AU599201B2 - Preparation of propylene/ethylene polymers - Google Patents
Preparation of propylene/ethylene polymers Download PDFInfo
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- AU599201B2 AU599201B2 AU11104/88A AU1110488A AU599201B2 AU 599201 B2 AU599201 B2 AU 599201B2 AU 11104/88 A AU11104/88 A AU 11104/88A AU 1110488 A AU1110488 A AU 1110488A AU 599201 B2 AU599201 B2 AU 599201B2
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- Prior art keywords
- propylene
- polymerization zone
- ethylene
- partial pressure
- zone
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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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
- C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
- C08F297/086—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene the block polymer contains at least three blocks
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (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)
Description
signs-.
ture of Applicant (s) or l of Comp.ny and 8iefltures of its Officers "s proscribed by its Article of Associationo by Louis C. G~dt 5999 COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFICATION
(ORIGINAL)
Class I t. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Pviority: Related Art Name of Applicant Address of Applicant I f Actual Inventor: Address for Service BASF AKTIENGESELLSCHAFT D-6700 Ludwigshaf en, Federal Republic of Germany OSIKAR BUECHNER and WOLFGANG GRUBER EDWD. WATERS SONS, 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.
Complete Specification for the invention entitled: PREPARATION OF PROPYLENE/ETHYLENE POLYMERS The following statement is a full description of this inventioai, including the best method of performing it known to US
A
a: I r O.Z. 0050/38931 Preparation of propylene/ethylene polymers The present invention relates to a process for the preparation of propylene/ethylene polymers, in which first in a first polymerization zone, propylene is homopolymerized in the presence of hydrogen as a molecular weight regulator, in a stirred bed of finely divided polymer and in the absence of a liquid reaction medium, from the gas phase, by feeding in a Ziegler-Natta catalyst system consisting of a titanium catalyst component and an organoaluminum catalyst component of the formula ALRmX3-m, where X is OR, chlorine, bromine or hydrogen, R is a C 1
-C
18 -hydrocarbon radical and 15 m is from 1 to 3, ae.,, with or without a further catalyst component, with the provisos that, in this first polymerization zone the reaction is carried out under a total pressure of from 20 to 35 bar and at from 60 to 900C and (ii) the ratio of the propylene partial pressure to the hydrogen partial pressure is from 100:0.1 to 100:15, and then in a second polymerization zone, a mixture of propylene and ethylene is polymerized with the propylene homopolymer present in the reaction product obtained in the first polymerization zone in the presence of hydrogen as a molecular weight regulator, in a stirred bed of finely divided polymer and in the absence of a liquid reaction medium, from the gas phase, by feeding in the reaction product obtained in the first polymerization zone, with or without additional catalyst component with the provisos that, in this second polymerization zone the reaction is carried out under a total pressure of from to 20 bar and at from 50 to 80 0 C, (ii) the ratio of the propylene partial pressure to the ethylene partial pressure is from 100:10 to 100:70 and the ratio of the propylene partial pressure to the hydrogen partial pressure is from 100:2 to 100:70, and (iii) the ratio of the weight aC 2 O.Z. 0050/38931 of the propyLene converted to polymer in the first poLymerization zone to the weight of the propylene/ ethylene mixture converted to polymer in the second polymerization zone is from 100:10 to 100:60.
Processes of this type have been disclosed in a number of variants, and reference may be made, for example, to US Pacent 4,454,299 and South African Patents 0084/3561, 0084/3563 and 0084/5261 as typicaL publications.
The known processes of the type under discussion an particular the resulting products have in general proven useful in industry, including, for example, automotive construction; however, they are still unsatisfactory in one respect or another. For example, it has to date been oooo 15 impossible to obtain polymers having a very advantageous a balance of rigidity, toughness at room temperature and Low temperature impact strength, ie. polymers which are °o particularly suitable for automotive construction, for o B example as material for bumpers or instrument panels. The production of such polymers is a worthwhile aim.
0 0 It is an object of the present invention to modify the process defined at the outset so that it permits poly- 0 00 o mers having the abovementioned property spectrum to be prepared in an advantageous manner.
