CN100418988C - Catalyst for propylene polymerization and its preparation method - Google Patents
Catalyst for propylene polymerization and its preparation method Download PDFInfo
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- CN100418988C CN100418988C CNB2004100506490A CN200410050649A CN100418988C CN 100418988 C CN100418988 C CN 100418988C CN B2004100506490 A CNB2004100506490 A CN B2004100506490A CN 200410050649 A CN200410050649 A CN 200410050649A CN 100418988 C CN100418988 C CN 100418988C
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Abstract
The present invention relates to the field of a catalyst component and a preparation method thereof, particularly to a catalyst for propylene polymerization and a preparation method thereof. The catalyst comprises raw materials by mol: 1 of MgCl2, 2 to 4 of solvent oil, 0.2 to 3 of isooctanol, 0.1 to 1 of ester titanate, 0.01 to 0.4 of estolide, 5 to 30 of TiCl4, 0.01 to 0.05 of diisobutyl phthalate, 5 to 20 of toluene and 10 to 30 of hexane. The preparation technology of the catalyst comprises the procedures that 1), the anhydrous MgCl2, the solvent oil with the concentration of 200 and the isooctanol are added in a reaction bulb; the materials start to be stirred and heated, and tetrabutyl titanate and phthalic anhydride are added into the reaction bulb; 2) a homogeneous solution prepared by the method is dropped in a glass reactor containing a mixture of the TiCl4 and the refined toluene at the temperature of minus 20DEGC, and the diisobutyl phthalate is added.
Description
Technical field
The present invention relates to a kind of preparation method field of catalyst component, particularly a kind of preparation method who is used for the catalyst component of propylene polymerization.
Background technology
At present, the catalyst component that uses of propylene polymerization mostly is that the Ziegler-Natta type is with the effective catalyst of magnesium chloride as carrier.Magnesium chloride and organic solvent reaction form homogeneous solution, again this drips of solution is added in the titanium tetrahalide or with halogenated titanium and is added in this solution, generate precipitation, handle precipitation with the multi-carboxylate, it is loaded with on solid precipitation, obtain the component of solid catalyst again through the washing of titanium tetrahalide and inert diluent.As Chinese patent CN85100997A and CN02148336.1 etc.During propylene polymerization, under the promotor effect, also must add external electron donor and just can obtain high isotactic product.
Use the internal electron donor of diether compound in addition, do not add external electron donor during propylene polymerization and can obtain higher isotactic product as catalyzer.CN1087094A etc. for example.
Though application effective catalyst patent is more, the catalyzer patent that produces different performance under a kind of system is considerably less.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of processing step simple, produces different performance under a kind of system, the preparation technology of the catalyst for polymerization of propylene component that catalytic efficiency is high.
Technical solution of the present invention can realize according to following mode:
A kind of preparation technology who is used for the catalyst component of propylene polymerization, carry out as follows successively:
1) in the glass reaction bottle after nitrogen is fully replaced, adds anhydrous MgCl
2With 200# solvent oil and isooctyl alcohol; Open to stir and begin and heat up, under 130 ℃, kept 2 hours; Titanic acid ester and acid anhydrides are added in the reaction flask, and reaction is 2 hours under this temperature, obtains the homogeneous complex solution, and cool to room temperature;
2), in 30 minutes, splash into-20 ℃ and fill TiCl with the homogeneous solution of method for preparing
4With the refined toluene mixture or fill TiCl
4In the glass reactor of 200# oil miscible solvent compound, under agitation keep 0.5h; Be warming up to 108 ℃ through 4h, under this temperature, add diisobutyl phthalate, continue to be warmed up to 110 ℃ of reaction 2h, after suction filtration goes out liquid, add TiCl again
4Be warmed up to 110 ℃ once more, reaction 2h, after reaction finished, elimination liquid 80 ℃ of washings one time, used hexane less than 2ppm to be washed till in the filtrate till the no free chlorion with purified toluene again, and the remaining solid product obtains ingredient of solid catalyst through vacuum-drying;
Above-mentioned raw materials thing: MgCl
2, 200# solvent oil, isooctyl alcohol, titanic acid ester, acid anhydrides, TiCl
4, diisobutyl phthalate, toluene, hexane mol ratio be followed successively by: 1: 2～4: 0.2～3: 0.1～1: 0.01～0.4: 5～30: 0.01～0.05: 5～20: 10～30;
Above-mentioned titanic acid ester is a tetrabutyl titanate; Described acid anhydrides is a Tetra hydro Phthalic anhydride.
Catalyst for polymerization of propylene processing step provided by the invention is simple, and by the adjustment of different condition, catalyzer will have different performances.
Embodiment
The preparation of catalyst component involved in the present invention comprises following two parts:
The preparation of A complex compound:
In the glass reaction bottle after nitrogen is fully replaced, add the anhydrous MgCl of 5g
2With 40ml200# solvent oil and 24ml isooctyl alcohol.Open to stir and begin and heat up, under 130 ℃, kept 2 hours.0.75ml tetrabutyl titanate and 1g Tetra hydro Phthalic anhydride are added in the reaction flask, and reaction is 2 hours under this temperature, obtains the homogeneous complex solution, and cool to room temperature.
