CN102336847A - Catalyst used in olefin polymerization, and component thereof - Google Patents
Catalyst used in olefin polymerization, and component thereof Download PDFInfo
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- CN102336847A CN102336847A CN2010102282983A CN201010228298A CN102336847A CN 102336847 A CN102336847 A CN 102336847A CN 2010102282983 A CN2010102282983 A CN 2010102282983A CN 201010228298 A CN201010228298 A CN 201010228298A CN 102336847 A CN102336847 A CN 102336847A
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Abstract
The invention relates to a catalyst used in olefin polymerization, and especially in propylene polymerization. The invention also relates to the application of the catalyst in olefin homopolymerization and copolymerization. Specifically, the catalyst includes a morpholinyl-containing alkoxysilane compound as an external electron donor component in the catalyst. When the catalyst with the component is used in propylene polymerization, an excellent effect can be obtained.
Description
Technical field
The present invention relates to a kind of catalyzer of for olefines polymerization, and its application in alkene homopolymerization and copolymerization.More particularly, relate to magnesium halide/Ti catalyst component and one type of alkoxysilane compound containing trialkylsilyl group in molecular structure component that contains the morpholine group as the common catalyzer of forming of external electron donor, and the application of this catalyzer in olefinic polyreaction.
Technical background
Vestolen PP 7052 is a kind of thermoplasticity synthetic resins of excellent property, is widely used in aspects such as automobile industry, electronic apparatus, packing and building materials furniture.And along with the continuous expansion of PP Application Areas, production capacity is also along with improve.In the behind of this throughput that increases rapidly of Vestolen PP 7052, the update of catalyzer is topmost impellent.The catalyzer that is used for polypropylene industrial production at present still is a Ziegler-Natta catalyst mainly, and electron donor plays crucial effects in the replacement process of catalyzer.Therefore, we can say just that on the basis of electron donor upgrading the continuous development of Ziegler-Natta catalyst is in recent years just arranged.
So-called electron donor is meant that the compound that is rich in electronics is Louis (Lewis) alkali.Usually will prepare the electron donor that adds in the process at solid catalyst and be called internal electron donor, the electron donor that joins in the olefin polymerization system is called external electron donor.External electron donor and internal electron donor are used, and play and improve catalyst activity and the normal effect of polymkeric substance.As the external electron donor compound aromatic carboxylic acid esters, organic amine, calixarene kind, siloxane compound arranged.Now normally used is the organo-siloxane compounds.Its general structure is generally: R
nSi (OR ')
4-n(wherein; N be 1～3 natural number-), like dimethoxydiphenylsilane (WO8805056, EP283011), methylcyclohexyl dimethoxy silane (JP02-170803, JP02-229807), diisopropyl dimethoxy silane (EP350170), second, isobutyl dimethoxy silane (EP250229, EP376145) and dicyclopentyl dimethoxyl silane (JP02-229807) etc.
Yet, above-mentioned known silane compound, some contains phenyl ring, in use might discharge harmful benzene, thus the health of causing and health problem; Some is owing to be connected with two sterically hindered very high cyclic alkyls on a Siliciumatom, and preparation is difficulty relatively, and cost is higher; Although some preparation is than being easier to, cost is also lower, and the degree of isotacticity of the polymkeric substance of the not high or gained of the activity of such catalysts of gained can not meet the demands.
One type of novel silane compound that contains the oxaza group provided by the invention contains the alkoxysilane compound containing trialkylsilyl group in molecular structure of morpholine group.Its preparation method has and reacts completely, and by product is few, and product is easy to separate, and can be made into different concns solution and advantage such as easy and simple to handle.And catalyzer has good catalytic activity when being used for olefinic polymerization, and the polymkeric substance of gained has higher degree of isotacticity.
