Universal alpha-olefin polymerization catalyst, and application thereof

Abstract

Disclosed are a universal alpha-olefin polymerization industrial catalyst, and an application thereof, specifically an industrial production catalyst which consists of (A) a solid catalyst component, (B) a cocatalyst organoaluminium compound and (C) an external electron donor compound, and is used for various alpha-olefin polymerization or copolymerization processes. The solid catalyst component (A) is prepared from a dibutyl phthalate or diisobutyl phthalate and 9,9-bis(methoxymethyl)fluorene composite internal electron donor. A hydrocarbyl alkoxy silicon, an organic acid ester or a hydrocarbyl alkoxy silicon and organic acid ester composite acts as the external electron donor component (C). The solid catalyst component (A), the cocatalyst organoaluminium compound (B) and the external electron donor compound (C) are used together in industrial devices for various alpha-olefin polymerization or copolymerization processes to produce new grades of poly-alpha-olefins.

Claims

1. A catalyst for large-scale industrial preparation of poly-α-olefins in various polymerization processes, comprising a catalyst component A, a cocatalyst alkyl aluminum B, and an external electron donor C; wherein: (1) the catalyst component A consists of titanium ions and a composite internal electron donor aromatic diaciddialkyl ester and 1,3-diether supported on magnesium chloride; (2) the cocatalyst alkyl aluminum B is triethyl aluminum, triisobutyl aluminum or a mixture thereof; and (3) the external electron donor C comprises an organic acid ester or a hydrocarbylalkoxy silicon and organic acid ester composite, and wherein the cocatalyst alkylaluminum B and titanium ions (Ti) have a molar ratio in the range of 60-75.

2. The catalyst according to claim 1, wherein in the catalyst component A, the aromatic diaciddialkyl ester is diisobutyl phthalate.

3. The catalyst according to claim 2, wherein in the catalyst component A, the 1,3-diether is 9,9-bis(methoxymethyl)fluorene.

4. The catalyst according to claim 3, wherein in the catalyst component A, the mass fraction of titanium is 2.0-3.8%, the mass fraction of magnesium is 15.0-20.0%, the mass fraction of diisobutyl phthalate is 1.0-7.0%, and the mass fraction of 9,9-bis(methoxymethyl)fluorene is 1.0-9.0%.

5. The catalyst according to claim 3, wherein a molar ratio of diisobutyl phthalate and 9,9-bis(methoxymethyl) fluorene is 1-9.9:10.

6. The catalyst according to claim 1, wherein the preparation method of the catalyst component A comprises one of a)-c): a) co-precipitation of a magnesium chloride alcoholate, a composite internal electron donor and titanium tetrachloride; b) supporting titanium tetrachloride and a composite internal electron donor on a spherical magnesium chloride alcoholate support; or c) supporting a composite internal electron donor on magnesium chloride generated by reaction of diethoxymagnesium and titanium tetrachloride.

7. The catalyst according to claim 1, wherein: the organic acid ester is a C.sub.10-20 linear natural fatty acid C.sub.3-5 branched alkyl ester; and the hydrocarbylalkoxy silicon and organic acid ester composite is selected from the group consisting of propyltrimethoxysilicon and isopropyl myristate, dicyclopentyldimethoxysilicon and isopropyl myristate, and diphenyldimethoxysilicon and isopropyl myristate composites.

8. The catalyst according to claim 1, wherein a molar ratio of the hydrocarbylalkoxy silicon and the organic acid ester is 1-9.9:10.

9. The catalyst according to claim 1, wherein the alpha-olefin polymerization is propylene polymerization, 1-butene polymerization, ethylene and propylene copolymerization, ethylene and 1-butene copolymerization, or propylene and 1-butene copolymerization.

10. A method of using the catalyst according to claim 1 in large-scale industrial production of poly-α-olefins in a polymerization process, the method comprising: providing the catalyst according to claim 1, contacting the catalyst with an α-olefin to effect polymerization of the α-olefin; wherein the process comprises: (1) a gas phase reaction which is: α-olefin polymerization in a gas-phase fluidized bed reactor process, α-olefin polymerization in a vertical stirred-tank gas-phase reactor process, α-olefin polymerization in a horizontal stirred-tank gas-phase reactor process, or α-olefin polymerization in the a horizontal stirred-tank gas-phase reactor process; (2) a batch bulk reaction which is an α-olefin polymerization process in a tank reactor; or (3) a continuous bulk reaction which is an α-olefin polymerization process in a loop reactor process or α-olefin polymerization process having one horizontal bulk reactor and one horizontal gas-phase reactor tank arranged in series.

11. The method of claim 10, wherein the catalyst is according to claim 4.

12. The method of claim 10, wherein the catalyst is according to claim 5.

13. The method of claim 10, wherein the catalyst is according to claim 8.

14. The catalyst according to claim 1, wherein in the catalyst component A, the aromatic diaciddialkyl ester is di-n-butyl phthalate.

15. The catalyst according to claim 14, wherein in the catalyst component A, the 1,3-diether is 9,9-bis(methoxymethyl)fluorene.

16. The catalyst according to claim 15, wherein a molar ratio of di-n-butyl phthalate and 9,9-bis(methoxymethyl) fluorene is 1-9.9:10.

17. The catalyst according to claim 15, wherein in the catalyst component A, the mass fraction of titanium is 2.0-3.8%, the mass fraction of magnesium is 15.0-20.0%, the mass fraction of di-n-butyl phthalate is 1.0-7.0%, and the mass fraction of 9,9-bis(methoxymethyl)fluorene is 1.0-9.0%.

