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WO1997010272A1 - Procede de production de copolymeres propene/but-1-ene - Google Patents

Procede de production de copolymeres propene/but-1-ene Download PDF

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Publication number
WO1997010272A1
WO1997010272A1 PCT/EP1996/003891 EP9603891W WO9710272A1 WO 1997010272 A1 WO1997010272 A1 WO 1997010272A1 EP 9603891 W EP9603891 W EP 9603891W WO 9710272 A1 WO9710272 A1 WO 9710272A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
aryl
cio
group
atoms
Prior art date
Application number
PCT/EP1996/003891
Other languages
German (de)
English (en)
Inventor
David Fischer
Franz Langhauser
Meinolf Kersting
Roland Hingmann
Günther SCHWEIER
Original Assignee
Basf Aktiengesellschaft
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Priority to EP96931022A priority Critical patent/EP0850255A1/fr
Priority to JP9511622A priority patent/JPH11512462A/ja
Publication of WO1997010272A1 publication Critical patent/WO1997010272A1/fr

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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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene

Definitions

  • the present invention relates to processes for the preparation of propene / but-1-ene copolymers, the molar ratio of propene to but-1-ene being in the range from 10,000: 1 to 4: 1, at temperatures in the range from 50 to 120 ° C continuously polymerized and used as catalyst systems that act as active ingredients
  • R 12 and R 13 are C 1 to C 10 alkyl, C 6 to C 5 aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical,
  • Rl and R 7 Ci to Cio alkyl or C ⁇ to C ⁇ 5 aryl
  • R 2 and R ⁇ are hydrogen, Ci- to Cio-alkyl, 5- to 7-membered cycloalkyl, which in turn can carry a C ⁇ ⁇ to Cio-alkyl as a substituent, or Si (R 14 ) 3 with
  • R 14 Ci- to Cio-alkyl or C 3 - to -CC 0 cycloalkyl
  • R 3 to R 5 and R 9 to R 11 are hydrogen, C 1 to C 0 alkyl, 5- to 7-membered
  • Cycloalkyl which in turn can carry a C 1 -C 8 -alkyl as a substituent, C 6 - to Cis-aryl or arylalkyl, where optionally two adjacent radicals together can also represent cyclic groups having 4 to 15 C atoms, or Si (R 15 ) 3 with
  • R 15 Ci to Cio alkyl, C 6 to C ⁇ aryl or C 3 to
  • R 15 is, wherein R 15 , R 16 and R 17 are the same or different and a hydrogen atom, a halogen atom, a C ⁇ -C ⁇ o-alkyl group, a C ⁇ -C ⁇ o-fluoroalkyl group, a C 6 -C ⁇ o ⁇ fluoroaryl group, a C ⁇ -Cio-aryl group mean a Ci-Cio-alkoxy group, a C 2 -C ⁇ alkenyl group, a C 7 -C 4 o-arylalkyl group, a C ⁇ -C 4 o-arylalkenyl group or a C 7 -C 4 o-alkyl aryl
  • M 1 is silicon, germanium or tin
  • R 18 to R 20 are fluorine, chlorine, bromine, iodine or C ⁇ ⁇ to Ci 2 ⁇ alkyl.
  • the present invention relates to the use of the copolymers thus obtained for the production of films or moldings and to the films and moldings obtainable here.
  • Binary propene / but-1-ene copolymers have recently received increased interest, for example as sealing layer materials as in AM Chatterjee et al. , Soc. of Plastics Engineers, ANTEC Conf. Proc. S. 1977-1981 (1994).
  • sealing layer materials as in AM Chatterjee et al. , Soc. of Plastics Engineers, ANTEC Conf. Proc. S. 1977-1981 (1994).
  • ethene / propene copolymers usually used for this application they are characterized, with the same melting point, by a significantly lower sealing temperature and, at the same time, higher rigidity.
  • Low sealing temperatures, ie low melting points of the polymer are desirable for the applications mentioned.
  • the object of the present invention was therefore to remedy the disadvantages mentioned, in particular to keep the amount of but-l-ene to be used as low as possible and to provide a process which can be carried out on an industrial scale.
  • the molar ratio of the monomers propene and but-1-ene used is in the range from 10,000: 1 to 4: 1, preferably 50: 1 to 5: 1, in particular 25: 1 to 7: 1 (propene: but-1-ene ). Small amounts of other monomers can also be present, but preferably not more than 1 mol%, based on the amount of propene used. Ethylene or other olefins are preferred here, preferably hex-1-ene, oct-1-ene and dec-1-ene.
  • the process according to the invention is carried out continuously at temperatures in the range from 50 to 120 ° C., preferably from 60 to 100 ° C.
  • M stands for zirconium or hafnium
  • X represents chlorine or C 1 -C 4 -alkyl, in particular chlorine or methyl
  • R 2 and R ⁇ are C 1 -C 4 -alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl,
  • R 3 to R 5 and R 9 to R 11 for hydrogen, Ci to C 4 alkyl, in particular methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, Ce, - to -C 2 aryl , in particular phenyl or where two adjacent radicals together represent 4 to 15 carbon atoms, in particular 8 to 12 carbon atoms, cyclic groups,
  • R 2 and R 3 together represent 4 to 15 carbon atoms, in particular cyclic groups containing 8 to 12 carbon atoms,
  • R 8 and R 9 together for 4 to 15 carbon atoms, in particular 8 to 12
  • M 1 is preferably silicon
  • R 15 and R 16 are hydrogen, C ⁇ to 4, in particular methyl or C ß - to C ⁇ 2 -aryl, especially phenyl.
  • Metallocene complexes of the general formula I which are symmetrical are preferred.
  • Such complex compounds can be synthesized by methods known per se, the reaction of the appropriately substituted cyclic hydrocarbon anions with halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum being preferred.
  • Suitable compounds B) forming metallocenium ions are in particular strong, neutral Lewis acids, ionic compounds with Lewis acid cations, ionic compounds with Bronsted acids as the cation and alumoxane compounds.
  • M 2 is an element of III.
  • Main group of the periodic table means, in particular B, Al or Ga, preferably B,
