CN1038755C - Ethylene polymer, process for preparing the same, solid titanium catalyst component for ethylene polymerization and ethylene polymerization catalyst - Google Patents

Abstract

The present invention discloses an ethylene polymer and a preparation method thereof, the ethylene polymer has small Mw/Mn value and Mz/Mw value, small long-chain branch proportion and high swelling ratio. The present invention also discloses a solid-state titanium catalyst component and an ethylene polymerization catalyst which comprises the solid-state titanium catalyst component and an organometallic compound catalyst component. The ethylene polymer has excellent mould pressing performance and can be used for producing moulding articles which have the advantages of high rigidity, good shock resistance and smooth external appearance. In addition, the ethylene polymer with superior properties can be obtained by the aid of the ethylene polymerization catalyst.

Description

Ethene polymers and polyvinyl preparation method

The present invention relates to ethene polymers, polyvinyl preparation method, the solid titanium catalyst component that is used for vinyl polymerization and ethylene rolymerization catalyst.Particularly, the present invention relates to the little ethene polymers of swelling ratio height, narrow molecular weight distribution and long chain branches ratio, this polymkeric substance the preparation method, be used for the solid titanium catalyst component of vinyl polymerization and be applicable to the preparation this polymkeric substance ethylene rolymerization catalyst.

Ethene polymers is widely used as the material of hollow moulded products, extrusion molding moulded product, film and thin slice at present.The required character of this ethene polymers is looked its purposes and method of moulding and is different.Must use the high ethene polymers of swelling ratio when for example, being used for the bottle of fine otch trace shape being arranged or the narrower blow molding of thickness distribution being arranged by hollow molding methods production.

Use Ziegler-Natta catalyst (as MgCl ₂The titanium catalyst of carrier solid-carrying type) ethene polymers that makes has good rigidity and shock-resistance, and this is because wherein almost do not have a long chain branches, but compare their moldability with the ethene polymers that makes with Cr type Phillips catalyzer relatively poor.On the other hand, than the ethene polymers that makes with Ziegler-Natta catalyst higher swelling ratio and higher moldability are arranged with high pressure method or the ethene polymers that makes with Cr type Phillips catalyzer, but owing to there is long chain branches, their rigidity and shock-resistance are lowered.

In these cases, to having carried out all research with Ziegler-Natta catalyst preparation and ethene polymers that have fine moldability etc.

For example, the open publication No. 12735/1980 of Japanese Patent narrated a kind of in the ethene polymers that high pressure method makes through mixing the ethene polymers that obtains with the ethene polymers of Ziegler-Natta catalyst preparation.In addition, the open publication No. 36546/1985 of Japanese Patent narrated a kind of in the ethene polymers that makes with Cr type Phillips catalyzer through mixing the ethene polymers that makes with Ziegler-Natta catalyst the ethene polymers that obtains.Yet,,, intrinsic rigidity and impact strength in the ethene polymers that makes with Ziegler-Natta catalyst have but been reduced because the long chain branches ratio increases though these polyvinyl moldabilities are improved.

In addition, the open publication No. 89341/1984 of Japanese Patent has been narrated and a kind ofly will be in the presence of radical initiator a kind of ethene polymers that is made by Ziegler-Natta catalyst have been carried out modification and the ethene polymers that obtains.The open publication No. 164347/1984 of Japanese Patent has been narrated a kind of ethene polymers that is made by Ziegler-Natta catalyst with the toxilic acid modification and the ethene polymers that obtains.Yet be too in these cases: though these polyvinyl moldabilities be improved because its rigidity of increase and the impact strength of long chain branches ratio reduced.

Also have, the open publication No. 158204/1982 and 106806/1985 of Japanese Patent has been narrated a kind of with special catalyst ethene polymers preparation, that the long chain branches ratio is low and moldability is fabulous.Yet these ethene polymerss have bigger Mw/Mn and Mz/Mw value, and comprise the polymkeric substance of the long-range dried molecular-weight average of molecular weight.This polymkeric substance causes the surface irregularity of its moulded product, as flake occurring under the multiple situation.

More have, the open publication No. 130314/1986 of Japanese Patent has been narrated the fabulous ethene polymers of a kind of moldability, and it is made by the multistep polymerization method.This ethene polymers has wider molecular weight distribution, thereby comprises the ethene polymers of molecular weight much larger than molecular-weight average, and the result causes the surface irregularity of its moulded product, as flake and so on occurs.

As mentioned above, to can be prepared with Ziegler-Natta catalyst, the moldability height, can be made into physical strength high and almost do not have the ethene polymers of uneven surface to carry out conscientious probing into, but fails to find any ethene polymers with these character.

The inventor probed into Ziegler-Natta catalyst preparation, moldability is fabulous, it is fabulous and almost do not have an ethene polymers of uneven surface to make physical strength.As a result, they have found that a kind of density and melt flow rate are in specified range, that particular kind of relationship is arranged between molten tension force and melt flow rate, molecular weight distribution mw/mn, molecular weight distribution Mz/Mw, have shown the g of long chain branches ratio ^*Value and swelling ratio be all in specified range, that fabulous moldability is arranged, it is fabulous and almost do not have an ethene polymers of uneven surface moulded product to be made into physical strength.The inventor also finds, can prepare aforesaid ethene polymers with the ethylene rolymerization catalyst that contains the specific solid state titanium catalyst component.Based on above-mentioned discovery, finished the present invention.

As mentioned above, finished the present invention in these cases.It is fabulous and can form that rigidity is strong, shock-resistance is high and not have the ethene polymers of the moulded product of uneven surface (as flake) to an object of the present invention is to provide a kind of moldability.Another object of the present invention is to provide polyvinyl a kind of preparation method.A further object of the present invention is to provide a kind of ethylene polymerization to use, and is suitable for the polyvinyl solid titanium catalyst component of preparation and a kind of ethylene rolymerization catalyst that contains solid titanium catalyst component is provided.

Ethene polymers of the present invention have following (i) to (character vii):

(i) density 0.90 to 0.98g/cm ³In the scope;

(ii) the melt flow rate of measuring under 190 ℃ and 2.16kg load is in 0.001 to 3000g/10min scope;

(iii) molten tension force (MT) and melt flow rate (MFR) satisfy the relation that following formula is represented:

logMT＜-0.4logMFR+0.75，

(iv) molecular weight distribution mw/mn is between 2 to 9;

(v) molecular weight distribution Mz/Mw is between 2 to 5;

(vi) g ^*Value (a kind of index of long chain branches ratio) reaches between 0.90 to 1.00

(VII) swelling ratio is 1.35 or higher.

Ethene polymers of the present invention can be prepared by Ziegler-Natta catalyst, as a kind of ethylene rolymerization catalyst that contains following component:

[I] is in contact with one another by oxygen and solid-state titanium organometallic compound title complex and the solid titanium catalyst component that obtains, and solid-state titanium organometallic compound title complex is in contact with one another and is got by following component:

(A) contain titanium, magnesium, halogen and contain the solid-state titanium complex of the compound of at least two ehter bonds that exist across a plurality of atoms, and it is in contact with one another and is got by following component:

(a) the liquid magnesium compound of no reducing power;

(b) contain the compound of at least two ehter bonds that exist across a plurality of atoms;

(c) liquid titanium compound; And randomly

(d) precipitation agent wherein (a) and (b), (c) and (d) in have at least a component to contain a kind of halide-containing, and

(B) contain be selected from I in the periodictable to a kind of organometallic compound of III-th family metal and

[II] contains and is selected from the periodictable I to the catalyst component of a kind of organometallic compound of III-th family metal.

Above-mentioned polyvinyl moldability is fabulous, and the rigidity and the shock-resistance of the moulded product of being made by it are fabulous, not the roughened appearance such as flake.

Preparation the present invention polyvinyl method is included under the existence of the ethylene rolymerization catalyst that contains following component with ethylene homo or with the olefin-copolymerization beyond ethene and the ethene:

[I] is a kind of to be in contact with one another and the solid titanium catalyst component that obtains by oxygen and solid organometallic compound title complex, and this solid-state titanium organometallic compound title complex is in contact with one another and is got by following combination:

(A) contain titanium, magnesium, halogen and contain the solid-state titanium complex of the compound of at least two ehter bonds that exist across a plurality of atoms, and the latter is in contact with one another and is got by following component:

(a) the liquid magnesium compound of no reducing power,

(b) contain at least two ehter bonds that exist across a plurality of atoms compound and

(c) liquid titanium compound, and randomly

(d) precipitation agent, wherein (a) and (b), (c) and (d) in have at least a component to contain a kind of halide-containing, and

(B) contain be selected from I in the periodictable to the organometallic compound of III-th family metal and

[II] contains and is selected from the periodictable I to the catalyst component of the organometallic compound of III-th family metal.

Prepare polyvinyl method according to the present invention, can obtain having above-mentioned (i) to (the vii) ethene polymers of every character.

The solid titanium catalyst component that is used for vinyl polymerization of the present invention is in contact with one another and is obtained by oxygen and solid-state titanium organometallic compound ligand thing, and this solid-state titanium organometallic compound title complex then is in contact with one another and is got by following component:

(A) titaniferous, magnesium, halogen and contain the solid-state titanium complex of the compound of at least two ehter bonds that exist across a plurality of atoms, and it is in contact with one another and is got by following component:

(a) the liquid magnesium compound of no reducing power,

(b) contain at least two ehter bonds that exist across a plurality of atoms compound and

(c) liquid titanium compound, and appoint selectively

(d) precipitation agent wherein (a) and (b), (c) and (d) in have at least a component to comprise halogen compound, and

(B) be selected from the periodictable I to the organometallic compound of III-th family metal a kind of containing.

Ethylene rolymerization catalyst of the present invention comprises:

[I] above-mentioned solid titanium catalyst component and

[II] contains and is selected from the periodictable I to the catalyst component of the organometallic compound of III-th family metal.

Solid titanium catalyst component for ethylene polymerization is applicable to the ethene polymers that preparation is above-mentioned with the catalyzer that contains the ethylene polymerization of solid titanium catalyst component.

Accompanying drawing is the explanatory view of step of the preparation method of expression ethylene rolymerization catalyst of the present invention.

To describe ethene polymers of the present invention in detail below. Polyvinyl preparation method, the solid titanium catalyst component of ethylene polymerization and ethylene rolymerization catalyst.

The meaning of terminology used here " polymerization " is not limited to " homopolymerization ", also can be regarded as " copolymerization ". Equally, terminology used here " polymer " is not limited to " homopolymers ", also can be regarded as " copolymer ".

Ethene polymers of the present invention is random copolymer or the block copolymer of homopolymers, ethene and a kind of alkene of ethene.

The copolymer of ethene and a kind of alkene can contain from the α of 3 to 20 carbon atoms-olefin component unit, as propylene, 1-butylene, 1-amylene,, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid and 1-eicosylene, content is 10 % by weight or still less, preferably is 5 % by weight or still less.

Copolymer also can contain the component units by the compound deriving of a plurality of unsaturated chains, for example vinyl aromatic compound such as styrene and allyl benzene; Ethene alicyclic compound such as vinyl cyclohexane; Cycloolefin such as cyclopentene, cycloheptene, ENB, 5-methyl-2-ENB, tetracyclododecen and 2-methyl isophthalic acid, 4,5,8-two methylene bridges-1,2,3,4,4a, 5,8,8a-octahydro naphthalene, and diene (conjugated diene and non-conjugated diene) is such as the 6-methyl isophthalic acid, the 6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1, the 6-octadiene, 6-propyl group-1, the 6-octadiene, 6-butyl-1,6-octadiene, the 6-methyl isophthalic acid, the 6-nonadiene, the 7-methyl isophthalic acid, the 6-nonadiene, 6-ethyl-1, the 6-nonadiene, 7-ethyl-1, the 6-nonadiene, the 6-methyl isophthalic acid, 6-11 carbon diene, isoprene and butadiene content are 10 % by weight or still less. Be preferably 5 % by weight or still less.

Copolymer also can contain the component units by the compound deriving that contains a plurality of unsaturated bonds, for example the ethene elegant compound of virtue such as styrene and allyl benzene; The profound cyclohexene of alicyclic vinyl cycle compound such as ethene; Cycloolefin such as cyclopentene, cycloheptene, ENB, 5-methyl-2-ENB, tetracyclododecen and 2-methyl isophthalic acid, 4,5,8-dimethylene bridge-1,2,3,4,4a-5,8,8a-octahydro naphthalene, and diene (conjugated diene and non-conjugated diene) is such as the 6-methyl isophthalic acid, the 6-octadiene, the 7-methyl isophthalic acid, the 6-octadiene, 6-ethyl-1, the 6-octadiene, 6-propyl group-1, the 6-octadiene, 6-butyl-1,6-octadiene, 6-methyl isophthalic acid, the 6-nonadiene, the 7-methyl isophthalic acid, the 6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1, the 6-nonadiene, the 6-methyl isophthalic acid, the 6-decadinene, the 7-methyl isophthalic acid, the 6-decadinene, the 6-methyl isophthalic acid, 6-12 carbon diene, isoprene and butadiene, content is 10 % by weight or still less, is preferably 5 % by weight or still less.

Ethene polymers of the present invention has 0.90 to 0.98g/cm³, be 0.92 to 0.98g/cm preferably³, better be 0.94 to 0.98g/cm³Density.

