FR2588872A1 - New trialkylaluminium cocatalysts - Google Patents

Abstract

The invention relates to the catalyst industry. Catalyst system comprising: a. a metallic titanium compound bound on to a support such as TiCl4 on MgCl2; b. at least one trialkylmetallic compound in which the metal is Al, Ga or In; and c. an alcoholate, carboxylate or arylate of a metal from groups IA to IIIA; the said system comprising a Lewis base. Application of the catalyst to the polymerisation of alpha-olefinic C2-C20 monomers in order to produce solid homo-, co- or terpolymers.

Description

 The invention relates to novel trialkyl aluminum co-catalysts and, more particularly, to catalytic compositions suitable for the polymerization of alpha-olefins.

The use of alkyl derivates of group metals
I-III of the classification of the elements, in combination with transition metal compounds of groups IVB-VIII, as catalyst systems for the polymerization of olefins is already well known (see in this regard patents and patent applications No. 3,953 414 of the United States of America, No. 846,314 of Belgium, No. 2,620,886 of the Federal Republic of Germany, No. 1,335,887 of Great Britain, 2,630,585 of the United Kingdom
Federal Republic of Germany, No. 1,140,659 of Great Britain, No. 2,612,650 of the Federal Republic of Germany, No. 7,503,470 of the Republic of South Africa, No. 2,355,886 of the Republic of
Federal Republic of Germany, No. 51064-586 of Japan, No. 7,507,382 of South Africa, No. 2,638,429 of the Federal Republic of Germany, No. 51057-789 of Japan, No. 3,992,322 of
United States of America, Nos. 52027-090 of Japan and No. 3 400 110 of the United States of America.) While almost all alkylated metal compounds are effective for the polymerization of ethylene, only a few of them are effective for the preparation of isotactic polymers of propylene and higher alpha-olefins, and only the compounds
And Al., A1E t3 and i-Bu2AlH find industrial applications
2 important trielles.It denotes here the ethyl, butyl and propyl radicals by the abbreviations Et, Bu and Pr.

 An important factor in the cost of alpha-olefin polymerization is that of the catalysts employed. As a result, the price of polymer manufacture can be substantially reduced by the use of catalytic systems with higher polymerization power. Another concern is that of producing polymers containing a minimal amount of catalyst residues in order to eliminate the expensive operation of ash removal. It is still necessary to produce polymers having a high degree of isotactic stereoregularity to suppress or reduce the expensive operation of removing the atactic polymer or separating it from the isotactic polymer. The improved system of the invention makes it possible to obtain, during manufacture, these desirable conditions.

 The catalyst systems of the present invention, which are suitable for alpha-olefin polymerizations, comprise a transition metal compound of groups IVB-VIII, one or more Lewis bases and at least one trialkyl derivative of Al, Ga or Wherein at least one of the alkyl groups belongs to the group of C3-C20 radicals, secondary or tertiary, alkyl, cycloalkyl, alkenyl or arayl.

 The transition metal compound is a transition metal halide of groups IVB-VIII, where the halide is a chloride or bromide, the metal halide being in the form of solid crystalline compounds, solid solutions or compositions. with other metal salts or being fixed on the surface of a wide range of solid supports.

To ensure the highest possible stereo specificity, it is desirable that the transition metal halide, or its carrier composition, have in its layered lattice structure very small crystallites, a large surface area, or sufficient deficiencies. or foreign components to promote high dispersion during polymerization. The transition metal halide may also contain various additives, such as Lewis bases, pI bases, polymers or organic or inorganic modifying agents. Vanadium halides and titanium halides are preferred, such as vc13, VBr3 Tical3, TiCl4, TiBr3 or
TiBr4, better still TiC1 TiCl3 or TiCl4 mixed colors.
Preferable TiCl3 are those which contain TiCl4 side sites on the layered support network, such as alpha, delta or gamma TiCl3 or various structures and modifications of TiCl3 MgCl2 or other inorganic compounds of similar layered network structures. Especially preferable TiCl4 are those which are attached to a chloride layer network such as MgCl 2. Other anions may also be present, such as other halides, pseudo-halides, alkoxides, hydroxides, oxides or carboxy laths, etc. provided sufficient chloride is available for the formation of iso-specific sites. Mixed or double salts, such as K2TiCl6 or MgTi C16, may be used alone or in combination with electron donor compounds. Other carriers than MgCl 2 are also suitable for the invention, such as hydroxides, oxides or inorganic or organic carriers. The particularly preferred compound of transition metal is TiCl.sub.4 containing MgCl.sub.2, especially in the presence of Lewis bases ( electron donor compounds.

 The Lewis bases can be used in combination with the trialkyl metal compound or the IVB-VIII transition metal compound, as long as they do not produce excessive opening of metal-carbon bonds or loss. active sites. A large number of Lewis bases are suitable for the invention, such as tertiary amines, esters, phosphines, phosphine oxides, (alkyl and aryl) phosphates, phosphites, hexaalkyl phosphor triamides, dimethylsulfoxide, dimethylformamide, secondary amines, ethers, epoxides, ketones, saturated or unsaturated heterocycles, cyclic ethers, or mixtures thereof.Examples of such compounds are given by diethyl ether, dibutyl ether, tetrahydrofuran ethyl acetates> methyl p-toluate, ethyl p-anisate, ethyl benzoate, phenyl acetate, amyl acetate, methyl octanoate, acetophenone, benzophenone, triethylamine, tributylamine, dimethyl decylamine, pyridine, N methylpiperidine, 2,2,6,6 tetramethylpiperidine and other similar compounds. Preferred compounds are carboxylic acid esters such as ethyl benzoate.

It is also possible to use salts of the metals of the groups
IA-IIIA with the catalysts of the invention, if they are totally or partially solubilized by reaction with the alkyl-metal components. Among the salts that are particularly suitable for the invention, mention may be made of magnesium aluminum carboxylates, alkoxides and aryloxides, examples of which are given by Mg (OCR ") 2>R" O Mg OOCR "ClMgOR", Mg ( OR ") 2, R" Al00CC6H5, R "Al (OOCR") 2, R "2AlORt 'and other similar compounds, wherein R" is a hydroxycarbyl group.The preferred compounds are the prepared magnesium and aluminum carboxylates in situ by reaction of organometallic compounds with carboxylic acids in hydrocarbon solvents.

