KR800001328B1 - High efficiency high temperature catalyst for polymerizing olefins - Google Patents

Abstract

Catalysts for soln. polymn. of olefins, sufficiently active at>140≰C that catalyst residues need not be removed from the polymers, were prepd. by reaction of transition metal compds. with organomagnesium compds. or their hydrocarbon-sol. complexes with organometallic compds. and R'X(R' = H or alky1 at least as active as sec-Bu, X = halogen), with Mg- transition metal at. ratio 20-2000: 1, X- transition metal at. ratio 40-2000: 1, and Mg-X at. ratio 0.1- 1: 1.

Description

High Efficiency High Temperature Catalyst Composition for Olefin Polymerization

The present invention relates to a polymerization catalyst, and even when the solution polymerization temperature is 140 ° C or higher, it is possible to sufficiently increase the amount of polymer produced per unit of the catalyst while eliminating the need for removing the catalyst residue in order to obtain a desired purity polymer. It is to provide a novel polymerization catalyst composition.

One object of the present invention,

A. Transition Metal Compound (TM);

B. (1) organic magnesium compounds or

(2) complexes with organometallic compounds in an amount sufficient to dissolve organic magnesium compounds in organic magnesium compounds and hydrocarbons,

C. Nonmetallic Halides Represented by General Formula R´X

Wherein X is hydrogen and R 'is hydrogen or an organic group of at least sec-butyl active groups, wherein the atomic ratio of Mg: TM is in the range of 20: 1 to 2,000: 1 It is intended to provide a catalytic reaction product in which the atomic ratio of TM is in the range of 40: 1 to 2,000: 1 and the atomic ratio of Mg: X is in the range of 0.1: 1 to 1: 1.

It is another object of the present invention to provide a method for achieving α-olefin polymerization under the specific conditions of Ziegler polymerization using the reaction product as a homocatalyst as described above.

Conventional Ziegler catalysts have reduced activity when the polymerization temperature is higher than 140 ° C. The novel catalyst reaction products according to the present invention are capable of weight per part of the transition metal even at a polymerization temperature of more than 150 ° C, for example, 185 ° C to 220 ° C or more. It is an object of the present invention to provide a high efficiency catalyst capable of producing an olefin polymer corresponding to 1 part by weight or more.

Therefore, the amount of catalyst contained in the olefin polymer produced by such a surprisingly high efficiency catalyst according to the present invention is generally less than the amount of residual catalyst contained after the catalyst is removed in the presence of a conventional total solvent.

Moreover, the catalytic reaction product according to the present invention can obtain a more homogeneous product because the control of the polymer is highly possible. And as an additional advantage, the polymers produced according to the invention are usually very narrow in their molecular weight distribution and thus are of great use in molding applications such as spraying, coating and rotary applications.

In the polymerization zone containing an inert dilution and the above-mentioned reaction product in the presence of hydrogen as a molecular weight controlling agent, the present invention can be carried out in a polymerization step of polymerizing α-olefins, which provides particularly great benefits. will be. Such a polymerization process can be carried out most advantageously under a low atmospheric pressure, with a relatively low temperature and a low pressure—very high pressure can also be applied.

Examples of such olefins which are suitably polymerized or copolymerized according to the process of the present invention include aliphatic α-monoolefins having generally 2 to 8 carbon atoms such as ethylene, furyrene, butene-1, pentene-1,3- Methylbutene-1, hexene-1, octene-1, didecene-1 and octadecene-1.

Such α-olefins may be a small amount of other (eg, buty-diene, isoprene, pentadiene-1,3, styrene, α-methylstyrene, etc.) within 10 weight percent of other α-olefins and / or polymers. Ethylene-unsaturated monomers of) and similar to them can be copolymerized with other ethylenically unsaturated monomers that do not destroy conventional Ziegler catalysts. However, among the aliphatic α-monoolefins, the present invention is particularly advantageous in the copolymerization of ethylene with higher-quality pseudo-α-olefins, especially from 0.1 to 5 percent by weight of pyropyrene, butene-1 or shear monomers. Gives.