Density system measures by laxative remedy. Put into 120 ℃ of constant temperature oil baths and be incubated therein 1 hour determining the sample (long 5 to 6cm rope strands) behind the melt flow rate. Then water is introduced oil bath bit by bit, make oil bath in 1 hour, be cooled to room temperature from 120 ℃. Allow then sample place 1 hour in 23 ℃ indoors. Sample is cut into two segments (sample). Behind this sample of wetted with methanol, it is put into density gradient column lightly. After 15 minutes, from the position that the scale of density gradient column is read sample, to measure the mean value of two samples. From the calibration curve between the scale of the density that obtains with standard buoy and density gradient column this mean value is changed into density. Standard buoy is the glass marble of a diameter 3 to 5mm, and it obtains by the following method: an end that with diameter is 1 to 2mm capillary glass tube seals. Temporary transient and the blind end clinkering capillaceous with a nickel filament is cut off capillary in the position from the about 2mm of blind end, utilizes the capillary after nickel filament is held such cutting, and heating is expanded its and formed. Liquid in the density gradient column be with regulation one-level reagent methyl alcohol among the JIS K 1501 and with the sodium acetate aqueous solution of the one-level reagent sodium acetate stipulated among JISK8371 preparation mix and mixture.

Ethene polymers of the present invention has 0.001 to 3000g/10min, is preferably 0.005 to 1000g/10min, better is 0.01 to 100g/10min, is preferably 0.02 to 10g/10min melt flow rate.

Be to measure as follows in the melt flow rate. The orifice plate of prescribed level among the JIS K7210 is assemblied in the MFR automatic analyzer of Tester Songyo K.K. Corp. manufacturing by JIS K7210 regulation. Thorax (putting the place of sample) is heated to 190 ℃. And be incubated in this same temperature. In thorax, add the 4g sample, and at the mid-piston of thorax. Remove then air bubble, with boring preheating 6 minutes. After the preheating, apply the load of 2160g to release sample. It is heavy to measure the sample that is pushed out from boring in 10 minutes. The value of measuring like this is decided to be melt flow rate.

In ethene polymers of the present invention, molten tension force (MT) and melt flow rate (MFR) satisfy the relation shown in the following formula:

    logMT＜-0.4log MFR+0.75

Be preferably logMT＜-0.4log MFR+0.745

Molten tension force is to record by measuring the tension force that provides when stretching the ethene polymers of fusing with fixed rate, and namely molten tension force is that 15mm/ min, rate of withdraw are 10 to 20m/min, nozzle diameter is that 2.09mm and nozzle length are to measure machine (manufacturing of Toyo Seiki Seisakusho K.K. Corp.) with MT under the 8mm condition to record in 190 ℃ of resin temperatures, rate of extrusion.

Ethene polymers of the present invention has 2 to 9, be preferably 3 to 8, better be 4 to 7 molecular weight distribution mw/mn (being that weight average molecular weight (Mw) is to the ratio of number-average molecular weight (Mn)) and have 2 to 5, be preferably 2.5 to 4.5, better be 3 to 4 molecular weight distribution Mz/Mw (being that Z-average molecular weight (Mz) is to the ratio of weight average molecular weight (Mw)).

Ethene polymers with the interior Mw/Mn of above-mentioned scope and Mz/Mw value demonstrates narrow molecular weight distribution and contains the molecular weight of low amount much larger than the polymer of mean molecule quantity. Therefore, do not contain roughened appearance such as flake by the mechanograph of this polymer.

Mw/Mn and Mz/Mw system measure as follows with gel permeation chromatography (GPC): instrument

ALC/GPC 150 C types, Milipore CO. produces. Condition determination

Chromatographic column: GMH-HT6 (internal diameter 7.5mm * 60cm). Produced by Toso K.K. Corp..

Mobile phase: o-dichlorohenzene (ODCB)

Column temperature: 138 ℃

Flow velocity: 1.0ml/min

Sample concentration: 30mg/20ml

Solution temperature: 140 ℃

Flow into liquid measure: 500ml

Detector: the mensuration of differential refractometer Mw/Mn and Mz/Mw

Elution time Rti, elution amount Hi, molecular weight Mi, at the macromolecular number N i of GPC elution curve i part following relation is arranged:

Mi＝(Ji/K) ^1/α+1

(K＝2.0922×10 ^-4，α＝0.735)

Ji＝P(1)+P(2)Rti+P(3)Rti ²+P(4)Rti ³

Hi=MiNi wherein P (1), P (2), P (3) and P (4) be under the said determination condition with GPC method measurement standard polystyrene (Mw/Mn)=1.1) numerical value by calculating on the calibration curve that shows elution amount and molecular weight Relations Among that obtains of sample.

From Mi and the Hi value of such acquisition, calculate Mn, Mw and Mz by following formula, to determine Mw/Mn and Mz/Mw.

Mn＝∑Hi/∑(Hi/Mi)

Mw＝∑HiHi/∑Hi

Mz＝∑HiMi ²/ ∑ HiMi (referring to Dollock, D. and kratz, F.F., the 6th international symposium of GPC (1968), and Mori, Sadao: " Size Exclusion Chromatography ", PP51～56,1991 publication (Kyoritsu shuppan) in year December 1

Polyvinyl g of the present invention^*Value, i.e. a kind of index of long chain branches ratio, its scope is 0.92 to 1.00 0.90 to 1.00 preferably, better is 0.95 to 1.00.

g ^*The ethene polymers of value in above-mentioned scope, the ratio of its long chain branches in polymer is lower. Therefore, the mechanograph of being made by it has fabulous rigidity and resistance to impact. g^*Value system measures as follows with the GPC method. That is, under aforesaid identical measuring condition, measure Mi and Hi value, use then as shown in the formula calculating [η]_GPC ^ODCBValue: $[\mathrm{\η}{]}_{\mathrm{GPC}}^{\mathrm{ODCB}}=K(\mathrm{\ΣHi}{\left(\mathrm{Mi}\right)}^{\mathrm{\α}}/\mathrm{\ΣHi})$ Wherein K, α, Hi and Mi are identical with above-mentioned definition.

According to document (" GPC Sisxth mternational Seminar " by Pollock, D. and Kratz F.F.1968), income value is corrected into [η] given in decahydronaphthalene_GPCValue. In 135 ℃ and decahydronaphthalene solvent, measure in addition the inherent viscosity ([η] of each sample_obs)。

Data with obtaining like this are calculated as follows out g^*Value,

    g ^*＝[η]obs/[η] _GPC

Ethene polymers of the present invention has 1.35 or higher swelling ratio, is 1.35 to 1.50 preferably.

Ethene polymers with the molten swollen ratio in above-mentioned scope has fabulous moldability.

For example, when with this ethene polymers during through bottle that hollow moulding method is produced, otch trace shape improves to some extent.Therefore the bottle of making has good physical strength.In addition,,, also have, when using the material of same amount, can increase the buckling strength of bottle so can reduce the amount of the bottle material of each bottle because the thickness distribution of hollow moulded products is narrowed down.

Swelling ratio system connects laxative remedy and records.With diameter (Do) is 3.0mm, and length is that the nozzle arrangement of 3mm is in Capillograph-IB instrument (production of Toyo seiki Seisakusho K.K. Corp.).Thorax (introducing the place of sample) is heated to 190 ℃, and is incubated in this same temperature.In thorax, add the 10g sample, and, remove air filled cavity then, with thorax preheating 6 minutes at the mid-piston of thorax.After the preheating, with 0.25,0.5,1,2.5,5,10 and 25 second ^-1Shearing rate extrude sample.Measure the diameter (Di) of the line at 15mm place under the nozzle tip with laser beam.Determine then the straight warp (Di) of the line record like this and the ratio of nozzle diameter (Do) (SRi, Ri/Do).

With each shearing rate and the SRi mapping of correspondence, obtain a curve on semilogarithmic paper, reading shearing rate from this curve is 9.98 seconds ^-1The value at place is got and is made swelling ratio.

Ethene polymers of the present invention has high molten tension force, high swelling ratio, narrow molecular weight distribution and the long chain branches of lesser amt.The still undiscovered so far mistake of this ethene polymers.

Because ethene polymers of the present invention has above-mentioned character, so its moldability is fabulous.In addition, the moulded parts of being made by this polymkeric substance has fabulous rigidity and shock-resistance, and does not have coarse outward appearance.This polymkeric substance is applicable to the material of making various moulded partss such as hollow moulded products and extrudate.

When ethene polymers of the present invention was used as the material of hollow moulded products, this polymkeric substance preferably had following character.

Density 0.94 to 0.97g/cm ³Between;

Melt flow rate (recording under 190 ℃, 2.16kg load) is between 0.01 to 10g/10min;

Molten tension force (MT) and melt flow rate (MFR) satisfy the relation that following formula is represented:

logMT＜-0.4log MFR+0.75；

Molecular weight distribution mw/mn is between 3 to 8;

Molecular weight distribution Mz/Mw is between 2.5 to 4.5;

g ^*Value is between 0.95 to 1.00; With

Swelling ratio is between 1.35 to 1.50.

When ethene polymers of the present invention was used as the extrudate material, this polymkeric substance preferably had following character:

Density 0.94 to 0.97g/cm ³Between;

Melt flow rate (under 190 ℃, 2.16kg load, recording) 0.01 to 10g/10min;

Molten tension force (MT) and melt flow rate (MFR) satisfy the relation that following formula is represented:

logMT＜-0.4log MFR+0.75；

Molecular weight distribution mw/mn is between 3 to 8;

Molecular weight distribution Mz/Mw is between 2.5 to 4.5;

g ^*Value is between 0.95 to 1.00;

Swelling ratio is between 1.35 to 1.50.

Under existing, the ethylene rolymerization catalyst that aforesaid ethene polymers of the present invention can will illustrate below makes by the homopolymerization of ethene or the olefin-copolymerization beyond ethene and the ethene.

The solid titanium catalyst component that is used for vinyl polymerization of the present invention is in contact with one another and is obtained by oxygen and a kind of solid-state titanium organometallic compound title complex, and solid-state titanium organometallic compound title complex then is in contact with one another and is got by following component:

(A) a kind of titaniferous, magnesium, halogen and comprise the solid-state titanium mixture of the compound of at least two ehter bonds that exist across a plurality of atoms, and it is in contact with one another and is got by following component:

(a) a kind of liquid magnesium compound that does not have reducing power,

(b) a kind of compound that contains at least two ehter bonds that exist across a plurality of atoms and

(c) a kind of liquid titanium compound, and randomly,

(d) a kind of precipitation agent, wherein (a) and (b), (c) and (d) in have at least a component to comprise halide-containing, and

(B) be selected from the 1st organometallic compound in the periodictable a kind of containing to the III-th family metal.

Ethylene rolymerization catalyst of the present invention comprises:

The solid catalyst component that [I] is above-mentioned and

[II] a kind of to be contained and is selected from the periodictable I to the catalyst component of the organometallic compound of III-th family metal.

For preparing solid titanium catalyst component of the present invention, at first make the liquid magnesium compound (a) of no reducing power, the compound (b) that contains at least two ehter bonds that exist across a plurality of atoms, liquid titanium compound (c) and randomly, precipitation agent (d) is in contact with one another, with preparation titaniferous, magnesium, halogen with comprise the solid-state titanium mixture (A) of the compound of at least two ehter bonds that exist across a plurality of atoms.

Be used for preparing the no reducing power of solid-state titanium mixture (A) liquid magnesium compound (a) or liquid magnesium compound, be dissolved in the magnesium compound solution that a kind of liquid towards magnesium compound has deliquescent solvent to become by the liquid magnesium compound, or be dissolved in by solid-state magnesium compound solid-state magnesium compound had the magnesium compound solution that become in the deliquescent solvent.

The magnesium compound of no reducing power (a) can be a kind of from the magnesium compound that reducing power is arranged derive and magnesium compound.

The example of magnesium compound (a) comprises magnesium halide such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride; Alkoxyl group magnesium halide such as methoxyl group chlorination magnesium, oxyethyl group magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride and octyloxy magnesium chloride; Aryloxy magnesium halide such as phenoxy group magnesium chloride and methylphenoxy magnesium chloride; Alkoxyl magnesium such as magnesium ethylate, isopropoxy magnesium, butoxy magnesium, octyloxy magnesium and 2-ethyl hexyl oxy magnesium; Aryloxy magnesium such as phenoxy group magnesium and dimethyl phenoxy magnesium; Carboxylic acid magnesium salts such as Magnesium monolaurate and Magnesium Stearate; Inorganic acid salt (as magnesiumcarbonate, magnesium borate and Magnesium Silicate q-agent).Magnesium compound can be the title complex of above-mentioned any compound and other metals, the mixture of the mixture of the mixture of above-mentioned any compound and other metal, above-mentioned any compound and other metallic compounds or above-mentioned two kinds or multiple compound.Wherein, magnesium halide is preferred, and magnesium chloride is particularly preferred.The magnesium compound of no reducing power also can be derived and gets from other materials.

When magnesium compound when being solid-state, it is dissolved in a kind of it is had in the solvent of dissolving power, gained solution is as the liquid magnesium compound (a) of no reducing power.When magnesium compound was liquid state, it self just can be used as the liquid magnesium compound (a) of no reducing power, or it is dissolved in a kind of it was had in the solvent of dissolving power for use.