The cocatalysts of the invention have the general formula R n MR 3-n where R belongs to the group of C 3 radicals
C20, secondary or tertiary, alkyl, cycloalkyl, alkenyl or aralkyl, R 'belongs to the group of primary C1-C20 radicals, alkyl, alkenyl, aralkyl or hydride; and n = 1-3 preferably 1-2 even better n = 2. Preferably R 'is a primary C 2 -C 10 alkyl, aralkyl or hydride group; still more preferably R 'is a primary C 2 -C 4 alkyl or hydride group, with the proviso that not more than one hydride group is present.The radical R is preferably an alkyl of about
C4-C16 secondary or tertiary, a cycloalkyl group; it must above all not be susceptible to elimination or easy movement by the monomer during the polymerization. In addition to the simple secondary alkyl groups, other groups are also effective in which the aluminum is linked to secondary or tertiary carbon atoms, such as, for example, cyclohexyl, cyclooctyl, tert-butyl, tert-amyl or s-norbornyl groups. etc. The preferred compositions have the formula RnAlR'3n in which the secondary and tertiary alkyl groups contain 4-10 carbon atoms and n = 2. Mixtures of the cocatalysts of the invention with customary cocatalysts of an alkylated metal also give improved results.

 Examples of compositions of the invention are given by i-Pr2AlEt, s-BuAlEt2 s-Bu2AlEt, t-BuAlEt2, t-Bu2AlEt, s-Bu3Al, 1,1-dimethylheptyl-AlEt2, s-Bu2Aln-C16H33 t-Bu2AlCH2 C6M5, s-Bu (t-Bu) Aln-Bu, cyclohexyl2AlEt, s-pentyl Ali-Bu2 t Bu2AlMe, t-Bu2Aln-C8H17, (2-ethylcyclopentyl) 2AlEt, 2- (3-ethylnorbonyl) AlEt2, 2-norbornyl Ali-Bu 2, (2-norbornyl) 2Al-Bu, acenaphthyl Ali-Bu 2, cyclooctyl (i-Bu) AlH, 3-ethyl-5-ethylidinenorbornyl-AlEt 2, 9-i-Bu-9-alumino-33I-bicyclononanet s -Bu2AlH, t-Bu2AlH, t-Bu2InEt, s-Bu2GaEt, etc. and other similar compounds.

Among the compounds mentioned above, the preferred compositions have the formula R1-2AlR'2-1, and the compositions
= still preferable have formula R2AlR '.

A production method according to the invention of the secondary alkyl aluminum compounds consists of reacting internal olefins with AliBu3 or i-Bu2Al H to add
Al-H on the double bond, to form the voltage-cycle secondary compound; we can use AlR3 to add
Al-R on the double bond and obtain preferable compounds highly resistant to displacement or elimination. Tight cycle olefins include cyclopentene, norbornene, norbornadiene, ethylidine-norbornene, dicyclopentadiene and the like. This process is preferable because of the availability of raw materials and the simplicity of the reaction, although the invention is not limited to the synthetic process.

 Other methods include direct synthesis from reactive metals and secondary or tertiary halides, the various organometallic syntheses comprising ligand exchange between the Al, Ga or In compounds and the secondary or tertiary alkyl metal compounds of more electro-positive metals such as those of groups IA and IIA, and the reaction of metals with alkyl mercury compounds. The general reaction of secondary or tertiary alkyl lithium compounds with R'MX2 or R'2MX is particularly suitable since it readily occurs in dilute solution in hydrocarbons.

 Although secondary dialkyl aluminum compounds are preferred to secondary monoalkyl compounds, the effectiveness of the compounds of this type of secondary mono-alkyl tends to increase with the steric hindrance of the group, inasmuch as it does not interfere with the formation of active sites or does not lead to decomposition under the reaction conditions.

 For the alkyl metal cocatalysts of the invention, the preferred transition metal compounds contain TiCl 4 on a MgCl 2 support and one or more Lewis bases. The concentration of the transition metal in the polymerization zone is 0.001 to 5mM and is preferably less than 0.1mM.

 The molar ratio of the trialkyl metal compound to the transition metal compound is 0.5: 1 to 50: 1, preferably 1: 1 to 20: 1, more preferably 5: 1. The molar ratio of Lewis base to organometallic compound may vary within wide limits, but is preferably from 0.1: 1 to 1: 1.

 The catalytic system of the invention allows the manufacture of alpha-olefin polymers with a high degree of isotactic stereoregularity, at a temperature of 25 to 1500C, preferably 40 to 80C, at pressures of about 1 to 50 atm .

The duration of the polymerization reaction is 0.1 to 10 h, preferably 1/2 h to 3 h. Due to the high catalytic activity, shorter reaction times and temperatures below 800C can also be employed.

 The solvent suitable for the reaction system may be any of the inert paraffinic, naphthenic or aromatic hydrocarbons such as benzene, toluene, xylene, propane, butane, pentane, hexane, heptane, cyclohexane or mixtures thereof.

Excess liquid monomer is preferably employed as a solvent. It is also possible to carry out gas phase polymerizations with or without small amounts of solvent.

 Examples of C2-C20 alpha-olefinic monomers employed according to the invention for the manufacture of homo-, co- or terpolymers are given by ethyl, propylene; butene-1, pentene-1, hexene-1, octadecene-1,3-methylbutene-1, styrene, ethylidene-norbornenea 1,5-hexadiene and other similar compounds and mixtures thereof. Isotactic polymerization of propylene and higher olefins is preferred, including sequential polymerization with ethylene.

 The trialkyl metal compound and the transition metal compound and its support may be introduced separately into the reactor or may be premixed, but it is preferable to introduce them separately. The replacement of the secondary or tertiary alkyl groups by alkoxy, phenoxy or dialkylamide steric hindrance or hinder groups does not make it possible to obtain the improved catalytic activity of the cocatalyst of the invention.

According to another embodiment of the invention, as regards the cocatalysts (RnMR 'n)', the products of the reaction are used directly.

