CN1050136C

CN1050136C - Preparation of high performance supported catalyst for propylene polymerization

Info

Publication number: CN1050136C
Application number: CN94115522A
Authority: CN
Inventors: 聂通元; 黄婉利; 耿英杰
Original assignee: Sinopec Zhenhai Refining and Chemical Co Ltd
Current assignee: Sinopec Zhenhai Refining and Chemical Co Ltd
Priority date: 1994-09-10
Filing date: 1994-09-10
Publication date: 2000-03-08
Anticipated expiration: 2014-09-10
Also published as: CN1118354A

Abstract

The present invention relates to a taniferous catalyst of a magnesium chloride carrier for the homopolymerization of olefin, and the preparation thereof. Magnesium chloride, benzoic anhydride, 2-ethylhexanol and an analyzing agent in the class of titanium are mixed and react for forming a homogeneous solution in the class of hydrocarbon; the solution is orderly treated by a mixed solution comprising titanium tetrachloride or itanium alkoxychloride and low-carbon saturated hydrocarbon and by dibutyl phthalate; a titaniferous solid catalyst obtained by the treatment of the titanium tetrachloride is used as a component A; AlEt3 is used as a component B; dibenzodimethoxysilane is used as a component C; and the component A, the component B and the component C form the catalyst system. The catalyst has the advantages of good poison resisting performance, high and stable activity, strong capacity of orientation, good obtained resinousness, no fine powder, etc.

Description

The preparation of propylene polymerization carried catalyst

The invention relates to the preparation method of carried catalyst for polymerization of olefin.The preparation method of carried catalyst for polymerization of olefin and relevant technologies have many patent documentations.One of characteristics of these technology are magnesium chloride and alcohol (＞C ₆) the uniform MgCl of effect generation ₂-ester compound solution is used TiCl again ₄Handle the crystallization MgCl that obtains containing titanium chloride with dibutyl phthalate ₂The catalyst A component, as EP282,341 (or JP87/56,726), GB2111066.Such catalyzer has higher activity and very high directional property.These class methods are owing to adopt dissolving crystallized method to obtain catalyzer, and fine powder content is higher, reaches 1～5%; Catalyst tolerates toxicity can be relatively poor, need use the higher propylene feedstocks of purity and the activator of higher concentration during polymerization, and the later stage activity has bigger decay when being used for polymerization, causes propylene conversion to decrease.In addition, because the MgCl of such catalyzer ₂-ester compound needs at comparatively high temps (100～130 ℃) synthetic, generally can only adopt the inert solvent of boiling point more than 120 ℃, this inert solvent and TiCl ₄Boiling point approaching, when useless raw material reclaims, separate difficulty, yield is low, so Catalyst Production cost height, environmental pollution is also bigger.Characteristics of the present invention are to adopt industrial raw material higher alcohols, lower carbon number hydrocarbons, phthalic anhydride cheap and easy to get and add an amount of titanium class and help and analyse agent and pressing synthetic MgCl under the heat condition ₂The homogeneous solution of-ester complex compound, then under the refrigerated condition with such solution and specific TiCl ₄Or inhomogeneous reaction is carried out in alkoxyl group titanium chloride-lower carbon number hydrocarbons mixing solutions contact, reach the purpose of control catalyst particle shape and surface tissue, after the processing of titanium tetrachloride or alkoxyl group titanium chloride and carboxylicesters, titanium tetrachloride is handled, obtain solids containing titanium catalyst component (A), constitute catalyst system of the present invention jointly with component (B), component (C).This catalyst activity is high and stable, and resistance to poison is good, applies on full scale plant at present.

The supported catalyst system of the present invention's preparation contains ingredient of solid catalyst (A), comprises magnesium chloride, carboxylicesters, titanium chloride etc.; Component (B) is a triethyl aluminum; Component (C) is a dimethoxydiphenylsilane.

