CN85106840A - Polymerizing catalyst, manufacturing and application - Google Patents

Abstract

In the presence of the catalyst system that contains a kind of organo-metallic promotor and a kind of titanium-containing catalyst component, all polymerizations of ethene and alpha-olefin, or ethene is with other alkene generation copolymerizations.Said titanium-containing catalyst component can be made by following method, porousness particulate matter, organo-magnesium compound, oxygenatedchemicals, acyl halide, titanium tetrachloride and Cl ₂, Br ₂Or interhalogen compound reacts simultaneously, and uses II a, and the organometallic compound of II b or III a family metal is handled the gained solid.

Description

Polymerizing catalyst, manufacturing and application

The application is the part continuation application of the United States Patent (USP) SN 637,985 that filed on August 6th, 1.

The present invention relates to a kind of new catalyst component, it is used from olefinic polymerization with promotor one and becomes polyolefine such as polyethylene, polypropylene etc., also can be used for ethene with the copolymerization of other alpha-olefins and diolefine to produce corresponding multipolymer, this catalyst component can provide high catalytic activity, the gained multipolymer has the improvement performance that can reflect the comonomer characteristic, and can make the polymeric articles of pine (heap) density that meets the requirements.This catalyst component is useful especially to production of linear high density polyethylene(HDPE) and LLDPE.The polymeric articles that makes has proved the good comprehensive performance, for example molecular weight distribution machine direction tear and the cross direction tear strength narrow, polymerisate that is made by this catalyst system all improves to some extent, consequently, the blown film that makes of the resin that makes with this catalyzer has higher comprehensive strength.

This catalyst component is the solid product that makes by following reaction; promptly with solid-state, granular; porous carrier; as silicon-dioxide, aluminum oxide, magnesium oxide or its mixture, for example; silica-alumina; contact mixing with acyl halide, transistion metal compound, organo-metallic component stage by stage, handle with alcohol, halide-containing, halogen or interhalogen compound then, in the presence of organo-aluminium compound, the solid pre-reduction is made.This new catalyst component when using aluminum alkyl catalyst, just can obtain new catalyst system of the present invention, and it can be used for the polymerization of alkene.

This catalyst system can be used for slurry, single-phase fusion, and solution or gas phase polymerization process, and also effective especially to the production of linear polyethylene such as high density polyethylene(HDPE) and LLDPE.

Recently, magnesium-titanium complex catalyst component is used for alpha-olefine polymerizing and has produced keen interest.For example, No. 27733, the european patent application of announcing on April 29th, 1, once revealed by excessive organo-magnesium compound and in the presence of silica supports, reduced transistion metal compound, subsequently with taking off agent alive such as hydrogenchloride makes excessive organo-magnesium compound inactivation and obtains catalyst component.

United States Patent (USP) the 4th, 136 has also been revealed a kind of catalyst component No. 058, and this catalyzer comprises a kind of organo-magnesium compound and a kind of transition metal halide, and this catalyst component takes off work with taking off agent alive such as hydrogenchloride subsequently.But this patent reveal adopt silica supported, yet but disclosed analogue with european patent application discussed above.

United States Patent (USP) the 4th, 250, revealed a kind of catalyzer No. 288, this catalyzer is a kind of transistion metal compound, a kind of organo-magnesium compound and a kind of active non-metallic halide such as HCl and the reaction product that contains the Organohalogen compounds of free halogen, and this catalyst reaction product also contains some aluminum alkylss.

The catalyst component that contains aluminum alkyls-alkyl magnesium complex compound and halogenated titanium reaction product at United States Patent (USP) the 4th, 004, discloses in No. the 4th, 276,191, No. 071 and the United States Patent (USP).

United States Patent (USP) the 4th, 173, No. 547 and United States Patent (USP) the 4th, 263, revealed a kind ofly contain the catalyst component of silicon-dioxide, aluminium-type titanous chloride and dibutylmagnesium and contain alkyl magnesium-aluminum alkyls complex compound to add with silicon-dioxide to be the catalyst component of the halogenated titanium of carrier for No. 171 respectively.

Using chlorine in polymerization process is at United States Patent (USP) the 4th, 267, informs in No. 292, reveals once in this patent that chlorine was to cause the back at the Ziegler catalyst that polymerization has been existed to import polymerization reactor.United States Patent (USP) the 4th, 248 was once informed for No. 735, and silica supports is handled with bromine or iodine earlier, subsequently chromium cpd is admixed on the carrier.United States Patent (USP) the 3rd, 513 has revealed with the gas chlorination test gama-alumina is added the processing of titanium tetrachloride that the catalyzer that adopts this processing is again with promotor and with making vinyl polymerization for No. 150.

European Patent Application No. is 32,308 have revealed a kind of ethylene polymerization catalysts system that makes, this catalyzer contains a kind of organometallic compound and a kind of titaniferous materials, it is with a kind of inertia particulate matter, a kind of organo-magnesium compound, a kind of titanium compound and halide-containing such as SiCl ₄, PCl ₃, BCl ₃, Cl ₂Make Deng common reaction.

United States Patent (USP) the 4th, 402,861; 4,378,304; 4,388,220; 4,301,029 and 4,385, No. 161, all once disclosed and contained oxide carrier such as silicon-dioxide, organo-magnesium compound, the supported catalyst system of transistion metal compound and one or more catalysis component modification agent.But these patents were not all revealed catalyzer of the present invention.

In English Patent the 2nd, 101, in No. 610, silicon-dioxide is with alkyl magnesium, alcohol, Benzoyl chloride and TiCl ₄Handle.In day disclosure special permission 56-098206 and 57-070107, adopted acyl halide in the process of preparation titanium carrier catalyzer.

The catalyst system that contains alkyl magnesium and titaniferous compound, though useful to the polymerization of alkene such as ethene or other 1-alkene usually, do not present excellent reactivity in polyreaction, controlling molecular weight with hydrogen; When producing the multipolymer of ethene, comonomer such as butene-1 can not enter polymkeric substance soon; Do not show high catalytic activity yet; By the film that resulting polymers makes, its anisotropic properties is also unbalanced.

The United States Patent (USP) of on May 29th, 1 promulgation has been revealed a kind of catalyst system the 4th, 451, No. 574, and this catalyzer makes with organometallic compound, halogenated titanium and halogen gas processing granular inert carrier such as silicon-dioxide.Though the catalyzer that makes has very high activity, the film performance of the polymerisate that olefin polymerization obtains in the presence of this catalyzer needs to improve, and the pine of polymerisate (heap) density also needs to improve.

Have been found that the catalyzer by the present invention has very high catalytic activity, the molecular weight that comes controlling polymers with hydrogen is had excellent susceptibility, good comonomer response capacity, the film performance of resulting polymers product can improve greatly.Resin has excellent melt strength, and its extrusioning power consumption reduces bubble stability increase when causing the production blown film.In addition, the extruded velocity of resin is accelerated.The present invention more is better than therewith relevant application, and the unexpected catalytic activity that makes of the present invention's catalyzer is improved greatly, and pine (heap) density of the polymkeric substance that is made by it also can obtain unexpected improvement.

Raw catalyst component of the present invention is by a kind of organometallic compound; a kind of oxygenatedchemicals such as ketone, aldehyde; siloxanes or alcohol, a kind of acyl halide; a kind of transistion metal compound; a kind of halogen or interhalogen compound; contact with each other reaction and make in the presence of oxide carrier, the gained solid is used periodictable II a again, and the organometallic compound such as the aluminum alkyls of II b or III a family metal handle.This catalyst system comprises catalyst component and organoaluminum promotor that contains transistion metal compound, its favourable part is to use in the vapour phase polymerization of ethene, because it is compared with the prior art of ethene gas-phase polymerization method, can reduce reactor dirt (or obstruction) in general, thereby cause reducing for the number of times that the cleaning reactor is stopped work.

