ACTA POL YMERICA SINICA

Transcript

1 ACTA POL YMERICA SINICA No 10 Oct, ( ) 3 ( + )24,4 2 [ ( S)222 ]22 2 ( p2 BMVT) ( + )23,3 2 [ (S)222 ]22 2 ( m2bmvt) ( + )22,2 2 [ (S)222 ]2 2 ( o2bmvt) p2 m2bmvt ; o2bmvt,,,,,, [19 21 ], [1 4 ] ( + )24, 4 2 [ ( S)222 ]22 2 ( p2bmvt) [22 ], ( ) { ( + )24,4 2 [ ( S)222 ]22 2 } (P( p2bmvt) ) p2bmvt ( + )23,3 2 [ (S)222 [5 18 ] ( m2bmvt) ( + )22,2 2 [ ( S)222 ]22 2 ( o2bmvt),,, 1 ( ) ( ) 111 [18 ], (S)2(2)222 (99 %, TCI),2,52 (97 %,Acros) (99 %,Acros), N2 (NBS,99 %,Acros),22 (,Acros),32 (,Acros) (,Acros) (40 % ) PdCl 2 ( ) (BPO) , ; ( , , ) ( ) ;33,E2mil edu cn 999

2 (m, 2H ; Ar) ; ( C 29 H 36 O 2 ) : C (AIBN) %,H 8165 % ; : C %,H 8186 % ; ( ) CH 2 ( EI, mπe, % reltive intensity) : 416 (M + ),, ( ) 346,276 (100),247,43 ; [ ] = (THF ) ( c = 012 gπdl,thf) ( + )232( (S) ( + )22,2 2 [ (S)222 ) ( + )222( (S)222 ) ( o2bmmt) o2bmmt [22 p2bmvt ] 1 H2NMR Bruker ARX400 (400 MHz),CDCl 3, TMS (t,3h ;CH 3 ), (d,3h ;CH 3 ), Finnign2MAT ZAB2HS (m, 1H ; CH 2 ), (m, 2H ; CH 2 ), 1148 Elementl Vrio EL 1152 (m,1h ;CH 2 ), (m,1h ;CH),1180 GPC 1183 (m,1h ;CH),2117 (s,3h ;Ar2CH 3 ), Wters 515 Wters Styrgel HT2 + (m, 4H ; OCH 2 ), ( m, 4H ; Ar), 7118 HT3 + TH4 Wters (m,2h ;Ar), (m,2h ;Ar), , 7141 (m,2h ;Ar),7146 (s,1h ;Ar) ; 110 mlπmin ( C 29 H 36 O 2 ) : C %, H 8165 % ; : C ( [ ] ) JASCO Model P %, H 8181 % ; ( EI, mπe, % reltive nm 10 cm intensity) : 416 (M + ),326,276,186,43 (100) ; THF ( c) 012 gπdl 2 [ ] = ( c = 012 gπdl,thf) Vrin Cry ( + )23,3 2 [ (S)222 JASCO J2810 ( m2bmvt) m2bmmt 011 mm (2108 g,5 mmol),nbs (0191 g,511 mmol) BPO 112 (24 mg,011 mmol) 25 ml ( + )23,3 2 [ (S)222 3 h, ( m2bmmt) ( + )232( (S)222 ) (912 g,44 mmol) 25 ml, ( 1131 g, 5 (01924 g,016 mmol) 250 ml mmol) 2 h 3 2,52 (510 g,20 mmol) (40 ml) 50 ml (20 ml) 70 ml 40 %, (119 molπl) (9 ml,10 wt %) 49 h 48 h 3,, 3Π1 Π 6Π1 Π m2bmvt 112 g 810 g, 56 % 1 H2NMR (CDCl 3 ) : % 1 H2NMR(CDCl 3 ) : (t,6h ; 0199 (d,6h ;CH 3 ), (d,6h ;CH 3 ),1125 CH 3 ), ( d, 6H ; CH 3 ), ( m, 1131 (m, 2H ; CH 2 ), (m, 2H ; CH 2 ), 2H ;CH 2 ), (m,2h ; CH 2 ), ( m, 2H ; CH), ( m, 4H ; (m,2h ;CH),2135 (s,3h ;Ar2CH 3 ), (m, OCH 2 ), (d,1h ; vinyl), ( d, 4H ;OCH 2 ), (m, 4H ; Ar), (m,2h ;Ar), (m,3h ;Ar), m2bmmt, 93 % 1 H2NMR (CDCl 3 ) : (d,6h ;CH 3 ), H ;vinyl), ( q,1h ; vinyl), (m,4h ;Ar), (m,2h ;Ar),

