DE2058852C3 - Process for the polymerization of ethylene - Google Patents

Description

It is already known, the polymerization or copolymerization of ethylene in an inert Carry out solvents in the presence of catalysts, the halogen compounds of transition metals, bound on the surface of inorganic solid particles, and organoaluminum compounds or dialkyl zinc compounds.

US Pat. No. 3,166,542 describes that it is important to use finely divided inorganic solids as inorganic, solid particles an average particle diameter of less than about 1 micron, especially less than 0.1 micron, and the use of finely divided inorganic solids having an average particle diameter of less than 0.1 microns is described. In this patent, the preferred inorganic solids are metal oxides, such as aluminum oxide, Titanium oxide, zirconium oxide, silicon dioxide, thorium oxide and magnesium oxide, silicates such as chrysotile, Actinolite and crocidolite, and aluminates such as corundum and bauxite. In this patent specification described that - the smaller the particle size of the inorganic solids and the greater the amount the hydroxyl groups on their surface - the greater the potential activity and effectiveness of the resulting catalyst component made therefrom.

In the laid-out documents of Belgian patent 705 220, a similar catalyst system is used suggested. In this document, there is no specific limitation on the particle diameter indicated, and it is recommended to use a solid that is an average ίο borrowed particle diameter of 0.1 mm (100 μ). In this document, preferred Solids called: oxides, sulfates, nitrates, phosphates, silicates and mono- and polycarboxylates of divalent metals such as magnesium and calcium. According to this document, it is important that the Conversion between the solid particles and the transition metal compound on the surface of the Particles on which the amount of hydroxyl groups is small.

With reference to the diameter of the solid particles and the hydroxyl groups on the particle surfaces both of the above documents give teachings that contradict one another. On the other On the other hand, with reference to the solids, they have in common that they both have a number of call the same connections.

Surprisingly, it has now been found that particles of a double oxide of magnesium and Aluminum give excellent results when used as solid particles for catalysts in polymerization or copolymerization of ethylene can be used.

The invention relates to a process for the polymerization of ethylene, alone or together with 1-olefins with 3 to 8 carbon atoms and / or diolefins with 4 to 10 carbon atoms, in one inert solvents in the presence of catalysts containing titanium or vanadium halogen compounds, bound on the surface of solid particles containing alumina, and organoaluminum compounds or contain dialkyl zinc compounds, which is characterized in that catalysts may be used in which the titanium or vanadium halide compounds are on the surface of particles of a synthetic double oxide of magnesium and aluminum with an atomic ratio of Mg / Al in the range of 0.02 to 100 are bound.

As previously described, U.S. Patent 3,166,542 does teach the use of solid particles from metal oxides, such as aluminum oxide and magnesium oxide, and the use of aluminates, the occur naturally, such as corundum and bauxite. The above-mentioned laid out documents of Belgian patent 705 222 teach the use of solid particles of oxygen-containing Compounds of divalent metals, such as magnesium and calcium, and of oxygen-containing ones Compounds of zinc. However, no solid particles are used in these references mentioned of synthetic double oxides of magnesium and aluminum.

As can be seen from the examples and comparative experiments below, one obtains significantly improved results when using the double oxides described above as a catalyst component - especially with regard to molecular weight distribution and workability -,

3 4

If one ciurcii the simple use of an aluminum of magnesium and aluminum was not fully determined, one assumes that the magnification of a mixture of the two olives or and aluminum atoms with one another is complicated ^; *? ^ u use of naturally occurring oxygen atoms are bound. “JS is not receiving. 5 As a process for the synthesis of such double oxides it has been found that the atomic ratio of the so-called coprecipi- "$ 'Ί / ΛΙΊη the double oxide in the range of 0.02 to tation process in which an aqueous solution can be mentioned ^ Kt * rit! I. It has been found that polymers of a magnesium salt of an inorganic or ^ P ^ s polymer of ethylene, which have a broad organic acid, such as magnesium chloride or magnesium chloride, as well as an excellent magnesium acetate, with a aqueous solution of a 3 ^^ formability and the hardly colored aluminum salt of an inorganic or organi ^s i ""l; produced with high catalylic activity see acid, such as aluminum nitrate or aluminum aines, if acetate is used as solid constituents, mixed and gradually one Alkaline substance. A catalyst uses such double oxides as aqueous ammonia, drop by drop to the mixture of such double oxides it is possible, ₅ viewing with stirring n adds, with the precipitate ^ iMSfe ΪΪ waive in which the catalyst are formed. Also to be mentioned are the so-called co-gel formation process, and even if one uses this called co-gelation process, the best one can then determine the amount of transition that one uses water-insoluble magnesium oxy-oil will reduce, magnesium hydroxide, magnesium bicarbonate od on ^{S m} ■ Ώ danger that the resulting zo water and the suspension with a S £ ^worsen.?; and since the carrier contains an aqueous solution of an aluminum salt, the polymers cause chemical or organic acid to react, what causes.

