DE2056749A1 - Process for the polymerization of alpha olefins - Google Patents

Description

The invention "is concerned with an improved stereospecific Polymerization processes for α-olefins, in particular with a process for the polymerization of cc-Oief inen using crystalline polymers with high productivity a catalyst system, which consists of a modified titanium trichloride obtained through a specific activation treatment.

A process for the polymerization of cc-olefins in the presence of a! A catalyst system which includes a titanium trichloride component and an organoaluraine prebond is well known. En int favorable, v / enn the crystalline act of the received pole, / jfj (; i'vm büi der atercoopezifisehon Polyraerloabion of α-0'Lef Lrion increases L wli'd and thereby dio inechaninche! '' Eotigkeit verberifjorL becomes. Simultaneously int an increase in the yield nn Vol.yw.r-.Fum-} <: i'M.nlieifcf; rriorige den ICabalynatorn from t; ec: hninehen wL.'n.JpiiiikL her f; Urj:; l; ig "J) from (jL not only occurs α lim Viü-ri ngorung the eirizufjfi bi'iondan amounts of catalyst.-on, ijondarn too

10 9 8 2 7/1724 _BAD

the omission or simplification of the step of removing the catalyst residues from the polymer obtained, as well as a increased production efficiency of reaction equipment.

Attempts to increase the stereospecificity and the activity of a catalyst for the polymerization of α-olefins have been made so far undertaken from various points of view. A typical attempt is to add a third ingredient to activate and improve the stereospecificity to titanium trichloride and the organoaluminum compound. A number of substances have been proposed as such a third ingredient. Another attempt is to improve the Organoaluminum compound as a component of this catalyst. It wasn't just trialkylaluminum and alkylaluminum halides suggested but also various organoaluminum derivatives with amide groups, alkoxy groups, nitrile groups or inorganic acid groups. It has also been found that polyolefins have very high levels of polymerization using a dialuminoxane, i.e. an organoaluminum compound with a grouping

^: Al-O- Al ^ L

can be obtained. Further attempts were made to modify it of titanium trichloride as the most important component of the catalyst and this is also the subject of the present invention.

Heretofore, various methods of modifying titanium trichloride to increase the activity of the catalyst have been used proposed and are known. These ancestors atopielr.wui.iuc include grinding titanium trichloride in a ball mill or by ui.no other suitable kin direction or marriage of titanium trichloride and a metal halide

BATH ORIGINAL

2056743

nid, such as telluric chloride, aluminum chloride, titanium tetrachloride, Titanium dichloride, nickel chloride or lithium chloride to form a solid solution or eutectic crystals. Such Titanium trichloride-based components are hereinafter referred to as the titanium trichloride component for convenience designated.

Despite these known proposals, it is difficult to find a method for modifying titanium trichloride due to more general Theories to obtain since the activity of the titanium trichloride component is largely of extremely specific physical and chemical conditions of the crystal, the concentration of lattice defects on the surfaces, the The type and amount of the absorbed inoculum, the degree of agglomeration of the crystal particles and the like is dependent.

It has now been found that the titanium trichloride component can still be modified to a surprising extent by contacting it with a specific treatment agent and then grinding it. A catalyst system containing such a modified titanium trichloride component gives a polymer of a α-olefin in a very increased degree of polymerization, for example an increase of about 10 to about 50 $ and in some cases three times the usual degree and that obtained polymers, has an increased stereospecificity with an increase of a few percent to about 10 % over the usual.

Therefore, one object of the invention is one Process for modifying the titanium trichloride component and to provide an improved process for making polymers of α-olefins having good mechanical strength and with: a very strong increase in productivity and

10 9 '' M.

ter use of a catalyst system which contains the titanium trichloride component modified in this way.

In the process of the invention for the polymerization of α-olefins by contacting an α-olefin under polymerization conditions with a stereospecific catalyst containing a titanium trichloride component and an organoaluminum compound has, the improvement achievable according to the invention is that this titanium trichloride component of the catalyst is used in a state where it has been contacted with a treating agent and ground

", wherein the treating agent is selected from at least one of the following materials (A) an alkylene oxide, (B) an organohydroxy compound having at least one alcoholic or phenolic hydroxyl group and (C) a lactone. The method for modifying the titanium trichloride according to the invention is on all titanium trichlorides applicable, by reduction of ^ itantetrachlorid with hydrogen (commonly referred to as titanium trichloride from the HA type hereinafter) or was obtained by reduction of ^T itantetrachlorid with titanium, aluminum or an organoaluminum compound or barren on a ground product of such a titanium trichloride or a solid solution eutectic crystals applicable.

k The method according to the invention is most favorable to one Titanium trichloride component (commonly referred to as AA-type titanium trichloride) is used, the aluminum chloride as a solid Solution contains.

One class of treatment agents for modification according to the invention consists of (A) alkylene oxides, which are can be reproduced by the following forrael: ■

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E ¹

_c l ₀ 2

12 3

wherein R, R and E have hydrogen atoms or alkyl groups no more than 10 carbon atoms, R is a hydrogen atom, an alkyl, alkenyl, cycloalkyl or aryl group with not more than 10 carbon atoms, optionally with a Halogen atom can be substituted, or a group

cc

-CHpOR ^ mean, wherein R is an alkyl, alkenyl, aryl or Represents glycidyl group with not more than 10 carbon atoms}

13th
where R and R together form a ring with 5 to 12 carbon

1 2 material atoms, which contains G and C, can form.

