Type Package Package HomoPolymer February 19, 2015 Title Theoretical Model to Simulate Radical Polymerization Version 1.0 Date 2014-12-23 Author Maintainer <gianmarco.polotti@gmail.com> A theoretical model to simulate radical polymerization. Material, energy and population balances are integrated for batch, semi batch and continuous process in a ideally mixed reactor. Limitations: single monomer (i.e.homo polymer), one phase (organic, aqueous). Datasets with chemical-physical data for the most common monomers is included. Some background in polymer science is suggested for its use. Graphical interface for a quick and friendly use is available. Depends R (>= 3.0.0), RGtk2, MenuCollection Imports desolve LazyData true LazyLoad true License GPL-2 NeedsCompilation no Repository CRAN Date/Publication 2015-01-12 10:27:23 R topics documented: homopolymer-package................................... 2 DBk............................................. 3 DBpp............................................ 4 func_homo......................................... 5 gel.............................................. 6 inpbox_computational_options............................... 7 inpbox_flow_options.................................... 8 inpbox_reaction_formulation................................ 9 1
2 homopolymer-package integral........................................... 10 PlotBasic.......................................... 10 PlotChoice.......................................... 11 polymer_toolbar....................................... 12 prepare........................................... 12 StopConditions....................................... 14 Index 15 homopolymer-package Mathematical Modelling of Homo Polymerization Process The package implements the theoretical model described in the references. It deals with the polymer production in a homogeneous phase (bulk, solution) with batch, semi batch and continuous process. Package: homopolymer Type: Package Version: 1.0 Date: 2014-12-23 License: GPL-2 The package tends to be friendly and flexible, fully driven by graphical menus. It also has a comprehensive database of physical/chemical characteristics for the different polymerization ingredients. Please note : the R-package is made using published information released in the references. It does not use any code of the original authors. So, there is no guarantee the code runs as described in the papers. However the package implements the material, energy and micro structural balances exactly as described and uses the optimal datasets highlighted. References Gao J., Penlidis A. (1996) A Comprehensive Simulator/Database Package for Reviewing Free- Radical Homopolymerization, J.M.S.-Rev.Macromol.Chem.Phys, C36(2),199-404 Kuindersma M., (1992) On the Modelling of Free-Radical Polymerization Reactions: Homopolymerization, M.A.Sc.Thesis, Chemical Engineering, University of Waterloo Gao J., (1992) Mathematical Modelling of Homopolymerizations: Simulation Package/Database Extensions, M.A.Sc.Thesis, Chemical Engineering, University of Waterloo Lawrence M.F.,Verzani J., (2012) Programming Graphical User Interfaces in R,CRC Press Taylor & Francis Group
DBk 3 DBk Kinetic constant data Pre-exponential and activation energy factor for kinetic constant of propagation, termination, transfer etc. data("dbk") Format A data frame with 99 observations on the following 8 variables. code1 code key for the chemical substance as in code in table DBpp code2 code key for the chemical substance as in code in table DBpp, value used only when binary interactions are involved type a factor with levels Kd initiator dissociation Kfm transfer to monomer Kfp transfer to polymer Kfs transfer to solvent Kft transfer to transfer agent Kfz termination to inhibitor Kp monomer propagation Kps terminal double bond polymerization Kpss internal double bond polymerization Kt bimolecular termination (global) Ktc bimolecular termination by combination Ktd bimolecular termination by disproportionation K0 pre-exponential factor (1/min, L/mol min) E activation energy (cal/mol) Ak pre-exponential factor for gel deactivation effect Ek activation energy for gel deactivation effect ABC exponential parameter for gel deactivation effect Examples data(dbk)
