CA1192537A - Catalysts for the polymerization and copolymerization of propylene and polymerization processes using these catalysts - Google Patents
Catalysts for the polymerization and copolymerization of propylene and polymerization processes using these catalystsInfo
- Publication number
- CA1192537A CA1192537A CA000431030A CA431030A CA1192537A CA 1192537 A CA1192537 A CA 1192537A CA 000431030 A CA000431030 A CA 000431030A CA 431030 A CA431030 A CA 431030A CA 1192537 A CA1192537 A CA 1192537A
- Authority
- CA
- Canada
- Prior art keywords
- support
- catalyst
- particles
- propylene
- mean diameter
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/904—Monomer polymerized in presence of transition metal containing catalyst at least part of which is supported on a polymer, e.g. prepolymerized catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/909—Polymerization characterized by particle size of product
Abstract
ABSTRACT
The present invention relates to catalysts which can be used for the polymerisation and copolymerisation of propylene with other alpha-olefins, characterised in that they comprise a support containing essentially magnesium chloride and possibly a chlorinated aluminium derivative, and occurring in the form of spheroidal particles having a mean diameter by mass comprised between 10 and 100 microns and a particle size distribution such that the ratio of the mean diameter by mass to the mean diameter by number is less than or equal to 3, which support has been treated by an electron donor compound chosen from among the aromatic ethers and aromatic acid esters and which when impregnated with titanium tetrachloride comprises 0.5 to 3% of atoms of titanium per atom of magnesium, and process for utilizing the said catalyst.
The present invention relates to catalysts which can be used for the polymerisation and copolymerisation of propylene with other alpha-olefins, characterised in that they comprise a support containing essentially magnesium chloride and possibly a chlorinated aluminium derivative, and occurring in the form of spheroidal particles having a mean diameter by mass comprised between 10 and 100 microns and a particle size distribution such that the ratio of the mean diameter by mass to the mean diameter by number is less than or equal to 3, which support has been treated by an electron donor compound chosen from among the aromatic ethers and aromatic acid esters and which when impregnated with titanium tetrachloride comprises 0.5 to 3% of atoms of titanium per atom of magnesium, and process for utilizing the said catalyst.
Description
70325-17 JEP~kar The present in~ention relates to new catalysts for -the polymerisation and co-polymerisation of propylene and processes using these cata]ysts.
It is known that polymerisation and co-polymerisation catalysts for alpha-olefinsr known as "Ziegler-Na-tta" catalysts, are obtained by the comblnatlon of transition me-tal compounds belonging to Groups IV, V or VI o:E the Periodic Table with at least one organome-tallic compound of Groups I to III of the Table.
It is also known that the properties of -these catalysts may be strongly influenced when the said transition metal com-pound is used with a solid mineral compound which may be co-preclpitated with the said transition metal compound or which is used as support for -the said transi-tion metal compound.
~s mlneral compound whlch can be used to advantage as the support, the oxides of magnesium and titanium, aluminium silicate, magnesium carbonate and magnesium chloride may be mentioned.
In this technique of a ca-talyst on a support, the properties o:E the support on the one hand and the process of preparation of the catalyst (deposition of the -transition metal compound) on the other hand have a very great importance for -the properties oE the said catalyst.
According to one aspect of the present invention there is provided a catalyst which can be used for the polymerisation and copolymerisation of propylene with other alpha-oleEins, comprising a support containing essentially magnesium chloride, _ ~ _ occurrin~ in -the fo:rm of spheroiclal particles, having a mean diameter by mass of between lO and lO0 microns and a par-ticle size distribution such that the ra-tio of the mean diameter by mass, Dm, -~o the mean diameter by number, Dn, is less -than or equal to 3, which suppor-t has been -treated with an electron donor compound chosen from among an aromatic e-ther and an ester of an aromatic acid and which when impregna-ted with ti-tanium tetrachloride comprises 0.5 to 3% of atoms of titanium per atom of magnesium.
According to another aspect of the present invention there is provided a process for preparing the above catalyst comprising -treating -the support at a temperature of between about 20C and 50C with the elec-tron donor compound employed in a quantity of between 0.06 and 0.2 mole of electron donor compound per mole of magnesium chloride support and impregna-ting the support with titanium tetrachloride at between about 30C and 100C.
According to a Eurther aspect of the present invention there is provided a process for polymerising propylene or copoly-merising propylene with another alpha-olefi.n, comprising effecting to polymerisation or copolymerisation in the presence of -the a.bove catalyst.
The present i.nvention relates to a suppor-ted catalyst, the support consisti.ng essentiall.y of magnesium chloride with speci.fic properties and the catalyst being a compound of a me-tal belonging to Groups IV~ V and VI of the Periodic Table of Elements ~ 3~
and in particular a -titani~lm compound known for i-ts catalytic properties which can be usecl for -the pvl.ymerisation and co-polymerisation of alpha-~olefins.
The support for the ca-talyst consists of particles based essen-tially on magnesium chloride, these par-ticles preferably having the following characteristics:
- -the particles have a spheroidal form defined by the fac-t that if D and d are respectively -the large and small diameters of the particles, D:d is less -than or equal to 1.3;
- the particles have a mean diameter by mass comprised between 10 and 100 microns approximately;
- the particle size distribution of -th.e particles is such that the ra-tio Dm:Dn of the mean diame-ter by mass, Dm, to the mean diame-ter by number, Dn, is less than or equal to 3, for example, comprised between 1.1 and 2.5;
more preferabl.y, the particle size distribution of the par-ticles is very narrow and such -that the ratio Dm:Dn is comprised between 1.1 and 1.5; furthermore -there is a 2Q practically comple-te absence of partic]es wi-th a diame-ter greater -than 2 x Dm or less -than n . 2 x Dm; the par-ticle size distri.bu-tion, fur-thermore, is such tha-t more than 90% by weigh-t of the particles of each ba-tch are comprised in the range Dm ~ 10~;
- the surface of the particles may be sli.ghtly dented such as that of a raspberry, bu-t is preferably very smoo-th;
t~4i~
- -the speci:Eic sur:Eace area o:E -the particles is comprised between about 20 and 60 m /g (BET);
- the densi-ty of -the particles is comprised between about 1.2 and 2.1;
- the partic].es consist essentially o.E ma~nesium chloride and possibly of a chlorina-ted compound of aluminium;
the atomic ratio Cl/(Mg ~ 3/2.Al) is more or less equal to 2; fur-thermore the particles contain no products comprising Mg-C bonds, but contain a low proporti.on of an electron donor compound.
The supports defined in -this way may be prepared in particular by reacting an organomagnesium compound wi-th a chlorinated organic compound, i.n -the presence of an electron donor compound. As organomagnesium compound one may select either a product of the formula R1MgR2, or an addition complex of the formula RlMgR2.xAl(R3)3, in t~hich formulae Rl, R2 and R3 are identical or different alkyl radicals having 2 to 1~ carbon atoms and x is comprised between 0.001 and 10, preferably betwen 0.01 and 2. ~s chlorinated organic compound one selects an alkyl chloride of the formula R4Cl in which R4 is a secondary or preferably a tertiary alkyl radical with 3 to 12 carbon atoms. The electron donor compound ernployed is an organic compound which comprises at -least one atom of oxygen, sulphur, nitrogen and/or phosphorus. It may be chosetl from among a wlde variety of products such as amines, amides, phosphines, sulphoxides, sulphorles or ethers.
Amongst electron donor compounds one may choose in particular an aliphatic ether-o~ide of the formula Rs-0--R6 in which Rs and R6 are identical or diEferent alkyl radicals with 1 to 12 carbon atoms.
Moreover, the various reactants involved in the preparation of the supports as defined above must be employed under the following conditions:
- the molar ratio R4Cl/~1MgR2 is comprised between 1.5 and 2.5 and preferably between 1.95 and 2.2;
- the molar ratio R4Cl/21MgR2.XAl(R3)3 is comprised between 1.5 (1 + 3/2.x ) and 2.5 (1 + 3/2.x ) and preferably between 1.95 (1+ 3/2.x) and 2.2 (11 3/2. x);
- the molar ratio between the electron donor compound and the organomagnesium compound (RlMgR2 or R1MgR2.xAl(R3)3) is comprised between 0.01 and 2~ and preferab1y between 0.01 and 1;
- the reaction between the organomagnesium compound and the chlorinated organic compound takes place with agitation in a liquid hydrocarbon at a temperature comprised between 5C and 80C, and preferably between 35C and 80C.
The preparation of the catalysts from the supports thus defined comprises two stages, namely:
30 a) a treatment of the said support by means of an electron donor compound which is an aromatic acid ester or an aromatic ether, b) an impregnation of the support thus treated by means of titanium t~trachloride.
'7 In the first stage the quantity of electron donor to be used is compri~ed between 0.06 and 0.2 mole of electron donor per mol~ of MgCl2 of the support, and the temperature to be used is comprised between a~out 20 and 50C.
S In the second stage the support is impregnated wlth titanium tetrachloride which may be used in the pure state or in solution in a liquid hydrocarbon; the quanrities of TiCl4 must be sufficient so that 0.5 to 3~ of titanium atoms per atom of magnesium present in the support can be fixed on the support; the temperature of impregnation is comprised between about 80 and 100C The catalyst obtained is washed several times with a liquid hydrocarbon.
The catalysts prepared accor~lng to the present invention consist of particles whose physical properties such as spheroidal form, surface appearance, mean diameter by mass and particle size di~tribu~ion a~ defined by the ratio D~:Dn, are more or less identical to those of the magnesium chloride support particles fro~ which they originated.
According to one known technique these catalysts are employed in the polymerisation of alpha-olefins in association with a co-catalyst. This association of a catalyst and co-catalyst constitutes what is referred to as the "catalyst complex".
The co-catalyst is generally an organoaluminium compound of the formula Al(R7)3, in which ~7 is an alkyl radical w~th 2 to 12 carbon atoms; it is preferably employed in the complexed state ~ith an electron donor compound, for example of the aromatic acid ester type.
The molar ratio between the electron donor compound and the organoaluminium compound is comprised between O.l and O.S and is preferably equal to about 0.3. An inadequate quantity or this electron donor compound diminishes the stereospecificity of the '-catalyst complex" and too great a quantity of this electron donor compound weakens the act~vity of the "catalyst complex".
