7. PRO/II Polymers User Guide P1-1
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Chapter P1
Introduction to Polymers
Polymer Overview
Polymers form the basis of many useful, synthetic materials com-
mon today. A polymer is a large molecule that has been constructed
from atoms linked together by covalent bonds. This large molecule
is formed by systematically joining together groups of simpler mol-
ecules or monomers. The result is a high molecular weight, long-
chain component made up of various combinations of monomer
units having a recurring chemical structure. The monomer unit
itself has a fixed molecular weight. Monomers may be combined to
produce a polymer by either of two basic mechanisms−addition or
chain polymerization or condensation or step polymerization.
Addition or Chain Polymerization
In this polymerization mechanism, a highly reactive center is cre-
ated, and the monomer is then incorporated into the live chain only
at this center. In the synthesis phase, the reactive center must be
maintained during monomer addition until a polymer of acceptable
molecular weight is generated. The monomer addition process con-
tinues rapidly until the reactive center is transferred away from the
growing chain or deactivated by a termination process. The transfer
or deactivation of the reactive center turns the live or growing poly-
mer chain radical into an inactive or dead polymer chain. Free radi-
cal, ionic, group transfer, metallocene or Ziegler-Natta
polymerization are special types of addition polymerization.
The recurring unit of the polymer structure that results from addi-
tion polymerization is identical to that of the monomer. Most poly-
mers formed by addition polymerization are thermoplastic; i.e., the
polymer softens or hardens by the addition or removal of heat. Typ-
ical polymers formed by this process include:
Polyethylene—used in packaging, pipes, and containers
Polystyrene—used in insulation, pipes, and car panels
Poly(vinylchloride) or PVC—used in pipes, adhesives, and
shoes.
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Condensation or Step Growth Polymerization
In this polymerization mechanism, monomers react with one
another to form larger monomers or macromolecules. These large
molecules essentially assume the role of macromonomers and con-
tinue to react with residual monomer and other macromonomers to
form progressively larger macromonomers. The terms monomer
and macromonomer will be used interchangeably unless some dis-
tinction between the two structures is required. Eventually, the
resulting molecules are of sufficient size that the term polymer is
applicable. This is the step growth polymerization method. In the
course of the polymerization reaction, a low molecular weight com-
ponent (such as H2O or HCl) is usually expelled, and therefore the
term condensation polymerization is common.
In this procedure, the recurring unit of the resulting polymer is not
identical to that of the monomer. Many polymers formed by con-
densation polymerization are thermosetting; i.e., the polymer
becomes rigid and insoluble when heat processed. In addition, poly-
mers created by condensation polymerization techniques may be
cross-linked; i.e., sections of the long-chain polymer react with
each other, resulting in an enhancement of their strength properties
(e.g., hardness or toughness). Typical polymers formed by conden-
sation polymerization include:
Polyesters (e.g., Mylar)—used in valves, pumps, and coatings
Polyurethane—used in foam linings, adhesives, and insulation
Polyamides (e.g., Nylon and Kevlar)—used in gears, bottles,
and appliances.
Polymerization reactions are exothermic in nature and require
sophisticated heat controls. The molecular structure and the bulk
polymer morphology are highly temperature dependent.
Polymers also occur naturally as derivatives of animal and plant
products, e.g., cellulose resins, proteins (soybean, casein), and lig-
nin. Both synthetic and natural polymer products may be spun and
stretched to form a wide variety of fibers. These fibers can then be
modified (e.g., by adding water repellents or flame retardants),
dyed, and woven to produce natural and synthetic fabrics and yarns.
9. PRO/II Polymers User Guide P1-3
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Terminology
Descriptions of common polymer terms are provided below.
Polymer chain A high molecular weight structure made up of a large
number of polymer segments. In a typical polymer, the
polymer chains may be of varying lengths, and their
distribution can, under certain polymerization condi-
tions, be represented by a Gaussian curve. The poly-
mer properties (e.g., molecular weight) are determined
by a statistical average of a sampling of the polymer
chains.
Polymer
segment
A representative section of the polymer chain that con-
tains a recurring chemical structural unit.
Cross-linking A process in which polymer chains react with each
other and increase the hardness of the polymer.
Monomer A building block unit of a polymer. Monomer units
can be combined by addition polymerization or con-
densation polymerization to form a polymer.
Homopolymer A polymer formed by a single type of monomer unit.
Copolymer A polymer formed by two types of monomer units.
Thermosetting
polymer
A polymer that remains rigid and insoluble when
heated.
Thermoplastic
polymer
A polymer that softens or hardens by the addition or
removal of heat.
Polymer blend A non-homogeneous mixture of polymers that results
in desired polymer properties. Special compatibilizers
are used to make the separate polymer components
adhere to each other while still maintaining distinct
phases.
Condensation or
step growth
polymerization
A process in which monomer units are combined by
eliminating small molecules (e.g., HCl, or H2O).
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Chain or free
radical
polymerization
A process in which monomer units are combined to
form polymers with recurring structures identical to
those of the monomer.
Bulk
polymerization
A process in which monomer units are combined in
bulk in the vapor or liquid phase or on a solid surface.
Solution
polymerization
A process in which monomer units are combined in the
presence of a solvent to control and slow the polymer-
ization reaction. This process is often used for highly
exothermic reactions and produces polymers of low to
medium molecular weights.
Suspension
polymerization
A process in which monomer units are combined in the
presence of water and stabilizers to prevent the result-
ing polymer globules from aggregating to each other.
Emulsion
polymerization
A process in which monomer units are combined in the
presence of water and emulsifiers to create aggregates
or micelles of polymer particles. This process can cre-
ate high molecular weight polymers.
11. PRO/II Polymers User Guide P2-1
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Chapter P2
Using the Polymer Module
with PRO/II
Steps for Using Polymers
To create a simulation for a polymer system using PRO/II, follow
these six steps:
1. Select the input units of measure to be SI.
2. Enter the segment data and select the polymer components
(required).
3. Enter the polymer molecular weight distribution and moments
of distributions (optional).
4. Select the polymer thermodynamic method.
5. Create the flowsheet by selecting the desired polymer reac-
tor(s) and other pre- and/or post-processing units (such as flash,
mixer, wiped film evaporator) and completing the stream con-
nections between each unit.
6. Solve the flowsheet and generate the output to view the results
of the simulation.
This chapter includes a brief overview of the first five steps. The
following chapters give a more detailed descriptions.
Selecting the Units of Measure
The current version of the polymers module in PRO/II requires the
units of measure basis for input data to be SI. To set the input units
basis to be SI, do the following:
Click the Units of Measure button on the toolbar (or select Input/
Units of Measure from the menu bar) to display the Default Units of
Measure for Problem Data Input dialog box.
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Figure P2-1: Default Units of Measure for Problem Data Input Dialog Box
Click Initialize from UOM Library... to display the Initialize Units
of Measure from UOM Library dialog box (Figure P2-2).
Figure P2-2: Initialize Units of Measure from UOM Library
Select SI-SET1 from the drop-down list, and click OK. The
units of measure for all properties will now be in SI units; e.g.,
temperature in degrees Kelvin, pressure in kilopascals, etc.
13. PRO/II Polymers User Guide P2-3
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Entering Polymer Segment and Component Data
First, enter the information regarding the segments that make up the
polymers, and then enter the polymer components based on the
selected segments.
To enter the segment and polymer component data:
Click the Component Selection button on the toolbar (or select
Input/Component Selection from the menu bar) to display the
Component Selection dialog box.
Click Polymer... to display the Definition of Polymer Compo-
nents dialog box (Figure P2-3).
Figure P2-3: Definition of Polymer Components Dialog Box
Complete all the segment data by entering the segment names
and their van Krevelen structures (required entry) and the
UNIFAC structures (optional entry).
After defining the segment data, enter the polymer components
by providing their names, average molecular weights, and the
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segment compositions that make up each of the polymer com-
ponents.
All the polymer components selected in this dialog box will be dis-
played in the List of Selected Components in the Component Selec-
tion dialog box after you click OK.
To delete a polymer component:
Select the desired component from the List of Selected Compo-
nents in the Component Selection dialog box and click Delete.
A segment can be deleted by selecting the desired row in the Poly-
mer Segments section of the Definition of Polymer Components dia-
log box and clicking Cut.
Calculating Molecular Weight Distributions
To calculate or input the molecular weight distributions, first enter
the molecular weight of the pseudocomponents that make up the
distribution. This can be achieved by entering the discrete molecu-
lar weight range values for each of the polymer components. Also,
you can specify the number of moments of the molecular weight
distribution that need to be considered during calculations. Each
moment can be assigned a name, or a default name will be used.
To enter data for the molecular weight distribution:
Click the Component Properties button on the toolbar, or select
Input/Component Properties from the menu bar, to display the
Component Properties dialog box.
Click Distribution Functions... under Polymer Properties to dis-
play the Distribution Functions for Components dialog box
(Figure P2-4). All the polymer components selected earlier
under the Component Selection dialog box will be available in
the drop-down lists.
15. PRO/II Polymers User Guide P2-5
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Figure P2-4: Distribution Function for Components Dialog Box
To enter the distribution data for a polymer component:
Select the desired polymer component from the drop-down list.
Select the appropriate kinetic type for the polymer (Free Radi-
cal, Ziegler-Natta, or Step Growth).
Click Enter Data... to display the Distribution Function Data
dialog box for the selected component (Figure P2-5).
Figure P2-5: Distribution Function Data Dialog Box
Select the desired distribution names from the list boxes in the
first column. If you select Discrete Mol. Wt. Cuts, enter the
molecular weight ranges by clicking Enter Data.... For the vari-
ous moments, specify the number of moments and optionally
enter the names of the moments by clicking Enter Data.... The
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moment names default to M0, M1, M2, etc., and up to five
moments can be selected (M0 through M4).
Choosing Thermodynamic Methods
PRO/II currently supports five polymer thermodynamic methods
[Advanced Lattice Model (ALM), Flory-Huggins Model (Flory),
Unifac Free Volume Model (UNFV), Statistical Associating Fluid
Theory (SAFT), and Perturbed Hard-Sphere-Chain Theory
(PHSC)].
To select the method to be used in the simulation:
Click the Thermodynamic Data button on the toolbar, or select
Input/Thermodynamic Data from the menu bar, to display the
Thermodynamic Data dialog box (Figure P2-6).
Figure P2-6: Thermodynamic Data Dialog Box
From the Category list, select Polymers. All five polymer ther-
modynamic methods are displayed in the Primary Method list.
Select the desired method, and click Add to include that
method in the simulation.
To change the thermodynamic method to be used for calculat-
ing various properties, click Modify.... The Modification dialog
box appears (Figure P2-7).
17. PRO/II Polymers User Guide P2-7
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Figure P2-7: Modification Dialog Box
To enter the following, click Enter Data.... Detailed information
on entering these data can be found in Chapter 7, Specifying the
Thermodynamic Method.
