CA1095017A - Preparation of violet ticl.sub.3 - Google Patents
Preparation of violet ticl.sub.3Info
- Publication number
- CA1095017A CA1095017A CA000280290A CA280290A CA1095017A CA 1095017 A CA1095017 A CA 1095017A CA 000280290 A CA000280290 A CA 000280290A CA 280290 A CA280290 A CA 280290A CA 1095017 A CA1095017 A CA 1095017A
- Authority
- CA
- Canada
- Prior art keywords
- complexing agent
- violet
- organo
- aluminium
- tic13
- 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
Links
Classifications
-
- 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
A process is disclosed for the preparation of violet TiCl3 suitable for use as a catalyst in olefin polymerization.
The process involves reducing TiCl4 with an organo-aluminium compound and is characterized in that:
(a) the TiCl4 is premixed with a complexing agent in an inert organic solvent, the molar ratio complexing agent:
TiCl4 being within the range from 0.3:1 to 2:1, (b) the organo-aluminium compound is premixed with a complexing agent in an inert organic solvent, the molar ratio complexing agent: organo-aluminium compound being at least 0.25:1;
(c) the reduction is carried out over a period of less than one hour at a temperature within the range 60° to 110°C;
and (d) the final concentration of violet TiCl3 in the reaction mixture is at least 0.2 mol./litre.
A process is disclosed for the preparation of violet TiCl3 suitable for use as a catalyst in olefin polymerization.
The process involves reducing TiCl4 with an organo-aluminium compound and is characterized in that:
(a) the TiCl4 is premixed with a complexing agent in an inert organic solvent, the molar ratio complexing agent:
TiCl4 being within the range from 0.3:1 to 2:1, (b) the organo-aluminium compound is premixed with a complexing agent in an inert organic solvent, the molar ratio complexing agent: organo-aluminium compound being at least 0.25:1;
(c) the reduction is carried out over a period of less than one hour at a temperature within the range 60° to 110°C;
and (d) the final concentration of violet TiCl3 in the reaction mixture is at least 0.2 mol./litre.
Description
1o9sol7 This invention relates to a process for the preparation o~ violet TiC13 which may be used as a component of a catalyst for the polymerization of olefins, in particular for the stereospecific polymerization of alpha-olefins.
It is well known that titanium te-trachloride (TiCl~) can be re-duced with an organo-aluminium derivative to give brown (beta-) TiC13. This form of TiC13 is unsuitable for the stereospecific polymerizationof alpha-olefins to give polymers having a high isotacticity. The brown form is therefore converted to the violet form by means of a heat treatment at a temperature up to 250 C, for example 150 to 200 C. In such preparations it is desirable to maintain the elevated temperature conditions for a sufficient period of time to ensure adequate conversion to the violet form. Violet TiC13 may also be prepared directly by reducing TiC14 with an alkyl aluminiu~
compound at an elevated temperature, for example 150 to 200 C. Examples of both of these methods of preparation are described in United Kingdom patent specification 1,152,1g2, which deals more specifically with the use of cer-tain ethers as the reaction medium.
It is observed, however, that at the elevated temperatures gen-erally used for these preparations the crystallites of violet TiC13 tend to grow in size; this means that the catalytic surface area per gram TiC13 and hence the catalytic ac-tivity will decrease gradually. The rate of crystal-lite growth depends on the time and temperature conditions employed, i.e., the longer the exposure and the higher the temperature, the greater will be the reduction in catalytic activity. A general discussion of the relation-ships between crystallite size, catalytic surface area and catalytic activity of TiC13 is given, for example, in Chapter 2 of "Kinetics of Ziegler-~atta Polymerization" by Keii, Kodunsha9 Tokyo 1972.
A number of substances have been found to catalyze the conversion of brown to violet TiC13 so that the formation of the violet form may be completed more rapidly and/or at lower temperatures. Examples of such 1~
~09S0~7 substances are organic halides (see published Netherlands patent application 76 06139) and TiC14 (see United Kingdom patent specification 1,337,764). A
particular method of preparing an active form of violet TiC13 incorporating a TiC14-catalyzed conversion is described in United Kingdom patent speci-fîcation 1,391,067. In this method browr. TiC13 is prepared by a low temper-ature reduction of TiC14 with an organo-aluminium compound, then washed with a complexing agent and finally converted to the violet form in the presence of TiC14, preferably at a temperature between 20 and 120 C.
The published Netherlands patent application 75 09129 describes an alternative procedure in which the TiC13 is completely solubilized by the complexing agent and the violet TiC13 is precipitated by heating the solubil-ized TiC13 in the presence of an excess of TiC14, preferably at 40 to 120 C.
Both of these processes involve at least two separate basic steps, i.e., a reduction step at ambient temperature or below and a violet TiC13 formation step at higher temperatures up to 120 C. The present invention is concerned with a new simplified process resulting in the direct formation of violet TiC13 at lower temperatures than have been used hitherto.
