CA1304883C - Preparation of homopolymers and copolymers of propene using a ziegler-natta catalyst system - Google Patents
Preparation of homopolymers and copolymers of propene using a ziegler-natta catalyst systemInfo
- Publication number
- CA1304883C CA1304883C CA000564511A CA564511A CA1304883C CA 1304883 C CA1304883 C CA 1304883C CA 000564511 A CA000564511 A CA 000564511A CA 564511 A CA564511 A CA 564511A CA 1304883 C CA1304883 C CA 1304883C
- Authority
- CA
- Canada
- Prior art keywords
- titanium
- stage
- component
- solid
- carrier
- 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 - Lifetime
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
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
- 19 - O.Z. 0050/39143 Abstract of the Disclosure: Polymers of propene are prepared using a Ziegler-Natta catalyst system consist-ing of (1) a titanium component which is based on a finely divided, shape-imparting silica gel and, in ad-dition to titanium, contains magnesium, chlorine and a benzenecarboxylic acid derivative, (2) an alumino com-ponent and (3) a silane component. The process employs a titanium component (1) which is obtained by a method in which (1.1) first (I) a carrier is prepared from (Ia) a silica gel, (Ib) an organomagnesium compound and (Ic) a gaseous chlorinating agent by a procedure in which (1.1.1) first (Ia) is reacted with (Ib), (1.1.2) then (Ic) is passed into the product obtained from (1.1.1) and (I) is isolated, (1.2) thereafter, a solid-phase interme-diate is prepared from (I), (II) an alkanol, (III) tita-nium tetrachloride and (IV) a phthalic acid derivative by a procedure in which (1.2.1) first (I) is reacted with (II), (1.2.2) then (III) is introduced into the product resulting from (1.2.1), with the proviso that (IV) is also introduced in (1.2.1) or (1.2.2), (1.3) then the solid-phase product resulting from (1.2) is extracted with titanium tetrachloride, and (1.4) finally, the solid-phase product resulting from (1.3) is washed with a liquid hydrocarbon.
Description
~3~ 3 ~ o.Z. 0050/39143 Preparation of homopolymers and copolymers of propene using_a Ziegler-Natta catalyst system The present ;nvention relates to a process for the preparation of homopolymers of propene and copolymers of propene w;th m;nor amounts of other C~-C12-~-mono-olefins, in particular Cz-C6-~-monoolefins, by polymeri-zation, in particular by dry-phase polymerization, of the monomer or monomers at from 20 to 160C, in particular from S0 to 120C, and under from 1 to 100, in particular from 20 to 70, bar using a Ziegler-Natta catalyst system consisting of t1) a titanium component which is based on a f;nely div;-ded, shape-imparting silica gel and, in addit;on to titanium, contains magnesium, chlorine and a benzene-carboxylic ac;d derivative,
5 (2) an aluminum component of the formula AlR3, where R is alkyL of not more than 8, in particular not more than ~, carbon atoms, and
0 (3) a silane component of the for~ula R1 SilOR2)4_n, where R1 is a saturated al;ph~tic and/or aromatic hydrocarbon radical of not more than 16, preferably ZS not more than 10, carbon atoms, R2 is alkyl of not ~ore than 15, preferabLy not more than 8, in particu-lar not more than 4, carbon atoms and n is from û to 3, preferably from 0 to 2, in particular 1, ~ith ~he pro~isos that the ato~ic ratio of titanium from
0 the titanium component tl) to aluminum -from the aluminum conponent (2l is from l : 10 to 1 : 800, in particular from 1 : 20 to 1 : 200~ and the molar ratio of aluminum component t2) to silane component t3) is from 1 : 0.03 to 1 : 0.8, ;n particular from 1 : 0.05 to 1 : O.S.
Polymerization processes of this type are known;
their special feature compared with other similar processes - 2 - O.Z. 0050/39143 is the specific embodiment of the catalyst system, and the processes disclosed in European Laid-Open Applica-tions 0,014,523, 0,045,977, 0,171,200 and 0,195,497 and in ~ritish Patencs 2,101,609 and 2,10i,611 may be mentioned as prototypes for the present case.
The specific embodiments of the catalyst systems are employed ;n order to açhieve certain purposes, such as the following:
The catalyst system should be easy to prepare and give a high yield of polymer which must contain a very large isotactic fraction. The catalyst system should moreover produce polymers having spec;al morpho-logical properties, for example uniform particle size and/or a smaller fraction of very ~ine particles and/or a high bulk density~ In addition to these parameters which are important for controlling the polymerization systems, ~ork;ng up the polymers and/or processing them, a lo~ halogen content in the polymer is also important, particularly with regard to corrosion problems; this can ZO be achieved by increasing the polymer yield and/or by means of a catalyst system which contains very little halogen.
In the prior art, some of these purposes can be achieved only by very expensive methods or if other purposes are neglected:
For example, European Laid-Open Application 0,045,977 descr;bes a catalyst system consisting of ac-tive MgClz, T;Cl4 and a phthal;c acid derivative. With sil;c3 gel as the shape-impart;ng carr;er, the produc-tivity of the catalyst system is, however~ no longersatisfactory; furthermore, the chlor;ne content of the polymers is comparatively high.
European Laid-Open Applications 0,014,523 and 0,171,200 and ~ritish Patents 2,101,609 and 2,101,611 describe catalyst systems whose t;tanium component is obtained by treating a solid, inorganic oxide ~ith an organ;c magnes;um compound, a Le~is base and titanium ~3~ 83 _ 3 _ o.z. 0050~39143 tetrachloride, it be;ng necessary in addition to use a halogenating agent ~hich is not titanium tetrachloride and/or an organic compound of the metals boron, aluminum~
silicon or tin or a boron trihalide or a halogen-containing alcohol. In spite of an expensive and tedious preparation procedure, the productivity of the corresponding catalyst system is unsatisfactory.
European Laid-Open Application 0,195,497 describes a catalyst system whose titanium component is obtained by treating SiO2 with an organic Mg compound, an alcohol, a Lewis base and TiCl4. In the case of this catalyst sys-tem too, the productivity ;s low.
The known processes are thus unsatisfactory, par-ticularly with regard to good productivity and a low chlorine content in the polymers, in combination with high isotacticity and good morphology.
It is an object of the present invention to pro-vide a titanium component which, compared with the prior art processes, has good productivity and is also capable of giving polymers hav;ng a low chlorine content, high isotacticity and good morphology.
~ e have found that this object is achieved by a catalyst system which contains a titanium component (1) prepared in a particuLar manner from (I) a special car-rier obtained in a defined manner from (Ia) a certa;n finely divided silica gel, (Ib) a certain organomagnesium compound and (Ic) a certain gaseous chlorinating agent, and (II) a certain alkanol, (III) titanium tetrachloride and (IV) a specially selected phthalic acid derivative.