The relative molar quantities of the organoaluminium compound in relation tO the titanium compound used may vary within a very wide field; for example the atomic ratio ~1:Ti may vary between 1 and 200.
The "catalyst complex" may be prepared by simply mi~ing the catalyst and co-catalyst. It may be employed in the polymerisation ln suspension in a liquid hydrocarbon or in the liquid monomer; however, it is possible, especially if it is desired to use the said "catalyst complex" in a dry polymerisa~ion or copolymerisation to carry out a coating of the said "catalyst complex" by prepolymerisation. This prepolymerisation must be performed in suspension in a liquid hydrocarbon medium until the product obtained comprises 0.1 to 10 g of polymer or copolymer per gra~ne~milliatom of titanium; it may then be continued either in suspension in a liquid hydrocarbon medium, or in the dry state, until the prepolymer obtained contains about 10 to 500 g of polymer or copolymer per gramme-~illiatom of titanium.
It is important to note that when using the support and the catalysts as described above, the development of each particle during the pre-polymerisation and subsequently during the polymerisation or copolymerisation is perfectly regular, so that one obtains polymer or copolymer powders whose dimensions are more or less proportional to those of the support particles and the catalyst particles.
Method for determining the mean diameters by mass (Dm) and by number (Dn) of the particles of magnesium chloride support or catalyst Accordlng to the invention, the mean diamecers by mass (Dm) and by number (Dn) of the particles of magnesi~lm chloride support or catalyst are ~easured by microscopic observation by means of the OPTOMAX image analyser (Micro-Measurements Ltd., Great ~ritain). The measuring principle consists in obtaining from the experimental study by optical microscopy of a population of particles a table of frequencies giving the nu~ber (ni) of particles belonging to each category (i) of diameters, each category (i) being characterised by an inter~ediate diameter (di) comprised bet-~een the limits for the said category. According to the French ~lorm ~IF X 11-630 of June 1981~ 3 and Dn are given by the follo~ing formula:
. mean diameter by mass: Dm = ~ ni(di)3di ni(di)~
. mean diameter by number: Dn 3 ~ ni.di ni ~
The ratio ~m:Dn characterises the particle size distribusion; it is sometimes referred to as the "width of particle size distribution".
rK
The measurement by the OPTOMlkY lmage ana1yser is performed by means of an inverted microscope which ~kes it possible to examine the suspensions of magnesium chloride or catalyst partlcles at an enlargement comprised between 16x and 200x. A television camera picks S up the images given by the inverted microscope and transmits them to a computer which analyses the images line by line and dot by dot on each line, in order to determine the dimensions or diameters of the particles and then to classify them.
The follorhring non-restrictive examples illustrate the invention.
Example 1 1.1 Preparation of the support Into a glass reactor r~ith a capacity of 1 litre and provided with an agigation system rotating at 750 revolutions per minute there are introduced at ambient temperature and under nitrogen 550 ~l of a solution of di-butyl magnesi~m in n-hexane containing 500 gramme-milliato~s of magnesium and 51 ml of di-isoamyl ether (250 millimoles).
The reactor is then heated to 50C and over 2 hours 115 ml of t-butyl chloride (1050 millimoles) are poured in drop by drop. At the end of this addieion the suspension is maintained at 50C for 2 hours and the precipitate obtained i'3 ~ashed at the same temperature with n-hexane.
The support thus formed contains per gramme-atom of magnesium:
It is known that polymerisation and co-polymerisation catalysts for alpha-olefinsr known as "Ziegler-Na-tta" catalysts, are obtained by the comblnatlon of transition me-tal compounds belonging to Groups IV, V or VI o:E the Periodic Table with at least one organome-tallic compound of Groups I to III of the Table.
It is also known that the properties of -these catalysts may be strongly influenced when the said transition metal com-pound is used with a solid mineral compound which may be co-preclpitated with the said transition metal compound or which is used as support for -the said transi-tion metal compound.
~s mlneral compound whlch can be used to advantage as the support, the oxides of magnesium and titanium, aluminium silicate, magnesium carbonate and magnesium chloride may be mentioned.
In this technique of a ca-talyst on a support, the properties o:E the support on the one hand and the process of preparation of the catalyst (deposition of the -transition metal compound) on the other hand have a very great importance for -the properties oE the said catalyst.
According to one aspect of the present invention there is provided a catalyst which can be used for the polymerisation and copolymerisation of propylene with other alpha-oleEins, comprising a support containing essentially magnesium chloride, _ ~ _ occurrin~ in -the fo:rm of spheroiclal particles, having a mean diameter by mass of between lO and lO0 microns and a par-ticle size distribution such that the ra-tio of the mean diameter by mass, Dm, -~o the mean diameter by number, Dn, is less -than or equal to 3, which suppor-t has been -treated with an electron donor compound chosen from among an aromatic e-ther and an ester of an aromatic acid and which when impregna-ted with ti-tanium tetrachloride comprises 0.5 to 3% of atoms of titanium per atom of magnesium.
According to another aspect of the present invention there is provided a process for preparing the above catalyst comprising -treating -the support at a temperature of between about 20C and 50C with the elec-tron donor compound employed in a quantity of between 0.06 and 0.2 mole of electron donor compound per mole of magnesium chloride support and impregna-ting the support with titanium tetrachloride at between about 30C and 100C.
According to a Eurther aspect of the present invention there is provided a process for polymerising propylene or copoly-merising propylene with another alpha-olefi.n, comprising effecting to polymerisation or copolymerisation in the presence of -the a.bove catalyst.
The present i.nvention relates to a suppor-ted catalyst, the support consisti.ng essentiall.y of magnesium chloride with speci.fic properties and the catalyst being a compound of a me-tal belonging to Groups IV~ V and VI of the Periodic Table of Elements ~ 3~
and in particular a -titani~lm compound known for i-ts catalytic properties which can be usecl for -the pvl.ymerisation and co-polymerisation of alpha-~olefins.
The support for the ca-talyst consists of particles based essen-tially on magnesium chloride, these par-ticles preferably having the following characteristics:
- -the particles have a spheroidal form defined by the fac-t that if D and d are respectively -the large and small diameters of the particles, D:d is less -than or equal to 1.3;
- the particles have a mean diameter by mass comprised between 10 and 100 microns approximately;
- the particle size distribution of -th.e particles is such that the ra-tio Dm:Dn of the mean diame-ter by mass, Dm, to the mean diame-ter by number, Dn, is less than or equal to 3, for example, comprised between 1.1 and 2.5;
more preferabl.y, the particle size distribution of the par-ticles is very narrow and such -that the ratio Dm:Dn is comprised between 1.1 and 1.5; furthermore -there is a 2Q practically comple-te absence of partic]es wi-th a diame-ter greater -than 2 x Dm or less -than n . 2 x Dm; the par-ticle size distri.bu-tion, fur-thermore, is such tha-t more than 90% by weigh-t of the particles of each ba-tch are comprised in the range Dm ~ 10~;
- the surface of the particles may be sli.ghtly dented such as that of a raspberry, bu-t is preferably very smoo-th;
t~4i~
- -the speci:Eic sur:Eace area o:E -the particles is comprised between about 20 and 60 m /g (BET);
- the densi-ty of -the particles is comprised between about 1.2 and 2.1;
- the partic].es consist essentially o.E ma~nesium chloride and possibly of a chlorina-ted compound of aluminium;
the atomic ratio Cl/(Mg ~ 3/2.Al) is more or less equal to 2; fur-thermore the particles contain no products comprising Mg-C bonds, but contain a low proporti.on of an electron donor compound.
The supports defined in -this way may be prepared in particular by reacting an organomagnesium compound wi-th a chlorinated organic compound, i.n -the presence of an electron donor compound. As organomagnesium compound one may select either a product of the formula R1MgR2, or an addition complex of the formula RlMgR2.xAl(R3)3, in t~hich formulae Rl, R2 and R3 are identical or different alkyl radicals having 2 to 1~ carbon atoms and x is comprised between 0.001 and 10, preferably betwen 0.01 and 2. ~s chlorinated organic compound one selects an alkyl chloride of the formula R4Cl in which R4 is a secondary or preferably a tertiary alkyl radical with 3 to 12 carbon atoms. The electron donor compound ernployed is an organic compound which comprises at -least one atom of oxygen, sulphur, nitrogen and/or phosphorus. It may be chosetl from among a wlde variety of products such as amines, amides, phosphines, sulphoxides, sulphorles or ethers.
Amongst electron donor compounds one may choose in particular an aliphatic ether-o~ide of the formula Rs-0--R6 in which Rs and R6 are identical or diEferent alkyl radicals with 1 to 12 carbon atoms.
Moreover, the various reactants involved in the preparation of the supports as defined above must be employed under the following conditions:
- the molar ratio R4Cl/~1MgR2 is comprised between 1.5 and 2.5 and preferably between 1.95 and 2.2;
- the molar ratio R4Cl/21MgR2.XAl(R3)3 is comprised between 1.5 (1 + 3/2.x ) and 2.5 (1 + 3/2.x ) and preferably between 1.95 (1+ 3/2.x) and 2.2 (11 3/2. x);
- the molar ratio between the electron donor compound and the organomagnesium compound (RlMgR2 or R1MgR2.xAl(R3)3) is comprised between 0.01 and 2~ and preferab1y between 0.01 and 1;
- the reaction between the organomagnesium compound and the chlorinated organic compound takes place with agitation in a liquid hydrocarbon at a temperature comprised between 5C and 80C, and preferably between 35C and 80C.
The preparation of the catalysts from the supports thus defined comprises two stages, namely:
30 a) a treatment of the said support by means of an electron donor compound which is an aromatic acid ester or an aromatic ether, b) an impregnation of the support thus treated by means of titanium t~trachloride.
'7 In the first stage the quantity of electron donor to be used is compri~ed between 0.06 and 0.2 mole of electron donor per mol~ of MgCl2 of the support, and the temperature to be used is comprised between a~out 20 and 50C.
