CA1217777A - Process for the preparation of oligomeric aluminoxanes - Google Patents

Process for the preparation of oligomeric aluminoxanes

Info

Publication number
CA1217777A
CA1217777A CA000440182A CA440182A CA1217777A CA 1217777 A CA1217777 A CA 1217777A CA 000440182 A CA000440182 A CA 000440182A CA 440182 A CA440182 A CA 440182A CA 1217777 A CA1217777 A CA 1217777A
Authority
CA
Canada
Prior art keywords
aluminum
trimethyl
trialkyl
crystallization
containing water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000440182A
Other languages
French (fr)
Inventor
Walter Kaminsky
Heinrich Hahnsen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hoechst AG
Original Assignee
Walter Kaminsky
Heinrich Hahnsen
Hoechst Aktiengesellschaft
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Walter Kaminsky, Heinrich Hahnsen, Hoechst Aktiengesellschaft filed Critical Walter Kaminsky
Application granted granted Critical
Publication of CA1217777A publication Critical patent/CA1217777A/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • C08G79/10—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/06—Aluminium compounds
    • C07F5/061—Aluminium compounds with C-aluminium linkage
    • C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
    • C07F5/068—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage) preparation of alum(in)oxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Abstract

Abstract of the disclosure:

The present invention relates to a process for the preparation of oligomeric alkylaluminoxanes of the general formulae:

for a linear aluminoxane and for a cyclic aluminoxane

Description

777~

The present invention relates to the preparation of aluminoxanes, preferably methylaluminoxane. Alum;n-oxanes of th;s type can be used as a component of cata-Lysts in the preparation of high-activity, homogeneous Ziegler catalysts.

Var;ous processes are known for the preparation aluminoxanes. Thus, aluminoxanes are obtained, foc example, by the act;on of steam on a benzene solut;on of a tr;aLkylaLum;num ~J. A. Chem. Soc. 90, 1968, 3173), by us;ng l;thium d;alkylaluminate as the organoaluminum starting compound (J. Chem. Soc. 89, 1967, 173), by oxi-dizing a~uminum~hydrocarbon compounds ~ith Lead dioxide (J. Organomet. Chem. 43, 1972, 81) and also be hydrolyz-ing aluminum alkyls uith copper suLfate containing ~ater of crystallization (Jzv. Akad. Nauk, USSR, Ser. Chim. 11, 1975, 2547), and also, in general, uith salts conta;n;ng ~ater of crystall;zat;on of the formula C A aH20 ~C 5 cation, A = anion and a = 2; USSR Patent 566,844), and also by adding ~ater sLowLy to aluminum alkyls ~U.S. Pat-ent No. 3,242,099). In all these processes, very short-cha;n aluminoxanes are obta~ned, uh;ch are predominantly or exclusively compounds of the formula R R
Al-O-Al . ;
R ~R

7~

in wh;ch R = methyl, ethyl, buty~, ;sobutyl and the l;ke.
Add;t;onally, methylaluminoxane can only be prepared ~ith d;ff;culty and ;n a very poor y;eld by the methods ment;oned.
It is also known to prepare o~;gomer;c m;xtures of alum;noxanes hav;ng a degree of ol;gomerization between 2 and 12 by react;ng tr;methylalum;num w;th cop-per sulfate conta;ning water of crystallization ~CuS04.5H20) in accordance with a method of J. Her~;g (thes;s, Hamburg Un;vers;ty, 1979). However~ in this case the yield ;s only approx. 30X, relative to the alu-minum tr;alkyl employed. A further d;sadvantage ;s that, as a result sf reduction reactions, traces of copper al~ays remain in the aluminoxane thus prepared, and these color the product yellow to red. Before being used as a component of the catalyst in the polymer;zat;on of ole-f;ns, ;t must be f;ltered, purified and recrys~allized, since otherwise the polymerization is ;nterfered w;th and the quality of the polymer ;s adversely affected. How-ever, even after pur;fication and recrystall;zat;on,these alum;noxanes can st;ll cont~;n res;dues of copper.
It has now been found that longer-chain, ol;go-mer;c, l;near and/or cycl;c alkylalum;noxanes of the formulae >Al _ O - ( Al~)n -Al R \ R for a l;near alum;noxane and '~