Preferred examples of the alkylene oxides include ethylene oxide, propylene oxide, isobutylene oxide, 2-butene oxide, butadiene monoxide, Butadiene dioxide, 1-octene oxide, vinylcyclohexane oxide, Styrene oxide, cyclohexene oxide, epichlorohydrin, allyl glycidyl ether and diallyl ether dioxide.

Another class of the treatment agent that can be used according to the invention consists of (B) organohydroxy compounds with at least one alcoholic or phenolic hydroxyl group in the molecule. Specific examples of the organohydroxy compounds are acyclic, cycloaliphatic or aralkyl-mono- or -Polyhydroxy alcohols, phenols and naphthols, respectively, if desired substituted with halogen atoms, alkyl, alkenyl, cycloalkyl, aryl, aralkyl, ester or alkoxy groups could be. Preferred examples of organohydroxy compounds include methanol, ethanol, propanol, butanol, hexanol, Octanol, lauryl alcohol, stearyl alcohol, benzyl alcohol, o- and p-methylbenzyl alcohol, a-methylbenzyl alcohol, cyclohexanol,

1 0 9 B Ί 7/17 2 4

Ethylene glycol, propylene glycol, glycerine, pentaerythritol, butanediol, Hexanediol, cyclohexanediol, phenol, hydroquinone, α- and ß-naphthol, with halogen, alkyl or alkoxy groups substituted phenols, 2-chloroethanol, 2-chlorobutanol and Alkyl esters of hydroxycarboxylic acids such as salicylic acid, tartaric acid, citric acid or malic acid.

Another class of treatment agents within the scope of the invention consists of (C) lactones. Specifically, the lactones are saturated or unsaturated 4- to 10-membered lactones _fc and lactones of o-hydroxy-aromatic carboxylic acids, each of which can be substituted by alkyl or alkenyl groups. Preferred examples of the lactones include propiolactone, butyrolactone, j-valerolactone, coumarin, -caprolactone, o-caprolactone, γ-caprylolactone, γ-laurolactone, γ-palmitolactone, γ-stearolactone, crotolactone, cc-angelicalactone and β-angelicalactone.

The above treating agents can be used alone or in admixture and can be used with the titanium trichloride component in the form of a vapor, a liquid or a solution or suspension in an inert solvent. The titanium trichloride component shows during contacting no noticeable change '' Since, however, a heat generation can be clearly observed, it is assumed that that a reaction between the titanium trichloride component und.the treatment agent takes place. The analysis shows that the reaction product contains the treatment agent incorporated.

The amount of the treating agent to be used may be small and is preferably 0.01 to 1 mol, preferably 0.02 to 0.5 moles of treating agent to 1 mole of titanium trichloride with intimate contact between them for incorporation. If the amount of the treating agent is less than

1 Π ⁽ ) M, '7/1 7 2 A

8AD ORIGINAL

0.01 mol ", the desired effect cannot be achieved and on the other hand, amounts in excess of 1 mole bring no particular advantage.

The titanium trichloride component must be completely milled during or after contact with the treatment agent. If it is not ground, the desired modifying effect cannot be obtained. It is advantageous if the grinding is carried out in an inert atmosphere, free of air and moisture, at room temperature or at an elevated temperature of up to about 200 ^° C. using a hammer mill, ball mill, vibration mill or other suitable pulverizing device. The amount of modification and activation of the titanium trichloride component depends on the amount of milling. For example, the changes in the degree of activation of the titanium trichloride component with the lapse of time of milling based on the rate of polymerization of propylene have been experimentally investigated5 and the results are summarized below. The comparative experiment shows the case where the titanium trichloride component was ground without contacting the treatment agent.

Meal rate of polymerization of propylene (Hours) (g / g TiCl- / hour)

treated with propylene 5,000 comparison oxide 10 700 8 800 12,000 9,000 12 500 9 100 13,000 9,300 13 500 9 400 13 700 9 500 13 800 10,000 10 100

1 0 9 8; 7/1 7 2

For this purpose, a titanium trichloride of the AA type was used among the in Example (A) -3 given conditions during different times "when milling using 1/5 mole, based treated on titanium trichloride, on propylene oxide. The polymerization was carried out under the polymerization conditions III according to Example (A) -3 carried out.

From the above values, there is a tendency that the size or degree of activation of the titanium

fc trichloride component, which with the treatment agent according to of the invention, increases sharply during the first 15 or 20 hours of vibratory milling and then only increases slightly and gradually until it reaches a certain constant value. Because the modifying effect of the titanium trichloride component not only on the amount of milling but also on the type of used Depending on the mill, it is recommended that the milling conditions be determined by previous experiments before the actual technical Determine practice.

The preferred embodiments of the application of the treatment agents are described below. The contacting of the titanium trichloride with the treatment agents (A), (B)

"And (C) can be carried out at room temperature, but temperatures may be used in the range from 0 to 150 ⁰ C. In case of application of the treating agent (A) it is particularly favorable, the treated mass of the ^ itantrichlorids at 70 to 200 ⁰ C., preferably 100 to 150 ^° C. and then grinding the heated mass. The heating time varies with the temperature, but usually less than about 3 hours under reduced pressure are sufficient Solvents and thus another

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ηΐ η pfifpr B "« "fP" II »

Increasing the grinding effect.

Also in the case of the treatment agent (B) it is favorable grinding after contacting the titanium trichloride component to execute. Heating the treated mass is not absolutely necessary, but is the same as in the case of Use of the treatment agent (A) is favorable. If the treatment agent (ö) is used, the titanium trichloride component can be used be ground after or during treatment with the same.

