CN101108884A - Imine compound activated iron polyolefin catalyzer - Google Patents
Imine compound activated iron polyolefin catalyzer Download PDFInfo
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- CN101108884A CN101108884A CNA2007100703539A CN200710070353A CN101108884A CN 101108884 A CN101108884 A CN 101108884A CN A2007100703539 A CNA2007100703539 A CN A2007100703539A CN 200710070353 A CN200710070353 A CN 200710070353A CN 101108884 A CN101108884 A CN 101108884A
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Abstract
The invention discloses an iron catalysts for polyolefine activated by the imine compounds, which comprises bridge-linked bis (imino) pyridyl compound in the structural formula (I) of the instruction book and FeAA or acetylacetone ferrous iron and MAO or alkyl aluminium compound. When carrying out the polymerization of the polyethylene, the high molecular weight polyethylene with molecular weight distribution from the singlet to the doublet can be gained by changing the polymerization condition. In the polyethylene with doublet distribution, the small molecular weight is obviously smaller than the occupied proportion of the large molecular weight, that is, the large molecular weight is dominant. The doublet molecular weight distribution can embody the good processability and can keep stronger mechanical property.
Description
Technical field
The present invention relates to a kind of polyolefin catalyst, relate in particular to a kind of imine compound activated iron polyolefin catalyzer.
Background technology
The article of Brookhart in 1998 " Highly Active Iron and Cobalt Catalysts for thePolymeriza tion of Ethylene " (" J Am Chem Soc ", 1998,120 (16): 4049-4050.), the article of Gibson " Novel Olefin Polymerization Catalysts Based on Iron andCobalt " (" Chem Commun ", 1998,7:849-850.) reported new pyridine diimine iron series catalysts respectively, under the activation of methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), can the highly active catalytic vinyl polymerization.When the promotor consumption is increased to a certain degree, can obtain broad peak even bimodal polyethylene.Under normal pressure, this type of Fe-series catalyst activity is not too high, and the gained molecular weight of polyethylene is also lower, though molecular weight of polyethylene presents bimodal distribution, low molecular weight part is preponderated.
Along with continuing to bring out of new technology and product innovation, market is increasing to the demand of polyethylene (PE), but simultaneously also to the PE performance as: the requirement of strength and toughness and resisting environmental stress and cracking (ESCR) is more and more higher.Improve these performances that relative molecular mass can improve PE.As prepare average molecular mass (Mw weight average relative molecular weight) above 2 * 10
5High molecular weight high density polyethylene(HDPE) (HMW-HDPE), but, when increasing the relative molecular mass of PE, because melt flow rate (MFR) (MFR) is low, processing characteristics (as molding, extrude, thermoforming and rotational molding performance) also descends thereupon, bimodal PE (be made up of high molecular and low molecular weight polyethylene, its GPC curve presents bimodal) can address this problem well.The bimodal polyethylene product is made up of High molecular weight polyethylene and low molecular weight polyethylene two portions, and wherein High molecular weight polyethylene is in order to guarantee physical mechanics intensity, and low molecular weight polyethylene is in order to improve processing characteristics.
U.S. Pat 5955555 discloses the Fe-series catalyst that contains pyridine diimine can prepare linear polyethylene, Chinese patent CN1431236 discloses a kind of catalyzer for preparing bimodal polyethylene, but two patents are two catalytic systems, used metal source is, the halogenide of metal, not relating to not, the acetylacetone based iron cpd and the three component iron of halogen atom are catalyst system.
Summary of the invention
The invention provides a kind of imine compound activated iron polyolefin catalyzer, the polyethylene iron that can be used for preparing broad peak or bimodal molecular weight distribution is catalyst system.