Such a novel catalyst composition according to the present invention is a reaction product as described below. In other words,

A. Transition metals belonging to Groups 4b, 5b, 6b, 7b and 8 of Mendeleev's Periodic Table of the Handbook of Chemistry and Physics, published by Low Chemical Lever Co., Ltd. (48) And "

B. the intermediate reaction product of

a. A hydrocarbon-soluble complex of a hydrocarbon-soluble organic magnesium compound or an organic magnesium compound and an organometallic compound represented by the general formula Mry. Wherein M is a metal of the Periodic Tables 2b, 3a (including boron), 1a, and 4a (including silicon), and R is a monovalent hydrocarbon group, i.e., alkyl, cycloalkyl, alkenyl, aryl, Hydrocarbyl or other monovalent organic groups such as arylalkyl and alkylaryl, such as alkoxy, allyloxy and alkoxyalkyl, Y being the number corresponding to the valence of M)

b. Active nonmetal halides represented by the general formula R'X. (Wherein R 'is hydrogen or hydrocarbyl such as alkyl and aryl such as at least sec-butyl active, and X is halogen, preferably chloride, sucrose or oxide).

As described above, the half-organic shares of the catalyst sphere components, R and R ', may be any of organic groups, but they should not contain functional grains that damage the conventional Ziegler catalyst. That is, such a half organic portion preferably contains no hydrogen as active as possible to react with Zerewitinoff reagent. Such a catalyst composition has a Mg: TM of 30: 1 to 60: 1, Mg: X of 0.2: 1 to 0.7: 1, preferably 0.4: 1 to 0.6: 1, and an X: TM of 50: 1 to 400: 1. Preferably they have an atomic ratio in the range of 60: 1 to 120: 1.

Among the suitable transition metal compounds, titanium, vanadium, zirconium, etc. are more advantageous for application, and titanium is most advantageous among them. Beneficial compounds include halides, oxyhalides, alkoholates, amides, acetylacetonates, alkyls, allyls, alkenyls, and alcadienyls, with the most beneficial of the titanium alcoholates, the so-called titanates.

Among the titanates, alkoxides or aryl oxides, especially alkoxides having 1 to 12 carbon atoms, or phenoxides of trivalent or tetravalent titanium, are preferable. Such titanates have one or more hydrogen atoms alkoxy. Or from an halide of trivalent or tetravalent titanium, including an alkyltitanium halide substituted with an aryloxy group. Preferred titanates include tetrabutoxytitanium, tetra (isopuroxy) titanium, diethoxytitanium embrittlement, dibutoxytitanium dichloride, n-butyltriisopuropoxytitanium, ethyldibutoxytitanium chloride, monoethoxytitanium trichloride and Tetraphenoxytitanium and the like. Of these preferred titanates, it is most preferred that all of the hydrogen atoms are tetravalent substituted with alkoxides, and tetra (isopuroxy) titanium and tetrabutoxytitanium are particularly preferred.

Examples of the transition metal compound which are advantageous for the present invention in addition to the above are vaginal compounds such as titanium tetrachloride, titanium trichloride, vanadium tetrachloride, vanadium oxychloride, zilkenium tetrachloride, titanocenedichloride, and tetrabutoxyzilkenium. Cornium tetraalcoholate and vanadium acetylacetonate.

