Via Method of Moments

Presented by: F. Tikhani – M. Habibi – M. Irannezhad – K.Farajzadeh

Polymerization Process Engineering Project | Dr. Najafi
Tehran University Faculty of Engineering | 2 Jan 2018
Mechanism & Stages

κίνησις
Vs.
 Stage I: Pure Monomer Mixture 0 < x < 0.1%

 Stage II: Monomer-rich & Polymer-rich Phases 0.1% < x < xf

 Stage III: Polymer Phase Swollen with Monomer xf < x < 1.0

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 Two Phase
Scheme for VCM
Polymerization
Radical Radical
Formation in Formation in
Monomer Phase Polymer Phase

Radical Migration
Chain Chain
Propagation in Propagation in
Monomer Phase Polymer Phase
Monomer Migration
Chain Chain
Termination in Termination in
Monomer Phase Polymer Phase

Polymer

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 𝐾𝑑𝑗
A. Initiation: 𝐼 2𝐼∗
𝐾𝑖𝑗
Kd 6.32 × 1016 exp (-15460/T) min-1 𝐼∗ +𝑀 𝑅1
𝑟𝑑 = 𝑟𝑑1 𝜙1 + 𝑟𝑑2 𝜙2
The Overall Initiator Consumption Rate:
𝑟𝑑𝑗 = 𝑘𝑑𝑗 𝐼𝑗
𝐼 = 𝐼1 𝜙1 + 𝐼2 𝜙2
𝑑𝐼1
Mass Balance for Initiator: Stage I: ൗ𝑑𝑡 = −𝑘𝑑1 𝐼1 ; 𝐼1 0 = 𝐼0

Stage II: 𝑑𝐼Τ = −𝑘𝑑1 𝐼1 − 𝑘𝑑2 𝐼2

𝑑𝑡
𝑑𝐼2
Stage III: ൗ𝑑𝑡 = −𝑘𝑑2 𝐼2
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B. Propagation: 𝐾𝑝𝑗
𝑅𝑥 + 𝑀 𝑅𝑥+1
Kp Kp0 exp [0.2(1/Vf – 1/Vfcr)]
Kp0 3 × 109 exp (-3320/T) L/(mol.min)
𝑟𝑝 = 𝑟𝑝1 𝜙1 + 𝑟𝑝2 𝜙2
The Overall Monomer Consumption Rate: 𝑟𝑝𝑗 = 𝑘𝑝𝑗 𝑀𝑗 ෍ [𝑅𝑥𝑗 ]
𝑥

𝑑𝑀1
Stage I: ൗ𝑑𝑡 = −𝑘𝑝1 𝑀1 σ𝑥[𝑅𝑥1 ] ; 𝑀 0 = 𝑀0
Mass Balance for Monomer:
Stage II: 𝑑𝑀Τ = −𝑘𝑝1 [𝑀1 ] σ𝑥 𝑅𝑥1 − 𝑘𝑝2 [𝑀2 ] σ𝑥[𝑅𝑥2 ]
𝑑𝑡
𝑑𝑀2
Stage III: ൗ𝑑𝑡 = −𝑘𝑝2 [𝑀2 ] σ𝑥[𝑅𝑥2 ]

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C. Transfer:
Ktm 5.78 exp (-2768/T)Kp
Ktp 0.32 Ktm (at 50 ֯C)
Kb 0.0115 ktm (at 50 ֯C)

𝐾𝑡𝑚𝑗
 To Monomer: 𝑅𝑥 + 𝑀 𝑃𝑥 + 𝑅1
𝐾𝑡𝑝𝑗
 To Polymer: 𝑅𝑥 + 𝑃𝑦 𝑃𝑥 + 𝑅𝑦
𝐾𝑏𝑗
 Intramolecular: 𝑅𝑥 𝑅𝑥
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D. Termination:

𝐾𝑡𝑑𝑗
Kt1 7.8 × 1013 exp (-2190/T) L/(mol.min) 𝑅𝑥 + 𝑅𝑦 𝑃𝑥 + 𝑃𝑦
Kt2 Kt20 ((1- xf )/(1- x ))2 (Kp/Kp0)2 𝐾𝑡𝑐𝑗
Kt20 Kt1/P2 𝑅𝑥 + 𝑅𝑦 𝑃𝑥+𝑦