Summary of the invention
A kind of catalyzer that is used for olefinic polymerization of the present invention comprises the product of following component reaction:
A) magnesium halide/Ti catalyst component;
B) alkylaluminium cpd;
C) a kind ofly be selected from the compound shown in the formula (I);
Wherein component a) magnesium halide/Ti catalyst component for using the catalyst component that known method prepares in the industry; As can prepare through following two kinds of cited methods.
A kind of is after magnesium halide is dissolved in the solvent system that contains organic epoxy compounds and organo phosphorous compounds, in the presence of one or more precipitation additive, above-mentioned solution and at least a titanium compound to be carried out contact reacts.In arbitrary step, introduce at least a electron donor compound such as succinate compounds, phthalate compound, diether compound, diol-lipid compound etc.
Above-mentioned organic epoxy compounds comprises at least a in oxide compound, glycidyl ether and the inner ether of 2～8 aliphatics alkene, diolefine or halogenated aliphatic alkene or diolefine of carbonatoms.Particular compound is like oxyethane, propylene oxide, butylene oxide ring, butadiene oxide, butadiene double oxide, epoxy chloropropane, methyl glycidyl ether, diglycidylether, THF.Above-mentioned organo phosphorous compounds comprises the hydrocarbyl carbonate or the halo hydrocarbyl carbonate of ortho-phosphoric acid or phosphorous acid, concrete as: ortho-phosphoric acid trimethyl, ortho-phosphoric acid triethyl, ortho-phosphoric acid tri-n-butyl, ortho-phosphoric acid triphenylmethyl methacrylate, trimethyl phosphite, triethyl-phosphite, tributyl phosphate, tricresyl phosphite benzene methyl.Above-mentioned precipitation additive is organic acid anhydride, organic acid, ether and ketone compounds.Concrete as: diacetyl oxide, Tetra hydro Phthalic anhydride, Succinic anhydried, MALEIC ANHYDRIDE, propionic acid, butyric acid, acetone, benzophenone, methyl ether, ether, propyl ether etc.
Wherein said titanium compound is selected from general formula Ti (OR
1)
4-nX
nCompound at least a, R5 is that carbonatoms is 1～20 alkyl in the formula, the aliphatic group of the preferred C1～C14 of R5, X is identical or different, is F, Cl or Br, n is selected from 1～4 integer.
According to another kind of method, a kind of is above-mentioned general formula Ti (OR
1)
4-nX
nTitanium compound.A kind of general formula is MgX
2(ROH)
mAdducts, X is a chlorine or bromine in the formula, R is C
1～C
12Alkyl, C
3～C
10Naphthenic base or C
6～C
10Aryl, wherein m is 1～5.Both contact reactss also add the electron donor compound in reaction process, like succinate compounds, phthalate compound, diether compound, diol-lipid compound etc.The dry solid particulate that obtains of washing at last obtains ingredient of solid catalyst.
Components b) alkylaluminium cpd; Its general formula is AlR
nX
3-n, R is hydrogen or C
1～C
20Alkyl, particularly alkyl, aralkyl, aryl etc.; X is halogen, particularly chlorine and bromine; N is the number of 0≤n≤3.Can select for use one or more aluminum alkyls to mix use, preferred triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, chlorination aluminum alkyls, Al (n-C
6H
13)
3, Al (n-C
8H
17)
3, AlEt
2Cl etc., its consumption are 50～1000 use abovementioned alkyl aluminum compounds with the Al/Ti molar ratio computing generally.
Amount of component b) be the compound shown in the general formula (I), wherein m is 0 or 1; When m is 0, represent that this Sauerstoffatom does not exist, the R that closes on
3Group links to each other with Siliciumatom; When m was 1, expression existed 1 Sauerstoffatom, the R that closes on
3Group links to each other with Sauerstoffatom;
R
1, R
2And R
3Be identical or different straight or branched C
1-C
20Alkyl, C
3-C
20Naphthenic base, C
6-C
20Aryl, C
7-C
20Alkaryl and C
7-C
20Aralkyl;
Preferred R
1And R
2Be identical or different straight or branched C
1-C
5Alkyl, R
3Be straight or branched C
1-C
8Alkyl or C
3-C
8Naphthenic base.
