CN1352202A - Double nuclear nickel olefine polymerization catalyst - Google Patents
Double nuclear nickel olefine polymerization catalyst Download PDFInfo
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- CN1352202A CN1352202A CN 01140469 CN01140469A CN1352202A CN 1352202 A CN1352202 A CN 1352202A CN 01140469 CN01140469 CN 01140469 CN 01140469 A CN01140469 A CN 01140469A CN 1352202 A CN1352202 A CN 1352202A
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Abstract
The present invention discloses a kind of double-nuclear nickel catalyst for olefine polymerization. After being activated by methyl aluminium alkoxide or modified methyl aluminium alkoxide, the catalyst may be used in ethylene polymerization to prepare branched polyethylene.
Description
Technical field: the present invention relates to a kind of olefin polymerization catalysis, its preparation method and the application in catalysis in olefine polymerization.
Background technology: polyolefine is the important macromolecular material of a class, accounts for 50% of plastics, is widely used in industry, agricultural, national defence, communications and transportation and the daily life.Alkene is under the effect of catalyzer, and polymerization reaction take place generates macromolecular compound, i.e. polyolefine.Catalyzer is the core of polyolefin industry development, is the key of control polyolefin structure and performance.Usually, prepare branched polyethylene with the method for ethene and an amount of alpha-olefin copolymer, as linear low density polyethylene (LLDPE).
Late transition metal catalyst for olefin polymerization is the new catalyst that development in recent years is got up, and particularly the organic nickel catalyzer is only used a kind of monomer of ethene, by changing the polyethylene with various branched structures that polymerizing condition can obtain to comprise LLDPE.The Phillips oil company disclosed a kind of pyridine imine nickel olefin polymerization catalyst (US Pat.5,932,670) in 1999, and under the homogeneous condition, catalyzed ethylene can get oligopolymer, under heterogeneous conditions, and the catalyzed ethylene weight northylen that can secure satisfactory grades.
Summary of the invention: the purpose of this invention is to provide a kind of double-core pyridine imine nickel catalyzator, this method for preparing catalyst is easy; Under the activation of methylaluminoxane (MAO), modified methylaluminoxane neutral Lewis acid such as (MMAO), easily obtain the high-molecular weight branched polyethylene during catalyzed ethylene polymerization.
Double nuclear nickel olefine polymerization catalyst disclosed by the invention has following structure:
R in the formula
1Be H or methyl; R
2And R
3Can be identical or different, be respectively methyl or sec.-propyl; R
4And R
5Can be identical or different, be respectively H, methyl, ethyl, butyl or R
4And R
5Form a ring; X, Y can be identical or different, are respectively Cl, Br or acetylacetone based.Under the activation of methylaluminoxane or modified methylaluminoxane, this catalyzer can be used for the catalyzed ethylene polymerization for preparing branched polyethylene.The preparation process of double nuclear nickel olefine polymerization catalyst disclosed by the invention is as follows:
HCOOH or CF
3Under the effect of COOH, in alcoholic solution, carry out the condensation reaction of the replacement aryl diamine shown in 2-formyl radical pyridine or 2-acetylpyridine and the following formula,
Obtain the western Buddhist alkali shown in the following formula,
R in the formula
1Be H or methyl; R
2And R
3Can be identical or different, be respectively methyl or sec.-propyl; R
4And R
5Can be identical or different, be respectively H, methyl, ethyl, butyl or R
4And R
5Form a ring; Under the anhydrous and oxygen-free condition, carry out the coordination reaction of above-mentioned western Buddhist alkali and Nickel Chloride or Nickel Bromide or diacetyl acetone nickel, obtain the olefin polymerization catalysis shown in the following formula,
R in the formula
1Be H or methyl; R
2And R
3Can be identical or different, be respectively methyl or sec.-propyl; R
4And R
5Can be identical or different, be respectively H, methyl, ethyl, butyl or R
4And R
5Form a ring; X, Y can be identical or different, are respectively Cl, Br or acetylacetone based.
Double-core nickel disclosed by the invention is under the effect of neutral Lewis acid such as MAO or MMAO, but catalyzed ethylene polymerization prepares high molecular weight branched polyethylene.
Embodiment is as follows:
Embodiment 1
In exsiccant 100ml reaction flask, add 4 in 2-acetylpyridine 1.82g (15.0mmol), two (4-amino-2,6-diisopropyl benzene) methane 2.75g (7.50mmol), methyl alcohol 15ml, formic acid, room temperature reaction 24h.Filtration, ethyl alcohol recrystallization, 60 ℃ of vacuum-drying 48h get faint yellow western Buddhist alkali (C
39H
48N
4) 2.92g, yield 68%.
