KR820001784B1 - Catalyst and catalyst componests for polimerizing olefins - Google Patents

Abstract

The catalyst comprises the redction products of a Ti halide with a solid support contg. an -contg. Mg compd. andan adduct of a Mg halide and l electron donor and/or the reaction product of the O-contg. Mg compd. and >=electron donor. Thus, 8.1 g MgO was refluxed 2hr with 238g SOCI2 and the product was filtered and washed CI-free with C6H14. The product was heated l hr in 100ml C6H4 contg. 3g EtOBz and 2.9 g EtOH. The solvent was evapd. at 30≰C and the residual solid treated 2 hr at 100≰C with 100g TiCI4, filtered, and washed CI-free with C7H16. The catalyst was used for polymn. of propylene.

Description

Olefin Polymerization Catalyst and Catalyst Components

The present invention relates to a catalyst component for olefin polymerization and a catalyst obtained therefrom.

More specifically, the present invention relates to a catalyst component for the polymerization of alpha-olefin CH ₂ = CHR, wherein R is an alkyl or aryl group having 1 to 8 carbon atoms.

Catalysts for alpha-olefin polymerization exhibiting high activity and stereospecificity obtained by reacting an Al-alkyl compound with a Ti compound supported on an Mg halide in an active form are known (see German Patent No. 2,643,143).

Comparable to the properties of the catalysts disclosed in the aforementioned Federal Republic of Germany patents, catalysts prepared from supports containing oxygen-containing Mg compounds, such as oxides, hydroxides, hydroxyhalides and salts of Mg of oxygen acids, are still Not known until.

It is also known that a Ziegler-type catalyst for polyethylene having high activity can be produced by initiating a reaction from a reaction product of a Ti halogenated compound and a support made of Mg oxide, Mg hydroxide and Mg salts of oxygen acid.

These catalysts, suitably transformed into electron donating compounds (or Lewis bases), can be used for the stereoregular polymerization of alpha-olefins, but their catalytic activity is not high enough and in some cases it is necessary to purify the polymer from the catalyst residues. There is. In order to increase the efficacy of these catalysts, a method of prehalogenating Mg oxygen compounds has been attempted. However, the results obtained were not satisfactory.

By initiating the reaction from a support comprising an oxygen compound, a catalyst having high activity and stereospecificity can be prepared for the polymerization of alpha-olefin CH ₂ = CHR, wherein R is an alkyl or aryl group having 1-8 carbon atoms. In this case, the oxygenated compound is pretreated before reacting with the Ti compound, in particular converting the oxygenated compound into an adduct between an Mg dihalide and an electron donating compound containing an active hydrogen atom (Compound HED). .

The catalyst thus obtained has the advantage that no planting phenomenon occurs in an apparatus (extruder or the like) used to transform the polymer into a molded article even when the polymer contains a relatively large amount of halogenated compound.

The catalyst component according to the invention consists of a product obtained by reacting at least the following materials.

a) Ti halogenated compounds having at least one Ti-halogenated bond

b) solid support, the essential component of which is

b ₁ ) Mg oxygen-containing compounds selected from Mg oxides, hydroxides, hydroxy halides and salts of oxygenated acids with at least one electron-donating compound HED and / or Mg dihalide in adduct form with ED, wherein each component Is at least 0.1 mole per mole of decomposition product of the adduct containing Mg dihalide and / or Mg dihalide, and the molar ratio between the oxygenated compound and the Mg dihalide (mixed or unmixed) is from 0.05: 1 to 20: 1

b ₂ ) A product obtained by reacting an oxygen-containing Mg compound of the type described in b ₁ ) with an electron donating compound ED or HED in an amount of at least 0.1 mole of ED and HED compound per mole of oxygenated compound. ED compounds or their adducts when the adducts thereof are not mixed or not contained in the support b), and present in the catalyst component in the form of a mixture which cannot be extracted with TiCi ₄ at 80 ° C. The amount of is between 0.05-5 moles per mole Ti compound present after treatment.

It is suitable that at least 50% of the Ti compound does not dissolve in TiCi ₄ at 80 ° C., more preferably at least 50% of the compound does not dissolve in TiCi ₄ at 135 ° C.

The adduct contained in the support b ₁ ) preferably contains the electron donating compound HED in an amount of between 0.1 and 6 moles per mole of Mg dihalide. If this adduct also contains an ED compound, it contains an amount between 0.1 and 1 mole of a halide.

The support b ₁ ) can be prepared by a variety of methods, suitable being reacting a halogenating agent capable of converting the oxygenated compound to Mg dihalide at least partially according to known methods and reacting the Mg oxygenated compound of the above-described type, Prepared by reacting from about 5% to 95% of the oxygenated compound under conditions capable of converting it to a halide.

Halogenation can be carried out in the presence of the electron donating compounds HED and / or ED, in which case an adduct is formed between the Mg dihalide and the HED and / or ED compound.

However, it is suitable for such a reaction to take place continuously, more particularly for the product of the prehalogenation to react simultaneously with HED and ED or with the first HED followed by ED.

The ED compound may also be reacted during the reaction with the Ti halogenated compound.

Sulfuryl or thionylchloride, phosgene, organohalide, hydrogen halide, carboxylic acid halide, -ammonium halide, Al-, B-, P- and Si- halides can be used as the halogenating agent.