~Z~777~

R \ for cycl;c aluminoxane wherein n is 2-40, preferably 10-ZO and R is C1-C6-alkyl, preferably methyl, are obta;ned if an aluminum trialkyl, preferably aluminum trimethyl, dissolved in an inert aLi-S phatic or aromatic solven~, preferably toluene or heptane,is reacted, at temperatures between -20 and 100~C, prefer-ably between 15 and 40C, with aluminum salts, preferably aluminum sulfate, containing water of crystallization.
In this reaction, the ratio by volume between the solvent and the aluminum alkyl used is 1:1 to 50:1 - pre-ferably 5~1 ~ and the reaction time, which can be checked by the elimination of the alkane, ;s 1 to 200 hours, pre-ferably 10 to 40 hours.
The aluminum salts containing water of crystal-l;zation which are used are preferably those which have a high content of water of crystallization. Hydrated alu-minum sulfate, above all the compound Al2tS04)3.18H20 and Al2(so4)3.16H20, having the particularly high content of water of crystallizat;on of 16 and 18 mole, respectively, of H20 per mole of Al2tS04)3 is particularly preferred.
It is particularly preferable to employ aluminum trimethyl as the aluminum alkyl. Other examples of suit-able aluminum alkyls are the compounds AlR3 in which R is ethyl, isopropyl, butyl, isobutyl and phenyl.
Aluminum trimethy~ which has been di~uted with an inert solvent, for example heptane or toluene, reacts ~'~177'77 with the Al2 (S~4)3.18H20 or AL2(so4)3.16H2o wh;ch are used part;cularly preferentially ;n accordance w;th the equation:

/CH3 ~ CH
x (Al2(S04)3 18~16)H20) ~ (nl 1)Al(~H3)3~ -~Al-O)n - Al m CH4 ~ x (Al2(S04)3 (18(16) 2x) 2 in which n = 2 to 40, preferably 10-20, m = 2n for linear aluminoxanes or 2n + 2 for cyclic alum;noxanes and x =
0.06n to 0.15n, preferably 0~11n.
When hydrated aluminum sulfate, wh;ch ;s read;ly access;ble, is reacted with aluminum trimethyl, it is possible, surpris;ngly, to ;ncrease the yield of methyl-aluminoxane to over 60% and to increase the average deg-ree of oligomerization to values of more than 20. The methylaluminoxane thus prepared is colorless and free from other meta~s which exert an adverse effect, for example when it is used as a co-catalyst for olefin polymerization.
Compared with the processes of the state of the art, the process according to the ;nvention has substan-t;al advantages which can be seen, above all, in the fact that a higher yield is achieved and that alum;noxanes of greater purity and a higher degree of ol;gomerization are obtained. This makes it possible also to use the alu-minoxane so~ution prepared in accordance w;th the inven-t;on d;rect, ~ithout the fi~tration, pur;fication and ~' .

