CA1158656A - Method for making titanium trichloride catalyst - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Para-acetamidophenol a-methyl-4(2'-thienyl-carbonyl) phenyl acetate, having anti-inflammatory activity, is pro-vided, along with a process for its preparation by reacting .alpha.-methyl-4(2'-thienyl-carbonyl) phenyl acetic acid or a reactive derivative thereof with p-acetamidophenol in an apro-tic organic solvent and, when the reactive derivative is an acid halide, the reaction is carried out also in the pres-ence of a hydrohalic binding compound.

Description

~1586~6 I
BACKGROUND OF ~HE INVENTION
The preparation of aluminum reduced titanium trichloride catalysts is well known, and such catalysts are widely employed in the production of polyolefins~ such as polyethylene and poly-~propylene. The preparation of such catalysts and their use in Ipolymerization reactions is discussed in a number of patents, for example, in U. S. Patents Nos. 3,121,063, 3,475,394, 4,154,702, ;642,746 and3647,772, and in British Patent No. 1,310,547.
It is also known that the performance of such catalysts lcan be improved by treatment with electron donor substances. De-!~tails of such treatment and examples of electron donors which have, ¦jbeen employed are disclosed in, among others, U. S. Patents Nos~ I
3,186,977, 4,110,248, 4,111,836, 4,115,319l 4,126,576, 4,127,504, 4,127,505, 4,142,991, and British Patent No. 1,310,547.
However, the treatment of aluminum-reduced titanium trichloride catalysts with electron donors containing an OR radicalj, illustratively with various ethers, may result in the generation of llby-products which adversely affect the catalysts. For example, jlthey can generate undesirable pressures in the shipping container.
¦jIn other instances the by-products which are formed may be toxic.
khis introduces an element of hazard which it is clearly desirable Ito avoid.

j SUMMARY OF THE INVENTION
In accordance with the present invention it has been found that the presence of the undesirable and potentially hazardous ¦Iby products can be eliminated by heat treating the modified 'I!aluminum reduced titanium trichloride catalyst, and thereafter re-,Loving such substances by volatilization or extraction with a suitable solvent. This heat treatment is most advantageously effected after modification of the catalyst by the particular Iselected electron donor has taken place but can also be effected hhile the modification or activation treatment is being carried outl~.

Broadly~ the modified catalyst is placed in a suitable vessel and the hea~ treatment is carried out at a temperature ~-~58~

and for a time sufficient to drive the reaction to completion.
In some instances this will involve removal of a gas formed in modification.
The temperature used in carrying out the heat treatment can be varied over the range of from about 40 to about 110.
The preferred range is from about 80 to about 100, with a temp-erature of about 90 being the most advantageous.
The time of treatment can likewise be varied and will of course be related to the particulartemperature at which the heat treatment is carried out. Thus, the time of treatment can be from about 10 minutes to about 300 minutes, with a preferred range of from about 60 to 120 minutes. In the usual practice of ¦the present invention, the time will be about 80 minutes.
¦ The heat treatment resulting in the elimination of the ¦by products can be effected at above or below ambient pressure, ¦illustratively from about 0.001 to about 2 atmospheres, but it is ¦preferred to carry out the heat treatment at atmospheric pressure.
¦ The heat treatment of the modified aluminum-reduced titanium trichloride catalyst in accordance with the present in-vention results in the production of a new and advantageous cata-lyst composition. ~hen the base aluminum-reduced titanium tri-¦chloride is treated with a small ~uantity o an electron donor containing the group -OR and activated by milling at a temperature f about -10C to about 40C, the following reaction will occur:

3 TiC13, AlC13 + x ROR' ~ x) (3TiC13,AlC13~x(3TiC13,AlC13, ROR') ~I) I ¦ On heating the above product, the electron donor modified aluminum-reduced titanium trichloride, according to the procedure disclosed in the instant application, the following reaction takes place:

~ 65~ `

(l-X)(3Tic13,AlC13)x(3TiC13,AlCl3,ROR') X)(3TiC13, AlC13)x(3TiC13,AlC12(0R')) + RCl. (II) In the above equations, x is a positive number equal to, r less then, one.
The product obtained after completion of the above eaction is a new catalytic agent of a composition hitherto unknown his catalyst has a high catalyst efficiency (CE) expressed as the ¦
eight of polymer produced in grams per gram of modified TiC13 atalyst used. The polymer which is produced using the new and mproved catalyst of the present invention has improved isotacticity, hat is, has a higher heptane insoluble ~HI) content.