In addition to the foregoing as specific examples of such compounds, hydrogen chloride and hydrogen embrittlement, CCl ₄ , benzoyl chloride, POCl ₃ , SiCl ₄ , halosilanes, AlCl ₃ , Al-alkyl halides (eg Al (C ₂ H ₅ ) ₂ Cl, Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ ) can be used.

The reaction is generally carried out by suspending the Mg oxygenated compound in a halogenated compound. If the halogenated compound is liquid under the reaction conditions, the mixture is heated by heating at a temperature lower than the decomposition temperature of the halogenated compound, generally 40 ° to 120 ° C.

If the halogenating agent is gaseous under the reaction conditions, its vapor can be flowed to the oxygenated compound. When using hydrogen halides, the resulting Mg halide contains hydrate molecules.

There is no need to anhydrous this product to obtain good results.

When Cl ₂ is used as the halogenating agent, it is generally treated at temperatures above 400 ° C. in the presence of CO.

Another method of preparing the support b ₁ ) is heating Mg hydride halides under conditions where dehydration and partial hydrolysis of the halides occur by known methods, and Mg dihalide Mg hydroxyhalide and / or temperature depending on the temperature. Or a mixture of Mg oxides. There is no need for complete anhydration of the raw halides. The amount of water in the final product of about 0.5 per mole of halide can be used without adversely affecting the catalytic performance.

Preferably, the reaction is initiated with a dihalide having 1-2 moles of H ₂ O and heated at a temperature generally between 350 ° and 550 ° C., and then the product is reacted with the electron donating compounds HED and ED.

According to another method of preparation, the Mg oxygenated compound is mixed with anhydrous Mg dihalide (e.g., in a mill), suitably in the proportions described above, and then the product is reacted with the HED and ED compounds. The adduct and any compound ED preformed between the Mg oxygenated compound, the Mg dihalide and the compound HED can be mixed with each other, and the support b ₁ ) also reacts the Mg dihalide with the compounds HED and ED, Prepared by treatment in the presence.

The support b ₁ ) containing the compound HED and optionally an adduct with ED is pretreated with a compound capable of reacting with the compound HED to form Mg dihalide. For example, this reaction can be carried out according to the method described in French Patent 7,724,238 using SiCl ₄ or Al-alkyl compounds.

Another feature of the present invention is that it is not necessary to pre-halogenize the Mg oxygenated compound to react with the HED compound before reacting with the Ti halogenated compound, which allows the aforementioned Ti compound to be used as the halogenating agent.

In this case, the Mg oxygenated compound needs to pretreat the compound ED or a mixture thereof with the HED in an amount between at least 0.1 and about 5 moles per mole of the oxygen compound. The product is then reacted with a Ti halogenated compound.

Preference is given to using from 0.1 to 3 moles of compound ED and from 0.5 to 2 moles of compound HED. It is heated between 40 ° and 120 ° C. and the resulting suspension is subsequently reacted with the Ti compound.

The reaction with the Ti compound can be carried out in the presence of halogenating agents other than the Ti compound.

For example, this reaction can be carried out in the presence of anhydrous hydrogen chloride, which can increase the amount of Ti compound and the resulting catalytic ability to adhere on the support.

As described above, when the Mg oxygenated compound is previously halogenated to convert the obtained Mg dihalide to an adduct having the compounds HED and / or ED to prepare the support b ₁ ), the reaction to form the adduct is halogenated. It is suitable to carry out after reaction. The practice is to react the halogenated product separated from the reaction mixture and then to suspend with compounds HED and ED in a hydrocarbon solvent.

Compounds HED and ED are suitably used in amounts of between 0.2 and 2 moles and 0.1 to 0.5 moles per mole of raw material oxygenated compound, respectively.

Reaction temperature is 40 degrees-120 degreeC, for example.

As mentioned above, the reaction between the Ti compound and the support b) is carried out in the presence of an adduct with the compound ED or Lewis acid, wherein the compound mentioned above should not be mixed or unmixed in the support.

In fact, the catalyst component should always contain a certain amount of compound ED in a mixed form that cannot be extracted with TiCl ₄ at 80 ° C.

The reaction with the Ti compound is carried out in several different ways, of which a suitable method is to suspend the support b) in the liquid Ti compound and the suspension onto the Ti compound support in such a form that the suspension cannot be extracted with TiCl ₄ at 80 ° C. The suspension is heated at 60 ° C. to 150 ° C. for a sufficient time to fix.

After completion of the reaction, the solid product is separated at 80 ° C. under conditions in which no soluble Ti compound is precipitated in TiCl ₄ and then washed until a trace amount of free Ti compound is also removed.

The amount of Ti compound indicated as Ti metal stuck on the catalyst component in a form that cannot be extracted with TiCl ₄ at 80 ° C. is generally included in an amount between 0.1 and 20% by weight.

More specifically, the amount of Ti compound represented as Ti metal fixed in the catalyst component after extraction with TiCl ₄ at 135 ° C. is 0.2 to 0.5% by weight.

A general method carried out between the Ti compound and the support is a compound resulting from the reaction between the Ti compound and the electron donating compound HED and optionally the ED contained in the support, which is dissolved in the reaction medium to the maximum possible from the support described above. To recover.

The adduct between the Mg dihalide and the electron donating compound HED and / or ED may contain Lewis acids other than Mg halide in addition to the above-mentioned compounds in mixed form and as other compounds.

