GB1565572A – Manufacture of homopolymers and copolymers of -monoolefins and ziegler catalyst components therefor
– Google Patents
GB1565572A – Manufacture of homopolymers and copolymers of -monoolefins and ziegler catalyst components therefor
– Google Patents
Manufacture of homopolymers and copolymers of -monoolefins and ziegler catalyst components therefor
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GB1565572A
GB1565572A
GB4168/77A
GB416877A
GB1565572A
GB 1565572 A
GB1565572 A
GB 1565572A
GB 4168/77 A
GB4168/77 A
GB 4168/77A
GB 416877 A
GB416877 A
GB 416877A
GB 1565572 A
GB1565572 A
GB 1565572A
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titanium
magnesium
weight
parts
catalyst component
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1976-02-03
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BASF SE
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BASF SE
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1976-02-03
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1977-02-02
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1980-04-23
1977-02-02
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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
Description
PATENT SPECIFICATION
Application No 4168/77 ( 22) Filed 2 Feb 1977 Convention Application No 2603920 Filed 3 Feb 1976 in Federal Republic of Germany (DE) Complete Specification published 23 April 1980
INT CL 3 CO 8 F 10/00 4/64 Index at acceptance C 3 P 404 440 446 448 452 474 484 486 574 582 590 600 602 GA ( 54) MANUFACTURE OF HOMOPOLYMERS AND COPOLYMERS OF ce-MONOOLEFINS AND ZIEGLER CATALYST COMPONENTS THEREFOR ( 71) We, BASF AKTIENGESELSCHAFT, a German Joint Stock Company of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following Statement:-
The present invention relates to a process for the manufacture of homopolymers and copolymers of a-monoolefins of 2 to 6 carbon atoms by polymerizing the monomer or monomers at from 30 to 2000 C and pressures of from 0 1 to 200 bars, using a Ziegler catalyst system comprising:
(I) a titanium-containing catalyst component and ( 2) a metal compound of the general formula Me A,__Xn where Me is aluminum, magnesium or zinc, preferably aluminum, A is a hydrocarbon radical of I to 12 carbon atoms, in particular alkyl of I to 12 carbon atoms, and preferably alkyl of 2 to 8 carbon atoms, X is chlorine, bromine, iodine or hydrogen, preferably chlorine or hydrogen, m is the valency of the metal Me and N is a number from 0 to m-I, preferably from 0 to 1, with the proviso that the atomic ratio of titanium from catalyst component (I) to metal (Me) from catalyst component ( 2) is from:0 1 to 1:500, preferably from 1:0 2 to 1:200.
Processes of this type have proved valuable in industrial operation, but still leave scope of a number of minor or major improvements Thus, for example, the titanium-containing catalyst component ( 1) to be employed is in many cases unsatisfactory This is true also of those titanium-containing catalyst components manufactured by starting from a finely divided carrier It is known that these supported catalysts are in general to be preferred, in industrial operation, to other titanium-containing catalyst components, since they permit smooth operation and give good results However, this advantage is offset by the disadvantage that the conventional supported catalysts of the type in question here present some hazards in handling and/or are expensive to manufacture, and cause a relatively high degree of pollution of the environment.
The present invention seeks to provide titanium-containing catalyst components ( 1) which are manufactured starting from a finely divided carrier but do not suffer from the above disadvantages, or do so to a substantially lesser degree, and furthermore prove advantageous in operation and in the result of the process, for example which are able to give a polymer which has particularly advantageous morphological properties.
We have now found that good results may be achieved by means of a titaniumcontaining catalyst component (I) obtained by bringing a particular finely divided silicon oxide carrier into contact with a particular solution formed from a particular alcohol, a titanium trihalide and a magnesium compound, and isolating a solid phase from the resulting dispersion by evaporation.
Accordingly, the present invention provides a process for the manufacture of homopolymer or copolymer of one or more a-monoolefins of 2 to 6 carbon atoms by polymerizing the monomer or monomers at from 30 to 2000 C and from 0 1 to 200 bars by means of a Ziegler catalyst system comprising:
(I) a titanium-containing catalyst component and ( 2) a metal compound of the general formula Me A_-_Xn where Me is aluminum, magnesium or zinc, preferably aluminum, A is a hydrocarbon radical of I to 12 carbon atoms, in particular rt ( 21) ( 31) ( 32) ( 33) ( 44) ( 51) ( 52) ( 11) 1 565 572 1,565,572 alkyl of I to 12 carbon atoms, and preferably alkyl of 2 to 8 carbon atoms, X is chlorine, bromine, iodine or hydrogen, preferably chlorine or hydrogen, m is the valency of the metal Me and N is a number from 0 to m-1, preferably from 0 to I, with the proviso that the atomic ratio of titanium from catalyst component (I) to metal (Me) from catalyst component ( 2) is from 1:0 1 to 1:500, preferably from 1:0 2 to 1:200, wherein the titanium-containing catalyst component ( 2) employed is the solid-phase product (IV) obtained by bringing into contact.
