DE3146524A1 - METHOD FOR POLYMERIZING 1-OLEFINS AND OLEFIN POLYMERIZATION CATALYST SYSTEM FOR CARRYING OUT THIS METHOD - Google Patents

Description

Process for polymerizing 1-olefins and olefin polymerization catalyst system for carrying out this process

The invention relates to intermetallic compounds of transition metal alkoxides and processes for their preparation; it relates in particular to catalyst precursors for the reaction with halide activators for the production of a catalyst component which is suitable for the polymerization of α-olefins suitable

Polyethylene prepared using solution or slurry processes at lower pressures or in an autoclave or manufactured in tubular reactors at higher pressures has been a target of commercial production for many years.

Recently, interest has turned to linear polyethylene resins Concentrated with low density, due to their linearity and short-chain branching resulting from alkene comonomers,

are characterized and a narrow molecular weight distribution,

improved strength properties, a higher melt viscosity

. viscosity, a higher softening point, an improved ESCR (resistance to stress cracking under environmental influences) and an improved low-temperature brittleness. These and related properties offer benefits to the consumer in various applications as blown film, wire and cable covering, cast film, coextrusion, and injection and rotational molding.
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Linear olefin polymers have heretofore been generally produced using catalysts of the general type described by Ziegler which comprise a transition metal compound, usually a titanium halide mixed with an organometallic compound such as alkyl aluminum. The transition metal component can be activated by Reaction with a halide promoter, for example a

2g alkyl aluminum halide. To the improved catalysts this type includes those who introduce a magnesium component, usually through interaction with magnesium or a compound thereof with the transition metal component

or the organometallic component, for example by Ein-30

mix or chemical conversion or by association.

There is also interest in the manufacture of an intermediate product for high density resins with modified properties using coordination catalysts this Type, In particular, resins having a broader molecular weight distribution and a higher melt index are desired.

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The present invention relates to an olefin polymer

cation catalyst system, which is a

Mixture of cocatalysts, one of which is one with one

Halide-activated intermetallic compound, which is the reaction product of a polymeric transition metal oxide alkoxide and a reducing metal with ¹ ^ a higher oxidation potential than the transition metal.

The invention also relates to a process for polymerizing 1-olefins alone or together with at least one

15 copolymerizable monomers under polymerization conditions of temperature and pressure with an olefin polymerization catalyst system which is a Mixture of cocatalysts, one of which is through a

20 is halide activated intermetallic compound, at which is the reaction product of a polymer Transition metal oxide alkoxide and a reducing metal with a higher oxidation potential than the transition metal.

Intermetallic compounds containing a transition metal

are produced by reacting a polymeric transition metal oxide alkoxide with at least one reducing metal, ie a metal with a higher oxidation potential than '

the transition metal. A polymeric titanium alkylate is used or oxoalkylate reacted with magnesium metal to form a reaction product that can be activated under

Formation of an olefin polymerization catalyst element.

The polymeric transition metal oxide alkylate can be prepared separately by controlled hydrolysis of the alkylate;

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or the polymeric oxoalkylate can by an in situ reaction, for example by hydrolysis in a reaction medium, wel-

ches containing the reducing metal. So can for example titanium or zirconium tetrabutoxide in a hydrocarbon solvent and in the presence of a controlled one Source of water, preferably a hydrated metal salt such as silicon halide hexahydrate with magnesium metal implemented.

Transition metal alkoxides, especially titanium alkoxides, are known for their concentration-related properties in organic solvents and their sensitivity to hydrolysis. It is reported ^ that the hydrolysis reaction which leads from the oligomers, emanating the trimeric Titanalkylaten _f generally to polymeric Titanoxidalkylaten, as generally illustrated by the equation:

Ti (OR) ₄ + nH ₂ 0 = »TiO _n (OR) ₄ _ _2n + 2n ROH '

Condensation reactions can also occur, in particular ■ ■

at elevated temperatures that lead to structures that have primary metal-oxygen-metal bridges, such as:

? R or

30th OR - ii - ο _ ji - OR

? or

- ii - ο _ ji OR O

which in turn participate in precursors for the hydrolysis reaction or can represent such.

These polymeric titanium alkylates or oxoalkylates (sometimes also known as u-oxoalkylates) can through the series

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Structure reflects the inclination of the metal, its coordi- 5

nation to expand beyond its primary valence, coupled with the ability of the alkylate to bridge two or connecting more metal atoms together can be represented.

¹ ^ Regardless of the particular form the alkylate takes,

It is sufficient in practice to recognize that the alkylate oligomers are a number of polymeric polymers in the controlled hydrolysis Oxide alkylates, from the dimer through the cyclic forms up to the linear chain polymer with a chain length up to infinite, form. The more complete hydrolysis on the other hand leads to the precipitation of insoluble products, which lead to orthotitanic acid on complete hydrolysis.

For ease of description of the invention, these materials are hereinafter referred to as polymeric oxide alkylates of the respective Transition metals, which represent the partial hydrolysis products. The hydrolysis reaction can be carried out separately

be carried out and the products can be used for further Use to be isolated and stored, but this is disadvantageous, especially with regard to the occurrence of a

further hydrolysis, so the preferred practice is 30th

to produce these materials in the reaction medium. It has namely, it has been shown that the same hydrolysis reaction occurs in situ.

The hydrolysis reaction itself can be controlled directly by the amount of water, which is fed to the transition metal alkoxide, and the rate or rate of addition can be monitored or controlled.

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The water must be in portions or in a graduated or

be added sequentially: adding in.

Mass does not lead to the desired reaction, but to excessive hydrolysis with precipitation of insoluble ones. Materials. The dropping is just as suitable as the use of reaction water, but it has proven to be more expedient to add the water as water of crystallization. lead, which is sometimes referred to as cation, anion, lattice or zeolite water. Usually conventional hydrated metal salts are used, the presence of the salts themselves not being detrimental to the system. It appears that the bonding achieved by the coordinated water sphere in a hydrated salt is useful for controlling the release and / or availability of the water or water-related residues to the system to the extent necessary to effect, initiate or control (control) the reaction.

As stated above, the total amount of water used has a direct influence on the form of the polymeric oxyalkylate, that is formed, and it is therefore selected depending on the catalytic performance (es

is believed to be without the invention being so limited

is that the stereoconfiguration of the partially hydrolyzed Transition metal alkoxide the nature or the result of the catalytic action of the activated catalyst component determined or partly contributes to it).

It has generally proven to be sufficient if only 0.5 mol of water is made available per mol of transition metal

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will. Quantities up to 1.5 moles are suitable, with higher

Amounts up to 2.0 moles are useful when there is a precipitation 5

hydrolysis products from the hydrocarbon solvent medium can be avoided. This can be done in principle be achieved by reducing the rate of addition and the addition after the first occurrence a precipitation stops · Although the reaction is believed to be essentially equimolar, in some Cases, as usual, expediently a certain excess of water

used.

It is clear that the sterebisomeric form, chain length and The like. The hydrolysis product can be changed somewhat with the elevated temperature that is required for the on final reaction with the reducing metal and the in situ processes also influence the equilibria via the mass action effect. Simultaneous education too of an alkanol, the equilibria, the reaction rate

2g dities or rates and the like. Influence.

The hydrolysis reaction runs under ambient conditions in relation on pressure and temperature and no special conditions are required. A hydrocarbon solvent can be used, but this is not required. A mere contact between the materials for a period of time, usually 10-30 minutes up to 2 hours; is sufficient. The resulting material is stable under normal storage conditions and can be simply Dilute with a hydrocarbon solvent as desired to bring it to a suitable concentration level.

-r-

The polymeric transition metal oxide alkylates are treated with a

reducing metal with an oxidation potential higher than 5

is implemented as that of the transition metal. Preferably a polymeric titanium oxide alkoxide is used together with magnesium, calcium, potassium, aluminum or zinc as a reducing agent Metal used. Combinations of transition metal alkoxide, reducing metal and hydrated metal salt are used expediently selected taking into account the electrical potentials, um.side reactions to keep minimal, as is known per se; and in general are preferred activity 15. Ensure values for olefin polymerization by appropriate selection of reducing metal / hydrated Metal salt Magnesium content added to the system.

In a preferred embodiment (discussed below for simplicity) is titanium tetrarn-butoxide (TBT) with magnesium turnings, and a hydrate of metal salt, particularly magnesium chloride, at a temperature of 50 to 15O ⁰ C in a reaction vessel under autogenous pressure,

implemented. TBT can be the reaction medium or it a hydrocarbon solvent can be used «The Ti / Mg molar ratios can vary from 1: 0.1 to 1: 1, with a stoichiometric one for the most homogeneous reaction system

30 IV 0

Ti: Mg ratio of 1: 1 is preferred with an amount of hydrated metal salt which during the reaction yields about 1 mole of water per mole of Mg.

The catalyst precursor soluble in a hydrocarbon comprises predominantly Ti contents in association with Mg contents in one or more stereo configuration complexes of which

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• / 13.

they are believed to be the major oxygen-containing compounds. Some signs of the titangoes

Holds in the mixed oxidation state indicate an interacting system of integral species

IV III II of Ti, Ti and Ti values, perhaps in a quasi Equilibrium relationship at least under dynamic reaction conditions. It is believed that the invention it is restricted to the fact that the preferred precursor introduces (Ti-O-Mg) bridge structures.

The intermetallic compounds are of particular interest as catalyst precursors in systems with or without Carrier for the isomerization, dimerization, oligomerization or polymerization of alkenes, alkynes or substitute

2ό ated alkenes in the presence or absence of reducing agents or activators, such as organometallic compounds of metals from group IA, HA, HIA or HB.

In the preferred use of such precursors, these

with a halide activator, for example an AlkylaIumi nium halide, reacted and combined with an organometallic compound to form a catalyst system,

which is particularly suitable for the polymerization of 30 ..

Ethylene and comonomers to make polyethylene resins.

The transition metal component is an alkylate, usually a titanium or zirconium alkoxide, which essentially has -OR substituents, wherein R has up to Contains 10, preferably 2 to 5, carbon atoms, and of these particularly preferred is n-alkyl, such as n-butyl.

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The selected component is normally liquid under ambient conditions and reaction temperatures for ease of handling and it is also hydrocarbon soluble, to facilitate their use.

It is generally preferred to be in a facility at the Carrying out the related hydrolysis reaction transition metal '. to use compounds which have only alkylate substituents, although other substituents are also possible there can be drawn where they can significantly modify performance in terms of the response Do not disturb use. Halide-free n-alkylates are generally used.

2Q The transition metal component is used in the highest oxidation state of the transition metal in order, among other considerations, to achieve the desired stereoconfiguration structure. Most conveniently, as noted above, the alkylate is a titanium or zirconium alkoxide. Too suitable .

Neten titanium compounds include titanium tetraethylate as well as the related compounds that contain one or more alkoxy radicals, such as n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec.-butoxy, tert.-butoxy, n-pentoxy, tert.-pentoxy, tert.-

3Ö

Amyloxy, n-hexyloxy, n-heptyloxy, nonyloxy and the like.

Some evidence also suggests, that the rate or rate of hydrolysis of normal derivatives increases with Chain length decreases and that the speed or rate with the complexity of the molecule (i.e. tertiary, secondary, normal) decreases, which is why these considerations are taken into account

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can be used in the selection of a preferred derivative. in the In general, titanium tetrabutylate has proven to be useful for practical purposes Implementation of the invention proved to be very suitable, and related tetraalkylates are also preferred. It is clear that mixed alkylates are perfectly suitable, and that they can be used where they are commercially available are. There can also be complex titanium alkoxides, sometimes containing other metal compounds can be used.