The present invention accordingly relates to a process for the preparation of homopolymers of propene and co~olymers of propene ~ith m;nor amounts of other C2-C12-~-mcnool~fins, in particular C2-C6-r~-mono-olefins, by polymerization, in particular by dry-phase polymerization of the monomer or monomers at from 20 to 160C, in particular fro~ 50 to 120C, uncJer from 1 to 100~ in particular from 20 ~o 70, bar using a Ziegler-13~1 !33 - 4 - o.z. OOS0/39143 Natta catalyst system consisting of (1) a titanium component which is based on a finely divi-ded, shape-imparting silica gel and~ in addition to titanium, contains magnesium, chlorine and a benzene-carboxylic acid derivative, ~2) an aluminum component of the formula AlR3, where R is alkyl of not more than 8, in particular not more than 4, carbon atoms, and (3) a silane component of the formula Rl si l oR2 ) 4-n where R1 is a saturated aliphatic and/or aromatic hydrocarbon radical of not more than 16, preferably not msre than 10, carbon atoms, R2 is alkyl of not more than 15, preferably not more than 8, in particu-lar not more than 4~ carbon atoms and n is from 0 to 3, preferably from 0 to 2, in particular 1, with the prov;sos that the atomic ratio of titanium from the titanium component (1) to aluminum from the aluminum component (2) is from 1 : 10 to 1 : 800, in particular from 1 : 20 to 1 : 200, and the molar ratio of aluminum component (2) to silane component (3) is from 1 : 0.03 to 1 : 0.8, in particular from 1 : 0.05 to 1 : 0.5.
In the novel process, the titanium component (1) used is one which is obtained by a method in ~hich first (1.1) in a first stage (1), a carr;er is prepared from (Ia) a finely divided silica gel uhich has a particle diameter of from 1 to 1,000 ~m, in particular from 10 to 4Q0 ~m, a pore volume of from 0.3 to 3, in particular from 1 to 2.5, c~3/g and a surface area of from 100 to 1,000, in particular from 200 to 400, m2/g and is of the formula SiO2 . a Al203, where a is from 0 to 2, in par-ticular from 0 to 0.5, (Ib) an organomagnesium compound of the formula MgR3R4, where R3 and R4 are each C2-C10-a~kyl, preferably C4 C8-alkyl, and (Ic) a gaseous 13()~3 _ 5 _ o z. 0050/39143 chlorinating agent of the formula ClZ, where Z is Cl or H, preferably H, by a method in which first (1~1.1) in a~
first substage, in a liquid inert hydrocarbon, in par-ticular an alkane, with constant thorough mixing at room temperature, the finely divided silica gel (Ia) and the organomagnesium compound (Ib) are combined, from 1 to 10, in particular from 1.5 to 4, molar parts of the organo-magnesium compound (Ib) being used per 10 molar parts of silicon of the silica gel (Ia), and the substances com-10 bined are kept at from 20 to 140C, in particular from 60 to 40C~ for from 0.5 to 5, in particular from 1 to 2, hours, then (1.1.2) in a second substage, with constant thorough mix-ing at from -20 to ~80C, in particular 0 to ~20C, the gaseous chlorinating agent (Ic) is passed into the pro-duct obtained from the first substage, from Z to 40, in particular from 10 to 20, molar parts of the chlorinat;ng agent (Ic) being used per molar part of the organomagnes-ium compound (Ib), the entire mix~ure is left at a te~-perature in the stated range for from 0.5 to 5 hours~ inparticular fro0 0.5 to 1 hour, and the resulting solid-phase product, ie. the carrier (I), is isolated with re-moval of the liquid phase, thereatter (1.2) ;n a second stage, a solid-phase intermediate is prepared from (I) the carrier obtained in the first stage, (II) a Cz-C6-alkanol, in particular ethano(, (III) titan-iu~ tetrachloride and (IV) a phthalic acid derivati~e of the for~ula , ~c~x co-r .
~here X and Y together form oxygen or X and r are each chlorine or C1-C10-alkoxy, preferably Cz-C8-alko~y, in particular butoxy, by a method in which first (1.2~1) in a first substage, in a liquid inert hydrocarbon, in particular an alkane, and with constant thorough mix-ing at room temperature, the carrier (I) and the alkanol ~3~ 83 - 6 - O.Z. 0050/39143 tII) are combined, from 1 to 5, in par~icular from 2.5 to 3.5, molar parts of the alkanol (II) being used per molar part of magnesium of the carrier (I), and the sub-stances combined are kept at from 20 to 140C, in particu-lar from 70 to 90C, for from 0~5 to 5, in particular from 1 to Z, hours, then (1.2.2) in a second substage, with constant thorough m;x-ing at room temperature, the titanium tetrachlor;de (III) is introduced into the react;on mixture resulting from the first substage, from 2 to 20, in particular from 4 to 8, molar parts of the titaniùm tetrachloride (III) being used per molar part of magnesium of the carrier (I), the substances combined are kept at from 10 to 150C, in particular from 90 to 120C, for from 0.5 to 5, in par-ticular from 1 to 2, hours, and the resulting solid-phase intermediate is isolated with removal of the liquid phase, with the proviso that the phthalic acid derivative (IV) is in~roduced in the course of one or both of the substages ~1.2.1) and (1.2.2), from 0.01 to 1, preferably from 0.1 20 to 0.4, in particular from 0.25 to 0.30, molar part of the phthalic acid derivative (IV) being used per molar part of magnesium of the carrier (I), then (1.3) in a third stage, the solid-phase intermediate ob-tained from the second stage ;s subjected to a single-stage or multi-stage or continuous extraction with titan-ium tetrachloride or a mixture of titanium tetrachloride and ethylbenzene, containing not less than 10, in particu-lar not less than 20, % by weight of titanium tetrachlor-ide, at from 100 to 150C, in particular from 115 to 30 135C, in the course of from 0.2 to 5, ;n part;cular from 1.5 to 3, hours, a total of from 10 to 1,000, preferably from Z0 to 800, in particular from 150 to 300, parts by weight of the extracting agent being used per 10 parts by weight of the solid-phase intermediate obtained from the second stage, and finally (1.4) in a fourth stage, the solid-phase product formed in the third stage is washed with a l;quid ;nert hydrocarbon, ~3~D4~33 - 7 - O.Z. 0050/39143 in particular an alkane, until the hydrocarbon takes up virtually no more titanium tetrachloride, and the titan-ium component (1) is obtained in this manner.
We have found that the novel process can be car-ried out particularly successfully if the catalyst sys-tem used contains a silane component (3) which is of the formula R~ Si(OR~ n where R1 is phenyl or C1-C4-alkylphenyl, especially methyl- or ethylphenyl, R2 is alkyl of not more than 4 carbon atoms, especially methyl or ethyl, and n is 1 or 2.
Regarding the process according to the invention, the following may be noted specifically:
Provided that the defining feature is taken into account, the polymerization process as such can be car-ried out in virtually any relevant conventional techno-logical embodiments, for example as a batchwise, periodic or, in particular, continuous process eg. a suspension polymerization process or, in parl:icular, dry-phase polymerization process. The stated technolog;cal embodi-ments, ie. the technological versions of the polymeriza-tion of ~-monoolefins by the Ziegler-Natta method~ are well known from the literature and in practice, so that no further discussion is required here.
For the sake of completeness, it may be mentioned that, in the novel process, it is also possible to regu-late the molecular weights of the poly0ers by the rele-vant conventional measures, for example by means of regu-lators, ;n particular hydrogen~
Regarding the composition of the novel catalyst system, the following may be stated specifically:
t1) the finely divided silica gel ~Ia) to be used for the preparation of the titanium component is in general an aluminosilicate or, in particular, a silica; it is im-portant that it has the required properties. We have ~3~ 3 - 8 - O.Z. 0050/39143 found that the commercial silica gels which meet the stated specification and are conventionally used for carriers are very suiteble.