( 1 1) a finely divided, porous, inorganic oxidic material (I) which has a particle diameter of from 1 to 1,000 um, preferably from I to 400 gm, a pore volume of from 0 3 to 3, preferably from 1 to 2 5, cm 3/g and a surface area of from 100 to 1,000, preferably from 200 to 400 m 2/g, and which has the formula Si O 2 a A 12 03, where a is a number from 0 to 2 especially from 0 to 0 5, and ( 1.2) a solution (II) obtained by bringing together (I 1 a) 100 parts by weight of an alcohol of the general formula Z-OH where Z is a saturated hydrocarbon radical of I to 8 carbon atoms, especially a saturated hydrocarbon radical of I to 6 carbon atoms, and preferably alkyl of 1 to 4 carbon atoms, (Ilb) from 0 01 to 6, preferably from 0 04 to 3 5, parts by weight (calculated as titanium) of a titanium trihalide, where the halogen is selected from chlorine and bromine, preferably a titanium trichloride, and (T Ic) from 0 01 to 4, preferably from 0 04 to 2 5, parts by weight (calculated as magnesium) of a magnesium compound which is soluble in the alcohol (Ila), especially of a compound which contains halogen and/or carbon, and preferably a compound which contains chlorine and carbon, to form a dispersion (III), with the proviso that the weight ratio of inorganic oxidic material I to titanium in the titanium trihalide (I 1 b) is from 1:0 01 to 1:0 2, preferably from 1:0 03 to 1:0 15, and the weight ratio of inorganic oxidic material 1 to magnesium in the magnesium compound (Tic) is from 1:0 01 to 1:0 25, preferably from 1:0 03 to 1:015, and the dispersion (III) is evaporated at below 2000 C, preferably below 160 ‘C, and above the melting point of the alcohol (lha) used, until a dry solid residue, i e the solid-phase product (IV), is formed.
The invention also provides the titanium-containing catalyst component (I) defined above and the Ziegler catalyst system defined above including that component.
In relation to comparable conventional processes, a process within the invention is distinguished by the fact that, for example, it provides technical and economic improvements Thus, manufacture of the catalyst is substantially simplified because it can be carried out in one stage, i e by a onevessel process; since, furthermore, it is not necessaryjto use an excess of the titanium compound, in contrast to conventional processes, there is also a significant improvement in respect of economy and reduced pollution of the environment.
Furthermore, a substantial advantage achievable by polymerizing olefins by means of a catalyst within the present invention is that the latter can be obtained in forms which have a relatively high productivity (expressed as amount by weight of polymer per unit weight of titanium) and a relatively low halogen content The inherently undesirable catalyst constituents in the polymer (titanium and halogen) are then present in such low amounts that they no longer interfere and that their removal-which would require a separate process step-is unnecessary The polymers obtainable by a process according to the invention furthermore exhibit other advantageous properties; for example, their morphology conforms to an important range of requirements, namely that the content of pulverulent polymer particles is very low, thereby greatly reducing the hazard of dust explosions, and the shape of the particles is such that not only can the material be stirred easily (an important aspect when manufacturing the polymer), but is also has a high tap density and good free-flowing characteristics, both being advantageous from the point of view of handling the polymers.
The following points of detail of the process of the invention may be noted:
The polymerization process as such cantaking into account the characteristic features thereof-be carried out in virtually all the relevant conventional technological embodiments, i e as a batchwise, cyclic or continuous process, which processes may be, for example, a suspension polymerization, solution polymerization or dry-phase polymerization The said technological embodiments, i e the technological variants of the Ziegler polymerization of olefins-are well known from the literature and from practical experience, so that further details are superfluous The only point still worth noting it that the new titanium-containing catalyst component ( I) can-like corresponding conventional catalyst components-be brought together with the catalyst component ( 2) either outside or inside the polymerization vessel, in the latter case, for example, by spatially 1,565,572 separate introduction of the components, which may be handled in the form of a suspension (catalyst component ( 1)) or of a solution (catalyst component ( 2)) It is also possible, for example, to employ the catalyst component (I) or the combined catalyst components (I) and ( 2) in the form of particles provided with a wax coating; this method is at times of advantage in dry-phase polymerization processes.