Preferred organomagnesium complexes for use in the present invention are hydrocarbon soluble complexes represented by the general formula MgR ₂ .XMRY, wherein R is hydrocarbyl, M is aluminum, zinc or mixtures thereof, and X is from 0.001 to 10 In particular 0.15 to 2.5 and Y represents the number of hydrocarbyl groupings compatible with the valence of M. This composite is made by reacting granular magnesium such as magnesium powder or magnesium powder with the stoichiometry of a hydrocarbon halide represented by RX. As a result, the hydrocarbon insoluble MgR ₂ is solubilized by adding an organometal such as AlR ₃ or a mixture of ZnR ₂ with it. In order to solubilize the MgR _2, if you want to apply a mixture of AlR ₃ and ZnR ₂ is the atomic ratio of Zn vs. Al 3,000: When 1, preferably 350:: O ₂ .01 in 1 gives a 1: 1: 1. The amount of the organic magnesium organometallic compound is added to the MgR ₂ to form a complex, more or less amount of MgR _2, that is at least 50 percent by weight of MgR ₂ to yiraya positive enough hwahal soluble to at least 5 weight percent of a MgR ₂ It is more preferable to solubilize, and it is best to solubilize the entire amount of MgR ₂ .

When the polymerization temperature exceeds 180 ° C., in order to obtain the highest efficiency of the catalyst, it is desirable to reduce the total amount of catalyst as well as the amount of aluminum in the complex. In the catalyst system using aluminum, the atomic ratio of Al: TM is 120: 1 or less, preferably 40: 1 or less. Therefore, for such a catalyst, the atomic ratio of Mg: Al is preferably 0.3: 1 or more, preferably 0.5: 1 to 10: 1 or more. In a suitable complex, a suitable ring of organometallic compounds (other than AlR ₃ , ZnR _2, or mixtures thereof) that solubilize the organomagnesium compound to hydrocarbons, and generally the atomic ratio of metal to magnesium of the organometallic compound at 0.01: 1 Use an amount of 10: 1. Such other organometallic compounds include boron trialkyls such as boron triethyl and alkylsilanes such as dimethyl siltan and tetraethylsilane.

It is also advantageous to use an organic magnesium compound as the organic magnesium quotient in place of the above hydrocarbon soluble complex. Such compounds are insoluble in conventional hydrocarbons, but can be suitably used by making them soluble in hydrocarbons by known methods in the art. When such organic magnesium compounds are used as an organic magnesium share, hydrocarbon-soluble organic compounds do not contain catalytic toxicity. Magnesium compounds are most preferred.

The organomagnesium compound is preferably dihydrocarbyl magnesium such as magnesium magnesium dialkyl and magnesium diaryl. Representative examples of suitable magnesium dialkyls include dibutylmagnesium, difurofilmagnesium, diethylmagnesium, dihexylmagnesium, furophilmagnesium and other alkyls having from 1 to 20 carbon atoms. Representative examples include diphenylmagnesium, dibenzylmagnesium, and dialkylmagnesiums such as ditorylmagnesium and dibutylmagnesium, with dialkyl magnesium being most preferred. Suitable organomagnesium compounds include alkyl and arylmagnesium alkoxides and aryloxides, and aryl and alkyl magnesium halides, with halogen free magnesium compounds being more preferred.

In the case where the organomagnesium quotient does not contain aluminum, it is highly necessary to include an alkyl aluminum compound such as trialkyl aluminum, or an alkyl aluminum halide or aluminum halide in a small proportion as described above. Since active trialkyl aluminum or dialkyl aluminum halide can be used, it is often preferable.

The active nonmetal halides represented by the above general formula include hydrogen halides and active organic halides such as t-alkyl halides, allyl halides, and benzyl halides, and others in which hydrocarbyl is a monovalent hydrocarbon group. Active hydrocarbyl halides and the like. Herein, the active organic halide refers to a hydrocarbyl halide containing an unstable halogen having an activity of easily changing to another compound, such as a halogen of sec-butyl chloride, preferably t-butyl chloride.

In addition to such organic monohalides, organic dihalides, trihalides, and polyvalent halides having the above-mentioned activities can also be used.

