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Solid composition as well as preparation method and application thereof

The technology of a solid composition and compound is applied in the application field as a carrier of an olefin polymerization catalyst, which can solve the problems of reducing the yield of the carrier per reactor, increasing the solvent recovery cost of the inert dispersion medium, etc., achieving good particle shape and improving the yield of the single reactor. , the effect of high stereoregularity

Active Publication Date: 2015-04-29
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0011] Although the technical solution disclosed in the above patent application reduces the cost of raw materials for carrier preparation and simplifies the carrier preparation process, due to the need to use a large amount of inert dispersion medium in the carrier preparation process, the single-pot yield of the carrier is reduced, and the inert dispersion The recovery of the medium increases the cost of solvent recovery; in addition, the stereoregularity of the polymer obtained during the olefin polymerization process using the olefin polymerization catalyst supported by the patent application needs to be further improved

Method used

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  • Solid composition as well as preparation method and application thereof
  • Solid composition as well as preparation method and application thereof
  • Solid composition as well as preparation method and application thereof

Examples

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preparation example Construction

[0068] In a more preferred embodiment, the preparation method of the solid composition may include:

[0069] (I) In a closed container, heat the mixture of magnesium halide, organic alcohol and at least one polymer dispersion stabilizer to 30-160℃, preferably 40-120℃, and react for 0.1-5 hours, preferably 0.5 -2 hours to form a magnesium halide alcoholate solution, wherein, per mole of magnesium, the amount of the organic alcohol is 3-30 moles, preferably 4-25 moles; the amount of the polymer dispersion stabilizer is The total amount of the magnesium halide and the organic alcohol is 0.1-10% by weight, preferably 0.2-5% by weight.

[0070] (Ii) Under stirring, add the alkylene oxide compound represented by formula (2) to the magnesium halide alcoholate solution, and react at 30-160°C (preferably 40-120°C) for 0.1-5 hours, It is preferably 0.3-1 hour to form solid composition particles, wherein, per mole of magnesium, the amount of the alkylene oxide compound is 1-10 moles, prefera...

Embodiment 1-17

[0080] These examples are used to illustrate the solid composition of the present invention and its preparation method.

[0081] In a 500mL airtight reactor, add magnesium chloride and organic alcohol (R 1 OH) and polymer dispersion stabilizer, heated to the reaction temperature (T) under stirring, after constant temperature reaction for 1 hour, add the alkylene oxide compound (E), maintain the temperature for 0.5 hours, filter off the liquid, and wash with hexane Five times, vacuum drying, to obtain solid composition particles, the specific preparation conditions are shown in Table 1, so as to prepare spherical solid compositions A1-A17, wherein the average particle size (D50) and particle size of each of these solid compositions The distribution value (SPAN) is shown in Table 1. The solid composition A1 1 The H-NMR spectrum is as figure 1 As shown, the solid composition A2 1 The H-NMR spectrum is as figure 2 As shown, the solid composition A13 1 The H-NMR spectrum is as image ...

Embodiment 18

[0115] This example is used to illustrate the application of the solid composition of the present invention.

[0116] (1) Preparation of solid catalyst

[0117] In a 300 mL glass reaction flask, 100 ml of titanium tetrachloride was sequentially added, cooled to -20°C, 8 g of the solid composition A1 prepared in Example 1 above was added, and the temperature was raised to 110°C. During the heating process, 1.5 ml of diisobutyl phthalate was added, the liquid was filtered off, washed twice with titanium tetrachloride, washed three times with hexane, and dried under vacuum to obtain a solid catalyst Cat-1.

[0118] (2) Liquid phase bulk polymerization of propylene

[0119] The liquid phase bulk polymerization of propylene was carried out in a 5L stainless steel autoclave. Under the protection of nitrogen, add 5ml triethylaluminum hexane solution (concentration 0.5mmol / ml) and 1ml cyclohexylmethyldimethoxysilane (CHMMS) hexane solution (concentration 0.1mmol) to the reaction kettle in se...

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Abstract

The invention relates to a solid composition as well as a preparation method and application thereof. The solid composition comprises a magnesium compound shown in the formula (1) (shown in the description) and an epoxy alkanes compound shown in the formula (2) (shown in the description), wherein R1 is linear or branched alkyl of C1-C12; R2 and R3 are identical or different, and are independently hydrogen or linear or branched alkyl with C1-C5; hydrogen on alkyl is alternately replaced by halogens; X is halogen; m is a number from 0.1 to 1.9, n is a number from 0.1 to 1.9, and m plus 2 is equal to 2; relative to each mole of the magnesium compound shown in the formula (1), the epoxy alkanes compound shown in the formula (2) is 0.01-0.8 mole. When being used for propylene polymerization, a catalyst prepared by the solid composition disclosed by the invention is higher in polymerization activity and higher in stereotactic capacity.

Description

Technical field [0001] The invention relates to a solid composition, a preparation method of the solid composition, a solid composition prepared by the method, and the application of the solid composition as a catalyst carrier, especially as an olefin polymerization catalyst carrier. Background technique [0002] Most of the catalysts used for olefin polymerization are prepared by supporting titanium halide on active anhydrous magnesium chloride. Among them, a common method used to prepare active magnesium chloride is to add anhydrous MgCl 2 It reacts with alcohol to form the general formula MgCl 2 ·MROH·nH 2 O's magnesium chloride-alcohol adduct, and then use this adduct to support titanium halide to prepare the solid component of the olefin polymerization catalyst. Such alcohol compounds can be prepared by spray drying, spray cooling, high-pressure extrusion or high-speed stirring. Such as: US4421674, US4469648, WO8707620, WO9311166, US5100849, US6020279, US4399054, EP0395383,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C08F10/00C08F10/06C08F4/02
Inventor 李威莅夏先知刘月祥凌永泰赵瑾张纪贵高富堂高平谭扬彭人琪张志会林洁段瑞林马长友
Owner CHINA PETROLEUM & CHEM CORP
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