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Ethene oligomerization and polymerization post transition metal complex catalyst

A late transition metal, coordination catalyst technology, applied in the directions of organic chemistry, hydrocarbons, hydrocarbons, etc., can solve the problems of complex synthesis steps and preparation methods, and achieve easy mass production, simple preparation, and good stability. Effect

Inactive Publication Date: 2003-03-12
INST OF CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the synthesis steps and preparation methods of the above-mentioned catalysts are relatively complicated, and the catalytic activity is between 10 4 to 10 6 g ethylene / (mole Ni·hour)

Method used

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  • Ethene oligomerization and polymerization post transition metal complex catalyst
  • Ethene oligomerization and polymerization post transition metal complex catalyst
  • Ethene oligomerization and polymerization post transition metal complex catalyst

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] 2,9-bis(2,6-diisopropylphenylimino)-1,10-phenanthroline (L 1 ) preparation of catalyst:

[0019] Under nitrogen protection, 2,9-diformyl-phenanthroline (1.0g, 4.2mmol) was dissolved in absolute ethanol solution (120mL), then 3 drops of acetic acid were added, then the temperature was raised to reflux, and stirred for half an hour A solution of 2,6-diisopropylaniline (4.0 g, 20 mmol) in absolute ethanol (15 mL) was added dropwise. After the dropwise addition, continue to stir and reflux for 5 hours, cool to room temperature, and evaporate most of the solvent under reduced pressure. The product mother liquor is placed in the refrigerator overnight, and 1.56 g of yellow crystals are precipitated, yield: 62%. m.p.269-270℃; IR(KBr): 3063(s), 2962(s), 1639(vs), 1586(s), 1550, 1499, 1462(m), 1383, 1363, 1251, 1182, 1086, 933(m), 860, 756(s). 1 H NMR (CDCl 3 ): δ1.18 (24H, d, J = 10.2Hz), 3.05 (4H, m), 7.15-7.23 (6H, m), 7.99 (2H, s), 8.47 (2H, d, J = 7Hz), 8.75 (2H, d, J=...

Embodiment 2

[0025] Ligand 2,9-bis(2,6-dimethylphenylimino)-1,10-phenanthroline (L 2 ) preparation: utilize synthetic ligand 2 in the embodiment 1, 9-two (2,6-diisopropylphenylimino)-1,10-o-phenanthroline (L 1 ) method, 2,9-diformyl o-phenanthroline and 2,6-dimethylaniline react to obtain yellow solid 2,9-bis(2,6-dimethylanilimino)-1,10 -O-phenanthroline, yield: 58%.m.p.132-133°C.IR (KBr):3449m 3325(m), 3018(m), 2969,2918(m), 1636(vs), 1591,1550( s), 1500, 1474, 1442(s), 1192, 1088(s), 861, 762(s). 1 H NMR (CDCl 3 )δ2.18 (12H, s), 6.94-7.14 (6H, m), 8.05 (2H, s), 8.42-8.52 (2H, d), 8.75-8.86 (4H, m); EI-MS (m / z): 442 (M + , 100%), 441 (39.5%), 427 (14.9%), 424 (16.7%), 337 (28.4%), 324 (18.2%), 323 (53.2%), 322 (14.1%), 311 (25.2 %), 310 (64.7%), 309 (14.3%), 308 (11.4%), 296 (14.1%), 295 (10.5%), 132 (13.5%); Anal. Calcd. For C 30 h 26 N 4 1 / 2H 2 O: C, 79.79; H, 6.03; N, 12.41. Found: C, 79.86%; H, 6.41; N, 12.13%.

[0026] Preparation of 2,9-bis(2,6-dimethylphenylimino)-1,10-p...

Embodiment 3

[0030] Ligand 2,9-bis(2,4,6-trimethylphenylimino)-1,10-phenanthroline (L 3 ) preparation: Utilize the synthetic ligand 2,9-bis(2,6-diisopropylphenylimino)-1,10-phenanthroline (L 1 ) method, 2,9-diformyl-phenanthroline and 2,4,6-trimethylaniline were reacted to obtain a yellow solid, yield: 77%. m.p.166-167℃; IR(KBr): 3394(br), 1724(s), 1633(vs), 1553(m), 1499, 1480(s), 1208(s), 854(s); 1 H NMR (CDCl 3 ): δ2.06(12H, s), 2.23(6H, s), 6.85(4H, m), 7.90(2H, s), 8.38(2H, d); 8.43-8.86(4H, m); FAB- MS (m / z): 471 (M + +1);Anal.Calcd.For C 32 h 30 N 4 h 2 O·H 2 O: C, 78.66; H, 6.60; N, 11.47. Found: C, 78.29%; H, 6.31; N, 11.06%.

[0031] Preparation of 2,9-bis(2,4,6-trimethylbenimino)-1,10-phenanthroline iron complex (3): Synthesis of 2,9-bis( 2,6-diisopropylphenylimino)-1,10-phenanthroline iron method, using the ligand 2,9-bis(2,4,6-trimethylphenylimino)- 1,10-Phenanthroline and FeCl 2 4H 2 O reaction gives green solid, yield: 91% yield.m.p. > 320 ℃.IR: 1610 (s), 1570 (...

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Abstract

A post-transition metal coordination catalyst for ethylene oligomerization and polymerization is disclosed. It is halogenated 2,9-bis(imino)-1,10-orthophenanthralloline Fe, Ni and Co complexes. Its advantages are simple preparing process, easy purification, and high stability.

Description

Technical field: [0001] The present invention relates to a class of ethylene oligomerization and post-polymerization transition metal coordination catalysts. Background technique: [0002] Catalytic ethylene oligomerization can produce linear olefins on a large scale. The products are important organic chemical intermediates and have become an independent branch of the petrochemical industry. Catalyzed ethylene polymerization can obtain polymer materials with different properties and uses. In recent years, the research on late transition metal olefin polymerization and oligomerization catalysts has developed rapidly (Angew. Chem. Int. Ed. 1999, 38, 428-447; Chem. Rev. 2000, 100, 1169-1203). [0003] Since the 1970s, the homogeneous catalysis of olefin polymerization and oligomerization by transition metal complexes has attracted people's attention, and people have made great efforts to study new catalysts and improve existing catalysts to improve the activity of catalysts a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C2/22C08F4/42C08F10/02
Inventor 孙文华王乐勇韩玲芹胡友良李秀华
Owner INST OF CHEM CHINESE ACAD OF SCI
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