The organomagnesium compound (Ib) likewise to be used may be, for example, dibutylmagnesium, dihe~ylmag-nesium or, in particular, butyloctylmagnesium.
The gaseous chlorinating agent tIc) also to be used should be very dry and pure; it consists of chlorine or, in particular, hydrogen chloride.
The liquid inert hydrocarbon which serves as an assistant can be a hydrocarbon of the type usually com-bined with titanium components for catalyst systems of the Ziegler-Natta type ~ithout damage to the catalyst system or its titanium component. Examples of suitable hydrocarbons are pentanes~ hexanes, heptanes, gasolines and cyclohexaneu The alkanols (II) to be used for the preparation of the titanium compcnent (1) can be commercial ones;
they should advan~ageously have very high purities. Exam-ples of highly su;table alkanols are ethanol, n-propyl alcohol, isopropyl alcohoL, n-butyl alcohol, isobutyl alcohol and tert-butyl alcohol; ethanol is particularly suitable.
The titanium tetrachloride (III) l ikewise to be used for the preparation of the titanium component (1) should be one convent;onally used in Ziegler-Natta catal-yst systems; the ethylben2ene which may be used as a mix-ture ~ith the t;tanium tetrachloride should be very pure and dry.
Further~ore~ the phthalic acid derivat;ve (IV) to be used, which ;s defined in detail above, can be a commercial one; it should advantageously have high pur-ity. We have found that dibutyl phthalate is very par-ticularly suitable for the purpose of the present inven-tion; however, other dialkyl phthalates and phthalic an-hydr;de and phthaloyl d;chlor;de are also su;table.
The hydrocarbon to be used for the preparation ~a3~ 8,3 - 9 - O.Z. 0050/39143 of the titanium component (1) in stage (1.4) can likewise be a conventional one; it should advantageously have a relatively high purity.
The preparation of the titanium component (1) is S simple and can be carried out by the skilled worker with-out explanations. Regarding stages (1.1), (1.2) and (1.3), all that need be stated is that the isolation of the par-ticular resulting solid is advantageously carried out by filtration under suction~
(2) Suitable aluminum components (2~ of the stated formula are the relevant conventional ones of this for-mula; they are sufficiently well known from the literature and in practice that no further discussion is required.
An example of an outstanding member is triethylaluminum.
(3) The silane component (3) which completes the catalyst system is, in particular, a trialkyoxy(alkyl)-phenylsilane or a dialkoxydi(alkyL)phenylsilane of the stated formula. Triethoxytoluylsilane is an outstanding member; other examples are triethoxyethylphenylsilane, dimethoxyditoluylsilane and diethoxyditoluylsilane.
The novel process permits the preparation of homo-polymers and copolymers, for e~am~)le of the binary or ternary type, including block copolymers, of propene with minor amounts of other C2-C~ monoolefins in an advantageous manner~ a-monoolefins wh;ch are particu-larly suitab~e comonomers to be polymerized being ethene, but-1-ene, 4-methylpent-1-ene and hex-1-ene;
however, n-oct-1-ene, n-dec-1-ene and n-dodec-1-ene are, for example, also suitable.
Preparation of the titanium component (1) The procedure is as follows: first (1.1) in a first stage (I), a carrier is prepared from (Ia) a finely divided silica gel which has a particle diameter of from 20 to 45 ~m, a pore volume of 1.75 cm3/g and a surface area of 320 m2/g ar,d is of the formula SiO2, (Ib) butyloctylmagnesium and (~c) hydrogen chloride, by ~3~ 3 - 10 - O.Z. 0050/39143 a method in which first (1.1.1) in a first substage, in n-heptane and with con-stant thorough mixing by means of stirring at room tem-perature, the finely divided silica gel (Ia) and the organo-magnesium compound (Ib) are combined, 2.5 molar parts ofthe organomagnesium compound (Ib) being used per 10 molar parts of silicon of the silica gel tIa), and the substances combined are kept at 90C for 1.5 hours, then (1.1.2) in a second substage, with constant thorough mix-ing by means of stirring at 10C, gaseous ch~orinatingagent (Ic) is passed into the product obtained from the first substage, 10 molar parts of the chlorinating agent (Ic) being used per molar part of the organomagnesium com-pound (Ib), the entire mixture is left at a temperature in the stated ran~e for 0.5 hour and the resulting solid-phase product, ie. the carrier (I), is isolated with re-moval of the liquid phase, thereafter (1.2) in a second stage, a solid-stage intermediate is prepared from (I) the carrier obtained in the first stage, 20 (II) ethanol, (III) titanium tetrachloride and (IV) di-n-butyl phthàlate, by a method in which first (1.2.1) in a first substage, ;n n-heptane and with con-stant thorough mixing by means of stirring at room tem-perature, the carrier (I) and the ethanol ~II) are com-bined, 3 molar parts of the ethanol (II) being used perm~lar part of magnesium of th~ carrier (I), and the sub-stances combined are kept at 80C for 1.5 hours, then (1.2.2) in a second substage, ~ith constant thorough mix-;ng by means of stirring at room temperature, the titan-ium tetrachloride (III) is introduced into the reactionmixture resulting from the first substage, 6 molar parts of the titanium tetrachloride (III) being used per molar part of magnesium of the carrier (I), after which the di-n-butyl phtha~ate is introduced, 0.30 molar part of the phthalate (IV) be;ng used per molar part of mag-nesium of the carrier (I), the substances combined are kept at 120C for 2 hours with stirring, and the resu~ting ~3~ 3`3 - 11 - O.Z. 0050/39143 solid-phase intermediate is isolated with removal of - the liquid phase by filtration under suction, then (1.3) in a third stage, the solid-phase intermediate ob-tained in the second stage is subjected to a continuous extraction with titanium tetrachloride at 125C in the course of 2 hours, 140 parts by weight of the titanium tetrachloride being used per 10 parts by weight of the solid-phase intermediate obtained in the second stage, after which the resulting solid-stage intermediate is isolated by filtration, and finally (1.4) in a fourth stage, the solid-phase product obtained in the third stage is washed with n-heptane until the n-heptane takes up virtually no more titanium tetrachloride, and the titanium component (1) is obtained in this man-ner; it contains 3.5% by weight of titanium, 6.0X byweight of magnesium and 23~ by weight of chlorine.
Polymerization A steel au~oclave, having a voLume of 10 l and er~uipped with a stirrer, is charged with 50 g of poly-propene powder~ 10 millimoles of triethylaluminum (in the form of a 1 molar solution in n-heptane) as aluminum component (2), 1 millimole of triethoxyphenylsilane (in the form of a 1 molar solution in n-heptane), as silane component (3), 5 liters (S.T.P.) of hydrogen and finally 100 mg (g 0.07 millimole of titanium) of the titanium component (1) described above, at 30C. The reactor tem-perature is brsught to 70C ;n the course of 10 minutes, and the reactor pressure is brought to 28 bar in this time by forcing in gaseous propene.
The actual polymerization is carried out with constant stirring at 70C and under 28 bar in the course of 2 hours, monomer consumed during this procedure being continuously replaced with fresh monomer.