The following points should be noted with regard to the new titanium-containing catalyst component (I):
It is manufactured by bringing a finely divided inorganic oxidic material (I) of the type defined above and a particular solution (II), as defined above, into contact with one another, resulting in the formation of a dispersion (III) which is then evaporated until a dry solid product is obtained.
Specifically, the procedure which may be followed is to combine the inorganic oxidic material (I), undiluted or dispersed in an alcohol (advantageously an alcohol as defined under ( 11 a), the dispersion having a solids content of not less than 5 per cent by weight) with the solution ( 11) It is advantageous to keep the batch, after combining the constituents, at from 10 to 160 ‘C, especially from 20 to 1200 C, for from 5 to 120 minutes, especially from 20 to minutes, and only then to evaporate the dispersion (III) which has been formed.
The solution ( 11) can itself be prepared by conventional methods and to this extent exhibits no special features An advantageous technique has proved to be the preparation of the solution (II) by combining a solution containing the alcohol (Ila) and the titanium trihalide ( 11 b) with a solution containing the alcohol ( 11 a) and the magnesium compound (Ic).
The final measure in manufacturing the titanium-containing catalyst component ( 1) is to evaporate the dispersion ( 111) to a dry consistency i e until a dry solid product is obtained, which is the new catalyst component (I) according to the invention.
Specifically, the procedure adopted can be one of the conventional methods of evaporating dispersions under gentle conditions, providing the temperatures specified above are observed This means that it is generally advantageous-and in the case of relatively high alcohols (I 1 a) at times essential-to carry out the evaporation under reduced pressure, the value of which depends on the case in question As a rule of thumb, the temperature/pressure combination should be selected so that the evaporation process is complete after from about I to 10 hours.
It is also advantageous to carry out the evaporation under conditions which ensure that the material undergoing treatment remains homogeneous throughout, for example, rotary evaporators have proved suitable for this purpose Any residual alcohol, for example alcohol bonded by complex formation, is generally not detrimental to the solid-phase product (IV).
The new titanium-containing catalyst components ( 1), i e the solid-phase products (IV), can be employed, within the scope of the process defined at the outset, for the manufacture of the polymers referred to, by the conventional methods employing titanium-containing compounds in the Ziegler polymerization of olefins To this extent, the process according to the invention thus exhibits no special features and reference may be made to the methods of using such catalysts which are wellknown from the literature and from practical experience It merely remains to record that the process is exceptionally suitable for the manufacture of homopolymers of ethylene, and that where copolymers of ethylene with higher amonoolefins, or homopolymers of higher amonoolefins are manufactured, such amonoolefins are, above all, propene, 1butene, 4-methyl-l-pentene and 1-hexene.
The molecular weights of the polymers may be regulated in the relevant conventional manner, especially by means of hydrogen as the regulator.
As regards the composition of the new titanium-containing catalyst components ( 1), the following details should also be noted: ( 1 1) The inorganic oxidic material (I) to be employed is in general an aluminosilicate or, in particular, a silicon dioxide; it is important that the material should have the requisite properties and should be very dry (no further weight loss after 6 hours at 1601 C under 2 mm Hg).
Particularly suitable inorganic oxidic materials are those in accordance with stage (I) of the process described in German Laid-Open Application DOS 24 11 735, especially if hydrogels obtained by the process described in German Laid-Open Application DOS 21 03 243 are used as starting materials.
( 1.2) The alcohols (h 1 a) employed may be, for example, methanol, ethanol, the propanols and the butanols Examples of alcohols which have proved particularly suitable are methanol, ethanol, isopropanol and n-butanol.
The alcohols (Iha) may be employed in the form of individual compounds or of mixtures of two or more of these.
The titanium trihalide ( 1 Ib) employed may be trihalide conventionally used in Ziegler catalyst systems, e g a reaction product obtained by reducing a titanium tetrahalide by means of hydrogen, aluminum or organo-aluminum compounds.
1,565,572 Examples of particularly suitable compounds have proved to be trichlorides of the formula Ti CI 3, as obtained by reduction of titanium tetrachloride by means of hydrogen, and trichlorides of the formula Ti CI 3 3 AICI 3, such as are obtained by reduction of titanium tetrachloride by means of metallic aluminum.
The titanium trihalides may be employed in the form of individual compounds or of mixtures of two or more of these.
The magnesium compound (ic) employed may advantageously be a compound from the following categories:
(A) Magnesium compounds of the general formula Mg(OR’)2, where R’ is a hydrocarbon radical of I to 10 carbon atoms, especially alkyl of I to 6 carbon atoms.