S In the second stage the support is impregnated wlth titanium tetrachloride which may be used in the pure state or in solution in a liquid hydrocarbon; the quanrities of TiCl4 must be sufficient so that 0.5 to 3~ of titanium atoms per atom of magnesium present in the support can be fixed on the support; the temperature of impregnation is comprised between about 80 and 100C The catalyst obtained is washed several times with a liquid hydrocarbon.
The catalysts prepared accor~lng to the present invention consist of particles whose physical properties such as spheroidal form, surface appearance, mean diameter by mass and particle size di~tribu~ion a~ defined by the ratio D~:Dn, are more or less identical to those of the magnesium chloride support particles fro~ which they originated.
According to one known technique these catalysts are employed in the polymerisation of alpha-olefins in association with a co-catalyst. This association of a catalyst and co-catalyst constitutes what is referred to as the "catalyst complex".
The co-catalyst is generally an organoaluminium compound of the formula Al(R7)3, in which ~7 is an alkyl radical w~th 2 to 12 carbon atoms; it is preferably employed in the complexed state ~ith an electron donor compound, for example of the aromatic acid ester type.
The molar ratio between the electron donor compound and the organoaluminium compound is comprised between O.l and O.S and is preferably equal to about 0.3. An inadequate quantity or this electron donor compound diminishes the stereospecificity of the '-catalyst complex" and too great a quantity of this electron donor compound weakens the act~vity of the "catalyst complex".
The relative molar quantities of the organoaluminium compound in relation tO the titanium compound used may vary within a very wide field; for example the atomic ratio ~1:Ti may vary between 1 and 200.
The "catalyst complex" may be prepared by simply mi~ing the catalyst and co-catalyst. It may be employed in the polymerisation ln suspension in a liquid hydrocarbon or in the liquid monomer; however, it is possible, especially if it is desired to use the said "catalyst complex" in a dry polymerisa~ion or copolymerisation to carry out a coating of the said "catalyst complex" by prepolymerisation. This prepolymerisation must be performed in suspension in a liquid hydrocarbon medium until the product obtained comprises 0.1 to 10 g of polymer or copolymer per gra~ne~milliatom of titanium; it may then be continued either in suspension in a liquid hydrocarbon medium, or in the dry state, until the prepolymer obtained contains about 10 to 500 g of polymer or copolymer per gramme-~illiatom of titanium.
It is important to note that when using the support and the catalysts as described above, the development of each particle during the pre-polymerisation and subsequently during the polymerisation or copolymerisation is perfectly regular, so that one obtains polymer or copolymer powders whose dimensions are more or less proportional to those of the support particles and the catalyst particles.
Method for determining the mean diameters by mass (Dm) and by number (Dn) of the particles of magnesium chloride support or catalyst Accordlng to the invention, the mean diamecers by mass (Dm) and by number (Dn) of the particles of magnesi~lm chloride support or catalyst are ~easured by microscopic observation by means of the OPTOMAX image analyser (Micro-Measurements Ltd., Great ~ritain). The measuring principle consists in obtaining from the experimental study by optical microscopy of a population of particles a table of frequencies giving the nu~ber (ni) of particles belonging to each category (i) of diameters, each category (i) being characterised by an inter~ediate diameter (di) comprised bet-~een the limits for the said category. According to the French ~lorm ~IF X 11-630 of June 1981~ 3 and Dn are given by the follo~ing formula:
. mean diameter by mass: Dm = ~ ni(di)3di ni(di)~
. mean diameter by number: Dn 3 ~ ni.di ni ~
The ratio ~m:Dn characterises the particle size distribusion; it is sometimes referred to as the "width of particle size distribution".
rK
The measurement by the OPTOMlkY lmage ana1yser is performed by means of an inverted microscope which ~kes it possible to examine the suspensions of magnesium chloride or catalyst partlcles at an enlargement comprised between 16x and 200x. A television camera picks S up the images given by the inverted microscope and transmits them to a computer which analyses the images line by line and dot by dot on each line, in order to determine the dimensions or diameters of the particles and then to classify them.
The follorhring non-restrictive examples illustrate the invention.
Example 1 1.1 Preparation of the support Into a glass reactor r~ith a capacity of 1 litre and provided with an agigation system rotating at 750 revolutions per minute there are introduced at ambient temperature and under nitrogen 550 ~l of a solution of di-butyl magnesi~m in n-hexane containing 500 gramme-milliato~s of magnesium and 51 ml of di-isoamyl ether (250 millimoles).
The reactor is then heated to 50C and over 2 hours 115 ml of t-butyl chloride (1050 millimoles) are poured in drop by drop. At the end of this addieion the suspension is maintained at 50C for 2 hours and the precipitate obtained i'3 ~ashed at the same temperature with n-hexane.
The support thus formed contains per gramme-atom of magnesium:
2.0 gramme-atomes of chlorine and 0.011 mole of di-isoamyl ether~
On examination under the microscope the support is seen to be in the form of spheroidal particles (the ratio D:d between the large and small axes of the particles is on average eq~lal to 1,2) havlng a particle size distribution such that Dm:Dn = 1.2, r~ith Dm = 38 microns; one finds that more than 90% by weight of the particles have a mean diameter comprised between 34 and 42 microns;
the particles have a smooth surface, a specific surface area equal to 42 m2/g (~ET) and a density equal to 1.3.
1.2 Preparation of the catalyst Into a glass reactor with a capacity of 1 litre and provided with an agitator system rotating at 250 revolutions per minute there are introduced Imder nltrogen 500 ml of a suspension in n-hexane of the support prepared Ln Exa~ple l.l~ this suspension containlng ~).2 gramme-atom of magnesium. After decanting, the supernatant hydrocarbon phase is removed. The reactor is then heated to 50C and 2 ml of ethyl~enzoate (14 millimoles) are introduced. The suspension is maintained under agitation for 2 hours, then 2 moles of pure titanium tetrachloride are introduced (220 ml). The temperature is raised to 80C and this temperature is maintained for 2 hours. The solid obta:ined is then washed ~ith n-hexane at 50C to produce the catalyst ready for use, in the form of a suspension in n-hexane.
Analysis of the catalyst shows that it contains per gramme-atom of magnesium 2.05 gramme-atoms of chlorine, 0.014 gramme-atom of titanium, 0.016 mole of ethylbenzoate and that it contains no trace of di-isoamyl ether.
The ca,alyst thus defined is a yellow-greyish powder, consisting of spheroidal particlesS having a particle size distribution such that Dm:Dn = 1.2, with Dm = 38 microns; it is found, furthermore, that more than 90% by weight of the particles have a mean diameter comprised between ~m i 10%; the particles have a surface as smooth as the initial support.
~xample ~
2.1 Preparation of the support The preparation of the support is identical to that of e~ample 1.1, except that 56 ml ~275 millimoles) of di-isoamyl ether are used instead of 51 ml (250 millimoles), and 120 ml (llOO millimoles) of t-butyl chloride instead of 115 ml (1050 millimo:Les), that is to say 0.55 moles of di-isoamyl ether and 2.2 moles of t-butyl chloride are used per mole of di--butyl magnesium.
The support thus obtained contains per gramme-atom of magnesium:
2.0 gramme-atoms of chlorine and 0.015 mole of di-isoamyl ether.
On exa~ination under the microscope the support is s2en to be in the form of spheroidal particles with a particle size distribution such ehat Dm:Dn = 1.3, with Dm = 40 microns; it is found that mo~e than 90% by weight of the particles ha~e a uean diameter by mass comprised between 36 and 44 micrOQs; the particles have a smooth surface.
On examination under the microscope the support is seen to be in the form of spheroidal particles (the ratio D:d between the large and small axes of the particles is on average eq~lal to 1,2) havlng a particle size distribution such that Dm:Dn = 1.2, r~ith Dm = 38 microns; one finds that more than 90% by weight of the particles have a mean diameter comprised between 34 and 42 microns;
the particles have a smooth surface, a specific surface area equal to 42 m2/g (~ET) and a density equal to 1.3.
1.2 Preparation of the catalyst Into a glass reactor with a capacity of 1 litre and provided with an agitator system rotating at 250 revolutions per minute there are introduced Imder nltrogen 500 ml of a suspension in n-hexane of the support prepared Ln Exa~ple l.l~ this suspension containlng ~).2 gramme-atom of magnesium. After decanting, the supernatant hydrocarbon phase is removed. The reactor is then heated to 50C and 2 ml of ethyl~enzoate (14 millimoles) are introduced. The suspension is maintained under agitation for 2 hours, then 2 moles of pure titanium tetrachloride are introduced (220 ml). The temperature is raised to 80C and this temperature is maintained for 2 hours. The solid obta:ined is then washed ~ith n-hexane at 50C to produce the catalyst ready for use, in the form of a suspension in n-hexane.
Analysis of the catalyst shows that it contains per gramme-atom of magnesium 2.05 gramme-atoms of chlorine, 0.014 gramme-atom of titanium, 0.016 mole of ethylbenzoate and that it contains no trace of di-isoamyl ether.
The ca,alyst thus defined is a yellow-greyish powder, consisting of spheroidal particlesS having a particle size distribution such that Dm:Dn = 1.2, with Dm = 38 microns; it is found, furthermore, that more than 90% by weight of the particles have a mean diameter comprised between ~m i 10%; the particles have a surface as smooth as the initial support.
~xample ~
2.1 Preparation of the support The preparation of the support is identical to that of e~ample 1.1, except that 56 ml ~275 millimoles) of di-isoamyl ether are used instead of 51 ml (250 millimoles), and 120 ml (llOO millimoles) of t-butyl chloride instead of 115 ml (1050 millimo:Les), that is to say 0.55 moles of di-isoamyl ether and 2.2 moles of t-butyl chloride are used per mole of di--butyl magnesium.
The support thus obtained contains per gramme-atom of magnesium:
2.0 gramme-atoms of chlorine and 0.015 mole of di-isoamyl ether.
On exa~ination under the microscope the support is s2en to be in the form of spheroidal particles with a particle size distribution such ehat Dm:Dn = 1.3, with Dm = 40 microns; it is found that mo~e than 90% by weight of the particles ha~e a uean diameter by mass comprised between 36 and 44 micrOQs; the particles have a smooth surface.