Examples of such active halides include hydrogen chloride, hydrogen embrittlement, t-butyl chloride, embrittlement t-amyl, allyl chloride, benzyl chloride, crotyl chloride, methylvinylcarvinyl chloride, α-phenylethyl sulfide and diphenylmethyl chloride. Preferred examples include hydrogen chloride, t-butyl chloride, allyl chloride and benzyl chloride.

The halide, which reacts the organomagnesium quotient with the active nonmetal halide in the hydrocarbon, is reacted by adding to the organomagnesium sorbent containing the hydrocarbon with stirring. Alternatively, the desired amount of intermediate reaction product can be formed by mixing the organomagnesium fraction with stirring and regulating the active halide to the active halide or by adding the halide and organomagnesium mixture simultaneously for some time. This reaction between the organomagnesium quotient and the active halide results in the formation of a finely divided insoluble material, which in addition to the soluble share has a hydrocarbon insoluble share. The amount of halides to be added to the organomagnesium quotient should be such that the atom ratio of Mg: X can be immediately determined. However, the amount of halides in the presence of aluminum or when used in the composition of the catalytic reaction product should not be sufficient to produce a monoalkylaluminum dihydride or similar catalyst releasing agent in a problematic amount. .

The intermediate reaction product is then mixed with the transition metal, preferably adding the transition metal to the intermediate reaction product to obtain a catalytic reaction product having an atomic ratio of X: TM and Mg: TM in the range specified above. .

Although the method described above is particularly preferred for obtaining the catalytic reaction product according to the present invention, on the other hand, by first mixing the active nonmetal halides with the transition metal compound to form their intermediate reaction biomolecules, the double hepatic product is then organic magnesium By reacting with the complex, a useful catalysis product can be prepared. In addition, although these methods are not preferable, there is also a method of preparing a catalytic reaction product by first mixing an organic magnesium complex with a transition metal compound and then adding an active ratio metal halide or adding and mixing all three components at the same time.

It is preferable to perform the above-mentioned process for producing the catalyzed product in the presence of an inert diluent. The concentration of the catalyst component is preferably in the case where the active nonmetal halide and the magnesium complex are combined, and the resultant needle-like product is 0.005 to 0.1 molta (mol / liter) relative to magnesium. Suitable examples of inert organic diluents include liquefied ethane, furophene, isobutane, n-butane, n-hexane, various isohexanes, isooctane, paraffin mixtures of alkanes having 8 to 9 carbon atoms, cyclohexane and methylsipillo Consists of saturated or aromatic hydrocarbons such as fen, tandimethylcyclohexane, dodecane, kerosene and gasoline, and especially industrial solvents having a boiling point in the range of -50 ° to 200 ° C., removing olefin compounds and other impurities. Benzene, toluene, ethylbenzene, cumene, decalin and the like can also be used as appropriate inert diluents.

Mixing of the catalyst sphere components to obtain the desired catalytic reaction product proceeds advantageously within a temperature range of -50 to 150 ° C, preferably 0 to 50 ° C, under a floating atmospheric pressure such as nitrogen, argon or other inert gas. The mixing period is usually not a big problem since the catalyst composition is sufficiently made within 1 minute. In the production of the catalysis product according to the present invention, it is not necessary to separate the hydrocarbon soluble share from the hydrocarbon non-soluble share of the reaction product. Furthermore, it is not necessary to add a cocatalyst or a starting agent such as an alkylaluminum compound to the catalyst reaction product in order to obtain a high efficiency catalyst, and in fact, any aluminum compound may be used to obtain the efficiency of the high catalyst at a high polymerization temperature. It is generally undesirable to add in excess of the amount defined above.

