WO1999055738A1 - Procede de polymerisation et de copolymerisation d'ethylene - Google Patents

Procede de polymerisation et de copolymerisation d'ethylene Download PDF

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Publication number
WO1999055738A1
WO1999055738A1 PCT/EP1999/002450 EP9902450W WO9955738A1 WO 1999055738 A1 WO1999055738 A1 WO 1999055738A1 EP 9902450 W EP9902450 W EP 9902450W WO 9955738 A1 WO9955738 A1 WO 9955738A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymerization
ethylene
carboxylic acids
peroxidic
initiators
Prior art date
Application number
PCT/EP1999/002450
Other languages
German (de)
English (en)
Inventor
Frank-Olaf Mähling
Roger Klimesch
Andreas Deckers
Michael Buback
Lars Wittkowski
Original Assignee
Elenac Gmbh
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 Elenac Gmbh filed Critical Elenac Gmbh
Priority to EP99917973A priority Critical patent/EP1090044A1/fr
Priority to HU0101834A priority patent/HUP0101834A3/hu
Priority to JP2000545896A priority patent/JP2002513048A/ja
Priority to BR9909845-8A priority patent/BR9909845A/pt
Priority to KR1020007011751A priority patent/KR20010034822A/ko
Publication of WO1999055738A1 publication Critical patent/WO1999055738A1/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
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • 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
    • C08F210/02—Ethene

Definitions

  • the present invention relates to a process for the polymerization of ethylene or copolymerization of ethylene with vinylically unsaturated comonomers at temperatures from 110 to 350 ° C. and pressures from 1000 to 4000 bar in the presence of peroxidic polymerization initiators.
  • the invention further relates to the use of non-polymerizable carboxylic acids in such processes.
  • the present invention was therefore based on the object of avoiding the use of such peroxides which decompose at low temperature and nevertheless of achieving an effective and controllable initiation of the polymerization.
  • Both homopolymers of ethylene and copolymers of ethylene with various vinylically unsaturated comonomers can be prepared by the process according to the invention.
  • One embodiment of the process according to the invention therefore consists in the copolymerization of ethylene with ⁇ , ⁇ -unsaturated carboxylic acids or derivatives of such carboxylic acids.
  • the ⁇ , ⁇ -unsaturated carboxylic acids which can be used as comonomers in the process according to the invention are generally short-chain carboxylic acids having 3 to 8 carbon atoms. Examples include acrylic acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid, acrylic acid and methacrylic acid being preferred comonomers.
  • esters of C to C 6 alkanols that is to say ethyl, propyl, butyl, pentyl and hexyl esters, can also be used as comonomers.
  • Another preferred embodiment of the process relates to the copolymerization of ethylene with vinyl acetate.
  • the polymerization and copolymerization process according to the invention is preferably carried out at temperatures between 140 and 320.degree. C., particularly preferably between 160 and 300.degree. C., with polymerizations being carried out with sensitive comonomers, in particular carboxylic acid esters, preferably at temperatures below 220.degree.
  • the preferred pressure range for carrying out the method according to the invention is between 1500 and 3500 bar, in particular between 2000 and 3000 bar.
  • the process according to the invention can be carried out in various reactors known to the person skilled in the art.
  • processes in Ruhr autoclaves such as those for 3
  • Tubular reactors are understood to mean tubular polymerization vessels, the ratio of the length to the diameter of the pressure-resistant tubes generally being in the range from 10,000 to 60,000 to 1.
  • Information on ethylene high-pressure polymerization processes using tubular reactors can be found, for example, in "Ulimanns Encyklpadie der technical chemistry", 1980, 4th edition, volume 19, pages 167 to 178, Verlag Chemie GmbH, D-6940 Wemheim.
  • reactor types can be used, e.g. Reactors with or without cold gas addition, reactors with pressurized water cooling, etc.
  • the polymerization is initiated by peroxidic polymerization initiators.
  • peroxides are considered which only decompose m radicals at relatively high temperatures. Decay temperature is understood to mean the temperature at which 50% of the peroxide molecules disintegrate within one minute.
  • Suitable peroxidic polymerization initiators are, for example, 1,1-bis (t-butyl peroxy) cyclohexane, 1,1-bis (t-butyl peroxy) butane, t. -Butylperoxy- 3, 5, 5 - t ⁇ methylhexanoat, t.-Butylperoxybenzoat, 2, 5 -Bis (t. -Butylperoxy) -2,5 -dimethylhexane, t. - Butyl cumyl peroxide, diet. -butyl peroxide and 2, 5 -bis (t .butylperoxy) 2, 5 -d ⁇ methyl-3 -hexin m consideration, particularly preferred is tert. -butyl peroxide used.
  • those with a decomposition temperature of at least 150 ° C. are used as peroxidic polymerization initiators. Both individual peroxides and mixtures of different peroxides can be used.
  • aliphatic and aromatic carboxylic acids come into consideration as non-polymerizable carboxylic acids with which the rate of decomposition of the peroxidic initiators can be influenced.
  • Short-chain aliphatic carboxylic acids in particular C 1 -C 4 -alkane carboxylic acid, have proven particularly useful for regulating the peroxide decomposition in the course of the polymerization.
  • the use of acetic acid is particularly advantageous.
  • the amount or concentration of the non-polymerizable carboxylic acids used depends on the type and decomposition temperature of the peroxides used and on the desired initiator activity. It must therefore be tailored to the specific polymerization requirements. In general, amounts of 0.05 to 1.0% by weight, in particular 0.08 to 0.8% by weight, based in each case on the total amount of ethylene in the polymerization mixture, have proven useful.
  • the polymerization mixture can additionally contain customary additives, such as molecular weight regulators.
  • molecular weight regulators such as hydrogen, ketones, aldehydes, alcohols, ethers and linear and branched hydrocarbons. Propane, propylene, methyl ethyl ketone or propionaldehyde are preferably used.
  • the polymerization regulators are generally used in amounts of 0.2 to 5 mol percent, based on the ethylene to be polymerized.
  • ethylene was polymerized at a throughput of 1.4 t / h under a pressure of 2800 bar and an inlet temperature of 180 ° C.
  • TBPIN tert-butyl per - 5 oxy-3, 5, 5 - trimethylhexanoate, decomposition temperature 160 ° C
  • DTBP di-tert-butyl peroxide , Decay temperature 190 ° C
  • Ethylene 5 was polymerized under conditions similar to those in Example VI, but without TBPIN and in the presence of 0.1% by weight of acetic acid. See Table 1 for results
  • Ethylene was polymerized under the conditions of Example 1, but in the presence of 0.5% by weight of acetic acid. See Table 1 for results