Pure species parameters
Binary interaction parameters between two non-polymer
components
Binary interaction parameters between two segments
Binary interaction parameters between a non-polymer com-
ponent and a segment.
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Building the Flowsheet and Selecting Polymer Reactors
Select the desired unit operations and the polymer reactors to be
used in the flowsheet from the unit operation palette by clicking on
the appropriate icons and placing them on the PFD.
To add a polymer reactor to the flowsheet:
Select the Polymer Reactors icon and click on the PFD. The
Polymer Reactors dialog box (Figure P2-8) appears.
Select the desired polymer reactor type from the drop-down list
box. PRO/II supports seven types of CSTRs and seven types of
PFRs.
Figure P2-8: Polymer Reactors Dialog Box
Double-click on the polymer reactor icon on the PFD to display
the dialog box for the selected calculation model. Figure P2-9
shows the CSTR for Free Radical Homopolymerization dialog
box.
19. PRO/II Polymers User Guide P2-9
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Figure P2-9: CSTR for Free Radical Homopolymerization Dialog Box
Enter reactor operating and kinetic data in the Real Data for
Unit (RPARM), Integer Data for Unit (IPARM), and Supple-
mental Data for Unit (SUPPLE) sections. See Chapter 8, Incor-
porating User-Added Polymer Reactor Models, for more
information on the data requirements for the polymer reactor.
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21. PRO/II Polymers User Guide P3-1
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Chapter P3
Estimating Polymer Properties
van Krevelen Group Contribution Method
PRO/II provides a segment approach to simulate polymer systems.
It requires you to input the van Krevelen structural groups for
defined segments. The segment approach is applicable to both
homopolymers and copolymers. The van Krevelen group contribu-
tion method is used to predict the properties of the segments that
make up the polymers on the basis of structural groups. This
method, based on the additivity principle, calculates the property of
a segment as the sum of the contribution of structural groups that
make up the segment. You provide information on the structure of
the segments in the form of group identifiers and counts. This
allows you to simulate processes that involve polymers for which
no experimental data are available, or for which no experimental
data are limited. The structure of a given segment is defined using a
unified set of groups. This unified set is a superset of a number of
group sets developed by van Krevelen for the prediction of various
properties of polymers.
Keyword Summary
Segment Definition (required)
SEGMENT DATA
SEGMENT α, name/…,
FILL= VANKREVELEN
STRUCTURE(VANKRE) α, igroup(n)/…
Component Definition (required)
COMPONENT DATA
POLYMER i, name/…
PCOMPOSITION(M or W) i, Xα,(α), Xβ(β), …/…
MWAVG i, value/…
PHASE VLS or LS or S = i, j…
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Input Description
SEGMENT DATA
SEGMENT α, name/…, FILL= VANKREVELEN
STRUCTURE(VANKRE) α, igroup(n)/…
All segments must be defined under SEGMENT DATA.
The STRUCTURE statement with a VANKRE qualifier is required for
the van Krevelen group contribution method. The default VANKRE
qualifier distinguishes this statement from the UNIFAC structural
group statement (STRUCTURE(UNIFAC)).
COMPONENT DATA
POLYMER i, name/…
PCOMPOSITION(M or W) i, Xα,(α), Xβ(β), …/…
MWAVG i, value/…
PHASE VLS or LS or S = i, j…
All polymer components must be defined as POLYMER components.
a Segment type letter.
name Name of segment α.
FILL This keyword is used to activate the van Krevelen
group contribution method.
a Segment type letter.
igroup(n) The seven-digit identifier for an individual structural
group contained in the segment α with n being used to
define the number of such groups.
i Component number.
name Name of component i (polymer).
MWAVG The molecular weight of each polymer component
must be supplied.
iComponent number.
value Molecular weight of component i.
23. PRO/II Polymers User Guide P3-3
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van Krevelen Structural Groups
In van Krevelen’s original work, different group sets are used for
each individual property. Numerous auxiliary rules are used to
account for the location of a group within a main chain or a side
chain and to describe the proximity effects between a number of
groups. Thus, the logical structure of the van Krevelen group sets is
much more complex than the structure of the UNIFAC group sets; a
set of structural groups of over 700 is identified and used to predict
properties of segments that make up polymers in the van Krevelen
method (see Appendix A, van Krevelen Structural Groups).
The van Krevelen structural group codes are constructed through
three subcodes, CC, SS, and GGG, combined into an integer with a
maximum of seven digits, CCSSGGG. The subcodes have the follow-
ing meanings:
PCOMPOSITION The segment compositions in the polymer must be
supplied.
MMole units.
WWeight units.
Xα(α)Composition of segment in the polymer.
PHASE The polymer phase type can be defined as VLS or
LS or S; default VLS.
i, j Component numbers continuously from
i to j.
CC An optional number of methylene (CH2) groups in a side chain;
this number can be entered only when the main chain unit con-
tains a methyl (CH3) group.
SS An optional code of the group system; it can equal 00 or 01. If
SS=00, the structure has to be constructed from only main chain
groups, which are marked by a plus (+) sign in the van Krevelen
Structural Groups Table. If SS=01, the structure can be con-
structed from any combination of the van Krevelen structural
groups.
GGG A code from the van Krevelen Structural Groups Table; it is
required.
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It is best to use the group system SS=00. This is due to the fact that
the van Krevelen group contributions have been developed primar-
ily for groups that can serve as main chain segments in a polymer. It
is anticipated that this group system will be used for the vast major-
ity of polymer segments of interest. However, it is possible that cer-
tain polymer segments cannot be constructed from the main chain
groups given in the van Krevelen Groups Table because of their
chemical complexity. For such cases, the SS=01 group system is
needed; it allows you to calculate the properties of polymer seg-
ments that are composed of any combination from the van Krevelen
Structural Groups Table.
When choosing the group codes GGG, it is recommended to start
with the most complex groups to construct the structural units of
polymer segments of interest. Select more elementary groups only
when an appropriate complex group is not found. While this is not
mandatory, it will maximize accuracy.
Example P3-1: Segment Structures
The segment structure of polystyrene is constructed using the
SS=00 system (the leading zeros are dropped):
SEGMENT DATA
SEGMENT A, STYRENE1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 144(1), 4(1)
COMPONENT DATA
POLYMER 1, POLYSTRENE
PCOMPOSITION 1, 1(A)
Example P3-2: Segment Structures
The segment structure of poly(1-pentene) (PP) is constructed using
the SS=00 system. The number of methylene groups in the side
chain (which is equal to 2) is specified using the CC subcode:
SEGMENT DATA
SEGMENT A, PENTENE1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 200015(1), 4(1)
COMPONENT DATA
POLYMER 1, PP
PCOMPOSITION 1, 1(A)
25. PRO/II Polymers User Guide P3-5
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Example P3-3: Segment Structures
The segment structure of poly(phenyl methacrylate) (PPMA) can-
not be constructed using the SS=00 system. Therefore, the SS=01
system is used:
SEGMENT DATA
SEGMENT A, PPMA1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 01004(1),
01001(1), 01012(1), 01110(1),
01238(1), 01710(2), 01708(2)
COMPONENT DATA
POLYMER 1, PPMA
PCOMPOSITION 1, 1(A)
Example P3-4: Segment Structures
The segment structure of poly(p-phenylene terephthalamide)
(Kevlar) is best defined by just one group (522), even though the
repeat unit of Kevlar is composed of two phenyl rings, two C=O
groups, and two N-H groups.
SEGMENT DATA
SEGMENT A, KEVLAR1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 522(1)
COMPONENT DATA
POLYMER 1, KEVLAR
PCOMPOSITION 1, 1(A)
The van Krevelen group technique can be used to predict polymer
segment properties if structural information is available for the
polymer segments of interest. In PRO/II, over 700 structural groups
have been identified and may be used to define the polymer seg-
ments.
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Table P3-1 shows the fixed and temperature-dependent properties
of polymer segments that are predicted by the van Krevelen group
method.
Reference
[1] D.W. van Krevelen, 1990, Properties of Polymers. Their Correlation with
Chemical Structure; Their Numerical Estimation and Prediction from Additive
Group Contributions, 3rd edition, Elsevier. Amsterdam.
Table P3-1: van Krevelen Properties of Polymers
Fixed Temperature-Dependent
Molecular weight Liquid density
Average segment number Liquid enthalpy
van der Waals volume Surface tension
Normal melting point (NMP) Solid density
Glass transition temperature Solid enthalpy
Specific gravity of liquid at 60 F
Enthalpy of fusion at NMP
Standard enthalpy of formation at 298.15 K
Standard Gibb’s energy of formation at
298.15 K
Solubility parameter
Liquid thermal conductivity at 298.15 K
27. PRO/II Polymers User Guide P3-7
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Example P3-5: Segment Property Prediction
This example uses the van Krevelen group contribution method to
predict properties of segments for polystyrene (PS),
poly(1-pentene) (PP), poly(phenyl methacrylate) (PPMA), and
poly(p-phenylene terephthalamide) (Kevlar). The polymer proper-
ties are generated from the calculated segment properties by the van
Krevelen method. Segment compositions are provided in the input.
TITLE PROB=HOMOPOLYMER
DIMENSION SI
PRINT INPUT = FULL
$
SEGMENT DATA
SEGMENT A, STYRENE1/B, PENTENE1/C,PPMA1/
D, KEVLAR1, FILL=VANKREVELEN
STRUCTURE(VANKRE)
A, 144(1), 4(1)/
B, 200015(1), 4(1)/
C, 01004(1), 01001(1), 01012(1),
01110(1), 01238(1), 01710(2), 01708(2)/
D, 522(1)
COMPONENT DATA
POLYMER 1, PS/ 2, PP/ 3, PPMA/ 4, KEVLAR
PCOMPOSITION 1,1(A)/ 2,1(B)/ 3,1(C)/ 4,1(D)
PHASE VLS = 1,4
MWAVG 1,10000/ 2,10000/ 3,10000/ 4,10000
$
LIBRARY 5, HEXANE
$
THERMODYNAMIC DATA
METHOD SYSTEM = LIBRARY
$
STREAM DATA
PROP STRM=F1L, TEMP=300, PRES=10, COMP=1,1
PROP STRM=F1S, TEMP=200, PRES=10,
SOLID STREAM=F1S, COMP=1,1
$
PROP STRM=F2L, TEMP=300, PRES=10, COMP=2,1
PROP STRM=F2S, TEMP=200, PRES=10,
SOLID STREAM=F2S, COMP=2,1
$
PROP STRM=F3L, TEMP=300, PRES=10, COMP=3,1
PROP STRM=F3S, TEMP=200, PRES=10,
SOLID STREAM=F3S, COMP=3,1
$
PROP STRM=F4L, TEMP=300, PRES=10, COMP=4,1
PROP STRM=F4S, TEMP=200, PRES=10,
SOLID STREAM=F4S, COMP=4,1
$
UNIT OPERATION
29. PRO/II Polymers User Guide P3-9
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Example P3-6: Segment Property Prediction
This example uses the van Krevelen group contribution method to
predict properties of segments for the copolymer poly(methyl meth-
acrylate-co-vinyl acetate) (PMMACcoVAC), which has 25% vinyl
acetate. The copolymer properties are generated using calculated
segment properties by the van Krevelen method. Segment composi-
tions are provided in the input.