3~
2.2 Preparation of the catalyst ... . . . .
Into a glass reactor with a capacity of 1 lltre and provided with an agitation system rotating at 250 revolutions per minute there are introduced under nltrogen 500 ml of a suspension in n-hexane of support prepared as in Example 2.1, containing 200 gramme-milliatoms of magnesium. ~fter decanting, the supernatant hydrocarboQ phase is removed. The reactor is then heated to 50~C and 3 ml (21 millimoles) of ethylbenæoate are introduced. The suspension is maintained under agitation for 1 hour, then the temperature is raised to 80C to eliminate the n-hexane by means of a current of nitrogen. Then 3 moles of pure TiCl4 (330 ml) are introduced into the reactor and the mixture is maintained under agitation for 2 hours at 80C. The catalyst obtained is washed wi~h n-hexane at 50C to glve the catalyst ready for use in the form of a suspension iII n~hexane.
Analysis of the catalyst thus obtained shows that ic contains per gramme-atom of magnesium 2.05 gramme-atoms of chlorine, 0.030 mole of ethylbenzoate, 0.020 mole of titanium, and that it contains no trace of di-isoamyl ether.
The catalyst thus defined is a powder consisting of spheroidal particles, having a particle size distribution such that Dm:Dn = 1.3 with Dm = 40 micrcns; it is found that more than 90% by weight of the particles have a mean diameter by mass comprised between 36 and 44 microns; the particles have a suriace as smooth as that of the initial support.
Examp1e 3 Thère are used in this Example as support a powder based on magnesium chloride, consisting of spheroidal particles having a particle size distribution sl1ch that Dm:Dn = 1.1, with Dm - 20 microns; more than 90% by weight of the particles of this powder have a mean diameter comprised between 18 and 22 ~icrons.
Preparation of the catalyst The preparation of the catalyst is identical to that of Example 1. A solid catalyst is obtainec1 ready for use in the form of a suspension in n-hexane. The chemical analysis of this catalyst shows that it contains, per gramme-atom of magnesium, 2.00 gramme-atoms of chlorine, 0.014 gral~me-atom of titanium, 0.016 mole of ethylben~oate and no trace of di-isoamyl ether.
This catalyst consists of spheroidal particles, having a particle si~e distribution such that Dm.Dn = 1.1 with Dm = 20 microns; it is found furthermore that more than 90% by weight of the particles have a mean diameter comprised between 18 and 22 microns; the particles have a surface appearance identical to that of the initial support.
Example 4 There is utilised as support a powder based on magnesium chloride consisting of spheroidal particles having a narrow particle size distribution, such that ~m:Dn = 1.5, with Dm = 30 microns; it has a density equal to 1.9 and a specific surface area equal to 46 m2/g (BET); the surface of the particles is very smooth.
Preparatlon of _he catalyst The preparation of the catalyst is identlcal to that of Example 1. There is obtained a solid catalyst ready for use, in the form of a suspension in n-hexane. The chemical analysis of the catalyst shows that it contains, per gra~me-atome of magnesium, 2~00 gramme-atoms of chlorine, 0.015 gramme-atom of titanium, 0.018 mole of ethylbenzoate and no trace of di-isoamyl ether.
This catalyst consists of spheroidal particles having a particle size distributiou such that Dm:Dn = 1.5 with Dm = 30 microns; the particles have a surface as smooth as that of the initial support.
~xample 5 . .
There is used as support a powder based on magnesium chloride consisting of spheroidal particles having a narrow particle si~e distribution, such that Dm:Dn = 2.5, with Dm = 35 microns; this powder contains less than 0.05% by weight of particles of diameter less than 7 microns; lt has a density equal to 1.~ and a specific surface area equal to 44 m2/g (~ET); the surface of the particles is smooth.
Preparation of the catalyst The preparation of the catalyst is identical to that of Example 1. There is obtained a solid catalyst ready for use, in the form of a suspension in n-hexane. The chemical analysis of the catalyst shows that it contains, per gra~me-atome of magnesium~ 2.05 gramme-atoms of chlorine, 0.018 gramme-a~om of titanium~ 0.018 mole of ethylbenzoate and no trace of di-isoamyl ether.
The catalyst consists of spheroidal particles having a particle slze distribution s~ch that ~m:Dn = 2.5 with Dm = 35 microns; the particles have a surface as smooth as that of the initial support.
Example 6 -Suspension polymerisation Into a 3tainless steel reactor with a capacity of 5 litres and provided with an agitation system rotating at 750 revolutions per minute there are introduced under a blanket of nitrogen 2 litres of n-hexane heated to 50C, 10 millimoles of tri-isobutyl aluminium (Ti3~), 3.7 millimoles of methyl paratoluàte and a quantity of catalyst prepared as in Example 1, corresponding to 0.08 gramme-milliatom of titanium. The reactor is heated to 60C and a volume of 40 ml of hydrogen measured under normal conditions is introduced, the~ propylene at a rate of 300 g/hr. for 2 hours. At the end of the one hour of introduction of propylene, a supplementary volu~e of 4n ml of hydrogen measured under normal conditions is added to the reactor. At the end of the introduction of propylene, the polypropylene suspension is maintained under agitation and at 60C for a further half-hour. Then the non-polymerised propylene is de-gassed and the n-hexane is evaporated from the polypropylene suspension.
480 g of a dry polypropylene powder are obtained having the following characteristics: 5 - titanium content: 8 ppm (corresponding to a polymerisation yield of 6 kg/gramme-milliatom of titanium of the catalyst) - apparent voluminal mass (A~): 0041 g/cm3 - content of polymer insoluble in boiling n-heptane: 92% by weight - melt index under 5 kg. at 190C: l.8 gllO minutes - mean diameter by mass (Dm): 250 microns - powder consisting of spheroidal particles with a narrow particle size distribution and a smooth surface.
Exa~ple 7 -Suspension polymerisation One proceeds exactly as in Example 6 except that the catalyst prepared as in Example 2 is employed instead of the catalyst prepared as in E~ample 1. 410 g of a dry polypropylene powder are obtained having the characteristics described in Table 1.
Suspension polymerisation One proceeds e~actly as in Example 6, except that the catalyst prepared as in Example 3 is employed. 395 g of a dry polypropylene powder are obtained having the characteristics described in Table 1.
Example 9 Suspension polymerisation -One proceeds exactly as in Example 6, except that 5 millimoles of methyl paratoluate are used instead of 3.7 millimoles, and a quantity of the catalyst prepared as in Example 1 corresponding to 0.135 gramme-milliatom of titanium, instead of 0.08 gramme-milliatom of titanium. 430 g of a dry polypropylene powder are ob~ained having the characteristics described in Table I.
~ .
Suspension polymerisation One proceeds exactly as in Example 6, except that one uses 2.5 millimoles of methyl paratoluate instead of 3.7 millimoles, and a qua~tity of catalyst prepared as in Example 1 corresponding to 0.135 gramme-milliatom of titanium instead of 0.08. 60n g of dry polypropylene powder are obtained having the characteristics described in Table I.
Example 11 Suspension ~olymerisation -One proceeds exactly as in E~ample 6, except that 10 millimoles of triethylaluminium (TE~) are used instead oE 10 millimoles of TiBA, and 3.3 millimoles of methyl paratoluate instead of 3.7 millimoles.
500 g of a dry polypropylene powder are obtained having the characteristics described in Table I.
Example 12 Suspension polymerisation One proceeds exactly as in Example 6, except that 10 millimoles of tri--n~octylaluminium (TnO~) are used instead of 10 millimoles of ~5jV~t~
TiBA, 4 millimoles of me~hyl paratoluate instead of 3.7 millimoles, and a quantity of the catalyst prepared as in E~ample 1 corresponding to 0.1 gramme-milliatom of titanium, lnstead of 0.08 gramme-milliatom. 450 g of a dry polypropylene powder are obtained having the characteristics described in Table I.
Example 13 Sequenced e~p~ly~erisatiorl in suspension One proceeds e~actly as in Example 6, except that propy]ene is introduced into the reactor at a rate of 300 g/hr. for an 'nour-and-a-half, instead of for two hours, and that at the end of this time thereactor is de-gassed to O.1 MPa and a mixture of ethy1ene and propylene containing 80% by weight or ethylene are introduced at a rate of 200 g/hr. for half-an-hour. At the end of this period the copolymer suspension is maintained under agitation and at 60~C for a further half-hour. 450 g of a dry sequenced copolymer powder of ethylene and propylene are obtained possessing a content of units derived from ethylene equal to 9% by weight (measured by infrared spectrography) and having the other characteristics described in Table I.
E~ample 14 Statistical copolymerisatiol~ in suspension One proceeds exactly as in Example 6, except that a mi~xture of propylene and ethylene containing 5% by weight of ethylene is introduced into the reactor instead of propylene alone. 400 g of a dry powder of a statistical copolymer of propylene and ethylene are obtained possessing a content of ~mits derived from ethylene equal to 5% by welght (measured by infrared spectrography) and having the other characteristics described in Table I.
Example 15 Suspension polymerisation One proceeds exactly as in Example 6, e-xcept that the catalyst prepared as in Example 4 is used. 460 g of a dry polypropylene powder are obtained having the characteristics described in Table I.
5~
Exa~ple 16 Suspension polymeri~ation One proceeds e~actly as in ~xample 69 except that the catalyst prepared as in Example 5 i5 used. 500 g of a dry polypropylene powder are obtained having the characteristics described in Table 1.
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'7 Example 17 _ lymerisation in liquid propylene Into a 5-litre stainless steel reactor equipped with an agitator rotating at 750 revolutions per minuce there are introduced under a blanket of nitrogen 10 millimoles of TiBA, 3.7 millimoles of methyl paratoluate and a quantity of the catalyst prepared as ia Example 1 corresponding to 0.1 gramme mllliatom of titanium.
