CN101250238B - Boroxol titanocene metal catalyzer and preparation method and application thereof - Google Patents
Boroxol titanocene metal catalyzer and preparation method and application thereof Download PDFInfo
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- CN101250238B CN101250238B CN2008101029374A CN200810102937A CN101250238B CN 101250238 B CN101250238 B CN 101250238B CN 2008101029374 A CN2008101029374 A CN 2008101029374A CN 200810102937 A CN200810102937 A CN 200810102937A CN 101250238 B CN101250238 B CN 101250238B
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Abstract
The invention relates to a boroxol monotitanocene catalyst with high polymerization activity to alpha-olefin and high solubility in water, a relative preparation method and an application. The preparation method comprises synthesizing borate titanium trichloride from borate and titanium tetrachloride at the mol ratio of 1.00-1.05, reacting trimethylsilyl compound of cyclopentadienyl, lindenyl or relative derivative with borate titanium trichloride at the mol ratio of 1.05-1.10 to obtain borate titanium trichloride, reacting phenol or alcohol, pyrindine and borate dichloro monotitanocene at themol ratio of 1:1:1.05-1:1:1.1 to obtain boroxol monotitanocene catalyst. The invention uses borate group to lead into oxygen atoms, thereby stabilizing molecule structure and improving the solubilityand stability of the product in hexane with confirmed catalysis efficiency. The product is suitable for the homogeneous or slurry polymerization whose solvent is hexane. The synthesis method is simple. And the product can be used to synthesize the homopolymer or copolymer from ethylene or/and alpha olefin.
Description
Technical field
The present invention relates to a kind of be soluble in hexane alpha-olefin is had boron oxygen base single metallocene-titanium catalyst than the boracic oxygen ylidene ligands of high polymerization activity and its production and application.
Background technology
The exploitation of high activity olefin polymerization catalyst is present researchist's a focus always, and the synthetic and exploitation of single in recent years cyclopentadienyl ligand catalyzer comes into one's own day by day.CN1065870C, CN1065871C and CN1340551A provide a kind of synthetic method that contains the luxuriant titanium of oxygen list, and institute's synthetic catalyzer has good activity to syndiotactic polymerization of phenylethylene; CN1345887A and CN1593763A provide a kind of synthetic method that contains the luxuriant titanium of oxygen list, and institute's synthetic catalyzer has good activity to ethene or ethene, propylene polymerization; Above-mentioned catalyzer generally is to introduce Sauerstoffatom by alkoxyl group, phenoxy group in catalyst molecule, has stablized the molecular structure of catalyzer, and final composite with aikyiaiurnirsoxan beta, formation olefinic polymerization efficient catalytic system; Above-mentioned catalyzer is generally poor to the solvability of hexane, and not being easy for the hexane is in the homogeneous phase or slurry polymerization of solvent.
Summary of the invention
The purpose of this invention is to provide a kind of be soluble in hexane (or other solvent) alpha-olefin is had boron oxygen base single metallocene-titanium catalyst than the boracic oxygen ylidene ligands of high polymerization activity and its production and application.
The boron oxygen base single metallocene-titanium catalyst of boracic oxygen ylidene ligands of the present invention is explained by formula (I):
Formula (I)
Cp is cyclopentadienyl, indenyl or their derivative in the formula; M is the boric acid ester or derivatives thereof; X, Y are halogen, alkoxyl group, phenoxy group or their derivative; Ti is a titanium atom.
It is synthetic that described boron oxygen base single metallocene-titanium catalyst can be eliminated the method for trimethylchlorosilane reaction by the trimethyl silicane compound of boric acid ester group titanous chloride and one of cyclopentadienyl, indenyl or their derivative.
The preparation method of described boron oxygen base single metallocene-titanium catalyst is as follows:
1) the synthetic luxuriant titanium of boric acid ester group dichloro list:
In the reactor of handling well that has bottom insert canal, add titanium tetrachloride (TiCl
4) hexane solution, with nitrogen by bottom insert canal to titanium tetrachloride hexane solution bubbling, titanium tetrachloride concentration 0.2mol/L, in order to dispel the hydrogenchloride that produces in the reaction, under agitation condition, slowly drip the boric acid ester hexane solution, boric acid ester concentration 0.5mol/L, the mol ratio of boric acid ester and titanium tetrachloride is to dropwise in 1.00～1.05,20 minutes; Nitrogen bubble continues reaction 2 hours; Obtain yellowish green boric acid ester group titanous chloride;
The trimethyl silicane compound of one of cyclopentadienyl, indenyl or their derivative and boric acid ester group titanous chloride 1.05～1.10 are added in the reactors in molar ratio, under agitation condition, 60～70 ℃ of reactions 24 hours; After reaction finishes, filter, the evaporation concentration solvent obtains the red luxuriant titanium of boric acid ester group dichloro list.