According to purpose of the present invention; be that polymerization for alpha-olefin provides a catalyst component that contains transition metal; this catalyst component is a solid reaction product; it is with II a in the periodictable; the organometallic compound (A) of II b or III a family metal; wherein all metallic valences are all saturated by the alkyl of alkyl or replacement; a kind of oxygenatedchemicals of from ketone, aldehydes, alcohols, siloxanes or its mixture, choosing (B); a kind of acyl halide (C); periodictable IV b selects a kind of transistion metal compound (D) and Cl in V b or the VIII family metal at least ₂, Br ₂Or a kind of interhalogen compound, handling inert solid carrier in inert solvent obtains, and then handle the product that contains transition metal with the organometallic compound (F) of II a, II b and III a family metal, its condition is, (I) (A) and (B) composition can use simultaneously; (II) used with (A) and reaction product form (B); (III) uses (A) to handle after handling with (B) immediately.

The ingredient of solid catalyst that contains transition metal, when uniting use with promotor such as aluminum alkyls, proved that this catalyst system can provide multiple particular performances, these performances have great importance in the polymerization technique of alkene, for example: high catalytic activity has the ability of controlling molecular weight in polyreaction, its result causes the improvement to hydrogen-sensitivity, to the reactive improvement of comonomer, improved the productive rate of polymkeric substance, reactor dirt (or obstruction) reduces.Special benefits of the present invention is to produce the catalytic capability with improvement pine (heap) density product.

The alternative concrete manifestation of the present invention is that organometallic compound (A) is a dialkyl magnesium compound, uses R ¹MgR ²Representative, R in the formula ¹And R ²Can be identical or different, the R base can be chosen alkyl, aryl, cycloalkyl, aralkyl, alkadienyl or the alkenyl of from 1 to 20 carbon atom; Oxygenatedchemicals (B) can be from following molecular formula R ³OH and R ⁴COR ⁵For the representative alcohols or ketone in choose R in the formula ³, R ⁴And R ⁵Can be identical or different, the R base can be the alkyl of 1 to 20 carbon atom, aryl, cycloalkyl, aralkyl, alkadienyl or alkenyl; Acyl halide (C) can be by molecular formula R ⁶COX represents, R in the formula ⁶Be C ₁-C ₂₀Alkyl, cycloalkyl or aryl, X is a halogen; It is representative TrX that transistion metal compound (D) can be chosen following molecular formula " _4-q(OR ⁸) q, TrX " _4-qR ⁹ _q, VO(OR ⁸) ₃And VOX " ₃A kind of transistion metal compound, or several transistion metal compound and usefulness, Tr is IV b in the formula, V b, the transition metal of VI b and VIII family is preferably selected titanium, vanadium or zirconium, R ⁸Be alkyl, aryl, the substituted aralkyl and the 1 base of aralkyl or 1 to 20 carbon atom; X " be halogen, q be zero or less than, equal 4, R ⁹Be alkyl, the aryl or aralkyl of 1-20 carbon atom, or the 1 base; Halogen (E) is Cl ₂; Organometallic compound (F) is with R ⁷ _nAlX ' _3-nThe alkylaluminium cpd of expression, X ' is halogen or hydrogen in the formula, R ⁷Be alkyl, be selected from the alkyl of 1-20 carbon atom, aryl, cycloalkyl, aralkyl, alkadienyl or alkenyl, 1≤n≤3.

All reference datas of periodictable are all taken from CRC and are published the chemistry of (1975) and physics handbook the 56th edition, the periodic table of elements that the B-3 page or leaf prints off.

When preparation contained the catalyst component of transition metal, the batching of catalyst component can any order be added to carrier get on (wherein (F) exception, it must add at last).For example:

(B), (A), (C), (D), (E) and (F)

(A+B), (C), (D), (E) and (F)

(A and B), (C), (D), (E) and (F)

(E), (B), (A), (C), (D) and (F)

(E), (A+B), (C), (D) and (F)

(E), (A and B), (C), (D) and (F)

(C), (B), (A), (E), (D) and (F)

(C), (A+B), (E), (D) and (F)

(C), (A and B), (E), (D) and (F)

(D), (C), (B), (A), (E) and (F)

(D), (C), (A+B), (E) and (F)

(D), (C), (A+B), (E) and (F)

(D), (E), (B), (A), (C) and (F)

(D), (E), (A+B), (C) and (F)

(D), (E), (A and B), (C) and (F)

(D), (B), (A), (C), (E) and (F)

(D), (A+B), (C), (E) and (F)

(D), (A and B), (C), (E) and (F)

(D), (B), (A), (E), (C) and (F)

(D), (A+B), (E), (C) and (F)

(D), (A and B), (E), (C) and (F)

(B), (A), (E), (D), (C) and (F)

(B+A), (E), (D), (C) and (F)

(B and A), (E), (D), (C) and (F)

(B), (A), (C), (E), (D) and (F)

(B+A), (C), (E), (D) and (F)

(B and A), (C), (E), (D) and (F)

(B), (A), (E), (C), (D) and (F)

(B+A), (E), (C), (D) and (F)

(B and A), (E), (C), (D) and (F)

And similarly-ordered etc.In the above-mentioned example, (A+B) be (A) and reaction product (B), (A and B) i.e. be (A) and (B) add reaction system simultaneously.

The preferential interpolation of selecting is in proper order: (A+B), and (C), (D), (E) and (F); (E), (A+B), (C), (D) and (F); (A+B), (E), (C), (D) and (F); Or (C), (A+B), (E), (D) and (F).If (E), (A+B), (C), (D) and (F); (A+B), (E), (C), (D) and (F); Or (A+B), (C), (D), (E) with (F) then better.The good especially preparation method of catalyst component who contains transition metal is, earlier with (E) Cl ₂, Br ₂Or interhalogen compound or its mixture process inert support; use the reaction product of organometallic compound (A) and oxygenatedchemicals (B) to handle subsequently, then, use acyl halide (C) to handle solid again; use transistion metal compound (D) to handle at last, and carry out prereduction with (F).

In second particular embodiment of the present invention,, adopt catalyzer of the present invention, polymerization under Ziegler polymeric specified conditions for the polymerization of alpha-olefin provides a kind of catalyst system that contains transition metal ingredient of solid catalyst and aluminum alkyl catalyst.

Compare with the Ziegler catalyst of routine, high reactivity in view of the catalyst system that makes by the present invention, in general, do not need from polymerisate, to remove ash content, because catalyst residue content is lower in the polymerisate that the resulting polymers product makes under existing than conventional Ziegler catalyst.

This catalyst system can be used for vapor phase process, single-phase scorification, solvent method or slurry process.This catalyst system is useful to the polymerization of ethene and other alpha-olefin, particularly to the polymerization of the alpha-olefin that contains 3 to 8 carbon atoms and they copolymerization with other 1-alkene such as propylene, butylene, amylene and hexene, or with the diolefine such as the divinyl, 1 of 2-20 carbon atom, the copolymerization of 4-pentadiene etc. can make the multipolymer of low density or middle density thus.This supported catalyst system is particularly useful with the gas phase copolymerization of other alpha-olefin to the vapour phase polymerization and the ethene of ethene.

The description of specializing according to qualifications

In brief, catalyst component of the present invention is by solid carrier and a kind of organometallic compound (A), a kind of oxygenatedchemicals (B), a kind of acyl halide (C), at least a transistion metal compound (D), and halogen (E) or the interhalogen compound formed solid reaction product of reaction that contacts, this product II a, II b, the organometallic compound (F) of III a family metal is handled, and its condition is: (I) (A) and (B) prepare burden and can add inert solid simultaneously; (II) (A) and (B) joins on the inert solid with the form of reaction product; Or after (III) usefulness (B) processing, use (A) to handle immediately.