The reducing metal is supplied at least in part in the zero oxidation state as a required element of the reaction system. The usual sources are a convenient source Shavings or a tape or a powder. Since they are commercially available, these materials can be oxidized in an . State with a passivated surface and it can grinding or grinding to achieve at least a certain fresh surface may be desirable, at least for Control or control of the reaction speed or

-rate. The reducing metal can expediently be in the form of 25

a slurry in the transition metal component and / or in the hydrocarbon diluent or it can be added directly to the reactor (reaction vessel) will.

In the case of in situ preparation (or in the case of independent preparation of the polymeric transition metal alkoxide) a source of water or water-related compounds is supplied, thereby releasing quantities of water or diffused or accessible, as is the case with a controlled species with a delayed speed or

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Rate during the reaction may be the case. As stated above, that of a hydrated metal salt has turned beige

controlled sphere of coordination as suitable for this purpose proven; but there are also other sources of water in the can be used in the same proportions. It can also be a calcined silica gel that is free of other active substances constituents, but controlled amounts of bound Contains water. In general, the preferred source of water is an aquocomplex in which water is coordinated in a known manner with the base material

Suitable materials include the hydrated metal salts, especially the inorganic salts such as the Halides, nitrates, sulfates, carbonates and carboxylates of Sodium, potassium, calcium, aluminum, nickel, cobalt, chromium, Iron, magnesium and the like.

The implementation of these components is expedient in one

closed reactor carried out, preferably with

a reflux for the two in the reaction vessel volatile components formed at elevated temperatures is coupled .. An autogenous pressure is applied because

the reaction proceeds smoothly under ambient conditions, "

heating to initiate and maintain the reaction. As with any such reaction, it is Stirring is preferred simply to avoid caking or coating of the surfaces of the container, to achieve an intimate mixture of the components and ensure a homogeneous reaction system *

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Typically, a hydrocarbon solvent such as hexane, heptane, octane, decalite, ligroin and the like is also used to prevent the components from being mixed together To facilitate heat transfer and the maintenance of a homogeneous reaction system.

Saturated hydrocarbons with a boiling point within the range from 60 to 190 ^° C. are preferred. The liquid transition metal component can also serve at least in part as a reaction medium, in particular where no added set solvent is used. The reaction includes

a stage in which additional volatile components with the. Solvents form azeotropes or, if the components are used in pure form, the source for the return

2Q represent flow, but in any case it is preferred to use the Carry out the reaction at least through intermediate stages while observing suitable reaction times to avoid the volatile Return materials to the reaction zone. To this

Butanol is formed when the titanium composite is 25

nent is titanium tetra-n-butoxide, which forms an azeotrope with the hydrocarbon solvent. The selection of the Solvent and / or the alkylate, based on the possible

Lowering the reaction temperature is therefore a facial

point, as is well known to those skilled in the art *

The reaction temperature can be selected to some extent within a wide range depending on the reaction to be carried out appropriately speed. It has been found that the reaction system (consisting of the liquid transition metal component, the

3 14652A "·· ^: " ■ "." · "■" - ■ Μ -

, A2-

dissolved hydrated metal salt, the reducing metal "

particles and the solvent, if desired) at about _O

60 to 70 C a visible gas formation shows what a.

Initiation temperature or an activation energy of about 50 C suggests, which is therefore the one for the implementation of the polymeric oxide alkoxide with the reducing metal is the minimum temperature required. The reaction proceeds somewhat exothermic during the consumption of the reducing metal, can therefore easily be incorporated into the subsequent Stage, which is the reflux temperature, are transferred. Since the alkanol formed is largely consumed during the course of the continuing reaction (as an independent compound), (the respective system temperature changes and the end of the reaction is indicated by the consumption of visible metal and / or waste achieving the reflux temperature of the pure solvent within a period of as little as 30 minutes to 4 hours or more. These temperatures can be 140 to 190 C. and, of course, higher temperatures can be used, but no obvious benefit is achieved work. In the absence of a solvent, the upper

Limit simply determined by the reflux temperature of the

alkanol formed in the course of the reaction.

The reaction of the components emerges most clearly from the pronounced color change that takes place under Exothermic, which accompanies the beginning of gas evolution

3U6524 """'" * ^: * * ^: * ■ "*" ■ · ■ ι · -W ·

due to lack of opacity or cloudiness of the solution can is the evolution of gas, which from a bubble formation up

can result in a strong foaming on the surface of the 5

The most easily recognizable metal and the generally bright

Colored solutions immediately turn greyish, then quickly darken to blue, sometimes purple, usually blue-black, sometimes with a greenish tinge. The analysis of the gas does not reveal any HCl and it is essentially H ₂ *. After the rapid color change, a certain increase in color occurs during a gradual increase in temperature with continued evolution of gas. In this stage the alkanol, corresponding to the alkyl solder compound, generated in an amount which is sufficient to lower the boiling point of the solvent and it is gradually consumed in a rate dependent manner along with the rest

20 reducing metal.

The reaction product is at least partially soluble in a hydrocarbon and is expedient for further processing

_n _ twist kept in the form of a slurry. The viscous 25

to semi-solid product shows an essentially amorphous character in the X-ray diffraction analysis after isolation.

The molar ratios of the components can be within certain

Ranges vary without significantly affecting the end-use performance of the catalyst precursor. To avoid competitive reactions that the The transition metal component will therefore make the reaction product undesirably gelatinous or untreatable usually in at least a molar amount, based on

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so·

the reducing metal, added, the ratio of excess

Common metal to be reduced can, however, within the

Range from about 0.5 r 1.0 to about 3.0: 1.0, preferably

from 1: 0.1 to 1: 1. An insufficient amount of reducing metal. leads to such a reduction in the Reaction temperature that the reflux temperature of the pure Solvent is not achieved, while an excess of reducing metal from the unused portion of the same is readily apparent so that the desired amount of this component will be readily determined by those skilled in the art can be.

Within these ranges, a varying proportion of the reaction product can represent a component insoluble in a hydrocarbon, which, however, is necessary for the use for example for the further reaction with a halide activator to form an olefin polymerization catalyst, can be slurried with the soluble component and in usually is also slurried. The amount of these insoluble

Component can be controlled in part by the use of a solvent having an appropriate partition coefficient, but where the use of a common hydrocarbon solvent such as octane is practical .

Is preferred for reasons of table equimolar ratios of, for example, Ti / Mg / hLO components than for the Proven formation of a homogeneous reaction product most suitable.

The water or the compound related to water will too preferably in a molar ratio of the transition metal

component supplied for similar reasons of homogeneity

and ease of reaction. Therefore, in the case of 5

MgCL.ofrLO an amount of 0.17 mol during the reaction approximately

1 mole of water and this amount up to about 2 moles Water gives the easiest reactions with one or more moles of transition metal component. In general, the h ^ O-set are within the range of about 0.66 to about 3 moles per mole of transition metal. The ones at any level The amount of water present in the reaction can of course also be used be considerably less and within the range of

up to catalytic amounts, based on the rest Components, depending on the type and speed or rate in which they participate in the reaction sequence, which is currently unknown, participates. The working hypothesis is currently in particular

2o assumed, without the invention being limited to that the water or the speed or rate of the reaction, controlling,! water-related compound, is activated, released, made accessible or in

one way / which diffuses this compound in a 25th

regular, graduated, constant or variable rate-dependent type delivers the same molar proportion of free water that is supplied at the beginning of the reaction

is, however, completely ineffective in initiating the Re- 30

action at this or a higher temperature and leads to

. unwanted complete hydrolysis reactions.

The measured amount of water is essentially in one molar equilibrium or in a molar excess, based on the reducing metal component, and appears in To be related to their consumption in response to there

a molar deficit of water inevitably leads to that excess reducing metal remains. In general

a moderate excess of water of 10 to 40 % is suitable for ensure a complete response. Higher proportions are also suitable without limitation, but they should are kept in a relative stuchiometric equilibrium, based on the transition metal component.

The choice of aquocomplexes or hydrated metal salts, if used, is essentially one thing the controlled availability of the water they provide Feed system. Sodium acetate trihydrate is therefore suitable as well as magnesium acetate tetrahydrate, magnesium sulphate heptahydrate and magnesium silicon fluoride hexahydrate. A salt with a maximum degree of hydration associated with a controlled release achieved through the coordination bond relationship is preferred. Will be most expedient a hydrated magnesium halide, such as magnesium chloride

hexahydrate or magnesium bromide hexahydrate is used. These 25th

Like other hygroscopic materials, salts contain even when supplied in the commercial anhydrous form, some sorbed water, e.g. 17 mg / kg

(cf. * GB-PS 1 401 708), if this value is also far below- '

half of the molar amounts provided according to the invention. Anhydrous salts are therefore, when they are not used for this purpose are specially modified, unsuitable according to the invention.

The reaction system as defined above does not require an electron donor or a Lewis base or solvent that in part performs these functions.

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.23.

although it tolerates them. As can be seen from the examples below, the reaction in a

■

preferred embodiment with water of crystallization and an alcohol component is introduced into the system. It is not known with certainty whether proton transfer or Electron donor mechanisms participate in or compete with the reaction system.

No partitions are required as there is at least one Part of the reaction product in the saturated hydrocarbon substance is soluble if such is used as a solvent is applied or gives a solvation medium so that even if precipitation also occurs, and even after long storage a workable reactive one

2Q slurry can be made easily.

According to a preferred aspect of the invention, the reaction product (the catalyst precursor) is further reacted with

a halide activator, for example an alkyl aluminum

halide, a silicon halide, an alkyl silicon halide, a titanium halide or an alkyl boron halide. It the catalyst precursor was found to be easily activated

can be achieved by simply using the Halöge 30

combined nide activator * The reaction is strongly exothermic, therefore, the halide activator is usually added in portions to the reaction system. Usually at Completion of the addition also completes the reaction and can be terminated. The solid reaction product or the Slurry can then be used immediately or stored (retained) for future use. In the

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Rule is used to achieve the best control (steering) upper

the molecular weight properties and in particular the 5

position a low density resin only that with one Hydrocarbon washed solid reaction product used as a catalyst.

The halide activator is usually used for the reaction in a molar ratio of 3: 1 to 6: 1 (aluminum, silicon or boron, based on the transition metal), although ratios of 2: 1 or more have also been used with success

15 can be.

The catalyst product thus obtained can be used directly in the polymerization reaction, although it is in the It is usually diluted, stretched or reduced to the extent desired to achieve a suitable batch Amount of catalyst corresponding to 80 to 100 mg of transition metal, based on .eine nominal productivity of more than.

200,000 g polymer / g transition metal for continuous

Polymerizations which, as a rule, exceed that of the current catalyst. A person skilled in the art can make appropriate adjustments, taking into account the ability to react and the degree of efficiency, usually by means of one

. fold dilution and by checking or controlling the

Feed rates.

The catalyst containing the transition metal is used for the Use in the polymerization with an organometallic cocatalyst, for example triethylaluminum or triisobutylaluminum, or a non-metal compound, such as

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Triethylborane, combined. A typical polymerizer charge thus contains 42 parts of isobutane solvent, 25 parts of ethylene, 0.0002 parts of catalyst (calculated as Ti) and 0.009 parts of cocatalyst (TEA, calculated as Al), which is fed into a reactor maintained at 46.7 kg / cm (650 psig) and 71 C (160 F). In general

becomes the amount of cocatalyst, if used

is calculated to be within the range of about 30 to about 50 ppm calculated as Al or B based on isobutane.