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 Parameters Values
Reactor Type Batch
Temperature (T) 323 (K)
Pressure (P) 27.0 + 0.14 (T- 273.16)
Volume (V0) 10 (L)
Initiator Concentration [I0] 0.2 (mol)
Monomer Concentration [M0] 25.25 (mol)

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 1 𝑥=1
𝑓 𝑥 =ቊ
0 𝑥>1

 Live Polymer Chains:

∗
𝑟𝑥𝑗

= 2𝑓𝑗𝑘𝑑𝑗 𝐼𝑗 + 𝑘𝑡𝑚𝑗 𝑀𝑗 ෍ 𝑅𝑥𝑗 𝑓 𝑥 − 𝑘𝑝𝑗 𝑀𝑗 𝑅𝑥𝑗 − 𝑘𝑡𝑚𝑗 𝑀𝑗 𝑅𝑥𝑗 − 𝑘𝑡𝑗 𝑅𝑗 ෍ 𝑅𝑥𝑗

𝑥 𝑥

+ 𝑘𝑝𝑗𝑀𝑗 𝑅𝑥−1,𝑗 1 − 𝑓 𝑥 − 𝑘𝑡𝑝𝑗( 𝑅𝑥𝑗 ෍ 𝑥 𝑃𝑥 − 𝑥 𝑃𝑥 ෍ 𝑅𝑥𝑗 )(1 − 𝑗)

𝑥 𝑥

 Dead Polymer Chains:

𝑟𝑥 = ෍ 𝑘𝑡𝑚𝑗 𝑀𝑗 𝑅𝑥𝑗 − ෍ [ 𝑘𝑡𝑗 𝑅𝑥𝑗 ෍ 𝑅𝑥𝑗 ] + 𝑘𝑡𝑝2( 𝑅𝑥2 ෍ 𝑥 𝑃𝑥 − 𝑥[𝑃𝑥] ෍ 𝑅𝑥2 )

𝑗 𝑗 𝑥 𝑥 𝑥

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How to develop and use them…
 Leading moments of live and dead polymer distributions:
[λij] = σ𝑥 𝑥i[Rxj] j = 1,2
[μi] = σ𝑥 𝑥i[Px] i=0,1,2,….

 Corresponding reaction rates leading moments of live and dead polymer

distributions:
(r𝞴)ij = σ𝑥 𝑥irxj* = 2fjkdj[Ij] + ktmj[Mj]([λ0j] – [λij]) + kpj[Mj]i[λi-1,j]
– ktj[λ0j][λij] – ktpj([μ1][λij] – [μi+1][λ0j])(1 – j)

(r𝞵)I = σxirx = σj(ktmj[Mj][λij]) + σj(ktj[λ0j][λij] + ktp2([μ1][λ i2] – [μi+1][λ 02])

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 (r𝞴)0j = ∑ 𝑥r0j* = (2fjkdj[Ij] + ktmj[Mj]∗ 0 ∗f(x)
– kpj[Mj]∗ 0 – ktmj[Mj] *0
– ktj∑ [Rxj] σ𝑥[𝑅xj]
+ kpjMj*0*[1-f(x)]
– ktpj(0* σ𝑥 𝑥[𝑝x]
– ∑ x[Px](0)(1– j)

(r𝞴)0j = 2fjkdj[Ij]– ktj[λ0j]2

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 (r𝞴)1j = ∑ 𝑥r1j* = (2fjkdj[Ij]
+ ktmj[Mj] σ𝑥 𝑥[𝑅xj])f(x) – kpj[Mj]∑ [Rxj]
– ktmj[Mj] ∑ [Rxj] – ktj∑ [Rxj] σ𝑥 𝑥[𝑅xj]
+ kpjMj i∑ [Rx-1,j][1-f(x)]
– ktpj(∑ [Rxj] σ𝑥 𝑥[𝑝x]
– ∑ x[Px]( σ𝑥 𝑥[𝑅xj])(1 – j)

(r𝞴)1j = 2fjkdj[Ij] + ktmj[Mj]([λ0j] – [λ1j]) + kpj[Mj] [λ0,j]