The following formula is obtained. Polymerization of ethylene with 1-olefins mMgO · AlO _1-5 · iH ₂ O

i 8 carbon atoms, such as propylene, 1-butene, _Λη η 09 hU 100

aESSS £ u „. DicCopentadie, »" wende, wer _m y, 0 , NuW ^^^^^ -

meet the following requirements. JOO, J ° ™ f J ™ £ ^ _A \ _omve rhäHni _S the above Bc-

(i) be particles of a synthetic _{rdch surplu} hreitet and the content of magnesium

Double oxide of magnesium and aluminum is _{high then} the catalytic activity

his and _ui . increased, but the molecular weight distribution in ^ dem

the above requirements ^

^^^ r ^ S ^ ySÄntr-Äff

such small amounts included that the atomic 7 ^{th> 's} "J / _d ™." polymer is colored and DAB eAältnis these metal elements to-Summ .: 55 ^ f' * J ^ ^1? JS £ using a Nach-Magnesium and Alumtmum in the range of 0.001 "^,""^","^ rfcn must be.

* άί% »synthetic double, o _iy d of" ^ "^^^! ^^ 'SffiS ^

would take from those compounds which simply have a specific surface area

Mixing magnesium and aminium compounds. una ciau » _{2Qm ln dncr} ^ special

fertilize. The synthesis can be done duoh 6 ₅ "ch £££ _{m [om habc} " die, particles ^ us

Procedures are carried out which are known per sl ^ ⁰ ™ t _{chcm Doppe} io _X yd of Magnesium and AIu-

ⁱ i the exact structure of the DoppCoxydc L ^ an average TcUchdiameter-

scr exceeding 1 micron but not greater than 70 microns and a specific surface area in the range of 40 to 500 m ² / g. A particularly preferred average particle diameter is in the range of 3 to 50 microns.

The expression "average pitch diameter", as used here, it is intended not only to give the average value of the diameter of the Specify particles in the particular range of the average particle diameter, but also mean that at least 80 percent by weight of the particles have a diameter that is within them specified area slurps. The value of the »specific surface« or the »specific surface area«, as used in the present invention is represented by nitrogen absorption according to the BET method (described in British Standards - BS 4359, part 1969).

The preferred water content de; synthetic double oxide as shown in the above form] , the above-mentioned preferred particle size and specific surface area are provided by appropriately combining a heat treatment and a chemical. The heat treatment can be carried out at temperatures of 200 to 1000 ¹ C and treatment times of 20 minutes to 10 hours.

The transition detail of the catalyst used in the present invention is on the surface of the particles of the aforementioned syn-Indian Double oxides of magnesium and aluminum bound. As titanium or vanadium halogen compounds can be mentioned titaniumrahalides, alkoxytitanium trihalides, dialkoxytilandihalides, Trialkoxytilane halides, vanadium octrahalides and vanadium oxytrihalides c.

Examples of these compounds are titanium chloride, titanium trabromide, ethoxy titanium trichloride, di- (n - butoxy) titanium dichloride, titanium tri (isopropoxy) chloride, vanadium tetrachloride and vanadium oxytrichloride.

Various methods can be used to bond the transition detail to the above-mentioned synthetic double oxide of magnesium and aluminum. This can be preferably achieved by by the solid particles of synthetic Doppeloxyd in the titanium or vanadium halogen compound, generally at a temperature ranging from room temperature to 300 ⁰ C, preferably from 80 to 200 'C, for about 30 minutes to about 5 Hours, although these conditions are not necessarily essential. Of course, the above treatment is carried out with the absence of oxygen and water as much as possible, generally working in an inert gas atmosphere. The above treatment can be carried out in the presence of a suitable inert solvent such as hexane or kerosene.

After the above treatment, unreacted titanium or vanadium halogen compound is passed through Filtration or decanting removed. Then the solid particles of the synthetic double oxide, to which the titanium or vanadium halogen compounds are bonded, generally mil a suitable inert solvent, such as hexane, heptane, or kerosene, to remove any existing or unbound titanium vanadium halides connection washed.

ι ο

To use the solid particles washed in this way as a Kalulysatorstoffleil they are in one Inert solvent suspended or converted into a solid powder by adding the washing liquid evaporated in a stream of dry inert gas or at reduced pressure. Although a separation of unbound titanium or vanadium compound on the particles is not beneficial the deposition of small amounts of such unbound compounds is allowed as long as that The object of the present invention continues despite the presence of such unbound compounds is achieved.

As another method of bonding the titanium or vanadium halogen compound to the solid particles of the synthetic double oxide of magnesium and aluminum, a method can be mentioned. This consists in the fact that the synthetic double oxide at 20 to 500 ¹¹ C, preferably at 20 to 250 C. Hall and it with the transition metal compound, which is from an inert gas such as nitrogen and argon. is accompanied.

A preferred amount of the titanium or vanadium compound so on the surface of the solid particles Bound from synthetic double oxide is generally in the range of 0.1 to 300 mg. calculated as the titanium or vanadium atom, per gram of the support.