The catalyst system containing a titanium trichloride component modified in the above manner increases markedly the productivity of the α-olefin polymers and yields polymers with higher stereospecificity. The catalyst system which the titanium trichloride component modified with the treating agent (A) contains, is particularly favorable for the production of highly crystalline polypropylene at a high rate of polymerization. The catalyst system, which contains a titanium trichloride component modified with the treating agent (B), is particularly favorable for the production of polyethylene and the catalyst system containing a titanium trichloride component modified with the treating agent (C) is particularly favorable for the production of highly crystalline polypropylene.

The polymerization of the α-olefins according to the invention can carried out in accordance with standard procedures, but using the modified titanium trichloride component, * Although these techniques are well known in the art, they are briefly outlined below.

The other essential part of the catalyst system consists of an organoaluminum compound and these include, for example, trialkylaluminum compounds, dialkylaluminum

1 0 ^c ) R ? 7/17 2 A

halides, alkyl aluminum dihalides, alkyl aluminum oesquihalides, Dialkyl aluminum alkoxides, dialkyl aluminum amides, Dialkylaluminum cyanides and substituted or unsubstituted tetraalkyldialuminoxanes.

There are numerous other connections that call third Ingredients may conveniently be added to improve stereoregularity and include typical examples Tetrabutylammonium iodide, trimethylsulfonium iodide, pyridine, Ν, Ν-dimethylethanolamine, piperidine, methylaniline, trimethylamine, Triethylamine, dibutylamine, tributylamine, tetramethylurea, Triethylenediamine, diethylene glycol, dimethyl ester, dimethylformamide, diethyl urethane, diphenyl urethane, triphenyl phosphine, Tributylstibine, triphenylarsine, menthylamine, hexaethylmelamine, Quinoline, dirnethylacetamide, trioctylphosphine, Hexamethylphosphoric triamide, triethylphosphine oxide, triethylphosphate, Tributyl phosphite, polymethylsiloxane, tetrakis-dimethylaminosilane, Trichloroborazole, Tris-dimethylaminobor, Dipyridinozinc chloride and dipicolino zinc chloride.

The polymerization temperature is usually in the range from 0 to 200 ^° C., preferably from 50 to 150 ^° C., and the pressure used in the context of the invention is normally in the range of 200 atm or below, preferably between 1 and 100 atm.

The polymerizable α-olefins according to the invention are a-01efine with 2 to 15 carbon atoms, such as ethylene, propylene, Butene-1, 3-methylbutene-1, 4-methylpentene-1, hexene, Vinyl cyclohexene, styrene, octene or decene. These olefins may be polymerized or copolymerized, or these «-Olefins can contain diene compounds, such as butadiene, isoprene or cyclohexadiene. Furthermore can the polymerization in the presence of hydrogen, halogenating

) 0 f) B ? 7/17 2 4

'■■'"■" ■ ''"'" ■ -' ■ "■""■' ^{: |} i -'" -. ■ ^{: l!} -: ¹ i; iii:.; Ili!: I! Iii; j | i! L! Jj |! ||| l! I ||| iJ |!;!; M | :: j! . "

th hydrocarbons or diethyl zinc, as is known, for Adjustment of the average molecular weight of the obtained Polymers are run.

The following examples are provided for further explanation the invention*

The examples (A), the examples (B) or. the examples (C) were using the treating agent (A) (alkylene oxides), the treating agent (B) (organohydroxo compounds) or the treatment agent (G) (lactones) carried out. Table I in Example (A) gives the conditions for modifying the titanium trichloride component and the Table II shows the results of olefin polymerization using the modified titanium trichloride ingredients.

Example (A) 1

A three-necked 300 ml flask was thoroughly purged with nitrogen and charged with about 50 g of titanium trichloride (Type AA, product of the Stauffer Company) and 80 ml of n-heptane. The compounds were cooled with ice and stirred with a magnetic stirrer. A solution of ethylene oxide in 20 ml of n-heptane in an amount corresponding to a molar ratio of 1:10 of the titanium trichloride was added dropwise through a dropping funnel. The mixture was then ^{heated to 60 °} C. and kept at this temperature for one hour. The heated mixture was decanted three times using 50 ml of n-heptane and kept at 5 mm Hg and 100 ^° C. for 3 hours. The obtained product was placed in a stainless steel vibrating ball mill of 1000 ml capacity packed with magnetic balls having a diameter of about 10 mm inside a dry box, and ground for 16 hours.

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An autoclave of 1.5 L dr. Content made of stainless steel from mechanical stirring type was with the obtained titanium trichloride, tetraethyldialuminoxane (TEDAO abbreviated), diethylaluminum monochloride (abbreviated DEAC) and hexamethylphosphoric triamide (abbreviated HPT) in the amounts given in Table II and 7.5 moles of liquid propylene are charged. The propylene was polymerized for about 1 hour at 85.degree. C. It became obtained a powdery polymer, which has a through-

W had average rate of polymerization (g / g / hr) (abbreviated RE) and boiling n-heptane extraction residue ($) (abbreviated HR) as shown in Table II.

For comparison, the above procedure was repeated, but treating the titanium trichloride with the solvent, heat-treated in vacuo and milled without the addition of ethylene oxide (comparison 1) and the titanium trichloride was only ground (comparison 2). The results obtained are shown in Table II. The effectiveness of the treatment of titanium trichloride with ethylene oxide is clear from the results obtained. This treated with ethylene oxide Titanium trichloride is also technically

I borrowed AA-type titanium trichloride (comparison 4, technical Quality AA-I) as shown in Table II, superior.