In the polymerization step using the catalytic reaction product described above, the polymerization is accomplished by adding the catalyst amount of the catalyst composition to the polymerization zone containing the α-olefin monomer or adding in the reverse order. The polymerization zone is maintained over a holding time of 10 minutes to several hours, preferably 15 minutes to 1 hour, in the range of 0 to 300 ° C., preferably in the melting polymerization temperature, that is, in the range of 150 ° to 250 ° C. In general, this polymerization is preferably carried out in the absence of moisture or oxygen, and the catalytic amount of the catalytic reaction product generally causes the transition metal per liter of dilution to be within the range of 0.0001 to 0.01 ml of atoms, temperature, pressure, solvent and The maximum catalyst yield can be obtained by assigning the most advantageous catalyst concentration depending on the polymerization conditions such as the presence of catalyst toxicity. Generally, in such a polymerization process, a carrier is applied, but the carrier may be an inert organic diluent or a solvent or excess monomer.

In order to sufficiently obtain the benefits of the high efficiency catalyst according to the present invention, care should be taken so that the solvent does not become supersaturated in the polymer. If such supersaturation is likely to occur before the catalyst is emptied, the full efficiency of the catalyst cannot be helped. Best results are obtained when the amount of polymer in the carrier does not exceed 50 weight percent of the total weight of the reaction mixture.

The pressure to be applied to the polymerization process may be a relatively low pressure, that is, 100 to 500 psig (70 to 350 kg / sqcm gauge). However, polymerization within the scope of the present invention can be achieved from atmospheric pressure within the range of pressures allowed by the capacity of the polymerization apparatus. It is desirable to stir the polymerization prescription to give better temperature control during the polymerization period and to maintain homogenization of the polymerization mixture throughout the polymerization zone.

In order to improve the catalyst yield in the polymerization of ethylene, it is preferable to maintain the ethylene concentration in the solvent at 1 to 10% by weight, most preferably at 1,2 to 2% by weight. To achieve this, if ethylene is supplied in excess, one part of ethylene must be withdrawn.

In the practice of the present invention, hydrogen is often used to lower the molecular weight of the resultant polymer. Such hydrogen is advantageous for the purposes of the present invention at concentrations ranging from 0.001 to 1 mole per mole of monomer. It has been found that macrohydrogens in this range generally produce polymers of low molecular weight. Hydrogen may be added to the polymerization bath together with the monomer stream, or hydrogen may be added before, during or after addition of the monomer to the polymerization bath, which must be done during or before addition of the catalyst.

The monomer or mixture of monomers is brought into contact with the catalysis product by conventional methods. Preferably, the catalysis product and the monomer are well mixed by stirring by a suitable stirring device or other means. Such stirring may be performed continuously during the polymerization period, and in some cases, the stirring may be stopped during the polymerization period. In the case of rapid reactions with more active catalysts, if a solvent is present and therefore the heat of reaction must be removed, a device for refluxing the monomers and solvents should be provided. In any case, suitable arrangements should be provided to eliminate the salts of polymerization. If necessary, the monomer is brought into contact with the catalytic reaction product in a gaseous phase. Such contact may be absent even in the presence of a liquid substance. In addition, the polymerization can be carried out in a dilute manner, for example, by passing the reaction mixture through a long reaction tube in external contact with the enemy's cooling medium, or by passing the reaction mixture into an equilibrium flow reactor or a mixture thereof. It may be carried out continuously by passing a series of devices.

The polymer is easily leached from the intermediate mixture by removing the solvent when unreacted monomer and solvent are used, and no more impurities need to be removed. As such, the present invention is of great significance in that it eliminates the cumbersome procedure of removing catalyst residues. However, of course, it is sometimes desirable to add a small amount of catalyst deactivation reagent. In any case, it was found that the polymer did not contain problematic amounts of catalyst residue and also had an extremely narrow molecular weight distribution.

In order to further clarify the benefits of the present invention as described above, some examples are described below, all parts and percentages being by weight unless otherwise specified.

(탄소원자 8∼9개를 갖는 포화 이소파라핀의 혼합물)에 이한 희석용액으로 적용한다. 중합반응은 5리터 스텐레스 스틸교반회분 반응기로 별도 명시하지 않는한 150℃로 시행한다.In the following examples, the catalyst is carried out without the presence of oxygen or water in the filling of nitrogen, and the catalyst composition is n-hexane or lsopar E.