The productivity of the catalyst component (1), the heptane-soluble fraction (as a measure of the iso-tacticity) and the particle size distribution of the re-sulting polymer are summarized in the Table below.
~31~8~33 - 12 - O.Z. 0050/39143 The procedure described in Example 1 is followed, with the sole exception that the same molar amount of di-methoxyditoluylsilane is used as silane component (3).
The result of the polymerization carried out in this manner is likewise shown in the Table below.
COMPARATIVE EXPERIMENT
Preparation of the titanium component The procedure described in Example 1 of European Laid-Open Application 0,195~497 is followed.
The resulting titanium component contains 3.6%
by weight of titan;um, 4.4X by weight of magnesium and 16X by weight of chlorine.
Polymerization This is carried out as described in Example 1, but using, instead of the titanium component described there, the same molar amount of the titanium component defined abo~e.
The polymerization result achieved is once again shown in the Table below.
~ :., .~.. - - . , ~3048~
- 13 - 0. Z . 0050/39143 o Q~
C V
o U E u~
U ~
~ ~ ~ `O
C O~ ~, ~
O
-U~ 00 0 N
E ~ ~ ~--~_ C ~ C~
O I O
~_ V U~ ~ O`
. U~
~ O
~:1 CJ U~
O ~ ~ ~0 I
Il~ O r- O~
U O
U~
`O O
~ o ~ r~
-,_ O C V
, O` O O
u r ~J ~ a~
~ ~ _, I
~ U
~ ~0 V O O O
U ~1 O O O
~ ~. O` ~ U~
O 1~ O ~i M
O
-(I) C
~ ~ ~ E
_ __' L ~ _ E E Q QJ
~ ~J E /:~
X X o X
~LI LLJ ~ ~
~L3~ 33 - 14 - O.Z. OOSC/39143 As shown in the Table, the catalyst component from the Comparative Experiment has a substantially lower productivity and stereospecificity than the catalyst com-ponents fro0 the Examples according to the invention.
S Moreover, the particle size distribution is shifted to a range of undesirably large particles.
Polymerization processes of this type are known;
their special feature compared with other similar processes - 2 - O.Z. 0050/39143 is the specific embodiment of the catalyst system, and the processes disclosed in European Laid-Open Applica-tions 0,014,523, 0,045,977, 0,171,200 and 0,195,497 and in ~ritish Patencs 2,101,609 and 2,10i,611 may be mentioned as prototypes for the present case.
The specific embodiments of the catalyst systems are employed ;n order to açhieve certain purposes, such as the following:
The catalyst system should be easy to prepare and give a high yield of polymer which must contain a very large isotactic fraction. The catalyst system should moreover produce polymers having spec;al morpho-logical properties, for example uniform particle size and/or a smaller fraction of very ~ine particles and/or a high bulk density~ In addition to these parameters which are important for controlling the polymerization systems, ~ork;ng up the polymers and/or processing them, a lo~ halogen content in the polymer is also important, particularly with regard to corrosion problems; this can ZO be achieved by increasing the polymer yield and/or by means of a catalyst system which contains very little halogen.
In the prior art, some of these purposes can be achieved only by very expensive methods or if other purposes are neglected:
For example, European Laid-Open Application 0,045,977 descr;bes a catalyst system consisting of ac-tive MgClz, T;Cl4 and a phthal;c acid derivative. With sil;c3 gel as the shape-impart;ng carr;er, the produc-tivity of the catalyst system is, however~ no longersatisfactory; furthermore, the chlor;ne content of the polymers is comparatively high.
European Laid-Open Applications 0,014,523 and 0,171,200 and ~ritish Patents 2,101,609 and 2,101,611 describe catalyst systems whose t;tanium component is obtained by treating a solid, inorganic oxide ~ith an organ;c magnes;um compound, a Le~is base and titanium ~3~ 83 _ 3 _ o.z. 0050~39143 tetrachloride, it be;ng necessary in addition to use a halogenating agent ~hich is not titanium tetrachloride and/or an organic compound of the metals boron, aluminum~
silicon or tin or a boron trihalide or a halogen-containing alcohol. In spite of an expensive and tedious preparation procedure, the productivity of the corresponding catalyst system is unsatisfactory.
European Laid-Open Application 0,195,497 describes a catalyst system whose titanium component is obtained by treating SiO2 with an organic Mg compound, an alcohol, a Lewis base and TiCl4. In the case of this catalyst sys-tem too, the productivity ;s low.
The known processes are thus unsatisfactory, par-ticularly with regard to good productivity and a low chlorine content in the polymers, in combination with high isotacticity and good morphology.
It is an object of the present invention to pro-vide a titanium component which, compared with the prior art processes, has good productivity and is also capable of giving polymers hav;ng a low chlorine content, high isotacticity and good morphology.
~ e have found that this object is achieved by a catalyst system which contains a titanium component (1) prepared in a particuLar manner from (I) a special car-rier obtained in a defined manner from (Ia) a certa;n finely divided silica gel, (Ib) a certain organomagnesium compound and (Ic) a certain gaseous chlorinating agent, and (II) a certain alkanol, (III) titanium tetrachloride and (IV) a specially selected phthalic acid derivative.
The present invention accordingly relates to a process for the preparation of homopolymers of propene and co~olymers of propene ~ith m;nor amounts of other C2-C12-~-mcnool~fins, in particular C2-C6-r~-mono-olefins, by polymerization, in particular by dry-phase polymerization of the monomer or monomers at from 20 to 160C, in particular fro~ 50 to 120C, uncJer from 1 to 100~ in particular from 20 ~o 70, bar using a Ziegler-13~1 !33 - 4 - o.z. OOS0/39143 Natta catalyst system consisting of (1) a titanium component which is based on a finely divi-ded, shape-imparting silica gel and~ in addition to titanium, contains magnesium, chlorine and a benzene-carboxylic acid derivative, ~2) an aluminum component of the formula AlR3, where R is alkyl of not more than 8, in particular not more than 4, carbon atoms, and (3) a silane component of the formula Rl si l oR2 ) 4-n where R1 is a saturated aliphatic and/or aromatic hydrocarbon radical of not more than 16, preferably not msre than 10, carbon atoms, R2 is alkyl of not more than 15, preferably not more than 8, in particu-lar not more than 4~ carbon atoms and n is from 0 to 3, preferably from 0 to 2, in particular 1, with the prov;sos that the atomic ratio of titanium from the titanium component (1) to aluminum from the aluminum component (2) is from 1 : 10 to 1 : 800, in particular from 1 : 20 to 1 : 200, and the molar ratio of aluminum component (2) to silane component (3) is from 1 : 0.03 to 1 : 0.8, in particular from 1 : 0.05 to 1 : 0.5.