A kind of imine compound activated iron polyolefin catalyzer comprises following (A), (B) and (C) three kinds of components:
(A) divalence or ferric iron compound specifically are ferric acetyl acetonade Fe (acac)
3Or the ferrous (Fe (acac) of methyl ethyl diketone
2);
(B) have the bridging pyridine diimine compound of structural formula (I):
R in the structural formula (I)
1Be H or methyl; R
2, R
3, R
4, R
5, R
8Respectively do for oneself methyl, ethyl or sec.-propyl; And R
1=R
1', R
2=R
2', R
3=R
3', R
4=R
4', R
5=R
5', R
8=R
8';
R
6And R
7Respectively do for oneself H, methyl, ethyl, butyl, phenyl or trifluoromethyl; Perhaps R
6And R
7Be connected to ring structure;
(C) methylaluminoxane (MAO) or alkylaluminium cpd; Described alkylaluminium cpd molecular formula is Al (R)
3Wherein R=ethyl or isobutyl-;
The mol ratio of each component is:
(B)∶(A)＝0.1～10∶1；
(C)∶(A)＝100～3000∶1；
Described preparation method with structural formula (I) bridging pyridine diimine compound:
Under the formic acid effect, substituted aniline shown in compound shown in the formula V and the formula (II) in alcoholic solution, carry out condensation reaction, obtain the Schiff's base shown in the formula (III), Schiff's base shown in the formula (III) is in the presence of strong acid, with bridging substituted aniline condensation shown in the formula (IV), obtain bridging pyridine diimine compound shown in the formula (I).
R in its Chinese style (II), formula (III), formula (IV) or the formula V
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
1', R
2', R
3', R
4', R
5', R
8' with structural formula (I) in R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
1', R
2', R
3', R
4', R
5', R
8' have an identical meanings.
The mol ratio of the substituted aniline shown in compound and the formula shown in the described formula V (II) is 1: 0.75～1.3; It is 30～200mL that substituted aniline shown in every mole of formula (II) uses the consumption of formic acid;
Described alcohol is ethanol or methyl alcohol
The mol ratio of bridging substituted aniline is 1.8～2.3: 1 shown in Schiff's base shown in the described formula (III) and the formula (IV); Schiff's base shown in every mole of formula (III) uses strong acid 4～100g.
Described strong acid is tosic acid or sulfuric acid.
Have in the process of structural formula (I) bridging pyridine diimine compound synthetic, when if the substituted aniline shown in compound shown in the formula V and the formula (II) carries out condensation reaction, when the substituted aniline usage ratio shown in the formula (II) strengthens, the mol ratio of the substituted aniline shown in compound and the formula shown in the formula V as described (II) is 1: 2 o'clock, can obtain compound shown in the formula (VI).
Discover that compound shown in the formula (VI) also can be combined into olefin polymerization catalysis with component (A) and the component (C) in the catalyzer of the present invention, but the activity of this olefin polymerization catalysis and the catalyst activity that contains described bridging pyridine diimine compound of the present invention are lower slightly.
Adopt saturated alkane, the naphthenic hydrocarbon (C of being commonly used when utilizing iron polyolefin catalyzer of the present invention to carry out catalyzed ethylene polymerization
5-C
8Saturated alkane or naphthenic hydrocarbon) or toluene be solvent, polymerization temperature is 0～90 ℃, preferred 10-50 ℃; Polymerization pressure is 0.1-1MPa, and prepared polyethylene has higher molecular weight, and molecular weight distribution is between 3.0-71.6.Can see bimodally on the GPC of polymkeric substance figure (as Fig. 1-5) significantly, and high molecular is partly preponderated.
In the polymerization process, the addition sequence of each component of catalyzer be component (A), component (B), component (C) add successively reaction system or earlier will component (A) with component (B) pre-mixing after add reaction system again, and then add component (C).
When utilizing catalyzer of the present invention to carry out polyethylene polymerization, change polymerizing condition, can obtain the High molecular weight polyethylene of molecular weight distribution from unimodal to bimodal.In having the polyethylene of bimodal distribution, small molecular weight partly is significantly less than the macromolecule proportion, that is to say that high molecular partly preponderates, and such bimodal molecular weight distribution could embody good processing properties, can keep more intense mechanical property again.