Examples (A) 2-4

The same procedure was used as in Example (A) 1, but using propylene oxide instead of ethylene oxide was used and the molar ratio of propylene oxide to 1/10, 1/3 and 1/2 of the titanium trichloride (Examples (A) 2, 3 and / j) has been discontinued. The results are given in Table II, from which it follows that when a larger amount of propylene oxide is used, a greater effect is achieved.

'"; ■' ■ T SS: ■

- 13 -

Example (A) 5

The procedure used in Examples (A) 2 Ms 4 was de repeated, but the decantation of the heat-treated titanium trichloride component omitted. From the values listed in Table II it can be seen in this Pail that the Treatment with propylene oxide was effective.

comparison 3

The same procedure as in Example (A) 2 was repeated, except that the squint treatment of the titanium trichloride was omitted. It follows from the values given in Table II that the polymerization activity of the catalyst used was low.

Example (A) 6

It was worked according to the same procedure as in Example (A) 5 but heating the composition obtained in the treatment with the treating agent to 15O ⁰ G.

Examples 7 "to 9

The same procedure as in Example (A) 1 was used, but a molar ratio of 1/3 of epichlorohydrin, a molar ratio of 1/10 of allyl glycidyl ether and a molar ratio 1/5 of 2-butene oxide was used in place of the ethylene oxide. Eo can be seen from Table II that better results when the comparison tests were obtained.

(I ^! ) 'Λ' ¹ II 1 7 _; ! U

(Lot)

Tabel

Treatment solvent Treatment agent (amount) (amount) conditions Heat the laundry to grind the obtained mass

-ithylene oxide
(I-Iol ratio
1/10)

n-heptane (100 ml)

nO

60 ^{υ 0.1} hours

ml
3 times

100 ^u C,
5 mm Hg
3 hours.

16 hours

Propylene oxide
(Hol ratio
1/10)

as well

also propylene oxide also (molar ratio
1/3)

as well as pronylene oxide as well (Koi ratio
1/2)

also propylene oxide

( Hol behälτηi s
1/10)

likewise likewise

as well

n-pentane (100 ml)

likewise eichlorohydrin n-heptane (Molar ratio (100 ml) 1/3)

as well

as well

likewise likewise

likewise likewise

likewise likewise likewise

likewise likewise likewise

30 ⁰ C, 1 hour without

.,O

80 ^u C, 1 hour without

60 ^° C, 1 hour 50 ml
3 times

likewise likewise

150 ⁰ C,
5 mm Hg
3 hours.

5 mm Hg
3 hours.

as well

as well

ro O cn

TiCl ₃
(Lot) • T a b e lie I (continued) 60 ⁰ C, 1 hour Laundry Heat
receive
ten mas meal
Time ■ at
games (A) Treatment
medium (amount) Solvent treatment
(Quantity) conditions as well se ί TiCl., Dated
AA type
(50 g) as well 50 ml
3 times 100 ⁰ C,
5 mm Hg
3 hours. 16 hours ι 1 8th as well Allyl glycidyl
ether (Molver
ratio 1/10) n-heptane
(100 ml) without as well as well as well H
VJI 9 as well 2-butene oxide
(Molar ratio
1/5) as well 60 ⁰ C, 1 hour as well as well as well I. Comparison 1 as well without as well without without as well Comparison 2 as well without without 50 ml
3 times 100 ⁰ C,
5 mm Hg • without Comparison 3 Propylene oxide
(Molar ratio n-heptane
(100 ml)

1/10)

3 hours.

Tabel

II

Example- Polymerisationsbe- Polymerisationsbe- Polymerisationsbe-Ie (A) conditions (I) conditions (II) conditions (III) conditions (IV)
(0.9 / 0.3 / 0.02) (0.9 / 0.3 / 0.05) (0.9 / 0.3 / 0.1) (0.9 / 0.6 / 0, 3)

R R (g / g / hr)

HR RR

: 1 °) (g / g / h)

HR RR HR (*) (g / g / hr.) (*

R R (g / g / hr)

MR

2 3 4 5 6 7 8

17,000 ** 72.2

17,000 71.4

17 400 70.7 16 100 70.4

18 700 *** 67.7 15 400 69.5 13 300 68.2

13 700 **

15 100 17 100

16 500 15 400 12 700 12 200

10 700

10 400

12 200 **
15 200

13 500
13 500

11 600
10 500
10 200

79.7 80.1 81.2 78.1 80.4 77.0

80.7 80.1 80.2

10 600 ** 10 000 10 200 10 400 8 600

81.6 83.3 83.6 82.8 82.8

comparison

(A) 1 - - - 10,000 78.9 8,800 80.5

2 - - - 6,800 79.2 6,300 78.8

3 - - - - 7 600 77.7 -

4 11 000 65.0 11 800 67.1 11 600 * 71.8 6 700 79.3 [AA (I)] -

5 - - - 11 500 75.6 8 800 78.9 [AA (2)]

The values in brackets under the polymerization conditions indicate mmol EEDAO / DEAC / HPT. The amount of propylene was 0.5 mol and that of titanium trichloride was about 20 mg. Polymerization time: * 50 minutes, ** 55 minutes, *** 40 minutes, otherwise 60 minutes.
Polymerization temperature: 85 ^{° C.} ,>

11 ■ ITlII Il Il. 11-11, ι π,,

¹ HI ¹ I Π Π Γ '"", ¹ ■' ■ ¹ I - ;! "- 1 11 ¹¹ · Ι · ^{| Μ} " | · '1! .1, Ji I ,; .Mr.hllnHII. ^ ,. |. IM, · | , i. "| Ί ,. |,. · Ι, | .ι ,, μ ,, ι. ,around. ; ,,,

Example (A) 10

An autoclave of the same type as in Example (A) 1, with 25.0 mg of a titanium trichloride modified according to Example (A) 1, 0.5 m-mol of triethylaluminum, 0.1 m-mol of ethylaluminum dichloride, 0.1 m -Moles of hexamethylphosphoric triamide and 7.5 moles of liquid propylene are charged. Me polymerization of propylene was carried out for 1 hour at 82.5 ⁰ C. 262 g of a polymer were obtained which had an extraction residue with boiling n-IIeptane (HR) of 74.7 / S.