  • X 2 , X 3 and X 4 for hydrogen, Ci- to Cio-alkyl, C 6 - to -C 5 aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 C atoms in the alkyl radical and 6 to 20 C- Atoms in the aryl radical or fluorine, chlorine, bromine or iodine are, in particular for haloaryls, preferably for pentafluorophenyl.
  • C 28 alkyl C 6 to C 5 aryl, alkylaryl, arylalkyl, haloalkyl, haloaryl each having 6 to 20 C atoms in the aryl and 1 to 28 C atoms in the alkyl radical,
  • Ci- to C ⁇ o * -cycloalkyl which can optionally be substituted with Ci- to Cio-alkyl groups, halogen, Ci to C 28 alkoxy, C $ to Cis-aryloxy, silyl or mercaptyl groups
  • a stands for integers from 1 to 6
  • z stands for integers from 0 to 5 d corresponds to the difference az, but d is greater than or equal to 1.
  • Carbonium cations, oxonium cations and sulfonium cations as well as cationic transition metal complexes are particularly suitable.
  • the triphenylmethyl cation, the silver cation and the 1,1'-dimethylferrocenyl cation should be mentioned in particular. They preferably have non-coordinating counterions, in particular boron compounds, as they are also mentioned in WO 91/09882, preferably tetrakis (pentafluorophenyl) borate.
  • Ionic compounds with Bronsted acids as cations and preferably also non-coordinating counterions are mentioned in WO 91/09882; the preferred cation is N, N-dimethylanilinium.
  • Open-chain or cyclic alumoxane compounds of the general formula III or IV are particularly suitable as compound B) forming metallocenium ions
  • R 21 represents a Cx to C 4 alkyl group
  • Methyl or ethyl group and m represents an integer from 5 to 30, preferably 10 to 25.
  • oligomeric alumoxane compounds are usually prepared by reacting a solution of trialkylaluminum with water and include in EP-A 284 708 and US A 4,794,096.
  • the oligomeric alumoxane compounds obtained are generally present as mixtures of both linear and cyclic chain molecules of different lengths, so that m is to be regarded as the mean.
  • the alumoxane compounds can also be present in a mixture with other metal alkyls, preferably with aluminum alkyls. 97/10272 9 PO7EP96 / 03891
  • component B) aryloxyalumoxanes, as described in US Pat. No. 5,391,793, aminoaluminoxanes, as described in US Pat. No. 5,371,260, aminoaluminoxane hydrochlorides, as described in EP-A 633 264, siloxyaluminoxanes, as in EP-A 621 279 described, or mixtures thereof are used.
  • metallocene complexes and the oligomeric alumoxane compound in amounts such that the atomic ratio between aluminum from the oligomeric alumoxane compound and the transition metal from the metallocene complexes is in the range from 10: 1 to 10 6 : 1, in particular is in the range from 10: 1 to 10 4 : 1.
  • the catalyst system used in the process according to the invention can optionally also contain an aluminum compound of the general formula II as component C)
  • R 18 to R 20 represent fluorine, chlorine, bromine, iodine or C 1 -C 1 -alkyl, preferably C 1 -C 6 -alkyl
  • the radicals R 18 to R 20 are preferably the same and stand for methyl, ethyl, isobutyl or n-hexyl.
  • Component C) is preferred in an amount of 500: 1 to
  • Aromatic hydrocarbons are usually used as solvents for these catalyst systems, preferably with 6 to 20 carbon atoms, in particular xylenes and toluene and mixtures thereof.
  • the catalyst systems are preferably used in supported form.
  • the support materials used are preferably finely divided supports which preferably have a particle diameter in the range from 1 to 300 ⁇ m, in particular from 30 to 70 ⁇ m.
  • Suitable carrier materials are, for example, silica gels, preferably those of the formula Si0 2 • a A1 2 0 3 , where a is a number in the range is from 0 to 2, preferably 0 to 0.5; these are therefore aluminosilicates or silicon dioxide.
  • Such products are commercially available, for example Silica Gel 332 from Grace.
  • Other carriers include finely divided polyolefins, for example finely divided polypropylene or magnesium chloride.
  • the process according to the invention can be carried out in the gas phase, in suspension and in liquid monomers.
  • Suitable suspending agents are, for example, aliphatic hydrocarbons.
  • the process according to the invention is preferably carried out in the gas phase.
  • a supported catalyst system is used and polymerized at a pressure of 10 to 40 bar, preferably 15 to 32 bar over a period of more than 12 hours, preferably more than 24 hours.
  • the average molecular weight of the copolymers formed can be controlled using the methods customary in polymerization technology, for example by adding regulators such as hydrogen.
  • the copolymers produced by the process according to the invention fall with good, i.e. process morphology.
  • the average particle diameter is preferably greater than 0.5 mm and preferably less than 5% by weight of the particles have a particle diameter of greater than 5 mm.
  • T m is the melting point of the copolymer
  • Copolymers have a narrow molecular weight distribution M w / M n (M w weight average, M n number average). M w / M n is preferably less than 3.
  • the process according to the invention can be carried out on an industrial scale, the amount of but-1-ene to be used is small and the copolymers produced by the process according to the invention can be used to produce films and moldings.
  • d a vg means the average particle diameter of the polymer powder.
  • the Staudinger index [ ⁇ ] was determined at 135 ° C in decalin, the melting point T m by means of DSC (differential scanning . Calorimetry), the amount of C 4 in the copolymer by IR and 13 C-NMR measurements, M w (Weight average) and M n (number average) by GPC (gel permeation chromatography).
  • the xylene-soluble fractions X L were determined as follows:
  • the xylene-soluble portion results from g x 500 x 100

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  • 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)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un procédé de production de copolymères propène/but-1-ène dont le rapport molaire entre le propène et le but-1-ène se situe entre 10 000:1 et 4:1. La polymérisation est mise en oeuvre de façon continue à des températures comprises entre 50 °C et 120 °C. On utilise des systèmes catalyseurs contenant comme composants actifs (A) des complexes métallocènes (B) un composé formant des ions métallocène et (C) éventuellement un composé aluminium.
PCT/EP1996/003891 1995-09-11 1996-09-04 Procede de production de copolymeres propene/but-1-ene WO1997010272A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP96931022A EP0850255A1 (fr) 1995-09-11 1996-09-04 Procede de production de copolymeres propene/but-1-ene
JP9511622A JPH11512462A (ja) 1995-09-11 1996-09-04 プロペン／１−ブテン共重合体の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19533336.5 1995-09-11
DE1995133336 DE19533336A1 (de) 1995-09-11 1995-09-11 Verfahren zur Herstellung von Propen/But-1-en-Copolymeren

Publications (1)

Publication Number Publication Date
WO1997010272A1 true WO1997010272A1 (fr) 1997-03-20

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/003891 WO1997010272A1 (fr) 1995-09-11 1996-09-04 Procede de production de copolymeres propene/but-1-ene