Examples of particularly suitable compounds are magnesium methylate, ethylate, n-propylate, i-propylate, cyclohexylate and phenolate.
Magnesium ethylate and magnesium npropylate are especially suitable.
(B) Complex alkoxides of magnesium with other metals, especially with lithium, boron, aluminum and titanium.
Examples of very suitable compounds are the complex alkoxides of the formulae:
and MglAI(OC 2 H 5)41 l 2, Mg 3 lAI(OC 2 H 5)612, Li 2 lMg(OC 3 H 7)4 l, MglTi(OC 3 H 7)6 l MglB(OC 2 H 5)412.
(C) Magnesium halides of the general formula Mg Z 2, where Z is chlorine, bromine or iodine, especially chlorine or bromine.
Examples of very suitable compounds are magnesium chloride and magnesium bromide.
(D) Complexes of the magnesium halides, mentioned under (C), with alcohols of 1 to 6 carbon atoms, especially with alkanols of I to 6 carbon atoms.
Amongst these, the complexes of the formulae Mg CI 2 6 C 2 H 5 OH and Mg CI 2 4 CH 3 OH are particularly suitable.
(E) Magnesium halide compounds of the general formula Mg Z(OR’), where Z is as defined under (C) and R’ as defined under (A).
A particularly suitable compound amongst these has the formula Mg Cl(OC 2 H 5).
(F) The carriers, containing chemically bonded magnesium, which characterize the subject of German Laid-Open Application DOS 21 63 851, especially manasseite (of the formula Mg 6 A 12 (OH)16 C Oa 4 H 20), which has been brought to a chlorine content of from 50 to 75 per cent by weight chlorination with phosgene.
The magnesium compounds (lic) may be employed in the form of individual compounds or of mixtures of two or more of these: they may of course also be compounds formed in situ when preparing the solution ( 11).
Magnesium compounds where are preferred are those of categories A, C, D and especially F.
The relevant conventional compounds may be used as catalyst component ( 2); examples of suitable compounds are Al(C 2 H 5)3, AI(C 2 H 5)2 C 1, AI(C 2 H 5)2 H, AI(i-C 4 Hg)3, AI(n-C 4 Hg)3, AI(C 8 H,7)3 and isoprenyl-aluminum.
In conclusion, it should be noted that the titanium-containing catalyst components (I) of the invention, i e the products (IV), are sensitive to hydrolysis and to oxidation To this extent, the relevant conventional precautionary measures for Ziegler catalysts (e.g exclusion of moisture, and working under an inert gas atmosphere) should be taken when handling these substances.
EXAMPLE 1
Manufacture of the titanium-containing catalyst component ( 1):
The starting material is a suspension of 20 parts by weight of silicon dioxide (Si O 2, particle diameter 2-40 Am, pore volume 1.6 cm 3/g, surface area 300 m 2/g) in 80 parts by weight of methanol.
This suspension is combined with a solution of 3 25 parts by weight of Ti CI 3 -A 1 C 13 and 5 parts by weight of manasseite (Mg 6 AI 2 (OH)16 CO 3 4 H 20), which has been brought to a chlorine content of 72 per cent by weight of chlorination with phosgene, in 140 parts by weight of methanol The resulting suspension is stirred for 15 minutes at 60 C and the resulting solid-phase reaction product is then isolated by driving off the volatiles on a rotary evaporator which is taken to an operating pressure of 20 mm Hg and an operating temperature of 80 C.
Analysis of the resulting product, i e of the titanium-containing catalyst component ( 1), shows a titanium content of 2 1 per cent by weight and a chlorine content of 13 4 per ceht by weight.
Polymerization:
0.32 part by weight of the titaniumcontaining catalyst component (I) is suspended in 20 parts by weight of heptane and 3 3 parts by weight of Al(C 2 H 5)3 ( 2) are 1,565,572 added (these amounts correspond to an atomic ratio of titanium from catalyst component (I) to metal (Me=aluminum) from catalyst component ( 2) of about 1:206).
The Ziegler catalyst system thus obtained is introduced into a stirred autoclave which is charged with 12 parts by weight (corresponding to about 50, of its capacity) of isobutane The polymerization is then carried out, whilst stirring, for a period of 2 hours, with the following parameters, which are each regulated to maintain constant values: ethylene pressure=l 5 bars, hydrogen pressure= 5 bars, temperature= 100 C The polymerization is then discontinued by letting down the autoclave.