Embodiment 2
With the 2-acetylpyridine among 2-formyl radical pyridine 1.72g (15.0mmol) the replacement embodiment 1, operation gets faint yellow western Buddhist alkali (C with embodiment 1
37H
44N
4) 3.18g, yield 78%.
Embodiment 3
With two (4-amino-2, the 6-diisopropyl benzene) methane among two (4-amino-2-methyl-6-isopropyl benzene) methane 2.33g (7.50mmol) replacement embodiment 1, operation gets faint yellow western Buddhist alkali (C with embodiment 1
35H
40N
4) 2.45g, yield 63%.
Embodiment 4
Use 2 respectively, 2-two (4-amino-2,6-isopropyl benzene) propane 2.96g (7.50mmol) and trifluoroacetic acid replace two (4-amino-2,6-diisopropyl benzene) methane and the formic acid among the embodiment 1, and operation gets faint yellow western Buddhist alkali (C with embodiment 1
41H
52N
4) 2.75g, yield 61%.
Embodiment 5
With 1,1-two (4-amino-2,6-isopropyl benzene) hexanaphthene 3.26g (7.50mmol) replaces two (4-amino-2, the 6-diisopropyl benzene) methane among the embodiment 1, and operation gets faint yellow western Buddhist alkali (C with embodiment 1
41H
56N
4) 3.17g, yield 66%.
Embodiment 6
With 2,2-two (4-amino-2,6-isopropyl benzene) phenylethane 3.42g (7.50mmol) replaces two (4-amino-2, the 6-diisopropyl benzene) methane among the embodiment 1, and operation gets faint yellow western Buddhist alkali (C with embodiment 1
46H
54N
4) 3.13g, yield 63%.
Embodiment 7
With 2,2-two (4-amino-2,6-isopropyl benzene) butane 3.07g (7.50mm0l) replaces two (4-amino-2, the 6-diisopropyl benzene) methane among the embodiment 1, and operation gets faint yellow western Buddhist alkali (C with embodiment 1
42H
54N
4) 3.00g, yield 65%.
Embodiment 8
Under the nitrogen protection, in exsiccant 50ml Schlenk bottle, add NiBr
20.437g (2.0mmol), anhydrous CH
2Cl
210ml, glycol dimethyl ether (DME) 0.19g stir 15min, add western Buddhist alkali 0.573g (1.0mmol), the anhydrous CH of embodiment 1 preparation
2Cl
25ml, back flow reaction 8h.Cooling, placement is spent the night, and filters, and precipitation is washed three times with a small amount of ether, and 60 ℃ of vacuum-drying 24h get khaki color double-core pyridine imine Ni (II) title complex 0.71g, yield 70%.
Embodiment 9
Use NiBr
20.259g (2.0mmol) NiBr among the replacement embodiment 8
2, operation gets khaki color double-core pyridine imine Ni (II) title complex 0.56g, yield 67% with embodiment 8.
Embodiment 10
Under the nitrogen protection, in exsiccant 50ml Schlenk bottle, add western Buddhist alkali 0.573g (1.0mmol), the anhydrous CH of diacetyl acetone nickel 0.514g (2.0mmol), embodiment 1 preparation
2Cl
215ml, back flow reaction 8h.Cooling, placement is spent the night, and filters, and precipitation is washed three times with a small amount of ether, and 60 ℃ of vacuum-drying 24h get khaki color double-core pyridine imine Ni (II) title complex 0.62g, yield 57%.
Embodiment 11
With chloro acetylacetonate nickel 0.385g (2.0mmol), operation gets khaki color double-core pyridine imine Ni (II) title complex 0.59g, yield 62% with embodiment 10.
Embodiment 12
The western Buddhist alkali that the western Buddhist alkali 0.545g (1.0mmol) for preparing with embodiment 2 replaces embodiment 1 to prepare, operation gets khaki color double-core pyridine imine Ni (II) title complex 0.80g, yield 72% with embodiment 8.
Embodiment 13
The western Buddhist alkali that the western Buddhist alkali 0.545g (1.0mmol) for preparing with embodiment 3 replaces embodiment 1 to prepare, operation gets khaki color double-core pyridine imine Ni (II) title complex 0.80g, yield 72% with embodiment 8.
Embodiment 14
The western Buddhist alkali that the western Buddhist alkali 0.601g (1.0mmol) for preparing with embodiment 4 replaces embodiment 1 to prepare, operation gets khaki color double-core pyridine imine Ni (II) title complex 0.75g, yield 64% with embodiment 8.
Embodiment 15
The western Buddhist alkali that the western Buddhist alkali 0.641g (1.0mmol) for preparing with embodiment 5 replaces embodiment 1 to prepare, operation gets khaki color double-core pyridine imine Ni (II) title complex 0.80g, yield 66% with embodiment 8.