4 DBpp DBpp Chemical-physical properties Data of chemical-physical properties for monomers, solvents, initiators, inhibitors, transfer agents and polymers data("dbpp") Format A data frame with 34 observations on the following 17 variables. name character vector with the chemical name of the substance type a factor with levels C catalytic transfer agent H inhibitor I initiator M monomer P polymer S solvent T transfer agent code factor with short symbol to replace chemical names when needed Medium a factor with levels B aqueous and organic compound O only organic compound W only water soluble compound Keq equilibrium pka for dissociating compound (dimensionless) delta segmental diffusion parameter a root-mean-square end-to-end distance per square root of the number of segments of polymer chain sigma Lennard-Jones diameter of the monomer jc entanglement spacing of polymer MW molecular weight (g/mol) ro1 intercept for linear dependency density vs. temperature (kg/l) ro2 slope for linear dependency density vs. temperature (kg/l K) V0f free volume alfa volumetric expansion vs. temperature Tg glass transition temperature (K) Cp specific heat capacity (cal/kg K) DHp homo polymerization heat (cal/mol) Examples data(dbpp)
func_homo 5 func_homo Model derivative function It supplies the derivatives of the model as requested by ode integrator in desolve package func_homo(t,y,pars,kpf,kdf,kfz,kfm,kfs,kfp,kps,kpss,kfcta,kfccta,ktf,ktd,ktc,rom,ros,rop) t y pars Kpf Kdf Kfz Kfm Kfs Kfp Kps Kpss KfCTA KfCCTA Ktf Ktd Ktc rom ros rop integration time actual value of the integrated variables vector of physical parameters function for propagation kinetic constant function for initiator decomposition kinetic constant function for inhibition kinetic constant function for transfer to monomer kinetic constant function for transfer to solvent kinetic constant function for transfer to polymer kinetic constant function for external terminal bond kinetic constant function for internal terminal bond kinetic constant function for transfer to agent kinetic constant function for transfer to catalytic agent kinetic constant function for bimolecular termination kinetic constant function for disproportion kinetic constant function for combination kinetic constant function for density of Monomer function for density of Solvent function for density of Polymer The function gives the vector of actual values of the derivative using the ancillary function gel A list of values with model derivatives as first element
6 gel gel Gel effect function The function calculate the change of kinetic constants due to gel effect gel(y, pars, rom, ros, rop) y pars rom ros rop vector of material and energy balance, as supplied by the function prepare vector of chemical-physical parameters, as supplied by the function prepare function of monomer density (Kg/L) vs. temperature (K) function of solvent density (Kg/L) vs. temperature (K) function of polymer density (Kg/L) vs. temperature (K) The function evaluate the reduction of kinetic constant of propagation, termination, initiation when gel effect take place. Several models are implemented: diffusional, segmental and reactive. User can choose among them by menu choice A list with the following elements: Kt decrease of bimolecular termination constant by diffusional model Kp decrease of propagation constant by diffusional model Kd decrease of initiator factor efficiency by diffusional model Kts decrease of bimolecular termination constant by segmental model Ktrmin minimal decrease of bimolecular termination constant by segmental model Ktrmax maximal decrease of bimolecular termination constant by segmental model PhiMvolumetric volume fraction for Monomer PhiS volumetric volume fraction for Solvent PHiP volumetric volume fraction for Polymer K3 gel point parameter K3test gel point test parameter MwrMolecular weight at the gel point start Vfr Free volume at the gel point start Mw Actual molecular weight Vf Actual free volume Vfcr Critical free volume
inpbox_computational_options 7 inpbox_computational_options Graphical menu for process input It allows the choice of many process conditions and constrains inpbox_computational_options(inp) inp initial value vector The function is exclusively used by the prepare function A vector with user choice
8 inpbox_flow_options inpbox_flow_options Graphical menu for flow input It allows the choice of inflow and outflow quantities and times inpbox_flow_options(inp) inp initial value vector The function is exclusively used by the prepare function A vector with user choice
inpbox_reaction_formulation 9 inpbox_reaction_formulation Graphical menu for recipe input It allows the choice of chemicals and the input of mass quantities of reacting ingredients inpbox_reaction_formulation(dbpp,inp) DBpp inp chemical-physical properties database initial value vector The function is exclusively used by the prepare function A vector with user choice
10 PlotBasic integral Homopolymer Integration The function integrate the material and energy balance over the time integral(out) out a list as given and described by the prepare function The function integrate the material and energy balances over the time considering all the physical constrains A table of several variable integrate in the required periods, ready for customer visualization and plotting PlotBasic Basic Plots Show major trends of polymerization: Conversion, Residual Monomer, Reactor Temperature, Molecular Weight vs. time PlotBasic(out, pars) out pars table of numeric results as given by the function integral vector of chemical-physical parameters, as supplied by the function prepare