Examples of useful Mg oxygen compounds include Mg oxides, hydroxides, oxyhalides and salts of organic or inorganic oxygen acids, as described above.

Although such a compound is suitably used in an anhydrous state, the compound may also contain a hydrate in an amount of 2 mol or less per mole of the Mg compound.

In the case of MgO and Mg (OH) ₂ , for example, products containing up to about 1 mole of water that are not chemically bound can be used.

Some specific examples of Mg compounds include mixed oxides of MgO, Mg, Al and / or Si, hydroxides, hydroxychlorides and bromide of Mg, carbonates and basic carbonates of Mg, basic carbonates of Mg and Al, for example hydrotalcite Obtained by dehydration under hydrolysis conditions of Mg carboxylates, hydrated Mg halides, such as Mg nitrates, Mg phosphates and silicates, Mg acetates, stearates, benzoates, oxalates, p-toluates and terephthalates And compounds produced by partial pyrolysis of Mg carboxylate.

As mentioned above, the Mg compound may also be used in the form of a complex of a compound of another metal, for example, Al, Fe, Mn, or a double salt or a metal compound of a solid solution.

Electron-donating compounds HED are aliphatic, cycloaliphatic, aromatic alcohols having 1 to 20 carbon atoms, for example phenol, silanium, polysiloxane compounds (including OH groups), thioalcohols, thiophenols, primary and secondary amines, amides, ammonia Choose from crowds.

Specific examples include ethanol, butanol, 2-ethylhexanol, octanol, cyclohexanol, phenol, t-butylphenol, triethylhydroxysilane, diethyldihydroxysilane, methyl-hydropolysiloxane, and thioethanol. .

The electron donating compound ED is suitably selected from alkyl, aryl or cycloalkyl esters of carboxylic acids, in particular esters of aromatic acids. Examples of other useful compounds include halides and anhydrides of carboxylic acids, in particular aromatic acids, ethers, ketones, tertiary amines and amides. As specific examples, these compounds are benzoic acid and derivatives thereof, such as p-toluic acid, benzoyl chloride, benzoic anhydride, n-butyl ether, isoamyl ether, acetophenone alkyl esters (methyl, ethyl, butyl ester, etc.).

When reacting in the form of adducts with dihalides and optionally HED compounds, compound ED is generally used in an amount between 0.1 and 1 mole per mole of Mg dihalide.

Ti compounds have at least one Ti-halogen bond and are selected from Ti tetrahalides, in particular TiCl ₄ , Ti halogen-alcoholates, for example (nC ₄ H ₉ O) ₂ TiCl ₂ , TiCl ₃ OCH ₃ Suitable.

Catalyst components comprising tetravalent Ti compounds can be treated with conventional methods, for example with Al-alkyl compounds, to reduce these compounds to lower valency, in particular trivalent compounds.

The catalyst according to the invention is prepared by reacting Al-alkyl compounds, in particular Al-trialkyl and mixtures thereof, with Al-dialkylhalides and the above-mentioned catalyst components.

The Al / Ti ratio is generally light level, but is between 1 and 1000, for example.

In the case of the polymerization of alpha-olefins, it is suitable to use Al-trialkyl compounds such as Al-triethyl and Al-triisobutyl in the form of adducts of these compounds with electron donating compounds, where The amount of Al-alkyl compound reacted is between 10 and 90%.

When using an Al-alkyl compound partially complexed with an electron donating compound, the Al-Ti ratio is generally 20 or more, and is between 30 and 300.

The electron donating compound to be reacted with the Al-alkyl compound is the same compound as used in the reaction for producing the catalyst component including the Mg oxygen compound. Suitable examples include alkyl, aryl or cycloalkyl esters of aromatic acids, in particular aromatic acids and derivatives thereof.

As examples of olefins that can be polymerized with the catalyst of the present invention, ethylene, propylene, butene-1,4-methyl-pentene-1, styrene and mixtures thereof can be used.

The polymerization method is well known, i.e., it is carried out in a liquid phase in the presence or absence of an inert hydrocarbon diluent such as butane, fenpan, hexane, heptane or in a gas phase.

Although the polymerization temperature is light level, for example, it is performed at 50-150 degreeC, suitably 60-90 degreeC. The pressure is at or above atmospheric pressure.

When polymerizing propylene, the catalyst is used to produce random copolymers of propylene homopolymers with small amounts of propylene and about 10% by weight of ethylene, for example by first polymerizing propylene and then in one or more stages. Ethylene or mixtures thereof yield propylene and polymer compositions.

The ethylene content in this composition is about 30% by weight.

Hereinafter, the present invention will be described in more detail with reference to the following Examples.