Preferred R
1And R
2Be methyl or ethyl, R
3Being methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-octyl, cyclopentyl or cyclohexyl, is the best with methyl, sec.-propyl, n-octyl, cyclopentyl and cyclohexyl.
Silane compound with general formula (I) structure provided by the invention can be the following specific examples:
Methylmorpholine base dimethoxy silane
Sec.-propyl morpholinyl dimethoxy silane
Cyclopentyl morpholinyl dimethoxy silane
Cyclohexyl morpholinyl dimethoxy silane
The morpholinyl Trimethoxy silane
The morpholinyl triethoxyl silane
N-octyl morpholinyl diethoxy silane
The consumption of above-mentioned silane compound is counted 0.005～0.5 mole with every mole of aluminum alkyl compound.
Above-mentioned silane compound with general formula (I) structure can adopt the several different methods preparation.First kind of preparation method provided by the invention is that morpholine and n-Butyl Lithium reaction are generated lithium salts, with the tetraalkoxysilane reaction, generates the morpholinyl trialkoxy silane then; Second kind of preparation method provided by the invention, morpholine and n-Butyl Lithium reaction generate lithium salts, with the alkyltrialkoxysilaneand reaction, generate alkyl morpholine base dialkoxy silicane then.
Above-mentioned butyllithium is butyllithium-hexane solution, is commercially available industrial chemicals.Above-mentioned alkyltrialkoxysilaneand and four alkoxyl group alkane, concrete like methyltrimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, n-octyl triethoxyl silane etc., be commercially available industrial chemicals; Other can prepare according to the method that US5248803 provides like cyclopentyl Trimethoxy silane, cyclohexyl trimethoxy silane, sec.-propyl Trimethoxy silane etc.
Among the above-mentioned preparation method, the two mol ratio of morpholine and alkyltrialkoxysilaneand is 1: 1～5, and preferred mol ratio is 1: 1～3; The mol ratio of morpholine and four alkoxyl group alkane is 1: 1～5, and preferred mol ratio is 1: 1～3; Morpholine is 1: 1～5 with the mol ratio of positive fourth lithium, and preferred mol ratio is 1: 1～3.
Above-mentioned preparation method can carry out at non-proton inert solvent.Non-proton inert solvent is selected from acid amides, halohydrocarbon, hydrocarbon, ether etc.; Concrete like methylene dichloride, trichloromethane, benzene, toluene, normal hexane, hexanaphthene, sherwood oil, ether, THF, MTBE and N; One or more of dinethylformamide, preferred solvent is a normal hexane.
Above-mentioned temperature of reaction is carried out under-20～100 ℃ usually, and preferably lower temperature of reaction is as-5～30 ℃.
Above-mentioned catalyzer is suitable for alkene CH among the present invention
2=CHR
6(R wherein
6Be the alkyl or aryl of hydrogen or 1～12 carbon) and the polyreaction that contains the mixture of (if necessary) a small amount of diolefine.Therefore another object of the present invention provides the application of this catalyzer in olefinic polymerization.
Catalyst olefinic polymerization provided by the present invention can be adopted the whole bag of tricks of the prior art, does not have special qualification.The polymerization of alkene is carried out according to currently known methods, in the liquid phase of liquid monomer or the solution of monomer in inert solvent, or in gas phase, or through operating in the polymerization mix technology of gas-liquid in mutually.Polymerization temperature is generally 0 ℃～150 ℃, preferred 60 ℃～100 ℃.Polymerization pressure is a normal pressure or higher.
It should be noted that the inventor herein at research process first with a kind of silane compound that contains ad hoc structure as electron donor synthetic catalyzer, be applied to olefinic polymerization particularly in the propylene polymerization, concrete good activity.
Embodiment
Following Example is used for explaining the present invention, is not to be used for limiting scope of the present invention.