The reactor is purged with gaseous propylene and 1.5 kg of liquid propylene is introduced, and a volume of 200 ml of hydrogen measured under normal conditions. The reactor is then heated to 60C and the polymerisation reaction lasts an nour and a half. At the end of this period, the excess propylene is de-gass~d and after steam d:Lstillation 6'00 g of a dry whlte polypropylene powder are recovered having the followlng characteristics:
- titanium content; 8 ppm - apparent voluminal mass (AVM): 0.4~ g/cm3 - content of polymer insoluble in boiling n~heptane: 92% by weight - melt index under 5 kg. at 190C: 2.3 g/10 minuces - mean diameter by mass (Dm): 250 microns - powder consisting of spheroidal p~rticles, with a narro~
particle size distribution and a smooth surface.
Example 18 Polymerisation in liquid propylene -One proceeds exaccly as in Example 17, e~cept thac a quantity of the catalyst prepared as in Example 2, corresponding to 0.08 gra~me-milliatom of titanium, is introduced into the reactor instead of the quantity of the catalyst prepared in Example 1 corresponding to 0.1 gram~e-milliatom of titanium, and a volume of 400 ml of hydrogen measured under normal conditions, instead of 200 ml, and that the reaction of polymerising the propylene lasts for two hours Lnstead of one-and-a-half hours~ 650 g of a dry polypropylene powder are obtained having the following characteristics:
- titani~l content: 6 ppm - apparent voluminal mass (AVM): 0.48 g/cm3 - content of polym~r insoluble in boiling n-heptane: 92~ by weight - melt index under 5 kg. at 190C: 3.g g/10 mlnutes S - mean diameter by mass (Dm): 280 ~icrons - powder conslsting of spheroidal particles with a narrow particle size distribution and a smooth surface.
Example 19 Polymerisation in liquid propylene One proceeds exactly as in Exa~ple 17, except that a qu~ntity of the catalyst prepared as in E~a~ple 3, corresponding to 0.05 grarnme-milliatom of titanium, is introduced into the reactor instead of the quantity of the catalyst prepared in Example 1 corresponding to 0.1 gramme-milliatom of titanium, and that Che polymerisation reaction of the propylene lasts for two hours instead of one-and-a-half hours.
450 g of a dry polypropylene powder are obtained having the following characteristics:
- titaniu~ content: 5 ppm - apparent voluminal mass (AVM): 0.50 g/cm3 ~0 - content of polymer insoluble in boiling n-heptane: 91~ by weight - melt index under 5 kg. at 190C: 1.6 g/10 minutes - mean diameter by mass (Dm): 150 microns - powder consisting of spheroidal particles with a narrow particle size distribution and a smooth surface.
Example 20 20.1 Preparation of a suspen ion prepolymer Into a stainless sLeel reactor ~ith a capaci~y of 5 litres and provided with an agitation system rotating at 750 revolutions per minute there are introduced under a blanket of nitrogen ~5 milllmoles of TiBA, 9.25 millimoles of meehyl paratoluate and a quantity of the catalyst prepared as in Example 1 corresponding to 2.5 gramme-milliatoms of titanium. The volume of the suspension is made up to 2 litres with n-hexane. At ambient temperature (20C) there is introduced into the reactor a volume of 30 ml of hydrogen measured under normal conditions, then propylene at a rate of 200 g/hr. for two and-a-ha:Lf hours. Ac the end of this period the prepolymer suspension is maintained under agitatlon for a further half-hour. The reactor i9 de-gassed and, still under a blanket of nitrogen, the prepolymer powder is washed 3 times with n-hexane. The prepolymer suspension in n-hexane is then decanted into a rotary evaporator under a vacuum.
510 g of a dry prepolymer powder are obtained, consisting of spheroidal particles with a narro~7 particle size distribution, a mean diameter by mass equal to 110 microns, a smooth surface and having a tLtaniu~ content equal to 240 ppm This powder l.s preserved unler nitroge~.
20.2 Dry-phase poly~erisation (agitated bed) 25 g of the dry prepolymer powder prepared as in Example 20.1 and containing 0.125 gra~me-milliatom of titanium are impregnated ~ith a mixture of 5 millimoles of a solutioQ of TEA in n-hexane and 1.65 ~illimoles of methy~ paratoluate. This impregnated powder is introduced into a stainless steel ~eactor wi~h a capacity of 2 litres and provided with an agitation system for dry powder. lO0 g of a perfrectly dry and anhydrous polypropylene powder are addedO This mixture of powders is maintained under agitation and scavenged with nitrogen at 80C until a powder which will flow well is obtained. The reactor is then heated to 60C. Propylene is introduced until a pressure of 1 MPa is obtained and this is maintained constant throughout the entire duration of the polymerisation by topping up with propylene. rn addition, a volume of 50 ml of hydrogen measured under normal conditions is added each hour to the reactor. After 5 hours of reaction, the reactor is de-gassed. 625 g of a dry powder are recovered of which 500 g produced by the present propylene polymerisation reaction have the following characteristics:
- titanium content: 12 ppm 30 - apparent voluminal mass (AVM): 0.48 g/cm3 - content of polymer insoluble in boiling n-heptane: 91% by weight - melt index under 5 kg. at 190C: l.l g/lO minutes - mean diameter by mass (Dm): 250 microns - powder consisting of spheroidal particles with a narrow particle size dist~ibution and a smooth surface.
Example 21 Dry-phase polymerisation (fluidised bed) Into a Eluldised-bed reactor with a diameter of 15 cm, operating ~ith a rising gas propelled at a speed of 15 cmlsec and under partial pres.sures of 0.1 ~Pa of hydrogen and 1.5 MPa of propylene, there are introduced in sequence lo g/hr of the dry prepolymer powder prepared as in Example 20.1 A solution in n-he~ane of a mixture of TnOA and methyl paratoluate in a molar ratio of 1:0.25 is introduced continuously at a rate corresponding to 9 milllmoles of TnOA per hour~ The temperature of the fluidised bed is ma~ntained at 60C
throughout the whole of the polymerisation. By sequenced withdrawals one obtains approximately 500 g/hr of a dry polypropylene powder which can be used directly and having the following characteristics;
- titanium content: 8 ppm - apparent voluminal mass (AVM): 0.45 g/cm3 - content of polymer insoluble in boiling n-heptane: 90~ by weight - melt index under 5 kg~ at 190C: 2.3 g/10 minutes - mean diameter by mass (Dm): 250 microns 0 - powder consisting of spheroidal particles with a narrow particle size distribution and a smooth surface.
Example 22 Dry-phase copolymerisation ( fluidised bed) .. .. . _ _ _ .
One proceeds exactly as in Example 21, except that the fluidised-2S bed reactor operates under partial pressures of 1.4 MPa of propylene and 0.1 MPa of ethylene instead of 1.5 MPa of propylene alone.
By a s~ries ofwi~rawals one obtains approximately 400 g/hr of a dry propylene and ethylene copolymer powder which can be used directly and having the following characteristics:
- titanium content: 10 ppm - apparent voluminal mass (A~): 0.44 g/cm3 - content of polymer insoluble in bolling n-heptane: 85~ by weight content of units derived from ethylene: 5% by weight (measured by infrared spectrography) - melt index under 5 kg~ at 190C: 3 g/10 minutes :L9 - mean diameter by mass (Dm): 240 microns - powder consisting o~ spheroidal particles with a narrow particle size distribution and a smooth surface.
2.2 Preparation of the catalyst ... . . . .
Into a glass reactor with a capacity of 1 lltre and provided with an agitation system rotating at 250 revolutions per minute there are introduced under nltrogen 500 ml of a suspension in n-hexane of support prepared as in Example 2.1, containing 200 gramme-milliatoms of magnesium. ~fter decanting, the supernatant hydrocarboQ phase is removed. The reactor is then heated to 50~C and 3 ml (21 millimoles) of ethylbenæoate are introduced. The suspension is maintained under agitation for 1 hour, then the temperature is raised to 80C to eliminate the n-hexane by means of a current of nitrogen. Then 3 moles of pure TiCl4 (330 ml) are introduced into the reactor and the mixture is maintained under agitation for 2 hours at 80C. The catalyst obtained is washed wi~h n-hexane at 50C to glve the catalyst ready for use in the form of a suspension iII n~hexane.
Analysis of the catalyst thus obtained shows that ic contains per gramme-atom of magnesium 2.05 gramme-atoms of chlorine, 0.030 mole of ethylbenzoate, 0.020 mole of titanium, and that it contains no trace of di-isoamyl ether.
The catalyst thus defined is a powder consisting of spheroidal particles, having a particle size distribution such that Dm:Dn = 1.3 with Dm = 40 micrcns; it is found that more than 90% by weight of the particles have a mean diameter by mass comprised between 36 and 44 microns; the particles have a suriace as smooth as that of the initial support.
Examp1e 3 Thère are used in this Example as support a powder based on magnesium chloride, consisting of spheroidal particles having a particle size distribution sl1ch that Dm:Dn = 1.1, with Dm - 20 microns; more than 90% by weight of the particles of this powder have a mean diameter comprised between 18 and 22 ~icrons.
Preparation of the catalyst The preparation of the catalyst is identical to that of Example 1. A solid catalyst is obtainec1 ready for use in the form of a suspension in n-hexane. The chemical analysis of this catalyst shows that it contains, per gramme-atom of magnesium, 2.00 gramme-atoms of chlorine, 0.014 gral~me-atom of titanium, 0.016 mole of ethylben~oate and no trace of di-isoamyl ether.
This catalyst consists of spheroidal particles, having a particle si~e distribution such that Dm.Dn = 1.1 with Dm = 20 microns; it is found furthermore that more than 90% by weight of the particles have a mean diameter comprised between 18 and 22 microns; the particles have a surface appearance identical to that of the initial support.
Example 4 There is utilised as support a powder based on magnesium chloride consisting of spheroidal particles having a narrow particle size distribution, such that ~m:Dn = 1.5, with Dm = 30 microns; it has a density equal to 1.9 and a specific surface area equal to 46 m2/g (BET); the surface of the particles is very smooth.
Preparatlon of _he catalyst The preparation of the catalyst is identlcal to that of Example 1. There is obtained a solid catalyst ready for use, in the form of a suspension in n-hexane. The chemical analysis of the catalyst shows that it contains, per gra~me-atome of magnesium, 2~00 gramme-atoms of chlorine, 0.015 gramme-atom of titanium, 0.018 mole of ethylbenzoate and no trace of di-isoamyl ether.