Example 1

a) preparation of catalyst components

8.1 g of MgO (200 mmol; commercially available, pure substance) was placed in a jacketed glass reactor filled with 500 ml of volume and filled with filtration fragments, and 238 g (2 mol) of thionyl chloride (SOCl ₂ ) was introduced thereto. Under stirring, the suspension was heated to boiling point (77 ° C.) for 2 hours and then filtered through to remove excess SOCl ₂ , and the remaining solid was washed with hexane at 60 ° C. until chlorine ions were removed from the filtrate. The resulting solid is resuspended in a solution containing 2.3 g (50 mmol) of ethanol distilled in 3 g (20 mmol) of ethylbenzoate and 100 mL of anhydrous hexane in the same reactor. This suspension was heated at 60 ° C. for 1 hour. This solvent was then evaporated at 30 ° C. under moderate pressure (40 Torr). The residual solid was reacted with 110 mL TiCl ₄ (1 mol) at 100 ° C. for 2 hours. TiCl ₄ was then filtered off at 100 ° C. and the residual solid was washed with heptane until no chlorine ions were lost.

b) Polymerization of propylene in hexane (solvent)

Al- butyl switch _{(Al-i-Bu 3 54.5} % by mole and Al-n-Bu ₃ 45.5% by mole) mixture of 5.05 mmol of anhydrous hexane methyl p- Tolu benzoate 1.69 mmol (254㎎) of 80㎖ at room temperature of And reacted for 5 minutes. 30 ml of the solution diluted with 50 ml of anhydrous hexane was contacted with 2 ml of the catalyst component suspension prepared in 1a) for 5 minutes. The suspension was introduced into a stainless-stirred autoclave with 870 ml of propylene saturated hexane at 40 ° C. equipped with a magnetic screw stirrer and thermocouple in a pure nitrogen atmosphere, followed by Al-butyl and methyl p-tolu 50 ml of the remaining solution of ate was introduced into the propylene stream. After closing the autoclave, 250 N cm 3 of hydrogen was introduced thereto, the temperature was raised to 60 ° C., and propylene was added to maintain the total pressure at 9 kg / cm 2 gauge pressure. The pressure was kept constant by feeding the monomers continuously.

After 2 hours, the gas was removed quickly and the synthesis slurry was cooled to stop the polymerization. The solvent was distilled off from the polymerization slurry and 470 g of dry polymer was obtained, which contained the catalyst residue as follows.

Ti-7.5 ppm, Mg = 112 ppm, Cl = 186 ppm.

The yield was 133,500 g polypropylene per g g Ti, and the residue extracted with boiling heptane was 93.5% by weight.

Example 2

a) preparation of catalyst components

8.1 g (200 mmol) of MgO were reacted with 238 g of SOCl ₂ for 2 hours at 77 ° C. as in Example 1a. The solid thus obtained was washed with warmed hexane to remove SOCl ₂ and then suspended in a solution containing 3 g (20 mmol) of ethyl benzoate and 9.22 g (200 mmol) of ethanol diluted with 100 mL of hexane. The suspension was reacted at 60 ° C. for 2 hours. This solvent was then evaporated as described above and the solid was reacted with 181 mL (1.65 mmol) of TiCl ₄ at 110 ° C. for 2 hours. Before filtering TiCl ₄ , the whole was filtered at 110 ° C. after introducing 45 ml of heptane. After washing with heptane, a portion of the catalyst component suspension was dried and the resulting solids were analyzed to yield the following results.

Ti = 2.96% by weight and ethylbenzoate = 4.65% by weight.

b) Polymerization of propylene in hexane (solvent)

0.8 ml of the liquid in which the catalyst component prepared in Example 2a was suspended in heptane was used under the conditions of the propylene polymerization test described in Example 1b). After polymerization for 4 hours, 363 g of a dry polymer having the following catalyst residues, namely Ti = 6ppm, Mg = 47ppm, Cl == 105ppm, were obtained with a yield of Ti g. The polypropylene 166, 500 g of sugar was 90.5 wt% of the residue extracted with boiling heptane.

Example 3

a) preparation of catalyst components

The starting material is chemically pure basic magnesium carbonate having the following composition (ie 4Mg (CO ₃ ) .Mg (OH) ₂ .5H ₂ O). This starting material was calcined at 400 ° C. in dry nitrogen for 69 hours to convert to magnesium oxide.

A catalyst was prepared according to the method of Example 2a) using 8.1 g (200 mmol) of magnesium oxide. At the end of the reaction a portion of the suspension of the catalyst component in haptan was dried. The dry solids contained 3.5 wt% Ti and 5.25 wt% ethylbenzoate.

b) Polymerization of propylene in hexane (solvent)

1 ml of a liquid in which the catalyst component prepared in Example 3a) was suspended in heptane was used under the polymerization conditions described in Example 1b). After polymerization for 4 hours, 422 g of dry polymer were obtained, which contained catalyst residues such as Ti = 5.7 ppm, Mg = 50 ppm, Cl = 154 ppm. Yield is Ti g. 175,000 g of sugar polypropylene and the residue extracted with boiling heptane corresponded to 92% by weight.

Example 4

a) preparation of catalyst components

Chemically pure commercial magnesium hydroxide was calcined in dry nitrogen at 500 ° C. for 24 hours to convert to magnesium hydroxide. A catalyst was prepared according to the method of Example 2a) using 8.1 g (200 mmol) of magnesium oxide thus obtained.

b) Polymerization of propylene in hexane (solvent)

1 ml of the liquid in which the catalyst component prepared in Example 4a) was suspended in heptane was polymerized under the polymerization test conditions described in Example 1b). After polymerization for 4 hours, 232 g of dry polymer were obtained, which contained catalyst residues of Ti = 6.7 ppm, Mg = 234 ppm, Cl = 273 ppm, the yield being 149,000 g of polypropylene per Tig, extracted with boiling heptane The residue was equivalent to 88.5% by weight.