Details of the product are to be found in the Table which follows:
EXAMPLE 2
Manufacture of the titanium-containing catalyst component ( 1):
The starting material is a suspension of 1,000 parts by weight of silicon dioxide (Si O 2, particle diameter 40-150 1 um, pore volume 2 1 cm 3/g, surface area 330 m 2/g) in 3,000 parts by weight of methanol.
This suspension is combined with a solution of 163 parts by weight of Ti CI 3 AICI 3 and 250 parts by weight of manasseite (Mg 8 AI 2 (OH),6 C 03 4 H 20), which has been brought to a chlorine content of 72 per cent by weight by chlorination with phosgene, in 4,000 parts by weight of methanol The resulting suspension is stirred for 60 minutes at 40 C and the resulting solid-phase reaction product is then isolated by driving off the volatiles on a rotary evaporator which is taken to an operating pressure of 20 mm Hg and an operating temperature of 85 C.
Analysis of the resulting product, i e of the titanium-containing catalyst component ( 1), shows a titanium content of 2 21 per cent by weight and a chlorine content of 13 1 per cent by weight.
Polymerization:
0.38 part by weight of the titaniumcontaining catalyst component ( 1) is suspended in 20 parts by weight of heptane and 1 1 parts by weight of AI(C 2 Hs)3 ( 2) are added (these amounts correspond to an atomic ratio of titanium from catalyst component (I) to metal (Me=aluminum) from catalyst component ( 2) of about 1:55).
The Ziegler catalyst system thus obtained is introduced into a stirred autoclave which is charged with 5 liters (corresponding to about 50 / of its capacity) of isobutane The polymerization is then carried out, whilst stirring, for a period of 2 hours, with the following parameters, which are each regulated to maintain constant values:
ethylene= 15 bars, hydrogen pressure= 5 bars, temperature= 100 C The polymerization is then discontinued by letting down the autoclave.
Details of the product are to be found in the Table which follows.
EXAMPLE 3
The titanium-containing catalyst component ( 1 I) is manufactured as in Example 2.
Polymerization:
0.026 part by weight of the titaniumcontaining catalyst component ( 1) is suspended in 10 parts by weight of heptane and 0 3 part by weight of AI(i-C 4 Hg)3 ( 2) is added (these amounts correspond to an atomic ratio of titanium from catalyst component ( 1) to metal (Me=aluminum) from catalyst component ( 2) of about 1:127).
The Ziegler catalyst system thus obtained is introduced into a stirred autoclave which is charged with 80 parts by weight (corresponding to about 20 %, of its capacity) of finely divided polyethylene The polymerization is then carried out, whilst stirring, for a period of 2 hours, with the following parameters, which are each regulated to maintain constant vaiues:
ethylene pressure= 27 5 bars, hydrogen pressure= 5 bars, temperature= 100 C The polymerization is then discontinued by letting down the autoclave.
Details of the product are to be found in the Table which follow.
EXAMPLE 4
Manufacture of the titanium-containing catalyst component ( 1):
The starting material is a suspension of 10 parts by weight of silicon dioxide (Si O 2, particle diameter 2-40 uum, pore volume 2.0 cm 3/g, surface area 320 m 2/g) in 120 parts by weight of ethanol.
This suspension is combined with a solution of 1 63 parts by weight of Ti CI 3 3 AIC 13 and 5 parts by weight of manasseite (Mg 6 A 12 (OH),, C 03 4 H 20), which has been brought to a chlorine content of 72 per cent by weight of chlorination with phosgene, in 40 parts by weight of ethanol.
The resulting suspension is stirred for 15 minutes at 60 C and the resulting solidphase reaction product is then isolated by driving off the volatiles on a rotary evaporator which is taken to an operating pressure of 20 mm Hg and an operating temperature of 80 C Analysis of the resulting product, i e of the titaniumcontaining catalyst component ( 1), shows a titanium content of 2 40 per cent by weight U and a chlorine content of 14 9 per cent by weight.
Polymerization:
0.40 part by weight of the titaniumcontaining catalyst component ( 1) is suspended in 20 parts by weight of heptane and 1 70 parts by weight of Al(C 2 H 5)3 ( 2) are added (these amounts correspond to an atomic ratio of titanium from catalyst component ( 1) to metal (Me=aluminum) from catalyst component ( 2) of about 1:75).
The Ziegler catalyst system thus obtained is introduced into a stirred autoclave which is charged with 5 liters (corresponding to about 50 , of its capacity) of isobutane The polymerization is then carried out, whilst stirring, for a period of 2 hours, with the following parameters, which are each regulated to maintain constant values:
ethylene pressure= 15 5 bars, hydrogen pressure= 5 bars, temperature= 100 C The polymerization is then discontinued by letting down the autoclave.