'

Examples of metallic cocatalysts include trialkylaluminum, such as triethylaluminum, triisobutylaluminum, Tri-n-octylaluminiura, Alkylalutniniurahalogenide, Alkylalumini-

nium alkylates, dialkyl zinc, dialkyl magnesium and metal borohydrides including those of the alkali metals, in particular sodium, lithium and potassium, and of magnesium, Beryllium and aluminum. To the non-metal cocatalysts include boron alkyls such as triethylborane, triisobutylborane and Trimethylborane, as well as borohydrides, such as diborane, pentaborane, Hexaborane and decaborane.

The polymerization reactor is preferably a serpentine reactor suitable for slurry operation, in which a solvent such as isobutane is used, from which the polymer is granular

Separates solid. The polymerization reaction turns 35

at a low pressure, for example at 14.1 to

70.3 kg / cm (200 to 1000 psi) and a temperature within the range of 38 to 93 ° C (100 to 200 ° F).

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_g2-

led, with hydrogen supplied in the desired amount to control the molecular weight distribution

·

(to control). Other n-alkenes can be used in the reactor lower proportion, based on the ethylene, for the Copolymerization are supplied with it. Usually butene-! or a mixture thereof with hexene-1 in an amount of 3 to 10 mol / S used, although other α-01efin comonomer proportions can be used Use of such n-alkene comonomers can increase resin densities can be achieved within the range of 0.91 to 0.96.

15th · ·

There can also be other α-olefin comonomers, such as e.g. 4-methyl-pentene-l, 3-methyl-butene-l, isobutylene, 1-heptene, 1-decene or 1-dodecene, in an amount of only 0.2% by weight, be used, especially when monomer mixtures be used.

However, if desired, the polymerization can also be carried out at

higher pressures, e.g. from 1410 to 2820 kg / cm (20,000 to 40,000 psi), in autoclaves or tubular reactors.

The term "intermetallic compound" used here or "intermetallic complex" means any Reaction product, regardless of whether it is obtained by coordination or association or in the form of an or multiple inclusion or occlusion connections, drusen or other entanglement under the applicable conditions is obtained, the integrated response generally being indicated by a color change and gas evolution,

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which is probably a sign of reduction-oxidation,

a «rearrangement and an association between the non-5 consumed elements of the reaction system.

The invention and its application are explained in more detail in the following examples without, however, affecting the invention is limited to it. Unless otherwise stated, all parts given therein relate to weight. The melt indices given therein were determined under conditions E or F according to ASTM D-1238-57T for the MI and HLMI Values determined with powder or resin samples as indicated. HLMI / MI or MIR is the melt index ratio, a measure of the shear sensitivity that the Molecular weight distribution reflects. The other tests

20 were as stated or as is customary in related fields carried out.

Example 1 ',

(Α) 6ρ parts of Ti (OBu) ₄ [TBT] and 4.2 parts of CrCl ₃ .6H ₂ O were combined with one another in a reaction vessel. The chromium salt was partially dissolved and some heat developed upon stirring. To achieve complete dissolution, the mixture was gently heated to 60 to 70.degree. A further 3.3 parts of chromium salt were dissolved with stirring over a period of 20 minutes. A total of 0.3 part of magnesium turnings was added in portions to the green solution, which caused a vigorous evolution of gas. The cooled reaction product, which was free of excess magnesium (which had completely disappeared), was a viscous green one

20 liquid that was soluble in hexane.

(B) In a similar experiment anhydrous chromium chloride was used together with titanium alkoxide, but there was no reaction when heated to more than 100 ⁰ C for a period of 1/2 hour. Even with the addition of zinc dust and further heating to more than 150 C, there was still no reaction * The introduction of magnesium shavings did not lead to any reaction either. It was concluded that the hydrated salt was a necessary component of the reaction system;

Example 2

(A) TBT (0.121m), CrCl ₃ .6H ₂ O (0.015m) and Mg ⁰ (0.0075m) were mixed together in a stirred reaction vessel equipped with an electric heating mantle

.39-

united. The chromium salt was completely dissolved at about 60 ⁰ C and the reaction with the magnesium turnings was seen at the evolution of gas at 85 ° C, which was vigorously at 100 ° C and at 116 C to hear, with some Mg remained. After the remaining Mg had dissolved, heating was continued for a total reaction time of 1 hour and 45 minutes. The reaction product was a dark green liquid at room temperature that easily dissolved in hexane.

(B) In the same way, a reaction product of 0.116m TBT, 0.29m CrCl ₃ .6H ₂ O and 0.029m Mg was prepared. A at 118 ° C dirty-green reaction product took a defined bluish color to under continued evolution of gas at 120 ⁰ C. The reaction was after the ver-20

magnesium disappearance ended within 1 hour and 15 minutes. The reaction product was soluble in hexane.

(C) The above experiments were repeated with the following amounts of reactants: 0.116m TBT, 0.058m CrCl ₃ . 6H ₂ O, 0.0145m Mg. The reaction was complete within 115 minutes and a hexane-soluble product was

³⁰ duct received.

(D) The amount ratio of the reactants was in one another attempt modified again so that it was:

0.115m TBT, O, O287m CrCl ₃ .6H ₂ O and 0.0144m Mg. A dirty green material at 114 C turned blue on the Mg surface. The separated reaction product was soluble in hexane.

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(E) In a similar experiment 0.176m TBT, 0.30m CrClo.6H ₂ O, 0.176m Mg in octane were reacted with one another.

The clear at 7O ⁰ C. The green color of the reaction mixture was dirty with increasing gas development and at 90 ⁰ C, dark to almost black. The color was green again at 119 ° C and the reaction was terminated at 121 ⁰ C with complete disappearance of the magnesium. The reaction product (6.9 wt% Ti, 3.5 wt% Mg, 1.3 wt% Cr) was a dark? Olive green liquid and a solid with a darker color (approx 50: 50 / -

₁₅ volumes).

(F) In another experiment in octane, the reactants were used in amounts of 0.150m TBT, 0.051m CrCl ₃ .6H ₂ O and 0.150m Mg. Again the dirty-

. green color with violent foaming to almost black, whereby at 109 ° C a dark green-black reaction product arose (5.7 wt% Ti, 2.9 wt% Mg, 2.1 wt% Cr).

^25th Example 3

(A) The reaction product from Example 2E was combined in a reaction vessel with isobutylaluminum chloride, which was added dropwise in portions to achieve an Al: Ti molar ratio of 3: 1. The green colored mixture was brown violet at 38 ° C that had been dyed after completion of the Reaktantenzugabe.bei 39 ⁰ C reddish brown. After stirring for a further 30 minutes, the reaction was ended. the product obtained was a dark red-brown liquid and a dark brown precipitate.

-27 -

34 ·

(B) The reaction product of Example 2F was reacted in a corresponding manner with isobutylaluminum chloride (molar ratio Al: Ti = 3.1). The peak temperature after the addition was complete was 48 ° G, but no brown color change could be seen. The reaction product therein was a clear liquid and a dark gray precipitate.
10

Example 4

The catalyst components prepared in Example 3 above were used for the polymerization of ethylene (88 ° C (190 ⁰ F), 10 mol% ethylene, 0.0002 parts of catalyst, calculated as Ti, about 45 ppm Triäthylalu-. Minium calculated as Al, H "as indicated), the results indicated in Table I below being obtained.

Table I.

Catalyst H ₉ , kg / cm product resin sheep

(psig) (g PE? g Ti. hrs.) th ■ MI HLMI HLMI / MI

3A 5.2 (60) 35 160 10.1 265 26.3

9.4 (120) 29220 18.9 618 32.6

3B 5.2 (60) 30 380 9.6 264 27

9.4 (120) 26880 32.8 855 26.1

*) PE s polyethylene

In the following example, the catalyst component of the invention was used prepared from the reactant mixture in the absence of an added solvent.

ι · 33 ·

Example 5

(A) 0.1212m Ti (OBu) ₄ [TBT], 0.121m magnesia chips and 0.0012m MgCl ₂ .6H ₂ O (TBT / Mg / MgCl ^ o ^ O = 1: 1: 0.01 molar) combined in a stirred reaction vessel equipped with an electric heating mantle. The magnesium salt completely dissolved at room temperature to form a homogeneous reaction mixture. The mixture was heated slowly and • at 95 ° C, gas evolution began on the surface of the magnesium shavings. At 140 C under reflux, the

15 ·

Blistering severe. The solution took on a dark color and the formation of bubbles stopped at 170 C, after which the Reaction ended. The reaction product contained excess magnesium - only about 8.5% of the amount used

Magnesium reacted - and was soluble in hexane.

(B) In a further experiment, the molar amount of Mg-Cl ₉ .6H ₉ O was increased (TBT / Mg / MgCl .6H ₉ O = 1: 1: 0.1 molar). The golden yellow liquid turned greyish at 104 ° C. with evolution of gas, and on further heating to 168 ° C. it turned dark. After 125 minutes of reaction, the reaction product contained excess magnesium - about 63% has-

30th responded.

(C) In a further experiment a molar ratio of 1: 1: 0, \ L7 was used. The dark blue reaction product was very viscous and couldn't work easily with hexane

be diluted. All of the magnesium was used up. The following example explains the production, - the in

3U6524 - ^; "'-' -

ι .33-

a hydrocarbon solvent.

⁵ Example 6

(A) 50.2 parts (0.148m) of TBT were added to a stirred reaction vessel with a electric heating jacket was introduced. Magnesium shavings (0.074 m) were added, it was with Stirring was started and then 0.0125m MgCl ".6H" 0 was added with heating over a period of 1 minute.

At 75 ° C. (after 20 minutes) the magnesium salt had completely dissolved and at 95 ^° C. (25 minutes) gas evolution began on the surface of the magnesium shavings, the evolution of gas increased, the solution turning grayish and then deep blue when heated under reflux to 117 C (35 minutes) · The magnesium metal had reacted completely within 1 hour (128 to 129 ° C) and the reaction was ended. The dark blue reaction product, which was dissolved in octane (a small amount of a greenish precipitate remained), contained, as was calculated, 6.8% by weight of Ti and 2.0% by weight of Mg (Ti / Mg - 3 / + to 1, based on the weight, - 1.7 to 1 molar).

(B) The above experiment was essentially repeated, this time modifying the molar ratios of the reactants - The following results were obtained

35 were:

Ti / Mg / MgCl ₂ .6H ₂ O molar ratio 1.0 / 0.65 / 0.11

1.0 / 0.75 / 0.128

10

15th

25th

1.0 / 1.0 / 0.085

1/1 / 0.17

1/1 / 0.34

1/1/0, -51

1/2 / 0.17 1/2 / 0.34

2/1 / 0.17 2/1 / 0.34

3/1 / 0.51

3U6524 - ^ e -

♦ 34-

(molar) 1, -32

1.14

0.92

0.85 0.75 0.66 0.46

0.43

1.70 1.50

1.99

Remarks

Dark blue-black liquid and green ~ precipitate. 6.6% by weight Ti, 2.6 wt% Mg (calc.)

blue solution with a greenish tinge.

6.5 wt% Ti, 2, -8 wt % Mg (calc.)

bluish black liquid with a light green precipitate (insoluble in acetone, alkane and methylene chloride), some unreacted Mg

dark blue-black liquid, - 6.6 wt .-% Ti, 3, -9 wt .-% Mg (calc.)

dark blue-black liquid, 6.7 Gevi-Τγ

4.6 wt% Mg (calc.)

milky blue liquid

3.7 wt% Ti, 2.9 wt % Mg (calc.) '

dark bluish black liquid and viscous green gel. Something not implemented Mg

dark bluish black liquid and viscous gel; Something not implemented Mg '.