TITLE PROB=COPOLYMER
DIMENSION SI
PRINT INPUT = FULL
$
SEGMENT DATA
SEGMENT A, MMAC1/B, VAC1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 5(1),252(1),9(1)/
B, 5(1),250(1),9(1)
$
COMPONENT DATA
POLYMER 1, PMMACcoVAC
PCOMPOSITION 1, 0.75(A),0.25(B)
PHASE VLS = 1
MWAVG 1,10000
$
LIBRARY 2, HEXANE
$
THERMODYNAMIC DATA
METHOD SYSTEM = LIBRARY
$
STREAM DATA
PROP STRM=F1L, TEMP=300, PRES=10, COMP=1,1
PROP STRM=F1S, TEMP=200, PRES=10,
SOLID STREAM=F1S, COMP=1,1
$
UNIT OPERATION
HCUR UID=HC1L
ISO STREAM=F1L, TEMP=200, 400, PRES=10,
POIN=20
PROP THERMO
HCUR UID=HC1S
ISO STREAM=F1S, TEMP=200, 300, PRES=10,
POIN=20
PROP THERMO
$
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Entering Polymer Segment and Component Data
To enter the segment and polymer component information:
Click the Component Selection button on the tool bar, or select
Input/Component Selection from the menu bar, to display the
Component Selection dialog box (Figure P3-1).
Figure P3-1: Component Selection Dialog Box
Click Polymer... to display the Definition of Polymer Compo-
nents dialog box (Figure P3-2).
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Figure P3-2: Definition of Polymer Components Dialog Box
Enter the names of the desired segments, and click Enter Data...
for each segment to display the Define van Krevelen Structures
dialog box (Figure P3-3).
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Figure P3-3: Define van Krevelen Structures Dialog Box
Enter the van Krevelen structure groups and counts by either
selecting from the lists at the top of the dialog box or by enter-
ing the group number directly into the table.
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You can also enter the UNIFAC structures for the segments by
clicking Enter Data... under UNIFAC Structures. The Define
UNIFAC Structures dialog box appears (Figure P3-4). UNI-
FAC structures are required if the selected polymer thermody-
namic method is UNIFAC Free Volume.
Figure P3-4: Define UNIFAC Structures Dialog Box
After the segment information is complete, enter the compo-
nent names in the Polymer Components table. Supply an aver-
age molecular weight for each component.
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To specify the segment composition for each component (in
either the mole or mass basis), click Enter Data... under Segment
Composition… to display the Segment Composition Data dia-
log box (Figure P3-5).
Figure P3-5: Segment Composition Data Dialog Box
35. PRO/II Polymers User Guide P4-1
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Chapter P4
Supplying Polymer Pure
Component Property Data
In PRO/II, component property data can be supplied for homo-
polymers and copolymers. You can provide polymer segment com-
positions, polymer phase types, and polymer molecular weights.
You can also provide the molecular weight distribution (MWD),
moments of the molecular weight distribution (MMWD), and other
moment distributions. You also supply values for a number of
invariant properties (e.g., heat of fusion, crystallinity, and tacticity)
and temperature-dependent properties (e.g., density, enthalpy, vis-
cosity, and thermal conductivity).
Keyword Summary
Polymer Definition (required)
POLYMER i, name/…
PCOMPOSITION(M or W) i, Xα,(α), Xβ(β), …/…
MWAVG i, value/…
PHASE VLS or LS or S = i, j…
Polymer Attributes (conditional)
ATTRIBUTE COMPONENT = i,j,
KINETICS = FR or ZN or SG,
MWD = mw1, mw2, …,
{MMWD = M0, M1, M2, M3, M4},
{MBCL = M0, M1, M2, M3, M4},
{MTTB = M0, M1, M2, M3, M4},
{MDSD(unit)= s0, s1, s2, …},
{PSD(unit) = s0, s1, s0, …},
GENERAL = 10,
{GNAME = text1, text2, text3, …}
Polymer Invariant Properties (optional)
NMP(utemp) i, value
TGLASS(utemp) i, value
HFUSION(unit) i, value
SOLUPARA(unit)i, value
36. P4-2 - May 2014 Supplying Polymer Pure Component Property
BATCH
POLYMERS
Polymer Temperature-Dependent Properties (optional)
DENSITY(L or S, propunit, tunit, WT or M)
CORRELATION=icorr,
DATA = i, tmax, tmin, C1, … , C8 / …
or
TABULAR= t1, t2, … /i, p1, p2, … /…
ENTHALPY(L or S, propunit, tunit, WT or M)
CORRELATION=icorr,
DATA = i, tmax, tmin, C1, … , C8 / …
or
TABULAR= t1, t2, … /i, p1, p2, … /…
SURFACE(L, propunit, tunit, WT or M)
CORRELATION=icorr,
DATA = i, tmax, tmin, C1, … , C8 / …
or
TABULAR= t1, t2, … /i, p1, p2, … /…
CONDUCTIVITY(L or S, propuom, utemp, WT or M)
CORRELATION=icorr,
DATA = i, tmax, tmin, C1, … , C8 / …
or
TABULAR= t1, t2, … /i, p1, p2, …/…
VISCOSITY(L, propunit, tunit, WT or M)
CORRELATION=icorr,
DATA = i, tmax, tmin, C1, … , C8 / …
or
TABULAR= t1, t2, … /i, p1, p2, … /…
37. PRO/II Polymers User Guide P4-3
POLYMERS
Input Description
Polymer Definition (required)
POLYMER i, name/…
PCOMPOSITION(W or M) i, Xα(α), Xβ(β),…/…
MWAVG i, value/…
PHASE VLS or LS or S = i, j…
Polymer Attributes (required for unit US21)
ATTRIBUTE COMPONENT = i,j,
KINETICS = FR or ZN or SG,
MWD = mw1, mw2, …,
{MMWD = M0, M1, M2, M3, M4},
{MBCL = M0, M1, M2, M3, M4},
{MTTB = M0, M1, M2, M3, M4},
{MDSD(unit)= s0, s1, s2, …},
{PSD(unit) = s0, s1, s0, …},
GENERAL = 10,
{GNAME = text1, text2, text3, …}
POLYMER Defines the polymer component.
PCOMPOSITION Provides the composition (e.g. Xα, Xβ, …) for each
segment in the polymer. The composition of seg-
ments can be given in weight or mole units and will
be normalized before calculation.
MWAVG Supplies the polymer molecular weight.
PHASE Provides the phase assignments for the polymer
components as well as for the regular components.
Because most polymers at normal processing con-
ditions can exist only in L and/or S phases, phase
designations of VLS, LS, or S are appropriate for
polymer components.
Note: Polymer components by definition are non-library compo-
nents and will not have any data stored in the component
library. All polymer properties must be either input or cal-
culated from properties of the constituent segments pre-
dicted by the van Krevelen method, known structure-
property relationships, and the input segment composi-
tions.
38. P4-4 - May 2014 Supplying Polymer Pure Component Property
BATCH
POLYMERS
Polymer component attributes consist of required defined attributes
(MWD) and optional defined attributes. General attributes may be
used by certain users for properties of interest to them, such as acid
number or special end-use properties. A PSD attribute must be
defined for modeling the particle size distribution of crystalline
polymer solids. The defined attributes are:
KINETICS Specifies the kinetics type of polymerization as Free
Radical (FR) Polymerization, Ziegler-Natta (ZN)
Polymerization, or Step Growth (SG) Polymerization.
MWD Specifies the molecular weight distribution (MWD) to
be used in the polymerization processes. If the poly-
mer component can be modeled as a distribution of
discrete pseudo-components, then mw1 is the average
molecular weight of the first pseudocomponent, mw2
is the average molecular weight of the second pseudo-
component, and so on.
Note: The MWD must be supplied for the polymer components if
the polymer reactor unit US21 is used.
MMWD Specifies the molecular weight distribution (MWD) that
will be used in the polymerization processes. M0 is the
zeroth order moment, M1 is the first order moment, M2
is the second order moment, and so on.
MBCL Specifies the moments with respect to the branch chain
length, measured as the numbers of average monomer
units in the branches. It is called Moments of
Branching Length.
MTTB Specifies the moments with respect to the number of
tri-functional and tetra-functional branches. It is called
Moments of Branching Density.
MDSD Specifies the distribution of monomer droplets in
emulsion and suspension polymerization. Monomer
droplets are dispersed in the liquid phase and may be
uniform in size (emulsion polymerization) or may fol-
low a size distribution (suspension polymerization).
The first range has particles with diameters ranging
from s0 to s1; the second range has particles from s1
to s2, and so on. The last range is sn-1 to sn, where
n is the size given for the component. It is called Drop-
let Size Distribution.
39. PRO/II Polymers User Guide P4-5
POLYMERS
Polymer Invariant Properties (optional)
NMP(unit) i, value
TGLASS(unit) i, value
HFUSION(unit) i, value
SOLUPARA(unit) i, value
PSD Specifies Particle Size Distribution, defaulting to
problem fine length units. The first range has particles
with diameters ranging from s0 to s1; the second
range has particles from s1 to s2, and so on. The last
range is
sn-1 to sn, where n is the number of size given for
the component.
GENERAL Specifies the number of user-defined solid attributes.
The default is 10. The range extends to 100.
GNAME Specifies the user-defined names for each of the
GENERAL attributes. A maximum of four alphanu-
meric characters are allowed. If the number of GNAME
arguments is less than the GENERAL integer value,
PRO/II fills in the remaining names. The default
assigned names are AT01, AT02, etc.
Property Unit Description
NMP Temperature Normal melting point
TGLASS Temperature Glass temperature
HFUSION Energy/Mole (default) or
Energy/Mass
Heat of fusion
SOLUPARA Fixed, (cal/cc)1/2 Solubility parameter
40. P4-6 - May 2014 Supplying Polymer Pure Component Property
BATCH
POLYMERS
Polymer Temperature-Dependent Properties (optional)
DENSITY(L or S, uprop, tunit, WT or M)
CORRELATION=icorr,
DATA = i, tmax, tmin, C1, … , C8 / …
or
TABULAR= t1, t2, … /i, p1, p2, … /…
ENTHALPY(L or S, uprop, tunit, WT or M)
CORRELATION=icorr,
DATA = i, tmax, tmin, C1, … , C8 / …
or
TABULAR= t1, t2, … /i, p1, p2, … /…
SURFACE(L, uprop, tunit, WT or M)
CORRELATION=icorr,
DATA = i, tmax, tmin, C1, … , C8 / …
or
TABULAR= t1, t2, …/i, p1, p2, … /…
CONDUCTIVITY(L or S, uprop, utemp, WT or M)
CORRELATION=icorr,
DATA = i, tmax, tmin, C1, … , C8 / …
or
TABULAR= t1, t2, … /i, p1, p2, … /…
VISCOSITY(L, propunit, tunit, WT or M)
CORRELATION=icorr,
DATA = i, tmax, tmin, C1, … , C8 / …
or
TABULAR= t1, t2, … /i, p1, p2, … /…
The defined attributes include:
allowable phase I-Ideal gas, V-Vapor, L-Liquid, S-Solid phase.
tunit Temperature units used in correlation or tabular data:
F, R, C, K. Defaults to problem units.
propunit Specific to each property. See Table 1.8-4 of the PRO/
II Thermodynamic Data Input Manual.
allowable basis M-Mole, WT-Weight
CORRELATION The correlation form for equation-based data. See
Table 1.8-5 of the PRO/II Component Data Input
Manual for the available equation forms for each
property.