The metal di- or tri-halides suitable for the formation of R2MR 'belong to the group consisting essentially of a metal halide of the group of RXMX2, MX3 and mixtures thereof, where M is a metal of the group of Al, Ga and In
R 'belongs to the group of primary C 1 -C 20 radicals, alkyl, alkenyl or aralkyl or hydride; and X belongs to the group of bromide chloride or a monovalent anion which can not initiate the polymerization of olefinic monomers belonging to the group of alkoxide, phenoxide, thioalkoxide, carboxylate, etc. and their mixtures. Examples of these compounds are given by ethyl aluminum dichloride, aluminum trichloride, ethyl aluminum dibromide, ethyl chloroaluminum bromide, octyl aluminum dichloride, ethyl dichloride, dichloride, and the like. butyl aluminum, benzyl aluminum dichloride, ethyl chloroaluminium butoxide and mixtures thereof. Mixtures of metal halides can easily be employed.

 C2-C4 alkyl-aluminum dihalides are preferred because of their high stereospecificity and monoalkylaluminum chlorides are still preferable.

 The diorganomagnesium compounds of general formula R 2 Mg, where R, which may be the same or different, belongs to the group of secondary or tertiary C 3 to C 20 radicals, alkyl, cycloalkyl, aralkyl or alkenyl. Examples are given by (s-Bu ) 2Mg, (t-Bu) 2Mg or (iPr) 2Mg. . Mixtures of diorganomagnesium compounds may be used, provided that at least one secondary or tertiary group is present. Preferred organic groups are secondary or tertiary alkyl groups, such as t-Bu or s-Bu.

 The molar ratio of the alkyl metal halide (R'MX2) to the diorganomagnesium compound, which is critical, is from 0.5: 1 to 2: 1, preferably from 0.7: 1, more preferably from : l.

For MX3 the ratio is 1: 1 to 1: 3, preferably 2: 3. The number of moles of the Lewis base may vary within wide limits but is preferably equal to or less than the sum of the moles of the metal halide and the diorganomagnesium compound. The molar ratio of the metal halide or the diorganomagnesium compound to the transition metal compound is less than about 1: 1, preferably less than 20: 1.

 The metal halide and the diorganomagnesium can be added separately to the reactor containing the transition metal compound, but it is preferable to mix them beforehand. The use of either the metal halide alone or the diorganomagnesium alone with the transition metal compound does not provide improved efficiency and stereospecificity of the catalysts of the invention. To achieve this result, it is necessary to use both the metal halide and the diorganomagnesium in combination with the transition metal compound in the critical proportions previously described. The concentration of the transition metal in the polymerization zone is 0.001 to 5 mM, and is preferably less than 0.1 mM.

The alkyl-metal compounds suitable for the formation of RMR'2 belong to the group consisting essentially of an alicyl group metal of R'2MX or R'3M and mixtures thereof, where M belongs to the group of Al, Ga and In ; R 'belongs to the group of radicals C1 to C20, primary alkyl, alkenyl alkyyl or hydride; and X belongs to the group of monovalent anions, which can not initiate the polymerization of olefins, such as F, Cl, Br, OR, SR ", and OOCR, where R" belongs to the group of C1-C20 alkyl, branched alkyl radicals. , cycloalkyl, aryl, naphthenic, aralkyl and alkenyl, X being preferably
Cl or Br, and even better Cl.Examples of these compounds are given by diethylaluminum chloride, triethylaluminum, diethylaluminum bromide, diethylaluminum iodide, diethylaluminum benzoate, diisobutylaluminum hydride, dioctylaluminum chloride, diethylgallium butoxide, neodecanoate. diethylindium, triethylindium, dibenzylaluminum chloride and mixtures thereof. Mixtures of alkyl metal compounds can easily be employed. The C2-C4 alkyl aluminum compounds are preferred because of their high stereospecificity and the dialkylaluminum chlorides are still preferable.

 The mono-organomagnesium has the general formula RMgX wherein R belongs to the group of secondary or tertiary n3-W20 radicals, alkyl, cycloalkyl, alkyl or alkenyl; X belongs to the group of anions which can not initiate the polymerization of olefins, such as Cl, Br, OR ", SR", and OOCR, where R "belongs to the group of C1-C20 alkyl, branched alkyl, cycloalkyl, naphthenic radicals. aryl, aralkyl, allyl and alkenyl Examples of these compounds are given by s-BuMgCl, t-BuMgCl, s-BuMgOOCC6H5 or s-BuMgOC15H3I and mixtures thereof.Mixtures of organomagnesium compounds can be readily employed. Preferred are the OR "and OOCR" groups and the preferred R groups are secondary or tertiary alkyls.

 The molar ratio of the organomagnesium RMgX to the alkyl metal (R'2MX or R '3M is from 2: 1 to 1: 2, preferably 1: 1.

The number of moles of the Lewis base may vary within wide limits, but it is preferably equal to or less than the sum of the moles of alkyl metal and organomagnesium. The molar ratio of the alkyl metal or organomagnesium to the transition metal compound is less than 20: 1, and preferably less than 10: 1.

 The alkyl metal (R'2MX or R'3M) and organomagnesium RMgX can be added separately to the reactor containing the transition metal compound, but it is preferable to pre-mix them. The use of either the alkyl metal alone or the organomagnesium alone with the transition metal compound does not provide the improvement in the efficiency and stereospecificity of the catalysts of the invention. To achieve this result, it is necessary to use both the alkyl metal and the organomagnesium in combination with the transition metal compound in the previously defined proportions. The concentration of the transition metal in the polymerization zone is 0.001 to 5mM, preferably less than Olim.

 The invention will be better understood on reading several nonlimiting examples which follow various embodiments of the invention.

EXAMPLES r
An alkylaluminium containing both sec-butyl and ethyl groups is prepared by mixing equimolar amounts of (sec-butyl) 2Mg .0, 15D-tO and ethylaluminum dichloride in heptane, with heating. at 650C for 15 min, then separating the solid magnesium chloride and evaporating the clear solution under vacuum. Nuclear magnetic resonance (NMR) analysis indicates a composition of sBu2AlEt · O, 45 Et2O. Metal analysis shows that only 0.50% Mg is present in this fraction.

 The liquid alkylaluminum described above (0.2 g) was used as a cocatalyst with 0.2 g of a catalyst prepared by reacting anhydrous MgCl 2 (5 moles) with TiCl 4 C 6 H 5 COOEt (1 mole) in a ball mill. 4 days, followed by treatment with TiCl4 without solvent at 80 ° C. for 2 hours, washing with heptane and drying under vacuum. The catalyst contains 2.68% Ti. Propylene is polymerized in 500 ml of nheptane at 650C for 1 hour at 765-770 mm. The polymerization rate is 130 g / g catalyst / h and the boiling thysteen insoluble polymer fraction is 97.6%.