Accordingly the present invention provides a process for the prep-aration of violet TiC13 by reducing TiC14 with an organo-aluminium compound, characterized in that (a) the TiC14 is premixed with a complexing agent capable of form-ing a complex with titanium atoms, in an inert orgnaic solvent, the molar ratio complexing agent: TiC14 being within the range from 0.3:1 to 2:1;
(b) the organo-aluminium compound is premixed in an inert organic solvent with a complexing agent capable of forming a complex with aluminium atoms, the molar ratio complexing agent: organo-aluminium compound being greater than 0.25:1;
(c) the reduction is carried out over a period of less than one hour at a temperature within the range 60 to 110 C; and (d) the final concentration of violet TiC13 in the reaction ~,, lO~S017 mixture is at least 0.2 mol./litre.
It is surprisingly found that by carrying out the process of the invention as defined above TiC14 may be reduced directly to violet TiC13 at lower temperatures than have hitherto been considered practically feasible.
The process therefore combines the convenience of single step process with the improved catalytic activities which stem from the use of a lower temper-ature for the formation of violet TiC13. A further advantage of the process of the invention is that it enables the preparation of violet TiC13 with very good stereospecific properties in polymerizations of alpha-olefins.
An essential requirement of the process of the invention is that both the TiC14 and the organo-aluminium compounds should be premixed with certain defined amounts of the complexing agents. If one or other of the reactants is not so premixed then brown TiC13 is formed instead, even when the other conditions used are according to the invention. Furthermore, once the brown form has been produced in this way it does not appear possible to convert it to the violet form, for example, in the presence of excess TiC14.
This appears to provide support for the view that the violet TiC13 is pro-duced in one step by the process of the invention and not via the inter-mediate formation of brown TiC13.
The term "complexing agent" as used herein means a compound cap-able of forming a complex with titanium and/or aluminium atoms. The complex-ing agent contains one or more atoms or groups which have one or more free electron pairs which will produce co-ordination with the metal. Atoms hav-ing one or more free electron pairs include the atoms of non-metals of groups 5a and 6a of the Periodic Table, for example, oxygen, sulphur, nitro-gen, phosphorus, antimony and arsenic. Examples of compounds containing such atoms are ethers, thioethers, thiols, phosphines, stibines, arsines, amines, amides, ketones and esters.
Preferably the complexing agent is a compound of one of the follow-ing general formulae:
R'-0-R", R'-S-R", R'-SH, R'R"R "'N, R'R"NH and R'-NH2, ;n which each of the groups R', R" and R "' is an alkyl, aryl, arylalkyl, alkylaryl or cycloalkyl group of up to 15 carbon atoms.
Particularly preferred complexing agents are dialkyl ethers of the general formula R'-0-R' in which each R' group is an alkyl group of 2 to 8 carbon àtoms, for example n-butyl.
The complexing agent with which the TiC14 is premixed may be the same as or different from that with which tne organo-aluminium compound is premixed. The preferred range for the molar ratio complexing agent: TiC14 is from 0.5:1 to 1.5:1, in particular from 0.7:1 to 1.5:1. The preferred range for the molar ratio complexing agent: organo-aluminium compound is from 0.5:1 to 1.5:1, with the use of equimolar portions of the two components being particularly preferred.
The organo-aluminium compound is preferably an aluminium alkyl derivative of empirical formula:
n 3-n in which R is an alkyl group of 2 to 12, preferably 2 to 6 carbon atoms, for example ethyl; X is a hydrogen atom or halogen, preferably chlorine, atom;
and n has a value fxom 0.1 to 3, preferably from 1.5 to 3. Particularly pre-ferred aluminium alkyl derivatives are triethylaluminium and the diethyl-aluminium chloride.
The relative amounts of TiC14 and the organo-aluminium compound used are preferably such that substantially all of the latter is consumed during the reduction. In the case of a trialkylaluminium derivative this means that the molar ratio TiC14: aluminium compound is preferably at least the stoichiometric ratio of 3:1. A relatively small excess of TiC14 may also be used, for example up to 100% molar excess over the stoichiometric ~0~017 amount required. Xowever, a large excess of TiC14, for example a 500%
molar excess, is not only unnecessary and wasteful, but in some cases may unexpectedly give rise to the formation of brown TiC13 instead of the violet form. This latter phenomenon is surprising in view of the known influence of TiC14 on the brown to violet conversion.
The inert organic solvent may comprise an optionally halogenated aliphatic, alicyclic and/or aromatic hydrocarbon. Preferred aliphatic or alicyclic solvents are optionally chlorinated alkanes or cyclo-alkanes of up to 12 carbon atoms. Preferred aromatic solvents are optionally alkylated benzene derivatives, in particular toluene or xylene. In one preferred em-bodiment of the invention the TiC14 is premixed in an aromatic hydrocarbon and the organo-aluminium compound is premixed in an aliphatic hydrocarbon.
In this case the relative amounts of the two solvents appear to influence the size and morphology of the TiC13 particles.
The concentrations of TiC14 and organo-aluminium compound respec-tively in the starting solutions may vary within wide limits provided these are chosen to give a final TiC13 concentration of at least 0.2 mol./litre, preferably from 0.3 to 1.0 mol./litre.
As mentioned above the reduction is carried out over a period of less than one hour. The reduction period is determined by the time taken to add one reactant solution completely to the other. This addition time may be varied widely within the required range, for example from 1 to 45 minutes. It is found in practice that it is convenient to add the solution of the organo-aluminium derivative to the TiC14 solution, the so-called forward addition, although equally satisfactory results may be obtained by the reverse addition.
