ot ei n adsor pt i on a n d s mo ot h [ 7] Tanahashi
i nt ai ned f or a very l ong t i me. Incr easi ng t he a m ou nt of
mus cl e cel l adhes i on on bi odegr ada bl e a gmat ine modi ie f d
c r o s s l i nki ng ag ent(N一 、1 P),t he hydmphi l i c pr ope r t i e s o f
p o l y( pr opy l e n e f u ma r a t e  ̄ c o- e hy t l e n e g l y )hy d r o ge l s [ J].
net w orks i ncr ea s ed.T h er ef or e , mo du lat ing t he amount s of
Jo u r n a l o fBi o me di c a l Ma t e r i al s es R ear ch,2 003,67A( 2):
N一 、1P a n d s eh a cat e s eg m ent s i n a cer t ai n s cope can obt ai n
448— 457.
8] Za d a A,Av 1 1 y Y,Zi k ha A.Mo n ome r f or n o n— on b d mat r i x ofbone cement wi h t appr opr iat e degr adat ion t i me a n d [
_
et b t er compr essi ve s t rengt h at yi el d,compr essi ve st r engt h at
c r ss o l i n ki ng o f v i n y l p o l y mer s[ J].Eu r o pe an ol P yme r J ou r.
f ract ure a n d compr es si ve mo du lus.
n a /,1 99 9,3 5( 6):11 59 - - - -11 64.
-。—
—
262 - - - — —
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