We have found that this object is achieved if, in the process in question, ethylene is homopolymerized in a further polymerization zone from the gas phase, with certain provisos, and the resulting reaction proo duct is likewise fed to this second polymerization zone The present invention accordingly relates to a process for the preparation of propylene/ethylene polymers, in which first in a first polymerization zone, propylene is homopolymerized in the presence of hydrogen as a molecular weight regulator, in a stirred bed of finely divided 3 O.Z. 0050/38931 polymer and in the absence of a liquid reaction medium, from the gas phase, by feeding in a Ziegler-Natta catalyst system consisting of a titanium catalyst component and an organoaluminum catalyst component of the formula ALRmX3-m, where X is OR, chlorine, bromine or hydrogen, R is a C 1
-C
18 -hydrocarbon radical and m is from 1 to 3, with or without a further catalyst component, with the provisos that, in this first polymerization zone the reaction is carried out under a total pressure of from 20 to 35 bar and at from 60 to 900C a and (ii) the ratio of the propylene partial pressure noOo to the hydrogen partial pressure is from 100:0.1 to 100:15, and then S in a second polymerization zone, a mixture of propylene and ethylene is polymerized with the propylene homopolymer present in the reaction product obtained in the first polymerization zone in the presence of hydrogen as a molecular weight regulator, in a stirred bed of finely *o 20 divided polymer and in the absence of a liquid reaction 09,° medium, from the gas phase, by feeding in the reaction product obtained in the first polymerization zone, with or S without additional catalyst component with the provisos that, in this second polymerization zone the reaction is carried out under a total pressure of from S to 20 bar and at from 50 to 800C, (ii) the ratio of the 0 S"propylene partial pressure to the ethylene partial pressure i"s from 100:10 to 100:70 and the ratio of the propylene partial pressure to the hydrogen partial pressure is from 100:2 to 100:70, and (iii) the ratio of the weight of the propylene converted to polymer in the first polymerization zone to the weight of the propylene/ethylene mixture converted to polymer in the second polymerization zone (B) is from 100:10 to 100:60.
In the process according to the invention, in addition,
I
4 O.Z. 0050/38931 in a further polymerization zone, ethyLene is homopolymerized in the presence or absence of hydrogen as a moLecular weight regulator, in a stirred bed of finely divided polymer and in the absence of a Liquid reaction medium, from the gas phase, by means of Ziegler or Phillips catalysis, with the provisos that, in this further polymerization zone, the reaction is carried out under a total pressure of from 20 to 45 bar and at from 80 to 120 0 C, (ii) where relevant, the ratio of the ethyLene partial pressure to the hydrogen partial pressure is from 100:0.01 to 100:20 and (iii) the ratio of the weight of the propylene converted to polymer in the first polymerization zone to the weight of the ethyLene converted to o0 <oo
L
°oo polymer in the further polymerization zone is from 100:5 to 100:40, and the resulting reaction product is Likewise fed to the second polymerization zone SRegarding the novel process, the following may be stated specifically: Provided that the defining feature is taken into 0 20 account, the polymerization process as such can be carried out in relevant conventional technological embodi- Jo 0 ments, in particular as a cyclic continuous process. The stated technological embodiments, ie. the technological S variants of gas phase block copolymerization, are discussed in sufficient detail in the publications cited at the outo set to make further description unnecessary here.
However, for completeness, it should be mentioned S" that, in the process according to the invention, the form of the further polymerization zone and the procedure in this zone are in the general sense similar to the form iof the first polymerization zone and the procedure in this zone; furthermore, in these two polymerization zones, it is advantageous if the total pressure in each of these zones is detectably (ie. 5 bar or more) higher than the total pressure in the second polymerization zone Regarding the composition of the catalyst systems to be used in the novel process, the following may be 5 O.Z. 0050/38931 stated specificaLLy: Titanium catalyst component The relevant conventional components are suitable here, especiaLLy those which give very uniformly round, readily free-flowing polymer particles; the following two groups which are particularly suitable for the novel process being noteworthy: fineLy divided titanium trichloride cocrystallization product of the formula TiCL 3 1/3 ALCL 3 and (ii) finely divided cocrystallization product of the formula TiCL 3 1/3 ALCL 3 which is modified with electron donors or Lewis bases and have ethers or esters as modifiers, and reaction products of magnesium o.n compounds with titanium halides with the addition of specific esters or anhydrides. Titanium catalyst components of this type are sufficiently well known from the Literature (cf. for example the publications cited at the outset) and in practice that no further description is O. required.