(A mixture of saturated isoparaffins having 8 to 9 carbon atoms) is applied with the following dilution solution. The polymerization is carried out at 150 ° C unless stated otherwise in a 5 liter stainless steel stirred batch reactor.

를 반응기에 가하여 150℃로 가열한다. 반응기에는 수소공급관이 마련되어 이를 통한 약 25psig(1.75kg/sg.cm게이지) 및 15내지 20psi(1.05 내지 1.4kg/sg.cm)의 수소첨가에 의하여 중합분자 중량제어를 한다. 이어 120psi(8.4kg/sg.cm)의 에틸렌을 반응기에 첨가하고, 에틸렌압을 조절하여 반응기 압력을 155내지 165psig (10.9내지 11.6kg/sgcm)로 유지해준다. 이제 질소를 사용하여 촉매를 압력하에 반응기로 주입하고, 반응기 온도를 소망의 중합시간동안 유지해 나간다. 그 후 중합반응기 내용물을 스텐레스스틸비커에 넣어 냉각시킨다. 이 결과 니상물을 여과하여 중합체를 건조하여 무게 측정을 한다. 중합과정의 에틸렌소모량을 DP조(槽)로 기록하여 중합율과 생성중합체량을 나타낸다. 촉매효율은 티타늄의 그램당의 폴리에틸렌촉매의 그램수, 즉 g.PE/g. Tc로 표시한다.2 liters of oxygen glass dry isopa E in this polymerization reaction

Is added to the reactor and heated to 150 ° C. The reactor is provided with a hydrogen supply pipe to control the weight of the polymer molecules by hydrogenation of about 25 psig (1.75 kg / sg.cm gauge) and 15 to 20 psig (1.05 to 1.4 kg / sg.cm). 120 psi (8.4 kg / sg.cm) of ethylene was then added to the reactor and the ethylene pressure was adjusted to maintain the reactor pressure at 155 to 165 psig (10.9 to 11.6 kg / sgcm). The catalyst is now injected into the reactor under pressure using nitrogen and the reactor temperature is maintained for the desired polymerization time. Thereafter, the contents of the polymerization reactor are placed in a stainless steel beaker and cooled. As a result, the needle-like material is filtered, the polymer is dried, and weighed. The amount of ethylene consumed in the polymerization process is recorded in a DP bath to indicate the polymerization rate and the amount of produced polymer. The catalytic efficiency is the number of grams of polyethylene catalyst per gram of titanium, ie g.PE/g. It is represented by Tc.

Example 1

중에 15ml의 0.123M 무수염화수소 용액에 교반과 더불어 0.946ml의 0.519M디(n-부틸)마그네슘. 2트리에틸 알루미늄을 첨가함으로서 촉매를 마련한다. 이에 마그네슘 복합체를 첨가하는 즉시 백색침전물이 생기는데, 이니상물(泥狀物)에 1.18ml의 0.01M 테트라(이소푸로폭시)티타늄과 82.9ml의 이소파 E

를 첨가한다. 이 촉매의 12.7ml몫(Ti 0.0015몫)를 중합반응기에 넣고 온도를 167℃로 올려준다. 30분 후에, 230g의 선상(線狀)폴리에틸렌이 형성되는데 여기에 있어서의 촉매효율은 3.2×10⁶g.PE/g.Ti로 나타났다.LsoparE

0.946 ml of 0.519 M di (n-butyl) magnesium with stirring in 15 ml of 0.123 M anhydrous hydrogen chloride solution. A catalyst is prepared by adding 2triethyl aluminum. As soon as the magnesium complex is added, a white precipitate is formed, which is 1.18 ml of 0.01M tetra (isopuroxy) titanium and 82.9ml of isopa E in the insulator.