It is surprising that the preparation of the violet TiC13 by the process of the invention involves the use of relatively short addition times and that longer addition times give the brown form. A slow forward addition, for example, would give a longer period of relatively high TiC14 concentra-lO~S017 tion, and such a situation would be expected to favour the formation of solid violet TiC13.
The temperature of the reduction is between 60 and 110 C. Pre-ferred temperatures are from 70 to 90 C. Although very short addition/reduc-tion times may be used at these temperatures to obtain active violet TiC13, it is found that the stereospecific properties of the violet TiC13 may be i~proved by maintaining the violet TiC13 at the reduction temperature after the reduction has been completed. This after treatment may be carried out over a period of 10 to 60 minutes.
The violet TiC13 is separated from the liquid reaction mixture, for example, by decantation or filtration, andmay then be washed with an aliphatic, alicyclic and/or aromatic hydrocarbon.
The violet TiC13 may be stabilized against deterioration of its catalytic activity by, for example, washing with an aluminium alkyl compound such as diethyl aluminium chloride, by storing at a temperature below 0 C, and/or by a prepolymerization as described below, As mentioned above the invention includes a process for the poly-merization ofolefins in which the violet TiC13 prepared according to the in-vention is used as catalyst together with an aluminium alkyl derivative, for example a trialkylaluminium or a dialkylaluminium halide, as activator. The activator is preferably diethylaluminium chloride. The molar ratio of tbe aluminium compound to TiC13 may be from 0.5:1 to 10:1, preferably from 2:1 to 5:1.
If desired, before the polymerization, the violet TiC13 together with some or all of the activator may be prepolymerized with a small amount of the olefin, e.g., 2-20 g per g TiC13. The prepolymerization is carried out under relatively mild conditions, for example, with propylene the tem-perature is preferably below 60 C and the pressure below 2 bar abs.
The olefins which may be polymerized according to the invention are preferably alpha-olefin of up to 8 carbon atoms, for example, ethylene, ~,.~
.~
~0!~5017 propylene, l-butene or l-pentene. The invention is of particular interest for the homopolymerization of propylene and the copolymerization of ethylene and propylene.
The polymerization may be carried out using any of the conventional procedures. Thus, the polymerization may be carried out in an inert liquid diluent medium such as an aliphatic hydrocarbon, or, in the absence of a diluent, in the vapour phase or in the liquid olefin monomer. Polymerization temperatures may be from 20 to 90C, preferably from 55 to 75C and pres-sures from-l to 50 bar abs. The polymerization may also be carried out in the presence of substances which lower the molecular weight of the polymer, for example gaseous hydrogen, or substances which decrease the soluble (non-stereospecific) polymer content of the polymer, for example amine or phos-phine derivatives.
The invention is illustrated further in the following Examples.
EXAMPLES I-XXXIX
(a) Preparation of violet TiC13 The same basic method was used in all of these Examples. Titanium tetrachloride was dissolved in the organic solvent and to the stirred solu-tion was added an ether-complexing agent. The mixture was warmed to the desired reduction temperature and then a mixture of an aluminium alkyl and an ether-complexing agent in an organic solvent was added over a period which was not more than 1 hour. In all but one Example the reaction mixture was stirred for a further period at the reduction temperature (after treatment), and then cooled to 25 C. The violet TiC13 was then filtered off, washed with isooctane and dried. The precise reaction conditions used in each Example are summarized in the following Table, in which the following abbre-viations are used.
I0 = iso-octane; DBE = di-n-butyl ether;
DDE = di-n-dodecyl ether; DEE = diethyl ether ~0~3~,0~7 (b) Polymeriæation The violet TiC13 thus obtained was tested in homopolymerizations of propylene at 70 C in the presence of o.6% v hydrogen. Aluminium diethyl chloride (9 mmol.) was added to iso-octane (1.5 1) at 70C in a 3 litre reactor, and to this mixture was added the TiC13 (1.7 mmol.). The reactor was then pressurized with propylene to 2.6 bar abs. The reactor was main-tained at 70 C for 4 hours and then the pressure was released. Butanol was added to inactivate the catalyst and the polymer was washed first with 1%
aqueous hydrochloric acid and then three times with water. The polymer sus-pension was then steam-distilled and the polymer was filtered off. The re-sults of the polymerization experiment are also su~marized in the following Table. The activity of the violet TiC13 is expressed as grams polymer per gram TiCl3 per hour per bar of propylene. The value of the xylene solubles is in each case the total amount of polymer which is soluble in xylene and represents the total a~ount of atactic material produced.
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It is well known that titanium te-trachloride (TiCl~) can be re-duced with an organo-aluminium derivative to give brown (beta-) TiC13. This form of TiC13 is unsuitable for the stereospecific polymerizationof alpha-olefins to give polymers having a high isotacticity. The brown form is therefore converted to the violet form by means of a heat treatment at a temperature up to 250 C, for example 150 to 200 C. In such preparations it is desirable to maintain the elevated temperature conditions for a sufficient period of time to ensure adequate conversion to the violet form. Violet TiC13 may also be prepared directly by reducing TiC14 with an alkyl aluminiu~
compound at an elevated temperature, for example 150 to 200 C. Examples of both of these methods of preparation are described in United Kingdom patent specification 1,152,1g2, which deals more specifically with the use of cer-tain ethers as the reaction medium.