In the process of the invention, the one component of the catalyst that is used is the so produced solid particles of synthetic double oxide containing a titanium or vanadium catalyst componentc contained bound to their surface, and as another catalyst component an organoaluminum compound or a zinc dialkyl is used.

Suitable organoaluminum compounds are those of the formulas R ₃ Al, R ₂ AlX, R ₁ MX ₂ , R ₂ AlOR, RAl (OR) X and R ₃ Al ₂ X ₃ (where R is an alkyl or aryl group and X is a halogen atom) .

Specific examples of organoaluminum compounds are trialkylaluminum compounds such as triethylaluminum, Tripropyl aluminum and tribute I aluminum; Dialkyl aluminum halides, such as diethyl aluminum chloride, Diethyl aluminum broinide. Dibutyl aluminum chloride and dibutyl aluminum bromide; Dialkylaluminum alcohol or dialkylaluminum alkoxides, such as diethylaluminum alhylai; Dialkyl aluminum pheriolates, such as diethyl aluminum colate; Dialkyl aluminum hydride such as diethyl aluminum hydride and dibulyl aluminum hydride: alkyl aluminum alkoxy halides such as ethyl aluminum ethoxy chloride; alkyl aluminum sesquihalides. such as ethyl aluminum sesquicloride. Specific examples for zinc dialkyls are diethyl zinc and dibutyl zinc.

In the mixing ratio of the two components of the catalyst, it is preferred that 0.5 to 300 mol Aluminum or zinc atoms per mole of titanium or vanadium atom bonded to the surface of the solid parts made of synthetic double oxide of Magnesium and aluminum, used willow. The catalyst concentration used can be changed but preferred concentrations are like this. that about 0.005 to 10 g, preferably 20 to 400 mg of solid parts, the titanium or vanadium bond contain bound to it, and 0.1 to 50 mmol of the organic aluminum or dialkvzinc compound in 1 l solvent are present.

The catalyst used in the process of the invention used contains three components, namely a halogen compound of a transition metal. an organic metal compound and a carrier made of synthetic double oxide of magnesium and aluminum. A catalyst that is one of the two crstere Does not contain compounds, namely a catalyst made from a synthetic double oxide of Magnesium and aluminum oxide and an organometal compound or a transition metal compound contains, does not show any olefin polymeric ionic activity. During the manufacture of the catalyst it is important that the connection of the transition mini is first present on the synthetic double oxide of magnesium and aluminum, and then the organometal compound is added to it. If the three ingredients are simply mixed together, so the use of synthetic double oxide as a carrier does not have any particular effect achieved.

The polymerization or copolymerization of ethylene using the aforesaid catalysts is carried out in a manner similar to that of ethylenic polymerisation or copolymerization using Ziegler-type catalysts. In other words, the polymerization or copolymerization of ethylene according to the invention is carried out essentially in the absence of oxygen and water. Preferred inert solvents such as hexane, heptane and kerosene can be used. The catalyst is added to such a solvent and the polymerization of ethylene can proceed by introducing ethylene or ethylene and a comonomer into the solvent containing the catalyst. The polymerization temperature is generally in the range from 20 to 250 ° C., preferably from 60 to 180 ° C. The polymerization is generally carried out at a pressure in the range from atmospheric pressure to an elevated pressure of 100 kg / cm ² , but it is preferred to carry out the polymerization to be carried out at an increased pressure of 2 to 60 kg / cm ² .

The said catalyst system can be used for solution polymerization at elevated temperatures as well as for slurry polymerization or suspension polymerization be used.

In the polymerization or copolymerization of ethylene using the compound according to the invention Catalyst it is possible to adjust the molecular weight to a certain extent by the Polymcrisalionsbcdbedingungen, like the Polymcrisaiionslcmpenitur and the molar ratio of the analyzer constituents, alleviates, and the addition of hydrogen to the polymerization system is to achieve this goal is effective.

Various known additives which are used in the Ziegler-type polymerization or copolymerization of ethylene using a catalyst, may also be used in the crflndungsgema ¹ -ssen method. For example, one can use methods to increase the yield or to improve the density in the bulk of the resulting polymer by adding polysiloxanes or ethers to the polymerisation system.

In addition to the advantages already described, the use of the aforementioned catalyst system is beneficial the following advantages: As the amount of titanium or vanadium compound used per unit of quantity of the resulting polyethylene is very low. can the treatment after the Polymerization can be extremely simplified or, in many cases, be unnecessary. In other words, since the amount of titanium or vanadium compound used in the present invention is very low and the titanium or vanadium compound is only present in a thin layer on the surface of the synthetic double oxide, which is used as a carrier, is bound, the deactivation of the titanium or Vanadium compound can be carried out comparatively with ease. Furthermore shows the Tilanodcr Vanadium compound, even if it is not specially deactivated, for example with alcohol, hardly negative influence on the resulting polyethylene, since it is only present in the catalyst in small quantities is available. In addition, since the catalyst that is used is free from halogen even if if it remains in the resulting polyethylene, it does not cause rust to appear in the mold in the subsequent machining processes and the molded polyethylene barely discolored and does not noticeably reduce their quality.