3 10 : 1001 (d,1h ; Ar), (m,2h ; Ar), (q,1h ;Ar), (d,1h ;Ar) ; 0116 g 76 % (C 30 H 36 O 2 ) : C %, H 8141 % ; : C %, H 8140 % ; ( EI, mπe, % reltive intensity) : 428 (M + ),358,288,71,43 (100),29 ; [ ] = ( c = 012 gπdl,thf) ( + )22,2 2 [ (S)222 ( + )2(S)222 2,52 ( o2bmvt) o2bmvt Suzuki p2bmmt m2 m2bmvt BMMT o2bmmt NBS 16 % 1 H2NMR (CDCl 3 ) : (d,6h ; Wittig p2bmvt m2bmvt o2bmvt p2 CH 3 ), (t,3h ;CH 3 ), (d,3h ; CH 3 ), (m,1h ; CH 2 ), (m, 2H ;CH 2 ), ( m, 1H ; CH 2 ), (m,1h ;CH), (m,1h ;CH), (m,4h ;OCH 2 ), (d,1h ; vinyl), (d,1H ;vinyl), (q,1h ;vinyl), (m,4h ;Ar), (q,1h ;Ar), (d,1H ; Ar), (m,2h ; Ar), (q,1h ;Ar), (q,1h ;Ar),7187 ( d, 1H ;Ar) ; (C 30 H 36 O 2 ) : C %, H 8141 % ; : C %,H 8121 % ; ( EI, mπe, % reltive intensity) : 428 (M + ),358,287,71, 43(100),29 ; [ ] = ( c = 012 gπdl,thf) m2bmvt { ( + )23,3 2 [ (S)222 } (P( m2bmvt) ) 1 H2NMR p2bmvt 1 H2NMR 60 = g (015 mmol), CH 2 CH 41 L AIBN 10 mgπml, 1 ml 3, o2bmvt h 20 ml THF 200 ml, BMVT m2bmvt 4, % o2bmvt 16 % m2bmmt m2bmvt P ( m2bmvt) p2 m2bmvt, h 50 %, Scheme 1 Synthetic route of p2bmvt, m2bmvt nd o2bmvt

4 Fig 1 1 H2NMR spectr of m2bmvt () nd its polymer (b) using CDCl 3 s solvent nd TMS s reference P( m2bmvt) p2bmvt P( p2bmvt) [22 ] 1 m2bmvt m2 BMVT [ ] , m2bmmt [ ] [ ] P ( m2bmvt), [22 P( p2bmvt) ] Tble 1 Free rdicl polymeriztion results of m2bmvt Smple T( ) Solvent M n 10-4 PDI Yield( %) [ ] Anisole Benzene Anisole ,4 2 3, 2 () m2bmmt, m2bmvt P( m2bmvt) 3 2 2,2 2, nm o2bmvt m2bmvt 2 3 m2bmvt o2bmvt 245 nm 22 CD 2 (b) [23 ] 9, nm 22 8,92 Cotton 188 nm [1, n ] 2 9,102 Cotton nm [23 ] Lewis 32, CD CD 32 Cotton 77 K,2,62 Polymeriztion condition : concentrtion, 015 mol L - 1 ; inititor, zobisisobutyronitrile (AIBN) for 60 nd benzoyl peroxide for 90 (015 %,bsed on totl molr numbers of monomers) ; time,24 h m2bmvt p2bmvt 2 [ ] P( p2bmvt) [ ] ;P( m2bmvt) [ ] o2bmvt Lewis, Cotton 2 4,4 3,3 2 [21 ] ; 2,2 2,

5 10 : 1003 [ ] 25 CD Cotton P ( p2bmvt) P ( m2 BMVT) Tble 2 Free rdicl polymeriztion results of solvents t 60 Solvent 365 p2bmvt in different M n 10-4 PDI Yield( %) [ ] (cm) THF CHCl Heptne Anisole Toluene Benzene Polymeriztion condition : concentrtion, 015 mol L - 1 ; inititor, zobisisobutyronitrile (AIBN) (015 %, bsed on totl molr numbers of monomers) ; time,24 h Tble 3 Free rdicl polymeriztion results of tempertures p2bmvt t different Solvent Heptne Anisole T( ) M n 10-4 PDI Yield( %) [ ] Fig 2 UV2visible bsorption () nd CD (b) spectr of m2bmmt (2), m2bmvt ( ), P ( m2bmvt) ( ), nd P ( p2bmvt) ( ) Mesured in n2hexne t 25, c = 112 gπl Polymeriztion condition : concentrtion, 015 mol L - 1 ; inititor, zobisisobutyronitrile (AIBN) for 60 nd 70,nd benzoyl peroxide for 80 nd 90 (015 %, bsed on totl molr numbers of monomers) ; time, 24 h P ( p2bmvt) [ ] P( m2bmvt) [ ] Okmoto [ ] 25 ( PTrMA) 365 P ( m2 BMVT) PTrMA P( p2bmvt) [ ] [24 ], 2 [ ] ; [ ] [24 ], P ( p2 BMVT), 3, P ( p2bmvt)