This catalyst consists of spheroidal particles having a particle size distributiou such that Dm:Dn = 1.5 with Dm = 30 microns; the particles have a surface as smooth as that of the initial support.
~xample 5 . .
There is used as support a powder based on magnesium chloride consisting of spheroidal particles having a narrow particle si~e distribution, such that Dm:Dn = 2.5, with Dm = 35 microns; this powder contains less than 0.05% by weight of particles of diameter less than 7 microns; lt has a density equal to 1.~ and a specific surface area equal to 44 m2/g (~ET); the surface of the particles is smooth.
Preparation of the catalyst The preparation of the catalyst is identical to that of Example 1. There is obtained a solid catalyst ready for use, in the form of a suspension in n-hexane. The chemical analysis of the catalyst shows that it contains, per gra~me-atome of magnesium~ 2.05 gramme-atoms of chlorine, 0.018 gramme-a~om of titanium~ 0.018 mole of ethylbenzoate and no trace of di-isoamyl ether.
The catalyst consists of spheroidal particles having a particle slze distribution s~ch that ~m:Dn = 2.5 with Dm = 35 microns; the particles have a surface as smooth as that of the initial support.
Example 6 -Suspension polymerisation Into a 3tainless steel reactor with a capacity of 5 litres and provided with an agitation system rotating at 750 revolutions per minute there are introduced under a blanket of nitrogen 2 litres of n-hexane heated to 50C, 10 millimoles of tri-isobutyl aluminium (Ti3~), 3.7 millimoles of methyl paratoluàte and a quantity of catalyst prepared as in Example 1, corresponding to 0.08 gramme-milliatom of titanium. The reactor is heated to 60C and a volume of 40 ml of hydrogen measured under normal conditions is introduced, the~ propylene at a rate of 300 g/hr. for 2 hours. At the end of the one hour of introduction of propylene, a supplementary volu~e of 4n ml of hydrogen measured under normal conditions is added to the reactor. At the end of the introduction of propylene, the polypropylene suspension is maintained under agitation and at 60C for a further half-hour. Then the non-polymerised propylene is de-gassed and the n-hexane is evaporated from the polypropylene suspension.
480 g of a dry polypropylene powder are obtained having the following characteristics: 5 - titanium content: 8 ppm (corresponding to a polymerisation yield of 6 kg/gramme-milliatom of titanium of the catalyst) - apparent voluminal mass (A~): 0041 g/cm3 - content of polymer insoluble in boiling n-heptane: 92% by weight - melt index under 5 kg. at 190C: l.8 gllO minutes - mean diameter by mass (Dm): 250 microns - powder consisting of spheroidal particles with a narrow particle size distribution and a smooth surface.
Exa~ple 7 -Suspension polymerisation One proceeds exactly as in Example 6 except that the catalyst prepared as in Example 2 is employed instead of the catalyst prepared as in E~ample 1. 410 g of a dry polypropylene powder are obtained having the characteristics described in Table 1.
Suspension polymerisation One proceeds e~actly as in Example 6, except that the catalyst prepared as in Example 3 is employed. 395 g of a dry polypropylene powder are obtained having the characteristics described in Table 1.
Example 9 Suspension polymerisation -One proceeds exactly as in Example 6, except that 5 millimoles of methyl paratoluate are used instead of 3.7 millimoles, and a quantity of the catalyst prepared as in Example 1 corresponding to 0.135 gramme-milliatom of titanium, instead of 0.08 gramme-milliatom of titanium. 430 g of a dry polypropylene powder are ob~ained having the characteristics described in Table I.
~ .
Suspension polymerisation One proceeds exactly as in Example 6, except that one uses 2.5 millimoles of methyl paratoluate instead of 3.7 millimoles, and a qua~tity of catalyst prepared as in Example 1 corresponding to 0.135 gramme-milliatom of titanium instead of 0.08. 60n g of dry polypropylene powder are obtained having the characteristics described in Table I.
Example 11 Suspension ~olymerisation -One proceeds exactly as in E~ample 6, except that 10 millimoles of triethylaluminium (TE~) are used instead oE 10 millimoles of TiBA, and 3.3 millimoles of methyl paratoluate instead of 3.7 millimoles.
500 g of a dry polypropylene powder are obtained having the characteristics described in Table I.
Example 12 Suspension polymerisation One proceeds exactly as in Example 6, except that 10 millimoles of tri--n~octylaluminium (TnO~) are used instead of 10 millimoles of ~5jV~t~
TiBA, 4 millimoles of me~hyl paratoluate instead of 3.7 millimoles, and a quantity of the catalyst prepared as in E~ample 1 corresponding to 0.1 gramme-milliatom of titanium, lnstead of 0.08 gramme-milliatom. 450 g of a dry polypropylene powder are obtained having the characteristics described in Table I.
Example 13 Sequenced e~p~ly~erisatiorl in suspension One proceeds e~actly as in Example 6, except that propy]ene is introduced into the reactor at a rate of 300 g/hr. for an 'nour-and-a-half, instead of for two hours, and that at the end of this time thereactor is de-gassed to O.1 MPa and a mixture of ethy1ene and propylene containing 80% by weight or ethylene are introduced at a rate of 200 g/hr. for half-an-hour. At the end of this period the copolymer suspension is maintained under agitation and at 60~C for a further half-hour. 450 g of a dry sequenced copolymer powder of ethylene and propylene are obtained possessing a content of units derived from ethylene equal to 9% by weight (measured by infrared spectrography) and having the other characteristics described in Table I.
E~ample 14 Statistical copolymerisatiol~ in suspension One proceeds exactly as in Example 6, except that a mi~xture of propylene and ethylene containing 5% by weight of ethylene is introduced into the reactor instead of propylene alone. 400 g of a dry powder of a statistical copolymer of propylene and ethylene are obtained possessing a content of ~mits derived from ethylene equal to 5% by welght (measured by infrared spectrography) and having the other characteristics described in Table I.
Example 15 Suspension polymerisation One proceeds exactly as in Example 6, e-xcept that the catalyst prepared as in Example 4 is used. 460 g of a dry polypropylene powder are obtained having the characteristics described in Table I.
5~
Exa~ple 16 Suspension polymeri~ation One proceeds e~actly as in ~xample 69 except that the catalyst prepared as in Example 5 i5 used. 500 g of a dry polypropylene powder are obtained having the characteristics described in Table 1.
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'7 Example 17 _ lymerisation in liquid propylene Into a 5-litre stainless steel reactor equipped with an agitator rotating at 750 revolutions per minuce there are introduced under a blanket of nitrogen 10 millimoles of TiBA, 3.7 millimoles of methyl paratoluate and a quantity of the catalyst prepared as ia Example 1 corresponding to 0.1 gramme mllliatom of titanium.
The reactor is purged with gaseous propylene and 1.5 kg of liquid propylene is introduced, and a volume of 200 ml of hydrogen measured under normal conditions. The reactor is then heated to 60C and the polymerisation reaction lasts an nour and a half. At the end of this period, the excess propylene is de-gass~d and after steam d:Lstillation 6'00 g of a dry whlte polypropylene powder are recovered having the followlng characteristics:
- titanium content; 8 ppm - apparent voluminal mass (AVM): 0.4~ g/cm3 - content of polymer insoluble in boiling n~heptane: 92% by weight - melt index under 5 kg. at 190C: 2.3 g/10 minuces - mean diameter by mass (Dm): 250 microns - powder consisting of spheroidal p~rticles, with a narro~
particle size distribution and a smooth surface.
Example 18 Polymerisation in liquid propylene -One proceeds exaccly as in Example 17, e~cept thac a quantity of the catalyst prepared as in Example 2, corresponding to 0.08 gra~me-milliatom of titanium, is introduced into the reactor instead of the quantity of the catalyst prepared in Example 1 corresponding to 0.1 gram~e-milliatom of titanium, and a volume of 400 ml of hydrogen measured under normal conditions, instead of 200 ml, and that the reaction of polymerising the propylene lasts for two hours Lnstead of one-and-a-half hours~ 650 g of a dry polypropylene powder are obtained having the following characteristics:
- titani~l content: 6 ppm - apparent voluminal mass (AVM): 0.48 g/cm3 - content of polym~r insoluble in boiling n-heptane: 92~ by weight - melt index under 5 kg. at 190C: 3.g g/10 mlnutes S - mean diameter by mass (Dm): 280 ~icrons - powder conslsting of spheroidal particles with a narrow particle size distribution and a smooth surface.
Example 19 Polymerisation in liquid propylene One proceeds exactly as in Exa~ple 17, except that a qu~ntity of the catalyst prepared as in E~a~ple 3, corresponding to 0.05 grarnme-milliatom of titanium, is introduced into the reactor instead of the quantity of the catalyst prepared in Example 1 corresponding to 0.1 gramme-milliatom of titanium, and that Che polymerisation reaction of the propylene lasts for two hours instead of one-and-a-half hours.
450 g of a dry polypropylene powder are obtained having the following characteristics:
- titaniu~ content: 5 ppm - apparent voluminal mass (AVM): 0.50 g/cm3 ~0 - content of polymer insoluble in boiling n-heptane: 91~ by weight - melt index under 5 kg. at 190C: 1.6 g/10 minutes - mean diameter by mass (Dm): 150 microns - powder consisting of spheroidal particles with a narrow particle size distribution and a smooth surface.
Example 20 20.1 Preparation of a suspen ion prepolymer Into a stainless sLeel reactor ~ith a capaci~y of 5 litres and provided with an agitation system rotating at 750 revolutions per minute there are introduced under a blanket of nitrogen ~5 milllmoles of TiBA, 9.25 millimoles of meehyl paratoluate and a quantity of the catalyst prepared as in Example 1 corresponding to 2.5 gramme-milliatoms of titanium. The volume of the suspension is made up to 2 litres with n-hexane. At ambient temperature (20C) there is introduced into the reactor a volume of 30 ml of hydrogen measured under normal conditions, then propylene at a rate of 200 g/hr. for two and-a-ha:Lf hours. Ac the end of this period the prepolymer suspension is maintained under agitatlon for a further half-hour. The reactor i9 de-gassed and, still under a blanket of nitrogen, the prepolymer powder is washed 3 times with n-hexane. The prepolymer suspension in n-hexane is then decanted into a rotary evaporator under a vacuum.