The titanizing of B complex compound:
With the homogeneous solution of method for preparing, in 30 minutes, splash into-20 ℃ and fill 200mlTiCl
4In the glass reactor of 10ml refined toluene mixture, under agitation keep 0.5h.Be warming up to 108 ℃ through 4h, under this temperature, add the diisobutyl phthalate of 1.5ml, continue to be warmed up to 110 ℃ of reaction 2h, after suction filtration goes out liquid, add 200ml TiCl again
4Be warmed up to 110 ℃ once more, reaction 2h, after reaction finished, elimination liquid 80 ℃ of washings one time, used hexane less than 2ppm to be washed till in the filtrate till the no free chlorion with purified toluene again.The remaining solid product obtains ingredient of solid catalyst through vacuum-drying.
Solid ingredient is analyzed as follows:
Titanium content %=1.8;
Mg content %=19.53;
Cl content %=58.4;
Ester content %=12.68;
Aggregation test
Volume is 3 liters a stainless steel autoclave, and motor revolution 0 to 1000 is adjustable, injects the polymerization-grade propylene of 2L, 6ml promotor triethyl aluminum (1.8mol/L, n-heptane solution) and 0.8ml dimethoxydiphenylsilane (volumetric concentration is 25%, n-heptane solution), hotwire, revolution are transferred to 500 to be changeed.The 0.015g catalyzer that measures is added in the still, treat pressure equilibrium after, add the hydrogen of 0.2MPa, autoclave is warmed up to 70 ℃ of reaction 2h.Reduce to room temperature, stop to stir and discharging residue gas reactor, obtain the 536g polymkeric substance.The polymkeric substance test result sees Table 1
Embodiment 2
The preparation of A complex compound is with embodiment 1.
The titanizing of B complex compound:
With the homogeneous solution of method for preparing, in 30 minutes, splash into-20 ℃ and fill 200mlTiCl
4Make with extra care in the glass reactor of 200# oil miscible solvent compound with 20ml, under agitation keep 0.5h.Be warming up to 108 ℃ through 4h, under this temperature, add the diisobutyl phthalate of 1.5ml, continue to be warmed up to 110 ℃ of reaction 2h, after suction filtration goes out liquid, add 200ml TiCl again
4Be warmed up to 110 ℃ once more, reaction 2h, after reaction finished, elimination liquid 80 ℃ of washings one time, used hexane less than 2ppm to be washed till in the filtrate till the no free chlorion with purified toluene again.The remaining solid product obtains ingredient of solid catalyst through vacuum-drying.
Aggregation test is with example 1.
Embodiment 3
The preparation of A complex compound is with embodiment 1
The titanizing of B complex compound:
With the homogeneous solution of method for preparing, in 30 minutes, splash into-20 ℃ and fill 1.2ml TiCl
4Make with extra care in the glass reactor of 200# oil miscible solvent compound with 80ml, under agitation keep 0.5h.Improve and stir revolution to 800 commentaries on classics, be warming up to 108 ℃ through 4h, under this temperature, add the diisobutyl phthalate of 1.5ml, continue to be warmed up to 110 ℃, reaction 2h after suction filtration goes out liquid, adds 200ml TiCl again
4Be warmed up to 110 ℃ once more, reaction 2h, after reaction finished, elimination liquid 80 ℃ of washings one time, used hexane less than 2ppm to be washed till in the filtrate till the no free chlorion with purified toluene again.The remaining solid product obtains ingredient of solid catalyst through vacuum-drying.