41. PRO/II Polymers User Guide P4-7
POLYMERS
PRO/II also predicts the (pseudo) critical properties of polymers
based on the molecular weight only. This method is an extension of
a correlation originally developed by Tsonopoulos and Tan1
for nor-
mal alkanes (from methane to polyethylene).
Reference
[1] C. Tsonopoulos and Z. Tan, 1993, The Critical Constants of
Normal Alkanes from Methane to Polyethylene II. Application of
the Flory Theory, Fluid Phase Equilibria, 83:127-138.
DATA Data entry for equation-based correlations:
iComponent number.
tmax, tminTemperature limits for the data. Required
for Chebychev equations, optional for others.
C1, … ,C8Equation coefficients.
or
TABULAR Data entry for tabular based data.
t1,… Temperatures at which tabular data are entered.
Correspond to data points p1,….
A minimum of two points must be given.
IComponent number
p1,… Data values at temperatures t1,.... A minimum
of one value must be given. It is not necessary to
provide a value for every temperature point. A
place-holding comma must be supplied for every
value skipped. For vapor pressures and viscosities,
ln(p) vs. 1/t, where t is absolute temperature, is used
for interpolation. For all others, linear pres vs. temp
is used.
42. P4-8 - May 2014 Supplying Polymer Pure Component Property
BATCH
POLYMERS
Example P4-1: WFE with Pseudocomponent Distribution
This example tests the wiped film evaporator (WFE) model with a
polymer pseudocomponent distribution. The WFE unit operation
model requires the transport properties.
TITLE PROJECT=WFE, PROBLEM=PS, USER=SIMSCI, DATE=Jan-07
DESC Test WFE with POLYMER PSEUDOCOMPONENT DISTRIBUTION
PRINT STREAM=ALL, RATE=WT, FRACTION=WT
DIMENSION SI
SEQUENCE PROCESS
SEGMENT DATA
SEGMENT A, STYR1, FILL=VANKREVLEN
STRUCTURE(VANKRE) A,144(1),4(1)
COMPONENT DATA
LIBID 2, STYRENE/3,EBZN/4,BOBZ, BANK=SIMSCI
POLY 1, PSTYR
PCOMPOSITION 1,1(A)
PHASE VLS=1
MWAVG 1,31000
ATTRIBUTE COMP=1, KINETICS=FR,
MWD= 1000, 3000, 5000, 7000, 10000,
30000, 40000, 60000, 80000, 100000,
120000,150000,200000, 300000,400000,
500000,600000,
MMWD=MU0,MU1,MU2
VISCOSITY(V,K,PAS) TABULAR= 300, 500/
1,0.001,0.001
VISCOSITY(L,C,PAS) TABULAR= 30,100,500/
1,500,450,300
CONDUCTIVITY(V,K,W/MK) TABULAR=300,500/1,1,1
THERMODYNAMIC DATA
METHOD SYSTEM=ALM, TRANSPORT=PURE,
DIFFUSIVITY=DATA, KVAL(VLE)
ALME 3,A, 0.022,11.02
ALMC A,1.338
DIFFUSIVITY(L)
DIFDATA(K) 1,2,1E-8
DIFDATA(K) 1,3,5E-8
DIFDATA(K) 1,4,1E-9
STREAM DATA
PROPERTY STREAM=F1, TEMPERATURE=343,
PRESSURE=1013.3,
COMPOSITION(WT,KG/M)=2,10.4188/4,0.15
UNIT OPERATIONS
PCSTR UID=REACTOR_1, NAME=1st PS REACTOR
FEED F1
PRODUCT P1
44. P4-10 - May 2014 Supplying Polymer Pure Component Property
BATCH
POLYMERS
Entering Molecular Weight Distributions
To enter the molecular weight distribution:
Click the Component Properties button on the tool bar, or
select Input/Component Properties from the menu bar, to dis-
play the Component Properties dialog box (Figure P4-1).
Figure P4-1: Component Properties Dialog Box
45. PRO/II Polymers User Guide P4-11
POLYMERS
Click Distribution Functions... in the Polymer Properties section
to display the Distribution Functions for Components dialog
box (Figure P4-2). All the polymer components selected earlier
under the Component Selection dialog box will be available in
the drop-down lists.
Figure P4-2: Distribution Functions for Components Dialog Box
To enter the distribution data for a polymer component:
Select the desired component from the drop-down list.
Select the kinetic type of the component (Free Radical, Ziegler-
Natta, or Step Growth).
Click Enter Data... to display the Distribution Function Data
dialog box for the selected component (Figure P4-3).
Figure P4-3: Distribution Function Data Dialog Box
46. P4-12 - May 2014 Supplying Polymer Pure Component Property
BATCH
POLYMERS
Select the desired distribution names from the list boxes in the
first column.
For Discrete Mol. Wt. Cuts, enter the molecular weight ranges
by clicking Enter Data.... The Molecular Weight Distribution
dialog box appears (Figure P4-4).
Figure P4-4: Molecular Weight Distribution Data Dialog Box
For the moments of various distributions, specify the number of
moments, and enter the names of the moments by selecting
them from the drop-down list box (optional task). The moment
names default to M0, M1, M2, etc., and up to five moments can
be selected (M0 through M4).
47. PRO/II Polymers User Guide P5-1
POLYMERS
Chapter P5
Supplying Polymer Stream Data
In addition to the composition of the polymer components, defined
streams containing polymers will also require input of MWD mole
fraction or weight fraction values to be interpreted in terms of
moments that might be submitted to a polymer reactor or other unit
operation process. You can also supply values of various moments,
size distributions, and general attributes that are defined in the poly-
mer component attributes. PRO/II will calculate the SCHULZ-
FLORY distribution from bulk moments generated from a polymer
reactor model or input by the user. PRO/II will also calculate the
number average molecular weight, weight average molecular
weight, and polydispersity index from the moments for various
chain types (e.g., live, dead, and bulk).
PRO/II provides the polymer characterization conversion utility to
establish a useful translation between the molecular weight distribu-
tion and the moments of the molecular weight distribution. You can
supply a molecular weight distribution to be interpreted in terms of
moments, or you can supply moments of a molecular weight distri-
bution to be converted to amounts of pseudocomponents that define
the molecular weight distribution.
Values of moments of distributions with respect to other parameters
of interest may also be input in the stream data section; e.g. moment
attributes for branch chain length for a branched polymer. Moments
or properties defined as general attributes in the component data
section will also have their values entered here. Mole fraction and
weight fraction attributes for the different types of polymer chains
as fractions of the total chains can also be input for the polymer in
the stream. If there are polymer solids in the stream and PSD attri-
butes have been defined for the solid components, then PSD weight
fractions can be input for the solid polymers.
48. P5-2 Supplying Polymer Stream Data
BATCH
POLYMERS
Keyword Summary
Stream Polymers (optional)
MWD(PA or PB or PC or PAA or PBB or PCC or PAB or PAC
or PBC or DA or DB or DAA or DBB,
L or S, M or WT),
COMPONENT = i, j,
DATA = value1, value2, ..., {STREAM = sid}
MMWD(PA or PB or PC or PAA or PBB or PCC or PAB or PAC
or PBC or DA or DB or DAA or DBB,
L or S, unit),
COMPONENT = i, j,
DATA = value1, value2, ..., {STREAM = sid}
PCFRAC(L or S, M or WT) COMPONENT = i, j,
DATA = value1, value2, value3, value4,
value5, value6, value7, value8,
value9, value10, value11, value12,
value13, {STREAM = sid}
MBCL(P or D, L or S, unit) COMPONENT = i, j,
DATA = value1, value2, ..., {STREAM = sid}
MTTB(P or D, L or S, unit) COMPONENT = i, j,
DATA = value1, value2, ..., {STREAM = sid}
MDSD COMPONENT = i, j,
DATA = value1, value2, ..., {STREAM = sid}
PSD COMPONENT = i, j,
DATA = value1, value2, ..., {STREAM = sid}
GENERAL COMPONENT = i, j,
DATA = value1, value2, ..., {STREAM = sid}
Polymer-specific data in the stream data section include composi-
tions of polymer components in the streams. This input is the same
as that for the regular components. Polymer solids in streams are
also specified using the same input as regular or low molecular
weight solids, i.e., using the SOLID and PSD statements.
Values of moments of distributions of polymer components with
respect to various parameters can be input as attributes. The
moments are defined in Chapter 4. For distributions that are func-
tions of the topology of the polymer, moments of live chains P and
dead chains D can be input for polymer components in the liquid (L)
and solid (S) phase in the stream.
49. PRO/II Polymers User Guide P5-3
POLYMERS
You can provide data for either the molecular weight distribution
through the MWD statement or for the moments of the molecular
weight distribution through the MMWD statement. Data input is not
allowed simultaneously for both of the MWD and MMWD statements.
The polymer characterization conversion utility will convert one
characterization into another. For instance, if mole or weight frac-
tion values are input for the MWD attributes, PRO/II will convert the
MWD attributes into the MMWD attributes (e.g., zero order, first
order, and second order). Conversely, if the moments are input for
the MMWD attributes, the MWD attribute values will be calculated and
then will be converted into the amounts of pseudocomponents that
define the molecular weight distribution.
The PCFRAC attribute refers to the mole or weight fraction compo-
sitions of the polymer chain types. These attributes can be input for
polymer components in the liquid (L) and solid phase (S) in the
stream. The PCFRAC attribute input is required for the MMWD
attributes and will be calculated for the MWD attributes.
For monomer emulsion/suspension in the stream, the distribution of
the monomer droplet size must be specified. Finally, values of gen-
eral attributes can also be entered here.
The moments or attributes of the polymer component in the stream
can be accessed and modified by the polymerization reactors and
unit operations in the flowsheet, although the type of the distribu-
tion function will continue to remain the same (or undefined)
throughout the flowsheet.
All data entered from POLYMER STREAM ATTRIBUTES affect all
components in sequence from component i through j. If j is not
given, only component i is activated. Separate statements are
allowed for each component having these attributes declared in
COMPONENT DATA. These attributes are listed below.