18. A catalyst for large-scale industrial preparation of poly-α-olefins in various polymerization processes, comprising a catalyst component A, a cocatalyst alkyl aluminum B, and an external electron donor C; wherein: (1) the catalyst component A consists of titanium ions and a composite internal electron donor aromatic diaciddialkyl ester and 1,3-diether supported on magnesium chloride; (2) the cocatalyst alkyl aluminum B is triethyl aluminum, triisobutyl aluminum or a mixture thereof; and (3) the external electron donor C is a hydrocarbylalkoxy silicon, an organic acid ester or a hydrocarbylalkoxy silicon and organic acid ester composite, and wherein the cocatalyst alkylaluminum B and titanium ions (Ti) have a molar ratio in the range of 60-75.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) The following non-limiting examples are provided to enable those skilled in the art to more fully understand the invention, and are not to be interpreted in any way as limiting the invention.

Example 1

(2) On an introduced 600,000-ton propylene polymerization device in the UNIPOL gas-phase fluidized bed reactor process, a Z-N catalyst component A which is a composite internal electron donor containing 5% of 9,9-bis(methoxymethyl) fluorene and 2.5% of di-isobutyl phthalate, a cocatalyst triethyl aluminum, and a propyltrimethoxysilicon and isopropyl myristate composite external electron donor were used. The operation parameters were as follows: reactor temperature of 68.5-71.5° C., partial pressure of propylene of 2.7-2.8 MPag, TEAL/Ti of 60-75, H.sub.2/C.sub.3 ratio of 0.0028, and catalyst retention time of 1.29 h. Polypropylene powders were produced respectively using the catalyst of the present invention and the catalyst along with the device, and were sampled for analysis. The results are shown in a table below:

(3) TABLE-US-00001 LT100 Production Melt Bulk mesh line Sampling index Tacticity density APS screen fine Residual Residual Residual comparison time g/10 min index % Kg/m3 mm powder % Al, ppm Ti, ppm Cl, ppm Catalyst of Day 18, 3.47 97.31 335 0.75 1.14 48.0 0.9 12.4 the present 09:00 invention Catalyst Day 18, 3.30 96.64 304 0.81 1.68 48.9 0.9 19.8 along with 09:00 the device

(4) By comparison, it is found that compared with polypropylene produced using the catalyst along with the device, polypropylene produced using the catalyst of the present invention has a larger tacticity index, a higher bulk density, a comparable average particle size, a lower fine powder content, and a higher activity.

(5) Compared with the polypropylene product produced using the catalyst along with the device, the polypropylene product produced using the catalyst of the present invention has a lower ash content and a lower yellowness index.

(6) The unit consumption of the catalyst of the present invention is lower than the unit consumption of the catalyst along with the device by 19.6% on average, the unit consumption of triethyl aluminum is lower than that for the catalyst along with the device by 30.6% on average, and the unit consumption of the external electron donor is lower than that of the imported electron donor by 32.6%.

(7) Polypropylene produced by the present fluidized bed reactor is a universal polypropylene. The efficiency of the catalyst is 24 kg.sub.PP/g catl.

Example 2

(8) On an introduced propylene polymerization process device in the NOVOLEN vertical stirred-tank gas-phase reactor process with a 550,000-ton annual output, a Z-N improved catalyst of the present invention consisting of a catalyst component A containing 2.7% of titanium, 18.5% of magnesium, 8% of 9,9-bis(methoxymethyl) fluorene, and 7% of di-isobutyl phthalate, a cocatalyst triethyl aluminum, and an external electron donor methylcyclohexyldimethoxysilicon was used. The operations were performed following process parameters along with the device, and 1638.5 tons of a wire drawing material of grade 1080K, 10984.4 tons of an injection molding material of grade 1100N, and 794.9 tons of a product of grade HPPSS, all qualified, were produced. The catalyst activity is 28.85 kgpp/g catalyst. By adjusting the process parameters, the tacticity of the wire drawing material of 1080K is adjusted to the tacticity for producing a thin film material of BOPP; and by hydrogen adjusting process, the polyolefin of an injection molding material of grade 1100N is transformed to produce a product with a high melt index. The catalyst activity is equal to or greater than 46 kgpp/g catalyst.

Example 3

(9) On a dual-reactor process with a 200,000-ton-annual-output gas-phase INNOVENE single-reactor process and an introduced 300,000-ton-annual-output INNOVENE process in series, a catalyst component A of the present invention containing 3%-5% of 9,9-bis(methoxymethyl) fluorene, 4%-5% of di-isobutyl phthalate, 2.5%-3% of titanium, and 18.0%-20% of magnesium, a cocatalyst triethyl aluminum, and an external electron donor methylcyclohexyldimethoxysilane were used. Propylene homopolymerization and ethylene/propylene copolymerization products could be produced, where the catalytic efficiency of the catalyst applied in the INNOVENE single reactor reaches 27 Kg.Math.PP/g.Math.cat, and the catalytic efficiency of the catalyst applied in the series dual reactor reaches 32 Kg.Math.PP/g.Math.cat.

Example 4

(10) In the continuous bulk method, on a propylene polymerization device in the SPHERIPOL loop reactor process with a 300,000-ton annual output of polypropylene, a catalyst component A of the present invention containing 2% of 9,9-bis(methoxymethyl) fluorene, 6% of di-isobutyl phthalate, 2.5% of titanium, and 18.9% of magnesium, a cocatalyst triethyl aluminum, and a typical external electron donor diisopropyldimethoxysilicon were used. The operations were performed following the production process parameters of the device (including prepolymerization) and the use evaluation conclusions were obtained: (1) the operation condition of the device is normal; (2) the activity is up to 52 kgPP/g cat, the hydrogen adjusting sensitivity is good, the tacticity of polypropylene is relatively high, and the fine powder amount in polypropylene is relatively low; (3) the control requirements in product quality can be satisfied; and (4) the use requirements in use can be satisfied.