WANG Ying, LIN Cheng, CUI Jing, XI Zhenhao, ZHAO Ling. New kinetic model for polymerization process of nylon 66 salt solution based on functional group non-isoactivity[J]. CIESC Journal, 2020, 71(11): 5208-5215
WANG Ying, LIN Cheng, CUI Jing, XI Zhenhao, ZHAO Ling. New kinetic model for polymerization process of nylon 66 salt solution based on functional group non-isoactivity[J]. CIESC Journal, 2020, 71(11): 5208-5215DOI: 10.11949/0438-1157.20200208.
New kinetic model for polymerization process of nylon 66 salt solution based on functional group non-isoactivity
The polymerization process of nylon 66 salt solution is a dynamically controlled process. Based on the assumption of unequal activity of functional carboxyl and amido groups
a new nylon 66 salt solution polymerization kinetic model was established by introducing the nylon salt dehydration reaction to the acid-catalyzed third-order reaction kinetic model and fitted to obtain the corresponding key kinetic parameters. The fitted salt dehydration reaction rate constant was 8.17×10
-3
kg∙mol
-1
∙h
-1
while the activation energy was 19859 cal∙mol
-1
respectively. Compared with Mallon model
the new developed model has a better fitting effect and can accurately predict the change of the polymerization process in a wider range of temperature and water content. Simulation results showed that salt dehydration reaction has an important effect on the polymerization process and the polymerization efficiency was relatively lower with higher concentration of nylon salt
especially under low temperature and high water content. Appropriately increase the reaction temperature or reduce the initial water content can accelerate the nylon salt dehydration reaction
thereby increasing the polymerization reaction efficiency. New nylon salt polymerization kinetics modeling method is not only applicable to nylon 66
but also to nylon 1212 and other salt solution polyme
rization systems.
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references
田璐璐 . 尼龙66聚合过程的模型化与模拟 [D ] . 杭州 : 浙江大学 , 2015 .
Tian L L . Modeling and simulation of the PA66 polymerization process [D ] . Hangzhou : Zhejiang University , 2015 .
Taylor G B . Process for making polyamides : US2361717A [P ] . 1944-10-31 .
Alsop A W , Blanchard E N , Cohen J D , et al . Process for preparing polyamides : US6069228A [P ] . 2000-05-30 .
Fergusson S B , Marchildon E K , Mutel A T . Process for making nylon 6 , 6 : US6472501B1 [P ] . 2002-10-29 .
Blondel P , Briffaud T , Werth M R G . Kinetics of polycondensation in an industrial environment [J ] . Macromolecular Symposia , 1997 , 122 ( 1 ): 243 - 248 .
Samant K D , Ng K M . Synthesis of prepolymerization stage in polycondensation processes [J ] . AIChE Journal , 1999 , 45 ( 8 ): 1808 - 1829 .
Flory P J . Principles of Polymer Chemistry [M ] . New York : Cornell University Press , 1953 : 70 - 79 .
Roerdink E , De J P , Warnier J . Study on the polycondensation kinetics of nylon-4,6 salt [J ] . Polymer Communications , 1984 , 25 ( 7 ): 194 - 195 .
Giori C , Hayes B T . Hydrolytic polymerization of caprolactam, I. Hydrolysis-polycondensation kinetics [J ] . Journal of Polymer Science Part A Polymer Chemistry , 1970 , 8 ( 2 ): 335 - 349 .
Ogata N . Studies on polycondensation reactions of nylon salt: II. The rate of polycondensation reaction of nylon 66 salt in the presence of water [J ] . Die Makromolekulare Chemie , 1961 , 43 ( 1 ): 117 - 131 .
Aumi S , Corbett B , Mhaskar P , et al . Data-based modeling and control of nylon-6,6 batch polymerization [J ] . IEEE Transactions on Control Systems Technology , 2012 , 21 ( 1 ): 94 - 106 .