Example I.

3.05 kg of magnesium chloride hydroxahydrate were dissolved in 7.5 l of distilled water and separated 1.91kg aluminum nitrate nonahydrate in 6.81 distilled Dissolved water. Both solutions were mixed together, and 3 liters of 28% aqueous ammonia were gradually added dropwise to the mongrel with stirring. After finishing the drop by drop Addition, stirring was continued for an additional hour. Then the mixture became overnight kept. The resulting precipitate was separated by filtration with distilled water washed sufficiently and dried under reduced pressure at 80 ° C. for 24 hours. This gave so 1.19 kg of a synthetic double oxide of magnesium and aluminum in a composition, which by the formula

3MgOAIO _ls 4H, O

is printed out. The resulting double oxide was characterized by an alloy ratio of 3 and a specific surface area, determined according to the BHT method (described in British Standards BS 4359, Part 1969), of 96 m ² / g. This Doppcloxyd (800 g) was erwiirmt 1 hour in a nitrogen stream at 600 "C. The thus treated solid had a specific surface area of 176 m ^J / g. And Erwlirmen wtthrcnd 2 hours at 95 (VC observed to a 2% decrease in weight.

The carrier so produced had an average particle diameter of about 20 microns. The Trliger (300 g) was in 1500 ml of titanium tetrahalloride suspended, and the suspension was heated for 1 hour at 135 "C. After the end of the warmth of the vortex the solids were separated by filtration and sufficed with purified hexane for removal washed of free tilane tetrachloride, then the solid was dried. You got one like that Trltger-Tllnnstoffleil in which the TUan connection to the solid support in an amount of 15 mg titanium was tied per inch of solid trilgers.

In an autoclave with a capacity of 5001

tna mn / mn

kerosene was filled in 2001 and flushed with sufficient nitrogen. Then, 1 mmole of triethylaluminum per liter of kerosene and 100 mg of the above solid support titanium ingredient per liter of kerosene were placed in the autoclave. The temperature of the system was then raised to 140 "C, and ^{hydrogen was introduced at a parallel pressure of 6 kg / cm 2.} Under pressure, ethylene was continuously introduced for 1 hour so that the total pressure was 40 kg / cm In the polymerization, the system was cooled to reduce the pressure, the resulting polymer was isolated, sufficiently washed with hexane, and dried in vacuo for 24 hours, as a result, 18.4 kg of polyethylene having a melt index of 0.42 was obtained of polyethylene per mg atom of titanium was 2940 g. The Mtv / M / i value of the polyethylene was 20.1 (Mu 'means the weight average molecular weight and Mn the number average molecular weight -Value of at least 10, preferably at least 15. A bottle was made from this polyethylene according to the blow molding process. The extrusion pressure was low and the resulting bottle had tte a nice interface.

Comparative experiment A

400 g of magnesium oxide powder were heated to 400 ° C. for 1 hour. The resulting calcined magnesium oxide powder (200g) was suspended in 1400 ml of titanium tetrachloride, and this suspension became In the same way as described in Example I, a Kalalysatorbcstandteil produced on a carrier. The titanium compound was titanium in an amount of 10 mg alloys per gram of the magnesia carrier present.

Using the magnesia-supported titanium component thus prepared, the polymerization of ethylene was carried out in the same manner as described in Example I except that the partial pressure of hydrogen was changed to 1 kg / cm. The amount of the above catalyst component used was 100 mg / liter of kerosene. The result was 18.8 kg of polyethylene with a melt index of 0.41. The yield of polyethylene per mg-atom of titanium was 4510 g. The polymer was found to be 6. When the manufacture of a bottle was attempted using the polyethylene thus obtained in accordance with a blow molding method, molding became very difficult because the extrusion pressure became particularly high, both inside and outside Fisheye appeared on surfaces of the flies, particularly on the inner surface. Accordingly, the resulting bottle has no practical value.

Comparative experiment B

200 g of aluminum oxide were calcined at 400 ° C. for 1 hour. The specific surface area of the calcined product was 120 nr / g. This calei nierle aluminum oxide (200 g) was suspended in 1400 m of titanium rachloride and reacted in the same way as in Example I to produce an aluminum oxide carrier-titanium component, the titanium compound being present on the carrier in an amount of 22 mg-atom of titanium per gram of the carrier was. Using the thus prepared aluminum oxide carrier-titanium component, ethyl was obtained under the same conditions as in Example
described, polymerized. The amount of the above catalyst component used was 100 mJ per liter of kerosene. As a result, only 1.0 k ethylene with a melt index of 0.05 was obtained. The polyethylene yield per mg atom of titanium was 110 g

Comparative experiment C

A carrier material was made by adding magncsium oxide and aluminum oxide, which one ir had used the comparison tests A and B in such proportions that the atomic ratio of Mg / Al in the mixture was the same as for example I (Mg / Al = 3). The support was made with titanium trachloride in the same way as described in Example I, implemented. A carrier-1 was obtained in this way itan compound, containing 15 mg-atom of titanium per Grams of the carrier.