There is the example of the solvent of dissolving power to comprise that titanic acid ester and electron donor (g) are as alcohol, aldehyde, amine, carboxylic acid and metal acid esters (except the titanic acid ester) to magnesium compound.These compounds can be used alone or in combination.

The example of titanic acid ester comprises that orthotitanate is (as titanic hydroxide methyl esters, titanic hydroxide ethyl ester, titanic hydroxide n-propyl, titanic hydroxide isopropyl ester, the positive butyl ester of titanic hydroxide, titanic hydroxide isobutyl ester, titanic hydroxide n-pentyl ester, titanic hydroxide 2-ethylhexyl, titanic hydroxide n-octyl, titanic hydroxide phenyl ester, titanic hydroxide cyclohexyl; Many titanic acid ester such as many metatitanic acids methyl esters, many titanium ethanolates, many metatitanic acids n-propyl, many isopropyl titanates, many tetrabutyl titanates, many iso-butyl titanates, many metatitanic acids n-pentyl ester, many metatitanic acids 2-ethylhexyl, many metatitanic acids n-octyl, many metatitanic acids phenyl ester and many metatitanic acids cyclohexyl.

The example of alcohol comprises Fatty Alcohol(C12-C14 and C12-C18) such as methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, methyl carbitol, 2-methyl amyl alcohol, 2-ethyl butanol, n-Heptyl alcohol, n-Octanol, 2-Ethylhexyl Alcohol, decyl alcohol, dodecanol, tetradecanol, undecylenic alcohol, oleyl alcohol and Stearyl alcohol; Alicyclic ring alcohol such as hexalin and methyl-cyclohexanol; Aromatic alcohol such as benzylalcohol, xylyl alcohol, Isobutyl Benzyl Carbinol, α-Jia Jibianchun and α, alpha-alpha-dimethyl benzylalcohol; With the Fatty Alcohol(C12-C14 and C12-C18) that contains alkoxyl group such as normal-butyl cellosolve and 1-butoxy-2-propyl alcohol.

The example of aldehyde comprises aldehyde such as hexanal, 2-ethyl hexanal, octanal and the undecenal that contains 7 or more carbon atoms.

The example of amine comprises and contains 6 or amine such as heptyl amice, octylame, nonyl amine, decyl amine, lauryl amine, 11 (alkane) amine and the 2 ethyl hexylamine of more a plurality of carbon atoms.

The example of carboxylic acid comprises the organic carboxyl acid that contains 7 or more a plurality of carbon atoms, as sad, 2 ethyl hexanoic acid, undecylenic acid, 11 (alkane) acid, n-nonanoic acid and sad.

The example of metal acid esters comprises four zirconium alkoxides such as tetramethoxy zirconium, tetraethoxy zirconium, tetrabutyl zirconate and zirconium-n-propylate.

These titanic acid ester and electron donor (g) can use together with inert solvent.

The example of inert solvent comprises:

Aliphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene;

Alicyclic hydrocarbon such as pentamethylene, hexanaphthene and methylcyclopentane;

Aromatic hydrocarbon such as benzene, toluene and dimethylbenzene;

Halohydrocarbon is as ethylene chloride and chlorobenzene; And

The mixture of above-mentioned hydrocarbon.

Being dissolved in by magnesium compound in the solvent that it is had dissolving power solution in, the content of magnesium compound rises solvent 0.1 to 20mol/, is to rise in the scope of solvent 0.5 to 5mol/ preferably.

When the solid-state titanium mixture of preparation (A), the compound (b) that will contain at least 2 ehter bonds that exist across a plurality of atoms joins in the liquid magnesium compound (a) of no reducing power.

Can mention some compounds like this as the compound (b) (being sometimes referred to as diether compounds (b) later on) that contains at least two ehter bonds that exist across a plurality of atoms that is used to prepare solid titanium catalyst component, one or more atoms that promptly wherein are selected from carbon, silicon, oxygen, nitrogen, phosphorus, boron and sulphur are present in the compound between these ehter bonds.Such some compounds preferably, wherein the atom that exists between huge relatively substituting group of volume and ehter bond joins, and the atom that is present between two or more ehter bonds contains a plurality of carbon atoms.Ethylidene is preferably the unit that is connected two ether oxygenses in these compounds with propylidene.

The ether compound represented for following formula of diether compounds (b) for example:

Wherein n is the integer of 2≤n≤10, R ¹To R ²⁶Respectively be the substituting group that contains at least a element of from carbon, hydrogen, oxygen, halogen, nitrogen, sulphur, phosphorus, boron and silicon, selecting, R ¹To R ²⁶, R preferably ¹To R ²ⁿArbitrary combination can form a ring except that phenyl ring together, and main chain can contain the atom beyond the de-carbon again.

Below listed be the example of diether compounds (b).

2-(2-ethylhexyl)-1, the 3-Propanal dimethyl acetal,

2-sec.-propyl-1, the 3-Propanal dimethyl acetal,

2-butyl-1, the 3-Propanal dimethyl acetal,

2-sec-butyl-1, the 3-Propanal dimethyl acetal,

2-cyclohexyl-1, the 3-Propanal dimethyl acetal,

2-phenyl-1, the 3-Propanal dimethyl acetal,

2-cumyl-1, the 3-Propanal dimethyl acetal,

2-(2-phenylethyl)-1, the 3-Propanal dimethyl acetal,

2-(2-cyclohexyl ethyl)-1, the 3-Propanal dimethyl acetal,

2-(right-chloro-phenyl-)-1, the 3-Propanal dimethyl acetal,

2-(diphenyl-methyl)-1, the 3-Propanal dimethyl acetal,

2-(1-naphthyl)-1,3-Propanal dimethyl acetal, 2-(2-fluorophenyl)-1, the 3-Propanal dimethyl acetal, 2-(1-decahydro naphthyl)-1,3-Propanal dimethyl acetal, 2-(right-tert-butyl-phenyl)-1,3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal, 2,2-diethyl-1,3-Propanal dimethyl acetal, 2,2-dipropyl-1,3-Propanal dimethyl acetal, 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2-methyl-2-propyl group-1, the 3-Propanal dimethyl acetal, 2-methyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-methyl-2-ethyl-1,3-Propanal dimethyl acetal, 2-methyl-2-sec.-propyl-1, the 3-Propanal dimethyl acetal, 2-methyl-2-phenyl-1,3-Propanal dimethyl acetal, 2-methyl-2-cyclohexyl-1,3-Propanal dimethyl acetal, 2, two (right-chloro-phenyl-)-1 of 2-, 3-Propanal dimethyl acetal, 2, two (the 2-cyclohexyl ethyls)-1 of 2-, 3-Propanal dimethyl acetal, 2-methyl-2-isobutyl--1, the 3-Propanal dimethyl acetal, 2-methyl-2-(2-ethylhexyl)-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2,2-phenylbenzene-1,3-Propanal dimethyl acetal, 2,2-dibenzyl-1,3-Propanal dimethyl acetal, 2, two (cyclohexyl methyl)-1 of 2-, 3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-di ethyl propyl ether, 2,2-diisobutyl-1,3-dibutoxy propane, 2-isobutyl--2-sec.-propyl-1,3-Propanal dimethyl acetal, 2,2-two-sec-butyl-1,3-Propanal dimethyl acetal, 2,2-two-tertiary butyl-1,3-Propanal dimethyl acetal, 2,2-two-neo-pentyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal, 2-phenyl-2-benzyl-1,3-Propanal dimethyl acetal, 2-cyclohexyl-2-cyclohexyl methyl-1,3-Propanal dimethyl acetal, 2,3-phenylbenzene-1,4-diethoxy butane, 2,3-dicyclohexyl-1,4-diethoxy butane, 2,2-dibenzyl-1,4-diethoxy butane, 2,3-dicyclohexyl-1,4-diethoxy butane, 2,3-di-isopropyl-1,4-diethoxy butane, 2, two (p-methylphenyl)-1 of 2-, 4-dimethoxy-butane, 2, two (rubigan)-1 of 3-, 4-dimethoxy-butane, 2, two (to fluorophenyl)-1 of 3-, 4-dimethoxy-butane, 2,4-phenylbenzene-1,5-dimethoxy pentane, 2,5-phenylbenzene-1,5-dimethoxy hexane, 2,4-di-isopropyl-1,5-dimethoxy pentane, 2,4-diisobutyl-1,5-dimethoxy pentane, 2,4-diisoamyl-1,5-dimethoxy pentane, 3-methoxymethyl tetrahydrofuran (THF), 3-methoxymethyl diox, 1,2-two isobutoxy propane, 1,2-two isobutoxy ethane, 1,3-diisoamyl oxygen base ethane, 1,3-diisoamyl oxygen base propane, 1,3-two different neopentyl oxygen ethane, 1,3-two neopentyl oxygen propane, 2,2-butylidene-1, the 3-Propanal dimethyl acetal, 2,2-pentylidene-1, the 3-Propanal dimethyl acetal, 2,2-hexylidene-1, the 3-Propanal dimethyl acetal, 1, two (methoxymethyl) hexanaphthenes of 3-, 2,8-dioxy spiral shell (5,5) undecane, 3,7-dioxy two rings (3,3,1) nonane, 3,7-dioxy two rings (3,3,0) octane, 3,3-diisobutyl-1,5-oxo nonane, 6,6-two isobutoxy heptane, 1,1-dimethoxy-methyl pentamethylene, 1, two (dimethoxy-methyl) hexanaphthenes of 1-, 1,1-two (methoxymethyl) two ring (2,2,1) heptane, 1,1-dimethoxy-methyl pentamethylene, 2-methyl-2-methoxyl methyl-1, the 3-Propanal dimethyl acetal, 2-cyclohexyl-2-ethoxymethyl-1,3-di ethyl propyl ether, 2-cyclohexyl-2-methoxyl methyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-dimethoxy hexanaphthene, 2-sec.-propyl-2-isopentyl-1,3-dimethoxy hexanaphthene, 2-cyclohexyl-2-methoxyl methyl-1,3-dimethoxy hexanaphthene, 2-sec.-propyl-2-methoxyl methyl-1,3-dimethoxy hexanaphthene, 2-isobutyl--2-methoxyl methyl-1,3-dimethoxy hexanaphthene, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxy hexanaphthene, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxy hexanaphthene, 2-sec.-propyl-2-ethoxymethyl-1,3-diethoxy hexanaphthene, 2-sec.-propyl-2-ethoxymethyl-1,3-dimethoxy hexanaphthene, 2-isobutyl--2-ethoxymethyl-1,3-diethoxy hexanaphthene, 2-isobutyl--2-ethoxymethyl-1,3-dimethoxy hexanaphthene, three (p-methoxyphenyl) phosphine, two (methoxyl methyl) silicon of aminomethyl phenyl, two (methoxyl methyl) silicon of phenylbenzene

Two (methoxyl methyl) silicon of methylcyclohexyl,

Two (methoxyl methyl) silicon of di-t-butyl,

Two (methoxyl methyl) silicon of cyclohexyl-tertiary butyl, and

Two (methoxyl methyl) silicon of sec.-propyl-tertiary butyl.

Wherein, preferably 1, the 3-diether particularly preferably is 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2-sec.-propyl-2-isopentyl-1,3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal and 2, two (cyclohexyl methyl)-1 of 2-, 3-Propanal dimethyl acetal.

The liquid titanium compound (C) that is used to prepare solid-state titanium mixture (A) is, for example, and the tetravalence Halogen titanium compound that is expressed from the next:

Ti(OR) _gX _4-g

Wherein R is that alkyl, X are that halogen atom, g are numbers of 0≤g≤4.

The object lesson of this compound comprises:

Titanium tetrahalide such as TiCl ₄, TiBr ₄, TiI ₄

Alkoxyl group three halogenated titaniums such as Ti (OCH ₃) Cl ₃, Ti (OC ₂H ₅) Cl ₃, Ti (On-C ₄H ₉) Cl ₃, Ti (OC ₂H ₅) Br ₃And Ti (OisoC ₄H ₉) ₂Br ₃

Alkoxyl group dihalide titanium such as Ti (OCH ₃) ₂Cl ₂, Ti (OC ₂H ₅) ₂Cl ₂, Ti (On-C ₄H ₉) ₂Cl ₂And Ti (OC ₂H ₅) ₂Br ₂

Alkoxyl group one halogenated titanium such as Ti (OCH ₃) ₃Cl, Ti (OC ₂H ₅) ₃Cl, Ti (On-C ₄H ₉) ₃Cl and Ti (OC ₂H ₅) ₃Br; With

Four titan-alkoxides such as Ti (OCH ₃) ₄, Ti (OC ₂H ₅) ₄, Ti (On-C ₄H ₉) 4, Ti (OisoC ₄H ₉) ₄With four (2-ethyl hexyl oxy) titanium,

Wherein titanium tetrahalide is preferred person, and titanium tetrachloride is preferred especially person.These titanium compounds can separately or be united use.In addition, use their also available hydrocarbon or halohydrocarbon dilution back.

The precipitation agent (d) that can selectively be used to prepare solid-state titanium mixture (A) is, for example, and silicon compound.