It is observed, however, that at the elevated temperatures gen-erally used for these preparations the crystallites of violet TiC13 tend to grow in size; this means that the catalytic surface area per gram TiC13 and hence the catalytic ac-tivity will decrease gradually. The rate of crystal-lite growth depends on the time and temperature conditions employed, i.e., the longer the exposure and the higher the temperature, the greater will be the reduction in catalytic activity. A general discussion of the relation-ships between crystallite size, catalytic surface area and catalytic activity of TiC13 is given, for example, in Chapter 2 of "Kinetics of Ziegler-~atta Polymerization" by Keii, Kodunsha9 Tokyo 1972.
A number of substances have been found to catalyze the conversion of brown to violet TiC13 so that the formation of the violet form may be completed more rapidly and/or at lower temperatures. Examples of such 1~
~09S0~7 substances are organic halides (see published Netherlands patent application 76 06139) and TiC14 (see United Kingdom patent specification 1,337,764). A
particular method of preparing an active form of violet TiC13 incorporating a TiC14-catalyzed conversion is described in United Kingdom patent speci-fîcation 1,391,067. In this method browr. TiC13 is prepared by a low temper-ature reduction of TiC14 with an organo-aluminium compound, then washed with a complexing agent and finally converted to the violet form in the presence of TiC14, preferably at a temperature between 20 and 120 C.
The published Netherlands patent application 75 09129 describes an alternative procedure in which the TiC13 is completely solubilized by the complexing agent and the violet TiC13 is precipitated by heating the solubil-ized TiC13 in the presence of an excess of TiC14, preferably at 40 to 120 C.
Both of these processes involve at least two separate basic steps, i.e., a reduction step at ambient temperature or below and a violet TiC13 formation step at higher temperatures up to 120 C. The present invention is concerned with a new simplified process resulting in the direct formation of violet TiC13 at lower temperatures than have been used hitherto.
Accordingly the present invention provides a process for the prep-aration of violet TiC13 by reducing TiC14 with an organo-aluminium compound, characterized in that (a) the TiC14 is premixed with a complexing agent capable of form-ing a complex with titanium atoms, in an inert orgnaic solvent, the molar ratio complexing agent: TiC14 being within the range from 0.3:1 to 2:1;
(b) the organo-aluminium compound is premixed in an inert organic solvent with a complexing agent capable of forming a complex with aluminium atoms, the molar ratio complexing agent: organo-aluminium compound being greater than 0.25:1;
(c) the reduction is carried out over a period of less than one hour at a temperature within the range 60 to 110 C; and (d) the final concentration of violet TiC13 in the reaction ~,, lO~S017 mixture is at least 0.2 mol./litre.
It is surprisingly found that by carrying out the process of the invention as defined above TiC14 may be reduced directly to violet TiC13 at lower temperatures than have hitherto been considered practically feasible.
The process therefore combines the convenience of single step process with the improved catalytic activities which stem from the use of a lower temper-ature for the formation of violet TiC13. A further advantage of the process of the invention is that it enables the preparation of violet TiC13 with very good stereospecific properties in polymerizations of alpha-olefins.
An essential requirement of the process of the invention is that both the TiC14 and the organo-aluminium compounds should be premixed with certain defined amounts of the complexing agents. If one or other of the reactants is not so premixed then brown TiC13 is formed instead, even when the other conditions used are according to the invention. Furthermore, once the brown form has been produced in this way it does not appear possible to convert it to the violet form, for example, in the presence of excess TiC14.
This appears to provide support for the view that the violet TiC13 is pro-duced in one step by the process of the invention and not via the inter-mediate formation of brown TiC13.
The term "complexing agent" as used herein means a compound cap-able of forming a complex with titanium and/or aluminium atoms. The complex-ing agent contains one or more atoms or groups which have one or more free electron pairs which will produce co-ordination with the metal. Atoms hav-ing one or more free electron pairs include the atoms of non-metals of groups 5a and 6a of the Periodic Table, for example, oxygen, sulphur, nitro-gen, phosphorus, antimony and arsenic. Examples of compounds containing such atoms are ethers, thioethers, thiols, phosphines, stibines, arsines, amines, amides, ketones and esters.
Preferably the complexing agent is a compound of one of the follow-ing general formulae:
R'-0-R", R'-S-R", R'-SH, R'R"R "'N, R'R"NH and R'-NH2, ;n which each of the groups R', R" and R "' is an alkyl, aryl, arylalkyl, alkylaryl or cycloalkyl group of up to 15 carbon atoms.
Particularly preferred complexing agents are dialkyl ethers of the general formula R'-0-R' in which each R' group is an alkyl group of 2 to 8 carbon àtoms, for example n-butyl.
The complexing agent with which the TiC14 is premixed may be the same as or different from that with which tne organo-aluminium compound is premixed. The preferred range for the molar ratio complexing agent: TiC14 is from 0.5:1 to 1.5:1, in particular from 0.7:1 to 1.5:1. The preferred range for the molar ratio complexing agent: organo-aluminium compound is from 0.5:1 to 1.5:1, with the use of equimolar portions of the two components being particularly preferred.
The organo-aluminium compound is preferably an aluminium alkyl derivative of empirical formula:
n 3-n in which R is an alkyl group of 2 to 12, preferably 2 to 6 carbon atoms, for example ethyl; X is a hydrogen atom or halogen, preferably chlorine, atom;
and n has a value fxom 0.1 to 3, preferably from 1.5 to 3. Particularly pre-ferred aluminium alkyl derivatives are triethylaluminium and the diethyl-aluminium chloride.