6 Tble 4 Free rdicl polymeriztion results of p2bmvt with different concentrtions Solvent c(molπl) M n 10-4 PDI Yield( %) [ ] Heptne Anisole Polymeriztion condition : concentrtion, 015 mol L - 1 ; temperture, (80 015) ; inititor, benzoyl peroxide (015 %, bsed on totl molr numbers of monomers) ; time,24 h, p2 m2bmvt P ( p2bmvt) o2bmvt, REFERENCES 1 Okmoto Y,Hond S,Okmoto I,Yuki H,Murt S,Noyori R,Tky HJ Am Chem Soc,1981,103 : Yuki H,Okmoto Y,Okmoto IJ Am Chem Soc,1980,102 : Reggelin M,Schultz M,Holbch M Angew Chem Int Ed,2002,41 : Pu L Tetrhedron :Asymmetry,1998,9 : Li B S,Cheuk K KL,Ling L,Chen J,Xio X,Bi C,Tng B Z Mcromolecules,2003,36 : Cheuk K KL,Lm J W Y,Chen J,Li L M,Tng B Z Mcromolecules,2003,36 : Lm J W Y,Dong Y,Cheuk K KL,Tng B Z Mcromolecules,2003,36 : Cheuk K KL,Lm J W Y,Li L M,Dong Y,Tng B Z Mcromolecules,2003,36 : Lm J W Y,Dong Y,Cheuk K KL,Lw C C W,Li L M,Tng B Z Mcromolecules,2004,37 : Ren C,Chen C,Xi FJ Polym Sci Prt A :Polym Chem,1998,36 : Vogl O,Xi F,Vss F,Ute K,Nishimur T,Htd K Mcromolecules,1989,22 : Ren C Y,Chen C F,Xi FJ Polym Sci Prt A :Polym Chem,1998,12 : Chen Chunfu( ),Liu Weihong( ),Chen Yongming( ),Ren Chngyu( ),Xi Fu( ) Act Polymeric Sinic( ),1996, (1) : Ren C Y,Chen C F,Xi F Chinese J Polym Sci,1994,12 : Wng Yuechun( ),Ding Mengxin( ),Hu Huizhen( ),Wng Fosong( ) Science in Chin,Ser B( B ), 1992,10 : Wng Yuechun( ),Ding Mengxin( ),Xu Jingzhe( ),Wng Fosong( ) Act Polymeric Sinic ( ),1988, (4) : Fujiki MJ Am Chem Soc,1994,116 : Nkno T,Okmoto Y Chem Rev,2001,101 : Green M M,Peterson N C,Sto T,Termoto A,Cook R,Lifson S Science,1995,268 : Rmos E,Bosch J,Serrno J L,Sierr T,Vecin J J Am Chem Soc,1996,118 : Med K,Okmoto Y Mcromolecules,1998,31 : Yu Z N,Wn X H,Zhng H L,Chen X F,Zhou Q F Chem Commun,2003,(8) : Lewis F D,Zuo X,Gevorgyn V,Rubin MJ Am Chem Soc,2002,124 : Nkno T,Mtsud A,Okmoto Y Polym J,1996,28(6) :

7 10 : 1005 INFL UENCE OF CHEMICAL STRUCTURE AND POLYMERIZAION CONDITIONS ON CHIROPTICAL PROPERTIES OF BUL KY VINYL POLYMERS CAO Hongqing, LIU Anhu, YU Zhenning, ZHANGJie, WAN Xinhu, CHEN Xiofng, ZHOU Qifeng ( Beijing Ntionl Lbortory for Moleculr Sciences, Key Lbortory of Polymer Chemistry nd Physics of Ministry of Eduction, College of Chemistry nd Moleculr Engineering, Peking University, Beijing ) Abstrct Three chirl bulky vinyl monomers, ( + )24,4 2bis [ ( S)222methylbutoxy ]22 2vinyl2pr2terphenyl ( p2 BMVT), ( + )23, 3 2bis [ ( S)222methylbutoxy ]22 2vinyl2pr2terphenyl ( m2bmvt) nd ( + )22, 2 2bis [ ( S)222 methylbutoxy ]22 2vinyl2pr2terphenyl ( o2bmvt) were synthesized The lter two were new molecules The dependence of polymerizbilities of monomers on the chemicl structures nd the dependence of chiropticl properties of polymers on the chemicl structures nd rection conditions were systemticlly studied p2bmvt nd m2bmvt were redily polymerized by rdicl mechnism to produce opticlly ctive helicl polymers Moving the chirl lkoxy groups on terphenyl by just distnce of one bond length inversed the direction of opticl rottion o2bmvt ws obtined with quite low yield nd couldn t undergo rdicl polymeriztion Using polr romtic solvent nd polr liphtic solvent, incresing rection temperture, nd reducing monomer concentrtion fvored the formtion of polymers with higher specific opticl rottion Key words pr2terphenyl, Helicl structure, Chirlity, Chiropticl property, Free rdicl polymeriztion, Rectivity, Vinyl polymer