Recent Developments of Self2Propagating Frontal Polymerization

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1 PROGRESS IN CHEMISTRY Vol. 17 No. 6 Nov ( ) : O ; TQ : A : X(2005) Recent Developments of Self2Propagating Frontal Polymerization Yan Qingzhi Su Xintai Ge Changchun 3 3 (Laboratory of Special Ceramics and Powder Metallurgy University of Science and Technology Beijing Beijing China) Abstract Frontal polymerization (FP) is a polymer synthesis technique that uses the exothermic reactions to form a self2sustaining wave. Because no additional heat is needed after the initial polymerization the process has potential advantages over traditional polymerization methods : lower processing costs less energy input and absence of solvent. These advantages make FP a potential viable option in polymer synthesis. The mechanism of FP frontal structure velocity front mode and properties of polymer produced via FP are reviewed. The future directions of FP research are prospected. Key words frontal polymerization( FP) ; self-propagating FP ; materials synthesis ; ; Fig. 1 Schematic representation of a frontal polymerization : : (No ) 3 3 e2mail : ustb. edu. cn

2 Chechilo [1 ] 300MPa P g g n + M P n+1 (3) [2 12 ] P g n+1 + P g n P n + P m ( P m+ n ) (4) Combust. Explos. Shock Waves Dokl. Phys. Chem. Pojman [13 ] 1990 E eff Pojman [43 ] : E eff = E P + E i Π2 - E t Π2 (5) i p t 300MPa [14 34 ] E i 125kJΠmol E p 29kJΠmol E t 17kJΠmol 1990 ;1990 [29 30 ] [47 ] [31 33 ] ;2001 [35 ] [36 ] [37 ] : (1) ; 1999 (2) ; (3) [38 ] ;2003 [39 41 ] 2003 ( ) ( ) Pojman [34 ] [42 ] : I f2 R g (1) f R g + M P 1 g : (2)

3 ; 15mm 20mm Π ( ) ( ) [19 ] ( ) (AETMA) [44 ] [45 ] [46 ] Chechilo Pojman Π 16 ] [ ( molΠL ; molΠL) [34 ( ) ] Fig. 2 Temperature profiles for polymerization front at different initiator concentrations( molΠL ; molΠL) 2 [48 ] [16 25 ] 015cm 100 [47 48 ] 120 [42 ] :

4 [42 ] [19 ] [43 ] : R P = k p f k i k t 1Π2 [ I] 1Π2 [M] (6) 4 I M k [ ] i p t Goldgeder [49 ] 20s u : [49 ] Spade [50 ] u 2 kj 0 R g T b = E d ( T b - T 0 ) k0 eff e - E eff ΠR T g b (8) 4 k ; J 0 ; R g ; T b ; E d ; T 0 ; k 0 eff E eff k 0 eff = k p [2f k 0 0 d Πk t ] 1Π2 (9) E eff = E p + ( E d - E t )Π2 (10) k d k p k T E d E p E t 50 Chechilio [5 ] 300MPa Apostole [30 ] Tredici [29 ] Perry [44 ] ;Pojman [17 ] ( ) 0131 : (1) 3 ; (2) : CO 2 CH 4 ; ; (3) 1mg 200 2cm 3 ; (4) ; (5) ; (6) [14 ] : v ( p) = v 0 + constπp (7) [33 ] ; (7) ;

5 ; [50 ] [ ] Pojman [22 ] 1 62 [ ] ( HDDA) 2 [38 ] : (TMPTA) HDDA ; HDDA (BzAc) TMPTA [19 ] ; : TMPTA [22 ] ; [24 ] : ( 3) 3 :a b c 1 62 Fig. 3 Modes of frontal propagation :a oscillating mode b spin mode c chaos mode Pojman [52 ] ; (2 wt % BPO ) [21 ] cmΠmin 50s 100 Fortenberry [25 ]

6 % 76 % [29 ] ( ) 120 Washington [53 ] 80 % Pojman [17 ] 32 Pojman [20 ] A 32 [46 ] : H 0 S 0 + Rln ([M] eq Π[M] 0 ) T = (11) [M] 0 S 0 H 0 : : 1 = 1 - exp H0 - T S 0 (12) (1) [M] initial RT : T = T i + H 0 ΠC p (13) [18 ] (2) Enikolopyan [2 ] 150 Pojman [17 ] 10 5 ( M W ΠM N = ) Pojman [20 ] Fortenberry [25 ] (3) Chekanov [26 ] Pujari [37 ] 22 5 Tredici