The transition metal catalyst component that contains of the present invention preferably is chosen in the inert solvent and chooses a kind of subsequent treatment inert solid carrier by the following step of respectively organizing.

(a) handle earlier with batching (E), subsequently by (A), (B), (C), (D) and batching subsequent treatment (F).

(b) handle earlier with batching (A) with (B), subsequently and (B) by (A), (C), (D), (E) with (F) batching subsequent treatment, or

(c) handle earlier with batching (C), subsequently and (B) by (A), (E), (D) and the processing successively of the order of batching (F).

(d) use batching (B) and (A) processing earlier,, (C), (D) handle successively with order (F) subsequently by batching (E).Further condition is: (I) batching (A) and (B) can add simultaneously; (II) batching (A) and (B) with the adding of the form of reaction product; (III) uses (A) to handle after handling with (B) earlier immediately.

The transition metal catalyst component that contains of the present invention, preferably select earlier to make by following two kinds of methods:

(I) earlier handles inert solid carrier with batching (E) in inert solvent, subsequently successively with batching (A), (B), (C), (D) and (F) handle, and prepare burden (A) and (B) can (I) add simultaneously; (II) adds as (A) and reaction product form (B); Or (III) uses (A) to handle earlier with after (B) processing immediately; Or

(II) in inert solvent with batching (A) and (B) processing inert solid carrier resulting solid reaction product, subsequently successively with batching (C), (D), (E) and (F) handle, further condition is: (I) prepared burden (A) and (B) can be added to simultaneously on the solid; (II) batching (A) and (B) with the adding of the form of reaction product; Or (III) immediately uses (A) to handle earlier with (B) processing inert solid.Be the best with (I) method especially.

According to polymerization process of the present invention, ethene, be the alpha-olefin that contains 3 or more carbon atoms at least, or ethene contact with catalyzer with the diolefine of other alkene or terminal band insatiable hunger key, under polymerizing condition, can form commercial useful polymerization product.Typical carrier is any solid granular porous carrier such as talcum powder, zirconium white, Thorotrast, magnesium oxide and titanium dioxide.Best carrier is the II a of finely divided form, III a, the oxide compound of IV a and IV b family metal.

According to the present invention, the suitable inorganic oxide that wish to adopt comprises II a, III a or IV a or IV b family metal oxide, silicon-dioxide for example, aluminum oxide and silica-alumina and composition thereof.Can for adopt separately or and silicon-dioxide, other inorganic oxide of aluminum oxide or silica-alumina and usefulness is magnesium oxide, titanium dioxide, zirconium white and analogue thereof.But other suitable carrier also can adopt for example finely divided polyolefine such as finely divided polyethylene.

Metal oxide contains the tart surface hydroxyl usually, it can with at first add the organo-metallic component or the transistion metal compound that go in the reaction solvent and react.Before using, inorganic oxide carrier needs earlier through dehydration, promptly in order to remove the concentration of moisture and the surperficial alkyl of reduction, carrier needs through heat-treated, thermal treatment is carried out in a vacuum, or under 100 ℃ to 1000 ℃ temperature, carry out purge with exsiccant rare gas element such as nitrogen, temperature is preferably selected 300 ℃ to about 800 ℃.Consideration to pressure is not really strict.Heat treatment time can be from 1 hour to 24 hours.No matter yet adopt the balance that all can set up surface hydroxyl than short or long period.

Chemical dehydration is the another kind of excellent method that makes the metal oxide carrier dehydration.Chemical dehydration is that all moisture and hydroxyl on the metal oxide surface are transformed into inert substance.For example, useful chemical reagent is SiCl ₄, chlorosilane such as trimethylchlorosilane, dimethyldichlorosilane(DMCS), silylamine be hexamethyldisilazane and dimethylamino trimethyl silane etc. for example.Chemical dehydration is by finishing inorganic particulate matter slurryization, and for example silicon-dioxide is in inert low boiling hydrocarbon kind solvent such as hexane.Should be kept at when silicon-dioxide carries out chemical dehydration reaction in the atmosphere of humidity and anaerobic, then the lower boiling unreactive hydrocarbons solution that contains chemical dehydrator such as dimethyldichlorosilane(DMCS) slowly be poured in the slurry of silicon-dioxide.In the chemical dehydration process, temperature should remain in 25 ℃ to 120 ℃ the scope, but also can adopt higher or lower temperature.Best temperature range is 50 ℃ to 70 ℃.Till the chemical dehydration step should be performed until all moisture and all removes from bead-type substrate, indicate to stop to emit gas.Under the normal circumstances, chemical dehydration reaction carried out 30 minutes to 16 hours approximately, preferably 1-5 hour.After chemical dehydration was finished, the solid particulate thing filtered in nitrogen atmosphere, and with anaerobic inert hydrocarbon solvent washing 1 time or repeatedly.Cleaning solvent and used thinner and the solution of chemical dehydrator when forming slurry can be any suitable unreactive hydrocarbons, and this class hydrocarbon is a heptane, hexane, toluene, iso-pentane and analogue thereof.

The selected organometallic compound of the present invention (A) is the organo-magnesium compound that dissolves in varsol, available R ¹MgR ²The molecular formula representative, R in the formula ¹And R ²Can be identical or different, R is an alkyl, aryl, cycloalkyl, aralkyl, alkadienyl, or alkenyl.Alkyl R ¹And R ²Can contain 1-20 carbon atom, preferably the alkyl of 1-10 carbon atom.But be not limited only to illustrational magnesium compound, the magnesium compound that is fit to adopt by the present invention is: magnesium ethide, dipropyl magnesium, di-isopropyl magnesium, two just-and dibutyl magnesium, diisobutyl magnesium, diamyl magnesium, two just-octyl group magnesium, two just-hexyl magnesium, two just-decyl magnesium and two just-dodecyl magnesium; Bicyclic alkyl magnesium, for example dicyclohexyl magnesium; Diaryl magnesium such as dibenzyl magnesium, xylyl magnesium and two (xylyl) magnesium etc.

Organo-magnesium compound is the alkyl of 1-6 carbon atom preferably, and R ¹And R ²Preferably select different alkyl.

Illustrating best magnesium compound is: ethyl just-propyl group magnesium, ethyl just-dibutyl magnesium, amyl group just-hexyl magnesium, just-butyl sec-butyl magnesium, just-butyl just-octyl group magnesium and analogue thereof.The mixture of alkyl magnesium compound may also be suitable for, for example two just-dibutyl magnesium and ethyl just-mixture of dibutyl magnesium.

Alkyl magnesium compound is normally obtained with the form of mixtures of alkyl magnesium with a small amount of alkylaluminium cpd by commercial source.The existence of a small amount of aluminum alkyls is in order to help solubilization and/or to reduce the viscosity of organo-magnesium compound in varsol.The varsol that organic-magnesium is suitable for can be a for example hexane of any known hydrocarbon liquids, heptane, octane, decane, 12 carbon alkane or their mixture.Aromatic hydrocarbon is benzene for example, and toluene and dimethylbenzene etc. are available equally.

Organic-magnesium is with the complex compound of a small amount of aluminum alkyls, useful molecules formula (R ¹MgR ²) p(R ¹⁰ ₃Al) s represents, R in the formula ¹And R ²Definition identical with above-mentioned person, R ¹⁰Definition and R ¹, R ²The same, p is greater than zero.S/s+p ratio is from 0 to 1, preferably selects 0 to 0.7, as get 0 to 0.1 better.