In the novel process, the titanium component (1) used is one which is obtained by a method in ~hich first (1.1) in a first stage (1), a carr;er is prepared from (Ia) a finely divided silica gel uhich has a particle diameter of from 1 to 1,000 ~m, in particular from 10 to 4Q0 ~m, a pore volume of from 0.3 to 3, in particular from 1 to 2.5, c~3/g and a surface area of from 100 to 1,000, in particular from 200 to 400, m2/g and is of the formula SiO2 . a Al203, where a is from 0 to 2, in par-ticular from 0 to 0.5, (Ib) an organomagnesium compound of the formula MgR3R4, where R3 and R4 are each C2-C10-a~kyl, preferably C4 C8-alkyl, and (Ic) a gaseous 13()~3 _ 5 _ o z. 0050/39143 chlorinating agent of the formula ClZ, where Z is Cl or H, preferably H, by a method in which first (1~1.1) in a~
first substage, in a liquid inert hydrocarbon, in par-ticular an alkane, with constant thorough mixing at room temperature, the finely divided silica gel (Ia) and the organomagnesium compound (Ib) are combined, from 1 to 10, in particular from 1.5 to 4, molar parts of the organo-magnesium compound (Ib) being used per 10 molar parts of silicon of the silica gel (Ia), and the substances com-10 bined are kept at from 20 to 140C, in particular from 60 to 40C~ for from 0.5 to 5, in particular from 1 to 2, hours, then (1.1.2) in a second substage, with constant thorough mix-ing at from -20 to ~80C, in particular 0 to ~20C, the gaseous chlorinating agent (Ic) is passed into the pro-duct obtained from the first substage, from Z to 40, in particular from 10 to 20, molar parts of the chlorinat;ng agent (Ic) being used per molar part of the organomagnes-ium compound (Ib), the entire mix~ure is left at a te~-perature in the stated range for from 0.5 to 5 hours~ inparticular fro0 0.5 to 1 hour, and the resulting solid-phase product, ie. the carrier (I), is isolated with re-moval of the liquid phase, thereatter (1.2) ;n a second stage, a solid-phase intermediate is prepared from (I) the carrier obtained in the first stage, (II) a Cz-C6-alkanol, in particular ethano(, (III) titan-iu~ tetrachloride and (IV) a phthalic acid derivati~e of the for~ula , ~c~x co-r .
~here X and Y together form oxygen or X and r are each chlorine or C1-C10-alkoxy, preferably Cz-C8-alko~y, in particular butoxy, by a method in which first (1.2~1) in a first substage, in a liquid inert hydrocarbon, in particular an alkane, and with constant thorough mix-ing at room temperature, the carrier (I) and the alkanol ~3~ 83 - 6 - O.Z. 0050/39143 tII) are combined, from 1 to 5, in par~icular from 2.5 to 3.5, molar parts of the alkanol (II) being used per molar part of magnesium of the carrier (I), and the sub-stances combined are kept at from 20 to 140C, in particu-lar from 70 to 90C, for from 0~5 to 5, in particular from 1 to Z, hours, then (1.2.2) in a second substage, with constant thorough m;x-ing at room temperature, the titanium tetrachlor;de (III) is introduced into the react;on mixture resulting from the first substage, from 2 to 20, in particular from 4 to 8, molar parts of the titaniùm tetrachloride (III) being used per molar part of magnesium of the carrier (I), the substances combined are kept at from 10 to 150C, in particular from 90 to 120C, for from 0.5 to 5, in par-ticular from 1 to 2, hours, and the resulting solid-phase intermediate is isolated with removal of the liquid phase, with the proviso that the phthalic acid derivative (IV) is in~roduced in the course of one or both of the substages ~1.2.1) and (1.2.2), from 0.01 to 1, preferably from 0.1 20 to 0.4, in particular from 0.25 to 0.30, molar part of the phthalic acid derivative (IV) being used per molar part of magnesium of the carrier (I), then (1.3) in a third stage, the solid-phase intermediate ob-tained from the second stage ;s subjected to a single-stage or multi-stage or continuous extraction with titan-ium tetrachloride or a mixture of titanium tetrachloride and ethylbenzene, containing not less than 10, in particu-lar not less than 20, % by weight of titanium tetrachlor-ide, at from 100 to 150C, in particular from 115 to 30 135C, in the course of from 0.2 to 5, ;n part;cular from 1.5 to 3, hours, a total of from 10 to 1,000, preferably from Z0 to 800, in particular from 150 to 300, parts by weight of the extracting agent being used per 10 parts by weight of the solid-phase intermediate obtained from the second stage, and finally (1.4) in a fourth stage, the solid-phase product formed in the third stage is washed with a l;quid ;nert hydrocarbon, ~3~D4~33 - 7 - O.Z. 0050/39143 in particular an alkane, until the hydrocarbon takes up virtually no more titanium tetrachloride, and the titan-ium component (1) is obtained in this manner.
We have found that the novel process can be car-ried out particularly successfully if the catalyst sys-tem used contains a silane component (3) which is of the formula R~ Si(OR~ n where R1 is phenyl or C1-C4-alkylphenyl, especially methyl- or ethylphenyl, R2 is alkyl of not more than 4 carbon atoms, especially methyl or ethyl, and n is 1 or 2.
Regarding the process according to the invention, the following may be noted specifically:
Provided that the defining feature is taken into account, the polymerization process as such can be car-ried out in virtually any relevant conventional techno-logical embodiments, for example as a batchwise, periodic or, in particular, continuous process eg. a suspension polymerization process or, in parl:icular, dry-phase polymerization process. The stated technolog;cal embodi-ments, ie. the technological versions of the polymeriza-tion of ~-monoolefins by the Ziegler-Natta method~ are well known from the literature and in practice, so that no further discussion is required here.
For the sake of completeness, it may be mentioned that, in the novel process, it is also possible to regu-late the molecular weights of the poly0ers by the rele-vant conventional measures, for example by means of regu-lators, ;n particular hydrogen~
Regarding the composition of the novel catalyst system, the following may be stated specifically:
t1) the finely divided silica gel ~Ia) to be used for the preparation of the titanium component is in general an aluminosilicate or, in particular, a silica; it is im-portant that it has the required properties. We have ~3~ 3 - 8 - O.Z. 0050/39143 found that the commercial silica gels which meet the stated specification and are conventionally used for carriers are very suiteble.
The organomagnesium compound (Ib) likewise to be used may be, for example, dibutylmagnesium, dihe~ylmag-nesium or, in particular, butyloctylmagnesium.
The gaseous chlorinating agent tIc) also to be used should be very dry and pure; it consists of chlorine or, in particular, hydrogen chloride.
The liquid inert hydrocarbon which serves as an assistant can be a hydrocarbon of the type usually com-bined with titanium components for catalyst systems of the Ziegler-Natta type ~ithout damage to the catalyst system or its titanium component. Examples of suitable hydrocarbons are pentanes~ hexanes, heptanes, gasolines and cyclohexaneu The alkanols (II) to be used for the preparation of the titanium compcnent (1) can be commercial ones;
they should advan~ageously have very high purities. Exam-ples of highly su;table alkanols are ethanol, n-propyl alcohol, isopropyl alcohoL, n-butyl alcohol, isobutyl alcohol and tert-butyl alcohol; ethanol is particularly suitable.
The titanium tetrachloride (III) l ikewise to be used for the preparation of the titanium component (1) should be one convent;onally used in Ziegler-Natta catal-yst systems; the ethylben2ene which may be used as a mix-ture ~ith the t;tanium tetrachloride should be very pure and dry.
Further~ore~ the phthalic acid derivat;ve (IV) to be used, which ;s defined in detail above, can be a commercial one; it should advantageously have high pur-ity. We have found that dibutyl phthalate is very par-ticularly suitable for the purpose of the present inven-tion; however, other dialkyl phthalates and phthalic an-hydr;de and phthaloyl d;chlor;de are also su;table.