Details of the product are to be found in the Table which follows.
EXAMPLE 5
Manufacture of the titanium-containing catalyst component ( 1):
The starting material is a suspension of 20 parts by weight of silicon dioxide (Si O 2, particle diameter 2-40 gum, pore volume 1.6 cm 3/g, surface area 300 m 2/g), in 150 parts by weight of n-butanol.
This suspension is combined with a solution of 3 25 parts by weight of Ti C 13 Á 1 CI 3 and 5 0 parts by weight of manasseite (Mg 6 A 12 (OH)16 CO 3 4 H 20), which has been brought to a chlorine content of 71 per cent by weight by chlorination with phosgene, in 400 parts by weight of n-butanol The resulting suspension is stirred for 15 minutes at 80 C and the resulting solid-phase reaction product is then isolated by driving off the volatiles on a rotary evaporator which is taken to an operating pressure of 20 mm Hg and an operating temperature of 80 C.
Analysis of the resulting product, i e of the titanium-containing catalyst component ( 1), shows a titanium content of 2 3 per cent by weight and a chlorine content of 14 0 per cent oy weight.
Polymerization:
0.04 part by weight of the titaniumcontaining catalyst component ( 1) is suspended in 10 parts by weight of heptane and 0 3 parts by weight of AI(i-C 4 H 9)3 ( 2) is added (these amounts correspond to an atomic ratio of titanium from catalyst component ( 1) to metal (Me=aluminum) from catalyst component ( 2) of about 1:79).
The Ziegler catalyst system thus obtained is introduced into a stirred autoclave which is charged with 80 parts by weight (corresponding to about 20 % of its capacity) of finely divided polyethylene The polymerization is then carried out, whilst stirring, for a period of 2 hours, with the following parameters, which are each regulated to maintain constant values:
ethylene pressure= 27 5 bars, hydrogen pressure= 5 bars, temperature= 100 C The polymerization is then discontinued by letting down the autoclave.
Details of the product are to be found in the Table which follows.
Yield of polyethylene parts by weight 2,800 2,800 320 2,100 225 Grams of polyethylene per gram of catalyst component ( 1) 8,750 7,630 12,300 5,250 5,625 gram of titanium 467,000 347,000 537,000 219,000 245,000 Tap density g/l 430 340 370 370 440 FT) sec 7.0 8.5 8.0 6.8 6.7 Melt index MI 2 16 g/10 min.
2.2 5.5 1.7 3.8 1.8 Residual amount of chlorine in the polymer ppm) 17 11 28 ) FT=flow test, carried out in accordance with ASTM D 1895-67, method A ) calculated from the productivity and from the chlorine content of the catalyst
Claims (12)
WHAT WE CLAIM IS:-
1 A process for the manufacture of a homopolymer or copolymer of one or more a-monoolefins of 2 to 6 carbon atoms by polymerizing the monomer or monomers at from 30 to 200 C and from 0 1 to 200 bars by means of a Ziegler catalyst system comprising:
( 1) a titanium-containing catalyst component and ( 2) a metal compound of the general formula Me Am_,Xn where Me is aluminum, magnesium or zinc, Example 1 2 3 4 1,565,572 r, 1,565,572 A is a hydrocarbon radical of I to 12 carbon atoms, X is chlorine, bromine, iodine or hydrogen, m is the valency of the metal Me and N is a number from 0 to m-l, with the proviso that the atomic ratio of titanium from catalyst component (I) to metal (Me) from catalyst component ( 2) is from 1:0 1 to 1:500, wherein the titanium-containing catalyst component ( 1 I) employed is the solid-phase product (IV) obtained by bringing into contact ( 1.1) a finely divided, porous, inorganic oxidic material (I) which has a particle diameter of from I to 1,000 pm, a pore volume of from 0 3 to 3 cm 3/g, and a surface area of from 100 to 1,000 m 2/g, and which has the formula Si O 2 a AI 203, where a is a number from 0 to 2, and ( 1.2) a solution (II) obtained by bringing together (I 1 a) 100 parts by weight of an alcohol of the general formula Z-OH where Z is a saturated hydrocarbon radical of I to 8 carbon atoms, (l Ib) from 0 01 to 6 parts by weight (calculated as titanium) of a titanium trihalide, where the halogen is selected from chlorine and bromine, and (I Ic) from 0.01 to 4 parts by weight (calculated as magnesium) of a magnesium compound which is soluble in the alcohol (I 1 a), to form a dispersion (III), with the proviso that the weight ratio of inorganic oxide material (I) to titanium in the titanium trihalide (l Ib) is from 1:0 01 to 1:0 2, and the weight ratio of inorganic oxidic material (I) to magnesium in the magnesium compound (I Ic) is from 1:0 01 to 1:0 25, and the dispersion (III) is evaporated at below 200 C, and above the melting point of alcohol (I Ia) used, until a dry solid residue, i e the solid-phase product (IV), is formed.