Illustrational organic-magnesium-organic aluminium compound is

〔（n-C ₄H ₉）（C ₂H ₅）Mg〕〔（C ₂H ₅） ₃Al〕0.02，

〔（n-C ₄H ₉） ₂Mg〕〔（C ₂H ₅） ₃Al〕0.013，

((n-C ₄H ₉) ₂Mg) ((C ₂H ₅) ₃Al) 2.0 Hes

〔（n-C ₆H ₁₃） ₂Mg〕〔（C ₂H ₅） ₃Al〕0.01。Suitable magnesium-aluminium complex is the Magala that Texas Alkyls affiliated company makes

BEM.

The organo-metallic component that dissolves in hydrocarbon is a known substance, can prepare according to a conventional method.It is an amount of aluminum alkyls to be added in the solid dialkyl magnesium go in the presence of inert hydrocarbon solvent that a kind of method is for example arranged.For example, organic-magnesium-organic aluminium compound is at United States Patent (USP) the 3rd, 737, and 393 and 4,004, the existing description in No. 071 here enumerated as a reference in the lump.But any other suitable method of preparation organometallic compound all can suitably adopt.

The oxygenatedchemicals useful according to the present invention is: alcohol, aldehyde, siloxanes and ketone.Best oxygenatedchemicals is to be R from general formula ³OH and R ⁴COR ⁵Pure and mild ketone in choose R in the formula ³, R ⁴And R ⁵Can be identical or different, R can be the alkyl of 2-20 carbon atom, aryl, cycloalkyl, aralkyl, alkadienyl or alkenyl.Preferentially select the R base of 2-10 carbon atom, preferably select the alkyl of 2-6 carbon atom.

Enumerate (but being not limited in this) for example and go out the alcohols that the present invention may adopt: alkyl alcohol such as ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols, 2-butanols, uncle-butanols, 1-hexanol, 2-ethyl 1-hexanol, 1-decanol; Cycloalkyl alcohol such as cyclobutanol, hexalin; Fragrant and mellow as phenol, 1-naphthols, beta naphthal; Aryl alcohol such as benzyl alcohol, p-Cresol ,-cresols; Alkenyl alcohol such as allyl alcohol, crotyl alcohol, 3-butenyl-1-alcohol; Alkadienyl alcohol as 2,4-hexadiene-1-alcohol.Best alcohol is the 1-butanols.

Ketone is preferentially chosen from the ketone of 3-11 carbon atom.The ketone that illustrates (but being not limited in this) has: alkyl ketone such as acetone, propione, dipropyl ketone, methyl ethyl ketone, methyl butyl ketone; Naphthenic one such as pimelinketone, cyclopentanone, 2-methylcyclohexanone; Aryl ketones such as benzophenone, methyl phenyl ketone, Propiophenone; Alkenyl ketone such as methyl vinyl ketone and methyl-allyl ketone.Best ketone is acetone.

The aldehydes that the preparation organo-magnesium compound adopts, it is as follows to illustrate (but being not limited only to this), comprises alkyl aldehyde such as formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde, valeral, hexanal, enanthaldehyde, octanal, 2 methyl propanal, 3-methyl butyraldehyde; Aryl aldehyde such as phenyl aldehyde; Alkenyl aldehyde such as propenal, crotonic aldehyde; Aralkyl aldehyde such as phenylacetic aldehyde, neighbour-tolyl aldehyde ,-methylbenzene methyl aldehyde, right-tolyl aldehyde.Preferably select acetaldehyde and formaldehyde for use.

Preparation organo-magnesium compound used siloxanes illustrates as followsly, comprises hexamethyldisiloxane, octamethyltrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentaandoxane, symmetry-dihydro tetramethyl disiloxane, pentamethyl-three hydrogen trisiloxanes, methyl hydrogen cyclotetrasiloxane; The polydimethylsiloxane of line style and branching, poly-methyl hydrogen alcoxyl alkane, poly-ethyl hydrogen siloxane, polymethy ethylsiloxane, poly-Methyl Octyl siloxanes and polyphenylene hydrogen siloxane etc. all can adopt.

The preferential acyl halide useful molecules formula of selecting is R ⁶COX represents, R in the formula ⁶It is the alkyl that contains the 1-20 carbon atom.R ⁶Can be alkyl, aryl, aralkyl, cycloalkyl, alkadienyl or alkenyl, X are halogens, the preferential halogen of selecting is a chlorine.R ⁶Preferably select the alkyl of 1-6 carbon atom, or phenyl or have the alkane phenyl of 6 to 10 carbon atoms.R ⁶Selecting methyl or phenyl, X is that chlorine is then better.

According to the present invention, used acyl halide, it is as follows to illustrate (but being not limited in this): alkyl acyl halogenide such as Acetyl Chloride 98Min., propionyl chloride, butyryl chloride, butyryl bromide, isobutyryl chloride: aroyl halide such as Benzoyl chloride, 1-naphthoyl chloride, 2-naphthoyl chloride; Cycloalkyl acyl halide such as ring are defended basic formyl chloride, the cyclohexyl formyl chloride; Aralkyl acyl halide such as the stupid formyl chloride of right-methyl ,-methyl benzoyl chloride; Alkenyl acyl halogenide such as acrylate chloride, 6-heptene acyl chlorides, crotonyl chloride.Chloride of acid based on polyprotonic acid also can adopt, 12 (alkane) diacid chloride for example, succinic chloride, camphor diacid chloride, right-phthalyl chloride etc.The preferential acyl halide of selecting is an Acetyl Chloride 98Min., Benzoyl chloride and right-methyl benzoyl chloride.

Prepare the used IV b of transition metal catalyst component that contains of the present invention, V b, the technology of the transistion metal compound of VI b or VIII family metal is well-known.According to the present invention, used transistion metal compound can be represented TrX ' with following general formula _4-q(OR ⁸) q, TrX ' _4-qR ⁹ _q, VOX ' ₃And VO(OR ⁸) ₃Tr is IV b, V b, and VI b and VIII family metal are preferably chosen IV b and V b family's metal such as titanium, vanadium or zirconium.Q is 0 or equals or less than 4 number; X ' is a halogen; R ⁸Be the alkyl of 1-20 carbon atom, aryl or cycloalkyl; R ⁹Be alkyl, aryl, aralkyl, the aralkyl of replacement, 1 base etc., aryl wherein, the aralkyl of aralkyl and replacement is to contain 1-20 carbon atom, preferably selects the group of 1-10 carbon atom.R in the transistion metal compound that contains alkyl ⁹Be alkyl, cycloalkyl, during aryl or aralkyl, alkyl is preferably not hydrogeneous on the β position of metal-carbon key.The examples of alkyl that illustrates (but being not limited in this) is a methyl, and is new-amyl group, 2, and 2-dimethylbutyl, 2,2-dimethyl hexyl; Aryl such as phenyl, naphthyl; Aralkyl such as benzyl; Cycloalkyl such as 1-norcamphyl.If desired, also can adopt the mixture of transistion metal compound.

Illustrating of transistion metal compound comprises: TiCl ₄, TiBr ₄, Ti(OC ₂H ₅) ₃Cl, Ti(OC ₂H ₅) Cl ₃, Ti(OC ₄H ₉) ₃Cl, Ti(OC ₃H ₇) ₂Cl ₂, Ti(OC ₆H ₁₃) ₂Cl ₂, Ti(OC ₈H ₁₇) ₂Br ₃And Ti(OC ₁₂H ₂₅) Cl ₃

As mentioned above, the mixture of transistion metal compound also can adopt, and the number of the transistion metal compound that may react with the organo-metallic component is not limit.The alkoxy compound of any halogenide and transition metal or its mixture all can use.In titanium tetrahalide, preferably select titanium tetrachloride for use.

According to the present invention, used suitable halogen (E) is Cl ₂, Br ₂, I ₂And composition thereof.Illustrational interhalogen compound is: ClF, ClF ₃, BrF, BrF ₃, BrF ₅, ICl, ICl ₃And IBr.Best halogen is Cl ₂And Br ₂Best interhalogen compound contains Br or Cl.