The hydrocarbon to be used for the preparation ~a3~ 8,3 - 9 - O.Z. 0050/39143 of the titanium component (1) in stage (1.4) can likewise be a conventional one; it should advantageously have a relatively high purity.
The preparation of the titanium component (1) is S simple and can be carried out by the skilled worker with-out explanations. Regarding stages (1.1), (1.2) and (1.3), all that need be stated is that the isolation of the par-ticular resulting solid is advantageously carried out by filtration under suction~
(2) Suitable aluminum components (2~ of the stated formula are the relevant conventional ones of this for-mula; they are sufficiently well known from the literature and in practice that no further discussion is required.
An example of an outstanding member is triethylaluminum.
(3) The silane component (3) which completes the catalyst system is, in particular, a trialkyoxy(alkyl)-phenylsilane or a dialkoxydi(alkyL)phenylsilane of the stated formula. Triethoxytoluylsilane is an outstanding member; other examples are triethoxyethylphenylsilane, dimethoxyditoluylsilane and diethoxyditoluylsilane.
The novel process permits the preparation of homo-polymers and copolymers, for e~am~)le of the binary or ternary type, including block copolymers, of propene with minor amounts of other C2-C~ monoolefins in an advantageous manner~ a-monoolefins wh;ch are particu-larly suitab~e comonomers to be polymerized being ethene, but-1-ene, 4-methylpent-1-ene and hex-1-ene;
however, n-oct-1-ene, n-dec-1-ene and n-dodec-1-ene are, for example, also suitable.
Preparation of the titanium component (1) The procedure is as follows: first (1.1) in a first stage (I), a carrier is prepared from (Ia) a finely divided silica gel which has a particle diameter of from 20 to 45 ~m, a pore volume of 1.75 cm3/g and a surface area of 320 m2/g ar,d is of the formula SiO2, (Ib) butyloctylmagnesium and (~c) hydrogen chloride, by ~3~ 3 - 10 - O.Z. 0050/39143 a method in which first (1.1.1) in a first substage, in n-heptane and with con-stant thorough mixing by means of stirring at room tem-perature, the finely divided silica gel (Ia) and the organo-magnesium compound (Ib) are combined, 2.5 molar parts ofthe organomagnesium compound (Ib) being used per 10 molar parts of silicon of the silica gel tIa), and the substances combined are kept at 90C for 1.5 hours, then (1.1.2) in a second substage, with constant thorough mix-ing by means of stirring at 10C, gaseous ch~orinatingagent (Ic) is passed into the product obtained from the first substage, 10 molar parts of the chlorinating agent (Ic) being used per molar part of the organomagnesium com-pound (Ib), the entire mixture is left at a temperature in the stated ran~e for 0.5 hour and the resulting solid-phase product, ie. the carrier (I), is isolated with re-moval of the liquid phase, thereafter (1.2) in a second stage, a solid-stage intermediate is prepared from (I) the carrier obtained in the first stage, 20 (II) ethanol, (III) titanium tetrachloride and (IV) di-n-butyl phthàlate, by a method in which first (1.2.1) in a first substage, ;n n-heptane and with con-stant thorough mixing by means of stirring at room tem-perature, the carrier (I) and the ethanol ~II) are com-bined, 3 molar parts of the ethanol (II) being used perm~lar part of magnesium of th~ carrier (I), and the sub-stances combined are kept at 80C for 1.5 hours, then (1.2.2) in a second substage, ~ith constant thorough mix-;ng by means of stirring at room temperature, the titan-ium tetrachloride (III) is introduced into the reactionmixture resulting from the first substage, 6 molar parts of the titanium tetrachloride (III) being used per molar part of magnesium of the carrier (I), after which the di-n-butyl phtha~ate is introduced, 0.30 molar part of the phthalate (IV) be;ng used per molar part of mag-nesium of the carrier (I), the substances combined are kept at 120C for 2 hours with stirring, and the resu~ting ~3~ 3`3 - 11 - O.Z. 0050/39143 solid-phase intermediate is isolated with removal of - the liquid phase by filtration under suction, then (1.3) in a third stage, the solid-phase intermediate ob-tained in the second stage is subjected to a continuous extraction with titanium tetrachloride at 125C in the course of 2 hours, 140 parts by weight of the titanium tetrachloride being used per 10 parts by weight of the solid-phase intermediate obtained in the second stage, after which the resulting solid-stage intermediate is isolated by filtration, and finally (1.4) in a fourth stage, the solid-phase product obtained in the third stage is washed with n-heptane until the n-heptane takes up virtually no more titanium tetrachloride, and the titanium component (1) is obtained in this man-ner; it contains 3.5% by weight of titanium, 6.0X byweight of magnesium and 23~ by weight of chlorine.
Polymerization A steel au~oclave, having a voLume of 10 l and er~uipped with a stirrer, is charged with 50 g of poly-propene powder~ 10 millimoles of triethylaluminum (in the form of a 1 molar solution in n-heptane) as aluminum component (2), 1 millimole of triethoxyphenylsilane (in the form of a 1 molar solution in n-heptane), as silane component (3), 5 liters (S.T.P.) of hydrogen and finally 100 mg (g 0.07 millimole of titanium) of the titanium component (1) described above, at 30C. The reactor tem-perature is brsught to 70C ;n the course of 10 minutes, and the reactor pressure is brought to 28 bar in this time by forcing in gaseous propene.
The actual polymerization is carried out with constant stirring at 70C and under 28 bar in the course of 2 hours, monomer consumed during this procedure being continuously replaced with fresh monomer.
The productivity of the catalyst component (1), the heptane-soluble fraction (as a measure of the iso-tacticity) and the particle size distribution of the re-sulting polymer are summarized in the Table below.
~31~8~33 - 12 - O.Z. 0050/39143 The procedure described in Example 1 is followed, with the sole exception that the same molar amount of di-methoxyditoluylsilane is used as silane component (3).
The result of the polymerization carried out in this manner is likewise shown in the Table below.
COMPARATIVE EXPERIMENT
Preparation of the titanium component The procedure described in Example 1 of European Laid-Open Application 0,195~497 is followed.
The resulting titanium component contains 3.6%
by weight of titan;um, 4.4X by weight of magnesium and 16X by weight of chlorine.
Polymerization This is carried out as described in Example 1, but using, instead of the titanium component described there, the same molar amount of the titanium component defined abo~e.
The polymerization result achieved is once again shown in the Table below.
~ :., .~.. - - . , ~3048~
- 13 - 0. Z . 0050/39143 o Q~
C V
o U E u~
U ~
~ ~ ~ `O
C O~ ~, ~
O
-U~ 00 0 N
E ~ ~ ~--~_ C ~ C~
O I O
~_ V U~ ~ O`
. U~
~ O
~:1 CJ U~
O ~ ~ ~0 I
Il~ O r- O~
U O
U~
`O O
~ o ~ r~
-,_ O C V
, O` O O
u r ~J ~ a~
~ ~ _, I
~ U
~ ~0 V O O O
U ~1 O O O
~ ~. O` ~ U~
O 1~ O ~i M
O
-(I) C
~ ~ ~ E
_ __' L ~ _ E E Q QJ
~ ~J E /:~
X X o X
~LI LLJ ~ ~
~L3~ 33 - 14 - O.Z. OOSC/39143 As shown in the Table, the catalyst component from the Comparative Experiment has a substantially lower productivity and stereospecificity than the catalyst com-ponents fro0 the Examples according to the invention.