2) synthetic boron oxygen base list cyclopentadiene titanium compound:
In reactor, add the luxuriant titanium hexane solution of boric acid ester group dichloro list, the luxuriant titanium concentration of boric acid ester group dichloro list 0.02mol/L, under agitation condition, slowly drip the hexane solution of phenols or alcohols and pyridine, the mol ratio of phenols or alcohols, pyridine and the luxuriant titanium of boric acid ester group dichloro list is 1: 1: 1.05-1: 1: 1.1; The concentration of phenols or alcohols is 0.05mol/L; Pyridine concentration is 0.05mol/L, dropwises in 20 minutes; Rise to room temperature gradually, continue reaction 8 hours; After reaction finishes, solvent evaporated, extraction liquid concentrates and obtains boron oxygen base single metallocene-titanium catalyst.
Above-mentioned boron oxygen base single metallocene-titanium catalyst is used for olefinic polymerization, and wherein Primary Catalysts is the boron oxygen base single metallocene-titanium catalyst of above-mentioned boracic oxygen ylidene ligands; Promotor is the Lewis acid (as tritane base four (pentafluorophenyl group) boron) in alkylaluminoxane, alkylaluminoxane mixture or other energy stable cationic active centre; Solvent is hexane or other solvent; Polymerization temperature is 30～110 ℃; Polymerization pressure is 0～1.0Mpa; Reaction times is 0.5～1.5 hour.Use general polymerization process, it can be batch polymerization, as successively add solvent, master, promotor in the reactor of handling, the Primary Catalysts concentration of formation is that 0.02mmol/L, cocatalyst concentration are 0.04mol/L, rises to the temperature of regulation, feed ethene or/and alpha-olefin, ethene, alpha-olefin ratio are 0～100%, and the reaction beginning adds terminator ethanol, reaction finishes, and evaporating solvent must be done glue; It also can be successive polymerization.Ethene, alpha-olefin content can be regulated arbitrarily by unstripped gas, liquid feed composition in the polymkeric substance.
The present invention adopts the boric acid ester group to introduce Sauerstoffatom in catalyst molecule, stablized the molecular structure of catalyzer, greatly increased solvability and the stability of catalyzer in hexane when guaranteeing catalytic efficiency, being specially adapted to the hexane is the homogeneous phase or the slurry polymerization of solvent; The method of synthetic single luxuriant titanium is easy, and can synthesize by ethene, alpha-olefin with catalyzer of the present invention simultaneously is the homopolymer or the multipolymer of raw material.
Embodiment
Embodiment 1:
The preparation of boric acid di-isooctyl base titanous chloride.
In 100 milliliters the stirring reaction bottle of handling well through anhydrous and oxygen-free, add 50 milliliters of hexanes, 1.90 gram TiCl
4(10 mmole) is with 0.025M
3/ h flow feeds nitrogen, at the uniform velocity drips boric acid di-isooctyl 2.86 grams (10 mmoles dilute with 20 milliliters of hexanes) in 20 minutes, reacts 2 hours, generates red solution.Evaporating solvent gets 4.38 gram sorrel liquid.Molecular formula C
16H
34BO
3Cl
3Ti, molecular weight are 439.23.Ultimate analysis: C (wt%), measured value (theoretical value): 43.70 (43.71); H (wt%), measured value (theoretical value): 7.75 (7.74); Chemical analysis: Cl (wt%), measured value (theoretical value): 24.28 (24.25).
Embodiment 2
The preparation of the luxuriant titanium of boric acid di-isooctyl base dichloro list.
In 100 milliliters the stirring reaction bottle of handling well through anhydrous and oxygen-free, add 50 milliliters of hexanes, 0.2134 gram 1,2,3,4-tetramethyl--5-is trimethyl silicon based-cyclopentadiene, stir down and drip 0.4392 gram boric acid di-isooctyl base titanous chloride (1 mmole) in room temperature, be added dropwise to complete the back and reacted 24 hours down, generate red solution in 65 ℃.The filtering precipitation, evaporating solvent gets 0.5048 gram sorrel liquid.Molecular formula C
25H
47BO
3Cl
2Ti, molecular weight are 525.Ultimate analysis: C (wt%), measured value (theoretical value): 57.18 (57.14); H (wt%), measured value (theoretical value): 8.96 (8.95); Chemical analysis: Cl (wt%), measured value (theoretical value): 13.53 (13.52).