For comparison purposes, the above procedure was used using 24.6 mg of the titanium trichloride of Comparison 2 repeated. There were 201 g of a polymer with a boiling n-heptane extraction residue of $ 74.5.

Example (A) 11

An autoclave of the same kind as in Example (A) 1 was with 0.215 g of titanium trichloride, 7.5 m-mol of ethylaluminum dichloride, 3.6 m-mol of tri-n-butylamine, 7.5 mol of liquefied propylene and 0.2 mol - $, based on propylene, charged to hydrogen. The polymerization of propylene was carried out v / hile 1 hour at 80 ⁰ C. After removal of the unreacted propylene 100 ml of isobutyl alcohol was added to treat the product for 30 minutes at 80 ⁰ C, followed by filtration and concentrated at reduced pressure was dried to obtain 121 g of polypropylene were obtained, which has an extraction residue with boiling n-heptane of 94, 4 % had.

For comparison, the above procedure was carried out using 0.203 g of the titanium trichloride of the comparison

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repeated. There were 98 g of polypropylene with an extraction residue with boiling n-heptane of 94.0> obtain.

Example (A) 12

An autoclave of the same type as in Example (A) 1, with 0.228 g of the titanium trichloride modified according to Example (A) 1, 2.0 m-mol of diethylaluminum ^ -caprolactam, 4.0 m-mol of ethylaluminum dichloride, 7.5 Mol of liquid propylene and 0.2 hol%, based on propylene, of hydrogen. The polymerization of propylene was carried out for one hour at 82.5 ⁰ C. The polymer obtained was purified and dried, whereby 136 g of polypropylene having an extraction residue with boiling n-heptane of 93.6 ^c / o were obtained.

For comparison, the above procedure was repeated using 0.214 g of the titanium trichloride of Comparison 1. There were obtained 111 g of polypropylene which had an extraction residue with boiling n-heptane of 92.8 i ".

Example (B) 1

W A three-necked flask of 300 ml was thoroughly purged with nitrogen and charged with about 50 g of AA-type titanium trichloride and 100 ml of purified toluene. These ingredients were ice-cooled and stirred with a hammer stirrer. A solution of methanol in 20 ml of toluene in an amount corresponding to a 1:10 ratio of the titanium trichloride was added dropwise through a dropping funnel. The mixture was then ^{heated to 80 to 90 p} 0 and held at this temperature for 1 hour. The heated mixture became three times

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BAD ORiGiHAL

decanted using 50 ml of toluene, and "mm at 5 Hg and 140 held to 15O ⁰ C for 3 hours. The product obtained was in a vibration ball mill made of stainless steel of 1000 ml, the mm with magnetic beads having a diameter of about 10 within in a dry box, placed and milled for 16 hours.

A stainless steel autoclave of 1.5 l capacity of the stirring type was with 26.4 mg of the above modified titanium trichloride, 1.5 m-mol of tetraethyldialuminoxane (abbreviated TEDAO), 0.3 m-mol of hexamethylphosphoric triamide (abbreviated to HFT) and 7.5 moles of liquid propylene charged. The polymerization of the propylene was carried out at 85 ^° C. for about 1 hour. 280 g of a powdery polymer were obtained, which had an average polymerization rate (RR) of 10,600 g / g / hour. and had a boiling n-heptane extraction residue (HR) of 77.3 f .

For comparison, the above process was repeated, but no methanol was added, but instead the titanium trichloride was treated with the solvent, heated in vacuo and ground. The polymer obtained had an average polymerization rate of 8000 g / g / hour. and a value of HR of 73.4 ? <>. It can be seen from this comparison that the activity of the titanium trichloride-containing catalyst according to the invention, when treated with methanol, increases by 32.5 ° in the process according to the invention.

Examples (B) 2 to 10

The same procedure as in Example (B) 1 was repeated, but the titanium trichloride with the different

109877/1724

different organohydroxy compounds or those in table III modified conditions specified. The polymerization of the propylene was carried out using the so obtained titanium trichloride component and the catalyst components indicated in Table IV among the the same conditions as in Example (B) 1 carried out. The results are in Table IV along with the results a comparison (B) 1 listed, from which it is clear that the inventive method for Activation of the titanium trichloride is very effective.

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Table III

Example (B)

TiCl ₃ (amount)

Treatment agent solution (Ko! Ratio) medium treatment number conditions of the hot washes obtained

Dimensions

Enjoy the meal

AA-Tvp
50 g tert-butanol
(1:10) ti phenol
(1:10) 11 Cyclohexanol
(1:10) U 2-chloroethanol
(1:10) η 2-ethoxyethanol
(1:10) I) Ethylene glycol
(1:10) Il Ethanol
(1:30) It Ethanol
(1:10) Il Ethanol
(1: 3)

Toluene - 90 ^° C
Hours.