EXAMPLE 2
Three alkyl-aluminum compounds containing sec-butyl groups are prepared by reacting the appropriate stoichiometric amounts of sec-butyllithium in heptane with either ethylaluminum dichloride or diethylaluminum chloride, bringing to boiling, then by filtering the insoluble halide and evaporating under vacuum the clear solutions.

We obtain with almost theoretical yields s-BuEtAlC1 (B), s-Bu2EtAl (E) and s-BuEt2Al (D). The compositions are determined by HN and C NMR and by gas chromatographic (GC) analysis of the alkyl moieties.

The polymerizations are carried out as in Example 1 using 1 mmol of alkylaluminium and 0.2 g of the catalyst.
TiCl4 on support. The results obtained, shown in Table I, are compared with those obtained using the control compounds of ethylaluminium. In each of the three tests with sec-butyls as alkyls, it is found that both the activity and the stereospecificity (insoluble in heptane: IH are greater than those obtained with the usual ethyl-aluminum compounds. trialkylaluminiums are far superior to dialkylaluminum chlorides and di-sec-butylethylaluminum is significantly superior to mono-sec-butyldiethylaluminum.

TABLE I
Alkyl-Al Speed Test
A control Et2AlCl 48.9 68.0
B s-Bu1.07EtAlCl 0.93 64.6 79.1
C Et3Al control 344 83.1
D-BuEt2Al 380 90.3
E s-Bu2EtA1 357 93a0
EXAMPLE 3
The sec-pentyl-diisobutylaluminum is prepared by reacting 19.57 g of i-Bu2AlH with 75 ml of pentene-2 in a 300 ml glass-lined bomb at 135-1400 ° C. for 16 hours and then at 150 ° C. for 7 hours. The solution was evaporated in vacuo at 250 ° C to obtain 28.1 g of the homogeneous secuentylaluminum compound.

 Propylene is polymerized as in Example 2 using 0.212 g (1 mmol) of sec-pentyl-diisobutylaluminum as cocatalyst. The polymerization rate is 383 g / g cat / h and the IH% (insoluble in heptane) = 92.7.

Comparison with the Et3Al control (Example 2, Run C) shows that the sec-pentylaluminum compound achieves effective improvement, particularly stereospecificity.

EXAMPLE 4
The cocatalysts of the alkyl metal invention are particularly advantageous in that they exert a much lower concentration (or alkyl-metal / Ti) effect on the stereospecificity, which simplifies the operation of the manufacture and allows better regulation of the quality of the products.Table II indicates the results obtained with di-sec-butylethylaluminium, compared to AlEt3, in the polymerization of propylene according to the process of Example 2
TABLE II
Test Alkyl-Al Conc., MM Speed IH%
F s-Bu2AlEt 2,357 93.0
G s-Bu2AlEt 4 484 83t4
H AlEt3 control 2 344 83.1
I AlEt3 witness 4 290 64.9
The following examples show that the tri-alkylaluminium compounds, containing at least one secondary alkyl group, are excellent cocatalysts for Ziegler-type polymerizations of alpha-olefins and that the di-sec-alkylaluminium compounds are preferable.

EXAMPLE 5
Various sec-norbornyl-n-alkylaluminum compounds are prepared by reaction in stoichiometric proportions of a norbornene compound with either i-Bu2AlH or AlEt3 at elevated temperature and removing excess reagents by evaporation in vacuo. H NMR and 13 C analysis show that the structures obtained correspond to the expected adducts of A1-H or Al-Et on the double bond of norbornene.

These mono- and di-sec-alkylaluminum compounds are used in the polymerization of propylene, according to the process of Example 2.

TABLE III
Test Alkyl-Al Speed 1H%
J 2-Norbornyl-AliBu2 344 90.2 *
K (2-Norbornyl) 2AliBu 247 91.8
L 3-ethyl-2-norbornyl-AlEt 2 322 92.5
M 3-Ethyl-5-ethylidin-2-yl 247 93a7 norbornyl-AlEt2 * a Other isomers may also be present.

 Comparison with the AlEt3 control (Run C of Example 2) shows that all the sec-norbonylalkylaluminum compounds give significantly higher percentages of insolubles in heptane, while having a high activity.

EXAMPLE 5
The sec-alkylaluminum hydrides also give improved results as compared to the primary alkyl-aluminum hydride (i-Bu2AlH) very similar in the process of Example 2.

TABLE IV
Test AV1-A1 Speed IH%
Control N i-Bu2AlH 456 83.1 O-Bu2.6AlH0.4 462 85.8
P AlEt3 control 241 82.3
O iBu3Al control 264 89.3
R s-Bu2.6AlH0.4 s-Bu AlH
2.6 0.4 284 90.7
S-Bu2,3A1H0.7 223 90.1 * Another catalyst preparation is used. In a ball mill, 5 moles of MgCl 2 are reacted with 1 mole of ethyl benzoate for one day, 1 mole of TiCl 4 is added and ground for 3 days, then treated with homogeneous TiCl 4 at 800 ° C. for 2 hours. washed with heptane and dried under vacuum. The catalyst contains 3.44% Ti.

 In the test where sec-butyl groups are used, greater activity and stereospecificity are obtained than in the NI test where the similar but primary groups of isobutyl are used. The results obtained are also better compared with those of the AlEt3 control where the same titanium supported catalyst is used (Example 2, Test C).

 In the R and S tests, where two different hydrides of sec-butylaluminum are used, the insolubles in heptane are significantly higher, compared to the P and Q tests of the AlEt3 and iBu3Al controls with the same catalyst.

EXAMPLE 7
The procedure of Example 2 is repeated except that various Lewis bases are mixed with the alkylaluminum solution prior to introduction into the reactor.

TABLE V
Alkvl-Al molar test Basic speed IH%
T AlEt3 control 5,16 Et2O 358 84,7
U s-Bu2AlEt 0.16 EtC 289 94B4
U s-Bu2AlEt 0.16 Et2O p-toluate Me 327 94.0
w t-Bu2AlEt 0.3 p-anisate Et 79 97.3
X t-Bu2AlEt 0.9 Et20 56 98.0
Y t-BuA1Et2 0.9 Et2O 101 97.1
Z t-Bu2AlEt 0.2 acetophenone 196 94.2
AA t-Bu2AlEt 0.2 ethyl acetate 74 97.6 * The catalyst preparation described in Example 6, tests P to S.