Description of drawings
Fig. 1 is embodiment 6 molecular weight of polyethylene distribution plans;
Fig. 2 is embodiment 8 molecular weight of polyethylene distribution plans;
Fig. 3 is embodiment 9 molecular weight of polyethylene distribution plans;
Fig. 4 is embodiment 10 molecular weight of polyethylene distribution plans;
Fig. 5 is embodiment 11 molecular weight of polyethylene distribution plans;
Fig. 6 is embodiment 12 molecular weight of polyethylene distribution plans.
Embodiment
The preparation of embodiment 1 Schiff's base
With the 30mL dehydrated alcohol is solvent, adds 2 successively, and (1.94g, 16.0mmol) with 2, (2.61g 16.0mmol), drips 1mL formic acid and makes catalyzer the 6-diacetyl pyridine 6-xylidine, stirs 48h under the room temperature.Yellow mercury oxide occurs, filter, cold absolute ethanol washing 3 times, the hot ethanol recrystallization obtains yellow needle-like Schiff's base crystal 3 .21g, productive rate 75.4%.
Proton nmr spectra
1H-NMR (400MHz, CDCl
3, TMS): δ=2.02 (s, 6H, CH
3), 2.22 (s, 3H, C (NAr) CH
3), 2.76 (s, 3H, C (O) CH
3), 6.89-7.10 (m, 3H Ar-H), 7.96 (m, 1H, Py-H), 8.10 (d, 1H, Py-H), 8.56 (d, 1H, Py-H).
Ultimate analysis C
17H
18N
2O (%): calcd.C 76.67, and H 6.81, and N 10.53; Found C 76.45, H 6.54, N 10.41.
The preparation of embodiment 2 Schiff's base
With 2, and 6-di-isopropyl base aniline (2.83g 16.0mmol) replaces 2, the 6-xylidine, and other are operated with embodiment 1, obtain yellow needle-like Schiff's base crystal 4 .25g, productive rate 82.5%.
Proton nmr spectra
1H-NMRH NMR (400MHz, CDCl
3, TMS): δ=1.16-1.17 (m, 12H, CH (CH
3)
4), 2.28 (s, 3H, C (NAr) CH
3), 2.74 (sept, 2H, CH (CH
3)
2), 2.81 (s, 3H, C (O) CH
3), 7.08-7.22 (m, 3H, Ar-H), 7.96 (t, 1H, Py-H), 8.16 (d, 1H, Py-H), 8.56 (d, 1H, Py-H).
Ultimate analysis: C
21H
26N
2O (%): calcd.C 78.22, and H 8.13, and N 8.69; Found C 78.39, H 8.17, N 8.84.
The preparation of embodiment 3 bridging pyridine diimine compounds
With the Schiff's base (1.5g that obtains among the embodiment 1,5.63mmol) with two (3,5-dimethyl-4-aminophenyl) methane (0.72g, 2.81mmol), tosic acid is as catalyzer (0.05g), heated and stirred, divide water backflow 15h, remove most of solvent, yellow mercury oxide is separated out in cooling, filter, washing with alcohol promptly gets bridging pyridine diimine compound L for several times
11.75g, productive rate 83.0%.
ESI-MS：m/z＝751.5[M
+].
Proton nmr spectra
1HNMR (400MHz, DCCl
3, TMS): δ=2.04 (m, 24H, Ar-Me), 2.27 (m, 12H, ArN=CMe), 3.88 (s, 2H ,-CH
2-), 6.95-7.09 (m, 10H, Ar-H), 7.92 (t, 2H, Py-H
p), 8.50 (d, 4H, Py-H
m).
Ultimate analysis: C
51H
54N
6(%): Calcd.C 81.56.H 7.25.N 11.19; Found:C81.48.H 7.19.N 11.25
The preparation of embodiment 4 bridging pyridine diimine compounds
(1.5g 4.65mmol) replaces embodiment 1 gained Schiff's base, and other are operated with embodiment 3, obtain bridging pyridine diimine compound L with gained Schiff's base in the embodiment 2
21.74g, productive rate 87.0%.
ESI-MS：m/z＝864.3[M
+].