Example 2A

bluish black solution. 7.1% by weight Ti, 2, -3% by weight Mg (calc.)

bluish black liquid with a pale green tint. 6.1 wt% Ti, 1.6 wt% Mg (ber;)

3U652A · ^: " ^: * ^: - · ^: ·

- JJI -

¹ .35 ·

(C) The 1/1 / 0.34 manufacturing process described above was repeated, but this time 63.7 Parts of TBT along with 67.5 parts of hexane as a solvent reaction medium were used. A dark blue-black liquid was obtained, which after calcination Contained 8.2 wt% Ti and 1.6 wt% Mg. 10

The following example explains the step-by-step production, the catalyst component.

15 Example 7

. 2.61 parts of MgCl ₂ .6H ₂ O and 34/2 parts of TBT were combined with one another with stirring. Within 30 minutes, the yellow liquid-crystal salt mixture was replaced by a milky-yellow, opaque, viscous liquid. After prolonged stirring, the cloudiness was lightened and within two hours a clear yellow liquid was obtained (in a second experiment, - the one in

Octane was carried out, I had the salt inside

. completely dissolved in 30 minutes to form a yellow liquid with no intervening precipitate or turbidity X
30th

To that described in the previous examples Thus, a TM-Mg reaction product was prepared using the clear yellow liquid prepared above and using 1.83 parts of Mg for a component mole ratio in octane of 1 / 0.75 / 0.128. The reaction proceeded smoothly and a dark-

-32 -

blue-black liquid and a green precipitate in the same manner as the others described above Reactions.

The reaction product was treated with ethylaluminum dichloride activated in an Al: Ti ratio of 3: 1 for manufacture a catalyst component for olefin polymerization.

The following example explains the meaning of the amount! 5 'of bound water. '

Example 8

A number of "identical" experiments were carried out using a molar ratio of 1 / 0.75 / 0.128 (TBT / Mg / -MgCl ₉ .6H ₉ 0), but this time the degree of hydration of the magnesium salt was modified.

When using MgCl ₂ .4H ₂ O (H ₂ O / Mg = 0.68 / 1, compared to 1: 1 with MgCl ₂ .6H ₂ O) only 89.1% reacted. Magnesium metalsi When using MgCl _{9 .2H 9} O in the same total molar ratio _{(H 2} O / Mg = 0, -34 / 1) only 62.1 % of the Mg ⁰ reacted.

In repeated experiments, the amount of hydrated salt added was increased to achieve an H ₂ O / Z * Ig ratio of 1/1. All of the magnesium metal reacted. It was also found that the amount of insoluble reaction product increased with increasing salt contents.

3UG524

The following example explains the use of others

Titanium compounds.

Example 9

(A) 45.35 parts (0.1595m) Ti (0Pr ^X ) ₄ , 0.1595m Mg ^0, and 50.85 parts octane were placed in a stirred reaction flask equipped with an electric heating mantle and O was added , O27m MgGl .6H ₂ O was added. The milky yellow mixture turned gray under reflux at about 88 C and at 90 C it turned blue with evolution of gas. In relation to the remaining magnesium, it was determined? represents that the reaction was partially suppressed by the octane / isopropanol azeotrope present.

(B) The reaction described in Section A was carried out

repeated at a reactant molar ratio of 1 / 0.75 / -0.128 using decalin (b.p. 185 to 189 ° C)

as a diluent. After 6 hours the reflux

25 ο

. temperature reached 140 C and the reaction was ended.

A dark blue-black liquid with a small amount of a dark precipitate was obtained. Only 8.8%

of magnesium had responded. 30th

(C) Similarly, it was reacted with tetraisobutyl titanate carried out in a molar ratio of 1 / 0.75 / 0.128, using a blue-black liquid and received a dark precipitate. About 50% of the magnesium had reacted;

- -84 -

(D) Similarly, titanium tetranonylate was used together with magnesium and MgCl-.6H ₂ O in a molar ratio of 1 / 0.75 / 0.128. A blue liquid formed, with 45% of the magnesium consumed ^.

(E) The reaction product of titanium tetrachloride and butanol (believed to be dibutoxytitanium dichloride) was mixed with magnesium and magnesium chloride hexahydrate in a molar ratio of 1 / 0.75 / -0.128 under similar conditions as in the above examples implemented. About half of the magnesium was consumed within about 3 hours, - leaving a dark blue-black liquid and an olive-green precipitate (50/50 vol / vol) were obtained.

The following example illustrates the use of a zirconium metal alkylate.

^25th Example 10

(A) 12.83 parts (0.028m) Zr (OBu) ₄ .BuOH, 0.34 part (0.14 m) Mg in the form of the commercially available chips and 8.8 parts of octane were introduced into a reaction vessel and under Stirring, refluxed at 125 ° C for 15 minutes without any reaction occurring. 0.97 parts (0.05 m) MgCl ^ 6H ₃ O were added, with a strong

Foaming was observed and the reaction mixture became milky in appearance.

3U652A

.39.

(B) In a second experiment, 31.7 parts (0.069m) of the zirconium compound were combined with the magnesium metal shavings (0.069m) and there were 57.6 parts of ligroin (boiling point 170 to 195 ° C.) and 4.79 parts (O, O235m) MgCl ₂ .6H ₂ O added with stirring. Heat was supplied to the reaction vessel through the electrical jacket. Within 5 minutes

IQ uten the reaction mixture took an opaque (cloudy)

Appearance and there was a gas evolution on the surface of the magnesium metal - than the temperature had reached 85 C after a reaction time of 8 minutes.

The evolution of gas continued with vigorous foaming continued, the temperature rose to 108 c, during which a gray-white solid appeared. With continued heating on At 133 ° C. (reaction time 1 hour) all of the magnesium metal disappeared, and the reactor contained a milky white color Liquid and a white solid. The reaction mixture was cooled and 92 parts of a mixture became collected - the 6.8% by weight of Zr and 2.4% by weight of Mg (Weight ratio Zr: Mg = 2.8: 1; molar ratio Zr: Mg « 0.75) - which was soluble in hydrocarbons;

The reaction product can be activated in a known manner, for example with an alkylaluminum halide by reaction with it, expediently with an Al / Zr-MoI ratio from about 3/1 to about 6/1 to in combination with an organic or organometallic reducing agent one suitable for the formation of polyethylene resin

35 to prepare olefin polymerization catalyst system.

The following example illustrates the replacement of magnesium by calcium as a reducing metal.

Example 11

(A) 0.074m Ti (OBu) ₄ , 0.074m Ca ⁰ (thick, commercially available chips that were mechanically cut into smaller pieces) and; Q, O125m MgCl ₉ , 6H ₉ O were dissolved in octane in a stirred reaction vessel, which was equipped with an electric heating jacket, combined. After reaching 105 ° C. the solution took on a dark color and at 108 ° C. the solution took on a dark gray appearance with evolution of gas. At 110, '5 ⁰ C was found to be rapid gas development - what'.

the formation of a dark blue liquid followed.

After 90 minutes the reaction was complete and it became a Reaction product from a dark blue-black liquid

■ isolated with a greenish tint.

20 -

The experiment was repeated with the same molar ratio. 50% of the calcium reacted to form a dark blue liquid and a gray solid, -der 6.2 wt% Ti ,. Contained 2.6 wt% Ca and 1.1 wt% Mg (Molar ratio 1 / 0.5 / 0, -34) (IIAl) i

In a further experiment the same reactants were combined in the molar ratio 0.75 / 0.128. 63 % of the calcium reacted to form a blue-black liquid and a green solid. The reaction product (molar ratio 1 / 0.47 / 0.128) contained __ 6.6% by weight of Ti, 2.6% by weight of Ca and 0.4% by weight of Mg (11A2).

(B) The reaction product! 1Al was treated with ethylaluminum chloride at an Al: Ti molar ratio of 3: 1 and

3U6524

.44

6: 1 implemented. The reaction products were with hexane

diluted and the halide activator was slowly added

give to control (control) the strongly exothermic reaction. In the 3: 1 experiment, the gray-white slurry initially formed dissolved after the reaction had ended forming a pink liquid and. of a white precipitate. At the Al: Ti ratio of 6: 1, the slurry turned gray and then turned lime green.

The reaction product 11A2 was prepared in a similar manner with ÄtAlCl «at an Al: Ti molar ratio of 3: 1 and 6: 1 treated. The reactions proceeded smoothly, giving a deep brown slurry at the 3: 1 ratio and at.

the ratio 6: 1 received a red-brown liquid with a brown precipitate.

(C) The reaction products prepared in Part B were used in the ethylene polymerization, the in results given in the following table were obtained *

ω σι.

ω ο

to

CJ!

cn

Table II

TBT / Ca / MgCl, i 6H "0 reaction (molar ratio) relationship

.H ₂ , kg / cm ² productivi resin powder properties

5/0. 34 3/1 5.2 (60) 40 öta,; MI HLMI 7th
7th ME 1/0. 47/0 .128 6/1 '
3/1 5.2 (60)
5, '2 (60 ^ 43
20th
11 950 3.84 131 0 34.1 1/0. • 6/1 5.2 (60) 27
33 810
930
260 1.03
• 1.73
7.0 47.
73.
320 46.3
42.6
45.7 420
050 0.35
1.75 21.
116 60.1
66.0

Reactor conditions on a laboratory scale

Diluent - Isobutane Temperature - 88 ° C (190 ⁰ F)

Hydrogen - as indicated

Pressure catalyst - Tr iä thy laluminium (TEAL) at about 45 ppm Al

Ethylene - 10 mol%

Duration of the experiment - 60 minutes

3U6524

■ The tests showed a somewhat broader molecular weight distribution in the resin compared to the use of magnesium as a reducing metal.

The use of zinc as a reducing metal is made explained in the following example.

Example 12

(A) O, -2O4m TBT, 0.153m Zn ° granules and 0.026m MgCl ₂

.6H „0 were in octane in a stirred closed ²

System - which was equipped with a reflux - with each other united and heated from the outside; A rapid color change occurred within 13 minutes (85 ° C.) Blue-black with increasing gas evolution up to

violent effervescence and foam formation.

The reaction product, a blue-black liquid (without Precipitate), - the 7.7 wt .-% Ti, 0.9 wt .-% Zn and 0, -5 Containing wt% Mg faded to yellow in air Product.

(B) The reaction product TiZnMg (molar ratio 1 / 0.86 / -0.128) was VJN in a molar ratio AItTi of 3: 1 in hexane at 10 to 13 ° C and reacted Isobutylaluminiumchlorid (12bl) i

(C) The preparation of the TiZnMg reaction product (12A) was repeated using Zn dust, with similar ones Results were obtained. In another experiment with zinc wool. only 7% of the zinc was consumed and it was forming a green layer on it

3U6524 -4α-

the zinc surface to be observed.

(D) The activated reaction product 12BL prepared above was thoroughly washed in hexane and lower for the preparation of a polyethylene resin density · used in the reactor was previously enough introduced butene-1, ¹ to the desired density leiäben to be granted, - and the reaction was at 77 ° C (170 ⁰ F) and an H ₉ pressure of 3.46

2
kg / cm (35 psig) in the presence of triethylaluminum as a cocatalyst. The resin obtained had the following properties: Density 0, -9165, MI 1.68, - HIMI 52.1 and MIR 31. '

• The following example illustrates the use of potassium

as reducing metal-20 - ■

Example 13 "·

62.7 mmol TBT, 47 mmol fresh potassium metal (freed from fine oxide / hydroxide coating by scraping off under octane) and 8.8 mmol MgCl ₂ .6H ₂ O were in octane in a closed system that was equipped with a reflux, · United with each other and heated from the outside. Within two minutes at 35 ° C., the color changed to blue-black and blistering occurred. This was followed by a strong evolution of gas and foaming. After the potassium metal had disappeared, the reaction was ended (after 5 hours); A dark blue-black liquid with a small amount of a dark blue precipitate was obtained.

3H652A

The following examples 14 and 15 illustrate the use of aluminum as a reducing metal.