 The improved stereospecificity obtained with the cocatalysts of the invention is further enhanced by the addition of Lewis bases (U-AA tests compared to the control T test and the C test of Example t. 97-98% of 1H is obtained, which is high enough to eliminate the need to evacuate the atactic polymer and greatly simplifies the process.The activity is somewhat diminished, but still remains 3 to 5 times that of the commercial catalyst Et 2 AlCl / TiCl 3 0.33 AlCl 3 (rate = 20, IH = 93) With the slightly lower base concentrations, the activity is 10 to 20 times greater than that of the commercial catalyst, with a IH still higher by 1 to 2%.

EXAMPLE 8
Following the procedures of Examples 2 and 7, an improvement in stereospecificity is also obtained using a t-Bu2InEt cocatalyst.

EXAMPLE 9
The procedure of Example 6, PS tests is repeated except that a 9-i-Bu-9alumino-3,3,1-bicyclononane cocatalyst is used. Polymerization rate = 97.5 g / g cat / h and IH = 85.1.

EXAMPLE 10
The procedure of Example 9 is repeated except that t-Bu2Al (n-octyl) is used as co-catalyst. The speed = 212 g / g cat / h and TH = 93.0
EXAMPLE li
Polymerizations were carried out in a 1-liter, synthetic resin, baffled flask, coupled with an efficient reflux condenser and a high speed stirrer.
According to a conventional process for the polymerization of propylene, 475 ml of n-heptane ((1 ppm of water) containing 10 mol of Et 2 AlCl (1.20 g), or the cocatalyst mixture, are introduced into the reactor under N 2 anhydride. The reaction mixture is heated to a reaction temperature (65.degree. C.) and saturated with pure propylene at 765 mm pressure. TiCl.sub.3 (1.0 g) (6.5 mmol) is introduced into a catalyst tube equipped with a tap. stop and a porous rubber cap Polymerization starts when the TiCl3 is sent into the reactor with 25 ml of n-heptane using a syringe. In order to maintain a gas exit velocity of 20000 ml / min at a pressure of 765 mm × After 1 hour, at the indicated temperature and pressure, the reactor slurry is poured into one liter of isopropyl alcohol, stirring is continued for 2 hours. at 4 hours, filtered, washed with alcohol and dried under vacuum.

 TiCl.sub.3 is prepared by reducing Tical with Et.sub.2 AlCl and then treating with diisopentyl ether and TiCl.sub.4 under specific conditions to obtain a delta-TiCl.sub.3 of high specific surface area with a low aluminum content.

 The sec-butyl-magnesium of tests B, D and E is prepared from the organometal and contains 72% nonvolatile substances in excess of the s-Bu2Mg measured by titration. IR, NMR and GC analyzes indicate the presence of butoxide groups and 0.07 moles of ethyl ether per s-Bu2Mg.

A second sample of (s-Bu) 2Mg was used in runs G and I. It consisted essentially of pure s-Bu2Mg but contained 0.33 moles of ethyl ether per s-Bu2Mg (Table VI).

TABLE VI
g moles speed 1H% TiC13 EtAlC12 (s-Bu) 2Mg Et2AlCl Test ~~~~~~~~ g / g / h
A (control) l (a) O 0 10 33 95s2
B l (a) 5 5 0 152 52.6
C (control) 1 (b) O 10 85 96.3
D 0.2 (b) 0.4 0.2 1.6 123 88.0
E 022 (b) 2 2 0 210 49.2
F (control) l (C) O 0 5 8 79.5
G l (c) 2.5 2.5 0 36 57.6
H (control) l (d) 0 0 10 20 91.7
I 0.2 (d) 1 0 200 57.4
(a) and (b) are different catalyst preparations
TiC13 low aluminum content.

(c) TiC13 sold by the company called Stauffer under the name
HA (reduced by hydrogen, dry-milled)
balls).

(d) TiCl3.0.33 AlCl3 sold by the company called Stauffer under
the trade name AA (reduced by aluminum, crushed
dry with balls).

Comparing the results of tests B, D, E, G and
I with those of their respective witnesses A, C, F and H shows
with each type of TiCl3 catalyst the new combination
its cocatalyst gives a 2 to 10 times higher activity
than the usual cocatalyst Et2AlCl.

The IH% decreases appreciably with the use of
new co-catalysts. These high activity catalysts are
so interesting for the preparation of low homopolymers
crystallinity of propylene and higher alpha-olefins.

they are particularly interesting for preparing poly
thermoelastic mothers and amorphous copolymers and terpolymers
phes for elastomers.

EXEYiPLE 12
A titanium catalyst containing 9C12 is prepared
by grinding dry in a ball mill, for 4 days,
a mixture of anhydrous MgCl 2 (1 mole), TiCl 4 (1 mole) and
& -TiCl3 (0.1 mole). Propylene is polymerized as in
Example 11, Test B, with the amounts indicated in
Table VIII. The activity obtained with the co-catalysts of
the invention (test L) is intermediate between those of the
less AlEt3 and AlEt2Cl (J and K tests), but the stereospecific
ficity, represented by IH, is much higher than
that of the witnesses.The significant increase of IH% obte
naked with this catalyst containing MgCl2 is in opposition with
the results of Example 1, where the activity of the catalysts of
TiCl3 increases markedly, but the IH% decreases.

TABLE VII
Test Catalytic Alkyl-Speed IH% Metals g / g Cat / h
J (control) 1 10 AlEt3 79 54.4
K (control) 1 10 AlEt 2 Cl 18 35.8
L 0.2 1 AlEtCl 2 + 42 81.0
1 (s-Bu) 2Mg
EXAMPLE 13
A titanium catalyst is prepared by grinding to
dried for 4 days, with a mixture of 5 MgCl 2,
1 TiCl4 and 1 ethyl benzoate heating a slurry of
solids in pure TiC14, for 2 hours at 80 C, then wash
by n-heptane and drying under vacuum. The catalyst contains
3.78% Ti.