The example of this silicon compound comprises:

Halogen silicon compound with following general formula:

SiXnR _4-n ^qWherein X is a halogen atom, R ^qBe the alkyl that contains 1 to 20 carbon atom, contain the cycloalkyl of 3 to 20 carbon atoms or contain the aryl of 6 to 20 carbon atoms that n is a real number of 1 to 4.

And,

With the polymer silicon compound of following general formula, R wherein ^sBe alkyl, p is 1 or a bigger integer.

The following describes and use general formula SiXnR _4-n ^qThe object lesson of the Halogen silicon compound of expression.

Use general formula SiX ₄The silicon tetrahalogen of (n is 4 in above-mentioned general formula) expression is as silicon tetrachloride, Silicon bromide, silicon tetraiodide, silicon tetrafluoride, trichlorine silicon bromide, three chlorosulfonylation silicon, trichlorine silicon chlorides, dichloro dibrominated silicon, dichloro silicon diiodide, dichloro bifluoride silicon, tribromo silicon chlorides, triiodo silicon chlorides, trifluoro silicon chlorides, triiodo silicon bromide, trifluoro silicon bromide, dibromo silicon diiodide, dibromo bifluoride silicon, tribromo iodate silicon, tribromo silicon fluoride, trifluoro iodate silicon, diiodo-bifluoride silicon and triiodo silicon fluoride.Wherein, preferably silicon tetrachloride, Silicon bromide, trichlorine silicon bromide, dichloro dibrominated silicon and tribromo silicon chlorides, silicon tetrachloride are particularly preferred.

Use general formula SiX ₃R ^qThe compound of (n=3 in the above-mentioned general formula) expression, for example:

Contain the alkyl trichlorosilane of 16 carbon atoms with interior saturated alkyl, as METHYL TRICHLORO SILANE, ethyl trichlorosilane, just or the sec.-propyl trichlorosilane, just, different, second month in a season or tertiary butyl trichlorosilane, just or isopentyl trichlorosilane, n-hexyl trichlorosilane, n-heptyl trichlorosilane, n-octyl trichlorosilane, dodecyl trichlorosilane, n-tetradecane base trichlorosilane and n-hexadecyl trichlorosilane;

The unsaturated alkyl trichlorosilane that contains the unsaturated alkyl of 1 to 4 carbon atom: as vinyl trichloro silane and isobutenyl trichlorosilane;

Saturated or unsaturated halo alkyl trichlorosilane, as chloromethyl trichlorosilane, dichloromethyl trichlorosilane, trichloromethyl trichlorosilane, (2-chloroethyl) trichlorosilane, (1,2-two bromotrifluoromethanes) trichlorosilane, trifluoromethyl trichlorosilane and (1-chlorovinyl) trichlorosilane;

Saturated or unsaturated cyclic hydrocarbon radical trichlorosilane, as cyclopropyl trichlorosilane, cyclopentyl trichlorosilane, cyclohexyl trichlorosilane and 3-cyclohexenyl trichlorosilane.

The aryl or aralkyl trichlorosilane, as phenyl-trichloro-silicane, 2-, 3-or 4-tolyl trichlorosilane and benzyl trichlorosilane; And

Mixing three halosilanes that alkyl, aryl or haloalkyl replace are as methyl dichloro chlorosilane, methyl dichloro silicon fluoride, ethyl two fluochloride silanes, ethyl dichloro silicon fluoride, just or sec.-propyl two fluochloride silanes, normal-butyl two fluochloride silanes, normal-butyl dichloro silicon fluoride, phenyl two fluochloride silanes, methyl dichloro bromo-silicane, ethyl dichloro bromo-silicane, methyl dichloro iodine silane and trifluoromethyl difluoro bromo-silicane.

By general formula SiX ₂R ² _qThe compound of expression, (n=2 in the following formula), as:

Dialkyl group two halosilanes, as dimethyldichlorosilane(DMCS), diethyl dichlorosilane, two just or di-isopropyl dichlorosilane, two just, two different, di-secondary or di-t-butyl dichlorosilane, two just or diisoamyl dichlorosilane, di-n-hexyl dichlorosilane, two n-heptyl dichlorosilanes and di-n-octyl dichlorosilane;

Bicyclic alkyl two halosilanes are as two cyclopentyl dichlorosilanes, dicyclohexyl dichlorosilane, dicyclohexyl two bromo-silicanes, dicyclohexyl diiodo-silane and dicyclohexyl two silicon fluorides; And

Diaryl or two aralkyl, two halosilanes are as diphenyl dichlorosilane, two-2-, two-3-, two-4-tolyl dichlorosilane and dibenzyl dichlorosilane.

By general formula SiXR ₃ ^qThe compound (n=1 in the above-mentioned general formula) of expression, for example:

The trialkyl halosilanes is as trimethylchlorosilane, chlorotriethyl silane, three (just or sec.-propyl) chlorosilane, three (just or isobutyl-) chlorosilane, three n-hexyl chlorosilanes, three n-heptyl chlorosilanes, three n-octyl chloride silane, dimethyl ethyl chlorosilane and methyl diethyl chlorosilane; And

Triaryl or three aralkyl halosilanes, for example tri-phenyl chloride, three (2-3-or 4-tolyl) chlorosilane and tribenzyl chlorosilane.

In these compounds, R in silicon tetrachloride and the above-mentioned general formula preferably ^qA chlorosilane, dichlorosilane and trichlorosilane for methyl, ethyl or phenyl.

The example of polymer silicon compound comprises methylhydrogenpolysi,oxane, ethyl hydrogen polysiloxanes, phenyl hydrogen polysiloxanes and cyclohexyl hydrogen polysiloxanes.These compounds can separately or be united use.

In above-claimed cpd, silicon tetrachloride and methylhydrogenpolysi,oxane are particularly preferred.

The polymerization degree for the polymer silicon compound has no particular limits, but considers from actual use angle, to use viscosity about 10 to 100) compound of cSt is good.The end structure of polymer silicon compound does not have very big influence to catalytic performance, but preferred the use with inertia group sealed terminal polymer silicon compound.

The organometallic compound [II] that another example of precipitation agent (d) will will illustrate after being.

The time spent of doing of precipitation agent can be played when other components and precipitation agent (d) needn't be used.

When the solid-state titanium mixture of preparation (A), the use precipitation agent (d), can use carrier compound, halide-containing and the electron donor except that diether compounds (b) except the liquid magnesium compound (a), diether compounds (b) and the liquid titanium compound (c) that use no reducing power and when needing in addition.

The example of carrier compound used herein comprises metal oxide such as AL ₂O ₃, SiO ₂, B ₂O ₃, MgO, CaO, TiO ₂, ZnO, ZnO ₂, SnO ₂, BaO and ThO and resin such as styrene diethylene benzene copoly mer.Wherein, Al preferably ₂O ₃, SiO ₂And styrene diethylene benzene copoly mer.

The example of halide-containing comprises above-mentioned Halogen silicon compound and contains halogenohydrin such as ethylene chlorhydrin, 1-chloro-2-propanol, trimethylene chlorohydrin, 1-chloro-2-methyl-2-propyl alcohol, 4-chloro-1-butanols, 5-chloro-1-amylalcohol, 6-chloro-1-hexanol, 3-chloro-1, the 2-propylene glycol, the 2-chloro cyclohexanol, the 4-chloro-di-phenyl-methanol, (neighbour, between, right)-chlorobenzyl alcohol, 4-chlorine pyrocatechol, the 4-chloro-(, adjacent)-first (benzene) phenol, the 6-chloro-(, adjacent) first (benzene) phenol, 4-chloro-3, the 5-xylenol, chlorohydroquinone, 2-benzyl-4-chlorophenol, 4-chloro-1-naphthols, (, adjacent, right) chlorophenol, to the chloro-α-Jia Jibianchun, Dowicide 4, the 6-chlorothymol, the 4-chloro resorcinol, ethylene bromohyrin, 3-bromo-1-propyl alcohol, 1-bromo-2-propyl alcohol, 1-bromo-2-butanols, 2-bromo-p-cresol, 1-bromo-beta naphthal, 6-bromo-beta naphthal, (, adjacent, right) bromophenol, 4-bromine Resorcinol, (, adjacent, right) fluorophenol, to iodophenol, 2, the 2-dichlroroethanol, 2,3-two trimethylewne chlorohydrin 3-s, 1,3-two chloro-2-propyl alcohol, 3-chloro-1-(α-chloromethyl)-1-propyl alcohol, 2,3-two bromo-1-propyl alcohol, 1,3-two bromo-2-propyl alcohol, 2, the 4-dibromophenol, 2,4-two bromo-1-naphthols, 2,2, the 2-ethapon, 1,1, the 1-trichloro-2-propanol, β, β, β-trichloro-butyl alcohol, 2,3, the 4-Trichlorophenol, 2,4, the 5-Trichlorophenol, 2,4, the 6-Trichlorophenol, 2,4, the 6-tribromophenol, 2,3,5-three bromo-2-hydroxytoluenes, 2,3,5-three bromo-4-hydroxytoluenes, 2,2, the 2-trifluoroethanol, α, α, α-trifluoro meta-cresol, 2,4, the 6-iodophenisic acid, 2,3,4, the 6-chlorophenol, the tetrachloro quinhydrones, tetrachlorobisphenol A, tetrabromo-bisphenol, 2,2,3,3-tetrafluoro-1-propyl alcohol, 2,3,5,6-polytetrafluoroethylene phenol and tetrafluoro Resorcinol.

Also can be used as having of halide-containing:

The halogen of elementary state is as chlorine, bromine and iodine;

Hydrogen halide is as hydrogenchloride, hydrogen bromide and hydrogen iodide;

Haloalkane, for example tetracol phenixin, chloroform, ethylene dichloride, ethylene tetrachloride, methylene dichloride, trieline, methyl chloride, chloric ethane, n-butyl chloride and n-octyl chloride;

Nonmetal oxyhalogenide is as SULPHURYL CHLORIDE, thionyl (two) chlorine, nitrosyl chloride, phosphoryl chloride photoreactive gas;

Non-metallic halide is as phosphorus trichloride and phosphorus pentachloride; With

Metal halide and ammonium halide are as aluminum chloride and ammonium chloride.

The example that may be used to prepare the electron donor (e) except that diether compounds (b) of solid state composite (A) comprises organic acid acetic, organic acyl halide, organic acid anhydride, ether, ketone, aldehyde, tertiary amine, phosphorous acid ester, phosphoric acid ester, phosphamide, carboxylic acid amide and nitrile.

Their object lesson comprises:

The ketone that contains 3 to 15 carbon atoms is as acetone, methylethylketone, methyl iso-butyl ketone (MIBK), methyl phenyl ketone, benzophenone, pimelinketone and benzoquinones;

The aldehyde that contains 2 to 15 carbon atoms is as acetaldehyde, propionic aldehyde, octanal, phenyl aldehyde, toluic aldehyde and naphthaldehyde;

The organic acid acetic that contains 2 to 18 carbon atoms is as methyl-formiate, methyl acetate, ethyl acetate, vinyl-acetic ester, propyl acetate, octyl acetate, hexalin acetate, ethyl propionate, methyl-butyrate, Valeric acid ethylester, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, the hexahydrobenzoic acid ethyl ester, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, n-octyl benzoate, the phenylformic acid cyclohexyl, phenol benzoate, peruscabin, methyl-toluate, the tolyl acid ethyl ester, the tolyl acid pentyl ester, the ethylamino benzonitrile acetoacetic ester, p-Methoxybenzoic acid methyl ester, ethyl anisate, the ethoxy benzonitrile acetoacetic ester, gamma-butyrolactone, δ-Wu Neizhi, tonka bean camphor, 2-benzo [C] furanone and ethylene carbonate;

The carboxylic acid halides that contains 2 to 15 carbon atoms, as Acetyl Chloride 98Min., Benzoyl chloride, methyl benzoyl chloride and anisyl chloride;

The ether that contains 2 to 20 carbon atoms is as methyl ether, ether, isopropyl ether, butyl ether, amyl ether, tetrahydrofuran (THF), phenylmethylether and phenyl ether;

Acid amides, as N,N-dimethylacetamide, N, N-diethylbenzene methane amide and N, N-dimethyl methyl yl-benzamide;

Tertiary amine is as Trimethylamine 99, triethylamine, Tributylamine, tribenzylamine and Tetramethyl Ethylene Diamine; And

Nitrile is as acetonitrile and benzonitrile;

Wherein, aromatic carboxylic acid esters is preferred,

Above-claimed cpd can separately or be united use.

Same preferred organic acid acetic is the multi-carboxylate.As the multi-carboxylate, the compound that can lift the structure with following general formula is an example:

With

In following formula, R ¹Be to replace or unsubstituted alkyl R ², R ⁵And R ⁶Be respectively hydrogen or replacement or unsubstituted alkyl, R ³And R ⁴Be respectively hydrogen or replacement or unsubstituted alkyl, preferably one of them is replacement or unsubstituting hydrocarbyl at least.R ³And R ⁴Can be in key and form ring texture.As alkyl R ¹To R ⁶Be when being substituted, substituting group contains just like the heteroatoms of N, O and S and has as C-O-C, COOR, OH, COOH, SO ₃H ,-C-N-C and NH ₂Group.