Proton nmr spectra
1H NMR (400MHz, DCCl
3, TMS): δ=1.12-1.26 (m, 24H, CH (CH
3)
2), 2.04 (s, 12H, Ar-Me), 2.27 (s, 12H, ArN=CMe), 2.78 (m, 4H, CH (CH
3)
2), 3.88 (s, 2H ,-CH
2-), 6.94-7.12 (m, 10H, Ar-H), 7.92 (t, 2H, Py-H
p), 8.50 (m, 4H, Py-H
m).
Ultimate analysis: C
59H
70N
6(%): Calcd.C 82.09.H 8.17.N 9.74; Found:C 81.89.H 8.23.N 9.63
The preparation of embodiment 5 bridging pyridine diimine compounds
(1.5g, 4.65mmol) (other are operated with embodiment 3, get bridging pyridine diimine L for 0.85g, 2.32mmol) reaction with two (3,5-di-isopropyl-4-aminophenyl) methane with gained Schiff's base among the embodiment 2
31.9g, productive rate 83.7%.
ESI-MS：m/z＝976.5[M
+].
Proton nmr spectra
1H NMR (400MHz, CDCl
3, TMS): δ=1.12-1.25 (m, 48H, CH (CH
3)
2), 2.27-2.29 (s, 12H, C (NAr) CH
3), 2.75 (m, 8H, CH (CH
3)
2), 4.04 (s, 2H ,-CH
2-), 7.02 (s, 4H, Ar-H), 7.10 (s, 2H, Ar-H), 7.16 (s, 4H, Ar-H), 7.92 (t, 2H, Py-H
p), 8.50 (d, 4H, Py-H
m).
Ultimate analysis: C
67H
86N
6: Calcd.C 82.50.H 8.89.N 8.61; Found:C 82.43.H8.91.N 8.66.
The reaction of embodiment 6 catalyzed ethylene polymerizations
Under the ethene atmosphere, to 50mL polymerization bottle in add ferric acetyl acetonade (Fe (acac) successively
3) 1 μ mol, embodiment 3 gained bridging pyridine diimine compound Ls
10.5 μ mol and methylaluminoxane (MAO) 1mmol, polymerization 20min under 20 ℃ of bath temperatures, reaction finishes, and adds the mixing solutions termination reaction of 15ml ethanol and 10ml hydrochloric acid, and adularescent polyethylene precipitation generates immediately.Filter, polyethylene is removed catalyzer and the acid that participates in ethanol and distilled water wash repeatedly, is dried to constant weight in 60 ℃ of vacuum drying ovens, obtains polyethylene 2.11g, and catalytic activity is 6.33 * 10
6GPE/ (molFeh), Mw are 24.2 * 10
4, Mw/Mn is 32.1, fusing point is 132.1 ℃.
The reaction of embodiment 7 catalyzed ethylene polymerizations
Under the ethene atmosphere, to 50mL polymerization bottle in add ferric acetyl acetonade (Fe (acac) successively
3) 1 μ mol, embodiment 4 gained bridging pyridine diimine compound Ls
20.5 μ mol and methylaluminoxane (MAO) 1mmol, polymerization 20min under 20 ℃ of bath temperatures, reaction finishes, and adds the mixing solutions termination reaction of 150ml ethanol and 10ml hydrochloric acid, and adularescent polyethylene precipitation generates immediately.Filter, polyethylene is removed catalyzer and the acid that participates in ethanol and distilled water wash repeatedly, is dried to constant weight in 60 ℃ of vacuum drying ovens, obtains polyethylene 1.73g, and catalytic activity is 5.21 * 10
6GPE/ (molFeh), Mw are 27.3 * 10
4, Mw/Mn is 56.3, fusing point is 131.8 ℃.
The reaction of embodiment 8 catalyzed ethylene polymerizations
Under the ethene atmosphere, to 50mL polymerization bottle in add ferric acetyl acetonade (Fe (acac) successively
3) 1 μ mol, embodiment 5 gained bridging pyridine diimine compound Ls
30.5 μ mol and methylaluminoxane (MAO) 1mmol, polymerization 20min under 20 ℃ of bath temperatures, reaction finishes, and adds the mixing solutions termination reaction of 150ml ethanol and 10ml hydrochloric acid, and adularescent polyethylene precipitation generates immediately.Filter, polyethylene is removed catalyzer and the acid that participates in ethanol and distilled water wash repeatedly, is dried to constant weight in 60 ℃ of vacuum drying ovens, obtains polyethylene 1.62g, and catalytic activity is 4.86 * 10
6GPE/ (molFeh), Mw are 28.8 * 10
4, Mw/Mn is 71.6, fusing point is 131.8 ℃.