Country Status (5)

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EP (1) EP0850255A1 (fr)
JP (1) JPH11512462A (fr)
CN (1) CN1201468A (fr)
DE (1) DE19533336A1 (fr)
WO (1) WO1997010272A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002518561A (ja) * 1998-06-19 2002-06-25 バーゼル、ポリプロピレン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング 抽出可能物質の含有量の少ないプロペンターポリマー

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4592848B2 (ja) * 1998-10-21 2010-12-08 三井化学株式会社 軟質透明性シンジオタクティックポリプロピレン組成物

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0384264A1 (fr) * 1989-02-15 1990-08-29 Hoechst Aktiengesellschaft Cire de polypropylène et procédé pour la préparer
EP0495099A1 (fr) * 1988-12-26 1992-07-22 Mitsui Petrochemical Industries, Ltd. Copolymeres olefines et leur production
EP0552945A2 (fr) * 1992-01-23 1993-07-28 Mitsui Petrochemical Industries, Ltd. Procédé de préparation de polyoléfines
DE4317654A1 (de) * 1993-05-27 1994-12-01 Basf Ag Statistische Copolymerisate des Propylens
EP0629632A2 (fr) * 1993-06-07 1994-12-21 Mitsui Petrochemical Industries, Ltd. Nouveau composé de métal de transition utilisable comme catalyseur de polymérisation
EP0668157A1 (fr) * 1994-02-21 1995-08-23 Hoechst Aktiengesellschaft Films stratifiés thermosoudables en polyoléfines, procédé pour leur fabrication et leur utilisation
EP0716121A1 (fr) * 1994-12-06 1996-06-12 Mitsui Petrochemical Industries, Ltd. Composée de polypropylène et élastomère de propylène-butène
WO1996022995A1 (fr) * 1995-01-23 1996-08-01 Montell Technology Company B.V. Composes metallocene, leur procede de preparation et leur utilisation dans des catalyseurs pour la polymerisation d'olefines
EP0733476A2 (fr) * 1995-03-02 1996-09-25 Mitsui Petrochemical Industries, Ltd. Film composite en polypropylène

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0769505B1 (fr) * 1988-12-26 2000-05-10 Mitsui Chemicals, Inc. Copolymères oléfiniques et leurs procédés de préparation
US5677408A (en) * 1993-11-29 1997-10-14 Mitsui Petrochemical Industries, Ltd. Propylene elastomer and process for preparation thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0495099A1 (fr) * 1988-12-26 1992-07-22 Mitsui Petrochemical Industries, Ltd. Copolymeres olefines et leur production
EP0384264A1 (fr) * 1989-02-15 1990-08-29 Hoechst Aktiengesellschaft Cire de polypropylène et procédé pour la préparer
EP0552945A2 (fr) * 1992-01-23 1993-07-28 Mitsui Petrochemical Industries, Ltd. Procédé de préparation de polyoléfines
DE4317654A1 (de) * 1993-05-27 1994-12-01 Basf Ag Statistische Copolymerisate des Propylens
EP0629632A2 (fr) * 1993-06-07 1994-12-21 Mitsui Petrochemical Industries, Ltd. Nouveau composé de métal de transition utilisable comme catalyseur de polymérisation
EP0668157A1 (fr) * 1994-02-21 1995-08-23 Hoechst Aktiengesellschaft Films stratifiés thermosoudables en polyoléfines, procédé pour leur fabrication et leur utilisation
EP0716121A1 (fr) * 1994-12-06 1996-06-12 Mitsui Petrochemical Industries, Ltd. Composée de polypropylène et élastomère de propylène-butène
WO1996022995A1 (fr) * 1995-01-23 1996-08-01 Montell Technology Company B.V. Composes metallocene, leur procede de preparation et leur utilisation dans des catalyseurs pour la polymerisation d'olefines
EP0733476A2 (fr) * 1995-03-02 1996-09-25 Mitsui Petrochemical Industries, Ltd. Film composite en polypropylène

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002518561A (ja) * 1998-06-19 2002-06-25 バーゼル、ポリプロピレン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング 抽出可能物質の含有量の少ないプロペンターポリマー

Also Published As

Publication number Publication date
CN1201468A (zh) 1998-12-09
EP0850255A1 (fr) 1998-07-01
DE19533336A1 (de) 1997-03-13
JPH11512462A (ja) 1999-10-26

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