Example 5

a) preparation of catalyst components

Chemically pure commercial magnesium oxide was reacted at 500 ° C. for 24 hours in a crude nitrogen atmosphere.

8.1 g (200 mmol) of calcined MgO was reacted with 238 g (2 mol) of SOCl ₂ for 2 hours at 77 ° C. The residual solid was washed with hexane at 60 ° C. to remove thionyl chloride, which was then suspended in a solution containing 3 g (20 mmol) ethylbenzoate and 14.82 g (200 mmol) n-BuOH suspended in 100 mL hexane. I was.

The suspension was reacted at 60 ° C. for 2 hours.

After continuing to evaporate the solvent as described above the residue was reacted with TiCl ₄ at 110 ° C. as in Example 2a). After washing with heptane (see Example 1a), all traces of free TiCl ₄ were removed.

b) Polymerization of propylene in hexane (solvent)

1 ml of a liquid in which the catalyst component prepared in Example 5a) was suspended in heptane was used under the polymerization test conditions described in Example 1b). After polymerization for 4 hours, 176g of dry polymer was obtained, which contained Ti = 36.2ppm, Mg = 137ppm, Cl = 263ppm catalyst residue and the residue after extraction with boiling heptane corresponded to 90% by weight.

Example 6

a) preparation of catalyst components

MgO, a commercially available pure product, 8.1 g (200 mmol) was treated at 80 ° C. for 2 hours with a solution of 18.44 g (400 mmol) of EtOH diluted in 3 g (20 mmol) of ethylbenzoate and 50 mL of heptane. The whole reaction was then cooled to 80 ° C. and 181 mL (1.65 mol) of TiCl ₄ was added dropwise thereto within 15 minutes under stirring. The mixture temperature was warmed up to 110 ° C. to release HCl gas, at which temperature HCl gas was introduced into the suspension for 2 hours at a feed rate of 1 g mol per hour to introduce 73 g of HCl.

After the HCl feed was stopped, the suspension was diluted with C ₇ +45 mL and filtered at 110 ° C. The solid residue was treated with 181 mL of TiCl at 110 ° C. for 2 hours. The solid was then washed three times with heptane (200 ml each time) at 80 ° C. and five times at room temperature.

b) Polymerization of propylene in hexane (solvent)

The catalyst component prepared in Example 6a) was used under the same polymerization test conditions as described in Example 1a, except that 1 ml of the liquid suspended in heptane was used at a temperature of 70 ° C.

After polymerization for 4 hours, 251 g of dry polymer containing catalyst residues of Ti = 35 ppm, Mg = 57 ppm and Cl = 175 ppm were obtained. This yields a yield of Ti g. 28,400 g of sugar polypropylene and the residue extracted with boiling heptane corresponded to 93% by weight.

Example 7

a) prehalogenation of MgO by HCl treatment

80.5 g (600 mmol) of commercially available MgO was added to 2HCl in a 500 ml oil phase reactor; The mixture was reacted with HCl gas (2.14 mol / hour) diluted with nitrogen in a volume ratio corresponding to 1N ₂ at 180 ° C. for 2 hours. It was cooled only in a stream of nitrogen.

The dilute solids exhibited the following composition.

Mg = 42.75g / 100g, Cl = 29.50g / 100g, H ₂ O = 12.0g / 100g.

b) preparation of catalyst components;

15.4 g of the product obtained in Example 7a) in a 250 ml flask was stirred with a solution consisting of 4.05 g (27 mmol) of ethylbenzoate and 12.45 g (270 mmol) of ethanol diluted in 100 ml of hexane at 60 ° C for 2 hours. Reacted for a while. The solvent was then evaporated at room temperature under vacuum with a residual partial pressure of 400 mm Hg.

30 g of the solid was collected, introduced into a reactor as described in Example 1a), and reacted with TiCl _{4 at} 181 mm (1.65 moles) at 110 ° C. for 2 hours. Subsequently, this was diluted with 45 ml of heptane, and the solid at 110 ° C was filtered off. Traces of TiCl ₄ were removed by repeated washing with heptane (200 ml each time), ie three times at 80 ° C. and five times at room temperature.

The solvent was evaporated from a portion of the catalyst component suspension at 30 ° C. and under vacuum (200 mmHg). Analysis of the fault residues revealed the following composition:

Ti = 11.70g / 100g, Mg = 17.75g / 100g, Cl = 55.0g / 100g, Ethylbenzoate = 3.53g / 100g.

c) polymerization of propylene in hexane (solvent)

0.5 ml of the suspension of the catalyst component prepared in Example 7b) was polymerized under the same polymerization test conditions as described in Example 1b). After polymerization for 4 hours 352 g of dry polymer were obtained, which contained the following catalyst residues: Ti = 25 ppm, Mg = 31 ppm, Cl = 114 ppm. Yield is Ti g. It was 40,000 g of sugar polypropylene, and the residue amounted to 93% by weight after extraction with boiling heptane.

Example 8

a) Preparation of the catalyst component.

In a 500 ml reactor as described in Example 1a), 39 g (20.8%) of the MgO substrate (a microspherical aluminum-magnesium silicate sold by Grace-Davidson as item SM / 30) was charged with 476 g of SOCl _2. The reaction was carried out at 77 ° C. for 3 hours.