Propylene is polymerized according to the process of
Example 11, Test B, except that a carrier of
catalyst. As shown in Table VIII, all witnesses
(tests M to S) have an activity and / or an IH% 4 substantially
lower than those of the combination AlStCl2 + s-Bu2Mg (T-test)
or AlCl3 + S-Bu2Mg (U test).

les résffttB auraient été sem-
blables a ceux des essais N+P. Mais les resultats obtenus
dans les essais T et U sont excessivement meilleurs, ce qui
montre la formation inattendue de R2AlR , comme précédemment
décrit.If the new catalysts had simply reacted
as the alkyl-metal compounds separately, the results
would have been similar to the M + Q trials. If the new cocatalysts were simply

the results would have been
similar to those of the N + P tests. But the results obtained
in the T and U tests are excessively better, which
shows the unexpected formation of R2AlR, as previously
described.

A much weaker synergistic effect is achieved
with the combination AlEt2Cl + s-Bu2Mg (test S), but the
results are worse than those obtained with AlEt3.

The combination of s-Bu2Mg with AlEt3 (test R) destroys the acti
presented by AlEt3 alone (test 0). We do not get
excellent results only by the combination of R2Mg with RAlCl2
TABLE VIII
Cataoles of the immoles of the Duration IH Speed%
Compound Lyser Test composed of hg / g Cat / h Al ~~~~~~ Al M9 ~~~~~ ~~~~~~~~~
M (control) 0.2 1 AlEtCl --- 0.5 0 -
2
N (control) 0.2 AlEt 2 Cl --- 1 47 61.1 0 (control) 0.2 1 AlEt -1 326 82.6
P (control) 0.2 --- 0.83 s-BuMgCl 0.25 0 -
Q (control) 0.2 --- 0.83 (s-Bu) 2Mg 0.25 0 -
R (control) 0.2 AlEt3 0.83 (S-Bu) 2Mg 0.25 -
S (control) 0.2 1 AlEt2Cl 0.83 (s-Bu) 2Mg l 165 80.5
T 0.2 1 AlEtCl 2 0.83 (s-Bu) 2Mg 1,367 91.9
U 0.2 1 AlCl3 0.83 (S-Bu) 2M9 1 220 88.9
EXAMPLE 14
The process of Example 13 is repeated using
0.2 g of the TiCl4 catalyst with support, with (s-Bu) 2Mg and
various aluminum compounds.

TABLE IX
moles moles Duration Speed
Al Compound Test (s-Bu) 2Mg h gig Cat / h 1H%
V 0 X 4 AlEtCl 2 0.33 1 60 94.5 w 1 AlEtCl 2 0.41 1 64 76.6
X 0.5 AlEtCl 2 0.83 1 26G 87.2
Y 0X5 AlCl3 0.83 2 136 90.7
Z 1 AlEtCl 2 + AlEt 2 Cl 0.83 1 404 86X9
AA 1 AlEtBr2 0.83 l 220 88.9
BB 1 AlC8Hl7Cl2 0.83 1 425 88.0
CC 0.63 EtClAlN (iPr) 2 0.53 1 6 -
DD 1 Br2AlN (iPr) 2 0283 1 16 -
Comparison of the Vs W and X tests shows that the highest HI% is obtained with approximately equimolar amounts of RA1C12 and R2Mg (test V), that a large excess of RA1C12 is undesirable (test W) and that low excess of
R2Mg increases activity (X test). The activity also increases by addition of AlEt 2 Cl to the AlEtCl 2 - (s-Bu) 2Mg system (Z test).

The other tests show that dibromide can be used instead of dichloride (AA test), that long chain aluminum alkyl compounds are very effective (BB test), but that the presence of dialkylamide groups on the compound of aluminum destroys catalyst activity (DC and DD tests).

EXAMPLE 15
The procedure of Example 13, Test T is repeated, except that Lewis bases are also added to the AlEtCl 2 - (s -Bu) 2Mg cocatalysts.

The addition of Lewis bases produces a decrease in catalytic activity, until it becomes zero for the molar ratio of a strong base per mole of RAlCl 2 +
R2Mg (Table X).

PAINTINGS
Hard Speed
Test Immoles Base / (dry Bu) 2Mg hg / g Cat / h IH%
EE 0.24 COOEt (a) 0.5 174 94.3
FF 0.5 Et3N (b) l 62 85a5
GG 2 Diisopentyl ether 1,128 78,8 HH 2 Tetrahydrofuran (c) O - (a) Added to (s-Bu) 2Mg (b) Catalyst total premixed in 100 ml of n-heptane at 650C, 5 min. addition of Et3N.

(C). Added to AlEtCl2- (s-Bu) 2Mg premixed.

 The EE test shows that small amounts of Lewis base effectively improve isotacticity (IH = 94.3% vs. 91.9% in the T> test while maintaining a high activity (almost 9 times that of the usual catalyst). AlEt2Cl / TiCl3.0,33A1C13, example 11, test H).

EXAMPLE 16
The procedure of Example 13, Test T is repeated, if xylene is used as the diluent for polymerization instead of n-heptane. The activity = 676 g / g cat / h and the polymer gives 90.9% insoluble in heptane. The polymer is precipitated with 1 liter of isopropyl alcohol, then filtered, dried and analyzed metals. 13 ppm of Ti and 83 ppm of Mg are found. It can be seen that with a high monomer concentration and longer polymerization times, the efficiency is high and the catalyst residues, very low, do not require ash removal.

EXAMPLE 17
The procedure of Example 13, Test T is repeated, except that the polymerization is carried out at 50 ° C. and 800 ° C. The polymerization rate and the IH% both decrease with increasing temperature, with the greatest decrease occurring above 650C (Table XI).

TABLE XI
Polymer test Duration
Temp. C hours IH speed%
II 50 1 474 90.4
T 65 1 367 91> 9
DD 80 0.5 148 74.6
EXAMPLE 18
Propylene is polymerized under a pressure of 690 kPa in an autoclave, with stirring, at 500C for 1 hour.

A second TiCl4 catalyst preparation containing MgCl2 (2.68% Ti) prepared as in Example 13 was used except that the TiCl4-ethyl benzoate complex was preformed, in combination with AlRC12-R2Mg. High stereospecificity is achieved with high catalyst speed and efficiency (Table XII).

TABLE XII
g moles moles
Cat AlEtCl2 Assay (s-Bu2) Mg IH Speed%
KK 0.10 0X5 0.5 1672 88.8
LL 0.10 0.25 0.25 696 95.0
EXAMPLE 19
The procedure of Example 13, Test T, is repeated except that the catalyst of Example 18 is employed and 1 mole of di-n-hexyl magnesium is used instead of 0, 83 mmol of (s-Bu) 2Mg. (N-hexyl) 2Mg in "soltrol nylon is from the so-called Ethyl Corporation, Lot No.BR-516.