12~77 recrystallization required in the processes of the state of the art, for example to use it as a co-catalyst together with a heavy metaL component in the polymer;za-tion of olefins. However, it is probably preferable in some cases to separate the aluminoxanes prepared in accordance with the invention from the hydrocarbon solu tion and to subject them to recrystallization and to purificat;on. It is also possible to work up the alumin-oxane solution to give solid aluminoxane.
As already mentioned, the longer-chain alkyl-aluminoxanes, above all methylaluminoxane, ~hich have been prepared in accordance with the invention can be used advantageously as a catalyst component in the poly-merization of olefins. It is of decisive importance in this connection that the degree of oligomerization of these aluminoxanes should be substantially h;gher than 2.
Short-chain aluminoxanes, such as the methylaluminoxane (CH3)2Al-OAl(CH3)2 known from the state of the art, pro-duce, together with a heavy metal component, catalyst systems uhich have only a very slight polymerization act-ivity or virtually none.
On the other hand, catalysts which are soluble in many hydrocarbons and which enable extremely high activi~
ties exceeding 25 million 9 of polyethylene per 9 of transition metal and per hour to be achieved in the poly~
merization of olef;ns are obtained, for example, by m;x-ing methylaluminoxane prepared in accordance ~ith the invention and bis-(cyclopentadienyl) compounds of tita-nium and especially zirconium. In addition, catalyst lZ17777 systems containing the longer-chain methylaLuminoxanes as the co-catalyst are fa;rly ;nsens;t;ve to~ards impuri-ties in, for example, the monomers.
It ;s also an advantage that the alum;noxanes accord;ng to the invention are less spontaneously inflam-mable and have a less corros;ve effect than the alum;num alkyl halides which are frequently ùsed as the co-catalyst ;n the polymerization of olef;ns.
Example 1 37.1 g of Al2(S04)3.18H20 (0.056 mole, corres-pond;ng to 1 mole of H20) were suspended in 250 ml of toluene, 50 ml of trimethylalum;num (0.52 mole) were added and the react;on was carr;ed out at 20C. After a react;on t;me of 30 hours, approx. 1 mole of methane had been evolved. The solut;on was then freed from the sol;d alum;num sulfate by f;ltration. On remov;ng the toluene, 19.7 9 of methylalum;noxane were obta;ned. The y;eld was 63X of theory. The average molecular weight, deter-m;ned cryoscop;cally in benzene, was 1,170. The number of tl~-) un;ts ~as found by calculat;on to be 20.2.

The average degree of ol;gomerization was approx.
15.
Example 2 The procedure was as in Example 1, but the reac-tion was carried out at a temperature of 40C. After only 11 hours, 1 mole of methane had been spl;t off. The solution ~as f;ltered and used d;rect as a stable co~

catalyst solution for the production of the soluble ~217~

Ziegler catalyst. Yield of methyla~uminoxane 60X.
Example 3 A procedure analogous to that of Example 1 ~as used, but w;th the modif;cation that heptane ~as used as the solvent and the reaction temperature was 15C. 40 hours ~ere required to split off 1 mole of methane. The reaction mixture, which contained the methylaluminoxane and aluminum sulfate, ~as suitable, even ~ithout filtra-tion, to form a highly active Z;egler catalyst ~hen bis-cyclopentadienylzirconium compounds were added. Part ofthe batch ~as ~orked up to give pure aluminoxane, ~hich had an average molecular weight of 1,210, determined cryoscopically. The number of (Al-0) un;ts uas calcu-~ated to be 20.9. The average degree of oligomerization ~as approx. 16.
Example 4 60 9 of hydrated aluminum chloride AlCl3.6H20 ~eresuspended in 150 ml of toluene, a solution of 50 ml (0.52 mole) of trimethylaluminum was added and the mixture was reacted for 75 hours at 40C. When one mole of methane had been evolved (66% conversion), the suspension was filtered and the methylaluminoxane uas obta;ned from the f;ltrate by removing the solvent (yield 18.4 9). ~he alum;noxane had an average molecular ~eight of 1,000, determ;ned cryoscopica~ly.
Example 5 47 9 of hydrated aluminum nitrate Al~N03)3.9H20 ~ere suspended in toluene as ;n Example 4, and trimethyl-6r '~

~Z177t77 aluminum was added. After a reaction time of 45 hours at 30C, the mixture ~as filtered and the f;ltrate was worked up to give methylaluminoxane, which had a slight brown color (yield 18.4 9).
Example 6 45 9 f Al2(S04)3-16HzO were suspended in 150 ml of toluene and reacted at 40C with 65 ml (0.47 mole~ of aluminum triethyl, dissolved in 100 ml of toluene. The el;mination of ethane took place more rapidly than the elimination of methane in the comparable methyl system.
Thus, it was possible to discon~inue the reaction after a reaction time of only 6 hours, ~hen 1 mole of ethane had been evolved, and to ~ork up the filtrate to g;ve ethyl~
aluminoxane. The yield ~as 18 9 of colorless, solid ethyl-aluminoxane. The molecular weight, determined cryo-scopically, was 1,511. This corresponds to approx. 21 aluminum units in a molecule of aluminoxane.