After washing several times with hexane at 60 ° C. to remove all traces of SOCl ₂ , the residual solid was suspended in a solution of 9.22 g (200 mmol) of ethanol diluted in 3 g (20 mmol) of ethyl benzoate and 100 mL of hexane. The reaction was carried out at 2 ° C. for 2 hours. Solvent hexane was evaporated and the solid residue was then treated with 181 mL (1.65 mol) of TiCl ₄ at 100 ° C. for 2 hours, then the suspension was diluted with 45 mL of heptane and filtered at 110 ° C.

b) Polymerization of propylene in hexane (solvent)

3 ml of the suspension of the catalyst component prepared in Example 8a) in heptane was polymerized under the same polymerization test conditions as described in Example 1b). After polymerization for 4 hours, 358 g of a fine spherical dry polymer having a narrow particle size distribution were obtained, the yield being Ti g. It corresponds to 10,000 g of sugar polymer and the residue after extraction with boiling heptane corresponds to 86.5.

c) polymerization of ethylene in hexane (solvent)

200 mg of dry catalyst component (Ti 10.8 mg) prepared in Example 8a) was suspended in 1000 ml of lactic acid containing 1.5 g of aluminum-butyls mixture (see Example 1a), and the whole was 2.5 in a weak ethylene atmosphere. It was introduced into an autoclave for l. The temperature was raised to 75 ° C. and hydrogen was fed up to 3 atmosphere gauge pressure and ethylene up to 13 atmosphere gauge pressure.

Ethylene was fed and maintained at 13 atmosphere gauge pressure for 4 hours. The total slur was released and the solvent was filtered to separate the polymer.

After drying, 347 g of polyethylene with narrow particle size distribution were obtained, with a yield of Ti g. It corresponds to 32,100 g of sugar polyethylene.

Example 9

a) preparation of catalyst components

MgO, a commercially available product, 8.1 g (200 mmol) was reacted at 60 ° C. for 2 hours with a solution made of 3 g (20 mmol) of ethylbenzoate and 9.22 g (200 mmol) of ethanol diluted with 100 of hexane. The solvent was evaporated slightly at room temperature under reduced pressure (40 Tprr). The solid residue was washed with TiClheptane (200 mL each time) at 110 ° C., as in Example 2a), ie twice at 80 ° C. and three times at room temperature, after which a portion of the suspension was dried and the remaining solid was As a result of analysis, the following composition was found.

Ti = 0.9g / 100g, Mg = 38g / 100g, Cl = 47.4g / 100g, ethylbenzoate = 1.8g / 100g.

b) Polymerization of propylene in hexane (solvent)

1.5 ml of the suspension of the catalyst component prepared in Example 9a) in heptane was polymerized under the same polymerization test conditions as described in Example 1b). After polymerization for 4 hours, 75 g of dry polymer were obtained, which showed the following catalyst residues: Ti = 9.5 ppm, Mg = 360 ppm, Cl = 420 ppm. The yield corresponds to 86.5% of the residue extracted with 105,263 g of polypropylene per gram of Ti and boiling heptane.

Example 10

a) preparation of catalyst components

Pure commercial product reacted with 8.1 g (200 mmol) of MgO with 238 g (2 mol) of SOCl ₂ at 77 ° C. for 2 hours.

After washing with hexane at 60 ° C. to remove all traces of SOCl ₂ , the remaining solid was reacted with 3 g (20 mmol) of ethylbenzoate diluted with 100 ml of hexane for 1 hour at 60 ° C. The solvent was subsequently evaporated at 30 ° C. under reduced pressure (residual partial pressure 40 Torr). The dried solid was treated with 110 mL (1 mol) of TiCl ₄ at 110 ° C. for 2 hours. TiCl ₄ was then filtered off at 100 ° C. The solid residue was washed three times at 80 ° C. and three times at room temperature with heptane (each time 200 ml).

b) Polymerization of propylene in hexane (solvent)

1.1 ml of the suspension of the catalyst component prepared in Example 10a) in heptane was polymerized under the same polymerization test conditions as described in Example 1b). After polymerization for 4 hours, 142 g of dry polymer were obtained, which contained the following catalyst residues: Ti = 35ppm, Mg = 183ppm, Cl = 290ppm, the yield being 28,571g polypropylene per g. Ti. The residue corresponds to 86% after extraction with boiling heptane.

Example 11

a) preparation of catalyst components

4.05 g (100 mmol) of MgO was reacted with 37.5 g (250 mmol) of ethyl benzoate diluted in 50 mL of heptane at 80 ° C. for 2 hours. 250 mL (2.28 mol) of TiCl ₄ were introduced continuously and the temperature was maintained at 110 ° C. for 2 hours. This was filtered at 110 ° C. and the solids thus separated were treated again with TiCl ₄ as described above. This was washed repeatedly with heptane (200 ml each time) three times at 80 ° C. and three times at room temperature.

b) Polymerization of propylene in hexane (solvent)

1.5 ml of the suspension of the catalyst component prepared in Example 11a) was polymerized under the same polymerization test conditions as in Example 1b). After polymerization for 4 hours, 30 g of a dry polymer having the following catalyst residues, ie, Ti = 12 ppm, Mg = 348 ppm and Cl = 700 ppm, were obtained, and the yield was 83,200 g of polypropylene per Tig., With boiling heptane. After extraction, the residue amounted to 94.5%. Intrinsic viscosity was 1.9 dl / g.