The polymerization rate = 551 g / cat / h, but IH% = 76.9, which is unacceptable. It can be seen that the n-alkyl magnesium compounds do not provide the high stereospecificity of the secondary and tertiary alkyl compounds of the invention.

EXAMPLE 20
The procedure of Example 15, Test EE, is repeated except that a new pure sample of (sec-Bu) 2Mg is used with 0.33 moles of ethyl ether instead of ethyl benzoate. and that the reaction time is 1 hour.

The speed = 268 9/9 cat / h and IH% = 92.2.

EXAMPLE 21
A catalyst is prepared by dry milling, for 4 days, with a mixture of 10 MgCl 2, 2 TiCl 4, 2 ethyl benzoate and 1 Mg powder, heating the solids in pure TiCl 4 for two hours at 80 ° C., then washing with n-heptane and drying under vacuum (Ti = 2.16%).

 Propylene is polymerized for 1 hour at 5 ° C., under atmospheric pressure, with 0220 g of this catalyst, under the conditions of Example 13, test T, except that only 0.4% of s-Bu) 2Mg and 0.4mmol of AlEtCl2.

The speed = 240 g / g cat / h and 1H% = 93.9.

EXAMPLE 22
A catalyst is prepared by dry ball milling for one day of a mixture of 5 MgCl 2 and 1 ethyl benzoate, 1 TiCl 4 is added and grinding is continued for a further 3 days, then the solids are treated with pure TiCl 4. for 2 hours at 80 ° C., washed with n-heptane and dried under vacuum (Ti = 3.44%).

 Propylene was polymerized according to the procedure of Example 13, Test T, except that 1 mole of (s-Bu) 2 Mg was used instead of 0.83 mmol. The speed = 298 9/9 cat / h and IH X = 89.

EXAMPLE 23
Following the procedure of Example 18, two catalysts containing different Mg / Ti ratios are prepared. Catalyst A was made with 1 MgCl 2 + 1 TiCl 4 -benzoate and Catalyst B (Ti = 2.10%) with 10 mgCl 2 + 1 TiCl 4 -benzoate complex. Propylene is polymerized according to the procedure of Example 13, Test T (Table XIII).

TABLE XIII
g mmoles mmoles
Test Cat AlEtCl (s-Bu) Mg Speed IH%
MM 0.107A 2 1.66 60 72.0
NN 0.3168 0.25 0.25 512 60.4
O (a) 0.3168 0.25 0.25 124 84.2 (a) 0.25 mmol of triethylamine is added to the alkyl metal cocatalysts.

 These results show that catalysts containing ratios of 1: 1 and 10: 1 MgCl 2: TiCl 4 are not as effective as those containing the 5: 1 ratio of the preceding examples.

EXAMPLE 24
The polymerization is carried out in a 1-liter flask of synthetic resin, baffled, equipped with a reflux condenser and stirrer. Following a usual propylene polymerization process, 475 ml of n-heptane (<1 ppm water) containing the alkyl metal cocatalysts are introduced into the reactor under N 2 and heated to the reaction temperature (650 ° C) while stirring. saturating with propylene under 765 mm pressure. The powder transition metal catalyst is introduced into a catalyst tube so that it can be supplied with 25 ml of n-heptane to the reactor using a syringe. propylene such that the exit rate of the gas is maintained at 200-500 ml / min. After one hour under the indicated temperature and pressure conditions, the reactor slurry is poured into one liter of isopropyl alcohol, stirring is effected. for 2 to 4 hours, filtered, washed with alcohol and dried under vacuum.

 A MgCl 2 supported Ti catalyst was prepared by combining 5 MgCl 2, 1 TiCl 2 and 1 ethyl benzoate by dry ball milling for 4 days, heating the solids slurry in pure TiCl 4 for 2 hours at 80 ° C. N-heptane washing and catalyst drying contained 3.78% Ti, Portions of this catalyst were used in the tests of Table XIV, and various comparative tests were carried out with the cocatalysts of the catalyst. invention (AF tests).

Sec-butyl-Mg, obtained from the organometal, contains 72% non-volatile matter in excess of the s-Bu2Mg measured by titration. IR, NMR, and GC analyzes showed the presence of butoxide groups and 0.07 moles of ethyl ether per s-Bu2Mg. The various s-Bu2MgX compounds are prepared directly by reaction of an equimolar amount of
ROH, RSH, RCOOH, etc. with the s-u2, g.

TABLE XIV
(C, 2 a Cat.550 ml n-C7 650C, 1h)
mmoles of anal moles Speed
Comoosed AI test composed of my base g / g Cat / h IH%
Control 1 AlEt2Cl - - 47 67.1
Witness 1 AlEt3 - - 326 82.5
Control 1 AlEt2C1 O, 83 (s-Bu) 2g - 165 80.5
Control 1 AlEt3 0.83 (s-Bu) 2Mg - 6 -
Witness - Oss83 (s-Bu, Mg - 0 -
Control - 0.83 s-BuMgCl - O -
A 1 AlEt 2 Cl 1 s Bu Bu OOC - 165 95.2
B 1 AlEt 2 Cl 1-s-Bu Mg OC 15 H 31 - 276 91.7
C 1 AlEt 2 Cl 1 s-Bu MgOC 2 H 5 - 261 91t 4
D 1 AlEt 2 Cl 2 s Bu MgSC12H25 - 310 93.2
E 1 AlEt2C1 0.83 s-Bu MgCl 1 Et3N 100 94ss6
F 1 Et2Ai00C 1 s-BuMgCl - 351 90.5
+ 1 and (s-Bu) AlCl
Compared to the control tests, which give either a weak activity or a low IH%, the novel combinations of cocatalysts of the invention have an ac
high stereospecificity (1H> 90%).

EXAMPLE 25
A second catalyst preparation containing 2.68% Ti is made according to the procedure of Example 24, except that a preformed 1: 1 complex of TiCl4OCO4Et is used.

