高乙烯基聚丁二烯橡胶
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o
o
30 C
30 C
o
o
0 C
0 1 0 2 0 3 0 4 0 5 0
o
0 C
o
2? ()
o
10
20
2? ( )
o
30
40
(EtO)2PH=O CIAC
(PhO)3P=O
21
Molecular Parameters
Microstructures Run
℃ ML1+4100℃
Tg, ℃ HVBR (CIAC) SL553k (JSR) VSL5525 (JSR) 66 70 52 -23 -50 -11
17
100
50 C 80
50 C
o
o
0.8
o
40 C
o
40 C
30 C
o
0.6
Yield (%)
-ln(1-X)
60 30 C 40
o
0.4
0.2
20 C
o
20
20 C
0.0
o
0 0 50 100 150 200 250 300
0
50
100
150
200
250
Time (min)
t (min)
CIAC
+
(1) (2)
Fe(0) + C4H10 + C4H8
Et Et
O
O
Al(iBu)3
2 Fe
O
P
Al(iBu)3 Et
2 O Fe
iBu
+
O
O
+ Fe 2
Et
O
Et
iBu O Et
O
Et
iBu
The proposed structure of the active site
CIAC
20
50 C
50 C
13
6 5
DEP/Fe molar ratio
4 atactic 1,2-PBD 3 2 syndiotactic 1,2-PBD 1 0 10
15
20
25
30
Al/Fe molar ratio
CIAC
14
a C3 n C3 C4 b C4
1
2
3
c 150 145 140 120 115 110
高乙烯基聚丁二烯橡胶
张学全
xqzhang@ciac.jl.cn
中国科学院长春应用化学研究所
CIAC
1
高乙烯基聚丁二烯橡胶 通用轮胎橡胶中以顺丁橡胶滚动阻力最 低（顺丁橡胶中稀土顺丁滚动阻力最低，抗 顺丁橡胶中稀土顺丁滚动阻力最低， 湿滑性能也稍好），但其抗湿滑性差（ 湿滑性能也稍好），但其抗湿滑性差（主要 ），但其抗湿滑性差 作为胎侧胶使用）；丁苯橡胶（胎面和胎体） 作为胎侧胶使用）；丁苯橡胶（胎面和胎体） ）；丁苯橡胶 抗湿滑性虽好，但其滚动阻力大，生热高。 抗湿滑性虽好，但其滚动阻力大，生热高。 乙烯基橡胶是集低滚动阻力、 乙烯基橡胶是集低滚动阻力、低生热和良好 的抗湿滑性于一身的理想轮胎胎面胶。 的抗湿滑性于一身的理想轮胎胎面胶。
CIAC
2
Vinyl PB
CIAC
3
抗湿滑性
生热性
CIAC
4
Fe-based Catalyst FeFe3+ + Al(R)3 → Fe0 (inactive) Fe3+ + Al(R)3 + Donor → ?
Problems
Relatively low activity and stereoselectivity Microstructure sensitive to polym. conditions Low polym. Temp. required
10
20
30
40
50
2? ()
o
Al/Fe = 10 (a), 20 (b) and 30 (c) (mol/mol).
CIAC
15
Atactic PB (high viny polybutadiene rubber)
SynSyn- PB with medium crystallinity (mp: 90-150℃) 90-150℃
9
Tm
oC
(mol%) (mol%)
177.4 180.1 189.0
CIAC
(OR)2
CIAC
10
CIAC
11
CIAC
12
Bd polymerization with different addition order of catalyst component Addition order BD+Fe+P+Al BD+Al+P+Fe BD+(Fe+Al)+P BD+(Fe+P)+Al CIAC Yield (%) 82.8 71.0 NP 76.5 1,2(%) 95.0 95.0 ---95.2 1,4(%) 5.0 5.0 ---4.8
Bidentated Nitrogen-containing NitrogenCompounds
N
Et Fe
N
N
Et
N
CIAC in 1980s, by Wang, F. S. et. al. PB with ca. 40-50% cis-1,4 and 40-45% 1,2-units with good cured properties Allyl-Cl as effective Mw agent PI with up to 70% 3,4-units, crystalline difficulty to indus. Appl.