Mallon F K , Ray W H . A comprehensive model for nylon melt equilibria and kinetics [J ] . Journal of Applied Polymer Science , 1998 , 69 ( 6 ): 1213 - 1231 .
Yao K Z , Mcauley K B , Berg D , et al . A dynamic mathematical model for continuous solid-phase polymerization of nylon 6,6 [J ] . Chemical Engineering Science , 2001 , 56 ( 16 ): 4801 - 4814 .
Tai K , Teranishi H , Arai Y , et al . The kinetics of hydrolytic polymerization of ϵ‐caprolactam [J ] . Journal of Applied Polymer Science , 1979 , 24 ( 1 ): 211 - 224 .
Schaffer M A , And M A , Cunningham M F , et al . Experimental study and modeling of nylon polycondensation in the melt phase [J ] . Industrial & Engineering Chemistry Research , 2003 , 42 ( 13 ): 2946 - 2959 .
Steppan D D , Doherty M F , Malone M F . A kinetic and equilibrium model for Nylon 6,6 polymerization [J ] . Journal of Applied Polymer Science , 1987 , 33 ( 7 ): 2333 - 2344 .
Zhu J , Gu X P , Feng L F , et al . Establishment of kinetic model for prepolymerization of nylon66 salt in aqueous solution [J ] . Chemical Reaction Engineering and Technology , 2018 , 34 ( 2 ): 51 - 56 .
Lenz R W , Handlovits C E , Smith H A . Phenylene sulfide polymers. III. The synthesis of linear polyphenylene sulfide [J ] . Journal of Polymer Science , 1962 , 58 ( 166 ): 351 - 367 .
Challa G . The formation of polyethylene terephthalate by ester interchange. II. The kinetics of reversible melt-polycondensation [J ] . Macromolecular Chemistry & Physics , 1960 , 38 ( 1 ): 123 - 137 .
Hodgkin J H . Reactivity changes during polyimide formation [J ] . Journal of Polymer Science Polymer Chemistry Edition , 1976 , 14 ( 2 ): 409 - 431 .
Yu T Y , Fu S K , Li S J , et al . Polycondensation kinetics of poly(phenylene ether sulphone) [J ] . Polymer , 1984 , 25 ( 9 ): 1363 - 1366 .
Lu J M , Sun M . Monte Carlo studies on the condensation polymerization of unequal functional group reactivity [J ] . Acta Polymerica Sinica , 1994 , 1 ( 5 ): 565 - 572 .
Puffr R . Structure and properties of polyamides [J ] . Kolloid-Zeitschrift und Zeitschrift für Polymere , 1968 , 222 ( 2 ): 130 - 135 .
Mansfield P , Bowtell R , Blackband S . Ingress of water into solid nylon 6.6 [J ] . Journal of Magnetic Resonance ( 1969 ), 1992 , 99 ( 3 ): 507 - 524 .
Stuart B H . A Fourier transform Raman study of water sorption by nylon 6 [J ] . Polymer Bulletin , 1994 , 33 ( 6 ): 681 - 686 .
Iwamoto R , Murase H . Infrared spectroscopic study of the interactions of nylon-6 with water [J ] . Journal of Polymer Science , 2003 , 41 ( 14 ): 1722 - 1729 .
Born M . Volume and heat of hydration of the ions [J ] . Zeitschrift für Physik , 1920 , 1 ( 1 ): 45 - 48 .
Scatchard G . Statistical mechanics and reaction rates in liquid solutions [J ] . Chemical Reviews , 1932 , 10 ( 1 ): 229 - 240 .
林程 . 尼龙66连续缩聚过程模拟与优化 [D ] . 上海 : 华东理工大学 , 2017 .
Lin C . Simulation and optimization of nylon66 continuous polymerization process [D ] . Shanghai : East China University of Science and Technology , 2017 .
Zou L , Pan X Y , Hu A X , et al . Modification trend of horizontal piping PA66 continuous polymerization [J ] . Techniques of Manufacture , 2007 , 36 ( 3 ): 40 - 44 .