Use II a, the organometallic compound of II b or III a family metal is handled when containing the catalyst solid of transition metal, handles a step at (F), and best organometallic compound is with following formula R ⁷ _nAlX _3-nBe the alkylaluminium cpd of representative, X is halogen or hydrogen in the formula, R ⁷Be C ₁-C ₁₈Saturated hydrocarbyl, 1≤n≤3.

Used this compounds in the treatment step of the present invention illustrates as follows: Al(C ₂H ₅) ₃, Al(C ₂H ₅) ₂Cl, Al(i-C ₄H ₉) ₃, Al ₂(C ₂H ₅) ₃Cl ₃, Al(i-C ₄H ₉) ₂H, Al(C ₆H ₁₃) ₃, Al(C ₈H ₁₇) ₃, Al(C ₂H ₅) ₂H.The preferential organo-aluminium compound of selecting is a trialkylaluminium, and alkyl contains preferably 2-8 carbon atom of 1-10 carbon atom.Three-just-hexyl aluminium and three-just-octyl group aluminium is best.

As mentioned above, the processing of carrier is carried out in inert solvent.Before handling, also can dissolve each furnish component with inert solvent earlier.Alternative solvent comprises mineral oil and various hydrocarbon, and this hydrocarbon need be liquid and each component that can dissolve batching in temperature of reaction.The illustrational solvent that share comprises alkane such as pentane, iso-pentane, hexane, heptane, octane and nonane; Naphthenic hydrocarbon such as pentamethylene and hexanaphthene; Aromatic hydrocarbons such as benzene, toluene, ethylbenzene and dimethylbenzene.The consumption of solvent is not really strict, and in any case, the amount of solvent for use should derive reaction heat from catalyst component, and can allow good mixing.

Used organo-metallic component (A) is not the form with organometallic compound, and the reaction product with (A) and oxygenatedchemicals (B) is dissolved in the form adding that is solution in the inert solvent exactly.For organometallic compound, best solvent is alkane such as hexane, heptane, octane and analogue thereof.But, make the used same solvent of granular inert carrier slurryization need to dissolve organic metal component.The concentration of organo-metallic component in solvent is not too strict, only is subjected to the restriction of operational requirement.

The consumption of ingredient of solid catalyst can change in very wide scope, the concentration range that is deposited on the magnesium on the dried inert support is from 0.1 to 2.5 mmole/gram carrier, but the concentration of magnesium compound is preferably 0.5-2.0 mmole/gram carrier, and particularly 1.0-1.8 mmole/gram carrier is better.Magnesium is from 0.01 to 2.0 to the molar ratio range of oxygenatedchemicals, and the preferential proportional range of selecting is 0.5-1.5, preferably 0.8-1.2.The upper limit of this scope depends on the selection and the addition manner of oxygenatedchemicals.When oxygenatedchemicals was not pre-mixed with magnesium compound, just before oxygenatedchemicals is adding magnesium compound or be added in the carrier more later on and go, proportional range was 0.01 to 2.0; When oxygenatedchemicals earlier with the organo-magnesium compound premix, the alkyl on this moment oxygenatedchemicals must be enough big, with the solvability of assurance reaction product, otherwise oxygenatedchemicals should be 0.01 to 1.0 to the organo-magnesium compound mol ratio, preferably 0.8 to 1.0.

For magnesium compound, it is 0.1 to 10 that the consumption of acyl halide should be controlled at mol ratio, preferably 0.5 to 2.5, and optimum mol ratio is 1 to 2.The concentration that is added to the transistion metal compound on the inert support is about the dried carrier of 0.01 to 1.5 mmole/restrain, and the preferential concentration range of selecting is the dried carrier of 0.05 to 1.0 mmole/restrain, preferably the dried carrier of 0.1-0.8 mmole/restrain.Halogen or interhalogen compound are handled needs excessive halogen or interhalogen compound, and in general, used halogen is Cl for example ₂It should be the form of gas.

The halogen of catalyzer is handled and can be finished like this, promptly be not the exsiccant catalyzer, exactly the paste-like catalyzer to be exposed to total pressure in 0 °-100 ℃ temperature range be in 1.0 to the 10 atmospheric chlorine 10 minutes to 4 hours.Cl ₂Also can adopt with the mixed gas of rare gas element such as argon gas or nitrogen, the volumetric molar concentration scope of chlorine in rare gas element is 1 mole of-100 moles of %.

Use II a, the alkyl metal cpd of II b or III a family metal is handled solid and is finished like this, promptly not II a, the alkyl metal cpd of II b or III a family metal joins solid mixture, be exactly solid mixture slurryization in inert solvent of doing, add an amount of organo-metallic treatment agent subsequently.

For titanium compound, it is 0.5 to 50 that the consumption of treatment agent (F) should be controlled at mol ratio, preferentially selects 1-20, and best mol ratio is 3 to 10.

Usually the temperature range of each reactions steps should be controlled at-50 ℃ to 150 ℃, and the preferential temperature range of selecting is-30 ℃ to 60 ℃, preferably-10 ℃ to 50 ℃.The reaction time range of each treatment step is 5 minutes to 24 hours, and the best reaction times is from 0.5 hour to 8 hours, wishes to keep all the time stirring in reaction process.

When preparation contains the catalyst component of transition metal, after finishing, any step all to wash.But once found, because washing reduces the advantage of catalyst system up to finishing (F) step gradually.

According to the prepared transition metal catalyst component that contains of the present invention, in the Ziegler of alkene catalysis polymerization technology, use with promotor as everyone knows.Relatively being typically, is I a with containing the promotor that transition metal catalyst component uses, II a, the organometallic compound of II b and III a family metal, aluminum alkyls for example, alkyl-al hydride, lithium alkylide aluminium, zinc alkyl(s) and alkyl magnesium etc., desirable promotor is an organo-aluminium compound.The preferential alkylaluminium cpd of selecting can be used general formula AlR ^{" '} _nX " _3-nRepresent 1≤n in the formula≤3, R " ' be hydrogen, the alkyl of alkyl or replacement, X " are halogens.The preferential R that selects " ' be the alkyl of 2-8 carbon atom, illustrational promotor is: ethylaluminum dichloride, sesquialter ethyl aluminum chloride, diethyl aluminum chloride, triethyl aluminum, three-just-butyl aluminium, diisobutyl aluminium hydride, diethylaluminum ethoxide etc.Preferential trialkylaluminium, the preferably triisobutyl aluminium selected.

The catalyst system that contains aluminum alkyl catalyst and transition metal catalyst component is applicable to the alpha-olefin such as the propylene of ethene and 3-20 carbon atom, butene-1, amylene-1, hexene-1, the polymerization of 4-methylpentene-1 grade, and ethene with other alpha-olefin or diolefine as 1, the 4-pentadiene, 1,5-hexadiene, divinyl, the 2-methyl isophthalic acid, the copolymerization of 3-divinyl etc.Preferential polymerisable monomer is an ethene.This catalyzer can be in order to producing high density polyethylene(HDPE), by ethene and other alpha-olefin or diolefine propylene particularly, and butene-1, amylene-1, hexene-1 and octene-1 copolymerization can make LLDPE.Alkene can for example suspend by any suitable currently known methods in the presence of catalyzer of the present invention, solution and vapour phase polymerization.