Feature of the present invention is magnesium chloride to be helped with phthalic anhydride, 2-Ethylhexyl Alcohol and titanium class analyse the agent hybrid reaction and make MgCl in varsol ₂The homogeneous solution of-ester complex compound, hydro carbons.This homogeneous solution successively through the mixed solvent of titanium tetrachloride or alkoxyl group titanium chloride and hydrocarbon composition and dibutyl phthalate handle, titanium tetrachloride handles to make and contains magnesium chloride and carboxylicesters and titaniferous ingredient of solid catalyst (A).Concrete steps are: magnesium chloride, 2-Ethylhexyl Alcohol, varsol etc. are added reactor, be warming up to 90～130 ℃ after the sealing, pressure rises to 0.1～0.7MPa, reacts 1.0～3.0 hours, adds phthalic anhydride, titanium class again and helps and analyse agent and continue to react under this temperature and pressure 1.5～2.0 hours.The mole of magnesium chloride and phthalic anhydride 1: 0.1～1: 0.2; Magnesium chloride is 1: 2.5～1: 4 with the mol ratio of alcohol, and varsol and magnesium chloride ratio are 6ml/g, and it is 0.2g/g that the titanium class helps the ratio of analysing agent and magnesium chloride.The mixing solutions that 1: 1.7 volume ratio of this homogeneous solution and titanium tetrachloride or alkoxyl group titanium chloride and hydro carbons is formed generates magnesium chloride-ester-titanium chloride cenotype at-35 ℃～0 ℃ after contacting, and is warming up in 2～6 hours in 100～130 ℃ of this section intervals then.At 65 ℃ of recovery part varsols in the scope of the temperature spot that is risen to.Add dibutyl phthalate and handled 1～3 hour, dibutyl phthalate and magnesium chloride mol ratio are 0.010～0.015.Filtered while hot is removed TiCl ₄Or the alkoxyl group titanium chloride gets solid chemical compound, continues to use TiCl ₄New liquid is handled once, removes by filter TiCl ₄Waste liquid is used hexane wash 4～6 times again, and obtaining with the magnesium chloride is the titaniferous of carrier and the solid catalyst of carboxylicesters (A).The general formula of titanium compound is Ti (OR) _nCl _4-n, wherein R is an alkyl, 0≤n≤3.

The varsol that the present invention uses is C ₅～C ₈Straight or branched or ring-type saturated alkane or its hydrocarbon mixture, preferably hexane, pentane or heptane.The general formula of alkoxyl group titanium chloride is Ti (OR) _xCl _4-xWherein R is an alkyl, 1≤x≤4.Ti (OC preferably ₈H ₁₇) ₂Cl ₂

It is Ti (OC that the titanium class helps the general formula of analysing agent ₈H ₁₇) _mCl _4-m, 0≤m≤3.Ti (OC preferably ₈H ₁₇) ₂Cl ₂

When catalyst system of the present invention was used for polymerization, the mol ratio of the titanium in the triethyl aluminum in aluminium and the component (A) was 30～500, preferably 50～200.The mol ratio of the aluminium in the dimethoxydiphenylsilane in silicon and the component (B) is 0.02～1.0, preferably 0.05～0.3.

The catalyst system that adopts the present invention to make is applicable to the body batchwise polymerization.Its catalyst system salient features with at present similar preferably outside catalyst system is equal to or slightly better, also has following advantage as catalytic activity, directional property, apparent density etc.:

1, catalyst tolerates toxicity can be good, and initial reaction stage is steadily active, and is active high and stable lasting, is applicable to general refinery gas to be the polypropylene production technique of raw material.

2, the polypropylene product that obtains with the polymerization catalyst of the present invention preparation, mechanical property is good, and melting index is regulated easily, helps many trades mark Products Development.

3, Preparation of Catalyst adopts the lower carbon number hydrocarbons solvent, and main raw material recovery technology is simple and easy and yield is high, has alleviated environmental pollution greatly, and has reduced the Catalyst Production cost.