S Moreover, the particle size distribution is shifted to a range of undesirably large particles.
Claims (3)
1. A process for the preparation of homopolymers of propene and copolymers of propene with minor amounts of other C2-C12-.alpha.-monoolefins by polymerization of the mono-mer or monomers at from 20 to 160°C and under from 1 to 100 bar using a Ziegler-Natta catalyst system consisting of (1) a titanium component which is based on a finely divi-ded, shape-imparting silica gel and, in addition to titanium, contains magnesium, chlorine and a benzene-carboxylic acid derivative, (2) an aluminum component of the formula AlR3, where R is alkyl of not more than 8 carbon atoms, and (3) a silane component of the formula R? Si(OR2)4-n where R1 is a saturated aliphatic and/or aromatic hydrocarbon radical of not more than 16 carbon atoms, R2 is alkyl of not more than 15 carbon atoms and n is from 0 to 3, with the provisos that the atomic ratio of titanium from the titanium component (1) to aluminum from the aluminum component (2) is from 1 : 10 to 1 : 800 and the molar ratio of aluminum component (2) to silane component (3) is from 1 : 0.03 to 1 : 0.8, wherein the titanium component (1) used is one which is obtained by a method in which first (1.1) in a first stage (I), a carrier is prepared from (Ia) a finely divided silica gel which has a particle dia-meter of from 1 to 1,000 µm, a pore volume of from 0.3 to 3 cm3/g and a surface area of from 100 to 1,000 m2/g and is of the formula SiO2 . a Al2O3, where a is from 0 to 2, (Ib) an organomagnesium compound of the formula MgR3R4, where R3 and R4 are each C2-C10-alkyl, and (Ic) a gaseous chlorinating agent of the formula ClZ, where Z is Cl or H, by a method in which first (1.1.1) in a first substage, in a liquid inert hydrocarbon, - 16 - O Z. 0050/39143 with constant thorough mixing at room temperature, the finely divided silica gel (Ia) and the organomagnesium compound (Ib) are combined, from 1 to 10 molar parts of the organomagnesium compound (Ib) being used per 10 molar parts of silicon of the silica gel (Ia), and the sub-stances combined are kept at from 20 to 140°C for from 0.5 to 5 hours, then (1.1.2) in a second substage, with constant thorough mix-ing at from -20 to +80°C, the gaseous chlorinating agent (Ic) is passed into the product obtained from the first substage, from 2 to 40 molar parts of the chlorinating agent (Ic) being used per molar part of the organomagnesium compound (Ib), the entire mixture is left at a temperature in the stated range for from 0.5 to 5 hours, and the result-ing solid-phase product, ie. the carrier (I), is isolated with removal of the liquid phase, thereafter (1.2) in a second stage, a solid-phase intermediate is prepared from (I) the carrier obtained in the first stage, (II) a C1-C8-alkanol, (III) titanium tetrachloride and (IV) a phthalic acid derivative of the formula where X and Y together form oxygen or X and Y are each chlorine or C1-C10-alkoxy, by a method in which first (1.2.1) in a first substage, in a liquid inert hydrocarbon and with constant thorough mixing at room temperature, the carrier (I) and the alkanol (II) are combined, from 1 to 5 molar parts of the alkanol (II) being used per molar part of magnesium of the carrier (I), and the substances combined are kept at from 20 to 140°C for from 0.5 to 5 hours, then (1.2.2) in a second substage, with constant thorough mix-ing at room temperature, the titanium tetrachloride (III) is introduced into the reaction mixture resulting from the first substage, from 2 to 20 molar parts of the titan-ium tetrachloride (III) being used per molar part of - 17 - O.Z. 0050/39143 magnesium of the carrier (I), the substances combined are kept at from 10 to 150°C for from 0.5 to 5 hours, and the resulting solid-phase intermediate is isolated with re-moval of the liquid phase, with the proviso that the phthalic acid derivative (IV) is introduced in the course of one or both of the substages (1.2.1) and (1.2.2), from 0.01 to 1 molar part of the phthalic acid derivative (IV) being used per molar part of magnesium of the carrier (I), then (1.3) in a third stage, the solid-phase intermediate ob-tained from the second stage is subjected to a single-stage or multi-stage or continuous extraction with titan-ium tetrachloride or a mixture of titanium tetrachloride and ethylbenzene, containing not less than 10% by weight of titanium tetrachloride, at from 100 to 150°C in the course of from 0.2 to 5 hours, a total of from 10 to 1,000 parts by weight of the extracting agent being used per 10 parts by weight of the solid-phase intermediate obtained from the second stage, and finally (1.4) in a fourth stage, the solid-phase product formed in the third stage is washed with a liquid inert hydro-carbon until the hydrocarbon takes up virtually no more titanium tetrachloride, and the titanium component (1) is obtained in this manner.
2. A process as claimed in claim 1, wherein a cata-lyst system is used whose silane component (3) is of the formula R? Si(OR2)4-n where R1 is phenyl or C1-C4-alkylphenyl, R2 is alkyl of not more than 4 carbon atoms and n is 1 or 2.