The above-mentioned catalyst consumption that polyreaction is used under known conditions, can be implemented by the Ziegler polymerization technique.For example polymerization under 50 ℃ to 120 ℃ temperature range, 1 to 40 normal atmosphere in inert diluent; Or, carry out vapour phase polymerization under 1-50 the normal atmosphere in 70 ℃ to 100 ℃ temperature range.Illustrating of gaseous polymerization at United States Patent (USP) the 4th, 302,565 and 4,302, the existing disclosure listed here as a reference in No. 566.As mentioned above, a catalyst system of the present invention superior character is to reduce the amount of dirt in the gas-phase polymerization reactor.This catalyst system also can make olefinic polymerization under single-phase condition, i.e. polymerization under 150 ℃ to 320 ℃, a 1000-3000 normal atmosphere.Under this condition, the phase in longevity of catalyzer is short, but catalytic activity is very high, so that need not to remove from polymkeric substance catalyst residue.But the preferential polymerization pressure of selecting is from 1-50 normal atmosphere, preferably 5-25 normal atmosphere.

According to method of the present invention, found once that catalyst system had high susceptibility to hydrogen, thereby can control molecular weight effectively.But other known molecular weight regulators and conditioning agent also can use.

According to the polyolefine that the present invention makes, can extrude as required, mechanics fusion, casting or molding.They can be used for sheet material, sheet material, film and other multiple purposes.

When illustrating with following example when of the present invention, it will be appreciated that these examples only are illustrative purposes for example, concerning those are proficient in the people of technology by means of following example, multiple choices, improvement and variation will be obvious.And these selections, improvement and variation all will belong within the present technique claimed range usually.

In example 1 to 3 and comparison example 1, silica supports makes like this, promptly the G-952 silica gel of Davison chemical company is placed in the vertical tower, and the N upwards to blow ₂Air-flow makes it fluidization, and vertical tower slowly is heated to 600 ℃, keeps 12 hours in this temperature, afterwards silicon-dioxide is cooled off to room temperature.In example 4 to 9 and comparison example 2, silica supports is to be 45.7 microns by median size, and its particle diameter is with Leeds and Northrup Microtrac

Instrument records, and surface-area is 311 meters ²/ gram, pore volume is 1.59 centimetres ³The micro-spherical silica gel of/gram makes.Silica dioxide gel in 800 ℃ with the similar dehydrated form of G-952 at N ₂Dehydration is 5 hours in the air-flow, then silica gel is cooled to room temperature.In example 10 to 13, this silicon-dioxide is in N at 500 ℃ ₂Dehydration is 5 hours in the air-flow.Melting index (MI) and melting index are pressed ASTM test D1238(condition E than (MIR)) measure.The density of resin is to measure by ASTM test D1505 with density gradient column.Pine (heap) density is that the bottom of the resin of nearly 120cc from the polyethylene funnel fallen, fall into 100cc plastic cylinder (2.6 centimetres of the diameters of calibration through the slit of 1 inch, high 19.0 centimetres) in, funnel bottom covers up to sample with a slice hard card paper and is full of funnel, then all samples is fallen into graduated cylinder; Do not stir sample, scrape off superfluous resin, container is full of by sample fully like this, does not have superfluous sample, measures the weight of resin in the 100cc graduated cylinder, and such mensuration repeats 3 times, reports its mean value.

Example 1

In a bottle that fills 20 milliliters of hexanes, inject 10 milliliters of butyl ethyl magnesium (BEM) (6.8 mmole magnesium), in this solution, add 0.5 milliliter (6.8 mmole) just-butanols.Mixture at room temperature reacted 1.5 hours, this solution is joined in the bottle that fills 3.5 gram Davison silicon-dioxide, at room temperature make it and silicon dioxde reaction 1 hour, the Benzoyl chloride (BzCl) that in this reaction mixture, under stirring, adds 6.8 mmoles, this reaction mixture is added to the titanium tetrachloride of 2.3 mmoles in this slurry then and goes in stirring at room reaction 1 hour, leaves standstill 1 hour in room temperature, bottle is communicated with chlorine tube afterwards, in 7.5 pounds/inch ²Pressure under in room temperature reaction 1 hour, bottle N ₂Air-blowing is washed, and the material in the bottle is filtered, solids hexane wash 3 times, vacuum-drying then.Catalyzer slurryization again in 20 milliliters of hexanes adds 15 milliliters trioctylaluminum (accounting for 25%, 0.47 mmole Al/ milliliter of hexane weight) then, and so just having made aluminium is 3 to 1 products to the titanium mol ratio.This reaction mixture left standstill under room temperature 1 hour, filtered, with hexane wash 3 times and dry, last catalyzer titaniferous 1%.

In 1.8 liters reactor, add the hexane of 800cc, titanium-containing catalyst and 1.7 milliliters of triisobutyl aluminum cocatalysts (in heptane, accounting for 25%, 0.9 mmole Al/ milliliter) of 0.15 gram, this moment, aluminium was 50 to the mol ratio of titanium.Reactor H ₂Be forced into 30 pounds/inch ², be pressed into ethene to 300 pound/inch then ²Reactor is heated to 85 ℃, and in this temperature polymerization 90 minutes.The gained result takes passages in table 1.

Example 2 and 3

These examples and example 1 are basic identical, and the consumption that has treatment agent (F) aluminum alkyls only increases.Polymerization reactor H ₂Be forced into 50 pounds/inch ², being forced into stagnation pressure with ethene then is 300 pounds/inch ², add 40 milliliters of butene-1 injecting reactors, in 85 ℃ of polymerizations 40 minutes.The consumption of treatment agent (F) and polymerization result thereof are taken passages in table 1.

Comparative example 1

Preparation of catalysts is with example 1, and its exception is the processing of omitting with three-just-octyl group aluminium, the carrying out of polyreaction and finishing with example 1, and experimental result is taken passages in the table I.

In example 4 to 7, the reaction product of butyl ethyl magnesium (BEM) and 1-butanols prepares as follows, in 125 milliliters of vials of a clean dried anaerobic, put into and contain the 9.6%(w/w) 50 milliliters of the n-heptane solutions of BEM, be placed with stirring rod in the bottle, the pure anhydrous 1-butanols that under agitation slowly adds 2.84 milliliters then in room temperature, escaping gas is discharged by syringe needle.Colourless solution adds 9.16 milliliters hexane, to obtain the solution that ultimate density is 0.5 mmole Mg/ milliliter in stirring at room 3 hours.

Example 4

In 50 milliliters of vials that fill 2 gram dehydration silica gel, 30 milliliters of hexanes, feed the nitrogen mixture body that contains 10 volume % chlorine, the feeding speed of chlorine remains on 0.014 Grams Per Minute, keeps continuously stirring SiO 2 slurry ventilation 40 minutes under room temperature.Chlorination reaction finishes the back and feeds pure N with same speed ₂5 minutes with the superfluous Cl in the eccysis vial ₂Then in the chlorine processing SiO 2 slurry of continuous stirring, slowly adding 6.0 milliliters of BEM/ butanol solutions that prepared under the room temperature, reaction flask stirred under room temperature 1 hour, dripped 2 milliliters of hexane solutions that contain 0.5 mmole/milliliter Benzoyl chloride subsequently in slurry.After Benzoyl chloride solution added, slurry stirred under room temperature 1 hour, dripped 1.2 milliliters subsequently in slurry and contained 0.5 mmole/milliliter TiCl ₄Hexane solution, slurry at room temperature stirred 1 hour, dripped 18.8 milliliters in the slurry again and contained the 25.2%(w/w) n-heptane solution of three-just-hexyl aluminium, slurry restir 1 hour.Solid catalyst solvent by inclining and is reclaimed, and washing is 30 minutes in 30 milliliters fresh hexane.Solids containing titanium reclaims by decantation, drying under room temperature, nitrogen gas stream.

In 1.8 liters polymerization reactor, add 850 milliliters of hexanes, 2.4 milliliters contain the 25%(w/w) n-heptane solution of triisobutyl aluminium.Reactor is forced into 30 pounds/inch with hydrogen ², be heated to 85 ℃ then, 20 milliliters of butene-1s are pressed into reactor, be pressed into enough ethene simultaneously and make total reactor pressure reach 150 pounds/inch ², again 25 milligrams of exsiccant solids containing titanium injecting reactors,, by cutting off the ethene air-flow polymerization is stopped at last in 85 ℃ of polymerizations 60 minutes, rapidly with reactor cooling to room temperature.Polymerization experiment result takes passages in the table II.Comparative result in the table II shows that the catalyzer that makes by the present invention can improve pine (heap) density, and molecular weight distribution is also narrow in general, and the susceptibility of hydrogen is bigger.