DESCRIPTION OF THE PREFERRED EMBODIMENT

As has been discussed under the heading SUMMARY OF THE
NVENTION, the treatment of aluminum-reduced titanium trichloride atalysts to improve their effectiveness is known. Specific eference to patents teaching such treatment has already been made nd the relevant disclosures of such patents is incorporated herein y reference.
The starting catalyst employed in the practice of the resent invention can be aluminum-reduced, activated (AA-TiC13) r aluminum-reducedj unactivated (A-TiC13) titanium trichloride.
ptionally, extra aluminum chloride, titanium tetrachloride, or itanium trichloride may be added.
The particular electron donor compounds which are mployed as modifying agents in the activation of the catalysts ith which the present invention is concerned are compounds of he following general formula -Rl - X - R2 here X is 0, S, Se or Te, and wherein Rl and R are the same or are different, and are lkyl, cycloalkyl, aryl, or substituted derivatives thereof or a rouping of the formula -x ~3 -llS86S6 ~herein X is O, S, Se or ~e, and R3 is alkyl, cycloalky, aryl, or ~substituted derivatives thereof.
The sole limitation on Rl and R2 is that the compounds Cl and/or R Cl, should be readily removable from the reaction product or their presence should be innocuous.
Examples of the modifier Rl -X-R2 in the case where X
j35 oxygen are organic oxygen-containing compounds such as the laliphatic ethers, aromatic ethers, aliphatic carboxylic acid esters ¦and anhydrides, aromatic carboxylic acid esters and anhydrides, and ~nsaturated carboxylic acid es~e~s and anhydrides. Specific ¦examples of illustrative compounds are !2 5)2~ C6H5 CH3l C6H5cH2~o~cH3 CH3.CH (OC2H5)2,~ (CH3)2.C(Oc2H5)2~ 2 5 3 CH3co~oc2H5 C6H5-CO-Oc2H5' C2 5 2 5 C2~5O.CO-Oc2H5 and (CH3CO)20-Special instances are compounds where R1 and R2 are ~!Part of a heterocylic system as, for example, in tetrahydrofuran ¦lor ~-butyrolactone.
~ ydrogen in the foregoing examples can be substituted by any one or more of the following groupings, for example, , t , CH2Cl, OC2H5, -CH20CH3, OCOCH3 and I! As earlier noted, there are certain art recognized ¦problems associated with such modified catalysts. Among these !~ problems are a lack of storage stability and a potential hazard arising from the generation of volatile or toxic substances.
~This is known to arise according to the following reaction:
R

Il ~ + AlC13 ~~~~ R - OAlC12+RCl (III) I R
which has been discussed in the text "Friedel - Crafts and Related Reactions, Edited by George A. Olah; 1963, published by Interscience Publishers, New York, pages 572 and 585.
. . I

~ ~1S8~S6 ~

It has most surprisingly been found that the above roblems can be overcome without loss of catalytic activity and efficiency by subjecting the electron donor modified aluminum-reduced titanium trichloride catalyst to a heat treatment at a temperature and for a period of time sufficient to effect the elimination of the RCl generated in accordance with reaction III.
The A or the AA-TiC13 is mixed with the electron donor compound in an inert atmosphere and the mixture is heated to effect reaction. The heating according to the present invention can be done simultaneously with ball milling for activation or further activation of the catalyst, or the mixture can be heated fter activation.
Gas products which are volatile can be removed by levaporation at elevated or at reduced pressure. Other products ¦can also be removed by solvent extraction followed by filtration lor can be left in the catalyst mixture if innocuous.
¦ Other operations can be carried out after the heat ¦treatment. ~or example, a low temperature milling or a grinding ¦step may be run to adjust catalyst particle size. These subsequent ¦steps could include the addition of further modifiers, especially to improve efficiency further and control particle size.
The following Examples which illustrate certain pre-ferred embodiments of the present invention are intended only to illustrate the invention and are not to be construed in any ¦limiting sense.
l ~XAMPLE I
¦ 7~6 kg of crystalline titanium trichloride compound of the approximate formula TiC13Ø33 AlC13 (AA-TiC13 manufactured by Purechem Co.~ are put in a ~ibratory ball mill having a 40 liter inner volume and containing 144 kg of steel balls of 1 inch diameter, under a nitrogen atmosphere. Anisole, in an amount of 12% wt. based on the amount of TiC130.33 AlC13 is dispersed onto the catalyst over a period of 1 hour, while the mixture is being ~' ¦¦milled lCC for 4 ho~rs at a peed of 1500 rp~.

llS86S6 A sample of the catalyst was tested in the liquid propylene polymerization test as follows:
0.052g of the modified TiC13 catalyst and 1.2 ml of a 0.66 M DE~C
solution in n-heptane (DE~C/Ti (moles) = 3.0) are charged into a 1 liter stainless steel autoclave equipped with an agitator.
0.027 moles of H2 is then charged follwed by the addition of 250g of liquid propylene. The polymerization is carried out at 75C for 2 hours after which the unreacted propylene is vented off. The p~lymer thus obtained weighs 133g and the catalyst productiyity is 2557g PP/g Cat.
A fraction of the polymer is extracted with boiling n-heptane for 16 hours in a Soxhlet E~tractor and the n-heptane insoluble fraction is dried.
The weight percent of the n-heptane insoluble polymer is 93.5.
EXAMPLE II