– ktj[λ0j][λ1j] – ktpj([μ1][λ0j] – [μ2][λ0j])(1 – j)
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 (r𝞵)1 = ∑ 𝑥rx = σ𝑗(𝑘tmj[Mj] ∑ x[Rxj])
+ σ𝑗[𝑘tj∑ x[Rxj]( σ𝑥 𝑥[𝑅xj])]
+ ktp2(∑ [Rx2] ∑x2[Px]
– ∑x[Px] σ𝑥 𝑥[𝑅x2])

(r𝞵)1 = ∑j(ktmj[Mj][λ1j]) + ∑j(ktj[λ0j][λ1j]

+ ktp2([μ1][λ12] – [μ2][λ 02])
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 Moment balances for live polymer radicals:
dλ01/dt = 2f1kd1I1 – kt1λ012/V1
dλ11/dt = 2f1kd1I1 – kt1λ01λ11/V1 + ktm1[M1](λ01 – λ11) + kp1[M1]λ01
dλ21/dt = 2f1kd1I1 – kt1λ01λ 21/V1 + ktm1[M1](λ01 – λ11) + kp1[M1]λ11

 Moment balances for dead polymer radicals:

dμ0/dt = ktm1 M1[λ01] + kt1[λ01]2V1
dμ1/dt = ktm1 M1[λ11] + kt1[λ01][λ11]V1
dμ2/dt = ktm1 M1[λ21] + kt1[λ01][λ21]V1

 Fractional monomer conversion: dx/dt = kp1(1 – x)[λ01]

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 Moment balances for live polymer radicals:
dλ0j/dt = 2fjkdjIj – ktjλ0j2/Vj + (-1)j F([λ01],[λ02])
dλ1j/dt = 2fjkdjIj – ktjλ0jλ1j/Vj + ktmj[Mj])λ0j – λ1j) + kpj[Mj]λ0j
– ktpj(μ1λ1j/Vj – μ2λ0j/Vj)(1 – j ) + (-1)j F([λ11],[λ12])

dλ2j/dt = 2fjkdjIj – ktjλ0jλ 2j/Vj + ktmj[Mj])λ0j – λ2j) + 2kpj[Mj]λ1j

– ktpj(μ1λ2j/Vj – μ3λ0j/Vj)(1 – j ) + (-1)j F([λ21],[λ22])
 Moment balances for dead polymer radicals:
dμ0/dt = σj(ktmj[Mj]λ0j) + σj ktjλ0j2/Vj)
dμ1/dt = σj(ktmj[Mj]λ1j) + σj(ktjλ0jλ1j/Vj) + ktp2(μ1la12/V2 – μ2λ02/V2)
dμ2/dt = σj(ktmj[Mj]λ2j) + σj(ktjλ0jλ2j/Vj) + ktp2(μ1λ22/V2 – μ3λ02/V2)

 Fractional monomer conversion: dx/dt = kp1[λ01](1 - x – Ax) + kp2[λ02]Ax

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 2fjkdj[Ij] + ktmj[Mj] σ𝑥 𝑥 [𝑅xj])f(x) – kpj[Mj]∑ x[Rxj]
– ktmj[Mj] ∑x [Rxj] – ktj∑x [Rxj] σ𝑥 𝑥 [𝑅xj] + kpjMj i∑x [Rx-1,j][1-f(x)]
– ktpj(∑x [Rxj] σ𝑥 𝑥 2 [𝑝x] – σ𝑥 𝑥 2 [𝑝x]( σ𝑥 𝑥[𝑅xj]))(1 – j)
μ3 μ3

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𝑑(μ2−λ22)
=
𝑑𝑡

σ𝒋(𝒌tmj[Mj]𝞴2j) + σ𝒋(𝒌tj 𝞴0j𝞴2j/Vj) + ktp2(𝞵1𝞴22/V2 – 𝞵3𝞴02/V2)

- {2f2kd2I2 – kt2λ02λ 22/V2 + ktm2[M2])λ02 – λ22) + 2kp2[M2]λ12

+ ktp2(μ1λ 22/V2 – μ3λ 02/V2)}

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 𝑑(λ22) QSSA 𝑑(μ2−λ22) 𝑑(μ2)
=0 =
𝑑𝑡 𝑑𝑡 𝑑𝑡

𝑑(μ2)
= σ𝒋(𝒌tmj[Mj]𝞴2j) + σ𝒋(𝒌tj 𝞴0j𝞴2j/Vj) - {2f2kd2I2 – kt2λ02λ22/V2 +
𝑑𝑡
ktm2[M2])λ02 – λ22) + 2kp2[M2]λ12}