Example 5

The preparation of titanium-containing catalyst component is with example 4, but uses 4 milliliters Benzoyl chloride solution when the preparation ingredient of solid catalyst.The polymerization of ethene is also finished by example 4 steps, and with 100 milligrams ingredient of solid catalyst, polymerization result is taken passages in the table II when being polymerization.

Example 6

The titanium-containing catalyst component is used 8 milliliters Benzoyl chloride solution by the preparation of example 4 methods when different is the preparation ingredient of solid catalyst.The polymerization of ethene is finished by example 4 steps, just during polymerization with 100 milligrams ingredient of solid catalyst.Polymerization result is taken passages in the table II.

Example 7

The titanium-containing catalyst component is used 8.4 milliliters Benzoyl chloride solution by the preparation of example 4 methods when different is the preparation ingredient of solid catalyst.The polymerization of ethene is also finished by example 4 steps, just during polymerization with 75 milligrams ingredient of solid catalyst.Polymerization result is taken passages in the table II.

Comparative example 2

The titanium-containing catalyst component is by example 4 methods preparations, and the adding of different is Benzoyl chloride is not included among the preparation of ingredient of solid catalyst.The polymerization of ethene is finished by example 4 steps, adds 25 milligrams ingredient of solid catalyst when being polymerization.Polymerization result is taken passages in the table II.

Example 8

903 restrain silicon-dioxide in 5000 milliliters of iso-pentane, at 25 ℃, and slurryization under the nitrogen protection.Slurry temp is elevated to 35 ℃, and reactor is forced into 11 pounds/inch with chlorine ², chlorine feeds reactor with the constant speed of 1.2 standard liters per minute subsequently, and the logical chlorine time is 1.25 hours, can see that after this it no longer absorbs chlorine.Slurry is at 11 pounds/inch ²Chlorine depress again and to continue to stir 0.75 hour.Remove chlorine with nitrogen gas stream then, the reaction mixture that in slurry, adds 2050 milliliters of butyl ethyl magnesium and butanols, this reaction mixture is to be reacted in advance with pure butanols by the hexane solution that contains 10%BEM to make, and wherein the concentration of magnesium is 0.62 mmole Mg/ milliliter, and alcohol/magnesium mol ratio is 0.95.Reaction mixture added in 29 minutes, stirred subsequently 2 hours, kept 35 ℃ of pure Benzoyl chlorides that added 268 grams in 15 minutes in slurry afterwards.Reaction mixture restir 45 minutes maintains 35 ℃ this moment in stirring the pure TiCl of adding 51.4 grams in following 15 minutes ₄Reactor continues to stir 45 minutes, adds 2350 milliliters of isopentane solution that contain 25% 3-just-hexyl aluminium this moment again in slurry in 15 minutes.Solution removes with the decantation method then and desolvates keeping under 35 ℃ the temperature restir 45 minutes, and solid washs 3000 milliliters of different defending in the alkane, at last with decantation method recovery solid, and under nitrogen gas stream in 60 ℃ of dryings 4 hours.Vapour phase polymerization

Diameter is the fluidized-bed reactor of 36 inch, keeps continuous duty, is 300 pounds/inch in 82 ℃ at stagnation pressure ²Under make ethene-1-Butylene copolymer.Reaction mixture contains the 31.4(mole) ethene of %, enough butene-1s and hydrogen are keeping C ₄H ₈/ C ₂H ₄Mol ratio is 0.390, H ₂/ C ₂H ₄Mol ratio be under 0.092 the condition continuously circulation with the surface velocity of the 48 cels fluidized-bed that stimulates the menstrual flow.The remainder of reaction mixture is a nitrogen, Zhi solids containing titanium is squeezed into reactor with the input speed of 9.6 Grams Per Hours continuously with pump as stated above, the isopentane solution that contains 11% triethyl aluminum is also squeezed into reactor with pump with 511 milliliters/hour input speed.Production rate is 76 kilograms/hour, and average retention time is 5 hours.The polymerisate that generates regularly takes out the polymkeric substance that keeps constant weight in the reactor substantially to keep, and the polymerization result of operating under steady state conditions is listed in the table III.

Example 9

872 gram silicon-dioxide are in 5000 milliliters of iso-pentane; in 25 ℃ of slurryization under nitrogen protection; slurry is warming up to 35 ℃; under agitation in 30 minutes 1; 980 milliliters of hexane solutions that contain the reaction product of butyl ethyl magnesium and butanols (react in advance with enough hexane solutions that contains 10% butyl ethyl magnesium and butanols that to make magnesium density be 0.62 mmole/milliliter; alcohol/magnesium mol ratio is 0.95 product) add in the trip slurry; reaction mixture stirred 2 hours; in reaction mixture, add 257 pure Benzoyl chlorides in 15 minutes keeping under the continuous stirring then in 35 ℃; kept 35 ℃ of restir subsequently 45 minutes, keep slurry temp be 35 ℃ in 15 minutes, adding the pure TiCl of 49.8 grams under the constant agitation ₄, reaction mixture continued to stir 1 hour again under this temperature, and chlorine feeds slurry with the speed of 1.2 standard liters per minute during this period.The pressure of reactor remains on 11 pounds/inch ², superfluous chlorine is discharged as required, and logical chlorine is after 2 hours, and residue chlorine nitrogen replacement keeps constant agitation in 35 ℃ then in the slurry that chlorine is handled, and adds 2,235 milliliters of isopentane solution that contain 25% 3-just-hexyl aluminium in 15 minutes.Add solution afterreaction mixture restir minute, remove with the decantation method and desolvate, solid washs in 3000 milliliters of iso-pentane, and solid reclaims with the decantation method, subsequently in nitrogen gas stream in 60 ℃ of dryings.

Polymerization is finished by example 4 steps, and that different is H ₂/ C ₂H ₄Mol ratio is 0.135, C ₄H ₈/ C ₂H ₄Mol ratio is 0.415, and the input speed of catalyzer is 11.1 Grams Per Hours, and aluminium/titanium mol ratio is 22.8, and production of resins speed is 63 kilograms/hour, and the residence time is 3.6 hours.Polymerization result is taken passages in the table IV.

Example 10

Fill silica gel 2 grams of 500 ℃ of dehydrations, 50 milliliters of vials of 20 milliliters of hexanes feed the nitrogen that contains 10 volume % chlorine, and the flow velocity of chlorine is 0.014 Grams Per Minute, keep the SiO 2 slurry continuously stirring to lead to chlorine 40 minutes under room temperature, chlorination finishes the back and is blown into pure N with same speed ₂5 minutes with superfluous chlorine in the flushing reactor.The SiO 2 slurry that chlorine was handled is the solution of 0.5 mmole/milliliter keeping slowly adding 8.0 milliliters of BEM/ butanols (1: 1) concentration in room temperature under the constant speed stirring condition.Reaction mixture stirred under room temperature 1 hour, and dripping 4.8 ml concns then in slurry is the Benzoyl chloride hexane solution of 1.0 mmole/milliliters.After Benzoyl chloride solution added, slurry stirring at room 1 hour, was 1.6 ml concns the TiCl of 0.5 mmole/milliliter more subsequently ₄-hexane solution splashes into slurry.Slurry at room temperature stirred 1 hour again, and then dripped three hexyl aluminium-hexane/n-heptane solutions that 3.8 ml concns are 0.629 mmole/milliliter, and slurry restir 1 hour is removed the solvent recuperation solid catalyst in a vacuum.