The object lesson of the polynary carboxylic phenolic ester of this class comprises aliphatic polycarboxylic acid's ester such as diethyl succinate, dibutyl succinate, the pyrovinic acid diethyl ester, Alpha-Methyl pentanedioic acid diisobutyl ester, methyl-malonic ester, ethyl malonic acid diethylester, diethyl isopropyl, the butyl malonic acid diethyl ester, phenyl ethyl malonate, diethyl malonic ester, dibutyltin diethyl malonate, single-ethylhexyl maleate, dioctyl maleate, dibutyl maleinate, the butyl dibutyl maleinate, the butyl ethyl maleate, Beta-methyl pentanedioic acid diisopropyl ester, the ethyl succinic acid diallyl, fumaric acid two (the 2-ethyl is own) ester, diethyl itaconate and citraconic acid dioctyl ester; Alicyclic multi-carboxylate is as 1,2-cyclohexane dicarboxylic acid diethyl ester, 1,2-cyclohexane dicarboxylic acid diisobutyl ester, tetrahydrophthalic acid diethyl ester and interior-suitable-two rings [2,2,1] heptan-5-alkene-2,3-diethyl dicarboxylate; Aromatic series multi-carboxylate such as phthalic acid mono ethyl ester, dimethyl phthalate, the phthalic acid methyl ethyl ester, phthalic acid list isobutyl ester, diethyl phthalate, phthalic acid second isobutyl ester, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, diisobutyl phthalate, heptyl phthalate ester, phthalic acid two (the 2-ethyl is own) ester, dinoctyl phthalate, phthalic acid two peopentyl esters, didecyl phthalate, Unimoll BB, diphenyl phthalate, the naphthalic acid diethyl ester, the naphthalic acid dibutylester, triethyl trimellitate and trimellitic acid dibutylester; With the heterocycle multi-carboxylate as 3,4-furans dicarboxylic ester).

Other examples of multi-carboxylate have long chain dicarboxylic acid ester such as diethylene adipate.Diisobutyl adipate, Wickenol 117, n-butyl sebacate, dioctyl sebacate and sebacic acid two (the 2-ethyl is own) ester.

In the above-claimed cpd, what preferably used is carboxylicesters, and what preferably used especially is, the multi-carboxylate, what the most preferably used is phthalic ester.

Electron donor (e) does not always need as starting raw material, and is used, and can make it to produce in preparation solid titanium catalyst component process.

Solid-state titanium mixture (A) is to make by following each thing is in contact with one another: the liquid magnesium compound (a) of no reducing power, diether compounds (b), liquid titanium compound (c) and randomly, precipitation agent (d) also has carrier compound, electron donor (e) and halide-containing in addition.In liquid magnesium compound (a), diether compounds (b), liquid titanium compound (c) and the precipitation agent (d) of no reducing power, have at least a component to contain halide-containing.

Preparation method to solid-state titanium mixture (A) is without particular limitation.

The following stated is the example of the method for making of solid-state titanium mixture (A):

(1) in the presence of diether compounds (b), makes the liquid magnesium compound (a) of no reducing power and the method for liquid titanium compound (c) reaction.

(2) in the presence of diether compounds (b) and electron donor (e), make the liquid magnesium compound (a) of no reducing power and the method for liquid titanium compound reaction.

(3) the liquid magnesium compound (a) of no reducing power is contacted with precipitation agent (d), make consequent precipitation and diether compounds (b) and liquid titanium compound (c) then, and the method that reacts of electron donor (e) randomly.

(4) the liquid magnesium compound (a) of no reducing power is contacted with precipitation agent (d), make then consequent precipitation and halide-containing, diether compounds (b), liquid titanium compound (c) and randomly, the method that reacts of electron donor (e).

(5) method that the reaction product that obtained by the arbitrary method in (1) to (4) is further reacted with liquid titanium compound (c).

(6) method that the reaction product that obtained by arbitrary method in (1) to (4) is further reacted with diether compounds (b) and liquid titanium compound (c); And

(7) method that the reaction product that obtained by arbitrary method in (1) to (6) is reacted with diether compounds (b) again.

Employed component (a) and (b), (c) and amount (d) are according to their kind in the method for the solid-state titanium mixture of above-mentioned preparation (A), condition during contact, the contact sequential scheduling and become, but in general, the consumption of diether compounds (b) does not have the liquid magnesium compound (a) of reducing power for 1mol, be approximately 0.01 to 5mol, be about 0.1 to 1mol preferably, and the consumption of liquid titanium compound (c) does not have the liquid magnesium compound (a) of reducing power for 1mol, being 0.1 to 1000mol, is 1 to 200mol preferably.The consumption of precipitation agent (d) is as the criterion with enough formation solid products, and its consumption does not have the liquid magnesium compound (a) of reducing power to 1mol, is 0.1 to 1000mol, is 1 to about 200mol preferably.

Make component (a) and (b), (c) and (d) temperature when being in contact with one another be 10 to 150 ℃ preferably generally at-70 to 200 ℃.

As above solid-state titanium mixture (A) titaniferous, magnesium, halogen and the diether compounds of gained,

In solid-state titanium mixture (A), halogen requires between 2 to 100 the atomic ratio (halogen/titanium) of titanium, be between 4 to 90 preferably, diether compounds (b) requires between 0.01 to 100 the molar ratio (diether compounds (b)/titanium) of titanium, is between 0.2 to 10 preferably; Magnesium requires between 2 to 100 the atomic ratio (magnesium/titanium) of titanium, is between 4 to 50 preferably.

Solid titanium catalyst component of the present invention can by earlier with solid state composite (A) with contain the organometallic compound that is selected from the metal in I to the III family in the periodictable and contact to make solid-state titanium organometallic compound title complex, then, again this solid-state titanium organometallic compound title complex is contacted and makes with oxygen.

The example that contains the organometallic compound (B) that is selected from I to III family metal in the periodictable with will illustrate later on those contain that to be selected from the periodictable I identical to the example of the Organometal compound catalyst component [II] of III-th family metal.

As for used here oxygen, that can be given an example has oxygen, air, ozone and an organo-peroxide.

Solid-state titanium mixture (A) can carry out in solvent with contacting of organometallic compound (B).The example of this solvent with the preparation no reducing power liquid magnesium compound (a) time used inert solvent example identical.In above-mentioned solvent, be preferably aliphatic hydrocarbon, be more preferably the aliphatic saturated hydrocarbon that contains 6 to 10 carbon atoms.

At solid-state titanium mixture (A) and organometallic compound (B) when contacting, the consumption of organometallic compound (B), with the titanium atom in the solid-state titanium thing of 1mol (A) is that benchmark is 0.1 to 100mol, is 1 to 50mol preferably, the concentration of solid-state titanium mixture (A) is 0.1 to 100mol/ to rise between the solvent, is preferably 0.5 to 50mol/ to rise (with the titanium atom standard in the solid-state titanium mixture (A)) between the solvent.Be between 1 to 300 minute duration of contact, is between 5 to 180 minutes preferably, and the temperature during contact is between 0 to 100 ℃, is between 10 to 50 ℃ preferably.

When solid-state titanium organometallic compound title complex contacted with oxygen, the consumption of oxygen was 0.1mol or more.Be 0.1 to 100mol preferably, better be 0.2 to 10mol, be preferably 0.3 to 3mol (is benchmark with the 1mol titanium atom in the solid-state titanium organometallic compound title complex).Be between 1 to 300 minute duration of contact, be between 5 to 180 minutes preferably, the temperature during contact is 0 to 100 ℃, is between 10 to 50 ℃ preferably.

There is no particular limitation to method that solid-state titanium organometallic compound title complex contacts with oxygen, but can use following contact method:

(1) a kind of method that the suspension of solid-state titanium organometallic chemistry thing title complex in inert solvent is contacted with air;

(2) a kind of method that the suspension of solid-state titanium organometallic compound title complex in inert solvent is contacted with ozone;

(3) a kind of method that the suspension of solid-state titanium organometallic compound title complex in inert solvent is contacted with oxygen;

The example that solid-state titanium organometallic compound title complex and oxygen contact time institute's solvent during with the liquid magnesium compound (a) of the no reducing power of preparation the example of used inert solvent identical.

In above-mentioned solvent, preferably aliphatic hydrocarbon particularly preferably is the aliphatic saturated hydrocarbon that contains 6 to 10 carbon atoms.

When solid-state titanium organometallic compound title complex contacted with oxygen, its contained titanium probably combined with oxygen.

Ethylene rolymerization catalyst of the present invention comprises solid titanium catalyst component [I] and contains and is selected from the periodictable I to the Organometal compound catalyst component [II] of III-th family metal.

Accompanying drawing is the key drawing of ethylene rolymerization catalyst preparation method step of the present invention.

As Organometal compound catalyst component [II], what can be used for example has: the alkyl complexes of organo-aluminium compound, I family metal and aluminium and the organometallic compound of II family metal.

Organo-aluminium compound has, for example, and the compound of following general formula:

R _n ^aAlX _3-nR wherein ^aBe the alkyl that contains 1 to 12 carbon atom, X is halogen atom or hydrogen atom, and n is 1 to 3.

In above-mentioned general formula, R ^aFor the alkyl that contains 1 to 12 carbon atom, as alkyl, cycloalkyl or aryl, more particularly, methyl, ethyl, n-propyl, sec.-propyl, isobutyl-, amyl group, hexyl, octyl group, cyclopentyl, cyclohexyl, phenyl or tolyl.

The example of this organo-aluminium compound comprises:

Trialkylaluminium is as trimethyl aluminium, triethyl aluminum, triisopropylaluminiuand, triisobutyl aluminium, trioctylaluminum and three (2-ethylhexyl) aluminium;

Alkenyl aluminium is as pseudoallyl aluminium;

Dialkylaluminum halides is as dimethylaluminum chloride, diethyl aluminum chloride, di-isopropyl aluminum chloride, diisobutyl aluminum chloride and dimethyl aluminum bromide.

Alkyl sesquialter aluminum halide, as methylaluminum sesquichloride, ethyl sesquialter aluminum chloride, sec.-propyl sesquialter aluminum chloride, butyl sesquialter aluminum chloride and ethyl sesquialter aluminum bromide.

Alkyl dihalide aluminium is as methylaluminum dichloride, ethylaluminum dichloride, sec.-propyl al dichloride and ethyl aluminum dibromide; And

Alkyl-al hydride is as ADEH and diisobutyl aluminium hydride.

The compound of having that also can be used as organo-aluminium compound with following general formula:

R _n ^aAlY _3-nR wherein ^aIdentical for above-mentioned definition, Y is-OR ^b,-OSiR ₃ ^c,-OAlR ₂ ^d,-NR ₂ ^e, SiR ₃ ^fOr-N (R ^g) AlR ₂ ^h, n is 1 or 2, R ^b, R ^c, R ^dAnd R ^hBe respectively methyl, ethyl, sec.-propyl, isobutyl-, cyclohexyl or phenyl, R ^eBe hydrogen, methyl, ethyl, sec.-propyl, phenyl or three silyls, R ^fAnd R ^gBe respectively methyl or ethyl.

The example of this organo-aluminium compound comprises:

(i) general formula is R _n ³Al (OR ^b) _3-nCompound, as dimethyl methoxy base aluminium, diethylaluminum ethoxide and diisobutyl aluminum methoxide;

(ii) general formula is R _n ^aAl (OSiR ₃ ^c) _3-nCompound, as Et ₂Al (OSiMe ₃), (iso-Bu) ₂Al (OSiMe ₃) and (iso-Bu) ₂Al (OSiEt ₃);

(iii) general formula is R _n ^aAl (OALR ₂ ^d) _3-nCompound, as Et ₂AlOAlEt ₂(iso-Bu) ₂AlOAl (iso-Bu) ₂

(iv) general formula is R _n ^aAl (NR ₂ ^e) _3-nCompound, as Me ₂AlNEt ₂, Et ₂AlNHMe, Me ₂AlNHEt, Et ₂AlN (Me ₃Si) ₂(iso-Bu) ₂AlN (Me ₃Si) ₂

(v) general formula is R _n ^aAl (SiR ₃ ^f) _3-nCompound, as (iso-Bu) ₂AlSiMe ₃With

(vi) general formula is R _n ^aAl (N (R ^g) AlR ₂ ^h) _3-nCompound, as Et ₂AlN (Me) AlEt and (iso-Bu) ₂AlN (Et) Al (iso-Bu) ₂

In the example of above-mentioned organo-aluminium compound, preferably general formula is R ₃ ^aAl, R _n ^aAl (OR ^b) _3-nAnd R _n ^aAl (OAlR ₂ ^d) _3-nCompound.

The alkyl complexes of I family metal and aluminium has the compound of for example using following general formula:

M ¹AlR ₄ ^jM wherein ¹Be Li, Na or K, R ^jBe the alkyl that contains 1 to 15 carbon atom,

The object lesson of this alkyl complexes comprises LiAl (C ₂H ₅) ₄And LiAl (C ₇H ₁₅) ₄

The organometallic compound of II family metal is, for example, and the compound of following general formula:

R ^kR ^lM ²R wherein ^kAnd R ^lBe respectively alkyl or the halogen atom that contains 1 to 15 carbon atom, except R ^kAnd R ^lBe beyond the halogen group, R ^kAnd R ^lCan be identical or different.M ²Be

Mg, Zn or Cd.

The object lesson of this class organometallic compound comprises zinc ethyl, magnesium ethide, butyl ethyl magnesium, ethylmagnesium chloride and butylmagnesium chloride.