- 80 ⁰ C
Hours.

ml
Toluene times

ml of heptane times

140 -150 ⁰ C 16 hours, 3 hours (5 mm Hg)

90-100 ⁰ C 3 hours 5 mm Hg

30 hours

Comparison "

Toluene to 70 - 80 ⁰ C for 1 h.

ml of heptane 2 times

90-100 ⁰ C 3 hours 5 mm Hg

30 hours

Table IV the end
prey
(G) Polymer HR {%) R R (g / g / hr) at catalyst 294 77.7 game
(B) components 254 11 200 78.5 2 ^ TiCl ₃ : 26.4 mg 316 9 600 74.9 iTEDAO: 1.5 m-mol
1, HPT: 0.3 m-mol 322 12,000 76.0 3 Il Il 235 12 400 78.1 4th Il Il 278 8 900 72.9 5 It Il 10 500 6th Il Il 7th Il Il

TiCl ₅ : 25 mg

TEDA0: 1.5 m-mol ZnClp-pyridine-

complex (molar ratio 2: 1): 0.2 m-mol

320

275 280

comparison
(B) 1

218

12 800

11,000
11 400

8 700

76.2

75.1 77.0

74.0

From the results of Examples (B) 8 to 10, it is clear that, if the amount of the treating agent ethanol used in the range of a molar ratio of 1/30 to 1/3, based on titanium trichloride, the treating agent does not give a great change in the activity of titanium trichloride.

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Example (B) 11

An autoclave of the same type as in Example (B) 1 was charged with 46 mg of the modified titanium trichloride according to Example (B) 2, 3.0 m-mol of triethylaluminum, 222 g of liquid butene-1 and 100 ml of n-pentane ". the polymerization of butene-1 was lead out-r 1 hour at 60.0 ⁰ C. It was thereby 83 g of a polymer obtained, which had an extraction residue with boiling ether of 69.0 $.

For comparison, the above procedure was repeated, however, 46 mg of unmodified titanium trichloride was used. 63 g of a polymer were obtained, which a boiling ither extraction residue of $ 61.6 would have.

Example (B) 12

An autoclave of the type used in Example (B) 1 was charged with 0.215 g of the titanium trichloride modified according to Example (B) 9, 7.5 m-mol of ethylaluminum dichloride, 3.6 m-mol of tri-n-butylamine, 7.5 mol of liquid Propylene and 0.2 mol ~ $, based on propylene, charged to hydrogen. The polymerization cfes propylene was carried out for 1 hour at 80 ^c C. · After removal of the nichtumgesetsten propylene, 100 ml of isobutyl alcohol for the treatment of the product during 30 minutes at 80 ^{ς ΰ} added, then filtered and dried under reduced pressure to obtain 115 g of a Polypropylene having a boiling n-heptane extraction residue of $ 94.4.

For comparison, the above procedure was repeated, but 0.203 g of a titanium trichloride which does not contact the treating agents according to the invention

109827/1724

had been used. There were 91 g of polypropylene with an extraction residue with boiling n-heptane received from $ 92.0.

Example (B) 15

An autoclave of the type used in Example (B) 1 was charged with 0.239 g of the modified titanium trichloride according to Example (B) 2, 3.0 m-mol of diethylaluminum chloride and 100 ml of n-pentane, whereupon 200 g of liquid butene-1 were added. The polymerization of butene-1 was carried out at 80 ^° C. for 1 hour. The polymer obtained was washed with isobutanol and dried, thereby obtaining 102 g of polybutene-1 having a boiling ether extraction residue of $ 70.2.

For comparison, the above procedure was repeated, but 0.244 g of a titanium trichloride, which was not contacted with the treatment agent according to the invention had been used. 82 g of polybutene-1 with an extraction residue with boiling ether of $ 65.5 were obtained obtain.

Example (B) 14

A three-necked flask of 300 ml capacity was thoroughly purged with nitrogen and charged with about 50 g of titanium trichloride (HA type, product of the Stauffer Company) and 100 ml of purified toluene, the compounds being stirred with a magnetic stirrer. A solution of ethanol in toluene in a length corresponding to a molar ratio of 1:10 of the titanium trichloride was added dropwise over 15 minutes, after which the mixture was kept at 80 ° ^C. for 1 hour to complete the reaction

109827/1724

held. The supernatant toluene layer was removed and the residue heated at 90 to 100 ⁰ C dried, the mass was ground for 20 hours in the same manner as in Example 1 (B), the propylene was for 1 hour using a combination of 60.3 mg of the titanium trichloride modified in this way, 1.0 mol of tetraethyldialuminoxane and 0.1 mol of hexamethylphosphoric triamide polymerized and gave 135 g of a polymer with an average polymerization rate of 2240 g / g / h, and an extraction residue with boiling n-heptane (HR) of 75.4 ^C / O. For comparison, the above procedure was repeated with HA-type titanium trichloride. The polymer obtained had an average polymerization rate of 1860 g / g / hr, and an HR value of 73.3 ^.

Example (B) 15

An autoclave of 1 1 was charged with 62.8 mg of the modified titanium trichloride in accordance with Example 8 (b), 1.5 m-mol Tetraäthyldialuminoxan and 600 ml isopentane were charged, ethylene was introduced under pressure with stirring at 8O ⁰ C. While the partial pressure of the ethylene was kept at 5 kg / cm, the polymerization of the ethylene was continued for 60 minutes. This gave 210 g of a high density polyethylene.