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 Moment balances for live polymer radicals:
dλ02/dt = 2f2kd2I2 – kt2λ022/V2
dλ12/dt = 2f2kd2I2 – kt2λ02λ12/V2 + ktm2[M2])λ02– λ12) + kp2[M2]λ02 – ktpj(μ1λ12/V2 – μ2λ 02/V2)
dλ22/dt = 2f2kd2I2 – kt2λ02λ22/V2 + ktm2[M2])λ02– λ22) + 2kp2[M2]λ12 – ktpj(μ1λ22/V2 – μ3λ02/V2)

 Moment balances for dead polymer radicals:

dμ0/dt = ktm2[M2]λ02) + 𝑘t2λ022/V2
dμ1/dt =𝑘tm2[M2]λ12) + 𝑘t2λ02λ12/V2) + ktp2(μ1λ12/V2 – μ2λ02/V2)
dμ2/dt =𝑘tm2[M2]λ22) + 𝑘t2λ02λ22/V2) + ktp2(μ1λ22/V2 – μ3λ02/V2)

 Fractional monomer conversion: dx/dt = kp2(1 – x)[λ02]

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 Instantaneous number-average chain length:
xnj = (dμ1j/dt)/( dμ0j/dt)

 Instantaneous weight-average chain length:

xwj = (dμ2j/dt)/( dμ1j/dt)

 Cumulative weight- and number-average chain lengths:

Xn = μ1/ μ0
Xw = μ2/ μ1

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 Average number of long branches per polymer chain:
d(μ0Ln)/dt = M0(ktp/kp)[x/(1 – x)]dx/dt

 Average number of short branches per polymer chain:

dSn/dt = kbλ0

Long Chain Branching:

LCB = 1000(Ln μ0/μ1)

Short Chain Branching:

SCB = 1000(Sn μ0/μ1)
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Via MathWorks MATLAB®
 Coding Flowchart Matrix dy1 (1×17) & dt Initial Values Start

yp & yc
Increment with dt

dt=2dt Yes No Yes dt=dt/2

|yi-yc|<0.001 |yi-yc|>0.1yi
Calculate yc Calculate yc
No
Yes
y(i+1)=yc y(ii+1)=y(i)
dy1=dy2 t(i+1)=t(i)+dt i-ii=1000? i=ii+1
i=i+1 ii=i
No

Yes
No No No Yes
t=te? dy1=dy3 y<xc? y<0.001?
Yes

Display Values & Plots End

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  y(12)=MIU 0;
 y(6)=LANDA 01;  y(13)=MIU 1;
 y(1)=I1
 y(7)=LANDA 11;  y(14)=MIU 2;
 y(2)=I2
 y(8)=LANDA 21;
 y(3)=M1
 y(9)=LANDA 02;  y(15)=T;
 y(4)=M2
 y(10)=LANDA 12;  y(16)=Ln;
 y(5)=X
 y(11)=LANDA 22;  y(17)=Sn;

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27
28
29
30
31
With Conclusion!
 Semi-Batch Feeding
if i-ii==1000
y(:,ii+1)=y(:,i);
 Fight Against Time (Step size Control) i=ii+1;
ii=i;

 Fight Against Memory

Error: Requested 17x62546342 (7.9GB) array exceeds maximum array size preference. Creation of
arrays greater than this limit may take a long time and cause MATLAB to become unresponsive. See
array size limit or preference panel for more information.

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 Plot of Conversion

(min)

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 Plot of Mn
(g/mol)

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 Plot of PDI

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 Plot of d32 Zerfa and Brooks; 1996

d32(1)=0.0002243 m
d32(i)=0.0002113 m

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 Present Model Papers Model

(min)
V For
Validation 38
[1] Methods of Moments A versatile Tool for Deterministic Modeling of Polymerization Kinetics;
Erlita Mastan, Shiping Zhu; European Polymer Journal; 2015

[2] Mathematical Modeling of PVC Suspension Polymerization; E. SIDIROPOULOU and C.

KIPARISSIDES; Journal Journal of Macromolecular Science; 1990.

[3] Suspension, Bulk, and Emulsion Polymerization of Vinyl Chloride-Mechanism, Kinetics, and
Reactor Modelling; XIE et al; 1991

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Answering
Questions…

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