510 g of a dry prepolymer powder are obtained, consisting of spheroidal particles with a narro~7 particle size distribution, a mean diameter by mass equal to 110 microns, a smooth surface and having a tLtaniu~ content equal to 240 ppm This powder l.s preserved unler nitroge~.
20.2 Dry-phase poly~erisation (agitated bed) 25 g of the dry prepolymer powder prepared as in Example 20.1 and containing 0.125 gra~me-milliatom of titanium are impregnated ~ith a mixture of 5 millimoles of a solutioQ of TEA in n-hexane and 1.65 ~illimoles of methy~ paratoluate. This impregnated powder is introduced into a stainless steel ~eactor wi~h a capacity of 2 litres and provided with an agitation system for dry powder. lO0 g of a perfrectly dry and anhydrous polypropylene powder are addedO This mixture of powders is maintained under agitation and scavenged with nitrogen at 80C until a powder which will flow well is obtained. The reactor is then heated to 60C. Propylene is introduced until a pressure of 1 MPa is obtained and this is maintained constant throughout the entire duration of the polymerisation by topping up with propylene. rn addition, a volume of 50 ml of hydrogen measured under normal conditions is added each hour to the reactor. After 5 hours of reaction, the reactor is de-gassed. 625 g of a dry powder are recovered of which 500 g produced by the present propylene polymerisation reaction have the following characteristics:
- titanium content: 12 ppm 30 - apparent voluminal mass (AVM): 0.48 g/cm3 - content of polymer insoluble in boiling n-heptane: 91% by weight - melt index under 5 kg. at 190C: l.l g/lO minutes - mean diameter by mass (Dm): 250 microns - powder consisting of spheroidal particles with a narrow particle size dist~ibution and a smooth surface.
Example 21 Dry-phase polymerisation (fluidised bed) Into a Eluldised-bed reactor with a diameter of 15 cm, operating ~ith a rising gas propelled at a speed of 15 cmlsec and under partial pres.sures of 0.1 ~Pa of hydrogen and 1.5 MPa of propylene, there are introduced in sequence lo g/hr of the dry prepolymer powder prepared as in Example 20.1 A solution in n-he~ane of a mixture of TnOA and methyl paratoluate in a molar ratio of 1:0.25 is introduced continuously at a rate corresponding to 9 milllmoles of TnOA per hour~ The temperature of the fluidised bed is ma~ntained at 60C
throughout the whole of the polymerisation. By sequenced withdrawals one obtains approximately 500 g/hr of a dry polypropylene powder which can be used directly and having the following characteristics;
- titanium content: 8 ppm - apparent voluminal mass (AVM): 0.45 g/cm3 - content of polymer insoluble in boiling n-heptane: 90~ by weight - melt index under 5 kg~ at 190C: 2.3 g/10 minutes - mean diameter by mass (Dm): 250 microns 0 - powder consisting of spheroidal particles with a narrow particle size distribution and a smooth surface.
Example 22 Dry-phase copolymerisation ( fluidised bed) .. .. . _ _ _ .
One proceeds exactly as in Example 21, except that the fluidised-2S bed reactor operates under partial pressures of 1.4 MPa of propylene and 0.1 MPa of ethylene instead of 1.5 MPa of propylene alone.
By a s~ries ofwi~rawals one obtains approximately 400 g/hr of a dry propylene and ethylene copolymer powder which can be used directly and having the following characteristics:
- titanium content: 10 ppm - apparent voluminal mass (A~): 0.44 g/cm3 - content of polymer insoluble in bolling n-heptane: 85~ by weight content of units derived from ethylene: 5% by weight (measured by infrared spectrography) - melt index under 5 kg~ at 190C: 3 g/10 minutes :L9 - mean diameter by mass (Dm): 240 microns - powder consisting o~ spheroidal particles with a narrow particle size distribution and a smooth surface.
Claims (14)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. A catalyst which can be used for the polymerisation and copolymerisation of propylene with other alpha-olefins, comprising a support containing essentially magnesium chloride, occurring in the form of spheroidal particles, having a mean diameter by mass of between 10 and 100 microns and a particle size distribution such that the ratio of the mean diameter by mass, Dm, to the mean diameter by number, Dn, is less than or equal to 3, which support has been treated with an electron donor compound chosen from among an aromatic ether and an ester of an aromatic acid and which when impregnated with titanium tetra-chloride comprises 0.5 to 3% of atoms of titanium per atom of magnesium. - 2. A catalyst according to claim 1, wherein the support has a particle size distribution such that the ratio Dm:Dn of the mean diameter by mass to the mean diameter by number of the particles is between 1.1 and 2.5.
- 3. A catalyst according to claim 1, wherein the support has a particle size distribution such that the ratio Dm:Dn is between 1.1 and 1.5.
- 4. A catalyst according to claim 1, wherein the support has a particle size distribution such that more than 90% by weight of the particles of each batch are comprised with the range Dm + 10%.
- 5. A catalyst according to claim 1, wherein the support contains an electron donor compound hut does not contain any product having a Mg-C bond, and the density of the particles is between 1.2 and 2.1.
- 6. A catalyst according to claim 1, wherein the support has a specific surface area of between about 20 and 60 m2/g (BET).
- 7. A catalyst according to claim 6 wherein the support has a smooth surface.
- 8. A catalyst according to claim 1 wherein the support further comprises a chlorinated derivative of aluminium.
- 9. A process for preparing a catalyst as defined in claim 1, comprising treating the support at a temperature of between about 20°C and 50°C with the electron donor compound employed in a quantity of between 0.06 and 0.2 mole of electron donor compound per mole of magnesium chloride support and impregnating the support with titanium tetrachloride at between about 80°C and 100°C.
- 10. A process for polymerising propylene or copolymer-ising propylene with another alpha-olefin, comprising effecting to polymerisation or copolymerisation in the presence of a catalyst as defined in claim 1.
- 11. A process according to claim 10 wherein the poly-merisation or copolymerisation is effected in the presence of a co-catalyst of the formula Al(R7)3, in which R7 is an alkyl radical having 2 to 12 carbon atoms.
- 12. A process according to claim 11, wherein the co-catalyst is in the complexed state by the addition of 0.1 to 0.5, mole per mole of A1(R7)3 of an electron donor compound, which is an ester of an aromatic acid.
- 13. A process according to claim 12, wherein 0.3 mole electron donor compound is added per mole of A1(R7)3.
- 14. A process according to claim 10, 11 or 12, wherein the polymerisation or copolymerisation of propylene, is carried out in such a way that the prepolymer obtained contains from 0.1 to 500 g of polymer or copolymer per gramme-milliatom of titanium.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8211056A FR2529209A1 (en) | 1982-06-24 | 1982-06-24 | CATALYSTS FOR THE POLYMERIZATION AND COPOLYMERIZATION OF PROPYLENE AND POLYMERIZATION METHODS USING THESE CATALYSTS |
| FR8211056 | 1982-06-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1192537A true CA1192537A (en) | 1985-08-27 |
Family
ID=9275353
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000431030A Expired CA1192537A (en) | 1982-06-24 | 1983-06-23 | Catalysts for the polymerization and copolymerization of propylene and polymerization processes using these catalysts |
Country Status (13)
| Country | Link |
|---|---|
| US (2) | US4511703A (en) |
| EP (1) | EP0099773B2 (en) |
| JP (1) | JPH0784490B2 (en) |
| AT (1) | ATE17740T1 (en) |
| AU (1) | AU562669B2 (en) |
| CA (1) | CA1192537A (en) |
| DE (1) | DE3362002D1 (en) |
| ES (1) | ES8403936A1 (en) |
| FI (1) | FI75848C (en) |
| FR (1) | FR2529209A1 (en) |
| NO (1) | NO161324C (en) |
| NZ (1) | NZ204669A (en) |
| PT (1) | PT76923B (en) |
Families Citing this family (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2560200B1 (en) * | 1984-02-23 | 1986-06-27 | Bp Chimie Sa | PROCESS FOR THE PREPARATION OF SUPPORTED CATALYSTS BASED ON VANADIUM COMPOUNDS FOR THE POLYMERIZATION AND COPOLYMERIZATION OF ETHYLENE |
| FR2566781B1 (en) * | 1984-06-28 | 1986-11-14 | Bp Chimie Sa | PROCESS FOR THE POLYMERIZATION OR CO-POLYMERIZATION OF ALPHA-OLEFINS IN A FLUIDIZED BED, IN THE PRESENCE OF A ZIEGLER-NATTA CATALYST SYSTEM |
| US4581342A (en) * | 1984-11-26 | 1986-04-08 | Standard Oil Company (Indiana) | Supported olefin polymerization catalyst |