Above-claimed cpd can separately or be united use.

If needed, when containing organo-metallic catalyst component (II), ethylene rolymerization catalyst also can contain above-mentioned diether compounds (b) and electron donor (f).Above-mentioned electron donor (e) and a kind of silicoorganic compound can be used as electron donor (f).Wherein, diether compounds (b) and silicoorganic compound are preferred.

Silicoorganic compound are, for example, and by the silicoorganic compound of following general formula:

RnSi (OR ') _4-nWherein R and R ' respectively are alkyl, and n is the number of a 0＜n＜4.

The example of the silicoorganic compound that above-mentioned general formula is represented comprises: trimethylammonium methoxyl group silicon, trimethylammonium oxyethyl group silicon, dimethylformamide dimethyl oxygen base silicon, dimethyl diethoxy silicon, di-isopropyl dimethoxy silicon, tertiary butyl methyl dimethoxy oxygen base silicon, tertiary butyl methyl diethoxy silicon, tert-pentyl methyl diethoxy silicon, phenylbenzene dimethoxy silicon, phenyl methyl dimethoxy silicon, phenylbenzene diethoxy silicon, two o-tolyl dimethoxy silicon, tolyl dimethoxy silicon between two, biconjugate tolyl dimethoxy silicon, biconjugate tolyl diethoxy silicon, two ethylphenyl dimethoxy silicon, dicyclohexyl dimethoxy silicon, cyclohexyl methyl dimethoxy silicon, cyclohexyl methyl diethoxy silicon, ethyl trimethoxy silicon, ethyl triethoxy silicane, vinyl trimethoxy silicon, methyl trimethoxy oxygen base silicon, the n-propyl triethoxysilicane, decyl trimethoxy silicon, the decyl triethoxysilicane, phenyl trimethoxy silicon, γ-r-chloropropyl trimethoxyl silicon, methyltriethoxy silane, ethyl triethoxy silicane, vinyl triethoxyl silicon, tertiary butyl triethoxysilicane, the normal-butyl triethoxysilicane, the isobutyl-triethoxysilicane, phenyltriethoxy silane, the gamma-amino propyl-triethoxysilicane, the triethoxy silicon chlorides, ethyl three isopropoxy silicon, vinyl three butoxy silicon, cyclohexyl trimethoxy silicon, the cyclohexyl triethoxysilicane, 2-norborneol alkyl trimethoxy silicon, 2-norbornane ethyl triethoxy silicane, 2-norbornane ylmethyl dimethoxy silicon, silicic acid (four) ethyl ester, silicic acid (four) butyl ester, trimethylammonium phenoxy group silicon, methyl three allyloxy silicon, vinyl three (beta-methoxy-oxyethyl group) silicon, vinyl triacetyl oxygen base silicon and dimethyl tetraethoxy sily oxide;

Cyclopentyl trimethoxy silicon, 2-methylcyclopentyl trimethoxy silicon, 2,3-dimethylcyclopentyl trimethoxy silicon, cyclopentyl triethoxysilicane;

Two rings, penta dimethoxy silicon, two (2-methylcyclopentyl) dimethoxy silicon, two (2, the 3-dimethylcyclopentyl) dimethoxy silicon, two cyclopentyl diethoxy silicon;

Three cyclopentyl methoxyl group silicon, three cyclopentyl oxyethyl group silicon, two cyclopentyl-methyl methoxyl group silicon, two cyclopentyl ethyl methoxyl group silicon, hexenyl trimethoxy silicon, two cyclopentyl-methyl oxyethyl group silicon, cyclopentyl dimethyl methoxy base silicon, cyclopentyl diethyl methoxyl group silicon, cyclopentyl dimethyl oxyethyl group silicon.

What wherein, preferably be used is ethyl triethoxy silicane, the n-propyl triethoxysilicane, tertiary butyl triethoxysilicane, vinyl triethoxyl silicon, phenyltriethoxy silane, vinyl three butoxy silicon, phenylbenzene dimethoxy silicon, phenyl methyl dimethoxy silicon, biconjugate tolyl dimethoxy silicon, p-methylphenyl methyl dimethoxy oxygen base silicon, dicyclohexyl dimethoxy silicon, cyclohexyl methyl dimethoxy silicon, 2-norbornane ethyl triethoxy silicane, 2-norbornane ylmethyl dimethoxy silicon, phenyltriethoxy silane, dicyclopentyl dimethoxyl silicon, hexyl trimethoxy silicon, the cyclopentyl triethoxysilicane, three cyclopentyl methoxyl group silicon and cyclopentyl dimethyl methoxy base silicon.

Except that silicoorganic compound, that can mention can be used as having of electron donor (f), for example, and the nitrogenous compound except that the above.P contained compound and oxygenatedchemicals.

The example of nitrogenous compound has following described:

2, the 6-substituted piperidine, as:

2, the 5-substituted piperidine, as

Replace methanediamine, as N, N, N ', N '-tetramethyl-methanediamine, and N, N, N ', N-tetraethyl-methanediamine.

Substituted imidazole alkane, as 1,3-dibenzyl imidazole alkane and 1,3-dibenzyl-2-phenylimidazolidines;

The example of P contained compound comprises phosphorous acid ester such as triethyl-phosphite, tricresyl phosphite n-propyl, triisopropyl phosphite, tri-n-butylphosphite, tricresyl phosphite isobutyl ester, the positive butyl ester of phosphorous acid diethyl and phosphorous acid diethyl phenyl ester.

The following describes the example of oxygenatedchemicals.

2,6-substituted-tetrahydro pyrans, as:

2,5-substituted-tetrahydro pyrans, as

Ethene polymers of the present invention can by make ethylene homo with ethylene rolymerization catalyst or make ethene and ethene beyond olefin-copolymerization and prepared.

The most handy ethylene rolymerization catalyst makes it pre-polymerization before alpha-olefine polymerizing and copolymerization.In pre-polymerization, the amount of the pre-poly-alpha olefins of every 1g ethylene rolymerization catalyst is 0.1 to 1000g, is 0.3 to 500g preferably, is preferably 1 to 200g.

The concentration of solid titanium catalyst component when pre-polymerization [I] requires generally to be approximately 0.001 to 200mmol, is approximately 0.01 to 50mmol preferably, better is 0.1 to 20mmol (in the amount of titanium atom, being benchmark with 1 liter of liquid medium).In prepolymerization reaction system, catalyst concentration can be higher than its concentration in main polymerization reaction system.

The amount of used Organometal compound catalyst component [II] should be such in pre-polymerization, be benchmark promptly with 1g solid titanium catalyst component [I], can produce 0.1 to 1000g, be 0.3 to 500g polymkeric substance preferably, just: with 1mol titanium atom in the solid titanium catalyst component [I] is benchmark, the consumption of Organometal compound catalyst component [II] generally is approximately 0.1 to 300mol, is approximately 0.5 preferably to 100mol.Better be 1 to 50mol.

When pre-polymerization,, can use diether compounds (b) and electron donor (e) as essential.In this case, component (b) and consumption (e) respectively be 0.1 to 50mol, be 0.5 to 30mol preferably, better is 1 to 10mol (is benchmark with 1mol titanium atom in the solid titanium catalyst component [I]).

Pre-polymerization can be undertaken by adding alkene and above-mentioned catalyst component in the inertia hydrocarbon medium under mild conditions.

Example of used inertia hydrocarbon medium comprises in this:

Aliphatic hydrocarbon such as propane, butane, pentane, hexane, heptane, octane, decane, 12 carbon alkane and kerosene;

Alicyclic hydrocarbon such as pentamethylene, hexanaphthene and methylcyclopentane;

Aromatic hydrocarbons such as benzene, toluene and dimethylbenzene;

Halohydrocarbon is as ethylene chloride and chlorobenzene; And

The mixture of above-mentioned hydrocarbon.

In these hydrocarbon medium, what preferably be used is aliphatic hydrocarbon.When using the inertia hydrocarbon medium, pre-polymerization is preferably carried out in batches.In addition, itself carries out pre-polymerization as medium available alkene, or in fact carries out pre-polymerization without medium.In this case, pre-polymerization is preferably carried out continuously.

Be used for pre-polymerization alkene can with to narrate later on to be used for polymeric alkene identical or different, but ethene preferably is used as alkene.

The temperature of reaction of pre-polymerization generally between-20 to+100 ℃, is about between-20 to+80 ℃ preferably, better is between 0 to+40 ℃.

When pre-polymerization, can use molecular weight regulator, as hydrogen.The consumption of molecular weight regulator is about 0.2dl/g or higher with the limiting viscosity [η] of the polymkeric substance that requires to make generation (measuring) in 135 ℃ and ten chloronaphthalenes, be about 5 to 10dl/g preferably and be as the criterion.

Pre-polymerization requires to be undertaken by such method, i.e. the amount of the polymkeric substance that pre-polymerization produces is approximately between 0.1 to 1000g, preferably for about 0.3 to 500g, better be 1 to 200g (is benchmark with 1g solid titanium catalyst component [I]).When the amount of the polymkeric substance that produces when pre-polymerization was too many, the polyvinyl production efficiency that produces when main gathering will reduce.

Pre-polymerization can be carried out in batches or carry out continuously.

The example of the alkene that uses together in main poly-neutralization of ethylene comprises alpha-olefin such as propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecylene, tetradecene, cetene, 1-vaccenic acid and the 1-eicosylene that contains 3 to 20 carbon atoms.

When vinyl polymerization, these alkene can separately or be united use.In addition, as polymer raw, contain the compound of a plurality of unsaturated link(age)s in addition, for example, aromatic vinyl compound such as vinylbenzene and allyl benzene, alicyclic ethylene based compound such as vinyl cyclohexane, cycloolefin such as cyclopentenes, suberene, norbornylene, 5-methyl-2-norbornylene, tetracyclododecane, the 2-methyl isophthalic acid, 4,5,8-two methylene bridges-1,2,3,4,4a, 5,8,8a-octahydro naphthalene, and diene (conjugation and non-conjugated diene) is as the 6-methyl isophthalic acid, the 6-octadiene, the 7-methyl isophthalic acid, the 6-octadiene, 6-ethyl-1, the 6-octadiene, 6-propyl group-1, the 6-octadiene, 6-butyl-1, the 6-octadiene, the 6-methyl isophthalic acid, the 6-nonadiene, the 7-methyl isophthalic acid, the 6-nonadiene, 6-ethyl-1, the 6-nonadiene, 7-ethyl-1, the 6-nonadiene, the 6-methyl isophthalic acid, the 6-decadiene, the 7-methyl isophthalic acid, 6 decadiene, the 6-methyl isophthalic acid, 6-11 carbon diene, isoprene and divinyl.

Polyvinyl polymerization can be with carrying out as any liquid polymerization method of solution polymerization and suspension polymerization and so on with gas phase polymerization process.

When carrying out main polymerization with liquid polymerization method, above-mentioned unreactive hydrocarbons can be used as reaction solvent, are that the alkene of liquid also can be used as reaction solvent under the temperature of reaction.

In main polymerization, the consumption of solid titanium catalyst (I) generally is approximately 0.001 to 0.5mmol, is approximately 0.005 to 0.1mmol (is benchmark in the Ti atom, with 1 liter of polymerization volume) preferably.Organometal compound catalyst component (II) consumption should be such, and promptly the amount of atoms metal generally is approximately between 1 to 2000mol, is (is benchmark with the 1mol titanium atom in the prepolymerization catalyst component in polymerization system) between 5 to 500mol preferably.

When hydrogen was used for main polymerization, the molecular weight of the polymkeric substance of generation can be regulated, and therefore can obtain having the polymkeric substance of high melt flow rate.

Polymerization temperature generally is set between about 20 to 200 ℃, preferably greatly between 50 to 150 ℃, polymerization pressure generally is set in normal pressure to 9.8 * 10 ⁶Pa is preferably greatly about 2.0 * 10 ⁵To 4.9 * 10 ⁶Pa.Polymerization can be interrupted, semicontinuous, carry out continuously.In addition, polymerization can be carried out in two or more different steps of reaction conditions.

As above the ethene polymers of gained can be any in Alathon, ethylene-olefin random copolymers and the ethylene-olefin segmented copolymer.

Ethene polymers of the present invention has density and the melt flow rate (MFR) in specified range, has particular kind of relationship between molten tension force (MT) and melt flow rate (MFR), has Mw/Mn value, Mz/Mw value in specified range, g ^*Value and swelling ratio.Therefore, this polyvinyl moldability is fabulous, and can make good rigidly from this polymkeric substance, the moulded parts of shock-resistance height and no roughened appearance (as flake).

By means of polyvinyl preparation method of the present invention, can prepare ethene polymers in high polymerization activity ground with above-mentioned superior character.

The solid titanium catalyst component and the ethylene rolymerization catalyst for ethylene polymerization of the application of the invention can prepare the ethene polymers with above-mentioned superior character in high polymerization activity ground.

