Analysis of a styrene-divinylester copolymerization: reaction heats, double bond conversions and average sequence lengths

被引:4
作者
Auad, ML [1 ]
Aranguren, MI [1 ]
Borrajo, J [1 ]
机构
[1] Univ Mar del Plata, Inst Mat Sci & Technol, Nat Res Council CONICET, RA-7600 Mar Del Plata, Argentina
关键词
crosslinking copolymerization; reactivity ratios; divinylester resins;
D O I
10.1016/S0032-3861(99)00517-0
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
A simple model, based on the free radical copolymerization theory of Mayo and Lewis, is developed to predict reaction heats, calorimetric and molar conversions and average sequence lengths, during the crosslinking reaction between a monounsaturated monomer (M-1) and a multiunsaturated comonomer (M-2) The M-2-double bonds are assumed to react independently with equal initial reactivities. The input variables of the model are the initial reactivity ratios (r(10), r(20)) and their variation with the global molar conversion, the initial composition of the reactive mixture (f(10)) and the molar heat of formation of the different bonds formed during the copolymerization (Delta H-11, Delta H-22, Delta H-12) The application of this model allows to calculate the overall molar and calorimetric double bond conversions (P-m and P-c), the heat developed during the reaction (Delta H-T), the conversions corresponding to each type of unsaturations (P-c1, P-c2, P-m1, P-m2), and the average sequence lengths of the reacted bonds ([N-11] and [N-22]) Published data of experimental comonomers conversions in the system styrene-divinylester (S-DVER) were satisfactorily reproduced by including a functionality of both reactivity ratios with the overall conversion. Finally, it was shown that the assumption implicitly made in most published kinetic studies from the differential scanning calorimetric (DSC) data, that P-c and P-m are equivalent, is not general and this feature must be investigated in order to perform correct kinetic calculations. (C) 2000 Elsevier Science Ltd. All rights reserved.
引用
收藏
页码:3317 / 3329
页数:13
相关论文
共 33 条
[1]  
AUAD ML, 1997, J APPL POLYM SCI, V64, P59
[2]   KINETIC-MODEL FOR CROSS-LINKING FREE-RADICAL POLYMERIZATION INCLUDING DIFFUSION LIMITATIONS [J].
BATCH, GL ;
MACOSKO, CW .
JOURNAL OF APPLIED POLYMER SCIENCE, 1992, 44 (10) :1711-1729
[3]  
BUFFA FA, UNPUB
[4]  
BURNS RB, 1992, POLYESTER MOLDING CO
[5]  
Cook WD, 1997, J APPL POLYM SCI, V64, P769, DOI 10.1002/(SICI)1097-4628(19970425)64:4<769::AID-APP16>3.0.CO
[6]  
2-P
[7]   ON THE CURING KINETICS OF UNSATURATED POLYESTERS WITH STYRENE [J].
CUADRADO, TR ;
BORRAJO, J ;
WILLIAMS, RJJ ;
CLARA, FM .
JOURNAL OF APPLIED POLYMER SCIENCE, 1983, 28 (02) :485-499
[8]  
Dellerba R, 1997, POLYM NETWORK BLEND, V7, P1
[9]   Diffusion control in the kinetics of cross-linking [J].
Dusek, K .
POLYMER GELS AND NETWORKS, 1996, 4 (5-6) :383-404
[10]   INFLUENCE OF THE STYRENE RATIO ON THE COPOLYMERIZATION KINETICS OF DIMETHACRYLATE OF DIGLYCIDYL ETHER OF BISPHENOL A VINYLESTER RESINS CROSS-LINKED WITH STYRENE [J].
GANEM, M ;
MORTAIGNE, B ;
BELLENGER, V ;
VERDU, J .
JOURNAL OF MACROMOLECULAR SCIENCE-PURE AND APPLIED CHEMISTRY, 1993, A30 (11) :829-848