50. P5-4 Supplying Polymer Stream Data
BATCH
POLYMERS
MWD or MMWD Attributes for Free Radical (FR) Polymerization
MWD or MMWD Attributes for Coordination Complex (ZN) Polymerization
(Monomers are up to two, A and B)
PA refers to live chains terminating in single type A bond
PB refers to live chains terminating in single type B bond
PC not used for FR
PAA refers to live chains terminating in double type A bonds
PBB refers to live chains terminating in double type B bonds
PCC not used for FR
PAB not used for FR
PAC not used for FR
PBC not used for FR
DA refers to dead chains terminating in single type A bond
DB refers to dead chains terminating in single type B bond
DAA refers to dead chains terminating in double type A bonds
DBB refers to dead chains terminating in double type B bonds
(Monomers are up to two, A and B)
PA refers to live polymer chain bounded by monomer A at site 1
PB refers to live polymer chain bounded by monomer A at site 1
PC refers to dead polymer chain generated from site 1
PAA refers to live polymer chain bounded by monomer A at site 2
PBB refers to live polymer chain bounded by monomer A at site 2
PCC refers to dead polymer chain generated from site 2
PAB refers to live polymer chain bounded by monomer A at site 3
PAC refers to live polymer chain bounded by monomer A at site 3
PBC refers to dead polymer chain generated from site 3
DA refers to live polymer chain bounded by monomer A at site 4
DB refers to live polymer chain bounded by monomer A at site 4
DAA refers to dead polymer chain generated from site 4
DBB not used for ZN
51. PRO/II Polymers User Guide P5-5
POLYMERS
MWD or MMWD Attributes for Step Growth (SG) Polymerization
PCFRAC Attributes for Free Radical (FR) Polymerization
(Monomers are up to three, A, B, and, C)
PA refers to monofunctional live chains terminating in A
PB refers to monofunctional live chains terminating in B
PC refers to monofunctional live chains terminating in C
PAA refers to bifunctional live chains terminating in A and A
PBB refers to bifunctional live chains terminating in B and B
PCC refers to bifunctional live chains terminating in C and C
PAB refers to bifunctional live chains terminating in A and B
PAC refers to bifunctional live chains terminating in A and C
PBC refers to bifunctional live chains terminating in B and C
DA refers to dead chains
DB not used for SG
DAA not used for SG
DBB not used for SG
(Monomers A and B)
value1 fraction of live chains terminating in single type A bond
value2 fraction of live chains terminating in single type B bond
value3 zero, not used for FR
value4 fraction of live chains terminating in double type A bonds
value5 fraction of live chains terminating in double type B bonds
value6 zero, not used for FR
value7 zero, not used for FR
value8 zero, not used for FR
value9 zero, not used for FR
value10 fraction of dead chains terminating in single type A bond
value11 fraction of dead chains terminating in single type B bond
value12 fraction of live chains terminating in double type A bonds
value13 fraction of live chains terminating in double type B bonds
52. P5-6 Supplying Polymer Stream Data
BATCH
POLYMERS
PCFRAC Attributes for Coordination Complex (ZN) Polymerization
(PCFRAC Attributes for Step Growth (SG) Polymerization
(Monomers A and B)
value1 fraction of live polymer chain bounded by monomer A at site 1
value2 fraction of live polymer chain bounded by monomer B at site 1
value3 fraction of dead polymer chain generated from site 1
value4 fraction of live polymer chain bounded by monomer A at site 2
value5 fraction of live polymer chain bounded by monomer B at site 2
value6 fraction of dead polymer chain generated from site 2
value7 fraction of live polymer chain bounded by monomer A at site 3
value8 fraction of live polymer chain bounded by monomer B at site 3
value9 fraction of dead polymer chain generated from site 3
value10 fraction of live polymer chain bounded by monomer A at site 4
value11 fraction of live polymer chain bounded by monomer B at site 4
value12 fraction of dead polymer chain generated from site 4
value13 not used for ZN
(Monomers A, B, and C)
value1 fraction of monofunctional live chains terminating in A
value2 fraction of monofunctional live chains terminating in B
value3 fraction of monofunctional live chains terminating in C
value4 fraction of bifunctional live chains terminating in A and A
value5 fraction of bifunctional live chains terminating in B and B
value6 fraction of bifunctional live chains terminating in C and C
value7 fraction of bifunctional live chains terminating in A and B
value8 fraction of bifunctional live chains terminating in A and C
value9 fraction of bifunctional live chains terminating in B and C
value10 fraction of dead chains
value11 zero, not used for SG
value12 zero, not used for SG
value13 zero, not used for SG
53. PRO/II Polymers User Guide P5-7
POLYMERS
Example P5-1: Component and Stream Attribute Input
This example illustrates the input of the polymer component attri-
butes and the polymer stream attributes. This sequence converts the
input MWD attributes into the MMWD attributes for the kinetics of free
radical polymerization. The PCFRAC attributes will be calculated.
TITLE PROJ=MWD, PROB=TEST, USER=SIMSCI, DATE=1997
DIME METRIC
PRINT RATE=WT, INPUT=ALL
SEGMENT DATA
SEGMENT A, STY1/B, MMAC, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 146(1), 4(1)/B, 5(1), 252(1), 9(1)
COMPONENT DATA
POLYMER 1, PScoVAC
PCOMPOSITION 1, 0.7(A), 0.3(B)
LIBRARY 2, BENZENE
PHASE VLS = 1
MWAVG 1, 8578.6
$ POLYMER COMPONENT ATTRIBUTES
ATTRIBUTE COMPONENT = 1, KINETICS = FR,
MWD = 1000, 2000, 5000, 7000, 10000, 15000, 20000,
MMWD = MU0, MU1, MU2, MU3
THERMODYNAMICS DATA
METHODS SYSTEM = ALM
KVALUE
ALMC A, 1.338/B, 1.441
ALME 2,A, 0.022,11.02/2,B, 0.010, 16.36
STREAM DATA
PROP STRM=FEED, TEMP(K)=298.15, PRES(ATM)=1,
COMP(WT,KG/MIN)=100/20
$ POLYMER FEED STREAM ATTRIBUTES
$ COMPONENT 1 (TWO SEGMENTS A AND B)
MWD(PA,L) COMP= 1, DATA = 25,10, 5,30,50,20,40, NORM, STREAM = FEED
MWD(PB,L) COMP= 1, DATA = 5,30,15,25,50,20,10, NORM, STREAM = FEED
MWD(PAA,L) COMP= 1, DATA = 35, 5,20,30,40,15,25, NORM, STREAM = FEED
MWD(PBB,L) COMP= 1, DATA = 15,40,30,20,10, 5,25, NORM, STREAM = FEED
MWD(DA,L) COMP= 1, DATA = 25,35,45,20,15,50,30, NORM, STREAM = FEED
MWD(DB,L) COMP= 1, DATA = 15,25,35,10, 5,40,20, NORM, STREAM = FEED
MWD(DAA,L) COMP= 1, DATA = 5,45,55,25,20,10,30, NORM, STREAM = FEED
MWD(DBB,L) COMP= 1, DATA = 25,30,20,40,10,50,15, NORM, STREAM = FEED
MBCL(P,L) COMP = 1, DATA = 1, 1000, 100000, STREAM=FEED
MTTB(P,L) COMP = 1, DATA = 50,45000,3500000, STREAM=FEED
MBCL(D,L) COMP = 1, DATA = 5, 5000, 500000, STREAM=FEED
MTTB(D,L) COMP = 1, DATA = 20,40000,7000000, STREAM=FEED
MDSD COMP = 1, DATA = 30, 30, 40, STREAM=FEED
PSD COMP = 1, DATA = 0.3, 0.7, STREAM=FEED
GENERAL COMP = 1, DATA = 100,200,300, STREAM=FEED
UNIT OPERATION
FLASH UID=FEED
FEED FEED
PRODUCT V=V1, L=L1
ISOT TEMP(K)=298.15, PRES(ATM)=1
END
54. P5-8 Supplying Polymer Stream Data
BATCH
POLYMERS
Example P5-2: Component and Stream Attribute Input
This example shows the input of the polymer component attributes
and the polymer stream attributes. This sequence converts the input
MMWD attributes into the amounts of the pseudocomponents that
define the molecular weight distribution. The input PCFRAC attri-
butes are required for the conversion.
TITLE PROJ=MMWD, PROB=TEST, USER=SIMSCI, DATE=1997
DIME METRIC
PRINT RATE=WT, INPUT=ALL
SEGMENT DATA
SEGMENT A, STY1/B, MMAC1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 146(1), 4(1)/
B, 5(1), 252(1), 9(1)
COMPONENT DATA
POLYMER 1, PScoVAC
PCOMPOSITION 1, 0.7(A), 0.3(B)
LIBRARY 2, BENZENE
PHASE VLS = 1
MWAVG 1, 11276
$ POLYMER COMPONENT ATTRIBUTES
ATTRIBUTE COMPONENT = 1, KINETICS = FR,
MWD = 1000,2000, 5000, 6000,8000,10000,
12000,15000,20000,50000,70000,100000,
MMWD = MU0, MU1, MU2, MU3
MBCL = BCL0, BCL1, BCL2,
MTTB = TTB0, RHO1, RHO2,
MDSD = 10, 100, 1000,
PSD = 20, 200, 2000,
GENERAL = 3,
GNAME = ATT1, ATT2, ATT3
THERMODYNAMICS DATA
METHODS SYSTEM = ALM
KVALUE
ALMC A, 1.338/ B, 1.441
ALME 2, A, 0.022, 11.02/
2, B, 0.010, 16.36
STREAM DATA
PROP STRM=FEED, TEMP(K)=300, PRES(ATM)=1,
COMP(WT,KG/MIN)=100/20
$ POLYMER FEED STREAM ATTRIBUTES
55. PRO/II Polymers User Guide P5-9
POLYMERS
$ COMPONENT 1 (TWO SEGMENTS A AND B)
MMWD(PA,L) COMP = 1,
DATA = 0.1,10,2500,1000000, STREAM = FEED
MMWD(PB,L) COMP = 1,
DATA = 0.2,20,3500,2000000, STREAM = FEED
MMWD(PAA,L) COMP = 1,
DATA = 0.3,30,4500,3000000, STREAM = FEED
MMWD(PBB,L) COMP = 1,
DATA = 0.4,40,5500,4000000, STREAM = FEED
MMWD(DA,L) COMP = 1,
DATA = 0.5,50,6500,5000000, STREAM = FEED
MMWD(DB,L) COMP = 1,
DATA = 0.6,60,7500,6000000, STREAM = FEED
MMWD(DAA,L) COMP = 1,
DATA = 0.7,70,8500,7000000, STREAM = FEED
MMWD(DBB,L) COMP = 1,
DATA = 0.8,80,9500,8000000, STREAM = FEED
PCFRAC(L,WT)COMP=1,
DATA= 0.1, 0.2, 0.0, 0.05, 0.05,
0.0, 0.0, 0.0, 0.0, 0.1,
0.1, 0.1, 0.1, NORM, STREAM=FEED
BCL(P,L) COMP = 1,
DATA = 1, 1000, 100000, STREAM=FEED
MTTB(P,L) COMP = 1,
DATA = 50,45000,3500000, STREAM=FEED
MBCL(D,L) COMP = 1,
DATA = 5, 5000, 500000, STREAM=FEED
MTTB(D,L) COMP = 1,
DATA = 20,40000,7000000, STREAM=FEED
MDSD COMP = 1,
DATA = 30, 30, 40, STREAM=FEED
PSD COMP = 1,
DATA = 0.3, 0.7, STREAM=FEED
GENERAL COMP = 1
DATA = 100,200,300, STREAM=FEED
UNIT OPERATION
FLASH UID=FEED
FEED FEED
PRODUCT V=V1, L=L1
ISOT TEMP(K)=300, PRES(ATM)=1
END
56. P5-10 Supplying Polymer Stream Data
BATCH
POLYMERS
Entering Stream Polymer Data
Stream data for the polymer components can be supplied for the
various distributions that were selected previously in the Compo-
nent Property section of Chapter P4, Supplying Polymer Pure Compo-
nent Property Data.
