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Synthesis of Polymers Steps MIT PDF
Synthesis of Polymers Steps MIT PDF
Rp = rate of polymerization
−d ⎡⎣M ⎤⎦ −d ⎡⎣a⎤⎦ −d ⎡⎣b⎤⎦
Rp = = = = k ⎡⎣a⎤⎡
⎦⎣b⎤⎦
dt dt dt
a
Assume r =1, where r is the stoichiometric ratio. r =
b
⎡⎣a⎤⎦ = ⎡⎣b⎤⎦
⎣⎡a⎦⎤o
Terminology pn varies with t → pn =
⎣⎡a⎦⎤
( Xn ) p. 50
−d ⎡⎣a⎤⎦ 2
= k ⎡⎣a⎤⎦
dt
−d ⎡⎣a⎤⎦
2
= kt
⎡⎣a⎤⎦
1 1
− = kt
⎡⎣a⎤⎦ ⎡⎣a⎤⎦o
⎡⎣a⎤⎦o ⎡a⎤
− 1 = ⎡⎣a⎤⎦o kt π =1− ⎣ ⎦
⎡⎣a⎤⎦ ⎡⎣a⎤⎦o
in book, π = p (p. 46)
⎡⎣a⎤⎦o 1
=
⎡⎣a⎤⎦ 1 − π
1
⎡⎣ao ⎤⎦ kt = − 1 = pn − 1
1− π
Notes:
1
1. ⎡⎣M ⎤⎦ ∝ as time ↑, concentration of monomer ↓
t
2. pn increases linearly with time
kf kf >> kr
a+b c+d LeChatlier’s Principle: remove water
kr To drive reaction forward
Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 course materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date
Making esters:
O
Keq
COOH + OH C O + H2O
⎡COO⎤⎦ ⎡⎣H2O⎤⎦
Keq = ⎣
⎣⎡COOH ⎦⎣
⎤⎡OH ⎦⎤
Assume at t = 0 : ⎡⎣M ⎤⎦ = ⎡⎣M ⎤⎦o
Put in terms of π:
⎣⎡COO⎦⎤ = π ⎡⎣COOH ⎦⎤o = π ⎡⎣OH ⎦⎤o = π ⎡⎣M ⎦⎤o
[OH ] = “ “
⎣⎡COOH ⎦⎤ = ⎡⎣OH ⎦⎤ = ⎣⎡M ⎤⎦o − π ⎡⎣M ⎦⎤o = ⎡⎣M ⎦⎤o (1 − π )
( π ⎡⎣M ⎤⎦ )
2
o
K =
⎡⎣M ⎤⎦o (1 − π )
2 2
π2
K =
(1 − π )
2
1
K2
π= 1
In closed system, limited by K (reaction constant).
1+ K 2
1
1
pn = = 1 + K2
1− π
where pn is the # average degree of polymerization (# of units in polymer)
Polyesterification: K: 1 ∼ 10
pn ∼ 2 - 5 monomers
Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 course materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date
O O
COH + OH C O + H2O
1 π ⎣⎡H2O⎦⎤eq
K = ⋅ ⋅
1 − π 1 − π ⎡⎣M ⎤⎦o
1
pn =
1− π
π 1 1− π 1
= − = − 1 = pn − 1
1− π 1− π 1− π 1− π
⎡H2O⎤eq
(
K = pn ⋅ pn − 1 ) ⎣ ⎡⎣M ⎤⎦⎦
o
⎣⎡M ⎦⎤o K
⎣⎡H2O⎦⎤eq = only get down to a certain water concentration
(
pn pn − 1 )
→ solve for best p n possible
O OH
k1
COH + HA C OH
k2 +
-
Acid A
More active than COOH
catalyst
⎡ OH ⎤
⎢ C OH ⎥
⎢ + - ⎥
= 1 =⎣ ⎦
k A
K12
k2 [HA][COOH ]
OH OH
k3
Slow step
C OH + OH C OH
+ k4 - (rate-determining step)
- A +
A OH
Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 course materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date
..
OH O
..
.. k5
C OH
.. C O + H2O + HA
- k6
A +
OH catalyst regeneration
− d [COOH ]
Rp = Rate of disappearance of carboxylic monomer
dt
−d ⎣⎡COOH ⎦⎤
Rp = = k ' ⎣⎡COOH ⎦⎣
⎤⎡OH⎤⎦ where k ' = k3 K12 ⎣⎡HA⎦⎤ constant
dt
−d ⎡⎣COOH ⎤⎦ 2
Rp = = k " ⎡⎣COOH ⎤⎦ ⎡⎣OH⎤⎦ where k " = k3 K12
dt
−d ⎡⎣M ⎤⎦ 3
Rp = = k " ⎣⎡M ⎦⎤ separate and integrate
dt
1 1
2k "t = 2
− 2
⎡⎣M ⎤⎦ ⎡⎣M ⎤⎦o
1
(p )
2 2
= = 2 ⎡⎣M ⎤⎦o k 't + 1
(1 − π )
n 2
High Temperature
- increase k
- remove byproduct (evaporate H2O)
Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 course materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date
- viscosity η low until high π
- direct processing
Use solvent
- monomers are not miscible with each other but miscible with solvent
- allow high T
- dilute viscous media (carrier for viscous media)
→ improves processing
- improves heat and mass transfer
Citation: Professor Paula Hammond, 10.569 Synthesis of Polymers Fall 2006 course materials, MIT
OpenCourseWare (http://ocw.mit.edu/index.html), Massachusetts Institute of Technology, Date