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WO1993002116A1 - Procede de preparation de copolymeres d'ethylene-propylene sous forme particulaire - Google Patents

Procede de preparation de copolymeres d'ethylene-propylene sous forme particulaire Download PDF

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Publication number
WO1993002116A1
WO1993002116A1 PCT/FI1991/000219 FI9100219W WO9302116A1 WO 1993002116 A1 WO1993002116 A1 WO 1993002116A1 FI 9100219 W FI9100219 W FI 9100219W WO 9302116 A1 WO9302116 A1 WO 9302116A1
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WO
WIPO (PCT)
Prior art keywords
ethylene
propylene
particle form
copolymer
preparation
Prior art date
Application number
PCT/FI1991/000219
Other languages
English (en)
Inventor
Jukka Veli SEPPÄLÄ
Jari Juhani KOIVUMÄKI
Original Assignee
Neste Oy
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 Neste Oy filed Critical Neste Oy
Publication of WO1993002116A1 publication Critical patent/WO1993002116A1/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
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • 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
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers

Definitions

  • the present invention relates to a process for preparation of elastomeric ethylene-propylene copolymers in particle form.
  • the ethylene-propylene elastomers or EPR gums can be divided into two groups: the saturated ethylene-propylene copolymers (EPM) and the ethylene-propylene-diene terpolymers (EPDM) . These are mainly amorphous co- or terpolymers, the statisti ⁇ cal structure of the repeating units of which has an influence on the crystallinity of the polymer and its behavior in different weather conditions, such as on its resistance to atmospheric oxygen and ozone.
  • a Ziegler-Natta catalyst system In the copolymerization of these olefin elastomers a Ziegler-Natta catalyst system generally is used comprised of a so-called procatalyst and a co-catalyst.
  • the procatalyst is based on a compound of a transition metal belonging to some of the groups IVB-VII of the periodic system of the elements
  • the co-catalyst is based on an organometallic compound of a metal belonging to some of the groups IA-IIIA of the periodic system of the elements.
  • the catalyst system can also comprise a carrier on which the transition metal compound has been superposed, and electron donating compounds enhancing and modifying the catalytic properties.
  • U.S. Patent No. 4,013,823 describes the preparation of an elastomeric ethylene-propylene copolymer with aid of a catalyst mixture containing Al halide and Ti halide and wherein the Ti-compound has been superposed on an anhydrous Mg halide carrier, which catalyst mixture has then been co plexed with an electron donor.
  • thermoplastic ethylene- propylene copolymer having elastomeric properties in the unvulcanized state, by copolymerizing propylene and ethylene which is present in an amount of 10-50 wt%, by using a mixture of a catalyst system comprising an optionally with a donor complexed Al alkyl and a Ti halide, which has been complexed with a donor and supported on an activated, anhydrous Mg halide carrier.
  • EP Patent Application 60,090 described an ethylene-propylene copolymer which is prepared by polymerizing monomers at a temperature of 22-27°C (according to the examples) with the aid of a catalyst mixture which is obtained by reacting one ore more of an Al trialkyl and/or an Al alkyl monohalide and a Ti halide which is on a MgCl 2 or MgBr 2 carrier.
  • the product obtained comprises 40-60 wt% propylene units, no polypropylenic crystallinity and less than 10 % polyethyle ⁇ nic crystallinity.
  • the problem is that in the formation of a particle form product the particles are adhered to each others and polymer is precipitated also on the inner walls of the reactor and other apparatus co ing into contact with the reaction mixture such as mixers. It is thus necessary to clean the reactor apparatus often, a tedious and time consuming procedure.
  • the present invention has as a goal to provide such a process for the preparation of elastomeric, particle form ethylene-propylene copolymer wherein the particle form copolymer particles built up in the polymerization are not adhering to each others nor the walls of the polymerization reactor or the other surfaces in the apparatus coming into contact with the reaction mixture.
  • the most preferred monomer combination is comprised of propylene and ethylene.
  • a diene can also be used as a third monomer.
  • Typical dienes are dicyclopentadiene, ethylidene-norbornene and hexa-1,4-diene.
  • the co-polymerization is thus carried out with aid of a Ziegler-Natta catalyst composition consisting of a so-called procatalyst and a co-catalyst.
  • the procatalyst is based on a compound of a transition metal belonging to some of the groups IVB-VIII of the periodic system of elements
  • the co-catalyst is based on an organometallic compound of a metal belonging to some of groups IA-IIIA of the periodic system of the elements.
  • To the catalyst system usually also belongs a carrier on which the transition metal has been superposed, and electron donating compounds which enhance and modify the catalytic properties of the system.
  • the procatalyst can be for example a quadrivalent Ti halide which has been superposed on a Mg halide carrier, and as the co-catalyst can be for example an organoaluminum compound such as an Al trialkyl. Specific homogenous catalyst systems can also be used.
  • the ratio procatalyst to co-catalyst is about 20-200 and preferably about 100.
  • the polymerization is carried out as a precipitation polymerization wherein the polymer is not dissolved in the medium.
  • the medium preferably propylene in a liquid form can be used.
  • the reactor used is an autoclave provided with a mixer, which autoclave is purged with gaseous nitrogen in order to reduce the oxygen content in a very essential degree before the polymerization. Hydrogen can preferably be used to regulate the chain length of the copolymer thus obtained.
  • the elastomeric copolymer of ethylene and propylene is obtained in a particle form when the amount of units originating from ethylene in the co-polymer exceeds 35 wt% (cf. Fig. 1) .
  • the adhesion of the product is reduced with growing sequences of crystalline polyethylene and reducing amount of sequences of atactic polypropylene, but first when at the same time the polymerization temperature is kept low, ie. below 15°C, the particles obtained do not adhere on the different parts of the reactor.
  • the ethylene-propylene copolymer in a particle form is easy to handle so it can be used for a myriad of purposes which can gain profit of this property.
  • the copolymer can be vulcanized, especially when it contains as a ter-monomer component some diene compound, by known methods with elementary sulphur, different sulphur compounds, peroxy compounds, azo compounds, by radiation, etc.
  • the low degree of adhesion is an advantage both by the preparation of the polymer and by its vulcanization or other treatment, resulting in savings both in the investment and running costs of the production.
  • the invention is illustrated in the following with examples the obtained products of from which were analyzed with methods mentioned below.
  • the crystallinity and the glass transition temperature of the product were determined with the DSC method.
  • the intrinsic viscosity was determined with a capillary visco- meter at 135°C in decaline.
  • the ethylene content of the product was determined by IR spectroscopy using the absorption at 1,150 cm" 1 and 720 cm" 1 .
  • the content correlation was calibrated with the 13 C NMR analysis.
  • the density of the product was determined in a mixture of ethanol and water in a density gradient column.
  • An EPM elastomer was produced in a liquid propylene in a 2 L autoclave provided with a mixer, which autoclave had two small windows at the sides in order to observe the particles formed in the polymerization.
  • the polymerization was started by adding a catalyst system comprised of TiCl 4 on a magnesium chloride carrier and triethyl Al (a 10-wt% solution in heptane) in a mole ratio of 100.
  • the catalyst components were mixed before feeding to the reactor.
  • After the addition of hydrogen, propylene and the catalyst the pressure was raised to 8.0 bars by leading gaseous ethylene to the reactor (the over pressure of the ethylene was 0.5 bars).
  • the pressure was kept constant by the continuous addition of ethylene, and the reaction mixture was stirred with a constant speed of 600 rp .
  • the temperature was 0°C.
  • the polymerization was stopped after 30 minutes by letting the unreacted monomer out from the reactor.
  • the activity of the catalyst was 14 kg copolymer/g-h.
  • the copolymer contained 37 wt% ethylene according to IR analysis. According to the DSC analysis there were no polyethylene type crystallinity in the copolymer, its intrinsic viscosity in decaline was 2,53 at 135°C, the Shore A hardness according to ASTM D 2240-81 was 49, and as density a gradient column revealed 0.861 g/cm 2 .
  • the product was in a particle form and the particles didn't adhere to each others after removal of the monomers.
  • Example 18 This example was carried out as example 1 but the temperature was 14°C and the total pressure was 12.6 bars. In the polymerization as an external donor diphenyldimethyl- silane was used and the TEA/donor mole ratio was 10. The product was in a particle form and its properties were like the ones given in Table 3. From Fig. 1, it can be seen that when the ethylene content of the product varied between 37 wt% and 64 wt% (correspon ⁇ dingly, its polyethylene type crystallinity varied between 0% and 13%, and the glass transition temperature between 27°C and -30°C, cf. Tables 1 and 2) and the product was polymerized at a temperature below 14°C, the product obtained was in form of particles which were not tacky nor tended to adhere to each others or to reactor parts.

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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)

Abstract

L'invention concerne un procédé de préparation d'un copolymère d'éthylène-propylène élastomère obtenu sous forme de particules ne tendant pas à coller les une aux autres ni sur les parties du réacteur de polymérisation ou de l'appareil de traitement pendant le traitement ultérieur. On prépare le copolymère par polymérisation d'éthylène dans un propylène liquide à une température faible inférieure à 15 °C, à l'aide d'un système catalytique Ziegler-Natta. La nature du produit sous forme de particules est plus prononcée lorsque la teneur en unités d'éthylène dans le copolymère obtenu est supérieure à 35 %, de préférence supérieure à 50 %.
PCT/FI1991/000219 1990-01-18 1991-07-17 Procede de preparation de copolymeres d'ethylene-propylene sous forme particulaire WO1993002116A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FI900301A FI87360C (fi) 1990-01-18 1990-01-18 Foerfarande foer framstaellning av eten-propen-kopolymerer i partikelform

Publications (1)

Publication Number Publication Date
WO1993002116A1 true WO1993002116A1 (fr) 1993-02-04

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Application Number Title Priority Date Filing Date
PCT/FI1991/000219 WO1993002116A1 (fr) 1990-01-18 1991-07-17 Procede de preparation de copolymeres d'ethylene-propylene sous forme particulaire

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FI (1) FI87360C (fr)
WO (1) WO1993002116A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996030417A1 (fr) * 1995-03-24 1996-10-03 The University Of North Carolina At Chapel Hill Procede de polymerisation multiphase
US5986021A (en) * 1995-05-02 1999-11-16 Borealis A/S Process for manufacturing LLDPE polymers
US6365350B1 (en) 1997-07-07 2002-04-02 The Institute Of Physical And Chemical Research Method of DNA sequencing
US6680387B2 (en) 2000-04-24 2004-01-20 Aryx Therapeutics Materials and methods for the treatment of diabetes, hyperlipidemia, hypercholesterolemia, and atherosclerosis
US7208413B2 (en) 2000-06-27 2007-04-24 Applied Materials, Inc. Formation of boride barrier layers using chemisorption techniques

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3789036A (en) * 1970-10-13 1974-01-29 Montedison Spa Process for preparing saturated and unsaturated elastomeric copolymers of ethylene and/or higher alpha-olefins
EP0060090A1 (fr) * 1981-03-06 1982-09-15 Montedison S.p.A. Procédé de préparation de copolymères éthylene/propylène
EP0177622A1 (fr) * 1984-10-08 1986-04-16 Sumitomo Chemical Company, Limited Procédé de préparation d'un copolymère d'éthylène
DE2505825C2 (fr) * 1974-02-15 1988-06-30 Montedison S.P.A., Mailand/Milano, It

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3789036A (en) * 1970-10-13 1974-01-29 Montedison Spa Process for preparing saturated and unsaturated elastomeric copolymers of ethylene and/or higher alpha-olefins
DE2505825C2 (fr) * 1974-02-15 1988-06-30 Montedison S.P.A., Mailand/Milano, It
EP0060090A1 (fr) * 1981-03-06 1982-09-15 Montedison S.p.A. Procédé de préparation de copolymères éthylene/propylène
EP0177622A1 (fr) * 1984-10-08 1986-04-16 Sumitomo Chemical Company, Limited Procédé de préparation d'un copolymère d'éthylène

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996030417A1 (fr) * 1995-03-24 1996-10-03 The University Of North Carolina At Chapel Hill Procede de polymerisation multiphase
US5986021A (en) * 1995-05-02 1999-11-16 Borealis A/S Process for manufacturing LLDPE polymers
US6365350B1 (en) 1997-07-07 2002-04-02 The Institute Of Physical And Chemical Research Method of DNA sequencing
US6680387B2 (en) 2000-04-24 2004-01-20 Aryx Therapeutics Materials and methods for the treatment of diabetes, hyperlipidemia, hypercholesterolemia, and atherosclerosis
US7208413B2 (en) 2000-06-27 2007-04-24 Applied Materials, Inc. Formation of boride barrier layers using chemisorption techniques

Also Published As

Publication number Publication date
FI87360C (fi) 1992-12-28
FI87360B (fi) 1992-09-15
FI900301A0 (fi) 1990-01-18
FI900301L (fi) 1991-07-19

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