For comparison, the above procedure was repeated, but using an unmodified titanium trichloride. This gives 70 g of the polymer. It results that the modification treatment of the titanium trichloride component a 3-fold increase in the polymerization rate of ethylene results.

10 9 8 2 7/1724

-26- 205.8749

Example (C) 1

Inside a dry box flushed with nitrogen, a stainless steel ball mill vessel with a capacity of 1000 ml, which was packed with 600 ml magnetic balls with a diameter of about 10 mm, was filled with a mixture of 60 g of AA-type titanium trichloride and 8.9 g (corresponding to a molar ratio of 1: 3 of the titanium trichloride) charged to γ-butyrolactone and the ball mill vessel closed. The ball mill jar was removed from the drying

} box removed and attached to a vibratory grinder. The mixture was then milled for 17.5 hours at room temperature.

A stainless steel autoclave of 1.5 l content of the mechanical stirring type was with 23.8 mg of the modified titanium trichloride obtained above, 0.9 mol of tetraethyldialumonoxane, 0.6 mol of diethylaluminum chloride, 0.3 mol Charged hexamethylphosphoric triamide and 7.5 moles of liquid propylene. The polymerization of propylene in the absence of a solvent was carried out ^{at 85 ° C. for 60 minutes.} 250 g of a white powdery polymer were obtained, which had an average polymerization rate of 10,500 g / g

* AATiCl, / hour and had a boiling n-heptane extraction residue of $ 82.4.

For comparison, the above procedure was repeated, but only a milled titanium trichloride component verv / ends. A polymer with an average polymerization rate of 8000 g / g / otd. and an extraction residue with boiling n-heptane of 73.4; ^ obtained.

109827/1724

It follows from this comparison that the application a titanium trichloride modified with γ-butyrolactone to a $ 31.2 increase in polymerization activity and an increase of $ 9 »0 in terms of which leads to stereoregularity "

Example (C) 2

The polymerization of propylene in the absence of a solvent was carried out for 1.5 hours at 80 ^ο Π in the presence of 0.15 mol-yS hydrogen by the method according to Example (C) 1, with a 0.22 g of the according to Example ( C) 1 modified ethane trichloride, 7.5 m-mol of ethylaluminum dichloride and 5.3 m-mol of tri-n-butylamine built-up catalyst was used. The polymer obtained was treated with 500 ml of isobutanol for 0.5 hours at 70 ^° C. to dissolve the catalyst, then filtered and dried, whereby 245 g of a white polymer were obtained which had an average polymerization rate of 744 g / g AATiCl-z / Hours. would have. To the obtained polymer 0.2 io Ionol were added as a stabilizer and molded the mixture for 5 minutes at 230 G ⁰ at a pressure of 50 kg / cm. A Versuch'sprobestück of the molded product showed a melting viscosity index of 8.2 g / 10 minutes (230 ⁰ C; load 2,1.6 g), a bending rigidity (ASTM D 747-61T) of 18.1 χ 1O ⁴ psi, and a yield strength (ASTM D638-58T) of 344 kg / cm ² . '

Propylene was modified in the same manner as above using one not modified with γ-butyrolactone Titanium trichloride polymerizes. The polymer obtained had an average degree of polymerization of

1098277 1724

600 g / g / hour and a flexural strength of 15.8 10 psi and a yield strength of 314.6 kg / cm '. These numerical values clearly demonstrate the modifying effect for the titanium trichloride.

Example (0) 3

An autoclave of the same type as in example (C) 1, was replenished with 0.225 g of the modified titanium trichloride Example (C) 1, 3.0 m-mol diethyl aluminum chloride and 100 ml isopentane charged. Then add 200 g

"Introduced into the autoclave and stirring for 1 hour at 80 ^c C polymerized liquid butene-1. After removal of the unreacted monomers and of the solvent by evaporation the resulting polymer with 500 ml of isobutanol at 7C ^C C for 0.5 hours, washed and dried, thereby obtaining 121 g of polybutene-1, which had an extraction residue with boiling ether of $ 75.2.

For comparison, the above procedure was repeated, but 0.230 g of an unmodified titanium trichloride used. 82 g of polybutene-1 were obtained, which was an extraction residue with boiling

| Had ether of 65.5 / 5.

Examples (C) 4 to 5

A three-necked flask with a capacity of 300 ml and flushed with nitrogen was charged with 50 g of titanium trichloride of the AA type and 100 ml of n-heptane and a solution of γ-butyrolactone (example (C) 4) or γ-caprolactone (example ( C) 5) in 30 ml of toluene added dropwise. After the addition, that became

109827/1724

BATHROOM OBlGiNAL

Mixture was kept at 60 to 7O ⁰ C for 1 hour to complete the reaction. The supernatant liquid was decanted off and the titanium trichloride was then washed twice with 100 ml of n-heptane. The solvent was evaporated for 3 hours at 150 ^c C and the product obtained is dried. The titanium trichloride thus treated was placed in a vibrating ball mill of the same type as in Example (G) 1 and milled for 16 hours.

The polymerization of propylene was carried out at 82.5 ⁰ C in the presence of 0.2 Mo1- $ hydrogen in the same manner as in Example (C) 2, carried out with a 0.18 g of the modified this Vieise titanium trichloride, 1, BSm-MoI diethylaluminum - & - caprolactamide and 3.76 m-mol of ethylaluminum dichloride was used. The results obtained are shown in Table V below together with those of a comparative experiment in which no treating agent was used.

Table V

(C) 4

(C) 5

comparison

Treatment agent γ-butyrolactone t-caprolactone -

average

Polymerization 425 405 335

speed

(g / g TiCi ^ / .; td.)