Double-click on the desired stream to display the Stream Data
dialog box (Figure P5-1).
Figure P5-1: Stream Data Dialog Box
Click Stream Polymer Data... to display the Polymer Distributions
dialog box (Figure P5-2). The distribution data must be sup-
plied on a component-by-component basis. Only those compo-
nents with distributions that were specified in the Component
Properties section in Chapter P4 will be available in the drop-
down lists.
57. PRO/II Polymers User Guide P5-11
POLYMERS
Figure P5-2: Polymer Distributions Dialog Box
Select the desired component, and click Enter Data... under MW/
Moment Distributions to display the Polymer Component
Distributions dialog box (Figure P5-3), in which the various
distribution types can be selected. Only those distributions that
were selected for the current component in the Component
Properties section in Chapter 4 will be displayed in this dialog
box.
Figure P5-3: Polymer Component Distributions Dialog Box
58. P5-12 Supplying Polymer Stream Data
BATCH
POLYMERS
Also, data for only one of Molecular Weight Distribution or
Moments of Molecular Weight Distribution can be supplied. If one
is selected, the other will not be available.
After selecting the distributions, click Enter Data... under
Additional Data to supply data for various chain types of the
polymer component in the Polymer Distribution Data dialog
box (Figure P5-4). Note that the chain type available will
depend on the polymer type (homopolymer or copolymer) and
the selected kinetic type (free radical, Ziegler-Natta, or step
growth).
Figure P5-4: Polymer Distribution Data Dialog Box
Click Enter Data... under Additional Data to supply the data for
that chain type.
If Discrete Mol. Wt. Cuts (MWD) is selected, supply the molecular
weight fractions (Figure P5-5).
59. PRO/II Polymers User Guide P5-13
POLYMERS
Figure P5-5: Discrete Mol. Wt. Cuts Dialog Box
If Moments of Mol. Wt. Distribution (MMWD) is selected, sup-
ply the values for the moments for the selected chain type and
the chain type fraction (PCFRAC) (Figure 5-6). Data can be sup-
plied for liquid and/or solid phase.
60. P5-14 Supplying Polymer Stream Data
BATCH
POLYMERS
Figure P5-6: Moments of Mol. Wt. Distribution Dialog Box
61. PRO/II Polymers User Guide P6-1
POLYMERS
Chapter P6
Stream Output Report Options
By default, the weight rates of the individual polymer pseudo-com-
ponents (which result from the MWD attributes given for the poly-
mer) are printed in the Stream Weight Component Rates section of
the Stream Summary output. By using the optional PWRATE key-
word on the PRINT statement in the General Data category of input,
the weight rate of the TOTAL polymer is printed instead.
Also by default, the polymer characterization conversion utility is
activated for a simulated system containing polymers, and the con-
verted results either for the MWD attributes or for the MMWD attributes
will be printed out in the stream output. By using the optional
PCONV keyword on the PRINT statement in the General Data cate-
gory of input, the polymer characterization conversion utility is dis-
abled.
Keyword Summary
PRINT …, PWRATE, PCONV
Typical Usage
TITLE
DIME METRIC
PRINT RATE=WT, INPUT=ALL, PWRATE, PCONV …
PWRATE This optional keyword specifies that the rate (on a weight
basis) of the total polymer component be printed in the
Stream Component Rates section of the output report.
PCONV This optional keyword disables the polymer characterization
conversion utility that converts one characterization (e.g. the
MWD attributes or the MMWD attributes) into another.
62. P6-2 Stream Output Report Options
BATCH
POLYMERS
Entering PWRATE and PCONV
To enter PWRATE:
Select Output/Report Format from the menu bar, and then
select Stream Properties to display the Stream Property Report
Options dialog box (Figure P6-1). By default, the Include Poly-
mer Pseudocomponent Flowrates option is checked, indicating
that the output report includes pseudocomponent flow rates.
Uncheck this box to obtain the total polymer component rate
(on a weight basis) in the Stream Component Rates section of
the output report.
Figure P6-1: Stream Property Report Options Dialog Box
To toggle PCONV, the polymer characterization conversion:
63. PRO/II Polymers User Guide P6-3
POLYMERS
Select Input/Miscellaneous Data from the menu bar to display
the Input Miscellaneous Data dialog box (Figure P6-2). By
default, the Polymer Consistency Check option is set to Yes. To
turn off the polymer characterization conversion utility, select
No in the drop-down list.
Figure P6-2: Input Miscellaneous Data Dialog Box
65. PRO/II Polymers User Guide P7-1
POLYMERS
Chapter P7
Specifying the Thermodynamic
Method
In addition to the van Krevelen group contribution method for pre-
dicting thermophysical properties of polymers from structures of
segments, PRO/II also provides a set of superior polymer-specific
thermodynamic methods for phase equilibrium calculations for the
system containing polymers. These methods include the classical
Flory-Huggins model (FLORY), the popular UNIFAC-Free Volume
model (UNFV), the Advanced Lattice Model (ALM) developed by
SIMSCI, and the two state-of-the-art polymer equations of state,
i.e., the Statistical Associating Fluid Theory (SAFT) and the
Perturbed Hard-Sphere-Chain (PHSC) Theory.
All these methods have been implemented in PRO/II using the seg-
ment approach. For the pure component parameters, data may be
input for non-polymer components (solvents) and for segments that
make up the polymers. The polymer component parameters will be
generated from the segment properties predicted by the van
Krevelen method and segment compositions through input. For the
binary parameters, data can be input for non-polymer component
pairs (solvent-solvent), solvent-segment pairs, and segment-
segment pairs.
PRO/II automatically uses a new polymer flash algorithm devel-
oped by SIMSCI when a polymer-specific method is specified in
the input.
66. P7-2 Specifying the Thermodynamic Method
BATCH
POLYMERS
Advanced Lattice Model (ALM)
The advanced lattice model (ALM) is used to predict VLE and
VLLE phase behavior for mixtures containing polymers. ALM is a
segment-based activity coefficient model and is especially useful
for polymer solutions and polymer blends. It gives much more
accurate VLE and LLE correlations than the commonly used Flory-
Huggins model.
Typical Usage
…
SEGMENT DATA
SEGMENT A, IB1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 16(1), 4(1)
COMPONENT DATA
LIBID 1,BENZENE
POLYMER 2, PIB
PCOMPOSITION 2, 1(A)
MW 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=ALM
…
METHOD Statement
METHOD SYSTEM(VLE or VLLE)=ALM,
PHI=IDEAL, {HENRY},…
or
METHOD KVALUE(VLE and/or LLE or VLLE)=ALM,
PHI=IDEAL, {HENRY},…
Properties predicted by ALM methods K-values
Required pure component properties* Molecular weight
Liquid molar volume
Two liquid phase behavior VLLE Supported
* Automatically supplied by PRO/II for library and petroleum
components. Must be supplied or estimated using the van Krevelen
group contributions method for polymer components.
SYSTEM Selects a combination of consistent thermodynamic
property generators. When SYSTEM=ALM is chosen,
ALM K-values, IDEAL enthalpies, IDEAL liquid den-
sities, and IDEAL vapor densities are the defaults.
67. PRO/II Polymers User Guide P7-3
POLYMERS
KVALUE Selects the method for K-value calculations. Both
VLE and LLE K-value calculations are available with
the ALM method. The VLLE option automatically
selects both. See Section 2.1.7 of the SIMSCI Compo-
nent and Thermodynamic Data Input Manual
(CTDIM) for more details on liquid-liquid equilibrium
calculations.
PHI Selects the option used to calculate pure component
and mixture vapor phase fugacity coefficients (φi). A
vapor fugacity method should generally be selected for
high pressure applications. The options are the equa-
tions of state methods SRK, PR, SRKM, PRM, SRKH,
PRH, SRKP, PRP, SRKS, SRKKD, BWRS, and UNI-
WAAL (see Section 2.4 of the SIMSCI CTDIM and
HOCV (the Hayden-O’Connell method), TVIRIAL
(the Truncated Virial method), and the IDIMER
method. See sections 2.5.12, 2.5.13, and 2.5.14,
Hayden-O’Connell, Vapor Fugacity, Truncated Virial
Vapor Fugacity, and IDIMER Vapor Fugacity, of the
SIMSCI CTDIM for details on these last three options.
The default is PHI=IDEAL.
HENRY Selects Henry’s Law data (either user-supplied or from
databanks) to model dissolved gases in a liquid solu-
tion. See Section 2.5.11, Henry’s Law for Non-
condensable Components, of the SIMSCI CTDIM for
details.
Note: A heat of mixing option, HMIX, is available for the
enthalpy method selected. See Section 2.5.15, Redlich-Kister,
Gamma Heat of Mixing, of the SIMSCI CTDIM for details on the
use of this option.
68. P7-4 Specifying the Thermodynamic Method
BATCH
POLYMERS
K-Value Data (optional)
KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON
ALME a, b, e1, e2, e3/…
ALMC a, c/…
Table P7-1 lists values of c for ALMC, and e1, and e2 for ALME
(e3 = 0) for homopolymer segment-solvent component pairs.
POYNTING Selects whether to apply the Poynting correction to
fugacities of components in the liquid phase. The
default is OFF unless a PHI method is selected, in
which case the default is ON.
ALME Used to introduce binary energetic parameters. The
default values are zero. The temperature-dependent
energy parameter is calculated as:
ALMC Used to introduce the size correction factor c. The
default value is 1.
α or β Non-polymer component (solvent) number or segment
type letter.