Mg(OEt)
2/Di+TiCl
4→Mg(OEt)Cl+Di+Ti(OEt)Cl
3
Mg(OEt)Cl+Di+TiCl
4→MgCl
2·Di+Ti(OEt)Cl
3
Mg(OEt)
2/Di+TiCl
4→MgCl
2·Di+Ti(OEt)
2Cl
2
D1, D2 represent the ester class, and ROH represents alcohols;
Aggregation test is with example 1
Obtain the 566g polymkeric substance, test result sees Table 1
Table 1
| Example | Titanium content wt% | Active kgPP/gCat | Apparent density g/cm 3 | Catalyzer median size D50um |
| Embodiment 1 | 1.8 | 35.73 | 0.43 | 17-20 |
| Embodiment 2 | 1.76 | 33.86 | 0.44 | 21-25 |
| Embodiment 3 | 1.92 | 37.73 | 0.44 | 10-12 |
The specific surface area of three kinds of catalyzer of table 2, mean pore size, pore volume test result
| Catalyzer | Titanium content wt% | Active Kgpp/gCat | Apparent density g/cm 3 | Catalyzer median size D50um | Specific surface area (m 2/g) | Pore volume (cm 2/g ) |
| Domestic | 1.8 | 35.73 | 0.43 | 17-56 | 170 | 0.25 |
| DJD | 1.76 | 25.86 | 0.44 | 49 | 206 | 0.25 |
| The import similar catalyst | 1.92 | 26.13 | 0.44 | 49 | 205 | 0.25 |
Claims (2)
1. a preparation method who is used for the catalyst component of propylene polymerization is characterized in that, carries out successively as follows:
1) in the glass reaction bottle after nitrogen is fully replaced, adds anhydrous MgCl
2With 200# solvent oil and isooctyl alcohol; Open to stir and begin and heat up, under 130 ℃, kept 2 hours; Titanic acid ester and acid anhydrides are added in the reaction flask, and reaction is 2 hours under this temperature, obtains the homogeneous complex solution, and cool to room temperature;
2), in 30 minutes, splash into-20 ℃ and fill TiCl with the homogeneous solution of method for preparing
4With the refined toluene mixture or fill TiCl
4In the glass reactor of 200# oil miscible solvent compound, under agitation keep 0.5h; Be warming up to 108 ℃ through 4h, under this temperature, add diisobutyl phthalate, continue to be warmed up to 110 ℃ of reaction 2h, after suction filtration goes out liquid, add TiCl again
4Be warmed up to 110 ℃ once more, reaction 2h, after reaction finished, elimination liquid 80 ℃ of washings one time, used hexane less than 2ppm to be washed till in the filtrate till the no free chlorion with purified toluene again, and the remaining solid product obtains ingredient of solid catalyst through vacuum-drying;
Above-mentioned raw materials thing: MgCl
2, 200# solvent oil, isooctyl alcohol, titanic acid ester, acid anhydrides, TiCl
4, diisobutyl phthalate, toluene, hexane mol ratio be followed successively by: 1: 2～4: 0.2～3: 0.1～1: 0.01～0.4: 5～30: 0.01～0.05: 5～20: 10～30.
2. according to the described preparation method who is used for the catalyst component of propylene polymerization of claim 1, it is characterized in that: described titanic acid ester is a tetrabutyl titanate; Described acid anhydrides is a Tetra hydro Phthalic anhydride.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100506490A CN100418988C (en) | 2004-10-22 | 2004-10-22 | Catalyst for propylene polymerization and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100506490A CN100418988C (en) | 2004-10-22 | 2004-10-22 | Catalyst for propylene polymerization and its preparation method |
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| CN1763108A CN1763108A (en) | 2006-04-26 |
| CN100418988C true CN100418988C (en) | 2008-09-17 |
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| CN113896817B (en) * | 2021-10-26 | 2022-12-02 | 茂名实华东成化工有限公司 | g-C 3 N 4 /MgCl 2 Preparation method of composite carrier type propylene polymerization catalyst |
| CN117736357B (en) * | 2024-02-21 | 2024-04-16 | 淄博新塑化工有限公司 | Polypropylene catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198751A (en) * | 1995-10-11 | 1998-11-11 | 三井化学株式会社 | Process for the preparation of solid titanium catalyst component for the polymerization of olefins and process for the production of polyolefins |
| JP2003026719A (en) * | 2001-07-17 | 2003-01-29 | Mitsui Chemicals Inc | Method for producing solid titanium catalyst component for olefin polymerization, olefin polymerization catalyst, prepolymerization catalyst for olefin polymerization, and method for olefin polymerization |
-
2004
- 2004-10-22 CN CNB2004100506490A patent/CN100418988C/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1198751A (en) * | 1995-10-11 | 1998-11-11 | 三井化学株式会社 | Process for the preparation of solid titanium catalyst component for the polymerization of olefins and process for the production of polyolefins |
| JP2003026719A (en) * | 2001-07-17 | 2003-01-29 | Mitsui Chemicals Inc | Method for producing solid titanium catalyst component for olefin polymerization, olefin polymerization catalyst, prepolymerization catalyst for olefin polymerization, and method for olefin polymerization |
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| CN1763108A (en) | 2006-04-26 |
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Assignee: Yingkou Dingjide Petrochemical Co., Ltd. Assignor: Zhang Lizhi|Zhang Zaiming|Zhang Jindi|Zhang Libo Contract fulfillment period: 2009.3.18 to 2024.10.22 contract change Contract record no.: 2009210000023 Denomination of invention: Catalyst for propylene polymerization and its preparation method Granted publication date: 20080917 License type: Exclusive license Record date: 2009.3.19 |
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Effective date of registration: 20160105 Address after: 115006 lime village, willow town, old border area, Yingkou, Liaoning Patentee after: Liaoning Dingjide Petrochemical Co., Ltd. Address before: 115005 science and Technology Committee of old border area, Yingkou, Liaoning Patentee before: Zhang Lizhi Patentee before: Zhang Zaiming Patentee before: Zhang Libo Patentee before: Zhang Jindi |