Example 12

a) preparation of catalyst components

Except for extracting EtOH from the reaction mixture, 8.1 g (200 mmol) of MgO were reacted under the same conditions as in Example 6a).

b) polymerization of propylene in a solvent

5 ml of the catalyst component suspension prepared in Example 12a) in heptane was polymerized under the same polymerization test conditions as in Example 1b) except the temperature was raised to 70 ° C. At the end of the reaction, 193 g of dry polymer was obtained, which contained the following catalyst residues: Ti = 13.2ppm, Mg = 908ppm, Cl = 1.075ppm, the yield was 75,757g polypropylene per gram Ti. The residue extracted with heptane corresponded to 91.5%. The polymer exhibited the following properties. Intrinsic viscosity = 2.2 dl / g, apparent density = 0.46 kg / l.

Example 13

a) preparation of catalyst components

Composite MgCl ₂ calcined at 400 ° C. for 1 hour. A microspherical support (20-70 microns) of 1.237H ₂ O (H ₂ ) 18.8% was used.

10.2 g of the calcined product in a 250 ml flask equipped with a stirrer was treated with a solution of 4.6 g (100 mmol) of ethanol diluted with 50 ml of heptane for 1 hour at 0 ° C., followed by 3 g of ethylbenzoate ( 20 mmol) was added and the temperature was raised to 60 ° C. and maintained for 1 hour. After continuously introducing 154 mL (1.4 mol) of TiCl ₄ , the temperature was raised to 110 ° C. and maintained for 2 hours. The solids were then decanted and the TiCl ₄ solution was removed with by-products dissolved by siphoning at 110 ° C.

b) polymerization of propene in hexane (solvent)

0.6 ml of the suspension of the catalyst component in heptane prepared in Example 13a) was polymerized under the polymerization test conditions of Example 1b). After polymerization for 4 hours, 433 g of dry polymer were obtained, which contained the following catalyst residues: Ti = 4.4 ppm, Mg = 66 ppm, Cl = 150 ppm, the yield being 227,000 g of polypropylene per g g. It was. The residue was 90.5% after extraction with boiling heptane.

Example 14

a) preparation of catalyst components

95.3 g (1 mol) of anhydrous MgCl _{2 and} 40.3 g (1 mol) of MgO (chemically pure) were introduced into a 1 L vibrating ball mill.

The mixture was ground together for 30 hours and then released from the mill. 13.56 g (MgCl ₂ 9.53 g + MgO 4.04 g) of the mixture was reacted at 60 ° C. for 2 hours with a solution of 3 g (20 mmol) of ethylbenzoate and 9.22 g of EtOH diluted in 100 ml of n-hexane in a 250 ml flask. . The solvent was evaporated from the suspension at room temperature under slightly reduced pressure (residual pressure of 40 Torr), and 25.43 g of a solid was obtained at the end of the reaction. This was placed in a 500 ml jacketed reactor filled with magnetic filtration sections at the bottom, 181 ml (1.65 mmol) of TiCl ₄ was introduced thereto, the mixture was contacted at 110 ° C. for 2 hours, and the suspension was diluted with 45 ml of heptane. The solids were separated by filtration at 110 ° C. The catalyst component was washed with heptane four times at 80 ° C. and three times at room temperature (using 200 ml of heptane each time).

b) Polymerization of propylene in hexane (solvent)

0.6 ml of the suspension of the catalyst component prepared according to Example 14a) was polymerized under the intermediate test conditions of Example 1b).

After polymerization for 2.5 hours, 432 g of dry polymer were obtained.

It contained the following catalyst residues Ti = 4.5ppm, Mg = 25ppm, Cl = 105ppm and the yield was 222,000g polypropylene per Tig. The solid residue extracted with boiling heptane corresponded to 89% by weight.

Example 15

a) preparation of catalyst components

Synthetic hydrotalcite of Structural Formula Mg ₆ Al ₂ CO ₃ (OH) ₁₆ 4H ₂ O (manufactured by Kyowa Chemical Co., Ltd.) calcined in dry air at 450 ° C. for 24 hours was used. 11.5 g of the product (6MgO.Al ₂ O ₃ ) obtained by calcination of the hydrotalcite was refreshed and suspended in a solution of 4.2 g (28 mmol) of ethylbenzoate and 12.9 g of EtOH diluted with 50 ml of heptane. The suspension in a 500 ml jacketed reactor filled with filtered sections was heated at 60 ° C. for 2 hours and then 181 ml (1.65 mmol) TiCl ₄ was introduced into the reactor at a constant temperature. The temperature was then rapidly raised to 110 ° C. by simultaneously supplying HCl gas to the reaction mixture for 2 hours at a rate of 1 mole per hour. After the HCl feed was stopped, the mixture was distilled off by introducing 45 ml of heptane, which was then filtered at 110 ° C. and the solid phase separated from the product soluble in TiCl ₄ . After diluting the reaction product with 45 ml of heptane, it was washed four times at 80 ° C. and three times at room temperature to remove all traces of free TiCl ₄ .

b) Polymerization of propylene in hexane (solvent)

2 ml of suspension in heptane of the catalyst component prepared as described in Example 15a) was polymerized under the same polymerization test conditions as described in Example 1b). After 4 hours of polymerization, 243 g of dry polymer were obtained, which contained the following catalyst residues: Ti = 13ppm, Mg = 133ppm, Cl = 222ppm, the yield being 77,000g of polypropylene per Tig. The solid residue extracted with boiling heptane was 88%.