OrganoaLuminum catalyst components Suitable organoaluminum catalyst components are af once again the relevant conventional ones; they are likewise sufficiently well known from literature and in practice that no further description is required. Triethylaluminum and diethylaluminum chloride are typical exampies.
Further catalyst components which may or may not be used: SThe relevant conventional components, in particu- 'ar phenolic substances and silane compounds, are suitable in this case too; they are Likewise sufficiently well known from the Literature and in practice that no further description is required here.
The Ziegler and Phillips catalysts and catalyst systems for ethylene homopolymerization: The relevant conventional ones are again suitable in this case, especially those which give very uniformly iI 1 i 6 O.Z. 0050/38931 round, readily free-fLowing polymer particles; these catalysts and catalyst systems too are sufficiently well known that no further description is required here.
In general, it may therefore be stated that the substances used in the novel process as such are the relevant conventional ones and have no special features.
EXAMPLE 1 The process is carried out by a cyclic continuous procedure in a kettle cascade consisting of three stirred kettles, each having a useful volume of 200 L; the kettles are connected in a V shape: both a kettle for the preparation of the propylene homopolymer (first polymerization zone A) and a kettle for the preparation of the ethylene homopolymer (further polymerization zone C) are upstream from the kettle for the preparation of the end product (second polymerization zone B).
The propylene/ethylene polymer is prepared by a procedure in which, first, in the first poLymerizaion zone, propylene is homopolymerized in the presence of hydrogen as a molecular weight regulator, in a stirred bed of finely divided polypropylene and in the absence of a liquid reaction medium, from the gas phase, by feeding in a Ziegler-Natta catalyst system consisting of a titanium(III) component of the formula TiCl 3 1/3 AICL 3 1/3 n-propyl benzoate, diethylaluminum chloride and n-octadecyL B-(4'-hydroxy-3',5'-di-tert-butylphenyl)propionate (with the proviso that the atomic ratio of titanium from the titanium(III) component to aluminum from the diethylaluminum chloride 1:6 and the molar ratio of diethylaluminum chloride to the further catalyst component ie. the n-octadecyL B-(4'-hydroxy-3',5'-ditert-butylphenyL)propionate, is 1:0.04) with the provisos that, in the first polyeferization zone, the reaction is carried out under a total pressure s 7 O.Z. 0050/38931 of 28 bar and at 700C and (ii) the ratio of the propylene partial pressure to the hydrogen partial pressure is 100:2, and then in a second polymerization zone, a propylene/ethyLene mixture is polymerized with the propyLene homopoLymer present in the reaction product obtained in the first polymerization zone, in the presence of hydrogen as a molecuLar weight regulator, in a stirred bed of finely divided polymer and in the absence of a Liquid reaction medium, from the gas phase, by feeding in the reaction product obtained in the first polymerization zone, and additional catalyst component in an amount such that o the atomic ratio of titanium from the titanium(III) comua ponent to aluminum from the additional diethylaluminum 15 chloride is 1:4, with the provisos that, in this S second polymerization zone, the reaction is carried out under a total pressure of 15 bar and at 550C, (ii) Bono the ratio of the propylene partial pressure to the ethy- Lene partial pressure is 100:35 and the ratio of the propylene partial pressure to the hydrogen partial pressure is 100:38 and (iii) the ratio of the weight of the propy- SLene converted to polymer in the first polymerization zone to the weight of the propylene/ethylene mixture "converted to polymer in the second polymerization zone is 100:30.
According to the invention, in addition in a further polymerization zone, ethylene is homopolymerized in a stirred bed of finely divided polyethy- Lene in the absence of a Liquid reaction medium, from the gas phase, by means of a commercial Phillips catalyst of Cr0 3 on SiO 2 activated at 900 0 C in a stream of air), with the provisos that, in this further polymerization zone the reaction is carried out under a total pressure of 35 bar and at 1080C and (ii) the ratio of the weight of the propylene converted to polymer in the first polymerization zone to the weight of the ethylene converted to polymer in the further polymerization zone 8 O.Z. 0050/38931 is 100:17, and the resulting reaction product is Likewise fed to the second polymerization zone The propyLene/ethylene polymer thus obtained (26.5 kg/h) is dechLorinated, stabilized and granulated in an extruder in a conventional manner; it has a very advantageous balance of rigidity, toughness at room temperature and Low temperature impact strength.