7 Masere [28 ] Schult [54 ] (4) 214 : [48 ] ; 80 % (5) 31 Pojman [55 ] : : T g ; 30 % Mariani [36 ] ( ) ; ; : : ; [ 1 ] Chechilo N M Khvikivitskii R J Enikolopyan N S. Dokl. Akad. Nauk USSR : [ 2 ] Enilolopyan N S Kozhushner M A Khanukave B B. Dokl. Phys. Chem : [ 3 ] Khanukave B B Kozhushner M A Enikolopyan N S. Dokl. Phys. Chem : [ 4 ] Chechilo N M Enilolopyan N S. Dokl. Phys. Chem [ 5 ] Chechilo N M Enilolopyan N S. Dokl. Phys. Chem : [ 6 ] Chechilo N M Enilolopyan N S. Dokl. Phys. Chem : [ 7 ] Surkov N K Davtyan S P Rozenberg B A Enikolopyan N S. Dokl. Phys. Chem : [ 8 ] Davtyan S P Surkov N K Rozenberg B A Enikolopyan N S. Dokl. Phys. Chem : [ 9 ] Begishev V P Volpert V A Davtyan S P Malkin A Y. Dokl. Acad. Nauk USSR : [10] Volpert V A Megrabova I N Davtyan S P Begishev V P. Comb. Explosion Shock Waves : [11] Babadzhanyan A S Volpert V A Davtyan S P Megrbova I N. Comb. Explos. Shock Waves : 23 [12] Davtyan S P Zhirkov P V Vol fson S A. Russ. Chem. Rev : [13] Pojman J A. J. Am. Chem. Soc : [14] Pojman J A Craven R Khan A West W. J. Phys. Chem. [15] Pojman J A Willis J R Khan A M West W. Polym. Prepr. (Am. Chem. Soc. Div. Polym. Chem. ) : [16] Pojman J A Nagy I P Salter C. J. Am. Chem. Soc : [17] Pojman J A Willis J Fortenberry D Ilyashenko V Khan A M. J. Poly. Sci. A : [18] Nagy I P Sike L Pojman J A. J. Am. Chem. Soc : [19] Pojman J A Khan A M Mathias L. Microgravity Sci. Technol (1) : [20] Pojman J A Elcan W Khan A M Mathias L. Poly. Sci. A [21] Ilyashenko V M Pojman J A. Chaos (1) : [22] Masere J Stewart F Meehan T Pojman J A. Abstracts of Papers of the Amer. Chem. Soc U294 U294 [23] Masere J Chekanov Y Warren J R Stewart F D Al2Kaysi R Rasmussen J K Pojman J A. J. Polym. Sci. Part A : Polym. Chem : [24] Texier2Picard R Pojman J A Volpert V A. Chaos : [25] Fortenberry D I Pojman J A. J. Poly. Sci. A : [26] Chekanov Y A Pojman J A. J. Appl. Poly. Sci : [27] Manz B Masere J Pojman J A Volke F. J. Polym. Sci. Part A : Polym. Chem :

8 [28] Masere J Lewis L L Pojman J A. J. Appl. Poly. Sci : [29] Tredici A Pecchini R Morbidelli M. J. Polym. Sci. Part A : Polym. Chem : [30] Apostolo M Tredici A Morbidelli M Varma A. J. Polym. Sci. Part A : Polym. Chem : [31] Garbey M Tromeur2Dervout D. J. Comput. Phys : [32] Vladimir V I Christian D. Polym. Int : [33] Bazile J R M Nichols H A Pojman J A Volpert V. J. Polym. Sci. Part A : Polym. Chem : [34] Pojman J A Ilyashenko V M Khan A M. J. Chem. Soc. Faraday Trans (16) : [35] Huh D S Kim H S. Polym. Int : [36] Mariani A Bidali S Fiori S Sangermano M Malucelli G Bongiovanni R Priola A. J. Polym. Sci. Part A : Polym. Chem : [37] Pujari N S Vishwakarma A R Pathak T S Mule S A Ponrathnam S. Polym. Int : [38] ( Yin S). ( Combustion Synthesis ). (Beijing) : (Metallurgy Industry Press) [39] Ge C C Li J T. Int. J. Self2Propagating High2Temperature Synthesis : [40] Ge C C Li J T Cao Y G. Z. fur Metallkunde (2) : [41] Ge C C Chen K X Li J T Cao W B. Z. fur Metallkunde (2) : [42] Pojman J A West W W Simmons J. J. Chem. Edu : [43] (Pan Z R). (Macromolecule Chemistry). (Beijing) : ( Chemical Industry Press) [44] Perry M F Volpert V A Lewis L L Nichols H A Pojman J A. Macromol. Theory Simul (4) : [45] Chekanov Y Arrington D Brust G Pojman J A. J. Appl. Poly. Sci : [46] Mariani A Fiori S Chekanov Y Pojman J A. Macromolecules : [47] Davtyan S P Hambartsumyan A F Davtyan D S Tonoyan A O Hayrapetyan S Bagyan S H Manukyan L S. Eur. Polym. J : [48] Yan Q Z Zhang W F Lu G D Su X T Ge C C. Chem. Eur. J : 1 8 [49] Goldfeder P M Vopert V A Ilyashenko V M Khan A M Pojman J A Solovyov S E. J. Phy. Chem. B : [50] Spade C A Volpert V A. Chem. Eng. Sci : [51] Briskman V A Yudina T M Kostarev K G Kondyurin A V Leontyev V B Levkovich M G Mashinsky A L Nechitailo G S. Acta Astronautica : [52] Macfarland B Popwell S Pojman J A. Macromolecules : [53] Washington R P Steinbock O. J. Am. Chem. Soc : [54] Schult D A Spade C A Volpert V A. Appl. Math. Lett : [55] Chekanov Y A Arrington D Brust G Pojman J A. J. Appl. Poly. Sci :

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