Testing method:
1, melt index: measure according to ASTM D1238-99.
2, polymkeric substance isotactic index: adopt the heptane extraction process to measure (heptane boiling extracting 6 hours): two gram exsiccant polymer samples; Be placed in the extractor with the extracting of boiling heptane after 6 hours, the polymer weight (g) that residuum is dried to the constant weight gained is degree of isotacticity with 2 ratio.
3, polymericular weight and MWD MWD (MWD=Mw/Mn): adopt the gel permeation chromatography method; Use PL-GPC220 to measure (standard specimen as solvent down at 150 ℃ with trichlorobenzene; PS, flow velocity: 1.0ml/min, pillar: 3xPlgel 10 μ m MIXED-B 300x7.5nm)
Compound:
Embodiment 1: the preparation of methylmorpholine base dimethoxy silane
At N
2Under the protective condition, in reaction flask, add the 8ml morpholine successively, the 80ml normal hexane stirs.Under the condition of ice bath, dropwise add 33.6ml (2.87M) butyllithium-hexane solution, the dropping time is 45min.In reaction solution, dropwise add the 13ml methyltrimethoxy silane behind the 1h, continue reaction 5h.The spinning reaction solution, deposition washes twice with normal hexane, collects filtrating.Boil off the normal hexane solvent with Rotary Evaporators, 100～105 ℃/40pa cut is collected in underpressure distillation.Underpressure distillation is once collected 102～104 ℃/45Pa cut again, heavy 7.1g.
1H?NMR(CDCl
3/TMS，300MHz)δ(ppm)：0.11(s，3H，CH
3)，2.97(t，4H，2CH
2)，3.50(s，3H，OCH
3)，3.58(t，4H，2CH
2)
Embodiment 2: the preparation of sec.-propyl morpholinyl dimethoxy silane
At N
2Under the protective condition, in reaction flask, add the 4ml morpholine successively, the 40ml normal hexane stirs.Under the condition of ice bath, dropwise add 16.6ml (2.87M) butyllithium-hexane solution, the dropping time is 45min.In reaction solution, dropwise add 9.07g sec.-propyl Trimethoxy silane behind the 1h, continue reaction 6h.The spinning reaction solution, deposition washes twice with normal hexane, collects filtrating.Boil off the normal hexane solvent with Rotary Evaporators, 122～126 ℃/45hpa cut is collected in underpressure distillation, heavy 4.1g, content 99.0% (GC).
1H?NMR(CDCl
3/TMS，300MHz)δ(ppm)：1.0(m，7H，CH，2CH
3)，2.99(t，4H，2CH
2)，3.54(s，6H，2OCH
3)，3.66(t，4H，2CH
2)
Embodiment 3: the preparation of cyclopentyl morpholinyl dimethoxy silane
At N
2Under the protective condition, in reaction flask, add the 4ml morpholine successively, the 30ml normal hexane stirs.Under the condition of ice bath, dropwise add 16.8ml (2.87M) butyllithium-hexane solution, the dropping time is 45min.In reaction solution, dropwise add 8.76g cyclopentyl Trimethoxy silane behind the 1h, continue reaction 5h.The spinning reaction solution, deposition washes twice with normal hexane, collects filtrating.Boil off the normal hexane solvent with Rotary Evaporators, 120～124 ℃/60pa cut is collected in underpressure distillation, heavy 5.8g, content 99.0% (GC).
1H?NMR(CDCl
3/TMS，300MHz)δ(ppm)：1.09(m，1H，CH)，1.51(m，6H，3CH
2)，1.80(m，2H，CH
2)，2.99(t，4H，2CH
2)，3.54(s，6H，2OCH
3)，3.58(t，4H，2CH
2)
Embodiment 4: the preparation of cyclohexyl morpholinyl dimethoxy silane
At N
2Under the protective condition, in reaction flask, add the 4ml morpholine successively, the 40ml normal hexane stirs.Under the condition of ice bath, dropwise add 16.8ml (2.87M) butyllithium-hexane solution, the dropping time is 10min.In reaction solution, dropwise add the 9.4g cyclohexyl trimethoxy silane behind the 1h, continue reaction 5h.The spinning reaction solution, deposition washes twice with normal hexane, collects filtrating.Boil off the normal hexane solvent with Rotary Evaporators, 120～123 ℃/30pa cut is collected in underpressure distillation, heavy 6g, content 99.0% (GC).