3. A process as claimed in claim 2, wherein a cata-lyst system is used whose silane component (3) is of the formula R? Si(OR2)4-n where R1 is methyl- or ethylphenyl, R2 is methyl or ethyl - 18 - O.Z. 0050/39143 and n is 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3713943.6 | 1987-04-25 | ||
| DE19873713943 DE3713943A1 (en) | 1987-04-25 | 1987-04-25 | METHOD FOR PRODUCING HOMO AND COPOLYMERISATES OF PROPEN BY MEANS OF A ZIEGLER-NATTA CATALYST SYSTEM |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1304883C true CA1304883C (en) | 1992-07-07 |
Family
ID=6326327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000564511A Expired - Lifetime CA1304883C (en) | 1987-04-25 | 1988-04-19 | Preparation of homopolymers and copolymers of propene using a ziegler-natta catalyst system |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0288845B1 (en) |
| JP (1) | JP2594311B2 (en) |
| AR (1) | AR245149A1 (en) |
| AT (1) | ATE62697T1 (en) |
| AU (1) | AU600353B2 (en) |
| CA (1) | CA1304883C (en) |
| DE (2) | DE3713943A1 (en) |
| ES (1) | ES2021782B3 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3730022A1 (en) * | 1987-09-08 | 1989-03-16 | Basf Ag | METHOD FOR PRODUCING HOMO AND COPOLYMERISATS OF PROPEN BY MEANS OF A ZIEGLER-NATTA CATALYST SYSTEM |
| DE3829519A1 (en) * | 1988-08-31 | 1990-03-01 | Basf Ag | METHOD FOR PRODUCING HOMO AND COPOLYMERISATS OF PROPEN BY MEANS OF A ZIEGLER-NATTA CATALYST SYSTEM |
| DE3830195A1 (en) * | 1988-09-06 | 1990-03-15 | Basf Ag | Process for the preparation of homopolymers and copolymers of propene by means of a Ziegler-Natta catalyst system |
| FI90083C (en) * | 1990-12-20 | 1993-12-27 | Neste Oy | FOER OLEFINPOLYMERISATION AVSETT STEREOSPECIFIKT KATALYSATORSYSTEM |
| US5773537A (en) * | 1992-05-19 | 1998-06-30 | Basf Aktiengesellschaft | Ziegler-natta catalyst systems containing specific organosilicon compounds |
| US6184328B1 (en) | 1994-09-07 | 2001-02-06 | Showa Denko Kabushiki Kaisha | Propylene-based polymer, method for its production, composition thereof, catalyst component for polymerization, and method for its production |
| DE69412266T2 (en) * | 1994-05-12 | 1999-02-11 | Showa Denko K.K., Tokio/Tokyo | PROPYLENE POLYMER, MANUFACTURING METHOD, COMPOSITION THEREOF, POLMERIZATION CATALYST COMPONENT AND MANUFACTURING METHOD |
| WO2003037939A1 (en) | 2001-11-01 | 2003-05-08 | Idemitsu Petrochemical Co., Ltd. | Solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing olefin polymer |
| CN100471829C (en) | 2002-05-24 | 2009-03-25 | 出光兴产株式会社 | Magnesium compound, solid catalyst component for olefin polymerization, catalyst for olefin polymerization, and process for producing polyolefin |
| CN1946664B (en) | 2004-04-23 | 2012-08-15 | 出光兴产株式会社 | Magnesium compound, catalyst for olefin polymerization, and process for producing olefin polymer |
| WO2006013876A1 (en) | 2004-08-03 | 2006-02-09 | Idemitsu Kosan Co., Ltd. | Magnesium compound, solid catalyst component, olefin polymerization catalyst, and method for producing olefin polymer |
| KR20070045280A (en) | 2004-08-24 | 2007-05-02 | 이데미쓰 고산 가부시키가이샤 | Magnesium compound, solid catalyst component, olefin polymerization catalyst, and method for producing polyolefin |
| US7329626B2 (en) | 2004-09-07 | 2008-02-12 | Lummus Novolen Technology Gmbh | Ziegler-Natta catalyst, preparation, and use for the polymerization of alkenes |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301029A (en) * | 1979-01-10 | 1981-11-17 | Imperial Chemical Industries Limited | Olefin polymerization catalyst and the production and use thereof |
| IT1209255B (en) * | 1980-08-13 | 1989-07-16 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLEFINE. |
| US4565796A (en) * | 1984-08-06 | 1986-01-21 | Exxon Research & Engineering Co. | Polymerization catalyst, production and use |
| DE3629583A1 (en) * | 1986-08-30 | 1988-03-03 | Basf Ag | METHOD FOR PRODUCING HOMO AND COPOLYMERISATES OF PROPYLENE BY MEANS OF A ZIEGLER-NATTA CATALYST SYSTEM |
| DE3629932A1 (en) * | 1986-09-03 | 1988-03-10 | Basf Ag | METHOD FOR PRODUCING HOMO AND COPOLYMERISATES OF PROPYLENE BY MEANS OF A ZIEGLER-NATTA CATALYST SYSTEM |
| DE3711919A1 (en) * | 1987-04-08 | 1988-10-27 | Basf Ag | METHOD FOR PRODUCING HOMO AND COPOLYMERISATS OF PROPEN BY MEANS OF A ZIEGLER-NATTA CATALYST SYSTEM |
-
1987
- 1987-04-25 DE DE19873713943 patent/DE3713943A1/en not_active Withdrawn
-
1988
- 1988-04-16 DE DE8888106087T patent/DE3862417D1/en not_active Expired - Lifetime
- 1988-04-16 EP EP88106087A patent/EP0288845B1/en not_active Expired - Lifetime
- 1988-04-16 AT AT88106087T patent/ATE62697T1/en not_active IP Right Cessation
- 1988-04-16 ES ES88106087T patent/ES2021782B3/en not_active Expired - Lifetime
- 1988-04-19 CA CA000564511A patent/CA1304883C/en not_active Expired - Lifetime
- 1988-04-22 AR AR88310633A patent/AR245149A1/en active
- 1988-04-22 JP JP63098495A patent/JP2594311B2/en not_active Expired - Fee Related
- 1988-04-26 AU AU15087/88A patent/AU600353B2/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63280707A (en) | 1988-11-17 |
| ATE62697T1 (en) | 1991-05-15 |
| EP0288845B1 (en) | 1991-04-17 |
| AU600353B2 (en) | 1990-08-09 |
| ES2021782B3 (en) | 1991-11-16 |
| EP0288845A2 (en) | 1988-11-02 |
| DE3713943A1 (en) | 1988-11-03 |
| AU1508788A (en) | 1988-10-27 |
| JP2594311B2 (en) | 1997-03-26 |
| DE3862417D1 (en) | 1991-05-23 |
| AR245149A1 (en) | 1993-12-30 |
| EP0288845A3 (en) | 1989-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4857613A (en) | Preparation of homopolymers and copolymers of propene using a Ziegler-Natta catalyst system | |
| US5288824A (en) | Preparation of homo- and copolymers of propene by means of a Ziegler-Natta catalyst system | |
| US5773537A (en) | Ziegler-natta catalyst systems containing specific organosilicon compounds | |
| US4107414A (en) | Process for the stereoregular polymerization of alpha olefins | |
| CA1304883C (en) | Preparation of homopolymers and copolymers of propene using a ziegler-natta catalyst system | |
| CA2178077A1 (en) | Process for the (co)polymerization of olefins | |
| JP2999274B2 (en) | Method for producing ethylene polymer | |
| HU195841B (en) | Process for the polymerization of olefins and for the production of catalyst component applicable for the polymerization | |
| CA1339183C (en) | Preparation of homopolymers and copolymers of propene using a ziegler-natta catalyst system | |
| US4159256A (en) | Catalyst for polymerizing olefins and polymerization method of olefins carried out therewith | |
| US5006620A (en) | Preparation of homopolymers and copolymers of propene by means of a Ziegler-Natta catalyst system | |
| GB1566391A (en) | Impact-resistant propylene polymer composition and preparation thereof | |
| CA1332490C (en) | Highly crystalline poly-1-butene, the process for preparing it and the catalyst used in the process | |
| CA1302639C (en) | Preparation of homo- and copolymers of propene using a ziegler-natta catalyst system | |
| US4418184A (en) | Process for preparation of ethylene polymer wax | |
| JP3354987B2 (en) | Catalyst system for stereospecific polymerization of α-olefin, its polymerization method and obtained polymer | |
| JP4767373B2 (en) | Ziegler / Natta catalyst composition modified during manufacturing | |
| JPS6119644B2 (en) | ||
| US4892852A (en) | Transition metal composition | |
| EP1664133B1 (en) | High stereospecific polybutylene polymer and highly active process for preparation thereof | |
| US20030166804A1 (en) | Trivalent organic lanthanoid complex, catalyst for production of (meth) acrylic polymer, and (meth) acrylic polymer | |
| EP0565173B1 (en) | Process for preparing polyolefins with broad molecular-weight distribution | |
| US5773535A (en) | Ziegler-natta catalyst systems containing specific organosilicon compounds | |
| EP0508450A1 (en) | Process for the preparation of 1,5-hexadiene cyclopolymers | |
| CA1199317A (en) | Process of preparing a solid catalytic titanium component and process for the polymerization of 1- alkenes using such a titanium component |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |