+

WO1997010286A1 - Copolymeres propene/but-1-ene - Google Patents

Copolymeres propene/but-1-ene Download PDF

Info

Publication number
WO1997010286A1
WO1997010286A1 PCT/EP1996/003889 EP9603889W WO9710286A1 WO 1997010286 A1 WO1997010286 A1 WO 1997010286A1 EP 9603889 W EP9603889 W EP 9603889W WO 9710286 A1 WO9710286 A1 WO 9710286A1
Authority
WO
WIPO (PCT)
Prior art keywords
propene
alkyl
dimethylsilylenbis
ene
ene copolymers
Prior art date
Application number
PCT/EP1996/003889
Other languages
German (de)
English (en)
Inventor
David Fischer
Franz Langhauser
Dieter Lilge
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 JP9511621A priority Critical patent/JPH11512461A/ja
Priority to EP96931771A priority patent/EP0851889A1/fr
Publication of WO1997010286A1 publication Critical patent/WO1997010286A1/fr

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
    • 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
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
    • C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged

Definitions

  • the present invention relates to propene / but-1-ene copolymers with at least 80 mol% propene units, a melting point T m less than 145 ° C. and a molecular weight distribution M w / M n less than 2.5.
  • the present invention further relates to the use of these copolymers 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 A.M. Chatterjee et al., Soc. of Plastics Engineers, ANTEC Conf. Proc. S. 1977-1981 (1994).
  • sealing layer materials as in A.M. 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 with a higher rigidity. Low sealing temperatures are desirable for the applications mentioned, i.e. low melting points of the polymer.
  • the propene / but-1-ene copolymers according to the invention have at least 80 mol% propene units in the copolymer, preferably 85 to 99.9 mol%, in particular 93 to 99.5 mol%, a melting point T m less than 145 ° C, preferably less than 143 ° C and a molecular weight distribution M w / M n (M w weight average, M n number average) less than 2.5, preferably less than 2.3, particularly preferably less than 2, 15.
  • the polymers according to the invention preferably have a solubility in xylene X L (20 ° C.) of
  • Preferably 70% of the propene diads are in the form of meso diads.
  • Copolymers may also be present, but preferably not more than 1 mol%, based on the amount of propene used.
  • Ethene and higher 1-olefins such as hex-1-ene, oct-1-ene and dec-1-ene are suitable here.
  • copolymers according to the invention can be prepared in the gas phase, in suspension, in liquid monomers or in inert solvents. Suitable suspension or solvents are, for example, aliphatic and aromatic hydrocarbons. The copolymers according to the invention are preferably produced in the gas phase.
  • the process is carried out by continuously polymerizing at temperatures in the range from 50 to 120 ° C. and using those used as catalyst systems which are active ingredients
  • R 12 and R 1 3 Ci to Cio-alkyl, C 6 - to Ci s-aryl, alkylaryl, Aryl ⁇ alkyl, fluoroalkyl or fluoroaryl, each with 1 to 10 C atoms in the alkyl radical and 6 to 20 C atoms in the aryl radical mean,
  • R 1 and R 7 Ci - to Cio-alkyl or C 6 - to Cis-aryl
  • R 2 and R 8 are hydrogen, C ⁇ ⁇ to Cio-alkyl, 5- to 7-membered cycloalkyl, which is a C ⁇ ⁇ to C ⁇ o ⁇ alkyl
  • R 1 4 Ci - to Cio-alkyl or C 3 - to C ⁇ 0 cycloalkyl
  • R 3 to R 5 and R 9 to R 11 are hydrogen, C ⁇ to Cio-alkyl, 5- to 7-membered
  • Cycloalkyl which in turn can carry a C ⁇ ⁇ to C ⁇ o ⁇ alkyl as a substituent, C 6 - to Cis-aryl or arylalkyl, where optionally two adjacent radicals together can represent cyclic groups having 4 to 15 C atoms, or Si (R 15 ) 3 with
  • R 2 and R 3 together represent cyclic groups having 4 to 15 carbon atoms
  • R 8 and R 9 together represent cyclic groups containing 4 to 15 carbon atoms
  • 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 ⁇ -Cio-fluoroaryl group, a C ß -Cio aryl group, a C ⁇ -C ⁇ o ⁇ alkoxy group, a C 2 -C ⁇ o _ alkenyl group, a C 7 -C 4 o ⁇ arylalkyl group, a C 8 -C 4 o-arylalkenyl group or a C 7 -Cjo alkyl aryl group or R 15 and R 16 or R 15 and R 17 each
  • M 1 is silicon, germanium or tin contain,
  • R 18 to R 20 represent fluorine, chlorine, bromine, iodine or Ci- to -C 2 alkyl.
  • polymerization is carried out continuously at temperatures in the range from 60 to 100.degree.
  • M stands for zirconium or hafnium
  • X represents chlorine or C 1 -C 4 -alkyl, in particular chlorine or methyl
  • R 1 and R 7 is C ⁇ - to C 4 -alkyl, in particular methyl or ethyl, or phenyl,
  • R 2 and R 8 for -C ⁇ to C 4 alkyl in particular for methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl,
  • R 9 to R 11 are hydrogen, C ⁇ to C4 alkyl, especially methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl, C ß - to C ⁇ 2 -aryl, in particular phenyl, or where two neighboring radicals together represent 4 to 15 carbon atoms, in particular cyclic groups containing 8 to 12 carbon atoms,
  • 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 represent 4 to 15 carbon atoms, in particular cyclic groups containing 8 to 12 carbon atoms,
  • R 1 5 Rl 5 Rl 5 R 1 5 stands for - M 1 , c or c C '
  • M 1 is preferably silicon
  • R 15 and R 16 are hydrogen, Ci to C 4 , in particular methyl or C 6 to C 2 aryl, in particular 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, Ce to Cis-aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, each with 1 to 10 carbon atoms in the alkyl radical and 6 to 20 carbon atoms in the Aryl radical or fluorine, chlorine, bromine or iodine, in particular for haloaryls, preferably for pentafluorophenyl.
  • Ci- to Cio-cycloalkyl which can optionally be substituted with Ci- to Cio-alkyl groups, halogen, C ⁇ ⁇ to C 28 alkoxy, Ce 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 a-z, however, 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 is a -C ⁇ to C 4 alkyl group, preferred
  • 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 mixtures of different lengths, both linear and cyclic chain molecules, 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.
  • 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 US Pat
  • EP-A 621 279 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 in the range from 10: 1 to 10 4 : 1.
  • the catalyst system 5 used in the preferred process may 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 Ci - to -C 2 alkyl, preferably Ci - to C ⁇ -alkyl
  • the radicals R 18 to R 20 are preferably the same and stand for methyl, ethyl, isobutyl or n-hexyl.
  • Component C) is preferably present in the catalyst system in an amount of 500: 1 to 1: 1, in particular 350: 1 to 50: 1 (molar ratio Al from II to transition metal from I).
  • 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 5 carrier materials are, for example, silica gels, preferably those of the formula Si0 2 * a Al 2 O 3 , in which a stands for a number in the range from 0 to 2, preferably 0 to 0.5; these are therefore aluminosilicates or silicon dioxide. Products of this type are commercially available, for example Silica Gel 332 from Grace. More carriers
  • 40 include finely divided polyolefins, for example finely divided polypropylene.
  • a supported catalyst system is used and at a pressure of 45 10 to 40 bar, preferably 15 to 32 bar over a period of polymerized for 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 molar ratio of the propene and butene monomers used is preferably 10,000: 1 to 4: 1, in particular 200: 1 to 5.5: 1.
  • the propene / but-1-ene copolymers according to the invention have a low melting point, a narrow molecular weight distribution and low xylene-soluble fractions. They are suitable for the production of films and moldings, in particular sealing layers and injection molded articles.
  • Example 10 g / h g of the metallocene support catalyst produced in Example 1 were metered into a 200 1 gas phase reactor. Propene and but-l-ene were fed in and copolymerized at 24 bar reactor pressure and 60 ° C. polymerization temperature, 30 mmol of triisobutylaluminum being fed in per hour (1 molar solution in heptane). The polymerization was carried out continuously over a period of 48 hours. The reactor output was 20 kg / h. A copolymer grit was formed.
  • the following table provides information about the amount of propene and but-l-ene used and the properties of the copolymers formed.
  • d avg 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 emulsion chromatography).
  • the xylene-soluble fractions X L were determined as follows:

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

L'invention concerne des copolymères propène/but-1-ène contenant au moins 80 % en moles d'unités de propène et ayant un point de fusion Tm inférieur à 145 °C et une distribution du poids moléculaire inférieure à 2,5.
PCT/EP1996/003889 1995-09-11 1996-09-04 Copolymeres propene/but-1-ene WO1997010286A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP9511621A JPH11512461A (ja) 1995-09-11 1996-09-04 プロペン／ブタ−１−エン共重合体
EP96931771A EP0851889A1 (fr) 1995-09-11 1996-09-04 Copolymeres propene/but-1-ene

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1995133337 DE19533337A1 (de) 1995-09-11 1995-09-11 Propen/But-1-en-Copolymere
DE19533337.3 1995-09-11

Publications (1)

Publication Number Publication Date
WO1997010286A1 true WO1997010286A1 (fr) 1997-03-20

Family

ID=7771687

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/003889 WO1997010286A1 (fr) 1995-09-11 1996-09-04 Copolymeres propene/but-1-ene

Country Status (5)

Country Link
EP (1) EP0851889A1 (fr)
JP (1) JPH11512461A (fr)
CN (1) CN1202186A (fr)
DE (1) DE19533337A1 (fr)
WO (1) WO1997010286A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002518229A (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 プロペンターポリマーから構成されるヒートシールが可能な同時押出フィルム
WO2022078473A1 (fr) * 2020-10-15 2022-04-21 中国石油化工股份有限公司 Copolymère de propylène-butène, procédé de préparation associé et son utilisation

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19812229A1 (de) 1998-03-20 1999-09-23 Basf Ag Polymere des Propens
DE19813399A1 (de) * 1998-03-26 1999-09-30 Basf Ag Statistische Propylencopolymerisate
DE19827328A1 (de) 1998-06-19 1999-12-23 Targor Gmbh Propen-Terpolymere mit geringem extrahierbarem Anteil
CN107522801B (zh) * 2016-06-22 2020-07-31 中国石化扬子石油化工有限公司 一种丙烯丁烯共聚催化剂体系及其在制备丙烯丁烯共聚物的应用

Citations (7)

* 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
EP0395055A1 (fr) * 1989-04-28 1990-10-31 MITSUI TOATSU CHEMICALS, Inc. Copolymère syndiotactique de propylène
EP0495099A1 (fr) * 1988-12-26 1992-07-22 Mitsui Petrochemical Industries, Ltd. Copolymeres olefines et leur production
EP0629632A2 (fr) * 1993-06-07 1994-12-21 Mitsui Petrochemical Industries, Ltd. Nouveau composé de métal de transition utilisable comme catalyseur de polymérisation
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 (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2923754C3 (de) * 1978-06-14 1996-02-08 Sumitomo Chemical Co Verfahren zur Herstellung eines Propylencopolymeren und dessen Verwendung in einem vielschichtigen Polypropylen-Propylencopolymer-Film
MX154108A (es) * 1979-01-17 1987-05-11 Naphtachimie Sa Procedimiento para la obtencion de un copolimero de propileno y buteno-1
KR930009208B1 (ko) * 1988-12-26 1993-09-24 마쓰이 세끼유 가가꾸 고오교오 가부시끼가이샤 올레핀 공중합체 및 그의 제조방법
IT1249008B (it) * 1990-06-27 1995-02-11 Himont Inc Copolimeri cristallini sindiotattici del propilene
DE4317654A1 (de) * 1993-05-27 1994-12-01 Basf Ag Statistische Copolymerisate des Propylens
CN1052734C (zh) * 1993-11-29 2000-05-24 三井化学株式会社 丙烯高弹体

Patent Citations (7)

* 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
EP0395055A1 (fr) * 1989-04-28 1990-10-31 MITSUI TOATSU CHEMICALS, Inc. Copolymère syndiotactique de propylène
EP0629632A2 (fr) * 1993-06-07 1994-12-21 Mitsui Petrochemical Industries, Ltd. Nouveau composé de métal de transition utilisable comme catalyseur de polymérisation
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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002518229A (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 プロペンターポリマーから構成されるヒートシールが可能な同時押出フィルム
WO2022078473A1 (fr) * 2020-10-15 2022-04-21 中国石油化工股份有限公司 Copolymère de propylène-butène, procédé de préparation associé et son utilisation

Also Published As

Publication number Publication date
EP0851889A1 (fr) 1998-07-08
DE19533337A1 (de) 1997-03-13
CN1202186A (zh) 1998-12-16
JPH11512461A (ja) 1999-10-26

Similar Documents

Publication Publication Date Title
EP0803514B1 (fr) Procédé de préparation de polymères alc-1-ènes en présence d'un système catalytique à base de métallocène supporté et d'un agent antistatique
US6160064A (en) Ethylene enhancement of processes for synthesis of high melting theromoplastic elastomeric α-olefin polymers (PRE/EPE effects)
DE19812229A1 (de) Polymere des Propens
EP0633897B1 (fr) Systemes catalyseurs pour la polymerisation d'alcenes-1 en c 2- a c 10-
DE69504178T2 (de) Ethylen copolymere
EP0868440B1 (fr) Procede de fabrication de copolymeres d'ethylene sous haute pression
DE19757563A1 (de) Geträgertes Katalysatorsystem, Verfahren zur Herstellung und seine Verwendung zur Polymerisation von Olefinen
DE69810781T2 (de) Polydisperses propylenpolymer und verfahren zu dessen herstellung
DE3443087A1 (de) Verfahren zur herstellung von polyolefinen
EP1242479B1 (fr) Polypropylene macromoleculaire ayant une repartition importante de la masse moleculaire et une longueur sequentielle isotactique faible
EP0811642A2 (fr) Copolymères d'alcènes-1 et d'alpha,oméga-diènes ayant un indice de viscosité élevé
EP0851889A1 (fr) Copolymeres propene/but-1-ene
EP1090049B1 (fr) Terpolymeres de propylene a proportion extractible minime
EP0700406B1 (fr) Copolymerisats statistiques du propylene
DE69027652T2 (de) Verfahren zur Herstellung von syndiotaktischen Copolymeren aus Propylen und Olefinen
DE19826403A1 (de) Übergangsmetallkomplexe
EP0810233B1 (fr) Procédé pour la préparation de polymères d'alcènes en C2 à C12 utilisant un agent retardateur
EP0876408A1 (fr) Procede de preparation de polymeres d'alcenes c 2?-c 10? en presence de complexes metallocenes avec des ligands cyclopentadienyles fonctionnalises catiomiquement
WO1997010272A1 (fr) Procede de production de copolymeres propene/but-1-ene
DE102005007186A1 (de) Verfahren zum Herstellen von 1-Olefin(co)polymeren
WO2002038637A1 (fr) Procede de copolymerisation de propylene et/ou d"ethylene au moyen de 1-olefines sur des catalyseurs a supports metallocenes
EP1244714A1 (fr) Procede de production d'un catalyseur solide pour la polymerisation d'olefines
DE19720980A1 (de) Metallocenkatalysatorsysteme mit anorganischen Oxiden als Träger
WO1998016564A2 (fr) Systeme catalyseurs contenant des complexes metalliques d'une structure similaire a l'adamantane
WO1996026211A1 (fr) Complexes metallocenes a ponts cationiques

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 96198207.1

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): CN JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 1996931771

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 1997 511621

Country of ref document: JP

Kind code of ref document: A

WWP Wipo information: published in national office

Ref document number: 1996931771

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1996931771

Country of ref document: EP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载