SynSyn- PB with high crystallinity (mp: 150-210℃) 150-210℃
CIAC
16
Fe3+- AlR3- Phosphite —Polymerization Characteristics
Polymerization temperature High Temp. favarable Tp ↑→ Mw ↑ and MWD ↓ Tp ↑→ atactic → syndiotactic Tm ↑, ∆H ↑ CIAC
1,2-% 83 39 39
St-% 0 24 24
CIAC
22
硫化胶性能
CIAC
23
动态力学和生热行为
CIAC
24
0.6 0.5 0.4
HVBR/NR
Tan δ
0.3
SSBR/NR
0.2 0.1 -120 -100 -80 -60 -40 -20
O
0
20
40
60
80
100
T ( C)
CIAC
CIAC
26
sPB的性能与应用 的性能与应用 光降解性
CIAC
27
CIAC
28
CIAC
29
CIAC
30
平面 之字型正交堆积
CIAC
31
“Lath“Lath-like” structure from the solution-cast film solutionCIAC
sPB spherulite from bulk
32
Coexisting spherulite and singlesingle-faceted crystals CIAC
Hexagonal prismatic sPB single crystal
33
18
600 Mn×10 -3 g/mol
→
←
3.5
400
2.5
200 -20
1.5 0 20 40 Temp.(℃) 60 80
CIAC
Mw/Mn
19
-1/2C4H8 Fe(acac)3 + Al(iBu)3 (iBu)2Fe + Al(acac)3 -1/2C4H10 (iBu)2Fe
Et Et
25
间同1,2-聚丁二烯的生产 聚丁二烯的生产 间同 JSR
15-25%， 75- 中低结晶度 （15-25%，Tm: 75-90 ℃) - 催化体系 CoX2－AlR3－H2O /Ph3P，（MePh）3 P 等 ，（MePh） MePh 溶剂：卤代烷烃（ - 溶剂：卤代烷烃（CH2Cl2） - 专利：107篇 专利：107篇 产量：4.5万吨 - 产量：4.5万吨 • Ube ℃） - 高结晶度 （ Tm: 206 ℃） Co（acac） - 催化体系 Co（acac）3-AlEt3-CS2 少量生产？ - 少量生产？
CH3 CΒιβλιοθήκη Baidu2 P
OCH2CH3 OCH2CH3 OCH2CH3 OCH2CH3 O
CH3CH2O P
P O O P O
8
O P O
O
Different phosphorus compounds on the 1,3-butadiene 1,3polymerization with Fe(2-EHA)3-Al(i-Bu)3 catalyst Fe(2Al(iPhosphorus compound
CIAC
7
Phosphites as donors — Recent work in CIAC
RO P RO OH RO RO PH O
O H P O
OCH2CH3 OCH2 CH3 CH3CH2 P O CH3CH2O P
CH2CH3 CH2CH3 OCH2CH3 OCH2CH3
S. Luo first reported dialkyl phosphite (DAP) as ED in 2001. We have studied DAPs in different structure in details. Our own phosphits as CIAC ED (patented).
Potentialities
Versatility in polymer chain structure Continuous R&D on new electron donors Still highlighted in both olefin and diene polym.