Add. 12.7 ml (Ti 0.0015 lots) of this catalyst was added to a polymerization reactor and the temperature was raised to 167 ° C. After 30 minutes, 230 g of linear polyethylene was formed, with a catalyst efficiency of 3.2 × 10 ⁶ g.PE/g.Ti.

Example 2

와 2.5ml의 1.15 Mt-부틸클로라이드와, 3.05ml의 0.295M 디(n-부틸)마그네슘·2트리에틸알루미늄을 첨가하여 촉매를 마련하고, 그 결과 니상물에 1.5ml의 0.01M 테트라(이소푸로폭시)티타늄을 첨가한다. 이 촉매의 10ml(Ti 0.0015m몰 해당)를 중합반응기에 가하고 30분 후에 반응기 내용물을 쏟아낸다.93 ml of isopa E in a 4 oz bottle

And 2.5 ml of 1.15 Mt-butyl chloride and 3.05 ml of 0.295 M di (n-butyl) magnesium-2triethylaluminum were added to prepare a catalyst. As a result, 1.5 ml of 0.01 M tetra (isopuro) was added to the needle-like product. Foxy) Titanium is added. 10 ml of this catalyst (corresponding to 0.0015 mmol of Ti) were added to the polymerization reactor and after 30 minutes the contents of the reactor were poured out.

The yield of the polymer was 204 g and the catalytic efficiency in this case was 2.8 × 10 ⁶ g.PE/g.Ti.

Example 3

를에 133중량부의 0.516M 디(n-부틸) 마그네슘·2알루미늄 트리에틸복합체를 첨한다. 이 복합체의 용액에 11.75중량부의 염화수소 까스를 교반과 함께 첨가해주고, 이 결과 니상물을 주의온도(∼25℃)에서 냉각하고, 322ml의 순수테트라(이소푸로폭시)티타늄을 첨가한다. 이 결과 촉매를 이소파로 히석하여 촉매전량을 500중량부로 만든 다음 이 촉매를, 40,000 중량부/시간의 에틸렌과 Isopar E

를 함께하여 6900갈론 (26입방미터)의 반응기에 연속적으로 공급한다. 이 촉매량과 Isopar E

의 양을 변동해가면서 반응기 온도를 최소한 185℃로 유지시켜준다. 그리고, 수소를 반응기에 첨가함으로서, 중합체의 분자량을 제어하여 중합체의 용융지수(溶融指數)를 ASTM D-1238-65 T (조건 E)에 의한 2.5내지 12데시-드램/분 되게 한다. 본 실시예의 중합의 경우 촉매효율은 1×10⁶g.PE/g.Ti이상이었다.247 parts by weight of isopa E

To 133 parts by weight of 0.516 M di (n-butyl) magnesium-2 aluminum triethyl complex is added. 11.75 parts by weight of hydrogen chloride cutlet is added to the solution of the complex with stirring. As a result, the needle-like product is cooled at an ambient temperature (˜25 ° C.), and 322 ml of pure tetra (isopuroxy) titanium is added. This resulted in dilution of the catalyst with isopha to make the total catalyst 500 parts by weight, and then the catalyst, 40,000 parts by weight of ethylene and Isopar E.

Together to feed continuously 6900 gallons (26 cubic meters) of reactor. This catalytic amount and Isopar E

The reactor temperature is maintained at least 185 ° C with varying amounts of. And, by adding hydrogen to the reactor, the molecular weight of the polymer is controlled so that the melt index of the polymer is 2.5-12 dec-dram / min according to ASTM D-1238-65 T (Condition E). In the case of the polymerization of the present example, the catalyst efficiency was 1 × 10 ⁶ g.PE/g.Ti or more.

Example 4

In order to confirm the remarkable stability under the high temperature of the novel catalyst according to the present invention, only three different tests were carried out on catalysts which differ only in the source of the halide and the concentration of aluminum.