EXAMPLE 2 The process is carried out by a cyclic continuous procedure in a kettle cascade consisting of three stirred kettles, each having a useful volume of 200 L; the kettles are connected in a V shape: both a kettle for the preparation of the propylene homopolymer (first polymerization zone A) and a kettle for the preparation of the ethyLene homopolymer (further polymerization zone C) are upstream from the kettle for the preparation of the end o 0 product (second polymerization zone B).
Thu propylene/ethylene polymer is prepared by a procedure in which, first in the first polymerization zone, propylene is homopolymerized in the presence of hydrogen as a molecular weight regulator, in a stirred bed of finely divided polypropylene and in the absence of a liquid reaction medium, from the gas phase, by feeding in a ZiegLer-Natta catalyst system consisting of a titanium catalyst component prepared according to (I the Example of German Laid-Open Application DOS 44 4 3,428,478, C2) triethyLaluminum and triethoxyphenylsilane (with the proviso that the atomic ratio of titanium from the titanium catalyst component to aluminum from the triethylaluminum is 1:150 and the molar ratio of triethyLaLuminum to further catalyst component ie.
the triethoxyphenylsilane, is 1:0.1) with the provisos that, in the first polymerization zone, the reaction is carried out under a total pressure L I. I I I I
I..
8r 8 84 CI I 48 *0 4 9 O.Z. 0050/38931 of 28 bar and at 70°C and (ii) the ratio of the propyLene partiaL pressure to the hydrogen partial pressure is 100:0.2, and then in a second polymerization zone, a propylene/ethylene mixture is polymerized with the propylene homopoLymer present in the reaction product obtained in the first polymerizatior zone, in the presence of hydrogen as a molecular weight regulator, in a stirred bed of finely divided polymer and in the absence of a liquid reaction medium, from the gas phase, by feeding in the reaction product obtained in the first polymerization zone, with the provisos that, in the second polymerization zone, the reaction is carried out under a total pressure of 13 bar and at 50 0 C, (ii) the ratio of the propylene partial pressure to the ethylene partial pressure is 100:20 and the ratio of the propylene partial pressure to the hydrogen partial pressure is 100:10, and (iii) the ratio of the weight of the propylene converted to polymer in the first polymerization zone to the 20 weight of the propylene/ethylene mixture converted to polymer in the second polymerization zone is 100:40.
According to the invention, in addition in a further polymerization zone, ethylene is homopolymerized in a stirred bed of finely divided polyethylene in the absence of a liquid reaction medium, from the gas phase, by means of a Ziegler catalyst as described in Example 1 of German Laid-Ooen Application DOS 2,543,272, with the provisos that, in this further polym'erization zone the reaction is carried out under a total pressure of 30 bar and at 1040C and (ii) the ratio of the weight of the propylene converted to polymer in the first polymerization zone to the weight of the ethylene converted to polymer in the further polymerization zone is 100:26, and the resulting reaction product is likewise fed to the second polymerization zone The propylene/ethylene polymer thus obtained 8as 04~ 8t 04 t-l' O.Z. 0050/38931 (23.7 kg/h) is dechlorinated, stabiLized and granulated in an extruder in a conventional manner; it has a very advantageous balance of rigidity, toughness at room temperature and Low temperature impact strength.