Example 16

a) preparation of catalyst components

Microspherical complex MgCl ₂ .1.24H ₂ O (20-70 μ) was calcined at 525 ° C. for 3 hours. The product showed the following composition: Mg = 51.35 g / 100 g, Cl = 17.15 g / 100 g. The atomic ratio of Cl: Mg was 0.22g. In a 250 ml flask, 11 g of the product obtained by calcining MgCl ₂ .1.24H ₂ O was diluted with a solution of 2.74 g (18.25 mmol) of ethylbenzoate and 8.4 g (182 mmol) of EtOH diluted with 90 mL of hexane. The reaction was carried out for a time. After evaporating the solvent at 20 ° C. under reduced pressure (residual partial pressure 40 Torr), 21.35 g of solids were weighed and placed in a 500 ml reactor described in Example 16a, and 167 ml (1.52 mol) of TiCl ₄ and 2 at 110 ° C. The reaction was carried out for a time. After separating the solid from the TiCl ₄ solution containing the solution of the reaction byproduct, 42 ml of heptane were introduced, which was then filtered at 110 ° C.

b) Polymerization of propylene in hexane (solvent)

1 ml of the catalyst component suspension prepared in Example 16a) was polymerized under the test conditions described in Example 1b). After polymerization for 4 hours, 336 g of dry polymer were obtained, which contained the following catalyst residues: Ti = 4.3ppm, Mg = 62ppm, Cl = 122ppm, the yield was 232,000g polypropylene per Tig., The residue extracted with boiling heptane was 90.5%.

This polymer had the following properties.

Intrinsic viscosity 2.1dl / g Melt-flow rate 3.7g / 10。 Flexural strength 12.930kg / cm ² Apparent density 0.38kg / ι

Example 17

a) preparation of catalyst components

57.7 g of the composite MgCl ₂ ㆍ 1.24H ₂ O was introduced into the oil phase reactor, and a nitrogen stream humidified at 20 ° C. was introduced at a rate of 200 L per hour (linear rate = 4.4 cm / sec), followed by 6.5 hours at 220 ° C. for 270 hours. It was heated for 1 hour at < RTI ID = 0.0 > C < / RTI > The product recovered 36.3 g and was subjected to chemical analysis to confirm the following composition.

Mg = 28.85g / 100g, Cl = 48.05g / 100g, OH = 23.25g / 100g.

30 g of the product were mixed together with 33.6 g (353 mmol) of anhydrous MgCl ₂ under a 1 L vibrating ball for 60 hours. 17.3 g of the mixture obtained after mixing (MgCl ₂ + MgClOH) was placed in a 250 mL flask, and a solution of 9.2 g (200 mmol) of EtOH diluted with 6 g (40 mmol) of ethylbenzoate and 100 mL of n-hexane was added at 60 ° C. Processed for hours. The solvent was then evaporated under vacuum at 25 ° C. (40 Torr residual pressure).

32 g of solids were recovered and then introduced into a 500 mL reactor filled with filtration fragments at the bottom, followed by the rapid dropwise addition of 164 mL of TiCl ₄ , which was diluted at 110 ° C. The resulting solids were diluted with 41 ml of heptane and filtered and washed four times (150 ml each time) at heptane and three times at room temperature.

b) combination of products in a solvent

0.75 ml of the catalyst component C ₇ ⁺ suspension prepared in Example 17a) was used to polymerize under the same polymerization test conditions as in Example 1b), but the temperature was unexpectedly raised to 70 ° C. After polymerization for 4 hours, 298 g of dry polymer were obtained, which contained the following catalyst residuals: Ti = 5.5 ppm, Mg = 43 ppm, Cl = 185 ppm. The yield was 181,500 g of polypropylene per Tig. And the residue extracted with boiling heptane was 93.5%.

Claims (1)

A halogenated Ti compound (a) selected from the group consisting of Ti tetrahalide and Ti halo alcoholate; MgO, Mg, Al or Si mixed oxides, Mg hydroxide, Mg hydroxychloride or bromide, Mg nitrate, Mg phosphate, Mg silicate, Mg carboxylate and dehydration of Mg halide hydrated under hydrolysis conditions A component containing an adduct (B) of an oxygenated Mg compound (A) selected from the group consisting of the product and an decomposition product of an adduct containing Mg dihalide and at least one hydrocarbyl electron donating compound or Mg dihalide ( b ₁ ) or the above-mentioned oxygenated Mg compound (A) and a hydrocarbyl electron donating compound (component ED) containing no active hydrogen atom or an electron donating compound containing an active hydrogen atom and a mixture thereof (component HED) Solid supports containing essential components such as component (b ₂ ) obtained by the reaction or mixtures thereof; And at least the component ED present in the catalyst component in a form that cannot be extracted with TiCl ₄ at 80 ° C. when the component ED or derivative thereof is not used to prepare the support (b) is present after treatment at 80 ° C. A catalyst component for an olefin polymer, characterized in that it contains a product obtained by reacting in a reaction system containing component ED in the range of 0.05 to 5 moles per mole.