εr e1
e2
T
---- e3 T
ln
+ +
=
Table P7-1: Parameters for AML Methods
Segment Name Homopolymer
Symbol
Solvent ALM
c e1 e2
Butadiene PBD Benzene 1.370 0.017 11.12
Carbon tetrachloride 2.506 0.081
Chloroform 1.117 0.008
Cyclohexane 1.479 0.031 4.851
Dichloromethane 2.528 0.140
Ethylbenzene 0.710 -0.180 67.10
n-Hexane 1.663 0.058
n-Nonane 0.310 -0.258 88.54
Ethylene LDPE n-Butane 1.119 -0.488 192.7
1-Butene 0.554 -0.613 214.6
n-Heptane 1.837 0.007 41.82
n-Hexane 0.856 -0.210 90.55
71. PRO/II Polymers User Guide P7-7
POLYMERS
Example P7-1: ALM with Polyvinylacetate and Benzene
This example uses the ALM model to calculate the flash and BVLE
for a binary mixture containing benzene and polyvinylacetate
(PVAC). The van Krevelen group contribution method (VANKRE)
is used to predict the properties of the polymer segment, and the
properties of the polymer are calculated from the segment proper-
ties and the segment composition.
TITLE PROB=ALM
DIMENSION SI
PRINT INPUT = FULL
$
SEGMENT DATA
SEGMENT A, VAC1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 5(1),250(1), 9(1)
$
COMPONENT DATA
LIBRARY 1, BENZENE
POLYMER 2, PVAC
PCOMPOSITION 2, 1(A)
PHASE VLS=2
MWAVG 2, 48200
$
THERMODYNAMIC DATA
METHOD SYSTEM = ALM
KVALUE
ALME 1,A, 0.010,16.36
ALMC A, 1.441
$
STREAM DATA
PROPERTY STRM = F1, TEMP = 298.15, PRES =10.0,
COMP = 1, 0.93166/2, 0.06834
$
UNIT OPERATION
FLASH UID=FL1
FEED F1
PRODUCT V=V1, L=L1
BUBBLE TEMP=298.15
BVLE UID=BVLE1
EVAL COMP=1,2, TEMP(K)=298.15,
XVALUES=0.95,1.0, POINTS=51, PLOT=GAMMA
END
72. P7-8 Specifying the Thermodynamic Method
BATCH
POLYMERS
UNIFAC Free Volume K-Value Method
The UNFV free volume data method is designed to model both
VLE and VLLE for polymer solutions. It should not be used for
non-polymer systems.
Typical Usage
…
SEGMENT DATA
SEGMENT A, IB1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 16(1),4(1)
STRUCTURE(UNIFAC) A, 0900(2),0901(1),0903(1)
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
PCOMPOSITION 2, 1(A)
MWAVG 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=UNFV
…
METHOD Statement
METHOD SYSTEM(VLE or VLLE)=UNFV, PHI=IDEAL,
{HENRY},…
or
Note: When using the UNFV method for polymer systems, UNI-
FAC structural groups must be defined for the polymer segments
via a STRUCTURE(UNIFAC) statement under SEGMENT DATA.
For more information on non-polymer components, see Section
1.9, UNIFAC Structural Groups, of the SIMSCI Component and
Thermodynamic Data Input Manual.
Properties predicted by UNFV K-values
Required pure component
properties*
Molecular weight
Liquid molar volume
van der Waals volume
Suggested application ranges Pressure up to 10 atm
Temperature 70 - 300 F
Two liquid phase behavior Freewater decant not supported
VLLE supported
* Automatically supplied by PRO/II for library and petroleum
components. Must be supplied or estimated using the van Krevelen
group contributions method for polymer components.
73. PRO/II Polymers User Guide P7-9
POLYMERS
METHOD KVALUE(VLE and/or LLE or VLLE)=UNFV,
PHI=IDEAL, {HENRY},…
SYSTEM Selects a combination of compatible thermodynamic
property generators. The available option is:
UNFV When SYSTEM=UNFV is chosen, UNFV
K-values, IDEAL vapor enthalpies, IDEAL liquid
enthalpies, IDEAL liquid densities, and IDEAL vapor
densities are the defaults.
KVALUE Selects the method for K-value calculations. Both
VLE and LLE K-value calculations are available with
the UNFV method. The VLLE option automatically
selects both. See Section 2.1.7, Vapor Liquid-Liquid
Equilibrium Considerations, of the SIMSCI Compo-
nent and Thermodynamic Data Input Manual for more
details on liquid-liquid equilibrium calculations.
PHI Selects the option used to calculate pure component
and mixture vapor phase fugacity coefficients (fi). A
vapor fugacity method should generally be selected for
high pressure applications. The options are the equa-
tions of state methods SRK, PR, SRKM, PRM, SRKH,
PRH, SRKP, PRP, SRKS, SRKKD, BWRS, and UNI-
WAAL (see Section 2.4 of the SIMSCI Component and
Thermodynamic Data Input Manual) and HOCV (the
Hayden-O’Connell method), TVIRIAL (the Trun-
cated Virial method), and the IDIMER method. See
Sections 2.5.12, 2.5.13, and 2.5.14, Hayden-O’Connell
Vapor Fugacity, Truncated Virial Vapor Fugacity, and
IDIMER Vapor Fugacity, of the SIMSCI Thermody-
namic Data Input Manual for details on the last three
options. The default is PHI=IDEAL.
HENRY This option selects Henry’s Law data (either user-sup-
plied or from databanks) to model dissolved gases in a
liquid solution. See Section 2.5.11, Henry’s Law for
Non-condensable Components, of the SIMSCI Ther-
modynamic Data Input Manual for further details.
A heat of mixing option, HMIX, is available for the enthalpy method
selected. See Section 2.5.15, Redlich-Kister, Gamma Heat of Mixing,
of the SIMSCI Thermodynamic Data Input Manual for further
information on using this option.
74. P7-10 Specifying the Thermodynamic Method
BATCH
POLYMERS
Example P7-2: UNIFAC with Polyisobutylene and Benzene
This example uses the UNIFAC free volume method to perform a
VLE flash calculation for a binary mixture containing benzene and
polyisobutylene. The van Krevelen group contribution method
(VANKRE) is used to predict properties of the polymer segment,
and the UNIFAC-FV model (UNFV) is used as the thermodynamic
method for calculating activity coefficients of mixtures. You need
to provide information only on polymer molecular weight and seg-
ment structures for both the van Krevelen and UNIFAC group con-
tribution. The two methods are distinguished by different identifiers
VANKRE and UNIFAC, respectively, in the STRUCTURE statement.
TITLE PROB=UNFV
DIMENSION SI
PRINT INPUT=FULL, RATE=WT, FRACTION=WT
$
SEGMENT DATA
SEGMENT A, IB1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 16(1), 4(1)
STRUCTURE(UNIFAC) A, 0900(2),0901(1),0903(1)
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
PCOMPOSITION 2, 1(A)
MWAVG 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=UNFV
$
STREAM DATA
PROPERTY STRM = F1, TEMP = 400, PRES =10,
COMP = 1, 0.9/2, 0.1
$
UNIT OPERATION
FLASH UID=FL1, NAME=FL1, KPRINT
FEED F1
PRODUCT V=V1, L=L1
ISO TEMP = 400, PRES = 10
$
END
75. PRO/II Polymers User Guide P7-11
POLYMERS
Flory-Huggins Liquid Activity Method
The Flory-Huggins liquid activity method is used to predict VLE
and VLLE phase behavior. This method does not support free water
decant.
The Flory-Huggins liquid activity method is generally useful for
mixtures of components that differ vastly in size, e.g., polymer
solutions. This method should be used only for modeling polymer
systems. See the PRO/II Reference Manual for additional informa-
tion.
Typical Usage
…
SEGMENT DATA
SEGMENT A, IB1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 16(1), 4(1)
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
PCOMPOSITION 2, 1(A)
MWAVG 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=FLORY
Properties predicted by FLORY methods K-values
Required pure component properties* Molecular weight
Liquid molar volume
Solubility parameter
Two liquid phase behavior Freewater decant not
supported
VLLE supported
* Automatically supplied by PRO/II for library and petroleum
components. Must be supplied or estimated using the van Krevelen
group contribution method for polymer components.
76. P7-12 Specifying the Thermodynamic Method
BATCH
POLYMERS
METHOD Statement
METHOD SYSTEM(VLE or VLLE)=FLORY,
PHI=IDEAL,{HENRY},…
or
METHOD KVALUE(VLE and/or LLE or VLLE)=FLORY,
PHI=IDEAL, {HENRY},…
SYSTEM Selects a combination of compatible thermodynamic property
generators. When SYSTEM=FLORY is chosen, FLORY K-values,
IDEAL vapor enthalpies, IDEAL vapor densities, IDEAL liquid
densities, and IDEAL liquid enthalpies are the defaults.
KVALUE Selects the method for K-value calculations. Both VLE and LLE
K-value calculations are available with the Margules method.
The VLLE option automatically selects both. See Section 2.1.7,
Vapor-Liquid-Liquid Equilibrium Considerations, of the SIMSCI
Thermodynamic Data Input Manual for more details on liquid-
liquid equilibrium calculations.
PHI Selects the option used to calculate pure component and mixture
vapor phase fugacity coefficients (φi). A vapor fugacity method
should generally be selected for high pressure applications. The
options are the equations of state methods SRK, PR, SRKM,
PRM, SRKH, PRH, SRKP, PRP, SRKS, SRKKD, BWRS, and
UNIWAAL (see Section 2.4 of the SIMSCI Thermodynamic Data
Input Manual) and HOCV (the Hayden-O’Connell method),
TVIRIAL (the Truncated Virial method), and the IDIMER
method.
See Sections 2.5.12, 2.5.13, and 2.5.14, Hayden-O’Connell Vapor Fugacity,
Truncated Virial Vapor Fugacity, and IDIMER Vapor Fugacity, of the SIMSCI
Thermodynamic Data Input Manual for details on these last three options. The
default is PHI=IDEAL.
HENRY This option selects Henry’s Law data (either user-supplied or
from databanks) to model dissolved gases in a liquid solution.
See Section 2.5.11, Henry’s Law for Non-condensable Compo-
nents, of the SIMSCI Component and Thermodynamic Data Input
Manual for further details.
Note: A heat of mixing option, HMIX, is available for the enthalpy method
selected. See Section 2.5.15, Redlich-Kister, Gamma Heat of Mixing, of the SIM-
SCI Thermodynamic Data Input Manual for further information on the use of
this option.
77. PRO/II Polymers User Guide P7-13
POLYMERS
K-Value Data (optional)
KVALUE(VLE or LLE or VLLE) POYNTING=OFF or ON
CHI or FLORY α, β, a1, a2/…
The binary parameters for polymer segment-solvent systems are
given in Table P7-2.
POYNTING Selects whether to apply the Poynting correction to
fugacities of components in the liquid phase. The
default is OFF unless a PHI method is selected, in
which case the default is ON.
CHI or FLORY Allows entry of the binary temperature-dependent
parameters for the Flory-Huggins liquid activity coef-
ficient method.
The parameter is calculated as:
Missing parameters are estimated from solubility
parameters.