The reaction of embodiment 9 catalyzed ethylene polymerizations
Under the ethene atmosphere, to 50mL polymerization bottle in add ferric acetyl acetonade (Fe (acac) successively
3) 1 μ mol, embodiment 5 gained bridging pyridine diimine compound Ls
30.5 μ mol and methylaluminoxane (MAO) 1mmol, polymerization 20min under 0 ℃ of bath temperature, reaction finishes, and adds the mixing solutions termination reaction of 150ml ethanol and 10ml hydrochloric acid, and adularescent polyethylene precipitation generates immediately.Filter, polyethylene is removed catalyzer and the acid that participates in ethanol and distilled water wash repeatedly, is dried to constant weight in 60 ℃ of vacuum drying ovens, obtains polyethylene 1.51g, and catalytic activity is 4.53 * 10
6GPE/ (molFeh), Mw are 41.2 * 10
4, Mw/Mn is 51.7, fusing point is 134.1 ℃.
The reaction of embodiment 10 catalyzed ethylene polymerizations
Under the ethene atmosphere, to 50mL polymerization bottle in add ferric acetyl acetonade (Fe (acac) successively
3) 1 μ mol, embodiment 5 gained bridging pyridine diimine compound Ls
30.5 μ mol and methylaluminoxane (MAO) 1mmol, polymerization 60min under 20 ℃ of bath temperatures, reaction finishes, and adds the mixing solutions termination reaction of 150ml ethanol and 10ml hydrochloric acid, and adularescent polyethylene precipitation generates immediately.Filter, polyethylene is removed catalyzer and the acid that participates in ethanol and distilled water wash repeatedly, is dried to constant weight in 60 ℃ of vacuum drying ovens, obtains polyethylene 2.89g, and catalytic activity is 2.89 * 10
6GPE/ (molFeh), Mw are 66.7 * 10
4, Mw/Mn is 55.5, fusing point is 134.0 ℃.
The reaction of embodiment 11 catalyzed ethylene polymerizations
Under the ethene atmosphere, to 50mL polymerization bottle in add ferric acetyl acetonade (Fe (acac) successively
2) 1 μ mol, embodiment 5 gained bridging pyridine diimine compound Ls
30.5 μ mol and methylaluminoxane (MAO) 1mmol, polymerization 20min under 20 ℃ of bath temperatures, reaction finishes, and adds the mixing solutions termination reaction of 150ml ethanol and 10ml hydrochloric acid, and adularescent polyethylene precipitation generates immediately.Filter, polyethylene is removed catalyzer and the acid that participates in ethanol and distilled water wash repeatedly, is dried to constant weight in 60 ℃ of vacuum drying ovens, obtains polyethylene 0.21g, and catalytic activity is 0.63 * 10
6GPE/ (molFeh), Mw are 5.1 * 10
4, Mw/Mn is 5.5, fusing point is 120.0 ℃.
The reaction of embodiment 12 catalyzed ethylene polymerizations
Under the ethene atmosphere, to 50mL polymerization bottle in add ferric acetyl acetonade (Fe (acac) successively
3) 1 μ mol, embodiment 5 gained bridging pyridine diimine compound Ls
30.5 μ mol and triisobutyl aluminium 1mmol, polymerization 20min under 0 ℃ of bath temperature, reaction finishes, and adds the mixing solutions termination reaction of 150ml ethanol and 10ml hydrochloric acid, and adularescent polyethylene precipitation generates immediately.Filter, polyethylene is removed catalyzer and the acid that participates in ethanol and distilled water wash repeatedly, is dried to constant weight in 60 ℃ of vacuum drying ovens, obtains polyethylene 0.32g, and catalytic activity is 0.95 * 10
6G PE/ (molFeh), Mw are 35.3 * 10
4, Mw/Mn is 4.26, fusing point is 134.5 ℃.