Example 14

(A) 112.31 parts (0.33m) Ti (OBu) ₄ , 8.91 parts Al ⁰ (inorganic spherical α-aluminum powder, particle size ¹⁰ <0.35mm (-45 mesh) and 11.4 parts (0.056m ) MgCl ₂ .6H ₂ O [molar ratio 1: 1: 0.17] were mixed together in a reaction vessel with stirring and heated using an electric jacket.

After 100 C has been reached within about 10 minutes the yellow color intensified and at 118 ° C vigorous foaming began with evolution of gas. at 122 ° C, the refluxing liquid turned gray and the temperature stabilized when the Color of the reaction mixture from a deep gray with a bluish tint to a dark blue and then

to a blue-black after a reaction time of 27 Mi-25

The temperature was maintained -within increased from 1 hour and 20 minutes to 145 G, after which the evolution of gas was essentially ended and

the reaction was terminated. 30th

The reaction product was viscous at room temperature Liquid - which recognize unreacted aluminum particles let. The unreacted aluminum was separated, washed and weighed to determine that 6.7 parts of Al had reacted. The reaction product contained 7. -9% by weight Ti, -3.4% by weight Al and 0.7% by weight Mg

3U652A

• ki-

(Molar ratio 1: 0.75: 0.17).

(B) 9.10 parts of the reaction product prepared above (0.719 parts Ti or 0.015m Ti) were in 13.0 parts Hexane introduced into a reaction vessel in a cooling bath; There were 0.045m ethylaluminum dichloride in portions added, - the temperature being kept at 15 to 20 C. became. The mixture was stirred for 30 minutes, - whereby one dark red-brown slurry and one untreatable Solid obtained (B1).

A second experiment was carried out (O, \ L75m Ti / -15

-O, 'O525m Al) without cooling to a peak temperature

of 38 ° C, 'with a red-brown Aufsch. lamination was ■ formed · with a non-treatable solid precipitate (B2); .
20th

Example 15 - -

The reaction products of Example 14 were used as catalysts in the polymerization of ethylene under standard conditions (88 ° C (190 ° F), <5.2 kg / cm ² (60 psig) H ₂ ) using triethylaluminum as a cocatalyst, the the following results were obtained:

MI HLMI ME

Bl 0.4.4 6.45 46.1

35 B2 0.38 17.4 45.7

• (Π · ·

Example 16

(A) In a manner similar to the above, 0.133m TBT, -0.100 ra Al and 0.017m AlCl ₃ .6H ₂ O in octane were combined and reacted over a period of 7 hours and 15 minutes to produce a dark blue-black liquid and a received a small amount of a gray solid. About 40% of the aluminum reacted to form a reaction product comprising 6, .6 wt -% Ti and 1.6 wt .-% Al contained (16AL).

In the same way, the same reactants were combined in a ratio of 1/1 / 0.17m. About 58 % of the Al reacted to form a reaction product ¹ which contained 6.5% by weight of Ti and 2.7% by weight of Al. (16A2) i

(B) The reaction products (I6AI) and (16A2) were with Ethyl aluminum chloride with an Al: Ti ratio of 3: 1 activated.

The solids portion of the activated reaction product (16A2) was isolated from the supernatant liquid and used in the preparation with TEA as a cocatalyst in the polymerization of ethylene at 77 ° C (170 ° F) and 2.05 kg / cm ² (15 psig) H « a resin, which was characterized by a MI of 0.02, - a HLMI of 1.01 and a MIR of 50, ¹ S, and the second in an attempt ''

was characterized by an MI of 0.2, an HIMI of

and a MIR of 22.5.

Λ2-

The following examples explain catalyst components, produced using other aqua complexes: were presented;

Example 17

(A) 0, -0335 mol TBT and 0.0335 mole of Mg ⁰ were stirred in octane in a heated Reäktionsgefäß, then Ο were ΌΟ57 mol MgBr ₂ .6HoO added (reaction Mo1verhältnis 1/1 / 0.17) The i Salt dissolved within 6 minutes

Developed under heating to 65 Ci with evolution of gas 15th

turned gray and the solution turned blue, -then blue-black with a greenish tint. The reaction was terminated at 123 ° C (about 10% unreacted Mg) after a reaction time of 4 hours and 10 minutes (17A). -

In a corresponding manner, a reaction product was prepared with a molar ratio of Ti / Mg / MgBr ₂ i6H ₂ 0 = 1 / 0.65 / 0.11, a blue-black liquid and a dark green precipitate being obtained as the product (6, -5 wt .-% Ti, - 2.5 wt .-% Mg (calc.)) I

(B) The decanted reaction product (17A) was treated with isobutylaluminum dichloride at Al: Ti ratios of 3: 1 and 6: 1 combined by adding the alkylaiuminium halide in portions In the first attempt (AItTi = 3: 1) a peak temperature of 42 G was reached with a Add at a rate of 1 drop / 2 to 3 seconds, taking the green liquid turned brown. The reaction product was a red-brown liquid and a

- 4fr-

brown precipitate (4B-1). The 6: 1 product (4B-2) became produced in a corresponding manner, with the same

results were obtained.

In a separate experiment, the reaction product (17A) was combined with SiCl3 in the same way. The reaction product after 30 minutes of reaction at a Si: Ti ratio of 3: 1 was a light yellow liquid and a brown precipitate. A similar experiment gave a Si / Ti = 6/1 reaction product.

(C) The active reaction products UB-I and 17B-2 (1 wt% Ti) were used for the polymerization of ethylene (10 mol% in isobutane) at 88 ° C (190 ° F) with a hydrogen modifier and Triethylaluminum cocatalyst (45 ppm Al) was used and compared to an identical experiment ¹ in which magnesium chloride hydrate was used, the results given in Table III below being obtained.

ω ο

bo cn

Table III

Catalyst Al / Ti ⁺ Ti (OBu) ₄ -Mg-A (molar)

-6H ₂ O 3/1

3/1 5.2 (60)

9, -4 C. 20)

6/1 5, -2 ( ⁶⁰ ) 9 _f * 0 ²⁰ )

rock
(gPE / g cxvxtat -
TiiStd.) MI HLMI HLMI / Ml CO 42 870 1.7 61 35.9 ι J ^
^ CD
w> cn 49 100 12.2. 348 28.5 " I K) 105 190 24 698 29
(Γι 77 390 102 _—— - 8th
• 34 780 10.3 371 36. 37 050 17.8 639 35.9

3H6524

Example 18

(A) 42.23 parts (0.124m) TBT were mixed with 3.02 parts (0.124m) Mg in 42.8 parts octane in the presence of 5.7 parts (0.02m) FeCl ₃ .6H ₃ O (T / Mg / Fe = 1/1 / 0.17 molar) in a closed, stirred reaction vessel, 'equipped with a reflux and an electric heating jacket. .

tet was combined; Heating was started and gas evolution began at 65 ° C. within 6 minutes; The dirty yellow color changed at 8O ⁰ C (7 minutes) to dark brown and the Gasent-

"

winding stopped. Within about 30 minutes the evolution of gas had decreased and then it stopped when the Mg was consumed and the reaction was terminated. The very dark liquid showed no residue (18 Al); ·

In a second experiment the same reactants were used combined with each other in a molar ratio T / Mg / Fe = 1/1 / 0.34: with corresponding results being obtained. Dilution with hexane resulted in no precipitate or ai no deposition of a residue (18A2);

(B) The reaction product 18Al was obtained by reaction with a 50% strength by weight solution of ethylaluminum chloride activated in hexane at an Al: Ti ratio of 3: 1; A brown liquid and a solid were obtained which received 16.5 mg Ti / g (18Bl).

In a similar manner, the reaction product (18A2) was activated; The dark brown liquid became one

3H6524 · ^: " ^{: ϊ:} · · ^: ·" -

-.48-

• 52

purple slurry and then to a dark gray

Slurry; The clear liquid obtained thereby and 5

. the gray precipitate contained 16 mg Ti / g;

(C) The activated reaction product was 18Bl (190 ⁰ F) and 4, -2 kg / -cm ² (60 psi) was used for the polymerization of ethylene at 88 ⁰ C H _2; There were 114-320 g PE / g Ti / -h. which had the following properties, MI 5.1, · HIMI 155, -3y MIR 30, -3.

15 Example 19

(A) 0.160m Ti (OBu) ,, - 0.160m magnesium turnings and 0.027m CoCl; 6H ,, 0 were combined with 61.2 parts of octane in a stirred reaction vessel. The purple cobalt salt crystals, when dissolved, gave a dark blue solution. The mixture was heated using an electric jacket and at 58 C gas evolution occurred on the magnesium surfaces which increased to vigorous foaming at 107 C within 12 minutes; The clear blue color turned grayish on further heating and at 123 to 125 ° C, <when all the magnesium had disappeared, ¹ almost black and the reaction

ended after 90 minutes. The milky blue reaction product was soluble in a hydrocarbon and, on standing, separated into dark blue Liquid and into a dark precipitate.

The experiment was repeated - being practically identical Results have been achieved; -

S3

(B) The Realctioiicprodukt of the above preparation was shaken and there were 0, OlIm (Ti) with isobutylaluminum chloride (0.0333m Al), which was added dropwise to a reaction vessel, combined »The peak temperature was 40 C, whereby a grayish precipitate formed - which turned brown with the further addition of BuAlCl _2. After stirring for a further 30 minutes, the reaction was ended, a dark red-brown liquid and a brown precipitate being obtained.

(C) The catalyst component prepared in the above Example 19 was used in the polymerization of ethylene (88 ° C (190 ⁰ F), 10 Mo% ethylene, - 0.0002 parts catalyst - about as Ti, about 45 ppm Triethylaluminum, ¹ beri as Al, H ₉ as indicated), the results indicated in Table IV below being obtained.

Table IV

Catalyst H ₉ kg / cm

productivity
^Ti * ^std )

Resin sheep

MI HIHI HIHI / MI

19B

5, -2 (60) 9, -4 (120)

105 180 6, ^ 2 206 33, -6 75 290 33, <9 950 28.1

Example 20

(A) 0.169m ti (OBu). [TBT], O, 'magnesium turnings 169m and 0,029m AlCIoi6H ₉ O in octane as a diluent were mixed in a stirred reaction vessel, · equipped with an electric heating mantle, combining together

3H652A

ned. The hydrated aluminum salt partially dissolved and at 111 G the solution quickly darkened with the formation of a black liquid with strong foaming, which is caused by the evolution of gas on the surface of magnesium. The solution turned blue and up to at refluxing gently 122 C a dark blue-black liquid formed with some remaining magnesium. At 125 C all of the magnesium metal had disappeared and the solution exhibited a faint green tint. The reaction was stopped and a dark bluish black liquid and recovered a green precipitate in a volume ratio of about 95: 5;

(B) The reaction product described above was treated with isobutylaluminum chloride in a molar ratio of Al: Ti v-dn 3: 1 and 6: 1 by adding the chloride dropwise a reaction vessel, - which contained the titanium material, -

combined i In the first reaction (3: 1) the Al- Kylchloride added at a rate of 1 drop / 2 to 3 seconds - until a peak temperature of 42 C is reached had been / being the color from blue-green to brown other times After stirring for a further 30 minutes, the reaction

tion product isolated a red-brown liquid and a brown precipitate (20B) i

(C) An Al: Ti (6: 1) product was treated in a similar manner, whereby the same results were obtained (20iG).

10

• 55

(D) The reaction products 2OB and 2OC were used with a triethylaluminum cocatalyst (45 ppm Al) for the polymerization of ethylene (10 mol%) with isobutane as the diluent at 88 ° C (190 ^p F) and a hydrogen pressure as indicated. The experiments were ended after 60 minutes, the results given in Table V below being obtained.