Table P7-2: Parameters for Flory-Huggins Methods
a1 a2
Butadiene PBD Benzene -0.115 124.3
Carbon
Tetrachloride
0.101
Chloroform -0.004
Cyclohexane 0.109 41.23
Dichloromethane 0.295
Ethylbenzene -1.865 819.6
n-Hexane 0.419
n-Nonane -2.309 1124
Ethylene LDPE Butane -4.684 1892
1-Butene -4.609 1844
n-Heptane 0.087 507.4
n-Hexane -1.057 784.5
Isobutane -2.433 1168
χ
χ
χ a1
a2
T
----
-
+
=
χ
χ
79. PRO/II Polymers User Guide P7-15
POLYMERS
Any parameters for homopolymer segment-solvent interactions
not given in Table P7-2 may be derived from Brandrup, J. and
Immergut, E.H., 1989. Polymer Handbook, 3rd Ed., Wiley-Inter-
science, New York.
Carbon disulfide 2.444 1134
Carbon
tetrachloride
-6.331 1960
Chloroform 1.792 -506.8
Cyclohexane 1.355 -185.9
1,4-Dioxane 3.120 -757.4
Ethylbenzene -0.185 223.8
Nitromethane 1.670
n-Nonane -0.166 476.7
n-Propyl acetate 0.274 118.9
Di-n-Propyl ether 0.869
Toluene 0.418
1,2,4-
Trimethylbenzene
0.323
m-Xylene 0.385 -26.35
Tetrahydrofura
n
PTHF 1,4-Dioxane 0.333
Vinyl Acetate PVAC Benzene 0.346 4.916
Vinyl acetate 0.261
Vinyl Chloride PVC 1,4-Dioxane 0.563
Di-n-Propyl ether 0.759
Tetrahydrofuran 0.074
Toluene 0.390
Table P7-2: Parameters for Flory-Huggins Methods
a1 a2
χ
80. P7-16 Specifying the Thermodynamic Method
BATCH
POLYMERS
Example P7-3: Flory-Huggins with Polystyrene and Ace-
tone
This example uses the Flory-Huggins method to perform polymer
VLE flash calculations for a binary mixture containing acetone and
polystyrene. The van Krevelen group contribution method
(VANKRE) is used to predict properties of the polymer component.
TITLE PROJ=FLORY-HUGGINS METHOD
DIMENSION SI
PRINT INPUT = FULL, RATE=WT, FRACTION=WT
$
SEGMENT DATA
SEGMENT A, IB1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 144(1), 4(1)
COMPONENT DATA
LIBID 1, ACETONE
POLYMER 2, POLYSTYRENE
PCOMPOSITION 2, 1(A)
PHASE LS = 2
MWAVG 2, 20000
$
THERMODYNAMIC DATA
METHOD SYSTEM = FLORY
KVALUE
CHI 1,A, 0.729, 65.14
$
STREAM DATA
PROPERTY STRM= F1, TEMP= 400, PRES= 10.,
COMP(W) = 1, 0.9 / 2, 0.1
$
UNIT OP
FLASH UID = FL1, NAME = FL1, KPRINT
FEED F1
PRODUCT V=V1, L=L1
ISO TEMP=400., PRES=10
END
81. PRO/II Polymers User Guide P7-17
POLYMERS
SAFT and PHSC Equations of State
The statistical associating fluid theory equation of state (SAFT) and
the perturbed hard-sphere-chain equation of state (PHSC) are used
to predict VLE and VLLE phase behavior for mixtures containing
polymers. They predict K-values, enthalpies, entropies, and densi-
ties. Compared to commonly-used cubic equations of state, both of
the SAFT and PHSC equations of state are applicable to a wider
variety of systems, including small and medium molecules, as well
as large substances like polymers, and a wider range of fluid condi-
tions including vapor, liquids, and supercritical regions.
The SAFT and PHSC equations of state are especially useful for
polymer solutions and polymer blends. They are also uniquely
applicable to high-pressure polymer-supercritical solvent systems.
They are characterized by a much higher accuracy of VLE and LLE
correlation than any of the existing thermodynamic models for
polymer systems.
Typical Usage
…
SEGMENT DATA
SEGMENT A, IB1, FILL=VANKREVELEN
STRUCTURE(VANKRE)A, 16(1), 4(1)
COMPONENT DATA
LIBID 1, BENZENE
POLYMER 2, PIB
PCOMPOSITION 2, 1(A)
MW 2, 10000
PHASE VLS = 2
THERMODYNAMIC DATA
METHOD SYSTEM=SAFT or PHSC
Properties predicted by SAFT and
PHSC EOS
K-values, enthalpies,
entropies, vapor and liquid
densities
Required pure component properties* Segment size, energy, and
chain length parameters
Non-polymer component size,
energy, and chain length
parameters
Two liquid phase behavior VLLE Supported
* All required pure parameters must be supplied.
82. P7-18 Specifying the Thermodynamic Method
BATCH
POLYMERS
METHOD Statement
METHOD SYSTEM(VLE or VLLE)=SAFT or PHSC
or
METHOD KVALUE(VLE and/or LLE or VLLE)=SAFT
or PHSC
K-Value Data (required)
KVALUE (VLE or LLE or VLLE)
EPSILONα, value / …
SIGMA α, value / …
RMW α, value / …
KIJ α,β, value / …
SYSTEM When SYSTEM=SAFT or PHSC is chosen, K-values,
enthalpies, entropies, liquid densities, and vapor densi-
ties are assumed.
EPSILON Introduces the pure energy parameter ε.
SIGMA Introduces the pure size parameter σ.
RMW Introduces the pure chain length parameter. For non-
polymer components, it is the chain length r. For poly-
mer segments, it is the ratio of the chain length to the
molecular weight r/M.
KIJ Introduces the interaction binary parameters for seg-
ment-segment pairs, segment-solvent pairs, and non-
polymer component pairs. The default value is 0.
α or β Non-polymer component (solvent) number or segment
type letter.
83. PRO/II Polymers User Guide P7-19
POLYMERS
Table P7-3 lists values of the SAFT and PHSC EOS parameters for
common solvents. Table P7-4 lists values of the SAFT and PHSC
EOS parameters for some homopolymer segments. Table P7-5 lists
values of the SAFT EOS binary parameter for some homopolymer
segment-solvent pairs.
.
Table P7-3: SAFT and PHSC Parameters for Common Solvents
SAFT PHSC
Name ε
kB(K)
σ(Å)
size
r
chain
ε
kB(K)
σ(Å)
size
r
chain
Argon 150.9 3.370 1 143.2 3.757 1
Oxygen 126.7 3.480 1.235
Nitrogen 123.5 3.575 1 97.9 3.613 1.340
Carbon dioxide 216.1 3.171 1.417 153.7 2.774 2.859
Normal Alkanes
Methane 190.3 3.700 1 182.1 4.126 1
Ethane 191.4 3.238 1.941 206.3 3.916 1.694
Propane 193.0 3.162 2.696 219.0 3.998 2.129
Butane 195.1 3.093 3.458 231.3 4.085 2.496
Pentane 200.0 3.088 4.091 226.0 3.995 3.149
Hexane 202.7 3.083 4.724 235.6 4.084 3.446
Heptane 204.6 3.067 5.391 225.9 3.947 4.255
Octane 206.0 3.063 6.045 219.6 3.850 5.055
Nonane 203.6 3.063 6.883 217.3 3.804 5.748
Decane 205.5 3.020 7.527 212.7 3.723 6.616
Undecane 215.4 3.754 7.057
Dodecane 205.9 3.032 8.921 214.8 3.733 7.712
Tridecane 218.3 3.794 7.986
Tetradecane 209.4 3.076 9.978 213.7 3.682 9.023
Pentadecane 211.3 3.662 9.851
Hexadecane 210.7 3.068 11.209 214.2 3.703 10.168
Heptadecane 213.7 3.680 10.834
Octadecane 216.5 3.698 11.110
Nonadecane 216.1 3.718 11.659
88. P7-24 Specifying the Thermodynamic Method
BATCH
POLYMERS
References
[1] S. H. Huang and M. Radosz, 1990, Equation of State for Small, Large,
Polydisperse, and Associating Molecules, Ind. Eng. Chem. Res.,
29:2284-2294.
[2] Y. Song, T. Hino, S. M. Lambert, and J. M. Prausnitz, 1996, Liquid-
Liquid Equilibria for Polymer Solutions and Blends, Including Copoly-
mers, Fluid Phase Equilibria, 117:69-76.
[3] C. S. Wu and Y. P. Chen, 1994, Calculation of Vapor-Liquid Equilibria
of Polymer Solution Using the SAFT Equation of State, Fluid Phase
Equilibria, 100:103-119.
89. PRO/II Polymers User Guide P7-25
POLYMERS
Example P7-4: SAFT EOS with PVAC and Benzene
This example uses the SAFT equation of state to perform a vapor-
liquid flash calculation. The system is a binary mixture of PVAC
and benzene.
TITLE=SAFT
DIMENSION SI
PRINT INPUT = ALL
$
SEGMENT DATA
SEGMENT A, VAC1, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 5(1),250(1),9(1)
COMPONENT DATA
LIBRARY 1, BENZENE
POLYMER 2, PVAC
PCOMPOSITION 2, 1.0(A)
MWAVG 2, 12000
PHASE VLS=2
THERMODYNAMIC DATA
METHOD SYSTEM = SAFT
KVALUE
EPSI 1, 250.2/A, 275.1
SIGM 1, 2.993/A, 3.043
RMW 1, 3.749/A, 0.0394
KIJ 1, A, 0.0108
STREAM DATA
PROPERTY STRM = F1, TEMP = 500, PRES = 300, *
COMP = 1, 0.95 /2, 0.05
UNIT OP
FLASH UID=FL1, NAME=FL1, KPRINT
FEED F1
PRODUCT V=V1, L=L1
ISO TEMP = 500, PRES = 300
END
90. P7-26 Specifying the Thermodynamic Method
BATCH
POLYMERS
Example P7-5: PHSC EOS with PVAC and Benzene
This example uses the PHSC equation of state to perform a liquid-
liquid equilibrium calculation. The system is a binary mixture of
PVAC and benzene. The binary parameter kij is set to zero.
TITLE PROJ=PHSC
DIMENSION SI
PRINT INPUT = FULL
$
SEGMENT DATA
SEGMENT A, VAC, FILL=VANKREVELEN
STRUCTURE(VANKRE) A, 5(1),250(1), 9(1)
COMPONENT DATA
LIBRARY 1, BENZENE
POLYMER 2, PVAC
PCOMPOSITION 2, 1.0(A)
PHASE VLS = 2
MWAVG 2, 48000
THERMODYNAMIC DATA
METHOD SYSTEM (VLLE) = PHSC
KVALUE
EPSI 1, 291.6/A, 292.6
SIGM 1, 3.958/A, 3.346
RMW 1, 2.727/A, 0.05166
STREAM DATA
PROPERTY STRM = F1, TEMP = 298.15, PRES = 100.,
COMP = 1, 0.9996 / 2,0.0004
UNIT OP
FLASH UID=FL1, NAME=FL1, KPRINT
FEED F1
PRODUCT V=V1, L=L1, W=W1
ISOT TEMP=298.15, PRES=100.
END