The relative amounts of TiC14 and the organo-aluminium compound used are preferably such that substantially all of the latter is consumed during the reduction. In the case of a trialkylaluminium derivative this means that the molar ratio TiC14: aluminium compound is preferably at least the stoichiometric ratio of 3:1. A relatively small excess of TiC14 may also be used, for example up to 100% molar excess over the stoichiometric ~0~017 amount required. Xowever, a large excess of TiC14, for example a 500%
molar excess, is not only unnecessary and wasteful, but in some cases may unexpectedly give rise to the formation of brown TiC13 instead of the violet form. This latter phenomenon is surprising in view of the known influence of TiC14 on the brown to violet conversion.
The inert organic solvent may comprise an optionally halogenated aliphatic, alicyclic and/or aromatic hydrocarbon. Preferred aliphatic or alicyclic solvents are optionally chlorinated alkanes or cyclo-alkanes of up to 12 carbon atoms. Preferred aromatic solvents are optionally alkylated benzene derivatives, in particular toluene or xylene. In one preferred em-bodiment of the invention the TiC14 is premixed in an aromatic hydrocarbon and the organo-aluminium compound is premixed in an aliphatic hydrocarbon.
In this case the relative amounts of the two solvents appear to influence the size and morphology of the TiC13 particles.
The concentrations of TiC14 and organo-aluminium compound respec-tively in the starting solutions may vary within wide limits provided these are chosen to give a final TiC13 concentration of at least 0.2 mol./litre, preferably from 0.3 to 1.0 mol./litre.
As mentioned above the reduction is carried out over a period of less than one hour. The reduction period is determined by the time taken to add one reactant solution completely to the other. This addition time may be varied widely within the required range, for example from 1 to 45 minutes. It is found in practice that it is convenient to add the solution of the organo-aluminium derivative to the TiC14 solution, the so-called forward addition, although equally satisfactory results may be obtained by the reverse addition.
It is surprising that the preparation of the violet TiC13 by the process of the invention involves the use of relatively short addition times and that longer addition times give the brown form. A slow forward addition, for example, would give a longer period of relatively high TiC14 concentra-lO~S017 tion, and such a situation would be expected to favour the formation of solid violet TiC13.
The temperature of the reduction is between 60 and 110 C. Pre-ferred temperatures are from 70 to 90 C. Although very short addition/reduc-tion times may be used at these temperatures to obtain active violet TiC13, it is found that the stereospecific properties of the violet TiC13 may be i~proved by maintaining the violet TiC13 at the reduction temperature after the reduction has been completed. This after treatment may be carried out over a period of 10 to 60 minutes.
The violet TiC13 is separated from the liquid reaction mixture, for example, by decantation or filtration, andmay then be washed with an aliphatic, alicyclic and/or aromatic hydrocarbon.
The violet TiC13 may be stabilized against deterioration of its catalytic activity by, for example, washing with an aluminium alkyl compound such as diethyl aluminium chloride, by storing at a temperature below 0 C, and/or by a prepolymerization as described below, As mentioned above the invention includes a process for the poly-merization ofolefins in which the violet TiC13 prepared according to the in-vention is used as catalyst together with an aluminium alkyl derivative, for example a trialkylaluminium or a dialkylaluminium halide, as activator. The activator is preferably diethylaluminium chloride. The molar ratio of tbe aluminium compound to TiC13 may be from 0.5:1 to 10:1, preferably from 2:1 to 5:1.
If desired, before the polymerization, the violet TiC13 together with some or all of the activator may be prepolymerized with a small amount of the olefin, e.g., 2-20 g per g TiC13. The prepolymerization is carried out under relatively mild conditions, for example, with propylene the tem-perature is preferably below 60 C and the pressure below 2 bar abs.
The olefins which may be polymerized according to the invention are preferably alpha-olefin of up to 8 carbon atoms, for example, ethylene, ~,.~
.~
~0!~5017 propylene, l-butene or l-pentene. The invention is of particular interest for the homopolymerization of propylene and the copolymerization of ethylene and propylene.
The polymerization may be carried out using any of the conventional procedures. Thus, the polymerization may be carried out in an inert liquid diluent medium such as an aliphatic hydrocarbon, or, in the absence of a diluent, in the vapour phase or in the liquid olefin monomer. Polymerization temperatures may be from 20 to 90C, preferably from 55 to 75C and pres-sures from-l to 50 bar abs. The polymerization may also be carried out in the presence of substances which lower the molecular weight of the polymer, for example gaseous hydrogen, or substances which decrease the soluble (non-stereospecific) polymer content of the polymer, for example amine or phos-phine derivatives.
The invention is illustrated further in the following Examples.
EXAMPLES I-XXXIX
(a) Preparation of violet TiC13 The same basic method was used in all of these Examples. Titanium tetrachloride was dissolved in the organic solvent and to the stirred solu-tion was added an ether-complexing agent. The mixture was warmed to the desired reduction temperature and then a mixture of an aluminium alkyl and an ether-complexing agent in an organic solvent was added over a period which was not more than 1 hour. In all but one Example the reaction mixture was stirred for a further period at the reduction temperature (after treatment), and then cooled to 25 C. The violet TiC13 was then filtered off, washed with isooctane and dried. The precise reaction conditions used in each Example are summarized in the following Table, in which the following abbre-viations are used.