15 20

Table V 406 , Productivity Resin properties HlMI HLMI / MI Catalyst H _? , 542 tatCgPE / g
T ^ hours) MI 517 1/30 kg / cm "mol
(psig) 245 84-580 17th 1413 July 25 2OB 5, -2 (60) 183 75-280 54. 129 4/31 9.4 (120) 54 440 4th 2OC 5, -2 (60) 34 860 9, -4 (120) .2 , 9 , 11

25th

26.2 · 801 30.5

Example 21

(A) .0, tl53m Ti (OBu) ₄ [TBT], -O, -153m Mg-chips and O, O26m. NiCl ₂ i6H ₂ O was combined with 61.75 parts of octane in a stirred reaction vessel fitted with an electric heating mantle; When heated to 44 C the yellow color of the solution intensified and at about 57 C a gas evolution was observed on the magnesium metal surface.

-53--

zen did the gas development increase _? until at 102 ° C (after 15 minutes of reaction) the reaction system turned a light dirty brown color. The vigorous foaming continued with the brown color turning dark until all the magnesium had disappeared at 126 ° C. (after 75 minutes) and the reaction was ended. The reaction product (21al) was soluble in a hydrocarbon dark ^brown: liquid and a small amount of a fine precipitate.

In a second experiment, 0.149m TBT, 0/149In Mg

and 0.051m NiCl ₉ .6H ₉ O in octane combined in the same way; The magnesium metal disappeared after 120 minutes at 115 ° C and the reaction led to a dark brown-black, soluble in a hydrocarbon

liquid, which when left standing in a

very fine dark precipitate and in a yellow river. sigkeit, VoI; -ratio about 50:50, separated (21A2);

(b) The reaction product IAl was shaken and a portion of it (0.0137m Ti) was introduced into a reaction vessel with a hexane diluent - then at a rate of 1 drop / 2 to 3 seconds up to a temperature of 28 ⁰ Ci-BuAlCl ₂ (0, -0411 m Al) and at a rate (rate) of 1 drop / second up to a peak temperature of 39 C was added. After the addition was complete, the contents of the

_3b vessel stirred for 30 minutes and the reaction products, a dark red-brown liquid and a dark gray precipitate, were isolated (21 sheets).

- 93 -

The same reaction product (21Al) was combined in the same manner with ethylaluminum chloride in an Al: Ti molar ratio of 3: 1. The reaction product was a dark red-brown liquid and a dark gray one
Solid (21B2).

In a practically identical manner, the reaction pro-10

duct 21A2 (Ti / Mg / Ni molar ratio = 1/1 / 0.34) combined with i-Bu-AlCl ₂ in an Al: Ti ratio of 3: 1, the same results being obtained, but this time the supernatant liquid was pale red-brown in color (21B3);

In another experiment, the reaction product was
21A2 reacted in the same way with i-BuAlCl ₂ at an Al: Ti ratio of 6: 1, a dark liquid and a dark precipitate being obtained in a corresponding manner (21B4).

The same reaction product 21A2 was combined with ethylaluminum chloride in the same manner, whereby one a dark red-brown liquid and a dark gray solid were obtained; (21B5) i

Example 22

(A) Example 21A was repeated, but this time

the reactants in a molar ratio Ti: Mg: Ni of 1: - 35

0 ^ 65; 0.11 were supplied; The color change occurred

from a deep brown-yellow to a dark brown with evolution of gas and then to a gray-brown up to

52 ·

a dark blue black with consumption of the magnesium as part of a reaction / that occurred over a period of 6 hours (22A).

(B) Reaction product 22A was made in the manner set forth in Example 21B with ethylaluminum chloride in one Al: Ti-mol ratio of 3: 1 combined. A red-brown liquid and a red-brown precipitate became obtained (22B);

Example 23 .

15th

Example 22A was repeated, this time combining the reactants in a molar ratio of 1: 0.75: 0/128. The dark brown reaction product contained 5/9% Ti /% Mg 2/2 and 0/97% Ni.

The reaction product was then treated with isobutyl aluminum chloride treated in an Al: Ti molar ratio of 3: 1; 25th

Example 24

A series of TMgNi catalysts were prepared as indicated in Examples 21B and 22B / used as a catalyst component for the polymerization of ethylene (88 ° C (190 ° F), 10 mol% ethylene / about 45 ppm triethylaluminum / calc ; as Al / H ₂ as stated) / where the results given in Table VI below

were obtained.

3U6524

Table VI

_Ρ,. . . ^Η 2 »2 product - resin properties
Catalyst kg? _{Cm vity (gPE / g} - ^ £ S JEmT / ml

21 B-3 5y2 (60) 90 750 9.55 270 28

9 -4 (120) 104 980 24.6 683 27.8

B-3 5.-2 (60) 111 940 0.29 10.7 36.8

9.4 (120) 112 260 3.1 119 38.9

B-4 5, -2 (60) 59.790 0.25 10.9 43.6

9.4 (120) 62.720 1.0 43.6 43.6

, κ 22 B 5, -2 (60 57 890 1.66 54.9 33.1

9, -4 (12O) 64 740 6.13 183 29.8

B-2 5, '2 (6O) 238 670 0.65 19.5 30.2

9, -4 (120) 271 560 6.7 188 28.1

20 21 B-5 3.0. (3O] P 175 000 low -

Experiments with higher amounts of hydrogen were extreme

quickly and led 2u of a polymer enrichment, which required termination of the trials.

- 56--

Example 25

^b A) TBT, Mg ° and MgSiF., 6H ₂ O were combined in octane in a heated reaction vessel equipped with a cuckwheel in the manner indicated in the above examples, using molar ratios of 1/1/0, 34 and 1 / 0.75 / 0.128 reaction products were obtained.

B) The last-mentioned reaction product was obtained by reaction with ethylaluminum chloride in an AItTi ratio of 3: 1

15 activated.

C) The brown precipitate obtained was removed from the - standing red-brown liquid separated and together with

_9n TEA was used to give about 45 ppm Al under standard ethylene polymerization conditions (88 ° C (190 ° F), 5.2 kg / cra ² (60 psig) Η ») using a resin in an amount of 107,550 g PU / gTi / hour obtained by an MI of 2.85, characterized an HLMI of £ 4.5 and a MIR of 29.6.

D) The T / i / O.34 reaction product prepared above was in correspondingly with isobutylaluminum chloride in one

Al: Ti ratio of 3.1 activated. The solid reaction product

was washed several times with hexane and together with TEA in an ethylene polymerization reactor previously charged with butene-1, used to form a resin of the desired density at 77 ° C {170 ° F), 2.1 at (30 psi) W from the ethylon / butene-1- Feed. The resulting resin had a density of 0.9193, an MI of 1.91, an HLMI of 60.8 and an MIR of 31.8.

3H6524 · ^: " ^: ·" · GA-

The following example illustrates catalyst components that are activated by reaction with a halide component became.

Example 26

A) In the experiments below, TMMg reaction products were reacted with the halide component, which was added in portions, usually dropwise, in order to reduce the exothermic To control (steer) reaction. The response was

_15th conducted under ambient conditions for a period of time sufficient to completely add the reactant with stirring within 10 to 30 minutes after the peak temperature occurred (where applicable, a TMMg solid and liquid components were mixed together into a slurry and used as is) . The reactants and the proportions of reactants are given below:

30 35

10

25th 30th 35

Halide activator molar ratio 2/1 Al / Ti Bu ¹ AlCl ₀ Bu AlCl ₂ 3146524 " Bu ¹ AlCl ₂ - 58-- Bu ¹ AlCl ₂ 3/1 Catalyst component, molar ratio XtAlCl ₇ 4/1 Ti / Mg / MgCU * 6H "O (H ₀ O) XtBCl ₂ ' 6/1 1 / 0.65 / 0.11 (0.66) XtBCl ₂ 3/1 1 / 0.65 / 0.11 (0.66) SiCl ₄ 1.25 / 1 (B / Ti) 1 / 0.65 / 0.11 (0.66) SiCl ₄ 3/1 (B / Ti) j 1 / 0.65 / 0.11 (0.66) XtAlCl ₂ 3/1 (Si / Ti) j 1 / 0.65 / 0.11 (0.66) Et Al ₂ Cl ₃ 6/1 (Si / Ti) 1 / 0.65 / 0.11 (0.66) Bu AlCl ₂ 3/1 1 / 0.65 / 0.11 (0.66) BU ¹ AlCl ₂ 3/1 1 / 0.65 / 0.11 (0.66) XtBCl ₂ 3/1 1 / 0.65 / 0.11 (0.66) (CH ₃ ), SiCl ₂ 6/1 1 / 0.75 / 0.128 (.768) / f ^ Vi \ Q "ϊ Λ * Ί 3/1 (B / Ti) 1 / 0.75 / 0.128 (.768) (Ch ₃ ) ₂ SiHCl 6/1 (Si / Ti) 1 / 0.75 / 0.128 (.768) SiCl ₄ 6/1 (Si / Ti) "1 / 0.75 / 0.128 (.768) SiCl ₄ 6/1 (Si / Ti) 1 / 0.75 / 0.128C768) TiCl ₄ 3/1 (Si / Ti) 1 / 0.75 / 0.128 (.768) TiCl ₄ 6/1 (Si / Ti) l / 0.75 / 0.128 (.768) Bu AlCl ₂ 1.5 / 1 (Ti / Ti) 1 / 0.75 / 0.128 (.768) X tAlCl ₂ 3/1 (Ti / Ti) 1 / 0.75 / 0.128 (.768) Bu ¹ AlCl ₂ 3/1 1 / 0.75 / 0.128 (.768). Bu ¹ AlCl ₂ 3/1 1 / 0.75 / 0.128 (.768) BU ¹ AlCl ₂ 1 / 0.75 / 0.128 (.768) Bu ¹ AlCl ₂ 1/1 / .17 (1.02) Bu ¹ AlCl ₂ i / l / .17 (1.02) Bu ¹ AlCl ₀ 1/1 / .34 (2.04) 1
Bu AlCl ₂ 1/1 / .34 (2.04) Bu ¹ AlCl ₂ 1/1 / 0.51 (3 * 06) Bu ¹ AlCl ₂ 1/1 / 0.51 (3.06) Bu AlCl ₂ 2/1 / 0.17 (1.02) 2/1 / 0.17 (1.02) 2/1 / 0.34 (2.04) 2/1 / 0.34 (2.04) 3/1 / 0.51 (3.06) 3/1 / 0.51 (3.06) - 3/1. -, ■ j 6/1 3/1 6/1 3/1 - ⁶ A '" 3/1 6/1 371 6/1

3U652A

- 59--

Example 27

A) Catalyst samples activated ^{with Bu 1} _{AlCl 2} (Al: Ti = 3: 1) were used in a series of polymerization experiments, the results given in Table VII below being obtained.

co
σι ω ■ bo
Ό σι to
O
Tabel he.
VII l- ¹
O σι 61
348 . Resin powder
HLMI / MI Molar ratio Ti / MgCl '6H _? O
( MnIvprhH 1 + hi ς.) H ₂ , kg / cm
(psxg) ² productivity
(g PE / g Ti-StdJ Features d
MI HLMI 135
519 35.9
28.5 1/1 / 0.17 ·· 5.9 5.2 (60)
9.4 (120) 42 870
49 102 1.7
12.2 81
452 35.5
33.0 1/1 / 0.34 2.9 5.2 (60)
9.4 (120) 63 385
43 655 3.8
'15.7 89
■ 430 32.3
36.2 2/1 / 0.34 5.9 5.2 (60)
9 ^ 4 (120) 57 510
'54 200 2.5
12.5 179
630 37.1
32.6 * ι 3/1 / 0.51 5.9 5.2 (60)
9.4 (120) 53 975
56 560 2.4
13.2 245
1300 33.8? ^
27.6T ¹ 1 / 0.75 / 0.128 • 7.8 5.2 (60)
9.4 (120) 124 930
116 990 5.3
22.8 .67.3
491 30.2 1 / 0.65 / 0.11 9.1 5.2 (60)
9.4 (120) 76 785
61 550 8.1 '
44.5 29.9
28.2 2/1 / 0.17 · 11.8 5.2 (60)
9.4 (120) 138 820
89 900 2.25
17.4 Reactor conditions:

Diluent - isobutane

Temperature -88 ° C (19O ⁰ F) hydrogen - as indicated

Go-Catalyst - Tribthylaluminum (45 ppm Al). ,

Catalyst - Ti (OBu ^ -Mg-MgCl ₂ .O ^ O reaction product, activated with Bu ¹ AlCl ₂ (AIiTi '= 3: 1)

Ethylene - 10 mol- $ test duration - 60 min.