Using the carrier thus produced lian component, ethylene was polymerized under the same conditions as in comparative experiment A, 12.3 kg of polyethylene having a melt index of 0.28 were obtained. The polyethylene yield per mg-atom of titanium was 1970g. The ΛΤ »· / Λ? / Ι value this polyethylene was 6. If the polythene was blown in a bottle, it became the The extrusion pressure was particularly high and the occurrence of hook eyes in the water was extreme. Accordingly it was technically of no value.

The results of Example I and those of the comparative experiments A through C are given in Table I.

Comparative insurance I)

Table I also contains the results of the experiment in which Example I was repeated, but instead of a naturally occurring aluminum oxide with an average particle diameter of about 20 microns instead of the synthetic double oxide used in Example I ss magnesium and aluminum used.

Do belle

Triiger

Mg / Al-Alomverhillinis ArI

Example I.

sy η lh. Double oxide of Mg and Al

• VI TiCI ₄

MgO

I / o TiC ¹ I ₄ A | Compared to AI ₁ O,

0/1 TiCI ₄

H Vcrglelclisvcnmch C

mixture from MgO and AIjO,

3/1 TiCI ₄

Vcrylclisvorstich I) bauxite

TiCI ₄

11th

continuation

Titanium compound

Amount of titanium compound on the carrier (mg / g) *)

amount used (mg / solvent) ....

solvent

Organic Al compound

Art

amount used (mmol) **)

Polymerization conditions

Partial pressure of hydrogen (kg / cm ² )

Total pressure (kg / cm ² ) ...

Time (hours)

Temperature (C)

Yield (kg)

Polyethylene

Polymerization activity

(g / mg atom) ***)

Mw / MIi

Vcrpreßbaikeil

Exhalation pressure

Condition of the surface.

Example 1 Comparative Experiment A Comparative Experiment B Comparative Experiment C

15th

KX) kerosene

(C ₂ H ₅ IyM 1

40 1

140 18.4

2940 0.42 20.1

low glail

10

HX) kerosene

40 I.

140 18.8

4510 0.41 6.0

extremely high

Fish eyes * ♦ ** ♦) 22

100
Kerosene

(C, H ₅ )., Al

40

140

1.0

110
0.05
8.4

high
Fish eyes

100
Kerosene

(C ₂ Hs) ₃ Al

6th
40

140
12.3

1970
0.28 6.0

extremely high fisheye

Comparison search I)

33

KK) kerosene

(C ₂ H ₅ IjAI 1

40

1 140

1.5

IK) 0.02 8.8

high fisheye

mg of tilanaiom per (! ram carrier of the tilan compound provided with the

in moles of the organic aluminum compound. the pro liier solvents are used.

l'polymerisataiisheute pro ing-alom titanium.

Schiucl / indcx.

l-'ischaiigen mean that the samples comply with Malet ialfchijr

...., it ^CIS P ^ICI -

Using the ritank components provided with a carrier. prepared as in Example 1, ethylene was produced under the same conditions as in the liei _S pj _c | ι polymerized, but the Arl of the organoaluminum or the Diaikyl / inkkomponi-nic varied. The results are given in Table II.

Table U

Organimlutninium- inllcr Diiilkyl / mkvcrhirulurin

(C, II ₅ ) ₂ AICI (C ₂ II ₅ ) AICI (CjM ₅ ) ,. , AICI ₁ . j (C ₂ H ₅ ) JAI (OC ₂ 11.1 (C ₂ H ₅ I ₂ Zn

Howl in the l'olyfllhylen

13.2 7.0 4.6 3.1 3.3 l'olyiiihyltfn-

misheuie

ΙμΙ / with-atom

Tiliin

2110

1120

740

560

530

I'J. "
17.4
18.3
17.2
19.1

Example 3

A mixture of an aqueous solution of magnesium chloride and an aqueous solution of aluminum nilrat were hydrolyzed with ammonia, and the surrounding precipitate was dried at KK) C and in a StiekstofTsirom for 1 hour ) 'C erhil / .t. Knlalysulorbcslandteile with one Average pitch diameter of about 6 <i 20 microns and a specific surface area of KX) InVg were produced using (I high-quality double-oxides, the atomic compound hiilini.s (Mg / AI) imTr (tger was varied. Ethylene was

14th

inter the same conditions as described in Example I, polymerized, the resulting Catalyst components used individually. The results are given in Table III.

Table 111

MgAI atom .-> ratio / 10 HX) , 50 10 5 4th 2 I.
1 I. 1

Amount; m Howl bound TiUm (mg g carrier) Ikgl 12th 19.0 13th 18.4 13th 19.0 20th 16.0 23 16.1 27 12.2 31 8.0 33 8.4 40 4.6

l'olyälh \ lcn Schind / - Mw Mn Appearance was melted arlikels formed something Howl index formed something μ) mg atom of titanium H) Huilischhaui 3800 1.35 12th Shark skin 3400 0.41 16 Well 3520 0.84 19th Well 1820 0.61 18th Well 1680 0.72 16 Well formed see something 1090 0.38 13th Well formed something 620 0.33 12th Shark skin 610 0.30 IO riaifishhaiit 280 0.10

Example 4

The double oxide of magnesium and aluminum used in Example 1 was used in various Temperatures subject to heat treatment. When using the products that have been heat-treated in this way were carrier tilane components in the same way, as described in Example 1, prepared. Ethylene 2S was made under the same conditions as in the example I using 100 mg of the carrier titanium component produced in this way per liter of kerosene and 1 nmol polymerization catalyst per liter of kerosene polymerized. The results are in the table IV stated.