Example 1:

Anhydrous MgCl ₂(5.0g 52.5 mmole), anhydrous 2-Ethylhexyl Alcohol 24ml (157.5 mmole) and dry hexane 30ml, reaction is 1.5 hours under 100 ℃ of 0.25MPa pressure, add 1.5g phthalic anhydride (10.1 mmole) then, two different octyloxy titanium dichloride 1.0g, continue reaction 1.5 hours, form homogeneous solution.This solution was added in 30 minutes in the mixed solvent of being made up of 90 milliliters of titanium tetrachlorides and 150 milliliters of hexanes that is refrigerated to-16 ℃, in 3 hours, be warming up to 100 ℃ then, after 80 ℃, begin distillation and reclaim hexane solvent.Add dibutyl phthalate 1.8ml (0.7 mmole) and handled 2.0 hours, remove by filter reaction solution, once with 90 milliliters of titanium tetrachloride re-treatments.Filter, collect solid product,, wash altogether five times with 50 milliliters of dry hexane wash.With suspension vacuum-drying, obtain titaniferous ingredient of solid catalyst (A), mainly consist of: Ti 2.6% Mg 18.8% Cl 61.4%.Example 2:

At the clean volume of displacement is in 35 liters of autoclaves, add 24 liters of liquid refinery gas propylene (the propylene quality index sees Table 1), solids containing titanium catalyst component (A) 0.12 mmole (calculating) that adds 13.7 mmole triethyl aluminums, 2.0 mmole dimethoxydiphenylsilanes and example 1 preparation more successively with titanium, add hydrogen 40PPm, be warming up to 78 ℃ of polyase 13 .0 hours, and obtained 8.3 kilograms of polypropylene.Polymerizing condition and result are respectively referring to the example in table 2 and the table 32.Example 3:

With 150 milliliters of hexanes in 150 milliliters of heptane replacement examples 1, other condition is constant.Polymerization process is with example 2, and polymerizing condition and result are respectively referring to the example in table 2 and the table 33.Example 4:

With 90 milliliters of (i-C ₈H ₁₇O) ₂TiCl ₂Replace 90 milliliters of TiCl in the example 1 ₄, other condition is with example 1, and polymerization process is with example 2, and polymerizing condition and result are respectively referring to the example in table 2 and the table 34.Example 5:

Do not add titanium and help and analyse agent, other condition is with example 1, and polymerization process is with example 2, and polymerizing condition and result are respectively referring to the example in table 2 and the table 35.Example 6:

Utilize the catalyzer (A) in the example 1, Al/Ti changes 70 into during with polymerization, and other condition is with example 2, and the result is respectively referring to the example in table 2 and the table 36.Example 7:

Utilize the catalyst component (A) in the example 1, [H during with polymerization ₂] changing 190PPm into, other condition is with example 6, and the result is respectively referring to the example in table 2 and the table 37.Comparative example:

According to EP282, the preparation of 341 methods, catalyzer titaniferous 2.3%, Al/Ti in the polymerization process (mol ratio) changes 240 into, and other is with example 2, and the result is referring to the comparative example in table 2 and the table 3.

Table 1 raw material propylene (refinery gas) is formed

Form	C ^＝ ₃?％	C° ₃％	C ^≡ ₂PPm	C ₃ ^≡C ₃ ^＝＝PPm	H ₂O PPm	O ₂PPm	Total S PPm	CO PPm	CO ₂PPm
Form	C ^＝ ₃?％	C° ₃％	C ^≡ ₂PPm	C ₃ ^≡C ₃ ^＝＝PPm	H ₂O PPm	O ₂PPm	Total S PPm	CO PPm	CO ₂PPm	Content	99.8	＜0.2	1	15	15-28	8-9	2.0	1	1.5

Table 2 polymerizing condition and polymerization activity

Example	The Al/Ti mol ratio	The Al/Si mol ratio	[H ₂]/[C ^＝ ₃] PPm
Example	The Al/Ti mol ratio	The Al/Si mol ratio	[H ₂]/[C ^＝ ₃] PPm	3	110	6.7	40
3	110	6.7	40	3	110	6.7	40
3	110	6.7	40	4	110	6.7	40
5	110	6.7	40	4	110	6.7	40
5	110	6.7	40	6	70	6.7	40
7	70	6.7	190	6	70	6.7	40
7	70	6.7	190	Comparative example	240	6.6	40

Continuous table

Example	Active		Activity stability K
	Active			×10 ³PP/gCat	×10 ⁶PP/gTi
	3	36		×10 ³PP/gCat	×10 ⁶PP/gTi	1.38	0.8
3	3	36	30	1.10	0.8	1.38	0.8
3	4	27	30	1.10	0.8	1.05	0.7
5	4	27	25	0.85	0.8	1.05	0.7
5	6	35	25	0.85	0.8	1.35	0.8
7	6	35	37	1.40	0.8	1.35	0.8
7	Comparative example	16	37	1.40	0.8	0.70	0.4