An anisole modified titanium trichloride is prepared using the same conditions and quantities recited in EXAMPLE I, except that the milling is carried out at 40C. A sample of the co-pulverized mixture thus prepared, tested under the same polymerization conditions as in EXAMPLE I, gave a productivity of 2700g PP/g Cat and an II of 95.6%.
EXAMPLE III
An anisole modified titanium trichloride is prepared using the same conditions and quantities recited in EXAMPLE I, except that the amount of anisole used was 9% wt. based on the amount of TiC13 0.33 AlC13. A sample of the co-pulverized mixture thus prepared, when tested under the same poiymerization conditions as described in EXAMPLE I, gave a productivity of 2500g PP/g Cat and an II of 93.3%.
EXAMPLE IY
A sample of the anisole modified titanium trichloride prepared using the same conditions and quantities recited in EXAMPLE II was extracted with n-hexane using 10 ml of n-hexane per * DE~C = diethyl-aluminum chloride 1:~5~3656 gram of catalyst and then drled under nitrogen. A sample of the thus treated catalyst was tested under the same polymerization ' conditions as in EXA~PLE I. The following results were obtained:

CATALYST EFFICIENCY

I g PP/g Cat II %

Before solvent extraction 2692 95.7 After solvent extraction 2846 96.0 I .

EXAMPLE V
HEAT TREATMENT OF THE MODIFIED CATALYST
100g of an anisole modified titanium trichloride catalyst prepared as described in EXAMPLE II was placed in a sealed glass tube and treated at 85C and the gas evolved was monitored. Gas evolution was completed after 4 hours of heating. A sample of the heat treated catalyst was tested under the same polymerization conditions as in EXAMPLE I. The results obtained were as follows:

CATALYST EFFICIENCY
g PP/g Cat II %

Before heating 2385 95.5 After heating 2385 95.2 Samples of the modified catalyst were similarly heat treated at 90C and 110C. At these temperatures, the gas evolution was completed after 3 hours and 0.5 hours respectively.

,1

Claims (10)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A catalyst comprising (1-n)(3 TiCl3AlCl3)n (3 TiCl3-AlCl2) (XR) where (a) n is a positive number less than or equal to one, (b) X is selected from the group consisting of oxygen, sulfur, selenium and tellurium, (c) XR is derived from an electron donor compound R1-X-R2 wherein R1 is an organic grouping selected from the group consisting of alkyl, cycloalkyl, aryl, substituted derivations thereof and a grouping of the formula wherein X is oxygen, sulfur, selenium or tellurium and R3 is aklyl, cycloalkyl, aryl or substituted derivatives thereof, wherein R2 is an organic grouping selected from the group consisting of alkyl, cycloalkyl, aryl, and substituted derivatives thereof, and wherein R is R1 or R2, and wherein said catalyst is essentially free of any hydrocarbon solvent.

2. A catalyst according to claim 1 where R is a member selected from the group consisting of aryl, substituted derivatives thereof and a grouping of the formula wherein X is O, S, Se, or Te and R3 is aryl or substituted derivatives thereof.

3. A catalyst according to claim 1 where R is phenyl.

4. A process for providing a storage stable olefin polymerization catalyst which comprises heating an aluminum-reduced titanium trichloride catalyst which has been activated by treatment with an electron donor compound of the formula R1-X-R2 wherein X is oxygen, sulfur, selenium or tellurium, wherein R1 is alkyl, cycloalkyl, aryl, substituted derivatives thereof or a grouping of the formula wherein X is oxygen, sulfur, selenium or tellurium and R3 is alkyl, cyclo-alkyl, aryl, or substituted derivatives thereof, and wherein R2 is alkyl, cycloalkyl, aryl or substituted derivatives thereof, said heating being at a temperature and for a period of time sufficient to effect the elimination of substantially all of the R1Cl from said catalyst.

5. A process according to claim 4 wherein the electron donor compound is an organic ether or ester.

6. A process according to claim 5 wherein the electron donor is a compound of the formula R1-O-R2 wherein R1 and R2 are the same or different, and are alkyl, cycloalkyl, aryl, or substituted derivatives thereof or a grouping of the formula wherein X is S, Se or Te, and R3 is alkyl, cycloalkyl, aryl, or substituted derivatives thereof.

7. A process according to claim 6 wherein the electron donor compound is anisole.

8. A process according to claim 4 wherein the temperature is from about 40° to about 110°C and the period of heating is from about 10 minutes to about 12 hours.

9. A process according to claim 8 wherein the temperature is from about 80 to about 100°C and the period of heating is from ahout 20 minutes to about 3 hours.

10. A process according to claim 9 wherein the temperature is 90° and the period of heating is two hours.