In tests G and H, s-BuMgCl 2 .Et 2 O is obtained by evaporation under vacuum of an ether solution of the reagent of
Grignard. In Run I, n + s BuNgOOCC6H5 was prepared by reacting pure (n + s Bu) 2Mg with benzoic acid. On effec
kills the polymerization of propylene as in Example 24
(Table XV)

TABLE XV
moles of the comp: 2moles of the com- mols Speed Al posed test of my base g / g catch 1H%
G 1 AlEtCl2 1 s-BuMgCl 1 Et2O O -
H 1 AlEt 2 Cl 1 s-BuMgCl 1 Et 2 O 132 93.1
I 1 AlEt3 1 n + s-Bu - 123 89.7 MgOOCC6HS
Test G shows that the monoalkylaluminum compounds are not effective in combination with the mono-organo-Mg compounds in this invention. In contrast, in Example 13, the T-test shows that these mono-alkyl compounds
Al are preferred when the diorgano-Mg compounds are used.

 Tests H and I show that dialkyl- and trialkyl-Al compounds should be used with the monoalkyl-Mg compounds.

EXAMPLE 26
Propylene is polymerized under a pressure of 690 kPa in a 1 liter autoclave with stirring at 500C for one hour, using the supported TiC14 catalyst of Example 25 (Table XV). The Mg compound is prepared as in Example 24, Test A.

TABLE XVI
g mmoles of compomoles
Cat Assay of Mg AlEt2Cl Solvent IH Speed%
J 0.05 0.5 s-BuMgOOC 0.5 n-C7 1292 89.9
K 0.10 0.4 s-BuMgOOC 0.4 n-C7 317 96.9
L 0.10 0.4 s-BuMgOOC 0.4 Xylene 517 96.5
Comparison of the J and K tests shows that the lower alkyl metal / catalyst ratio in K gives a higher% HI. In test L, with xylene as diluent, higher activity is obtained than in test K with heptane.

EXAMPLE 27
The procedure of Example 25 is repeated except that organo-magnesium compounds containing alkoxy and nitrogen groups are used in combination with AlEt 2 Cl and with ethyl ether. The s-BuMgOsBu is prepared by reacting a dilute solution of sBu24g containing 0.33 Et20 with 1 mole of s-BuOH, and used without being isolated (Run M).

The test N mixture is prepared in a similar manner by reacting 1.55 mmol of n + s Bu2Ng with 1.10 s-butanol, adding 0.066 rt20, and then adding this product to a solution of 1 benzoic acid. in 275 ml of n-heptane.

TABLE XVII
moles of the moles
Test set of Mg AlEt2Cl Et2C Speed 1H%
M 1 s-BuMgOs-Bu 1 1/3 107 94.6
N 0X45 n + s BuMgOOC 1 0s065 101 95.9
0.55 n + s BuMgOsBu
0.55 s BuOMgOOC
Compared with Example 25, Test H shows that better results are obtained with smaller amounts of ethyl ether, using alkoxides and carboxylates instead of chloride.

EXAMPLE 28
The procedure of Example 7, Test Z is repeated, except that 0.25mmol Mg (OOCC6H5) 2 is used instead of acetophenone as the third component. The magnesium benzoate is prepared from a dilute solution in heptane of benzoic acid and n + s Bu2Mg. T-Bu2AlEt is added to the milky slurry of Mg (OOCC6H5) 2, the mixture is introduced into the reactor and heated at 650 ° C. for 5 minutes, after which the supported Ti catalyst is added.

 Propylene polymerization rate = 122 g / g cat / h and the polymer has a value of IH = 97.7%.

Claims (8)

 1. Catalytic composition for use in the polymerization of alpha-olefins C2 to C20, characterized in that it comprises a mixture  (a) a titanium metal compound supported on a layered network support, said titanium compound being TiCl3, TiCl4, TiBr3, TiBr4 or a mixture thereof  (b) at least one alkyl metal compound of formula RnMR'3 n wherein R 'is a primary alkyl, alkenyl or C1-C20 alkyl group or hydrogen, M represents Al, Ga or In, R is a C3-C20 secondary or tertiary alkyl group, neopentylalkyl, cycloalkyl or a secondary or tertiary alkenyl group or aralkyl, n is a value of 1-3 r said composition comprising at least one base of Lewis, provided that this Lewis base does not cause excessive cleavage of metal-a-carbon bonds or loss of active sites, the molar ratio of said alkyl metal compound to said transition metal compound being about 0, 5: 1 to 200: 1 and  (c) a salt of a Group IA to IIIA metal, said salt being an alkoxide, a carboxylate or an arylate, the concentration of the metal salt being from about 0.1 to 20 moles of said compound of formula RnMR ' 3-n  Catalytic composition for use in polymerizations, characterized in that it consists of a mixture comprising  (a) a titanium metal compound supported on a support, said titanium metal compound being TiCl3, TiCl4, TiBr3, TiBr4 or a mixture of these compounds;  (b) at least one alkyl metal compound of formula R3 "M wherein M represents Al, Ga or In and R "is a primary alkyl, secondary alkyl, tertiary alkyl, cycloalkyl, alkenyl or aralkyl group C1 to C20, said composition comprising at least one Lewis base, provided that this Lewis base does not cause excessive cleavage of metal-to-carbon bonds or loss of active sites, the molar ratio of said compound R "3M to said transition metal compound having a value of about 0.5: 1 to about 200: 1, and  (c) a salt of a Group IA to IIIA metal, said salt being an alkoxide, a carboxylate or an arylate, the concentration of said metal salt being from about 0.1 to about 20 moles per mole of said compound R 3 " Mr.  3. Composition according to one of claims 1 or 2, characterized in that said support consists of MgCl 2.  4. Composition according to any one of the preceding claims, characterized in that said Lewis base is a carboxylic acid ester.  5. Composition according to any one of claims 1 to 3, characterized in that the base of Lewis is a tertiary amine, an ester, a phosphine, a phosphine oxide or a phosphate or a mixture of these compounds.  6. Composition according to any one of claims 1 to 3, characterized in that said Lewis base is an aryl phosphate, an alkyl phosphite, a hexa-alkylphosphinic triamide, dimethylsulfoxide or a mixture of these compounds.  7. Composition according to any one of claims 1 to 3, characterized in that the base of Lewis is dimethylformamide, a secondary amine, an ether, an epoxide, a ketone or a mixture of these compounds.  8. Composition according to any one of claims 1 to 3, characterized in that said Lewis base is a saturated or unsaturated heterocycle, a cyclic ether or a mixture of these compounds.