Annotate: activity stability K=(the 3rd hour activity/first hour activity)

Table 3 acrylic resin performance index

Example	Degree of isotacticity %	Chlorine root PPm	Ash PPm	Apparent density g/ml	Melting index g/10min
Example	Degree of isotacticity %	Chlorine root PPm	Ash PPm	Apparent density g/ml	Melting index g/10min	2	97.2	10.8	120	0.41	3.8
3	97.5	15	127	0.41	3.0	2	97.2	10.8	120	0.41	3.8
3	97.5	15	127	0.41	3.0	4	97.2	20	150	0.41	1.9
5	95.0	33	160	0.39	2.1	4	97.2	20	150	0.41	1.9
5	95.0	33	160	0.39	2.1	6	97.7	11.2	90	0.42	3.3
7	97.4	10.4	95	0.42	25	6	97.7	11.2	90	0.42	3.3
7	97.4	10.4	95	0.42	25	Comparative example	98.0	47	205	0.41	2.1

Continuous table

Example	Granularity				Tensile strength MPa	Elongation %
	Granularity						＞40 orders	The 40-80 order	The 80-100 order	＜100 orders
	2	90.6	8.1	0.2			＞40 orders	The 40-80 order	The 80-100 order	＜100 orders	0	37.5	240
3	2	90.6	8.1	0.2	80.5	19.0	0.2	0.1	37.2	300	0	37.5	240
3	4	84.0	14.7	1.0	80.5	19.0	0.2	0.1	37.2	300	0.3	36.8	320
5	4	84.0	14.7	1.0	21	64.5	2.3	12	35.7	140	0.3	36.8	320
5	6	92	7.7	0.3	21	64.5	2.3	12	35.7	140	0	37.7	220
7	6	92	7.7	0.3	90.4	9.3	0.2	0	37.2	460	0	37.7	220
7	Comparative example	18	78.1	2.4	90.4	9.3	0.2	0	37.2	460	1.8	33.4	270

Claims

1, a kind of preparation method who is used for the carried catalyst of alkene homopolymerization, described catalyst system contains (A), (B), (C) three kinds of components:

(A) being is the titaniferous of carrier and the ingredient of solid catalyst of carboxylicesters with the magnesium chloride, titanium compound general formula Ti (OR) _nCl _4-n, wherein R is an alkyl, 0≤n≤3;

(B) be AlEt ₃

(C) be (C ₆H ₅) ₂Si (OCH ₃) ₂

Its invention is characterised in that uses MgCl ₂, 2-Ethylhexyl Alcohol, phthalic anhydride, titanium class help analyses agent Ti (OC ₈H ₁₇) _mCl _4-m, 0≤m≤3 wherein are at C ₅～C ₈Confined reaction in stable hydrocarbon or its hydrocarbon mixture, reaction pressure are 0.1～0.7MPa, and 90～130 ℃ of temperature generate magnesium chloride-ester compound homogeneous solution, more successively with titanium tetrachloride or alkoxyl group titanium chloride Ti (OR) _xCl _4-x, 1≤x≤4 wherein, R is an alkyl, handles with mixed solvent, the dibutyl phthalate of hydrocarbon composition, titanium tetrachloride handles and make (A) component.

2, Preparation of catalysts method as claimed in claim 1 is characterized in that described varsol is pentane, hexane or heptane.

3, Preparation of catalysts method as claimed in claim 1, adding titanium class helps and analyses agent Ti (OC when it is characterized in that preparing ₈H ₁₇) ₂Cl ₂

4, Preparation of catalysts method as claimed in claim 1 is characterized in that in 65～130 ℃ of this section intervals, and the part lower carbon number hydrocarbons solvent in the reaction solvent is reclaimed in distillation simultaneously.

5, Preparation of catalysts method as claimed in claim 1 is characterized in that the alkoxyl group titanium chloride is Ti (OC ₈H ₁₇) ₂Cl ₂