The catalyst according to the present invention was prepared in 30.16 kg of Isopar E. with the following components.

※ Di (n-butyl) magnesium, 2 aluminum triethyl

The atomic ratio of the resulting catalyst is as follows.

Cl / Mg / Al / Ti = 90 / 31.5 / 59.5 / 1

General polymerization procedure was carried out with the above catalysts under a stirring condition of 250 cal. (945 liters), but without a polymerization temperature of 184 ° C. In this case, the catalyst had a catalyst efficiency of 1.07 × 10 ⁶ g.PE/g Gave .Ti

에 다음의 구성분으로 촉매를 마련하였다.Isopar E weighs 25.54 kg for comparison purposes

The catalyst was prepared in the following components.

※ Di (n-butyl) magnesium, 2 aluminum triethyl

The atomic ratio of the resulting catalyst is as follows.

Cl / Mg / Al / Ti = 134/40/147/1

With this catalyst, the general polymerization procedure as described above was carried out, but the polymerization temperature was only 150 ° C and 170 ° C. The results of these two tests resulted in 1 × 16 ⁶ g.PE/g.Tidhk 0.43 × 10 ⁶ g.PE/g.Ti. In the same test with the polymerization temperature of 185 ° C, polyethylene was not formed in measurable amounts.

Example 5

In order to determine the preferred order of addition of the components in the preparation of the catalyst was tested three times by changing the order of addition of the catalyst sphere components under the same conditions as described above, the configuration of the test target catalyst was as follows.

※ Di (n-butyl) magnesium, 2 aluminum triethyl

The atomic ratio of the above-mentioned components is as follows.

Cl / Mg / Al / Ti = 130/40/80/1

The polymerization was carried out according to the procedure of Example 4 with 150 ° C as the polymerization temperature, and the results are shown in the following first table.

[Table 1]

(1) Added to catalysis in the order from left to right.

중의 HCl에 첨가했음.Number of Tests The mixture of DBMg 2ATE * + Tr (OiPr) ₄ in Isopar E

To HCl in water.

(2) Catalyst efficiency is expressed in grams of polyethylene per gram of titanium

※ Di (n-butyl) magnesium, 2 aluminum triethyl

Example 6

중의 하기의 촉매구성분의 비율을 달리하여 몇차례 시험을 하였다.Isopar E for the correlation of Al: Ti and Al: Mg ratio and the change of catalyst efficiency according to the temperature rise

The test was conducted several times by varying the proportion of the following catalyst sphere components in the mixture.

Anhydrous HCl

DBMg ・ ATE ※

Tetra (isopropoxy) titanium

* Di (n-butyl) magnesium X aluminum triethyl where X is a value between 1/6 and 2 obtained by the combination of the amounts of DBMg 1 / 6ATE and DBMg 2ATE.

Ethylene was polymerized according to the polymerization procedure of Example 4 in the presence of various catalysts having different atomic ratios and polymerization temperatures of the catalyst sphere components, and the results are shown in Table 2.

[Table 2]

As apparent from the data of Examples 4 and 2, the atomic ratio of Al: Mg and Al: Ti may be reduced as the polymerization temperature is increased to obtain high catalytic efficiency.

Claims (1)

As described above in the main text, a complex of a transition metal (TM) compound, an organic magnesium compound or an organic magnesium compound, and an organometallic compound in an amount sufficient to solubilize the organic magnesium compound in a hydrocarbon, and a general formula R ' A catalytic reaction product consisting of a nonmetallic halide represented by X (wherein X is halogen and R 'is hydrogen or an organic grouping having at least Sec-butyl activity), and the atomic ratio of Mg: X is from 20: 1 to 2000. High efficiency for olefin polymerization, characterized in that the atomic ratio of X: TM is in the range of 40: 1 to 2000: 1 and the atomic ratio of Mg: X is in the range of 0.01: 1 to 1: 1. High Temperature Catalyst Composition.