Properties of the polymer

Density (g / com)

Pi.egimgs stiffness (psi)

ochmelzvLslrositätöindex

0.9035 16.8x1O ⁴ 8.80

0.9031
17.4x1 θ '

9.01

0.9030 15.7x10 *

7.88

10982 7/1724

Examples (C) 6 to 10

AA-type titanium trichloride was treated with treating agents of the various types: ,, as indicated in Table VI, treated under the conditions described in Examples (C) 4 and (C) 5 and for 17.5 hours ground in a vibrating ball mill and the modified titanium trichloride obtained.

Using a catalyst consisting of 20 mg of the thus modified titanium trichloride, 0.9 m-mol Tetraäthylaluminoxan, 0.6 m-mol Diäthylaluminiumraonochlorid and 0.3 m-mol propylene hexamethylphosphoric triamide was for 60 minutes at 85 ⁰ C by the method of Example (C) 1 polymerized. The results are shown in Table VI together with those of a comparative experiment in which the titanium trichloride was not treated with a treating agent according to the invention.

Table VI

Treatment agents MoI-
behaved-
nis, Be
action
middle/
TiCl ₃ Poly
out
prey
(G) heptanun
more soluble
proportion of
(*) at
games
(C) ß-propiolactone 1/3 185 78.2 6th E-caprolactone 1/3 213 80.2 7th y-nonalactone 1/3 179 76.2 8th γ-valerolactone 1/3 182 77.0 9 Coumarin 1/3 201 76.5 10 - - 160 73.4 Ver
same

1 0 9 8 ? 7/1 7 2 4

Example (C) 11

An autoclave of 1 liter content was charged with 105 mg of the titanium trichloride modified according to Example (C) 1, 2.5 m-rlol tetraethyldialuminoxane and 600 ml isopentane and with stirring at 70 to 80 ⁰ C ethylene with a partial pressure of 5 kg / cm initiated, by parial pressure was held at this fourth and the ethylene polymerized for 60 minutes. After the end of the polymerization, the unreacted ethylene was removed and the polymer obtained was washed with isobutanol, then dried in vacuo and 147 g of high-density polyethylene were obtained.

For comparison, the above procedure was repeated, but no pretreated titanium trichloride is used. 112 g of the polymer were obtained.

Example (G) 12

The polymerization of propylene was carried out according to the method according to Example (C) 1, one of 28.9 mg of the titanium trichloride modified according to "Example (0) 1, 0.75 mol of tetraethyldialuminoxane, 2.0 mol of ethylaluminum dichloride and 1.3 hexamethylphosphoric triamide constructed catalyst mol m was used, and 0.3 m-mole diethylzinc and hydrogen was added at a partial pressure of 1.5 kg / cm to adjust the molecular weight. the polymerization was continued for 1 hour at 85 ^C, and C 222 g of polypropylene were obtained with an average polymerization rate of 7,700 g / g / hour and a heptane-insoluble fraction of 90.1 ^c / o

109827/1 724

of 2.9 g / 10 minutes. To the obtained polymer were 0.1 pulferfÖrmigen ⁰ /> Irganox added as a stabilizer, and the mixture was kneaded for 3 minutes at 170 to 185 ⁰ C. The kneaded product was press-molded at 230 ^c C. The molded product had a tensile strength of 302 kg / cm, a breaking strength of 323 kg / cm, an elongation of 900 $, and a flexural rigidity of 12.2 x 10 ⁴ psi.

109827/1 7.24

Claims (1)

Claims 1, Process for the polymerization of α-olefins by contacting α-olefins under polymerization conditions with a stereospecific catalyst, of a titanium trichloride component and an organoaluminum compound contains, characterized in that a titanium trichloride component · of the catalyst is used which was ground during or after contacting with a treatment agent, being used as a treatment agent at least one of the following compounds (A) alkylene oxides, (B) organohydroxy compounds with at least one alcoholic or phenolic hydroxyl group, (C) lactones
was used. 2. The method according to claim 1, characterized in that the alkylene oxide is a compound of the formula R ¹ C. 1 0 ^/ C ² R ⁵ \ \ R ² ν 4 12 3 used in which R, R and R are hydrogen atoms or alkyl groups with not more than 10 carbon atoms, R is a hydrogen atom., an alkyl, alkenyl, cycloalkyl or aryl group with not more than 10 carbon atoms, which are optionally substituted by halogen atoms can, or a group -CH ₂ OR, in which R is an alkyl, alkenyl, aryl or glycidyl group having not more than 10 carbon atoms, and where 109827/1724 BATH 1 "5 R and R together form a ring with 5 to 12 carbon 1 2 atoms including G 'and C can form. 3. The method according to claim 1 or 2, characterized in that the organohydroxy compound monohydric or polyhydric acyclic, cycloaliphatic or aralkyl alcohols, phenols and / or
Naphthols are used, these compounds being optionally substituted by halogen atoms, alkyl, alkenyl, cycloalkyl, aryl, aralkyl, ester or alkoxy groups
can. 4. The method according to claim 1 or 2, characterized in that the lactone saturated or unsaturated 4- to 10-membered lactones and / or Lactones from aromatic ortho-hydroxycarboxylic acids can be used, these lactones optionally being substituted by an alkyl or alkenyl group can. 5. The method according to claim 1 to 4, characterized in that the treatment agent with the titanium trichloride component is contacted so that 0.01 to 1 mole, preferably 0.02 to 0.5 mole, of the treating agent can be incorporated in 1 mole of the titanium trichloride. 10982 7/1724