CO Cn K)

If M <

.It f «T (

■ < i

i ■. ■ .65-

From a comparison of the Ti / MgCl ".6H ₂ 0 molar ratio, a peak melt index yielded at a ratio of 9: 1 ⁵ (Tith ₂ O = 1.5: 1).

B) In the following additional tests, the influence of the Al: Ti ratio in the activated TMMg 10 (molar ratio 1 / 0.65 / 0, li) catalysts in the polymerization of ethylene investigated * The results are given in Table VIII below.

03 O

to cn

t> o ο

cn

Table VIII

activating activating
. Connection / Ti H ₉ , kg / cm productivity Ti-StdJ Features d. HLMI Resin powder 1
2 CO
i ' ^: - * link (molar) (ps? g) . (g PE / g 285,
67.0 MI 489
1436 HLMI / MI 2 I ΟΊ
K) Bu ¹ AlCl ₂ 2/1 5.2 (60)
9.4 (120) 54
45 7 85
550 16.8
51 245 29
28. , 4
, 5
• Bu ¹ AlCl ₂ 3/1, 5.2 yo) 76
61 410
255 ",. ,
830
370 ■ 8.1
44.5 257
1119
105
495 30th • 6 flT> • Bu ¹ AlCl ₂
Bu ¹ AlCl ₂ 4.5 / 1
6/1 5.2 (60)
9.4 (120)
5.2 (60)
9.4 (120) 66
67
43
44 790
310 7.7
35.5
2.7
15.0 214 • 33.
31.
39
33 .6
.6 AtAlCl ₂ 3/1 , 5.2 (60Ϊ 60
'97 755
290 7.0
39 128
616 30, XtBl ₂ . 3/1 5.2 (60)
9.4 (120) 94
56 300
290 3.7
21.5 105
560 34.
28, StBCi ₂ 1.25 / 1 5.2 (60)
9.4 (120) 34
27 3.5
18th 30th
31

Reactor conditions

Diluent · »Isobutane

Temperature - 88 ° C (l90 ° F)

Hydrogen - as indicated

Cocatalyst - triethylaluminum (45 ppm Al)

Catalyst - Ti (0Bu) rt-Mg-MgClrt. 6Hrt0 reaction product, activated as stated above Ethylene - 10 Mol-J?

Duration of the experiment - 60 min,

3H6524

- 4Θ--

C) In another series of experiments, using a TMMg catalyst with a molar ratio 1 / 0.75 / 0.128 analyzed the influence of the activating agent, the results given in Table IX below were received

co
CJi CiD
O fco to
CJi 'O r- ¹ ·.
CJl 0 CJi 179
630 . Resin powder
HLMI / MI 33.8
27.6 CO Table IX 103 32.2 IP cn
1 cn Activation
middle Molar ratio
Cl / Ti ', ^H 2 f. Kg / cm
(psig) productivity
(g PE / g Ti ~ hours) Properties d,
MI HLMI 58.
259 24.0
24.9 Bu ¹ AlCl ₂ 6th .5.2 (60)
9.4 (120) 124 930
116 99.0 5.3
22.8 214
460 5 29.5
28.2
' 1 * «·
• · C
* «<*
C. StBCi ₂ 6th 5.2 (60)
9.4 (120) 94 850
'80 060. 3.2
29.0 51.
198
210
611 £ 26-6>
27.2 ⁰ P
23.7
24.2 ItUU
* Me ₂ SiOl ₂ 12th 5/2 (60)
9.4 (120). 24 860
21 l'2O 2.44
■ 10.4 29
229 7th 29.3
28.7 Me ₃ SlCl 4th 5.2 (60)
9.4 (120) 32 225
28 770 7.25
16.3 ' 61.
297 0 34.2
33.7 Me ₂ SiHCl
SiCl ₄ 6th
12th 5.2 (60)
9.4 (120)
5.2 (60)
9.4 (120) 33 010
18 140
61 210
55 435 1.94
7.29
8.86
25.2 Duration of experiment - 60 min 7th SiCl ₄ • 24 5.2 (60)
9.4 (120) 145 830
71 670 0.99
7.96 P. TiCi ₄ 6th 5.2 (60)
9.4 (120) 31 950
24 555
. , Ι ι, .. 1.8
8.8 Reaktorbedinqunqen : Thinner - isobutane
. Temperature - 88 ° C (19O ° F)

Hydrogen - as indicated cocatalyst - triethylaluminum (45 ppm Al)

Ethylene - 10 Mol- *

3H652A '"· ^: -M-

θ) were Polymerization in a larger scale at 71 ° C (160 ^° F) with the TMMG (I / O, 75 / 0.128) catalyst. (Slurry separated from the supernatant liquid and washed with hexane) and the TEA co-analyzer using ethylene and butene η-1 as comonotnerero and employing varying butene-1 feed and varying activators and activator ratios. The results are given in Table X below

co

to

to O

OT

Oi

Table X

_v , ethylene feed butene -1-

Versucn ( _{Gew #} _ ^ Monomeres "- · ■ ■ ^Nr * in the reactor)

DeSCniCKUny

(Weight -% Total-

4.41
2.39
3.02
2.43

2.32
2.34

1.75

monomeres; 7.55

7.14 11.56 11.59

14.66 15.77

17.82

0.12 0.06 0.05 0.07

0> 03 0.03

0.06

τ ■ *)

density

Pellet ·,. . * MI HLMI / MI (annealed;

Activator

, 0 .2

12.7 • 1.9 1. 3. 3.9 0.6 0.7 0.6 5.8 1.1

1300 0.948 6/1 Al / Ti iBuAlCl.

40 0.939 6/1 Al / Ti iBuAlCl,

41.2 0.934 6/1 Al / Ti iBuAlCl.

.28.5 0.939, 3/1 Al / Ti EADC

28.6 0.934 ■ 3/1 Al / Ti EADC 33.4 0.931! 3/1 Al / Ti EADC

30.2 0.929 3/1 Al / Ti EADC

31.3 0.928 3/1 Al / Ti EADC

29.7 0.935 3/1 Al / Ti EADC 43.9 0.924 6/1 Al / Ti EADC

3U6524

The resin batches collected as indicated above were used with 100 ppm calcium stearate and 1000 ppm Irganox 1076 stabilized, Characterized by conventional testing and in a 3.81 cm (1.5 inch) hard extruder (screw 60 rpm; 7.62 cn »(3 inch) nozzle with a 0.208 cm (0.082 inch) die gap, cooling air 2.8 to 4.4 C (34 to 40 F)) converted into a blown film and further tested as in the tables below XI and XII indicated.

ω αϊ

03 O

K) O

cn

Εΐα 1000 χ ΙΟ " ³

Nozzle swelling + Eta 1000

2 Tensile strength in kg / cm (psi) at 50.8 cm (20 inches) / min '

Yield Strength · in kg / cm (psi) at 50.8 cm (20 inches) / min • Table XI

Properties . '

of linear resins with lower

density
A.

JL
3.67

164

4.36MF

3.56
152

3.35
150

3.95MF 4.00MF 3.9OMF

.1

277.2 125.3 129.5 126.7 119 157.5 239.4

(3960) (179O) (185O) (1810). (1700) (2250) (3420)

224.7 193.9 225.4 198.1 Ί 86.9 173 ', 6

(3210) (2770) (3220) (2830) (2670) (2480)

Elongation in % at 50.8 cm (20 inches) / min 100 130 680 160 290 740 750

2 <3

Tensile modulus in kg / cm (psi) χ 10

Impact tensile strength, mkg / ct / (ft.-lb / inch)

Vicat softening point in C LTB in ⁰ C
Shore hardness "D"

4.64 3.64 2.95 3.44 2.73 2.77 2.37

(66.3) (52.0) (42.2) (49.1) (39.0) (39.5) (33.8)

1.03 2.03 2.80 1.90 1.70 4.59 5.75

(47.7) (94.6) (130) (88.3) (79.2) (213.7) (267.4)

115 115 114 115 -76 -76 -76 -76 61 58 57 59

114

58

112.

-76

57

112

-76

57

231.7 (3310)

168
(2400)

740

2.44 (34.8)

6.43 (299.0)

110 -76 56

I J

1.89 4.15 146

116.2 133.7 (1660) 0910)

203.7 143.5 (2910) (2050)

100

3.10 1.94 (44.3) (27.7)

2.08 3.91 (96.6) (181.9)

109

-76

58

100

-76

^ MF = at least part of the melt broke, indicating that an optimization of the conditions for the respective extrusion was required.

ω ω
σι ο MD TD bo to
σι ο M.
σι with lower ο σ F. TD MD Table XII 0.051 (2 * 0) Yield strength, kg / cm (psi) MD TD Properties of the blown 0.051 (2.0) 18.3 MD Linear resin films 28.4 density 7.1 Film thickness in mm (mils) Elongation in % TD B. , 4.9 (5500) 385 Turbidity in % MD 0.051 (2.0) 0.025 (1.0) (5620) 393.4 0.025. (1.0) (4900) 343 Shine,. 60 °,% : Elmendorf tear g / O, 025mm TD 45.5 30.0 (3320) 232.4 32.2 (218 0) 152.6 Tensile strength in kg / cm (psi) strength (mil) MD 3.3 4.4 (2390) 167.3 3.9 (2410) 168.7 ^ ASTM tear strength TD (3740) 261.8 (4130) 289.1 (2620) 183.4 (6060) 424.2 700 J ^ «
rn DI004 in kg / mm (lb / mil) (2940) 205.8 (2070) 144.9 670 (4410) 308.7 550 (J ₁ - * J Tensile modulus in kg / cm (psi) (2610) 182.7 (2550) 178.5 780 (2250) 157.5 35 ^^. (2840) 198.8 (2400) 168 21st (2330) 163.1 256 750 560 177 ■ 670 17.70 (0.99) 830 320 16.80 (0.94) 880 17.16 (0.96) _:> . _t 16 6 16, 8C (O.94) 21st (49830) 3488.1 Γ · .. " 17 346 (60130) 4211.1 492 (68520) 4796.4 ..: '"
• 19.13 (1.07) 20.02 (1.12) (74340) 5203, 13.23 (0.74) • ·
• * · · »β 17.34 (0.97) 17.34 (0.97) 14.66 (0.82) (72350) 5064.5 (68440) 4790.8 2 (55250) 3867.5 (92930) 6505.1 (87910) 6153.7 8 (67800) 4746

OO

σι

ω ο

to

. bO

CJi

Oil

Τα belle XII - continued

Dart drops in g Cmm (mi Is ₁ ) J

dynamic ball burst cm / kg fmm (miI) J

Sagging in mm (mils) (lowering)

Melting temperature in C (F)

Head pressure in kg / cm (psig)