2 A process as claimed in claim 1, wherein the inorganic oxidic material has a particle diameter of from I to 400 pm, a pore volume of from 1 to 2 5 cm 3/g, a surface area of from 200 to 400 m 2/g and the formula Si O 2 a A 1203 where a is a number from 0 to 0 5.
3 A process as claimed in claim I or 2, wherein the solution (II) is obtained by bringing together (I 1 a) 100 parts by weight of an alkanol of I to 4 carbon atoms, (l Ib) 0.04 to 3 5 parts by weight (calculated as titanium) of titanium trichloride, and (I Ic) 0 04 to 2 5 parts by weight (calculated as magnesium) of a magnesium compound which contains halogen and/or carbon and is soluble in the alcohol (I 1 a).
4 A process as claimed in any of claims I to 3, wherein the weight ratio of inorganic oxidic material (I) to titanium in the titanium trihalide (I Ib) is from 1:0 03 to 1:0 15 and the weight ratio of inorganic oxidic material (I) to magnesium in the magnesium compound (I Ic) is from 1:0 03 to 1:0 15.
A process as claimed in any of claims 1 to 4, wherein the magnesium compound (I Ic) is selected from magnesium alkylates of I to 6 carbon atoms in the alkyl, complex alkoxides of magnesium with any of lithium, boron, aluminum and titanium, magnesium chloride, magnesium bromide, complexes of magnesium chloride and of magnesium bromide with alkanols of I to 6 carbon atoms and magnesium halide alkylates in which the halide is chlorine or bromine and the alkylate has I to 6 carbon atoms.
6 A process as claimed in any of claims 1 to 4, wherein the magnesium compound (I Ic) is a carrier containing chemically bonded magnesium according to German Laid-Open Application 21 63 851 which has been brought to a chlorine content of from to 75 per cent by weight by reaction with phosgene.
7 A process as claimed in any of claims I to 6, wherein the titanium trihalide ( 1 Ib) has been obtained by reducing a titanium tetrahalide by means of hydrogen, aluminum or an organoaluminum compound.
8 A process as claimed in any of claims 1 to 7, wherein the metal compound ( 2) is selected from AI(C 2 H 5)3, AI(C 2 Hs)2 CI, AI(C 2 Hs)2 H, AI(i-C 4 Hg)3, AI(n-C 4 Hg)3, Al(C 8 H 17)3 and isoprenyl aluminum.
9 A process as claimed in claim 1 wherein the Ziegler catalyst system used is substantially as described in any of the foregoing Examples.
A Ziegler catalyst system for use in the manufacture of C 2-C 6 a-monoolefin homopolymers and copolymers and as defined in any of claims 1 to 9.
11 A titanium-containing catalyst component for use in a Ziegler catalyst system and as defined in any of claims I to 7.
12 C 2-C 6 a-Monoolefin polymers when manufactured by a process as claimed in any of claims 1 to 9.
J Y & G W JOHNSON, Furnival House, 14-18 High Holborn, London, WCIV 6 DE.
Chartered Patent Agents, Agents for the Applicants.
Printed for Her Majesty’s Stationery Office, by the Courier Press, Leamington Spa, 1980 Published by The Patent Office 25 Southampton Buildings London WC 2 A l AY from which copies may be obtained.