PlotChoice 11 Some basic graphics to follow the polymerization Just a graphical window with four plots PlotChoice Choose Plot User may choose the three quantities to plot in two different scale PlotChoice(out, otab) out otab table of numeric results as given by the function integral data.frame with quantities and their descriptions Some basic graphics to follow the polymerization Just a graphical window with a plot
12 prepare polymer_toolbar Main toolbar Main toolbar for HomoPolymer pacakage polymer_toolbar() Just a graphical menu to facilitate the sequence of User instructions None. After each command a function is activated and something is printed on the console or in a graphical window. prepare Define the polymerization condition It allows the user to define the polymerization condition trough graphycal menus and build the chemical-physical dataset prepare(dbpp,dbk,recipe.inp, process.inp, flow.inp, interact=true) DBpp DBk recipe.inp process.inp flow.inp interact chemical-physical properties database kinetic constant database a vector with the previous user choice for the polymerization recipe a vector with the previous user choice for the process conditions a vector with composition of in/out flow in case of continous polymerization logical, default=true graphical menus are visualized for user choice
prepare 13 The function prepare the system for the following integration. It defines the recipe, the process and the flow conditions. It also picks up the chemical physical quantities from the internal database required to perform calculation. Its output is a list with vectors and functions built following the user choice in the graphical menus. In case the function is used for parameter determination, graphical menus are disabled setting interact=false. A list with the following elements: y vector with the initial values for material and thermal balances required by integral function pars vector of chemical-physical parameters required by integral function tstep vector of integration step time interval required by integral function Kpf function of propagation constant (L/mol min) vs. temperature (K) Kdf function of initiator decomposition constant (1/ min) vs. temperature (K) Kfz function of inhibition constant (L/mol min) vs. temperature (K) Kfm function of transfer to monomer constant (L/mol min) vs. temperature (K) Kfs function of transfer to solvent constant (L/mol min) vs. temperature (K) Kfp function of transfer to polymer constant (L/mol min) vs. temperature (K) Kps function of terminal double bond termination (L/mol min) vs. temperature (K)erature (K) Kpss function of terminal internal double bond termination (L/mol min) vs. temperature (K) KfCTA function of transfer to chain transfer agent constant (L/mol min) vs. temperature (K) KfCCTA function of transfer to catalytic chain transfer agent constant (L/mol min) vs. temperature (K) Ktf function of overall bimolecular termination constant (L/mol min) vs. temperature (K) Ktd function of bimolecular termination by combination constant (L/mol min) vs. temperature (K) Ktc function of bimolecular termination by disproportion constant (L/mol min) vs. temperature (K) rom function of monomer density (Kg/L) vs temperature (K) ros function of solvent density (Kg/L) vs temperature (K) rop function of polymer density (Kg/L) vs temperature (K)
14 StopConditions StopConditions Physical conditions for stop Set the physical conditions that stop the reaction such as: temperature above limits, chemical concentrations close to zero, conversion close to unity, etc. StopConditions(t, y, pars,...) t y pars integration time (min) vector of material and energy balance, as supplied by the function prepare vector of chemical-physical parameters, as supplied by the function prepare... further functions to be passed through Return a vector of the residual for each constrain
Index Topic Constrain StopConditions, 14 Topic HomoPolymer polymer_toolbar, 12 Topic datasets DBk, 3 DBpp, 4 Topic derivatives func_homo, 5 Topic homopolymerization StopConditions, 14 Topic homopolymer gel, 6 inpbox_computational_options, 7 inpbox_flow_options, 8 inpbox_reaction_formulation, 9 integral, 10 PlotBasic, 10 PlotChoice, 11 prepare, 12 Topic package homopolymer-package, 2 Topic toolbar polymer_toolbar, 12 PlotChoice, 11 polymer_toolbar, 12 prepare, 12 StopConditions, 14 DBk, 3 DBpp, 4 func_homo, 5 gel, 6 homopolymer (homopolymer-package), 2 homopolymer-package, 2 inpbox_computational_options, 7 inpbox_flow_options, 8 inpbox_reaction_formulation, 9 integral, 10 PlotBasic, 10 15