| US4657882A (en) * | 1984-11-26 | 1987-04-14 | Amoco Corporation | Supported olefin polymerization catalyst produced from a magnesium alkyl/organophosphoryl complex |
| EP0200684B1 (en) * | 1985-05-02 | 1990-08-01 | Ciba-Geigy Ag | Method for stabilizing spherical polymerized polyolefins |
| FR2586022B1 (en) * | 1985-08-06 | 1987-11-13 | Bp Chimie Sa | POLYMERIZATION OF OLEFINS IN THE GASEOUS PHASE WITH A ZIEGLER-NATTA CATALYST AND TWO ORGANOMETALLIC COMPOUNDS |
| FR2588559B1 (en) * | 1985-10-11 | 1988-03-11 | Bp Chimie Sa | PROCESS FOR POLYMERIZATION OR COPOLYMERIZATION OF ALPHA-OLEFINS IN THE PRESENCE OF AN IMPROVED ZIEGLER-NATTA CATALYST SYSTEM |
| US4981929A (en) * | 1986-06-23 | 1991-01-01 | Union Carbide Chemicals And Plastics Company, Inc. | Catalyst productivity in the polymerization of olefins |
| JPS63168410A (en) * | 1987-01-06 | 1988-07-12 | Mitsui Toatsu Chem Inc | Preparation of supported titanium ingredient for polimerization of olefin |
| JPS63175005A (en) * | 1987-01-14 | 1988-07-19 | Mitsui Toatsu Chem Inc | Production of supported titanium component for olefin polymerization |
| CN1036852C (en) * | 1988-03-03 | 1997-12-31 | Bp化学有限公司 | Ziegler-Natta Catalyst |
| FR2628110B1 (en) * | 1988-03-03 | 1994-03-25 | Bp Chimie | CATALYST FOR POLYMERIZATION OF ZIEGLER-NATTA-TYPE OLEFINS, SUPPORTED ON SPHERICAL MAGNESIUM CHLORIDE PARTICLES, AND PROCESS FOR PREPARING THE SAME |
| FR2629461B1 (en) * | 1988-03-31 | 1993-05-07 | Bp Chimie Sa | PROPYLENE (CO) POLYMERIZATION CATALYST, SUPPORTED ON SPHERICAL PARTICLES OF MAGNESIUM CHLORIDE AND COATED WITH POLYPROPYLENE, AND METHODS OF PREPARATION |
| US5137996A (en) * | 1988-03-31 | 1992-08-11 | Bp Chemicals Limited | Ziegler-natta catalyst |
| FI85498C (en) * | 1988-11-08 | 1992-04-27 | Neste Oy | Process for polymerization and copolymerization of alpha-olefins and a catalyst system used in the process |
| FR2650827B1 (en) * | 1989-08-08 | 1993-03-05 | Bp Chem Int Ltd | PROCESS FOR THE PREPARATION OF A VANADIUM-BASED ZIEGLER-NATTA CATALYST |
| US5208303A (en) * | 1989-08-08 | 1993-05-04 | Bp Chemicals Limited | Process for preparing a vanadium-based catalyst suitable for olefin polymerization |
| FR2651001B1 (en) * | 1989-08-17 | 1993-03-12 | Bp Chemicals Sa | PROCESS FOR THE PREPARATION OF A ZIEGLER-NATTA CATALYST BASED ON VANADIUM AND TITANIUM |
| FR2651234B1 (en) * | 1989-08-29 | 1993-03-12 | Bp Chem Int Ltd | PROCESS FOR THE MANUFACTURE IN THE GASEOUS PHASE OF PROPYLENE COPOLYMERS USING A HIGH-ACTIVITY CATALYST SYSTEM. |
| ATE188712T1 (en) * | 1991-10-29 | 2000-01-15 | Huntsman Corp | POLYPROPYLENE EXTRUSION COATING RESINS AND METHOD FOR THEIR PRODUCTION |
| DE4306382A1 (en) * | 1993-03-02 | 1994-09-08 | Hoechst Ag | Process for the preparation of a poly-1-olefin |
| US6624264B2 (en) | 1995-09-20 | 2003-09-23 | Atofina | Alkoxysilacycloalkanes, process for their preparation and their use for the polymerization of olefins |
| US5955396A (en) * | 1995-10-17 | 1999-09-21 | Bp Amoco Corporation | Morphology-controlled olefin polymerization catalyst formed from an emulsion |
| JP3143057B2 (en) * | 1996-02-16 | 2001-03-07 | 日本ポリオレフィン株式会社 | Solid catalyst component for olefin polymerization, method for producing the same, and method for producing polyolefin |
| TWI224600B (en) * | 1998-05-06 | 2004-12-01 | Basell Technology Co Bv | Catalyst components for the polymerization of olefins |
| KR100430979B1 (en) * | 1999-02-04 | 2004-05-12 | 삼성아토피나주식회사 | Producing process for an olefin polymerization chelate catalyst |
| KR100430977B1 (en) * | 2000-12-29 | 2004-05-12 | 삼성아토피나주식회사 | Preparation method of catalyst for olefin polymerization |
| KR100430976B1 (en) * | 2000-12-30 | 2004-05-12 | 삼성아토피나주식회사 | Preparation method of supported catalyst for ethylene polymerization and ethylene/α-olefin copolymerization |
| US6767857B1 (en) | 2003-05-29 | 2004-07-27 | Fina Technology, Inc. | Process for forming a Ziegler-Natta catalyst system having a controlled morphology |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3135809A (en) * | 1960-07-21 | 1964-06-02 | Southern Res Inst | Isomerization process |
| CA920299A (en) * | 1968-08-01 | 1973-01-30 | Mitsui Petrochemical Industries | Process for the polymerization and/or copolymerization of olefins with use of ziegler-type catalytsts supported on carrier |
| NL160286C (en) * | 1971-06-25 | |||
| JPS5330681A (en) * | 1976-09-02 | 1978-03-23 | Mitsui Petrochem Ind Ltd | Preparation of polyalpha-olefin |
| US4250288A (en) * | 1977-02-03 | 1981-02-10 | The Dow Chemical Company | High efficiency, high temperature catalyst for polymerizing olefins |
| US4314912A (en) * | 1977-02-03 | 1982-02-09 | The Dow Chemical Company | High efficiency, high temperature catalyst for polymerizing olefins |
| GB1603724A (en) * | 1977-05-25 | 1981-11-25 | Montedison Spa | Components and catalysts for the polymerisation of alpha-olefins |
| JPS54123594A (en) * | 1978-03-17 | 1979-09-25 | Asahi Chem Ind Co Ltd | Olefin polymerization catalyst |
| IT1098272B (en) * | 1978-08-22 | 1985-09-07 | Montedison Spa | COMPONENTS, CATALYSTS AND CATALYSTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS |
| IT1099416B (en) * | 1978-10-23 | 1985-09-18 | Montedison Spa | COMPONENTS AND CATALYSTS FOR THE POLYMERIZATION OF OLEFINS |
| US4252670A (en) * | 1979-01-10 | 1981-02-24 | Imperial Chemical Industries Limited | Olefine polymerization catalyst |
| JPS5846202B2 (en) * | 1979-01-31 | 1983-10-14 | 住友化学工業株式会社 | Production method of olefin polymer |
| EP0019312B1 (en) * | 1979-04-30 | 1983-08-17 | Shell Internationale Researchmaatschappij B.V. | Olefin polymerization catalyst compositions and a process for the polymerization of olefins employing such compositions |
| CA1141093A (en) * | 1979-05-17 | 1983-02-08 | Brian L. Goodall | Olefin polymerization catalyst compositions and a process for the polymerization of olefins employing such compositions |
| JPS5634709A (en) * | 1979-08-31 | 1981-04-07 | Mitsui Petrochem Ind Ltd | Gas phase polymerization or copolymerization of olefin |
| JPS57205407A (en) * | 1981-06-11 | 1982-12-16 | Toyo Sutoufuaa Chem:Kk | Catalytic component for alpha-olefin polymerization and homopolymerization or copolymerization of alpha-olefin |
| JPS57205406A (en) * | 1981-06-11 | 1982-12-16 | Toyo Sutoufuaa Chem:Kk | Catalytic component for alpha-olefin polymerization and homopolymerization or copolymerization of alpha-olefin |
| FR2529207A1 (en) * | 1982-06-24 | 1983-12-30 | Bp Chimie Sa | PROCESS FOR THE PREPARATION OF CATALYST SUPPORTS FOR THE POLYMERIZATION OF ALPHA-OLEFINS AND SUPPORTS OBTAINED |
| FR2529206A1 (en) * | 1982-06-24 | 1983-12-30 | Bp Chimie Sa | PROCESS FOR THE PREPARATION OF MAGNESIUM CHLORIDE SUPPORTS FOR THE PREPARATION OF ALPHA-OLEFIN POLYMERIZATION CATALYSTS AND SUPPORTS OBTAINED |
-
1982
- 1982-06-24 FR FR8211056A patent/FR2529209A1/en active Granted
-
1983
- 1983-06-14 AT AT83401222T patent/ATE17740T1/en not_active IP Right Cessation
- 1983-06-14 DE DE8383401222T patent/DE3362002D1/en not_active Expired
- 1983-06-14 EP EP83401222A patent/EP0099773B2/en not_active Expired - Lifetime
- 1983-06-16 US US06/504,981 patent/US4511703A/en not_active Expired - Lifetime
- 1983-06-21 NZ NZ204669A patent/NZ204669A/en unknown
- 1983-06-22 NO NO832267A patent/NO161324C/en not_active IP Right Cessation
- 1983-06-22 AU AU16137/83A patent/AU562669B2/en not_active Expired
- 1983-06-23 CA CA000431030A patent/CA1192537A/en not_active Expired
- 1983-06-23 ES ES523559A patent/ES8403936A1/en not_active Expired
- 1983-06-23 PT PT76923A patent/PT76923B/en unknown
- 1983-06-23 FI FI832321A patent/FI75848C/en not_active IP Right Cessation
- 1983-06-24 JP JP58114152A patent/JPH0784490B2/en not_active Expired - Lifetime
-
1985
- 1985-01-15 US US06/691,539 patent/US4673662A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| FI75848B (en) | 1988-04-29 |
| AU562669B2 (en) | 1987-06-18 |
| NO832267L (en) | 1983-12-27 |
| FI75848C (en) | 1988-08-08 |
| FR2529209B1 (en) | 1984-11-23 |
| PT76923A (en) | 1983-07-01 |
| EP0099773B2 (en) | 1993-03-03 |
| US4511703A (en) | 1985-04-16 |
| EP0099773A1 (en) | 1984-02-01 |
| ATE17740T1 (en) | 1986-02-15 |
| NZ204669A (en) | 1986-05-09 |
| NO161324C (en) | 1989-08-02 |
| ES523559A0 (en) | 1984-04-01 |
| PT76923B (en) | 1986-01-27 |
| JPH0784490B2 (en) | 1995-09-13 |
| FI832321A0 (en) | 1983-06-23 |
| EP0099773B1 (en) | 1986-01-29 |
| FI832321L (en) | 1983-12-25 |
| DE3362002D1 (en) | 1986-03-13 |
| JPS598707A (en) | 1984-01-18 |
| AU1613783A (en) | 1984-01-05 |
| ES8403936A1 (en) | 1984-04-01 |
| US4673662A (en) | 1987-06-16 |
| NO161324B (en) | 1989-04-24 |
| FR2529209A1 (en) | 1983-12-30 |
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