GB4168/77A
1976-02-03
1977-02-02
Manufacture of homopolymers and copolymers of -monoolefins and ziegler catalyst components therefor
Expired
GB1565572A
(en)
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DE2603920A
DE2603920C2
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1976-02-03
1976-02-03
Process for the preparation of homo- and copolymers of C? 2? – to C? 6? -? -Monoolefins
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GB1565572A
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GB1565572A
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1980-04-23
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GB4168/77A
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GB1565572A
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1976-02-03
1977-02-02
Manufacture of homopolymers and copolymers of -monoolefins and ziegler catalyst components therefor
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JPS5295790A
(en)
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(1)
AT348757B
(en)
BE
(1)
BE850855A
(en)
DE
(1)
DE2603920C2
(en)
FR
(1)
FR2340327A1
(en)
GB
(1)
GB1565572A
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Title
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(en)
1980-07-21
1983-07-12
Imperial Chemical Industries Plc
Transition metal composition, production and use
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1978-07-06
1980-01-24
Basf Ag
Ziegler catalyst for alpha:mono:olefin (co)polymerisation – has solid titanium component treated with acyl halide, facilitating mol. wt. control
DE2838989A1
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*
1978-09-07
1980-03-27
Basf Ag
METHOD FOR PRODUCING HOMO AND COPOLYMERISATS FROM ALPHA MONOOLEFINES
DE2847757A1
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*
1978-11-03
1980-05-14
Basf Ag
METHOD FOR PRODUCING HOMOUND AND COPOLYMERISATS FROM ALPHA MONOOLEFINES
US4293673A
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1978-12-28
1981-10-06
Union Carbide Corporation
Spheroidal polymerization catalyst, process for preparing, and use for ethylene polymerization
IT1141068B
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*
1979-09-26
1986-10-01
Nippon Oil Co Ltd
POLYOLEFIN PREPARATION PROCEDURE
JPS5647407A
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1979-09-26
1981-04-30
Nippon Oil Co Ltd
Production of polyolefin
US4376062A
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1979-11-28
1983-03-08
Union Carbide Corporation
Spheroidal polymerization catalyst, process for preparing, and use for ethylene polymerization
US4446288A
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1981-05-05
1984-05-01
Chemplex Company
Polymerization method
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1981-05-05
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Chemplex Company
Polymerization catalyst and method
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1981-07-29
1984-10-23
Chemplex Company
Polymerization method
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Chemplex Company
Polymerization catalyst and method
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1986-01-11
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Basf Ag
USE OF ANTISTATICS TO PREVENT COATING IN THE PRODUCTION OF ULTRA HIGH MOLECULAR POLYETHYLENE IN GAS PHASE REACTORS
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1989-12-19
Mobil Oil Corporation
Catalyst composition for polymerizing alpha-olefins
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1986-01-24
1991-10-08
Mobil Oil Corporation
Process for polymerizing alpha-olefins with trimethylaluminum-activated catalyst
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1986-01-24
1991-09-03
Mobil Oil Corporation
Catalyst composition for polymerizing alpha-olefins
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1987-06-22
1990-06-26
Phillips Petroleum Company
Catalyst and polymerization of olefins
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1987-06-22
1989-08-08
Phillips Petroleum Company
Catalyst and polymerization of olefins
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1987-12-29
1989-09-05
Mobil Oil Corporation
Magnesium oxide-supported ziegler catalyst modified with acid and higher alkanol, and process for preparing narrow MWD HDPE
DE3938723A1
(en)
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1989-11-23
1991-05-29
Basf Ag
CATALYST FOR THE PRODUCTION OF HIGH MOLECULAR HOMO- OR COPOLYMERISATES OF ETHEN AND THE PRODUCTION THEREOF
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2008-06-26
2015-10-27
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process for producing an alpha-olefin polymer
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1976
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DE
DE2603920A
patent/DE2603920C2/en
not_active
Expired
1977
1977-01-17
IT
IT7719377A
patent/IT1076232B/en
active
1977-01-27
US
US05/762,856
patent/US4110523A/en
not_active
Expired – Lifetime
1977-01-28
BE
BE174464A
patent/BE850855A/en
not_active
IP Right Cessation
1977-02-02
AT
AT65577A
patent/AT348757B/en
not_active
IP Right Cessation
1977-02-02
GB
GB4168/77A
patent/GB1565572A/en
not_active
Expired
1977-02-02
FR
FR7702855A
patent/FR2340327A1/en
active
Granted
1977-02-03
JP
JP1030577A
patent/JPS5295790A/en
active
Pending
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Publication number
Priority date
Publication date
Assignee
Title
US4392983A
(en)
1980-07-21
1983-07-12
Imperial Chemical Industries Plc
Transition metal composition, production and use
Also Published As
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DE2603920A1
(en)
1977-08-04
FR2340327A1
(en)
1977-09-02
US4110523A
(en)
1978-08-29
JPS5295790A
(en)
1977-08-11
FR2340327B1
(en)
1982-10-22
ATA65577A
(en)
1978-07-15
DE2603920C2
(en)
1984-10-31
AT348757B
(en)
1979-03-12
IT1076232B
(en)
1985-04-27
BE850855A
(en)
1977-07-28
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Legal Events
Date
Code
Title
Description
1980-07-09
PS
Patent sealed [section 19, patents act 1949]
1993-09-29
PCNP
Patent ceased through non-payment of renewal fee
Effective date:
19930202