Table IV

carrier

conditions

hot heat-1

hehiinillun «

300 CxI
400 C "xl
800 C x I.

<^ vichtvcrlusl

". ¹¹ T ",""heat treatment

9.1%
4.1%

0.5 "/ u

Spe / ilisehe

surface

(na g)

IH) 165 153

Amount in
bound
titanium
mg g carrier) yield
(kg) 24 19.7 18th 18.2 15th 18.6

Howl

Ig) mg-Alom

Tiisin

1970
2430
2980

Melt index

1.31
0.84
0.41

Mw Mn

15.0
19.8
21.3

Appearance of

hliisgelormlen

! • "!« Ropes

Well

Well

is applicable

Example 5

300 g of the heat treatment plant. in the same manner Tärgers as prepared in Example I were mixed with 5 ml of a Uhergnngsmctallverbindung, as indicated in Table V, per gram Trilger umgeset / .l. wherein a carrier-transition rivet component was formed. Using the carrier-1 "original metal components so prepared, ethylene was polymerized under the conditions given in Table V. The results are given in Table V.

Table V Ti llger-tihi'i ιιιιημΜίκΜίιΙΙ ·

TiUr ₄

Ti (n-Uuioxy) CI _A

VOCI.,

Amount in bound ii

■ Hler V (ιημ μ Trltyor)

16 20 23

Ti'inp.

140 IKO UtO 160 HO

tctisitimnshci lingunpcn Ausheuii: (kg) Witsseiüliill- (K'snint- I'm I In ld ruck thin 15. « | ΙιμΛ ηι ') Ikg'cnr'l 12.1 ι 40 17.4 ft 40 lft. 6 4th 40 12.2 4th 40 4th K

l'nlylllhylen
Scliniel / Indcx

0.04
0.43
0.K2
0.75
0.51

Healed

Ιμ) / ηιμ Λ | οιη tih

meliill

2370
1450
1930
1840
l4ft0

Mw Mn

19.5 18.8 17.3 17.4 20.1

Terms and Conditions

1. 2001 Kerosene was used as a polymerization solvent used.

2. Concentration of triethylaluminum = 2 mmol / l solvent.

3. Concentration of carrier transition metal component = 100 mg / 1 solvent.

4. Polymerization time = 1 hour.

Example 6

In 2001, refined hexane and 2 mmol of triethylaluminum per liter of hexane and 100 mg of the carrier-transition metal component prepared in the same way as in Example 1 per liter of hexane were charged into an autoclave with a capacity of 500 l. The temperature of the system was increased to 140 ^° C., and hydrogen was introduced at a partial pressure of 6 kg / cm ² . Then, an ethylene-butene-1 gas mixture containing 0.8 mol% of butene-1 was continuously introduced under pressure into the system so that the total pressure was kept at 40 kg / cm ² . The result was 18.0 kg of polyethylene with a melt index of 0.65 and an Mw / Mn value of 19.4. The polyethylene contained three ethylene groups per 1000 carbon atoms. When bottles were blow molded from this polyethylene, no fish-eye formation was observed and the appearance of the bottle was good.

Example 7

About 20 g of the double oxide carrier, prepared according to Example 1, were placed in a glass filter, which is in a central position in a quartz glass reaction tube with a diameter of 30 mm and a Length of 900 mm. The carrier was made by introducing a stream of nitrogen gas from the lower Part of the reaction tube is fluidized, and in this state, the reaction tube was externally heated.

ίο and a certain temperature has been maintained. A nitrogen gas stream saturated with titanium tetrachloride formed by Nitrogen passed through liquid titanium tetrachloride at room temperature, was introduced into the reaction tube

while the carrier was kept in a fluidized state, the carrier reacting with the titanium tetrachloride at the predetermined temperature. The completion of the reaction was confirmed by a sudden increase in the titanium tetrachloride concentration in the exhaust gas taken out from the upper part of the reaction tube. In general, the reaction was complete within 20 to 30 minutes.
After the completion of the reaction, the resulting carrier titanium component was placed in an autoclave similar to that of Example 1, and ethylene was polymerized in the same manner as in Example 1 for snowing. The temperature used to manufacture the titanium carrier component,

and the Äiw / ÄT / i value of the resulting polymer are given in Table VI.

Table Vl

Temperature of implementation

between TiCl and carrier

( ⁰ C)

Room temperature
180
230
350

Amount of

bound ") titanium

(mg Ti / g carrier)

15th
16

24

7.3

Polymerization conditions

.. partial pressure

Trager-Ti- _{of water} .