Claims (15)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of a member of the group of oligomeric, linear and cyclic alkylaluminoxanes of the formulae:

for a linear aluminoxane and for a cyclic aluminoxane wherein n = 2 to 40 and R = C1-C6-alkyl, in which an aluminum trialkyl dissolved in an inert aliphatic or aromatic solvent is reacted, with the elimination of an alkane at a temperature between -20 and 100°C with an aluminum salt containing water of crystallization.
2. The process as claimed in claim 1, wherein toluene or heptane is used as the solvent.
3. The process as claimed in claim 1, wherein the reaction is carried out at temperatures between 15 and 40°C.
4. The process as claimed in claim 1, claim 2 or claim 3 wherein aluminum trimethyl is employed as the aluminum trialkyl.
5. The process as claimed in claim 1, claim 2 or claim 3 wherein a 1 to 30% strength solution of aluminum trimethyl is used as the aluminum trialkyl.
6. The process as claimed in claim 1, claim 2 or claim 3 wherein a 5 to 20% strength solution of aluminum trimethyl is used as the aluminum trialkyl.
7. The process as claimed in claim 1, claim 2 or claim 3 wherein aluminum sulfate is used as the aluminum salt containing water of crystallization.
8. The process as claimed in claim 1, claim 2 or claim 3 wherein hydrated aluminum sulfates containing 9 to 18 molecules of water of crystallization are used as the aluminum salt containing water of crystallization.
9. The process as claimed in claim 1, claim 2 or claim 3 wherein Al2(SO4)3 .18H2O or Al2(SO4)3 .16H2O
used as the aluminum salt containing water of crystalli-zation.
10. The process as claimed in claim 1, claim 2 or claim 3 wherein aluminum trimethyl is used as the aluminum trialkyl and hydrated aluminum sulfate is used as the aluminum salt containing water of crystallization, and the molar ratio between aluminum trimethyl and hydrated aluminum sulfate is 2 to 18.
11. The process as claimed in claim 1, claim 2 or claim 3 wherein aluminum trimethyl is used as the aluminum trialkyl and hydrated aluminum sulfate is used as the aluminum salt containing water of crystallization, and the molar ratio between aluminum trimethyl and hydrated aluminum sulfate is 9.
12. The process as claimed in claim 1, claim 2 or claim 3 wherein aluminum trimethyl is employed as the aluminum trialkyl, and the reaction mixture is used directly as a co-catalyst in the polymerization of olefins, when 1 to 2.5 mole of methane per mole of Al(CH3)3 have been eliminated.
13. The process as claimed in claim 1, claim 2 or claim 3 wherein aluminum trimethyl is employed as the aluminum trialkyl, and the reaction mixture is used directly as a co-catalyst in the polymerization of olefins when about 2 mole of methane per mole of Al(CH3)3 have been eliminated.
14. The process as claimed in claim 1, claim 2 or claim 3 wherein aluminum trimethyl is employed as the aluminum trialkyl, and the reaction mixture is filtered and the filtrate, containing methyl aluminoxane, is used as a co-catalyst in the polymerization of olefins.
15. The process as claimed in claim 1, claim 2 or claim 3 wherein aluminum trimethyl is employed as the aluminum trialkyl, and the reaction mixture is filtered and the filtrate is worked up to give solid methyl aluminoxane by removing the solvent.
CA000440182A 1982-11-02 1983-11-01 Process for the preparation of oligomeric aluminoxanes Expired CA1217777A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19823240383 DE3240383A1 (en) 1982-11-02 1982-11-02 METHOD FOR PRODUCING OLIGOMER ALUMINOXANES
DEP3240383.6 1982-11-02

Publications (1)

Publication Number Publication Date
CA1217777A true CA1217777A (en) 1987-02-10

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US (1) US4544762A (en)
EP (1) EP0108339B1 (en)
JP (1) JPS5995292A (en)
AU (1) AU557540B2 (en)
CA (1) CA1217777A (en)
DE (2) DE3240383A1 (en)
ES (1) ES8406079A1 (en)
ZA (1) ZA838140B (en)

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