I0 = iso-octane; DBE = di-n-butyl ether;
DDE = di-n-dodecyl ether; DEE = diethyl ether ~0~3~,0~7 (b) Polymeriæation The violet TiC13 thus obtained was tested in homopolymerizations of propylene at 70 C in the presence of o.6% v hydrogen. Aluminium diethyl chloride (9 mmol.) was added to iso-octane (1.5 1) at 70C in a 3 litre reactor, and to this mixture was added the TiC13 (1.7 mmol.). The reactor was then pressurized with propylene to 2.6 bar abs. The reactor was main-tained at 70 C for 4 hours and then the pressure was released. Butanol was added to inactivate the catalyst and the polymer was washed first with 1%
aqueous hydrochloric acid and then three times with water. The polymer sus-pension was then steam-distilled and the polymer was filtered off. The re-sults of the polymerization experiment are also su~marized in the following Table. The activity of the violet TiC13 is expressed as grams polymer per gram TiCl3 per hour per bar of propylene. The value of the xylene solubles is in each case the total amount of polymer which is soluble in xylene and represents the total a~ount of atactic material produced.
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10~;017 EXAMPLES XL and XLI
The violet TiC13 obtained under the conditions of Example XXVII was used as catalyst in a similar propylene polymerization experiment to tbat de-scribed for the previous Examples, the precise conditions being as follows:
temperature 80C
pressure 2~7 bar time 3.0 hours Al : Ti (molar)= 6:1 The results of this experiment are given as Example XL below.
Tbe polymeriztion was then repeated in tbe presence of triethyl-amine, the molar ratio triethylamine : TiC13 being 0.1 : 1. The results (Example XLI) are also given below.
Example ActivityXylene sol.
g/g TiC13/hr/bar %
XL 119 4.16 XLI 111 2.27 It is clear that the addition of the amine lowers the percentage of atactic material, i.e., improves the stereospecificity of the catalyst, with only a sm~ll accompanying reduction in the activity.
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r~ v ~ x c, ~ ~
10~;017 EXAMPLES XL and XLI
The violet TiC13 obtained under the conditions of Example XXVII was used as catalyst in a similar propylene polymerization experiment to tbat de-scribed for the previous Examples, the precise conditions being as follows:
temperature 80C
pressure 2~7 bar time 3.0 hours Al : Ti (molar)= 6:1 The results of this experiment are given as Example XL below.
Tbe polymeriztion was then repeated in tbe presence of triethyl-amine, the molar ratio triethylamine : TiC13 being 0.1 : 1. The results (Example XLI) are also given below.
Example ActivityXylene sol.
g/g TiC13/hr/bar %
XL 119 4.16 XLI 111 2.27 It is clear that the addition of the amine lowers the percentage of atactic material, i.e., improves the stereospecificity of the catalyst, with only a sm~ll accompanying reduction in the activity.
, ,~ .
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of violet TiCl3 by re-ducing TiCl4 with an organo-aluminium compound, characterized in that (a) the TiCl4 is premixed with a complexing agent capable of forming a complex with titanium atoms, in an inert organic solvent, the molar ratio complexing agent : TiCl4 being within the range from 0.3:1 to 2:1;
(b) the organo-aluminium compound is premixed with a complexing agent capable of forming a complex with aluminium atoms, in an inert organic solvent, the molar ratio complexing agent : organo-aluminium compound being at least 0.25:1;
(c) the reduction is carried out over a period of less than one hour at a temperature within the range 60° to 110°C; and (d) the final concentration of violet TiCl3 in the reaction mixture is at least 0.2 mol./litre.
(b) the organo-aluminium compound is premixed with a complexing agent capable of forming a complex with aluminium atoms, in an inert organic solvent, the molar ratio complexing agent : organo-aluminium compound being at least 0.25:1;
(c) the reduction is carried out over a period of less than one hour at a temperature within the range 60° to 110°C; and (d) the final concentration of violet TiCl3 in the reaction mixture is at least 0.2 mol./litre.
2. A process as claimed in claim 1, characterized in that the complexing agent is a dialkyl ether of general formula R'-O-R', in which each R' is an alkyl group of 2 to 8 carbon atoms.
3. A process as claimed in claim 1, characterized in that the molar ratio complexing agent : TiCl4 is from 0.5:1 to 1.5:1.
4. A process as claimed in claim 1, 2 or 3, characterized in that the molar ratio complexing agent : organo-aluminium compound is from 0.5:1 to 1.5:1.
5. A process as claimed in claim 1, 2 or 3, characterized in that the organo-aluminium compound is an alkyl aluminium de-rivative of empirical formula:
AIRnX3-n in which R is an alkyl group of 2 to 12 carbon atoms; X is a hydrogen or halogen atom; and n has a value from 0.1 to 3.
AIRnX3-n in which R is an alkyl group of 2 to 12 carbon atoms; X is a hydrogen or halogen atom; and n has a value from 0.1 to 3.
6. A process as claimed in claim 1, 2 or 3, characterized in that the organic solvent comprises an optionally chlorinated alkane or cycloalkane of up to 12 carbon atoms, or an optionally alkylated benzene derivative.