Embodiment 3
The preparation of boric acid di-isooctyl base dichloro list indenes titanium.
50 milliliters of hexanes of adding 0.2068 restrain 5-in 100 milliliters the stirring reaction bottle of handling well through anhydrous and oxygen-free, and trimethyl silicon based-indenes (1.1 mmole) hexane hangs the also turbid liquid of muddiness, stir down and drip 0.4754 gram boric acid di-isooctyl base titanous chloride (1 mmole) in room temperature, be added dropwise to complete the back and reacted 24 hours down, generate red solution in 65 ℃.The filtering precipitation, evaporating solvent gets 0.4302 gram sorrel liquid, productive rate 77.5%.Molecular formula C
25H
41BO
3Cl
2Ti, molecular weight are 519.Ultimate analysis: C (wt%), measured value (theoretical value): 57.83 (57.81); H (wt%), measured value (theoretical value): 7.89 (7.90); Chemical analysis: Cl (wt%), measured value (theoretical value): 13.70 (13.68).
Embodiment 4
The preparation of the luxuriant titanium of boric acid di-isooctyl base diisopropoxy list.
In 100 milliliters the stirring reaction bottle of handling well through anhydrous and oxygen-free, add 50 milliliters of hexanes, 0.5250 gram embodiment 2 synthetic catalyzer (1 mmole), at the uniform velocity drip the hexane solution (Virahol 0.0600 gram, pyridine 0.0790 gram are with 20 milliliters of hexane dilutions) of Virahol, pyridine in 20 minutes, reacted 2 hours, and generated orange-yellow solution and white precipitate.The filtering precipitation, evaporating solvent gets 0.5613 gram tawny liquid.Molecular formula is C
31H
61BO
5Ti, molecular weight 572.Ultimate analysis: C (wt%), measured value (theoretical value): 65.04 (65.03); H (wt%), measured value (theoretical value): 10.67 (10.66); Chemical analysis: not chloride.
Embodiment 5:
The preparation of boric acid di-isooctyl base diisopropoxy list indenes titanium.
In 100 milliliters the stirring reaction bottle of handling well through anhydrous and oxygen-free, add 50 milliliters of hexanes, 0.5190 gram embodiment 3 synthetic catalyzer (1 mmole), at the uniform velocity drip the hexane solution (Virahol 0.0600 gram, pyridine 0.0790 gram are with 20 milliliters of hexane dilutions) of Virahol, pyridine in 20 minutes, reacted 2 hours, and generated orange-yellow solution and white precipitate.The filtering precipitation, evaporating solvent gets 0.5558 gram tawny liquid.Molecular formula is C
31H
55BO
5Ti, molecular weight 566.Ultimate analysis: C (wt%), measured value (theoretical value): 65.79 (65.72); H (wt%), measured value (theoretical value): 9.74 (9.72); Chemical analysis: not chloride.
Embodiment 6:
The preparation of the single luxuriant titanium of boric acid di-isooctyl base-two (2,6-di-isopropyl phenoxy group).
In the stirring reaction bottle of the 100ML that handles well through anhydrous and oxygen-free, add 50 milliliters of hexanes, 0.5604 gram embodiment 2 synthetic catalyzer (1 mmole), at the uniform velocity drip 2 in 20 minutes, the hexane solution (2 of 6-diisopropyl phenol, pyridine, 6-diisopropyl phenol 0.1780 gram, pyridine 0.0790 gram are with 20 milliliters of hexane dilutions), reacted 2 hours, and generated orange-red solution and white precipitate.The filtering precipitation, evaporating solvent gets 0.8040 gram sorrel thick liquid.Molecular formula is C
49H
81BO
6Ti, molecular weight 808.Ultimate analysis: C (wt%), measured value (theoretical value): 72.77 (72.77); H (wt%), measured value (theoretical value): 10.04 (10.02); Chemical analysis: not chloride.