Embodiment 16
The western Buddhist alkali that the western Buddhist alkali 0.663g (1.0mmol) for preparing with embodiment 6 replaces embodiment 1 to prepare, operation gets khaki color double-core pyridine imine Ni (II) title complex 0.77g, yield 62% with embodiment 8.
Embodiment 17
The western Buddhist alkali that the western Buddhist alkali 0.615g (1.0mmol) for preparing with embodiment 7 replaces embodiment 1 to prepare, operation gets khaki color double-core pyridine imine Ni (II) title complex 0.82g, yield 69% with embodiment 8.
Embodiment 18
Under the ethene atmosphere, in 0.5 liter of autoclave of exsiccant, add double-core nickel catalyzator 1.0 μ mol, the absolute toluene 200ml of embodiment 8 preparations, stirring and dissolving, be warming up to 40 ℃, modified methylaluminoxane (MMAO) 5ml that adds 2.3M, pressurization, polyase 13 0min under the 1.0Mpa.Ethanol solution hydrochloride with 1% stops polyreaction, filters, and 60 ℃ of vacuum-drying 24h get polymkeric substance 15.8g, catalytic efficiency 1.58 * 10
4KgPE/molNih.Embodiment 19
The double-core nickel catalyzator that the double-core nickel catalyzator for preparing with embodiment 9 replaces embodiment 8 to prepare, operation gets polymkeric substance 14.4g, catalytic efficiency 1.44 * 10 with embodiment 18
4Kg PE/mol Nih.
Embodiment 20
The double-core nickel catalyzator that the double-core nickel catalyzator for preparing with embodiment 10 replaces embodiment 8 to prepare, operation gets polymkeric substance 17.5g, catalytic efficiency 1.75 * 10 with embodiment 18
4Kg PE/molNih.
Embodiment 21
The double-core nickel catalyzator that the double-core nickel catalyzator for preparing with embodiment 11 replaces embodiment 8 to prepare, operation gets polymkeric substance 16.3g, catalytic efficiency 1.63 * 10 with embodiment 18
4Kg PE/molNih.
Embodiment 22
The double-core nickel catalyzator that the double-core nickel catalyzator for preparing with embodiment 12 replaces embodiment 8 to prepare, operation gets polymkeric substance 12.3g, catalytic efficiency 1.23 * 10 with embodiment 18
4Kg PE/molNih.
Embodiment 23
The double-core nickel catalyzator that the double-core nickel catalyzator for preparing with embodiment 13 replaces embodiment 8 to prepare, operation gets polymkeric substance 9.7g, catalytic efficiency 9.7 * 10 with embodiment 18
3Kg PE/molNih.
Embodiment 24
The double-core nickel catalyzator that the double-core nickel catalyzator for preparing with embodiment 14 replaces embodiment 8 to prepare, operation gets polymkeric substance 14.1g, catalytic efficiency 1.41 * 10 with embodiment 18
4Kg PE/molNih.
Embodiment 25
The double-core nickel catalyzator that the double-core nickel catalyzator for preparing with embodiment 15 replaces embodiment 8 to prepare, operation gets polymkeric substance 13.6g, catalytic efficiency 1.36 * 10 with embodiment 18
4Kg PE/molNih.
Embodiment 26
The double-core nickel catalyzator that the double-core nickel catalyzator for preparing with embodiment 16 replaces embodiment 8 to prepare, operation gets polymkeric substance 11.9g, catalytic efficiency 1.19 * 10 with embodiment 18
4Kg PE/molNih.
Embodiment 27
The double-core nickel catalyzator that the double-core nickel catalyzator for preparing with embodiment 17 replaces embodiment 8 to prepare, operation gets polymkeric substance 13.1g, catalytic efficiency 1.31 * 10 with embodiment 18
4Kg PE/molNih.
Claims (5)
1. double nuclear nickel olefine polymerization catalyst, it has following structure:
R in the formula
1Be H or methyl; R
2And R
3Can be identical or different, be respectively methyl or sec.-propyl; R
4And R
5Can be identical or different, be respectively H, methyl, ethyl, butyl or R
4And R
5Form a ring; X, Y can be identical or different, are respectively Cl, Br or acetylacetone based.
2. according to the described double nuclear nickel olefine polymerization catalyst of claim 1, wherein, R
1It is methyl; R
2And R
3Be sec.-propyl; R
4And R
5Can be identical or different, be respectively H or methyl; X and Y are Cl or Br.
3. according to the described double nuclear nickel olefine polymerization catalyst of claim 1, wherein, R
1It is methyl; R
2And R
3Be sec.-propyl; R
4And R
5Form a ring; X and Y are Cl or Br.