t f t i a
I
Claims (1)
1. A process for the preparation of propylene/ethylene polymers, in which first in a first polymerization zone, propylene is homopoly- merized in the presence of hydrogen as a molecular weight regulator, in a stirred bed of finely divided polymer and in the absence of a liquid reaction medium, from the gas phase, by feeding in a Ziegler-Natta catalyst system consisting of a titanium catalyst component and an organoaluminum catalyst component of the formula ALRm X 3 where X is OR, chlorine, bromine or hydrogen, I R is a C--C 18 -hydrocarbon radical and m is from 1 to 3, with or without a further catalyst component, with the provisos that, in this first polymerization zone (i) the reaction is carried out under a total pressure of from 20 to 35 bar and at from 60 to 90°C and (ii) the ratio of the propylene partial pressure to the hydrogen partial pressure is from 100:0.1 to 100:15, and then in a second polmerization zone, a mixture of propylene and ethylene is polymerized with the propylene homopolymer obtained in the first polymerization zone in the presence of o" °o hydrogen as a molecular weight regulator, in a stirred bed of finely divided polymer and in the absence of a liquid reaction medium from the gas phase, by feeding in the reaction products obtained in the first polymerization zone and in the further polymerization zone with or 0o without additional catalyst component with the provisions that, in this second polymerization zone the reaction is carried out under a total pressure of from 10 to bar and at from 50 to 800C, (ii) the ratio of the propylene partial pressure to the ethylene partial pressure is from 100:10 to 100:70 and the ratio of the propylene partial pressure to the hydrogen partial pressure is from 100:2 to 100:70, and (iii) the ratio of the weight of the propylene converted to polymer in the first polymerization v jP^^ -12 O.Z. 0050/38931 zone to the weight of the propylene/ethylene mixture converted to polymer in the second polymerization zone (B) is from 100:10 to 100:60, wherein in addition in a further polymerization zone, ethylene is homo- polymerized in the presence or absence of hydrogen as a molecular weight regulator, in a stirred bed of finely divided polymer and in the absence of a liquid reaction medium, from the gas phase, by means of Ziegler or Phillips catalysis, with the provisos that, in this further poly- merization zone, the reaction is carried out under a total pressure of from 20 to 45 bar and at from 80 to 120 0 C, (ii) where relevant, the ratio of the ethylene Spartial pressure to the hydrogen partial pressure is from &oVe 100:0.01 to 100:20 and (iii) the ratio of the weight of 0 00" the propylene converted to polymer in the first polymeriza- oon tion zone to the weight of the ethylene converted to cne, polymer in the further polymerization zone is from 100:5 to 100:40, and the resulting reaction product is likewise fed to the second polymerization zone O DATED this 28th day of January 1988. BASF AKTIENGESELLSCHAFT EDWD. WATERS SONS PATENT ATTORNEYS 0 o 50 QUEEN STREET ao o MELBOURNE. VIC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU11104/88A AU599201B2 (en) | 1988-01-29 | 1988-01-29 | Preparation of propylene/ethylene polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU11104/88A AU599201B2 (en) | 1988-01-29 | 1988-01-29 | Preparation of propylene/ethylene polymers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU1110488A AU1110488A (en) | 1989-08-03 |
| AU599201B2 true AU599201B2 (en) | 1990-07-12 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU11104/88A Ceased AU599201B2 (en) | 1988-01-29 | 1988-01-29 | Preparation of propylene/ethylene polymers |
Country Status (1)
| Country | Link |
|---|---|
| AU (1) | AU599201B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU619357B2 (en) * | 1988-11-16 | 1992-01-23 | Union Carbide Chemicals And Plastics Company Inc. | Process for the in situ blending of polymers |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3827565A1 (en) * | 1988-08-13 | 1990-02-15 | Basf Ag | METHOD FOR PRODUCING PROPYLENE-ETHYLENE POLYMERISATES OF THE TYPE OF THE SOCIAL "IMPACT-MODIFIED POLYPROPYLENE" |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU3225378A (en) * | 1977-01-13 | 1979-07-19 | Mitsui Petrochemical Industries, Ltd. | Impact resistant chemically blended propylene polymer composition |
| AU4768885A (en) * | 1984-09-25 | 1986-04-10 | Shell Internationale Research Maatschappij B.V. | Sequential polymerisation of ethylene and propylene |
| EP0276734A2 (en) * | 1987-01-24 | 1988-08-03 | BASF Aktiengesellschaft | Process for the manufacture of copolymers of propylene and ethylene |
-
1988
- 1988-01-29 AU AU11104/88A patent/AU599201B2/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU3225378A (en) * | 1977-01-13 | 1979-07-19 | Mitsui Petrochemical Industries, Ltd. | Impact resistant chemically blended propylene polymer composition |
| AU4768885A (en) * | 1984-09-25 | 1986-04-10 | Shell Internationale Research Maatschappij B.V. | Sequential polymerisation of ethylene and propylene |
| EP0276734A2 (en) * | 1987-01-24 | 1988-08-03 | BASF Aktiengesellschaft | Process for the manufacture of copolymers of propylene and ethylene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU619357B2 (en) * | 1988-11-16 | 1992-01-23 | Union Carbide Chemicals And Plastics Company Inc. | Process for the in situ blending of polymers |
Also Published As
| Publication number | Publication date |
|---|---|
| AU1110488A (en) | 1989-08-03 |
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| Date | Code | Title | Description |
|---|---|---|---|
| MK14 | Patent ceased section 143(a) (annual fees not paid) or expired |