Properties of the blown

Linear low density resin films

0 B. 10 .5 (1.0)
Xp, 025] C. 92 (2.2)
[p, 056j • 45 (1.3)
[p, 033J F. co 72 (2. 2 y
β), 056] 1 .40 (1.0)
[0/025] 3.94 (2.2)
[0.056] 2.48 (1.2)
[0/030] 81 (2.0)
[0.051] VJ CO
® cn 2.44 (ο • 25) 0.005 (0.2) 4.26 (2.0
Op / 051] / 006 -

(331) 166.5 (330) 166

(34 00) 239

(359) 181.5 (359) 181.5

(4 0 5) 207

(3850) 270.5 (3850) 270.5 (4450) 312.5

Temp, the cooling air in ⁰ C ( ⁰ F) (38) 3.3

(38) 3.3

(39) 3.9

(39) 3.9

(38) 3.3

ω ο

Table XII - continued

Film thickness in mm (mils)

Turbidity in %

Gloss, 60 °, %

Tensile strength in kg / cm (psi) yield point, kg / cm (psi) elongation in %

Elmendorf tear strength, g / 0.025mm (mil)

Properties of the blown

Linear low density resin films

G 0.025
Ο, ο) 0.051
(2.0) H 0.025
Ο, ο) 0.051
(2.0) J OJ 0.051
(2.0) 22.6 24.4 28.9 24.5 0.025
Ο, ο) ^V ^ cn!, * 24.4 5.6 5.6 6.1 6.0 20.0 5.6 485.1
(6930) 399.7
(5710) 399
(5700) 303.8
(4340) 6.0 399.7
(5710) 370.3
(5290) 367.5
(5250) 350.7
(5010) 230.3
(3290) 432.6
(6180) • * ■ 367.5
(5250) 137.2
(1960) 137.2
(1960) 140.7
(2010) 144.9
(2070) 252.7
(3610) 137.2
(1960) 146.3
(2090) 154.7
(2210) 141.4
(2020) 128.8
(1840) 135.1
(1930) , »• ti · 154.7
(2210) 590 680. 520 670 114.8
(1640) a * 680 830 850 810 830 610 850 53 80 ■ 32 80 860 80 429 277 559 366 99 277 503

ω
ο

to σι

σι

Table XII - continued

Tear strength according to ASTM Dl004 in kg / mm (lb 18.41 (lb / mil) (1.03)

16.98 (0.95)

Tensile modulus in kg / cm (psi)

3234 (46200)

3961.3 (56590)

17.52 (0.98)

21.63 (1.21)

3261 (46585)

3841.6 (54880)

18.41 (1.03)

16.98 (0.95)

3234 (46200)

3961.3 (56590)

22.34
"(1.25),

20.38
0.14)

3005.8
(42940)

3524
(50343)

14.84
(0.83)

14.30
(0.80)

15.37 (0.86)

14.30 (0.80)

2621.5 2475.2 (37450) (35360)

3133.9 3385.9 (44770) (48370)

Cu

01

co

Table XII - continued

.bo

CJl

fco O

cn

Cn

Dart drops in gtmm (mils)] 109 (2.1) 38 (1.0)

tO, 0533 [0.025)

Properties of the blown films

made of linear low density resins

109 (2.1)
EO, 053]

36 (1.0)
LO, 025]

85 (2.5)
0>, 064]

43 (1.2) CO, 030]

(0.3) 0.008

Melting temperature in ⁰ C ( ⁰ F) (405) 207 (405) 207 (406) 208 (405) 207

O- / O

dynamic ball bursting 6.50 (2.3) 3.11 (1.0) 6.50 (2.3) 3.14 (1.0) 6.62 (2.4) 3.62 (1.2) cm / kg fmm (miIs) J ίρ, Οδδ] [p, 02 $] Co, O58] [θ, Ο2δ]

Sagging in now (mils) (lowering)

(° ³ ) '£ 0.008 cn

(360) 182 (360) 182 ^

Head pressure in kg / cm (psi'g) (4500) 316 (4500) 316 (4800) 337 (4800) 337 (3900) 274 (3900) 274

Temp, the cooling air in C (F) (38) 3 _f 3

(38) 3.3

(37) 2.8

(37) 2.8

(40) 4.4

(40) 4.4

3Η6524

Ε) In other large-scale polymerizations that are carried out in a corresponding manner using the TMMg catalyst (Slurry separated from the supernatant liquid and washed with hexane) at a molar ratio of I / O.75 / -0.128 (Al: Ti = 3: 1, EADC), hexene-1 was added to the reactor as a comonomer together with ethylene. leads and then the butene-1 was replaced, as shown out The exhaust gas analysis showed that ethylene / butene-1 / hexene-1 copolymers and terpolymers were formed in the course of the operation. The results are given in Table XIII below

10

3H6524

--75 -

H CS ro ro vo vo rs r, ro ro ro ro ro ro χ

15th

H CTi CTi 21st • • 1-1 VD ro ta rs CS

ro

CS

in rs

rs

in rs

CT. CS

20th

| 2

ro

co

ο r-

CTi ro in 05 OD in ro CTi rH "^ ro ro CS CTt i-H 1-1 CT. CT> O CT » CT> CTi O O O O O

U) β O Q) U X Q) QJ B. W. O β O B. O O

O) β • μ Q) + J 3 <ΰ CC κ Q) te

314652A · "- ^: " · "-." ■ - '-

. 20-

Example 28

A TMMg catalyst prepared according to the examples and activated with isobutylaluminum chloride (Al: Ti = 3: 1) was also used for the preparation of other copolymers with varying comonomer starting materials, using isobutane as a diluent, at a reactor temperature of 77 ° C (170 ^o F), at 3.1 to 3.8 kg / cm ² (30 to 40 psig) Η "and using TEA to achieve 60 ppm Al with the following results:

15th

Ethylene / 3-methy] butene -1 MI. ME density j

20th

Q R * - ■

Isobutylene

1.25 27.4 0.9488 1.25 28.9 0.9483 1.36 27.9 0.9507 1.55 - 27..7 0.9497 1.56 27. 5 0.9495 1.87 29. 9 0.9496 1.63 28.5 0.9455 2.25 28.8 0.9437 1.46 30.0 0.9428 5.01 30.3 0.9411 1.59 31.9 0.9400 0.37 32.4 0.9518 1.35 29.6 0.9564 1.79 31.1 0.9542 1.17 31.7 0.9567 4.20 30.1 0.9582 3.30 32.9 0.9557

■ _ ■■ -.

The polymerization or copolymerization of other α-01efin

monomers such as propylene, 4-methyl-pentene-1, the alkyl acrylates and methacrylates and the alkyl ester can be carried out in a similar manner be performed.

b.

In addition, the following comparative tests were carried out:

3U652A

-9T-

Comparative examples

.

A) In the same reaction vessel used in other preparations, TBT, Mg and anhydrous MgCl ₂ in octane in a molar ratio of 2/1 / 0.34 were combined and heated to reflux temperature for 15 minutes with none Reaction occurred. The anhydrous MgCl «remained undissolved. Compare also the example IB above.

B) The same system was given a lot of free water

added in bulk, which has a Mg ^ MgC ^ oH ^ O ratio of 1 / 0.34, but no change occurred.

C) TBT and Mg were combined in a molar ratio of 2: 1 in octane and at reflux temperature heated. While the yellow color became a little more intense, there was no reaction.

D) System C above became a lot of free water

added, which has a MgVMgClg.oHgO ratio of 1 / 0.34 corresponded. A small amount of a light yellow resulted

Precipitation that prevents the hydrolysis of the titanium compound

shows that the magnesium did not react.

E) TBT and MgCl ₃ .6H ,, 0 were combined in octane at a molar ratio of 1 / 0.34 and heated to reflux temperature. After the salt was completely dissolved, the solution became cloudy and somewhat viscous on continued 3 hours However, when refluxed, it became clear and

3H6524

Overnight it separated into a cloudy yellow liquid and into a gray-white precipitate. Another attempt at a molar ratio of 1 / 0.128 gave a clear one golden yellow liquid when heated to reflux temperature for only 16 minutes. At a molar ratio of 1 / 1.17, foaming and the formation of a thick cream colored gel occurred which followed the reaction 45 minutes ended. Compare example 7 above.

The invention has been described above on the basis of preferred embodiments explained in more detail, but it goes without saying for a person skilled in the art that it is by no means restricted thereto is, but that these can be changed and modified in many ways without affecting the scope of the the present invention is abandoned.

Claims (1)

Claims 1. Process for polymerizing 1-olefins alone or together with at least one copolymerizable therewith Monomers under polymerization conditions in relation to the temperature and pressure using an olefin. Polymerization catalyst system, characterized in that a mixture of cocatalysts is used, one of which is a halide activated intermetallic compound in which it is the reaction product of a polymeric transition metal oxide alkoxide and a reducing metal with a higher oxidation potential than the transition metal. 2. The method according to claim 1, characterized in that the polymeric transition metal oxide is produced by partial hydrolysis of the transition metal alkoxide. 3. The method according to claim 2, characterized in that the hydrolysis is carried out with an aquokomplex as the water source. 4. The method according to claim 3, characterized in that the water in the form of a hydrated salt, e.g. a hydrate of a salt of aluminum, cobalt, iron, magnesium or nickel is provided. 5. The method according to claim 3, characterized in that the water in the form of a hydrated oxide, preferably 3U6524 in the form of silica gel. 6. The method according to at least one of claims 3 to 5, characterized in that the molar ratio of transition metal to water is about 1: 0.5 to about 1: 1.5. 7. The method according to at least one of claims 1 to 6, characterized in that the reducing metal is magnesium, calcium, zinc, aluminum or a mixture thereof is used. 8. The method according to at least one of claims 1 to 7, characterized in that the transition metal or titanium Zirconium is used. 20 ■ 9. The method according to at least one of claims 1 to 8, characterized in that the transition metal and the reducing metal can be used in a molar ratio of from about 0.5: 1 to about 3: 1. 10. The method according to claim 9, characterized in that the transition metal and reducing metal are used in a molar ratio of from about 1: 0.1 to about 1: 1. 11. The method according to at least one of claims 1 to 10, characterized in that it is the halide activator at least one representative from the group of the alkylalurainiurahalides, the silicon halides, the alkylsiliconurahalides, the titanium halides and the alkylboron halides. 12. The method according to at least one of claims 1 to 11, characterized in that the cocatalyst 5. is an organoaluminum or organoboron compound, preferably triothyaluminum or triethylborane. 13 · olefin polymerization catalyst system characterized by a mixture of cocatalysts, one of which represents a halide activated intermetallic compound which is the reaction product a polymeric transition metal oxide and a reducing metal with a higher oxidation potential than the transition metal acts. 14. Catalyst system according to claim 13, characterized in that the halide activator is at least one member from the group consisting of the alkyl aluminum halides, the silicon halides, the alkyl silicon halides, the titanium halides and the alkyl boron halides acts. 15. Catalyst system according to claim 13 and / or 14, characterized characterized in that the transition metal is titanium or zirconium. 16. Catalyst system according to at least one of the claims 13 to 15, characterized in that the reducing metal is magnesium, calcium, zinc, aluminum or a mixture of these. 17. Catalyst system according to at least one of the claims 3U6524. 13 to 16, characterized in that it is the polymeric transition metal oxide alkylate to the product of controlled partial hydrolysis of a titanium alkoxide is. 18. Catalyst system according to at least one of the claims 13 to 17, characterized in that the transition metal and the reducing metal in a molar ratio of from about 0.5: 1 to about 3: 1. TL5 19. Catalyst system according to claim 18, characterized in that that the molar ratio is about 1: 0.1 to about 1.1.