7. A process as claimed in claim 1, 2 or 3, characterized in that the reduction temperature is from 70° to 90°C.
8. A process as claimed in claim 1, 2 or 3, characterized in that the final TiCl3 concentration is from 0.3 to 1.0 mol./litre.
9. A process as claimed in claim 1, 2 or 3, characterized in that the violet TiCl3 is given an after-treatment at the re-duction temperature over a period of 10 to 60 minutes.
10. Violet TiCl3 when prepared by a process as claimed in claim 1.
11. A process for the polymerization of olefins, which comprises polymerizing an olefin in the presence of a violet TiCl3 catalyst as claimed in claim 10 and an aluminium alkyl derivative as activator.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB28897/76 | 1976-07-12 | ||
| GB28897/76A GB1579725A (en) | 1976-07-12 | 1976-07-12 | Preparation of violet tici3 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1095017A true CA1095017A (en) | 1981-02-03 |
Family
ID=10282951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000280290A Expired CA1095017A (en) | 1976-07-12 | 1977-06-10 | Preparation of violet ticl.sub.3 |
Country Status (26)
| Country | Link |
|---|---|
| US (1) | US4195069A (en) |
| JP (1) | JPS539296A (en) |
| AR (1) | AR216476A1 (en) |
| AT (1) | AT355298B (en) |
| AU (1) | AU508618B2 (en) |
| BE (1) | BE856418A (en) |
| BR (1) | BR7704536A (en) |
| CA (1) | CA1095017A (en) |
| CS (1) | CS201505B2 (en) |
| DE (1) | DE2731241A1 (en) |
| DK (1) | DK314677A (en) |
| ES (2) | ES460610A1 (en) |
| FR (1) | FR2358360A1 (en) |
| GB (1) | GB1579725A (en) |
| HU (1) | HU177378B (en) |
| IL (1) | IL52500A (en) |
| IT (1) | IT1126749B (en) |
| LU (1) | LU77733A1 (en) |
| NL (1) | NL7707676A (en) |
| NO (1) | NO141847C (en) |
| PL (1) | PL109141B1 (en) |
| PT (1) | PT66790B (en) |
| SE (1) | SE7708055L (en) |
| SU (1) | SU664555A3 (en) |
| TR (1) | TR19723A (en) |
| ZA (1) | ZA774143B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1121329A (en) * | 1978-07-25 | 1982-04-06 | Andras G.T.G. Kortbeek | Olefin polymerization catalysts |
| JPS55116626A (en) * | 1979-03-01 | 1980-09-08 | Mitsubishi Chem Ind Ltd | Manufacture of solid titanium trichloride |
| US4366297A (en) * | 1979-10-23 | 1982-12-28 | Japan Ep Rubber Co., Ltd. | Process for producing olefinic copolymer rubber with improved titanium compound containing catalyst system |
| DE3368644D1 (en) * | 1982-07-13 | 1987-02-05 | Mitsubishi Chem Ind | Process for preparing solid titanium trichloride useful for the polymerization of an alpha-olefin |
| JPS61113823A (en) * | 1984-11-06 | 1986-05-31 | Toyobo Co Ltd | Latent crimping polyamide composite fiber |
| US5315053A (en) * | 1985-06-17 | 1994-05-24 | Chevron Research Company | Normally liquid alpha-olefin oligomers useful as base stocks and viscosity index improvers, and lubricating oils containing same |
| US5177276A (en) * | 1985-06-17 | 1993-01-05 | Chevron Research Company | Alpha-olefin oligomers useful as base stocks and viscosity index improvers, and lubricating oils containing same |
| JP2717306B2 (en) * | 1989-05-02 | 1998-02-18 | チッソ株式会社 | Composite spinneret device |
| BE1003968A3 (en) * | 1990-11-08 | 1992-07-28 | Solvay | SOLID CATALYST USED FOR stereospecific polymerization ALPHA-OLEFINS, METHOD FOR PREPARING AND METHOD FOR POLYMERIZATION OF ALPHA-OLEFINS IN HIS PRESENCE |
| US6696380B2 (en) | 2000-01-12 | 2004-02-24 | Darryl Stephen Williams | Procatalysts, catalyst systems, and use in olefin polymerization |
| BRPI0107604B1 (en) | 2000-01-12 | 2015-03-31 | Westlake Longview Corp | Solid procatalyst, catalyst system, and process for polymerizing at least one or more olefins |
| US6465383B2 (en) | 2000-01-12 | 2002-10-15 | Eastman Chemical Company | Procatalysts, catalyst systems, and use in olefin polymerization |
| RU2711226C1 (en) * | 2019-04-05 | 2020-01-15 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Method of producing titanium trichloride |
| RU2707362C1 (en) * | 2019-04-05 | 2019-11-26 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Российский химико-технологический университет имени Д.И. Менделеева" (РХТУ им. Д.И. Менделеева) | Method of producing titanium trichloride |