4. method for preparing the described double nuclear nickel olefine polymerization catalyst of claim 1:
HCOOH or CF
3Under the effect of COOH, in alcoholic solution, carry out the condensation reaction of the replacement aryl diamine shown in 2-formyl radical pyridine or 2-acetylpyridine and the following formula,
Obtain the western Buddhist alkali shown in the following formula,
R in the formula
1Be H or methyl; R
2And R
3Can be identical or different, be respectively methyl or sec.-propyl; R
4And R
5Can be identical or different, be respectively H, methyl, ethyl, butyl or R
4And R
5Form a ring;
Under the anhydrous and oxygen-free condition, carry out the coordination reaction of above-mentioned western Buddhist alkali and Nickel Chloride or Nickel Bromide or diacetyl acetone nickel, obtain the double nuclear nickel olefine polymerization catalyst shown in the following formula,
R in the formula
1Be H or methyl; R
2And R
3Can be identical or different, be respectively methyl or sec.-propyl; R
4And R
5Can be identical or different, be respectively H, methyl, ethyl, butyl or R
4And R
5Form a ring; X, Y can be identical or different, are respectively Cl, Br or acetylacetone based.
5. the method for a synthesizing polyethylene is comprising using the described double nuclear nickel olefine polymerization catalyst of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011404698A CN1169844C (en) | 2001-12-10 | 2001-12-10 | Double nuclear nickel olefine polymerization catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011404698A CN1169844C (en) | 2001-12-10 | 2001-12-10 | Double nuclear nickel olefine polymerization catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1352202A true CN1352202A (en) | 2002-06-05 |
| CN1169844C CN1169844C (en) | 2004-10-06 |
Family
ID=4675889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011404698A Expired - Fee Related CN1169844C (en) | 2001-12-10 | 2001-12-10 | Double nuclear nickel olefine polymerization catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1169844C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006104528A1 (en) * | 2005-03-28 | 2006-10-05 | Albemarle Corporation | Diimines and secondary diamines |
| EP1753773B1 (en) * | 2004-05-26 | 2010-03-24 | ExxonMobil Chemical Patents Inc. | Transition metal compounds for olefin polymerization and oligomerization |
| US7964695B2 (en) | 2005-03-28 | 2011-06-21 | Albemarle Corporation | Chain extenders |
| US8076518B2 (en) | 2005-03-28 | 2011-12-13 | Albemarle Corporation | Chain extenders |
| CN105732486A (en) * | 2016-04-19 | 2016-07-06 | 中国科学技术大学 | Pyridine imine compound and preparation method thereof, pyridine imine nickel catalyst and preparation method thereof and polyolefin |
| CN112159433A (en) * | 2020-04-14 | 2021-01-01 | 北京服装学院 | Pyridohexatomic ring binuclear-metal complex, preparation method thereof and application thereof in ethylene polymerization |
-
2001
- 2001-12-10 CN CNB011404698A patent/CN1169844C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1753773B1 (en) * | 2004-05-26 | 2010-03-24 | ExxonMobil Chemical Patents Inc. | Transition metal compounds for olefin polymerization and oligomerization |
| US7741240B2 (en) | 2004-05-26 | 2010-06-22 | Exxonmobil Chemical Patents Inc. | Transition metal compounds for olefin polymerization and oligomerization |
| WO2006104528A1 (en) * | 2005-03-28 | 2006-10-05 | Albemarle Corporation | Diimines and secondary diamines |
| US7288677B2 (en) | 2005-03-28 | 2007-10-30 | Albemarle Corporation | Diimines and secondary diamines |
| US7767858B2 (en) | 2005-03-28 | 2010-08-03 | Albemarle Corporation | Diimines and secondary diamines |
| US7964695B2 (en) | 2005-03-28 | 2011-06-21 | Albemarle Corporation | Chain extenders |
| US8076518B2 (en) | 2005-03-28 | 2011-12-13 | Albemarle Corporation | Chain extenders |
| US8080626B2 (en) | 2005-03-28 | 2011-12-20 | Albemarle Corporation | Chain extenders |
| US8212078B2 (en) | 2005-03-28 | 2012-07-03 | Albemarle Corporation | Diimines and secondary diamines |
| CN105732486A (en) * | 2016-04-19 | 2016-07-06 | 中国科学技术大学 | Pyridine imine compound and preparation method thereof, pyridine imine nickel catalyst and preparation method thereof and polyolefin |
| CN112159433A (en) * | 2020-04-14 | 2021-01-01 | 北京服装学院 | Pyridohexatomic ring binuclear-metal complex, preparation method thereof and application thereof in ethylene polymerization |
| CN112159433B (en) * | 2020-04-14 | 2023-08-01 | 北京服装学院 | Pyrido six-membered ring binuclear-metal complex, preparation method thereof and application thereof in ethylene polymerization |
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| Publication number | Publication date |
|---|---|
| CN1169844C (en) | 2004-10-06 |
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