1H?NMR(CDCl
3/TMS，300MHz)δ(ppm)：0.84(m，1H，CH)，1.23(m，5H，CH
2)，1.73(m，5H，CH
2)，2.97(t，4H，2CH
2)，3.53(s，6H，2OCH
3)，3.59(t，4H，2CH
2)
Embodiment 5: the preparation of morpholinyl triethoxyl silane
At N
2Under the protective condition, in reaction flask, add the 4ml morpholine successively, the 40ml normal hexane stirs.Under the condition of ice bath, dropwise add 19.4ml (2.5M) butyllithium-hexane solution, the dropping time is 30min.In reaction solution, dropwise add the 5.15ml tetraethoxysilane behind the 1h, continue reaction 17h.The spinning reaction solution, deposition washes twice with normal hexane, collects filtrating.Boil off the normal hexane solvent with Rotary Evaporators, 118～128 ℃/45pa cut ED-43-1 is collected in underpressure distillation, heavy 1.4g.
1H?NMR(CDCl
3/TMS，300MHz)δ(ppm)：1.23(t，9H，3CH
3)，3.00(t，4H，2NCH
2)，3.58(t，4H，2NCH
2)，3.80(q，6H，3OCH
2)
Preparation of Catalyst and propylene polymerization:
The preparation of embodiment 6:Mg/ titanium ingredient of solid catalyst
In the double glazing reaction flask of 300ML, add the anhydrous MgCl of 5.0g successively
2, 120ml toluene, 8.0ml epoxy chloropropane, 10.0ml tributyl phosphate are being cooled to-25 ℃ with this solution after the dissolving under 60 ℃ fully; Dropwise 5 0ml titanium tetrachloride is kept half a hour under-25 ℃, add silica gel (DavisonXP02485; Following dry 4 hours before using at 600 ℃) 3.0g; In temperature-rise period, add diisobutyl phthalate 5mmol, slowly be warming up to 90 ℃ then after elimination liquid, wash secondary with titanium tetrachloride; With hexane wash four times, obtain the spherical solid component after the vacuum-drying.
Propylene polymerization:
In the 5L autoclave, at room temperature introduce the hexane solution (concentration of triethyl aluminum is 0.5mmol/ml) of 5ml triethyl aluminum, hexane solution (concentration is 0.1mmol/ml), 10ml anhydrous hexane and the above-mentioned 10mg ingredient of solid catalyst that obtains of 1.25ml external electron donor in the stream of nitrogen gas.Close autoclave, introduce hydrogen 1L or 6L (standard volume) and liquid propene 2.3L, be warmed up to 70 ℃, kept this temperature 1 hour, pressure is put in cooling, obtains the PP resin, and polymerization result is seen table 1.
The performance of table 1 catalyzer
Claims (6)
1. a catalyzer that is used for olefinic polymerization is characterized in that, comprises the product of following component reaction:
A) magnesium halide/Ti catalyst component;
B) alkylaluminium cpd;
C) a kind ofly be selected from the compound shown in the formula (I);
Wherein component a) magnesium halide/Ti catalyst component for using the catalyst component that known method prepares in the industry;
Components b) alkylaluminium cpd; Its general formula is AlR
nX
3-n, R is hydrogen or C
1～C
20Alkyl, X is a halogen, n is the number of 0≤n≤3; Its consumption is 50～1000 with the Al/Ti molar ratio computing;
Amount of component b) be the compound shown in the general formula (I), wherein m is 0 or 1; When m is 0, represent that this Sauerstoffatom does not exist, the R that closes on
3Group links to each other with Siliciumatom; When m was 1, expression existed 1 Sauerstoffatom, the R that closes on
3Group links to each other with Sauerstoffatom;
R
1, R
2And R
3Be identical or different straight or branched C
1-C
20Alkyl, C
3-C
20Naphthenic base, C
6-C
20Aryl, C
7-C
20Alkaryl and C
7-C
20Aralkyl; Its consumption is counted 0.005～0.5 mole with every mole of aluminum alkyl compound.