Component conc. _sto n;

(mg / 1 solvent) (kg / cm ² )

100 100 100 100 8
6th

yield

(kg)

12.6

15.3

11.5

7.6

Polyethylene

yield

(g) / mg-atom
Ti

2020

2300
1150
2500

Melt index

0.42
0.45
0.51
0.36

Mw / Mn

18.7
18.2
19.0
17.6

Terms and Conditions

1. 2001 Kerosene was used as a polymerization solvent used.

2. Triethylaluminum concentration = 1 mmol per Liters of solvent.

3. Carrier Ti component concentration
= 100 mg / 1 solvent.

4. Polymerization was carried out at 14O ⁰ C for: 1 hour at a total pressure of 40kg / cm ^2;, is performed.

Example 8

In 1.5 liters of water, 1 mole of magnesium acetate and 2 moles of aluminum sulfate were dissolved, and then the The pH of the solution is increased to 10 by adding an aqueous solution of sodium carbonate, whereby a precipitate formed.

The precipitate was separated by filtration, washed with water, dried, ground and calcined at 600 ° C for 4 hours, mn η being a solid with an average particle size of 15 microns and a Mg / Al atomic ratio of 0.48. If this solid was subjected to a heat treatment at 950 ^° C. for 2 hours, the weight loss was 3.3%. The solid thus obtained was reacted with titanium tetrachloride in the same manner as in Example 1. As a result, the titanium compound was bound to the solid support in an amount of 24 mg in terms of titanium atom per gram of the support. Using 70 mg of the support titanium component thus formed and 1 mmol of triethylaluminum, ethylene was polymerized under the same conditions as described in Example 1. 85 g of polyethene with a melting index of 0.43 and an Mn / M / i value of 18.4 were obtained. The yield of polyethylene per mg-atom of titanium was 2430 g.

Example 9

In 10 liters of water, 15 moles became commercially available basic magnesium carbonate was suspended, and then the suspension became dropwise into a solution

of 5 mmol of aluminum nitrate (nonahydrate) in 51 water over a period of 30 minutes. The reaction mixture gelled with the formation of carbon dioxide. Then 50 liters of water were further added to the reaction mixture, and stirring was continued for 30 minutes. The pH of the mixture was raised to 9 by the addition of ammonium carbonate and then the mixture was stirred for 1 hour and stored overnight. The precipitate formed was separated off by filtration, washed sufficiently with water and dried ^{at 80 ° C. for 50 hours.} As a result, 1.22 kg of a compound having a composition expressed by the following formula was obtained:

15th

2.8 MgO-AlO, j4H ₂ O

1 kg of the thus obtained Doppeloxyds of magnesium and aluminum at 700 ⁰ C for 1 hour, calcined, so obtaining a solid with a specific surface area of 190 m ² / g, which showed a weight loss of 2.38% when at 2 Was heated at 95O ^{0 C hours.} 300 g of the support thus obtained with an average particle size of about 40 microns were suspended in 1500 ml of titanium tetrachloride, and the suspension was heated for 1 hour at 8O ⁰ C. The resulting mixture was filtered to separate the solids, which were stripped of titanium tetrachloride by the use of hexane. There was thus obtained a carrier titanium component in which the titanium compound was bonded to the solid carrier in an amount of 18 mg in terms of titanium atom per gram of the carrier.

Using 70 mg of the carrier titanium component thus obtained and 1 mmol of triisobutylaluminum, ethylene was polymerized under the same conditions as described in Example 1. The result was 14.0 kg of polyethylene with a melt index of 0.46 and an M w / Ä7n value of 0.46. The yield of polyethylene per mg-atom of titanium was 2660 g.

If a hollow bottle was produced from the polyethylene thus obtained by blow molding, so the extrusion pressure was low and the surface condition of the molded product was very good.

Example 10

^{An aqueous solution of 1 mmol of aluminum acetate in 500 cm 3 of} water was added dropwise over a period of 30 minutes to a dispersion of 1 mol of magnesium oxide in II water. The resulting mixture was stirred for 30 minutes and then the pH was raised to 9.5 by the addition of sodium hydroxide, after which the mixture was stirred for an additional hour and then stored overnight.

The resulting precipitate was collected by filtration, washed with water, dried, ground and calcined ^{at 500 ° C. for 2 hours.} The calcined solid product had a Mg / Al atomic ratio of 0.95 and when heated to 950 "C for 2 hours showed a weight loss of 4.5%.

The obtained carrier was suspended in titanium rachloride in an amount of I u per 5 cm ^{J of} titanium tetrachloride, and a carrier titanium component was prepared in the same manner as described in Example 1. The titanium was bound to the support in an amount corresponding to 20 mg atoms n ^ grams of support.