Embodiment 7:
The preparation of the single indenes titanium of boric acid di-isooctyl base-two (2,6-di-isopropyl phenoxy group)
In 100 milliliters the stirring reaction bottle of handling well through anhydrous and oxygen-free, add 50 milliliters of hexanes, 0.5550 gram embodiment 3 synthetic catalyzer (1 mmole), at the uniform velocity drip 2 in 20 minutes, the hexane solution (2 of 6-diisopropyl phenol, pyridine, 6-diisopropyl phenol 0.1780 gram, pyridine 0.0790 gram are with 20 milliliters of hexane dilutions), reacted 2 hours, and generated orange-yellow solution and white precipitate.The filtering precipitation, evaporating solvent gets 0.8013 gram tawny liquid, productive rate 95.6%.Molecular formula is C
49H
75BO
5Ti, molecular weight 802.Ultimate analysis: C (wt%), measured value (theoretical value): 73.34 (73.32); H (wt%), measured value (theoretical value): 9.36 (9.35); Chemical analysis: not chloride.
Embodiment 8:
Embodiment 2-7 institute synthetic catalyzer causes ethene, propylene polymerization result.
In 200 milliliters the glass autoclave of handling well through anhydrous and oxygen-free that has bottom insert canal, stirring, add 50 milliliters of hexanes, 0.4 milliliter ethyl aikyiaiurnirsoxan beta (hexane solution 2.5M), 0.4 milliliter sec.-propyl aikyiaiurnirsoxan beta (hexane solution 2.5M), be warming up to 50 ℃, add one of 1 milliliter of embodiment 2-7 institute synthetic Primary Catalysts (hexane solution 1 μ mol/ml), feed ethene, propylene gas mixture (weight ratio 1: 2.5) by bottom insert canal, reaction is 1 hour under 0.2Mpa pressure, stops ventilation.The glue of emitting adds 5 milliliter of 10% ethanol solution hydrochloride termination reaction.With the washing of 20% alkaline solution, vacuum evaporating solvent gets white polymer, calculates catalytic efficiency.Polymerization result sees Table one.
Table one polymerization result
| Sequence number | The Primary Catalysts source | Synthetic product (g) | Catalytic efficiency kg/mmol (polymkeric substance/catalyzer) |
| 1 | Embodiment 2 | 1.2556 | 1.2556 |
| 2 | Embodiment 3 | 1.2345 | 1.2345 |
| 3 | Embodiment 4 | 1.5105 | 1.5105 |
| 4 | Embodiment 5 | 1.5307 | 1.5307 |
| 5 | Embodiment 6 | 1.5113 | 1.5113 |
| 6 | Embodiment 7 | 1.5165 | 1.5165 |
| 7 * | Embodiment 5 | 1.1103 | 1.1103 |
* do not add aikyiaiurnirsoxan beta, add 50 μ mol triisobutyl aluminiums, 1 μ mol tritane base four (pentafluorophenyl group) boron.
Claims (1)
1. boron oxygen base single metallocene-titanium catalyst, it is characterized in that: its structure is by formula (I)
Statement:
In the formula: Cp is a cyclopentadienyl; M is a boric acid di-isooctyl base; X is chlorine or isopropoxy; Ti is a titanium atom.
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| CN101250238B true CN101250238B (en) | 2010-06-02 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5151399A (en) * | 1990-10-18 | 1992-09-29 | Shell Oil Company | Olefin polymerization catalyst |
| CN1340551A (en) * | 2000-08-29 | 2002-03-20 | 中国石油化工集团公司 | Metallocene titanium compound and its preparing process |
| CN1345887A (en) * | 2000-09-28 | 2002-04-24 | 中国石油化工股份有限公司 | Semi-metallocene supported polyvinyl catalyst and preparation method thereof |
| CN1593763A (en) * | 2003-09-10 | 2005-03-16 | 中国石油天然气股份有限公司 | Furan contained metallic catalyst, preparation method and application thereof |
-
2008
- 2008-03-28 CN CN2008101029374A patent/CN101250238B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5151399A (en) * | 1990-10-18 | 1992-09-29 | Shell Oil Company | Olefin polymerization catalyst |
| CN1340551A (en) * | 2000-08-29 | 2002-03-20 | 中国石油化工集团公司 | Metallocene titanium compound and its preparing process |
| CN1345887A (en) * | 2000-09-28 | 2002-04-24 | 中国石油化工股份有限公司 | Semi-metallocene supported polyvinyl catalyst and preparation method thereof |
| CN1593763A (en) * | 2003-09-10 | 2005-03-16 | 中国石油天然气股份有限公司 | Furan contained metallic catalyst, preparation method and application thereof |
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