CIAC
CIAC
6
Triphenyl phosphine Triethyl phosphite Triphenyl phosphite Diethyl phosphite Diphenyl phosphite Diethylethyl phosphonate Triethyl phosphate Tributyl phosphate Triphenyl phosphate (C6H5)3P (C2H5O)3P (C6H5O)3P (C2H5O)2P(O)H (C6H5O)2P(O)H (C2H5O)2P(O)C2 H5 (C2H5O)3P(O) (C4H9O)3P(O) (C6H5O)3P(O) Yield (wt%) oligomer oligomer oligomer 85.0 75.0 oligomer oligomer oligomer 82.8 1,2 90.9 84.8 95.0 1,4 9.1 15.2 5.0
o
30 C
30 C
o
o
0 C
0 1 0 2 0 3 0 4 0 5 0
o
0 C
o
2? ()
o
10
20
2? ( )
o
30
40
(EtO)2PH=O CIAC
(PhO)3P=O
21
Molecular Parameters
Microstructures Run
℃ ML1+4100℃
Tg, ℃ HVBR (CIAC) SL553k (JSR) VSL5525 (JSR) 66 70 52 -23 -50 -11
17
100
50 C 80
50 C
o
o
0.8
o
40 C
o
40 C
30 C
o
0.6
Yield (%)
-ln(1-X)
60 30 C 40
o
0.4
0.2
20 C
o
20
20 C
0.0
o
0 0 50 100 150 200 250 300
0
50
100
150
200
250
Time (min)
t (min)
CIAC
+
(1) (2)
Fe(0) + C4H10 + C4H8
Et Et
O
O
Al(iBu)3
2 Fe
O
P
Al(iBu)3 Et
2 O Fe
iBu
+
O
O
+ Fe 2
Et
O
Et
iBu O Et
O
Et
iBu
The proposed structure of the active site
CIAC
20
50 C
50 C
13
6 5
DEP/Fe molar ratio
4 atactic 1,2-PBD 3 2 syndiotactic 1,2-PBD 1 0 10
15
20
25
30
Al/Fe molar ratio
CIAC
14
a C3 n C3 C4 b C4
1
2
3
c 150 145 140 120 115 110
高乙烯基聚丁二烯橡胶
张学全
xqzhang@ciac.jl.cn
中国科学院长春应用化学研究所
CIAC
1
高乙烯基聚丁二烯橡胶 通用轮胎橡胶中以顺丁橡胶滚动阻力最 低（顺丁橡胶中稀土顺丁滚动阻力最低，抗 顺丁橡胶中稀土顺丁滚动阻力最低， 湿滑性能也稍好），但其抗湿滑性差（ 湿滑性能也稍好），但其抗湿滑性差（主要 ），但其抗湿滑性差 作为胎侧胶使用）；丁苯橡胶（胎面和胎体） 作为胎侧胶使用）；丁苯橡胶（胎面和胎体） ）；丁苯橡胶 抗湿滑性虽好，但其滚动阻力大，生热高。 抗湿滑性虽好，但其滚动阻力大，生热高。 乙烯基橡胶是集低滚动阻力、 乙烯基橡胶是集低滚动阻力、低生热和良好 的抗湿滑性于一身的理想轮胎胎面胶。 的抗湿滑性于一身的理想轮胎胎面胶。
CIAC
2
Vinyl PB
CIAC
3
抗湿滑性
生热性
CIAC
4
Fe-based Catalyst FeFe3+ + Al(R)3 → Fe0 (inactive) Fe3+ + Al(R)3 + Donor → ?
Problems
Relatively low activity and stereoselectivity Microstructure sensitive to polym. conditions Low polym. Temp. required
10
20
30
40
50
2? ()
o
Al/Fe = 10 (a), 20 (b) and 30 (c) (mol/mol).
CIAC
15
Atactic PB (high viny polybutadiene rubber)
SynSyn- PB with medium crystallinity (mp: 90-150℃) 90-150℃
9
Tm
oC
(mol%) (mol%)
177.4 180.1 189.0
CIAC
(OR)2
CIAC
10
CIAC
11
CIAC
12
Bd polymerization with different addition order of catalyst component Addition order BD+Fe+P+Al BD+Al+P+Fe BD+(Fe+Al)+P BD+(Fe+P)+Al CIAC Yield (%) 82.8 71.0 NP 76.5 1,2(%) 95.0 95.0 ---95.2 1,4(%) 5.0 5.0 ---4.8
Bidentated Nitrogen-containing NitrogenCompounds
N
Et Fe
N
N
Et
N
CIAC in 1980s, by Wang, F. S. et. al. PB with ca. 40-50% cis-1,4 and 40-45% 1,2-units with good cured properties Allyl-Cl as effective Mw agent PI with up to 70% 3,4-units, crystalline difficulty to indus. Appl.