| US20240018171A1 (en) | 2022-07-15 | 2024-01-18 | Hindustan Petroleum Corporation Limited | Novel titanium complexes as catalysts for alpha olefin polymerization |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1152192A (en) | 1965-07-23 | 1969-05-14 | Sir Soc Italiana Resine Spa | Method of Preparing Catalytically Active TiCI3 |
| US3466140A (en) * | 1967-03-31 | 1969-09-09 | Goodyear Tire & Rubber | Process for producing reduced transition metal halides |
| US3558271A (en) * | 1969-06-25 | 1971-01-26 | Benedetto Calcagno | Method of preparing catalytically active ticl3 |
| IE35231B1 (en) * | 1970-03-26 | 1975-12-24 | Solvay | Process for the preparation of a ziegler-natta type catalyst |
| CH543546A (en) | 1971-03-23 | 1973-10-31 | Solvay | Alpha-olefin polymerization catalytic system |
| US4060593A (en) * | 1974-07-31 | 1977-11-29 | Mitsubishi Chemical Industries | Preparation of titanium trichloride |
| DE2533511C2 (en) | 1974-07-31 | 1984-11-29 | Mitsubishi Chemical Industries Ltd., Tokio/Tokyo | Process for the preparation of solid purple colored finely granulated titanium trichloride and its use for the polymerization of α-olefins |
| NL7606139A (en) | 1975-06-11 | 1976-12-14 | Shell Int Research | PROCESS FOR PREPARING VIOLET TIC13. |
| US4085064A (en) * | 1975-12-12 | 1978-04-18 | Exxon Research & Engineering Co. | Purple TiCl3 by direct low temperature reduction |
-
1976
- 1976-07-12 GB GB28897/76A patent/GB1579725A/en not_active Expired
-
1977
- 1977-06-10 CA CA000280290A patent/CA1095017A/en not_active Expired
- 1977-06-17 US US05/807,696 patent/US4195069A/en not_active Expired - Lifetime
- 1977-07-04 BE BE1008252A patent/BE856418A/en unknown
- 1977-07-11 IL IL52500A patent/IL52500A/en unknown
- 1977-07-11 AR AR268392A patent/AR216476A1/en active
- 1977-07-11 HU HU77SE1862A patent/HU177378B/en unknown
- 1977-07-11 SE SE7708055A patent/SE7708055L/en unknown
- 1977-07-11 LU LU77733A patent/LU77733A1/xx unknown
- 1977-07-11 TR TR19723A patent/TR19723A/en unknown
- 1977-07-11 ES ES460610A patent/ES460610A1/en not_active Expired
- 1977-07-11 DK DK314677A patent/DK314677A/en unknown
- 1977-07-11 SU SU772500805A patent/SU664555A3/en active
- 1977-07-11 AT AT496177A patent/AT355298B/en not_active IP Right Cessation
- 1977-07-11 CS CS774623A patent/CS201505B2/en unknown
- 1977-07-11 PT PT66790A patent/PT66790B/en unknown
- 1977-07-11 DE DE19772731241 patent/DE2731241A1/en not_active Withdrawn
- 1977-07-11 FR FR7721279A patent/FR2358360A1/en active Pending
- 1977-07-11 ZA ZA00774143A patent/ZA774143B/en unknown
- 1977-07-11 JP JP8209277A patent/JPS539296A/en active Pending
- 1977-07-11 AU AU26904/77A patent/AU508618B2/en not_active Expired
- 1977-07-11 NO NO772440A patent/NO141847C/en unknown
- 1977-07-11 NL NL7707676A patent/NL7707676A/en not_active Application Discontinuation
- 1977-07-11 ES ES460624A patent/ES460624A1/en not_active Expired
- 1977-07-11 IT IT50215/77A patent/IT1126749B/en active
- 1977-07-11 BR BR7704536A patent/BR7704536A/en unknown
- 1977-07-11 PL PL1977199533A patent/PL109141B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| SE7708055L (en) | 1978-01-13 |
| BE856418A (en) | 1978-01-04 |
| FR2358360A1 (en) | 1978-02-10 |
| IT1126749B (en) | 1986-05-21 |
| PL199533A1 (en) | 1978-04-10 |
| NO141847B (en) | 1980-02-11 |
| PT66790A (en) | 1977-08-01 |
| NO772440L (en) | 1978-01-13 |
| ES460610A1 (en) | 1978-05-01 |
| AU2690477A (en) | 1979-01-18 |
| AU508618B2 (en) | 1980-03-27 |
| GB1579725A (en) | 1980-11-26 |
| ZA774143B (en) | 1978-05-30 |
| AR216476A1 (en) | 1979-12-28 |
| IL52500A0 (en) | 1977-10-31 |
| ES460624A1 (en) | 1978-05-01 |
| PT66790B (en) | 1978-12-19 |
| ATA496177A (en) | 1979-07-15 |
| JPS539296A (en) | 1978-01-27 |
| HU177378B (en) | 1981-09-28 |
| AT355298B (en) | 1980-02-25 |
| TR19723A (en) | 1979-10-16 |
| NO141847C (en) | 1980-05-21 |
| CS201505B2 (en) | 1980-11-28 |
| PL109141B1 (en) | 1980-05-31 |
| DK314677A (en) | 1978-01-13 |
| DE2731241A1 (en) | 1978-01-19 |
| BR7704536A (en) | 1978-06-06 |
| IL52500A (en) | 1980-01-31 |
| SU664555A3 (en) | 1979-05-25 |
| US4195069A (en) | 1980-03-25 |
| LU77733A1 (en) | 1978-02-02 |
| NL7707676A (en) | 1978-01-16 |
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