2. the catalyzer that is used for olefinic polymerization according to claim 1 is characterized in that, in the compound shown in the general formula (I), and R
1And R
2Be identical or different straight or branched C
1-C
5Alkyl, R
3Be straight or branched C
1-C
8Alkyl or C
3-C
8Naphthenic base.
3. the catalyzer that is used for olefinic polymerization according to claim 1 is characterized in that, in the compound shown in the general formula (I), and R
1And R
2Be methyl or ethyl, R
3Be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-octyl, cyclopentyl or cyclohexyl.
4. the catalyzer that is used for olefinic polymerization according to claim 3 is characterized in that, in the compound shown in the general formula (I), and R
3Be methyl, sec.-propyl, n-octyl, cyclopentyl or cyclohexyl.
5. the catalyzer that is used for olefinic polymerization according to claim 3; It is characterized in that the compound shown in the general formula (I) is at least a in methylmorpholine base dimethoxy silane, sec.-propyl morpholinyl dimethoxy silane, cyclopentyl morpholinyl dimethoxy silane, cyclohexyl morpholinyl dimethoxy silane, morpholinyl Trimethoxy silane, morpholinyl triethoxyl silane, the n-octyl morpholinyl diethoxy silane.
6. the described catalyzer of one of claim 1～5 is at CH
2=CHR
6Application in the olefinic polymerization, wherein R
6Be hydrogen or C
1-C
6Alkyl or aryl.
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ID=45512828
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002051545A1 (en) * | 2000-12-21 | 2002-07-04 | Exxonmobil Chemical Patents Inc. | Multi-donor catalyst system for the polymerization of olefins |
| CN1675255A (en) * | 2002-08-19 | 2005-09-28 | 宇部兴产株式会社 | Catalysts for polymerization or copolymerization of alpha-olefins, catalyst components thereof, and processes for polymerization of alpha-olefins with the catalysts |
| JP3766511B2 (en) * | 1997-07-22 | 2006-04-12 | 三井化学株式会社 | Olefin polymerization catalyst and olefin polymerization method |
| CN1887918A (en) * | 2005-06-30 | 2007-01-03 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization or copolymerization at high temperature |
| CN101735351A (en) * | 2008-11-07 | 2010-06-16 | 中国石油天然气股份有限公司 | Method for preparing high-fluidity and wide-distribution polypropylene and product |
-
2010
- 2010-07-16 CN CN2010102282983A patent/CN102336847A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3766511B2 (en) * | 1997-07-22 | 2006-04-12 | 三井化学株式会社 | Olefin polymerization catalyst and olefin polymerization method |
| WO2002051545A1 (en) * | 2000-12-21 | 2002-07-04 | Exxonmobil Chemical Patents Inc. | Multi-donor catalyst system for the polymerization of olefins |
| CN1675255A (en) * | 2002-08-19 | 2005-09-28 | 宇部兴产株式会社 | Catalysts for polymerization or copolymerization of alpha-olefins, catalyst components thereof, and processes for polymerization of alpha-olefins with the catalysts |
| CN1887918A (en) * | 2005-06-30 | 2007-01-03 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization or copolymerization at high temperature |
| CN101735351A (en) * | 2008-11-07 | 2010-06-16 | 中国石油天然气股份有限公司 | Method for preparing high-fluidity and wide-distribution polypropylene and product |
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Application publication date: 20120201 |