SynSyn- PB with high crystallinity (mp: 150-210℃) 150-210℃
CIAC
16
Fe3+- AlR3- Phosphite —Polymerization Characteristics
Polymerization temperature High Temp. favarable Tp ↑→ Mw ↑ and MWD ↓ Tp ↑→ atactic → syndiotactic Tm ↑, ∆H ↑ CIAC
1,2-% 83 39 39
St-% 0 24 24
CIAC
22
硫化胶性能
CIAC
23
动态力学和生热行为
CIAC
24
0.6 0.5 0.4
HVBR/NR
Tan δ
0.3
SSBR/NR
0.2 0.1 -120 -100 -80 -60 -40 -20
O
0
20
40
60
80
100
T ( C)
CIAC
CIAC
26
sPB的性能与应用 的性能与应用 光降解性
CIAC
27
CIAC
28
CIAC
29
CIAC
30
平面 之字型正交堆积
CIAC
31
“Lath“Lath-like” structure from the solution-cast film solutionCIAC
sPB spherulite from bulk
32
Coexisting spherulite and singlesingle-faceted crystals CIAC
Hexagonal prismatic sPB single crystal
33
18
600 Mn×10 -3 g/mol
→
←
3.5
400
2.5
200 -20
1.5 0 20 40 Temp.(℃) 60 80
CIAC
Mw/Mn
19
-1/2C4H8 Fe(acac)3 + Al(iBu)3 (iBu)2Fe + Al(acac)3 -1/2C4H10 (iBu)2Fe
Et Et
25
间同1,2-聚丁二烯的生产 聚丁二烯的生产 间同 JSR
15-25%， 75- 中低结晶度 （15-25%，Tm: 75-90 ℃) - 催化体系 CoX2－AlR3－H2O /Ph3P，（MePh）3 P 等 ，（MePh） MePh 溶剂：卤代烷烃（ - 溶剂：卤代烷烃（CH2Cl2） - 专利：107篇 专利：107篇 产量：4.5万吨 - 产量：4.5万吨 • Ube ℃） - 高结晶度 （ Tm: 206 ℃） Co（acac） - 催化体系 Co（acac）3-AlEt3-CS2 少量生产？ - 少量生产？
CH3 CΒιβλιοθήκη Baidu2 P
OCH2CH3 OCH2CH3 OCH2CH3 OCH2CH3 O
CH3CH2O P
P O O P O
8
O P O
O
Different phosphorus compounds on the 1,3-butadiene 1,3polymerization with Fe(2-EHA)3-Al(i-Bu)3 catalyst Fe(2Al(iPhosphorus compound
CIAC
7
Phosphites as donors — Recent work in CIAC
RO P RO OH RO RO PH O
O H P O
OCH2CH3 OCH2 CH3 CH3CH2 P O CH3CH2O P
CH2CH3 CH2CH3 OCH2CH3 OCH2CH3
S. Luo first reported dialkyl phosphite (DAP) as ED in 2001. We have studied DAPs in different structure in details. Our own phosphits as CIAC ED (patented).
Potentialities
Versatility in polymer chain structure Continuous R&D on new electron donors Still highlighted in both olefin and diene polym.
CIAC
CIAC
6
Triphenyl phosphine Triethyl phosphite Triphenyl phosphite Diethyl phosphite Diphenyl phosphite Diethylethyl phosphonate Triethyl phosphate Tributyl phosphate Triphenyl phosphate (C6H5)3P (C2H5O)3P (C6H5O)3P (C2H5O)2P(O)H (C6H5O)2P(O)H (C2H5O)2P(O)C2 H5 (C2H5O)3P(O) (C4H9O)3P(O) (C6H5O)3P(O) Yield (wt%) oligomer oligomer oligomer 85.0 75.0 oligomer oligomer oligomer 82.8 1,2 90.9 84.8 95.0 1,4 9.1 15.2 5.0