Synthesis, Characterization and in vitro Degradation ...

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lor. ide while t. he molarr. at. io of se. bacic acid to thionyl ch. lor. ide wa. s 1:3.T. h e mixture ref. luxe ..... of sebacate did not link with N.、1P by carbon.
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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 ・  





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



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  



. 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 ℃  ‘_。—



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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  -

-—



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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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I l , q 目 皇∞pl ∞一  

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.  

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