A 2 liter autoclave was filled with II kerosene, 1 millimole | Triethylaluminum and 80 mg of the carrier titanium component thus obtained and raised the temperature to 140 ° C. Then hydrogen was passed in at a partial pressure of 6 kg / cm ² , and ethylene was continuously added so that the total pressure was 40 kg / cm ^{2 was} held. The polymerization was continued for 1 hour. The result was 84 g of polyethylene with a melt index of 0.41 and a Mu '/ Mii value of 16.1. The yield of polyethylene per mg-atom of titanium was 2520 g,

Example 11

1 l of refined kerosene, 50 mg of the carrier titanium component prepared as in Example 1, 1 mmol of triethylaluminum and 32OmMoI of 1-hexene were poured into a 2-liter autoclave, and the temperature was increased to 140.degree. C. Hydrogen was added to the autoclave a partial pressure of 2 kg / cm ^{2 was} introduced, and ethylene was continuously added so that the total pressure was kept at 40 kg / cm ² . Polymerization was carried out for 1 hour. The result was 68 g of polyethylene with a melt index of 0.2, a density of 0.941 and an Ä7w / M; i value of 19.4 which contained 4.8 methyl groups per 1000 carbon atoms.

When the above experiment was repeated using 40 g of styrene instead of 1-hexene, 71 g of polyethylene were obtained with a melt index of 0.10 and an Mw / Mn value of 18.7, the polyethylene containing three phenyl groups per 1000 carbon atoms .

Example 12

In a 2-liter autoclave was added 1 1 of refined kerosene, 150 of the carrier-titanium component as prepared in Example 1 mg and 1 mmol of triethylaluminum and the temperature was increased to 14O ⁰ C. Then, into the autoclave at a partial pressure of hydrogen of 8 kg / cm ² and an ethylene-butadiene gas mixture with a volume ratio of 95; 5 introduced continuously so that the total pressure was kept at 45 kg / cm ² . The polymerization was continued for 1 hour. The result obtained was 68 g of Polyäthylen_mk with a melt index of 0.5 and an Mw / M / i value of 18.0, which contained 1.5 Iranian double bonds per 1000 carbon atoms.

If the above experiment was repeated using an ethylene-isoprene gas mixture with a volume ratio of 95: 5% instead of an ethylene-butadiene gas mixture, 59 g of polyethylene with a melt index of 0.22 and an Mw / Mn value of 17 were obtained , 4, which contained 1.2 trans double bonds per 1000 carbon atoms.

Example 13

1 l of refined kerosene, 1 mmol of triethylaluminum and 100 mg of carrier titanium component from Example I were placed in a 2 l autoclave and the temperature was increased to 140 ° C. A gaseous mixture of ethylene / hydrogen / propylene in a molar ratio of 85 : 2:40 was continuously introduced so that the total pressure was kept at 40 kg / cm ² , and the polymerization was continued for 1 hour.

guided. As a result, 71 g of polyethylene was obtained with a melt index of 0.97, a density of 0.923 and an Mw / ÄTii value of 19.2, the Polyethylene 30 methyl groups pi: o 1000 carbon atoms contained

Example 14

In a 2-1 autoclave , mim 11 charged refined kerosene, ImMoI triisobutylaluminum and 100 mg of the carrier titanium component prepared as in Example 1, and then cyclopentadiene or ethylidene norbornene was added. The temperature was increased to 140 ^° C., and hydrogen was introduced under a partial pressure of 6 kg / cm ² . Then, ethylene was continuously introduced so that the total pressure was kept at 40 kg / cm ² . The polymerization was continued for 1 hour. The results are given in Table VU.

Table VIl

Copolymerized diolefin crowd
(itiMol / l
Kerosene) Melt index Forming Polyälh
I. Mw / Mn Art 20th 0.13 yield
(S) 18.4 DicyclopenCadiene 40 0.11 51 18.8 Ethyliden-norbornen 49

Number of copolymers

Groups per 1000 carbon

iiiome

0.8
(Dicyclopentadiene)

0.8
(Ethylidene norbornene)

Claims (4)

20 53 852 Patent claims: 1, process for the polymerization of ethylene, alone or together with I-oleline with 3 to 8 carbon atoms and / or diolefins with 4 to 10 carbon atoms, in an inert solvent in the presence of catalysts containing titanium or vanadium halogen compounds, bound on the surface of solid particles containing aluminum oxide, and organoaluminum compounds or contain dialkyl zinc compounds, dad ur ch ge ken η zei chn.c t that Catalysts are used in which the titanium or vanadium halide compounds the surface of particles of a synthetic double oxide: made of magnesium and aluminum are bonded with an At (i> m ratio of Mg / Al in the range from 0.02 to 100. 2. The method according to claim 1, characterized in that catalysts are used in which the particles of synthetic double oxide have an average particle diameter from greater than 0.1 to 100 microns and a specific surface area of at least 20 nr / g. 3. The method according to claim 1, characterized in that catalysts are used in whose preparation the synthetic Doppeloxyd of magnesium and aluminum was heat-treated at a temperature in the range of 200 to 1000 ⁰ C. 4. The method according to claim I. characterized in that catalysts are used in which the atomic ratio of Mg / Al in said double oxide is in the range of 0, i to 10.