The present invention will be further described in conjunction with the following example, make explanations but tackle this, i.e. the present invention never is confined to these embodiment.The preparation of the solid-state titanium mixture of embodiment 1[(A)]

95.2g Magnesium Chloride Anhydrous, 442ml decane and 390.6g2-ethylhexanol were made the formation homogeneous phase solution in 2 hours in 130 ℃ of heating.In this solution, add the 21.3g Tetra hydro Phthalic anhydride, stir 1 hour with the dissolving Tetra hydro Phthalic anhydride at 130 ℃.The homogeneous phase solution that 75ml is generated thus is added drop-wise in the titanium tetrachloride that the 200ml temperature remains in-20 ℃ and lasts 1 hour then.After adding, the temperature with mixture in 4 hours is increased to 110 ℃.When temperature reaches 110 ℃, in this mixture, add 4.06g2-sec.-propyl-2-isopentyl-1, the 3-Propanal dimethyl acetal also stirred 2 hours under this temperature.Collect the solid that produces by heat filtering then, this solid is suspended in again in the titanium tetrachloride of 275ml, then 110 ℃ of heating 2 hours.Then, regather solid, wash until in washings, not detecting any titanium compound that discharges with the hexane of 110 ℃ decane and room temperature is thorough by heat filtering.By above-mentioned steps, made solid-state titanium mixture (A).Consisting of of this solid-state titanium mixture (A), 2.1 weight % titaniums, 18.0 weight % magnesium, 7.2 weight %2-sec.-propyl-2-isopentyl-1, the chlorine of 3-Propanal dimethyl acetal, 0.2 weight %2-ethyl hexyl oxy and 60 weight %.[preparation of solid titanium catalyst component (B)]

Under with nitrogen wash 200ml four neck flasks, when room temperature (26 ℃), add the 100ml hexane.In this flask, add the triethyl aluminum of 3mmol (in the aluminium atom) and the above-mentioned solid-state titanium mixture (A) that obtains of 1mmol (in titanium atom), according at room temperature stirring 1 hour.After stirring finishes, from liquid, isolate the solid of generation with decantation.Adding hexane in this solid is also stirred.Triplicate carries out the purification operations that decant is removed supernatant liquid then, to obtain solid-state titanium organometallic compound title complex.

Should be suspended in the 100ml hexane by solid-state titanium organometallic compound title complex.Then the dry air that contains 11.2Nml oxygen of 58.4ml is introduced gas phase, then at room temperature stirred 1 hour, in the whipping process, measure the gaseous phase volume reduction with gas burette.As a result, the volume reduction is 9.0ml, and the absorption amount of oxygen is 8.2Nml.

After stirring finishes, from liquid, isolate the solid of generation, in solid, add hexane, stirring with decantation.Repeat secondary and remove the washing operation of supernatant liquid, to obtain solid titanium catalyst component (B) with decantation.[polymerization]

In 2 liters of autoclaves, add 1 liter of hexane that purifying is crossed.In ethene atmosphere, under 60 ℃, in autoclave, add 1mmol triethyl aluminum and 0.01mmol (in titanium atom) solid titanium catalyst component (B).

Then, the temperature of system is increased to 75 ℃, introduces hydrogen, add-on is so that gauge pressure reaches 9.8 * 10 ⁴Pa is as the criterion.Then, feeding ethene makes gauge pressure reach 7.8 * 10 ⁵Pa then continues to feed ethene and kept uniform pressure 1 hour, feeds in the ethylene process, and temperature remains on 80 ℃.

After polymerization is finished, filter the slurry that contains solid product, be separated into white powder and liquid phase.The white powder that will obtain like this is dry 10 hours under 80 ℃ and decompression.In the dry white powder of crossing (ethene polymers) of 100g, add 200mg 3,5-di-t-butyl-4-hydroxytoluene and 100mg calcium stearate.The extruding machine (Thermo plasticCO. manufacturing) that with diameter is 20mm carries out granulation to the mixture that generates in the time of 200 ℃.Measured molten tension force (MT), melt flow rate (MFR), swelling ratio (SR), molecular weight distribution mw/mn, the molecular weight distribution Mz/Mw of this particle, g by former described method ^*Value and density.The results are shown in table 1.Embodiment 2[polymerization]

Except the amount that feeds hydrogen makes gauge pressure reach 2.9 * 10 ⁵Beyond the Pa, carry out the polymerization of ethene with embodiment 1 identical method.

After polymerization is finished, filter the slurry contain solid product, be separated into white powder and liquid phase, decompression and 80 ℃ with this white powder drying 10 hours.

Measure the dry various character of crossing white powder with the same procedure of explanation among the embodiment 1.The results are shown in table 1.Embodiment 3 [solid titanium catalyst component (B-1) preparation]

With nitrogen wash 200ml four neck flasks the time, when room temperature (26 ℃), add the 100ml hexane, in this flask, add the triethyl aluminum of 3mmol (in the aluminium atom) and the above-mentioned solid-state titanium mixture (A) that obtains of 1mmol (calculating) according to titanium atom, then at room temperature stirred 1 hour, after stirring finishes, from liquid, isolate the solid of generation with decantation, adding hexane in this solid is also stirred, triplicate carries out the purification operations that decant is removed supernatant liquid then, to obtain solid-state titanium organometallic compound title complex.

Should be suspended in the 100ml hexane by solid-state titanium organometallic compound title complex.Then the dry air that contains 5.6Nml oxygen of 29.2ml is introduced gas phase, then at room temperature stirred 1 hour.In the whipping process, measure the gaseous phase volume reduction with gas burette, result, volume reduction are 4.4ml, and the absorption amount of oxygen is 4.0Nml.

After stirring finishes, from liquid, isolate the solid of generation, in solid, add hexane, stir with decantation.The repetition secondary is removed washing of supernatant liquid with decantation and is striven operation, to obtain solid titanium catalyst component (B-1).[polymerization]

Except replace solid catalyst component (B) with solid titanium catalyst component (B-1), carry out the polymerization of ethene with embodiment 1 identical method.

After polymerization is finished, filter the slurry contain solid product, be separated into white powder and liquid phase, decompression and 80 ℃ with this white powder drying 10 hours.

Measure the dry various character of crossing white powder with the same procedure of explanation among the embodiment 1.The results are shown in table 1.Embodiment 4[polymerization]

In 2 liters of autoclaves that thoroughly cleaned with nitrogen, add the hexane that the 850ml purifying is crossed, at room temperature clean autoclave with ethene.Then, system temperature is increased to 60 ℃.Adding 1.25mmol triethyl aluminum, 0.025mmol (in titanium atom) prepare in embodiment 1 in autoclave solid catalyst component () and 150ml 4-methyl-1-pentene are sealed this autoclave.Feed hydrogen then and reach 1.2 * 10 up to pressure ⁵Pa.Then, feeding ethene makes total pressure reach 3.9 * 10 ⁵Pa then connects feeding ethene and keep-uped pressure 2 hours.

After polymerization is finished, from autoclave, take out slurry when temperature reaches 55 ℃ in autoclave, from liquid phase, filter to isolate the polymeric white powder rapidly.Dry 10 hours of the polymkeric substance that under 80 ℃ of decompressions, will obtain like this.

Measure the various character of the white powder (ethene polymers) that this drying crosses with embodiment 1 identical method.The results are shown in table 1.The preparation of comparative example 1[solid titanium catalyst component (A-1)]

130 ℃ of heating 95.2g Magnesium Chloride Anhydrouss and 44.2ml decane and 390.6g 2-Ethylhexyl Alcohol 2 hours to form homogeneous phase solution.In this solution, add the 21.3g Tetra hydro Phthalic anhydride, stir 1 hour with the dissolving Tetra hydro Phthalic anhydride at 130 ℃.The homogeneous phase solution that 75ml is generated thus is added drop-wise to 200ml (temperature remains in-20 ℃ the titanium tetrachloride then.Last 1 hour, after adding, be increased to 110 ℃ 4 hours temperature with mixture.When temperature reaches 110 ℃, in this mixture, add the 5.22g diisobutyl phthalate and under this temperature, stirred 2 hours.Collect the solid that produces by heat filtering then, this solid is suspended in again in the titanium tetrachloride of 275ml, then 110 ℃ of heating two hours.Regather solid by heat filtering then, until in washings, not detecting any titanium compound that discharges,, made solid-state titanium mixture (A-1) by above-mentioned steps with the thorough washing of the hexane of 110 ℃ decane and room temperature.This solid-state titanium mixture (A-1) consists of: the chlorine of 2.4 weight % titaniums, 19.0 weight % magnesium, 12.4 weight % diisobutyl phthalates and 60 weight % does not detect the 2-ethyl hexyl oxy.[polymerization]

The solid catalyst component (A-1) that adds 20ml decane, 5mmol triethyl aluminum and 0.1mmol (in titanium atom) in the catalyzer bottle of crossing with the nitrogen cleaning down at room temperature stirs 5 minutes to obtain decane slurry (C-1).

Under nitrogen atmosphere, rise in the autoclave and add l and rise the hexane that purifying is crossed at 2-.Then the atmosphere in the autoclave is changed over ethene atmosphere, system temperature is elevated to 60 ℃, in autoclave, add 4ml (counting 0.02mmol) decane slurry (C-1) with titanium atom.

Then, the temperature of system is increased to 75 ℃, introduces hydrogen, add-on is so that gauge pressure reaches 9.8 * 10 ⁴Pa is as the criterion.Then, feeding ethene makes gauge pressure reach 7.8 * 10 ⁵Pa then continues to feed ethene and kept uniform pressure 1 hour.Feed in the ethylene process, temperature remains on 80 ℃.

After polymerization is finished, filter the slurry that contains solid product, be separated into white powder and liquid phase.The white powder that will obtain like this is dry 10 hours under 80 ℃ and decompression.

Cross the various character of white powder with the drying of the same procedure measurement that illustrates in the EXAMPLE l.The results are shown in table 1.Comparative example 2[solid titanium catalyst component (A-2)]

Be the Magnesium Chloride Anhydrous of floating 0.75mol in 1 liter of decane, in the suspension that generates, add the 2.25mol 2-Ethylhexyl Alcohol.Stir the temperature of rising system down, this mixture is heated 2 hours to form water white homogeneous phase solution at 120 ℃.Be cooled to room temperature though let alone to place, this solution still keeps colourless, transparent and homogeneous phase.

In nitrogen atmosphere, rise adding 400ml decane and 400mmol (440ml) titanium tetrachloride in the glass flask, and it is cooled to 0 ℃ at l.In this flask, in 20 minutes, splash into the above-mentioned water white transparency homogeneous phase solution that obtains of 100mmol (in magnesium atom) with dropping funnel.This solution is once being added dropwise to regard to bubbling, and the mixture of generation becomes yellow suspension.After adding,, and continue to stir these suspension 1 hour at 80 ℃ with the temperature of the speed rising suspension of 4 ℃/min.Then, under nitrogen atmosphere, from liquid phase, isolate the solid of generation, wash this solid with 2 liters of decane with glass filter.This solid is suspended in the 900ml decane again, the suspension that generates was thus heated 1.5 hours at 120 ℃.Obtain solid titanium catalyst component (A-2) by above-mentioned steps.

Solid titanium catalyst component (A-2) consists of: 8.1 weight % titaniums, 55.0 weight % chlorine, 17.0 weight % magnesium and 0.04 weight %2-ethyl hexyl oxy.[polymerization]

In nitrogen atmosphere, rise 1 liter of hexane that purifying is crossed of adding in the autoclave to 2-, system temperature is increased to 50 ℃, in autoclave, add the above-mentioned gained solid titanium catalyst component (A-2) of 1.0mmol triisobutyl aluminium and 0.02mmol (in titanium atom), seal autoclave.Introduce hydrogen then, add-on is so that gauge pressure reaches 3.9 * 10 ⁵Pa is as the criterion.Then, feeding ethene makes gauge pressure reach 7.8 * 10 ⁵Pa then continues to feed ethene and kept uniform pressure 1 hour.Feed in the ethylene process, temperature remains on 80 ℃.

After polymerization is finished, filter the slurry that contains solid product, be separated into white powder and liquid phase.The white powder that will obtain like this is dry 10 hours under 80 ℃ and decompression.

Measure the various character of the dry white powder of crossing with the same procedure of explanation among the embodiment 1.The results are shown in table 1.The preparation of comparative example 3[solid titanium catalyst component (A-3)]

Suspension 19.1g magnesium chloride in the 88.4ml decane adds the 78.1g 2-Ethylhexyl Alcohol in this system, the temperature of system is increased to 135 ℃, stirs this mixture 4 hours when keeping system temperature to be 135 ℃, to obtain the water white transparency homogeneous phase solution.After this solution is cooled to 100 ℃, in the time of 100 ℃, add the 9.58g tetraethoxy-silicane, stirred 1 hour, to obtain to contain the decane solution of magnesium chloride at 100 ℃.In the 400ml flask, add the 200ml titanium tetrachloride, this system is cooled to-20 ℃.In this flask, in 2 hours, be added dropwise to the above-mentioned decane solution that contains magnesium chloride that obtains of 50ml (concentration of magnesium chloride is the 1mol/ liter) then.Slowly with this system heating.At 90 ℃ the mixture that generates was stirred 2 hours, then heat filtering.With the solid that 90 ℃ decane washings obtain, the decane with room temperature thoroughly washs this solid then, to obtain solid titanium catalyst component (A-3).

The component of this solid titanium catalyst component (A-3) is: 10.7 weight % titaniums, 57 weight % chlorine, 12.0 weight % magnesium and 8.4 weight %2-ethyl hexyl oxies.

