Equation 3. Rate laws for polyolefin formation with BIP FeCl 2 /MAO
At low [MAO]:
d½C 2 H 4 =dt ¼ k½C 2 H 4
1 ½MAO
1 ½BIP FeCl 2
1
(3a)
At high(er) [MAO]:
d½C 2 H 4 =dt ¼ k½C 2 H 4
1 ½MAO
0À x
½BIP FeCl 2
1 ðx > 0Þ
(3b)
The rate constants k p of ethylene polymerization with MAO- and AlR 3 -activated
iron complexes have been evaluated by quenching with
14 CO [61]. Carbon monoxide has been shown to react with iron alkyls and form carbonyl-terminated polymer
chains. The radioactivity in the polymer product was used to calculated the number
Table 1 Selected data on BIP FeCl 2 catalytic action, dependence on iron, ethylene and aluminum
concentration
Parameter/Ref. Catalyst
Amount
(μmol)
T (˚C)
p ethylene
(bar)
Ratio
Al/Fe
Rate/activity/
productivity
(min
−1
)
Fe
[50]
1/MAO
0.07
25
2
10,000
0.02
[50]
1/MAO
0.34
25
2
10,000
0.1
Parameter/Ref. Catalyst
Amount
(μmol)
T (˚C)
p ethylene
(bar)
Ratio
Al/Fe
Rate/activity/
productivity
[kg/(mol Fe bar h)]
Ethylene
[48]
2/MAO/TIBA
0.57
50
2
100
5,260
[48]
2/MAO/TIBA
0.57
50
4
100
4,780
[48]
2/MAO/TIBA
0.57
50
6
100
4,980
Parameter/Ref. Catalyst
Amount
(μmol)
T (˚C)
p ethylene
(bar)
Ratio
Al/Fe
Rate/activity/
productivity
[kmol/(mol Fe h)]
Ethylene
[30]
2/MMAO
0.6
60
14
4,800
[30]
2/MMAO
0.5
60
28
7,000
[30]
2/MMAO
0.5
60
41
11,800
Parameter/Ref. Catalyst
Amount
(μmol)
T (˚C)
p ethylene
(bar)
Ratio
Al/Fe
Rate/activity/
productivity
[kg/(mol Fe h)]
Al
[51]
3/MMAO
1.5
20
10
1,000
2,450
[51]
3/MMAO
1.5
20
10
2,000
5,340
[51]
3/MMAO
1.5
20
10
3,000
8,400
[51]
3/MMAO
1.5
20
10
4,000
4,840
1: BI
Cl2 P FeCl 2 , 2: BI
iPr2 P FeCl 2 , MMAO modified MAO, 3: BI
Et2ðp-MeÞ P FeCl 2 +DBM: 2,4dibenzhydryl-6-methyl phenyl is one of the aryl entities
350
R.S.A. Meyer and G.A. Luinstra
At low [MAO]:
d½C 2 H 4 =dt ¼ k½C 2 H 4
1 ½MAO
1 ½BIP FeCl 2
1
(3a)
At high(er) [MAO]:
d½C 2 H 4 =dt ¼ k½C 2 H 4
1 ½MAO
0À x
½BIP FeCl 2
1 ðx > 0Þ
(3b)
The rate constants k p of ethylene polymerization with MAO- and AlR 3 -activated
iron complexes have been evaluated by quenching with
14 CO [61]. Carbon monoxide has been shown to react with iron alkyls and form carbonyl-terminated polymer
chains. The radioactivity in the polymer product was used to calculated the number
Table 1 Selected data on BIP FeCl 2 catalytic action, dependence on iron, ethylene and aluminum
concentration
Parameter/Ref. Catalyst
Amount
(μmol)
T (˚C)
p ethylene
(bar)
Ratio
Al/Fe
Rate/activity/
productivity
(min
−1
)
Fe
[50]
1/MAO
0.07
25
2
10,000
0.02
[50]
1/MAO
0.34
25
2
10,000
0.1
Parameter/Ref. Catalyst
Amount
(μmol)
T (˚C)
p ethylene
(bar)
Ratio
Al/Fe
Rate/activity/
productivity
[kg/(mol Fe bar h)]
Ethylene
[48]
2/MAO/TIBA
0.57
50
2
100
5,260
[48]
2/MAO/TIBA
0.57
50
4
100
4,780
[48]
2/MAO/TIBA
0.57
50
6
100
4,980
Parameter/Ref. Catalyst
Amount
(μmol)
T (˚C)
p ethylene
(bar)
Ratio
Al/Fe
Rate/activity/
productivity
[kmol/(mol Fe h)]
Ethylene
[30]
2/MMAO
0.6
60
14
4,800
[30]
2/MMAO
0.5
60
28
7,000
[30]
2/MMAO
0.5
60
41
11,800
Parameter/Ref. Catalyst
Amount
(μmol)
T (˚C)
p ethylene
(bar)
Ratio
Al/Fe
Rate/activity/
productivity
[kg/(mol Fe h)]
Al
[51]
3/MMAO
1.5
20
10
1,000
2,450
[51]
3/MMAO
1.5
20
10
2,000
5,340
[51]
3/MMAO
1.5
20
10
3,000
8,400
[51]
3/MMAO
1.5
20
10
4,000
4,840
1: BI
Cl2 P FeCl 2 , 2: BI
iPr2 P FeCl 2 , MMAO modified MAO, 3: BI
Et2ðp-MeÞ P FeCl 2 +DBM: 2,4dibenzhydryl-6-methyl phenyl is one of the aryl entities
350
R.S.A. Meyer and G.A. Luinstra