Claims (4)
1. imine compound activated iron polyolefin catalyzer comprises following (A), (B) and (C) three kinds of components:
(A) ferric acetyl acetonade or methyl ethyl diketone are ferrous;
(B) have the bridging pyridine diimine compound of structural formula (I):
R in the structural formula (I)
1Be H or methyl; R
2, R
3, R
4, R
5, R
8Respectively do for oneself methyl, ethyl or sec.-propyl; And R
1=R
1', R
2=R
2', R
3=R
3', R
4=R
4', R
5=R
5', R
8=R
8';
R
6And R
7Respectively do for oneself H, methyl, ethyl, butyl, phenyl or trifluoromethyl; Or R
6With R
7Be connected to ring structure (as cyclopentyl, cyclohexyl);
(C) methylaluminoxane, triethyl aluminum or triisobutyl aluminium;
The mol ratio of each component is:
(B)∶(A)＝0.1～10∶1；
(C)∶(A)＝100～3000∶1；
2. iron polyolefin catalyzer as claimed in claim 1, it is characterized in that: described synthetic method with bridging pyridine diimine compound of structural formula (I) is under the formic acid effect, substituted aniline shown in compound shown in the formula V and the formula (II) in alcoholic solution, carry out condensation reaction, obtain the Schiff's base shown in the formula (III), Schiff's base shown in the formula (III) is in the presence of strong acid, with bridging substituted aniline condensation shown in the formula (IV), obtain bridging pyridine diimine compound shown in the formula (I).
R in its Chinese style (II), formula (III), formula (IV) or the formula V
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
1', R
2', R
3', R
4', R
5', R
8' with structural formula (I) in R
1, R
2, R
3, R
4, R
5, R
6, R
7, R
8, R
1', R
2', R
3', R
4', R
5', R
8' have an identical meanings.
3. the application of iron polyolefin catalyzer as claimed in claim 1 when catalyzed ethylene polymerization.
4. application as claimed in claim 3 is characterized in that: polymerization temperature is 0～90 ℃ when carrying out polyethylene polymerization, and ethylene pressure is 0.1-1MPa.
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100703539A CN100497403C (en) | 2007-07-26 | 2007-07-26 | Imine compound activated iron polyolefin catalyzer |
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| Publication Number | Publication Date |
|---|---|
| CN101108884A true CN101108884A (en) | 2008-01-23 |
| CN100497403C CN100497403C (en) | 2009-06-10 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9139699B2 (en) | 2012-10-04 | 2015-09-22 | Dow Corning Corporation | Metal containing condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts |
| CN110183496A (en) * | 2018-02-23 | 2019-08-30 | 中国科学院化学研究所 | Pyridine diimine class dual-nuclei structure model, preparation method and application |
| CN114656581A (en) * | 2022-03-28 | 2022-06-24 | 安徽泽升科技有限公司 | Preparation method of pyridine diimine iron catalyst regulated and controlled by electronic effect |
-
2007
- 2007-07-26 CN CNB2007100703539A patent/CN100497403C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9469799B2 (en) | 2011-10-04 | 2016-10-18 | Dow Corning Corporation | Metal containing condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts |
| US9139699B2 (en) | 2012-10-04 | 2015-09-22 | Dow Corning Corporation | Metal containing condensation reaction catalysts, methods for preparing the catalysts, and compositions containing the catalysts |
| CN110183496A (en) * | 2018-02-23 | 2019-08-30 | 中国科学院化学研究所 | Pyridine diimine class dual-nuclei structure model, preparation method and application |
| CN110183496B (en) * | 2018-02-23 | 2020-10-23 | 中国科学院化学研究所 | Pyridine diimine binuclear metal complex, preparation method and application thereof |
| CN114656581A (en) * | 2022-03-28 | 2022-06-24 | 安徽泽升科技有限公司 | Preparation method of pyridine diimine iron catalyst regulated and controlled by electronic effect |
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