Add the 400ml decane in 500ml alkane bottle, add 3.59g solid titanium catalyst component (A-3) in this flask, adding the 20ml average group again becomes Al (O-i-C ₃H ₇) Cl ₂The decane solution and the 0.15ml Virahol of the aluminum compound of (Al concentration is the 1mol/ liter).The temperature of system is raise, the mixture that generates was stirred 3 hours at 150 ℃.The solid that generates by heat filtering collect, with 130 ℃ decane washings, the decane to room temperature thoroughly washs then, with acquisition solid titanium catalyst component (A-4).

This solid catalyst component (A-4) consists of: 4.1 weight % titaniums, 11 weight % magnesium, 49 weight % chlorine, 12.9 weight % aluminium and 0.2 weight % isopropoxy.[polymerization]

In nitrogen atmosphere, rise 1 liter of hexane that purifying is crossed of adding in the autoclave to 2-, system temperature is raise 50 ℃, in autoclave, add the above-mentioned gained solid titanium catalyst component (A-4) of 1.0mmol triisobutyl aluminium and 0.02mmol (in titanium atom), seal autoclave.Introduce hydrogen then, add-on is so that gauge pressure reaches 3.9 * 10 ⁵Pa is as the criterion.Then, feeding ethene makes gauge pressure reach 7.8 * 10 ⁵Pa then continues to feed ethene and kept uniform pressure 2 hours.Feed in the ethylene process, humidity remains on 80 ℃.

After polymerization is finished, filter the slurry that contains solid product, be separated into white powder and liquid phase.The white powder that will obtain like this is dry 10 hours under 80 ℃ and decompression.

Measure the various character of the dry white powder of crossing with the same procedure of explanation among the embodiment 1.The results are shown in table 1.The preparation of comparative example 4[solid catalyst component (A-5)]

Thoroughly clean 3-with nitrogen and rise autoclave, in this still, add kerosene, 75g Magnesium Chloride Anhydrous, 109g ethanol and the 10g Emasol320 that 1.5 liters of purifying cross (the pure SUNSOFT Q-182S of the sorb of dehydration (sugar), can be available from Kao Atlas Co., Ltd).Stir the temperature of rising system down, and stirred 20 minutes at 125 ℃, the mixture that will generate thus with 600rpm.With nitrogen the pressure of system is increased to 9.8 * 10 ⁵Pa.Then, open the cock that directly links to each other and be heated to 125 ℃ SUS (stainless steel) pipe (internal diameter 3mm) with autoclave.Liquid in the autoclave is transferred to one to be equipped with 3 liters of 5-in the purifying kerosene that is cooled to-15 ℃ of kerosene in advance and to rise in the flask and (agitator is housed).So the amount of liquid that shifts is 1 liter.Shifting the required time is approximately 20 seconds.Filtration is collected the solid of generation and is thoroughly washed with hexane.

In this solid of 12g, add the 200ml decane to form slurry.This slurry is cooled to 0 ℃ and be incubated in this temperature.In 30 minutes, in this slurry, be added dropwise to the 125mmol diethyl aluminum chloride.After adding, at room temperature be incubated 1 hour, be heated to then 90 ℃ and under this temperature the insulation 3 hours.By this operation, organoaluminum is immobilized on magnesium chloride by part.Allow slurry leave standstill, and remove supernatant liquid.In the material that produces, add decane and form slurry again.This operation repeats secondary.In this slurry, add the 200ml decane then.Under stirring consequent slurry is incubated in 0 ℃, then in 15 minutes, is added dropwise to the 5mmol vanadylic chloride of 10ml decane dilution and the mixture of 5mmol titanium chloride.After adding, the temperature of system is increased to 80 ℃, insulation is 1 hour under this temperature.Collect the solid product that generates by filtering then, and wash in washings, can not detecting any vanadium that discharges and titanium, obtain solid catalyst component (A-5) with decane.[polymerization]

Rise 1 liter of decane, 2.0mmol triisobutyl aluminium and 0.01mmol (in total atoms metal of titanium and vanadium) solid catalyst component (A-5) that purifying is crossed of adding in the autoclave at 2-.The temperature of this system is heated to 40 ℃, feeds ethene, make total pressure reach 7.8 * 10 ⁵Pa carries out 1 minute (fs) of polymerization then, discharges ethylene gas then, feeds hydrogen and makes pressure reach 9.8 * 10 ⁴Pa.Then, the temperature of system is increased to 70 ℃, enters ethylene gas again and make stagnation pressure reach 7.8 * 10 ⁵Pa restarts polymerization then.Then, feeding ethene continuously makes total pressure remain on 7.8 * 10 ⁵Pa.And 80 ℃ of continuation polymerizations 80 minutes.

After polymerization is finished, filter the slurry contain solid product, be separated into white powder and liquid phase, decompression and 80 ℃ with this white powder drying 10 hours.

Measure the various character of the dry white powder of crossing with the same procedure of explanation among the embodiment 1.The results are shown in table 1.[comparative example 5] [preparation of solid titanium catalyst component (B-2)]

With nitrogen wash 200ml four neck flasks the time, when room temperature (26 ℃), add the 10ml hexane, in this flask, add the triethyl aluminum of 3mmol (in the aluminium atom) and the above-mentioned solid-state titanium mixture (A) of 1mol (in titanium atom), then at room temperature stirred 1 hour, after stirring finishes, from liquid, isolate the solid of generation with decantation, adding hexane in this solid is also stirred, triplicate is removed the washing operation of supernatant liquid by decant then, to obtain solid titanium catalyst component (B-2).[polymerization]

Except replace solid titanium catalyst component (B) with solid titanium catalyst component (B-2), carry out the polymerization of ethene with the same procedure that embodiment 1 describes.

After polymerization is finished, filter the slurry that contains solid product, be separated into white powder and liquid phase.The white powder that will obtain like this is dry 10 hours under 80 ℃ and decompression.

Measure the various character of the dry white powder of crossing with the same procedure of explanation among the embodiment 1.The results are shown in table 1.The preparation of the solid-state titanium component of comparative example 6[(A-6)]

In the 400ml four neck flasks that thoroughly cleaned with nitrogen, add the decane that 5g (52.5mmol) Magnesium Chloride Anhydrous and 190ml purifying are crossed.Under stirring, room temperature (26 ℃) in 45 minutes, in this flask, is added dropwise to 18.4ml (3.5mmol) ethanol.After adding, at room temperature this mixture was stirred 1 hour.

Then, when system temperature being controlled in 35～40 ℃, in 1 hour, be added dropwise to 17.2ml (137mmol) diethyl aluminum chloride.After adding, at room temperature this mixture was stirred 1 hour.

Then, in this mixture, add 69.2ml (630mmol) titanium tetrachloride, stirred 2 hours at 80 ℃.For from liquid phase, isolating solid, reaction product is carried out heat filtering with the glass funnel that has chuck.The decane of crossing with the 600ml purifying washs this solid.

By above-mentioned steps, obtain solid-state titanium component (A-6).The composition of this solid-state titanium composition (A-6) comprising: 4.8 weight % titaniums, 2.2 weight % aluminium, 15.0 weight % magnesium, 56.0 weight % chlorine and 8.8 weight % oxyethyl groups.[preparation of solid titanium catalyst component (B-3)]

With nitrogen wash 200ml four neck flasks the time, when room temperature (26 ℃), add the 100ml hexane.In this flask, add the triethyl aluminum of 3mmol (in the aluminium atom) and the above-mentioned solid-state titanium mixture (A-6) that obtains of 1mmol (in titanium atom), then at room temperature stirred 1 hour, after stirring finishes, from liquid, isolate the solid of generation with decantation, add hexane and also stirred in this solid, triplicate is removed the purification operations of supernatant liquid by decant then.

With gained material resuspending in the 100ml hexane.Then the dry air of 58.4ml is introduced gas phase, then at room temperature stirred 1 hour, in the whipping process, measure the gaseous phase volume reduction with gas burette, result, volume reduction are 10.1ml.

After stirring finishes, from liquid, isolate the solid of generation through decantation.In solid, add hexane, stirring.Repeat secondary and roll over the washing operation of removing supernatant liquid, to obtain solid titanium catalyst component (B-3) through inclining.[polymerization]

Except replace solid titanium catalyst component (b) with solid titanium catalyst component (B-3), carry out the polymerization of ethene with embodiment 1 identical method.

After polymerization is finished, filter the slurry contain solid product, be separated into white powder and liquid phase, decompression and 80 ℃ with this white powder drying 10 hours.

Measure the various character of the dry white powder of crossing with the same procedure of explanation among the embodiment 1.The results are shown in table 1.Table 1

	Productive rate	Catalytic activity * 1	MFR g/10 branch	MT g	α *2	SR	Mw/Mn	Mz/Mw	g *	Density g/cm 3
											Embodiment 1 embodiment 2 embodiment 3 embodiment 4	161.6 106.6 164.2 78.7	8100 5300 8200 3900	0.06 1.80 0.07 0.90	16.5 4.3 16.0 5.5	0.73 0.74 0.74 0.72	1.37 1.36 1.36 1.35	5.18 6.31 5.25 6.04	3.11 3.54 3.17 3.22	1.00 0.99 1.00 0.98	0.96 0.96 0.97 0.93
Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 comparative examples 5 comparative examples 6	207.9 184.2 189.7 343.7 225.0 378.2	10400 9200 9500 34400 11300 18900	0.04 0.75 0.21 0.19 0.05 0.07	15.5 12.0 30.0 18.2 26.9 14.5	0.62 1.03 1.21 0.97 0.91 0.70	1.20 1.43 *3 1.34 1.32 1.29	5.22 10.30 13.87 9.86 5.73 5.70	3.18 6.44 7.96 6.37 3.14 3.75	1.00 1.00 0.99 1.00 1.00 0.99	0.95 0.96 0.96 0.97 0.96 0.97

* 1.g-PE/mmol-Ti * 2: α=logMT+0.4 * logMFR*3: can't measure (generation melt fracture)

From the result of table 1 as seen, ethene polymers of the present invention satisfies aforementioned (i) to (character vii), therefore, this ethene polymers has high density, has special relationship between molten tension force and melt flow rate and has high swelling ratio, narrow molecular weight distribution (Mw/Mn, Mz/Mw) and approach 1 ^*The g value.The moldability of this polymkeric substance is fabulous, and it is high and almost do not have a moulded parts of roughened appearance to make rigidity height, impact strength by this polymkeric substance.

Claims (6)

1. One kind have following (i) to (the vii) ethene polymers of character:

   (i) density 0.92 to 0.98g/cm ³In the scope,

   (ii) the melt flow rate of measuring under 190 ℃ and 2.16kg load is in 0.01 to 100g/10min scope,

   (iii) molten tension force (MT) and melt flow rate (MFR) satisfy the relation of following formulate:

   logMT＜-0.4log MFR+0.75

   (iv) molecular weight distribution mw/mn is between 3 to 8,

   (v) molecular weight distribution Mz/Mw is between 2.5 to 4.5.

   (vi) g ^*Value, the index of a long chain branches ratio, between 0.95 to 1.00, and

   (vii) swelling ratio is between 1.35 to 1.50.
2. 2. ethene polymers as claimed in claim 1, it is characterized in that described density 0.94 to 0.98g/cm ³In the scope.
3. 3. ethene polymers as claimed in claim 1, the melt flow rate that it is characterized in that measuring under 190 ℃ and 2.16kg load is in 0.02 to 10g/min scope.
4. 4. ethene polymers as claimed in claim 1 is characterized in that it is made by using Ziegler-Natta catalyst.
5. 5. ethene polymers as claimed in claim 1 is characterized in that it is made by the ethylene rolymerization catalyst that use comprises following component:

   [I] is in contact with one another by oxygen and solid-state titanium organometallic compound mixture and the solid titanium catalyst component that obtains, and this solid-state titanium organometallic compound mixture is in contact with one another and is got by following component:

   (A) contain titanium, magnesium, halogen and comprise the solid-state titanium mixture of the compound of at least two ehter bonds that exist every a plurality of atoms, and it is in contact with one another and is got by following component:

   (a) the liquid magnesium compound of no reducing power, it is in contact with one another and is made by magnesium halide, pure and mild acid anhydrides,

   (b) contain the compound of at least two ehter bonds that exist every a plurality of atoms,

   (c) liquid titanium tetrahalide,

   (B) organo-aluminium compound and

   [II] organo-aluminium compound.
6. 6. one kind prepares polyvinyl method as claimed in claim 1, it is characterized in that in the presence of the ethylene rolymerization catalyst that comprises following component with ethylene homo or with ethene and other olefin-copolymerizations except that ethene:

   [I] is in contact with one another by oxygen and solid-state titanium organometallic compound mixture and the solid titanium catalyst component that obtains, and this solid-state titanium organometallic compound mixture is in contact with one another and is got by following component:

   (A) contain titanium, magnesium, halogen and comprise the solid-state titanium mixture of the compound of at least two ehter bonds that exist every a plurality of atoms, and it is in contact with one another and is got by following component:

   (a) the liquid magnesium compound of no reducing power, it is in contact with one another and is made by magnesium halide, pure and mild acid anhydrides,

   (b) contain the compound of at least two ehter bonds that exist every a plurality of atoms,

   (c) liquid titanium tetrahalide,

   (B) organo-aluminium compound and

   [II] organo-aluminium compound.