2 liters polymerization reactor adds 850 milliliters of hexanes, 4.2 milliliters and contains the 25%(w/w) n-heptane solution of triisobutyl aluminium.Reactor is forced into 30 pounds/inch with hydrogen ², be heated to 85 ℃ then, in reactor, be pressed into 20 milliliters the butene-1 and the ethene of q.s again and make reactor general pressure reach 150 pounds/inch ²75 milligrams dry solids containing titanium is slurryization in 3.0 milliliters of white oils, injecting reactor then, and controlled polymerization 40 minutes stops polymerization by cutting off the ethene air-flow, and reactor is cooled to room temperature rapidly.Polymerization result is taken passages in the table IV.

Example 11

The preparation of titanium-containing catalyst component is with example 10, and different is to lead to the chlorine step after adding the BEBEM/ butanol solution, and before Benzoyl chloride is handled.The polymerization of ethene is finished by the step of example 10.Polymerization result is taken passages in the table IV.

Example 12

The preparation of titanium-containing catalyst component is with example 10, and different is that being added in of chlorine adds after the Benzoyl chloride solution.The polymerization of ethene is with example 10.Polymerization result is taken passages in the table IV.

Example 13

The preparation of titanium-containing catalyst component is with example 10, and different is that logical chlorine is adding TiCl ₄After the solution, the polymerization of ethene is with example 10.Polymerization result is taken passages in the table IV.

The table II

Instance number specific activity (1) melting index molten resin density pine (heap)

MI index specific density

(restraining/10 minutes) MIR ⁽²⁾(gram per centimeter ³) (pound/Foot ³)

4 45.0 1.32 29.4 0.9420 25.0

5 31.2 1.87 26.0 0.9427 25.6

6 21.4 1.98 26.9 0.9429 25.6

7 11.5 1.13 26.5 0.9447 23.7

Comparative example 2 53.8 1.09 31.7 0.9417 12.5

(1) unit of specific activity be a kilogram polyethylene/gram titanium-hour-ethylene pressure

(2) MIR is the ratio of high low melt index (HLMI) and melting index (MI), measures (condition E) by ASTM D1238

The table III

Example 8 examples 9

Productivity (gram/gram) 8,000 5,700

Resin density (gram per centimeter ³) 0.9195 0.9190

Melting index (MI) (0.1 Grams Per Minute) 1.29 0.98

Melting index is than (MIR) 30.7 33.4

Reactor pine (heap) density (pound/Foot ³) 24.6 20.6

The table IV

Instance number specific activity (1) melting index fusion pine (heap)

MI index specific density

(restraining/10 minutes) MIR(2) (pound/Foot ³)

10 157.3 0.4 30 19.3

11 272.5 0.7 34 22.5

12 157.9 0.7 29 20.6

13 395 0.6 24 19.3

(1) unit of specific activity be a kilogram polyethylene/gram titanium-hour-mol ethene,

(2) MIR is the ratio of high low melt index (HLMI) and melting index (MI), measures (condition E) by ASTM D1238

Claims (12)

1, a kind of catalyst component that contains transition metal; it comprises; the solid reaction product that in inert solvent, is obtained with following compound treatment inert solid carrier; (A) II a; the organometallic compound of II b or III a family metal; wherein the valency of metal is next saturated with the alkyl of alkyl or replacement, and (B) oxygenatedchemicals is from ketone; aldehydes; alcohols is chosen (C) acyl halide in siloxanes or their mixture; (D) IV b; V b, at least a transition metal of VI b or VIII family metal, (E) Cl ₂, Br ₂Or interhalogen compound, (F) use II a, II b, or the product that contains transition metal of the organometallic compound prereduction of III a family metal, its condition is: batching (A) and (B) can (ⅰ) be added in the inert solid simultaneously, (ⅱ) be added in the inert solid, use (A) to handle immediately after (ⅲ) handling with (B) as (A) and reaction product (B).

2, the transition metal catalyst component that contains according to claim 1, wherein, solid reaction product is handled inert solid and is obtained according to choose a kind of order from following reaction sequence in inert solvent,

(a) at first handle,, (B), (C), (D) and (F) handle subsequently successively with batching (A) with batching (E),

(b) handle with batching (A) with (B) earlier, successively with batching (C), (D), (E) and (F) handle subsequently, or

(c) handle earlier with batching (C), subsequently successively and (B) with batching (A), (E), (D) and (F) processing,

(d) handle with batching (B) with (A) earlier, successively with batching (E), (C), (D) and (F) handle subsequently,

Further condition is: (ⅰ) batching (A) and (B) can add simultaneously, (ⅱ) (A) and (B) add as reaction product (ⅲ) use (A) to handle after energy enough (B) processing immediately.

3, the transition metal catalyst component that contains according to claim 1, wherein, organometallic compound (A) is that general formula is R ¹MgR ²The dialkyl magnesium compound, R in the formula ¹And R ²Can be identical or different, they contain 1-20 carbon atom, can be from alkyl, aryl, cycloalkyl, aralkyl is chosen in alkadienyl or the alkenyl; Oxygenatedchemicals (B) is R from general formula ³OH and R ⁴COR ⁵Alcohols and ketone in choose, in the formula, R ³, R ⁴, and R ⁵Respectively for containing the group of 1-20 carbon atom, they can be identical or different, R ³, R ⁴, and R ⁵Can be alkyl, aryl, cycloalkyl, aralkyl, alkadienyl or alkenyl; Acyl halide (C), its general formula are R ⁶COX, in the formula, R ⁶But C ₁-C ₁₂Alkyl, cycloalkyl, the aryl of aryl or replacement, X are halogens; Halogen (E) is Cl ₂; (F) be that general formula is R ⁷ _nAlX ' _3-nThe aluminum alkyls organometallic compound, in the formula, X ' is halogen or hydride, R ⁷Be to be selected from C ₁-C ₁₈Alkyl, 1≤n≤3.

4, the transition metal catalyst component that contains according to claim 1, inert support wherein is a silicon-dioxide.

5, the transition metal catalyst component that contains according to claim 3, wherein, oxygenatedchemicals be just-butanols.

6, the transition metal catalyst component that contains according to claim 3, wherein transistion metal compound is TiCl ₄

7, the transition metal catalyst component that contains according to claim 3, wherein, R ⁶It is methyl or phenyl.

8, according to claim 1,2,3, the 4 or 5 described transition metal catalyst components that contain, organo-magnesium compound wherein (A) are ethyl-just-dibutyl magnesiums, oxygenatedchemicals (B) be just-butanols, and (A) He (B) one react.

9, the transition metal catalyst component that contains according to claim 3, wherein, aluminum alkyls is three-just-hexyl aluminium.

10, the transition metal catalyst component that contains according to claim 3, wherein, inert support is a silicon-dioxide, batching (A) and (B) be with just-butyl-magnesium ethide is with the adding of the form of the reaction product of butanols, (C) is Benzoyl chloride, (D) is TiCl ₄, (E) be Cl ₂, (F) be three-just-hexyl aluminium.

11, the same C of ethene or ethene ₃-C ₁₂Alpha-olefine polymerizing or the catalyst system of copolymerization, contain:

(a) molecular formula is AlR " _nX " _3-nOrgano-aluminium compound, in the formula, R " be hydrogen, alkyl or have the substituted hydrocarbon radical of 1-20 carbon atom, X is a halogen, the n value is from 1 to 3, and

(b) according to claim 1, any transition metal catalyst component that contains in 2,3,4,5,6,7,8,9 or 10.

12, ethene, C ₁-C ₂₀Alpha-olefin, or ethene, the polymerization process of the mixture of alpha-olefines and alkadiene, this method comprises, carries out polymerization in the presence of the described catalyst system of claim 11.