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)

Abstract

L'invention concerne un procédé de polymérisation ou de copolymérisation d'éthylène avec des comonomères vinyliquement insaturés, à des températures comprises entre 110 et 350 °C et des pressions comprises entre 1000 et 4000 bars en présence d'initiateurs de polymérisation de type peroxyde. Selon ce procédé, pour influencer la vitesse de décomposition des initiateurs de polymérisation de type peroxyde, on ajoute au mélange de polymérisation au moins un acide carboxylique non polymérisable dans des proportions comprises entre 0,01 et 2,0 % en poids, par rapport à la proportion totale d'éthylène dans le mélange de polymérisation.
PCT/EP1999/002450 1998-04-24 1999-04-12 Procede de polymerisation et de copolymerisation d'ethylene WO1999055738A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP99917973A EP1090044A1 (fr) 1998-04-24 1999-04-12 Procede de polymerisation et de copolymerisation d'ethylene
HU0101834A HUP0101834A3 (en) 1998-04-24 1999-04-12 Method for polymerising and copolymerising ethylene
JP2000545896A JP2002513048A (ja) 1998-04-24 1999-04-12 エチレンの重合及び共重合
BR9909845-8A BR9909845A (pt) 1998-04-24 1999-04-12 Processo para polimerizar etileno ou copolimerizar etileno, e, uso de ácidos carboxìlicos não polimerizáveis
KR1020007011751A KR20010034822A (ko) 1998-04-24 1999-04-12 에틸렌의 중합 및 공중합 방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19818216A DE19818216A1 (de) 1998-04-24 1998-04-24 Verfahren zur Polymerisation und Copolymerisation von Ethylen
DE19818216.3 1998-04-24

Publications (1)

Publication Number Publication Date
WO1999055738A1 true WO1999055738A1 (fr) 1999-11-04

Family

ID=7865598

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/002450 WO1999055738A1 (fr) 1998-04-24 1999-04-12 Procede de polymerisation et de copolymerisation d'ethylene

Country Status (8)

Country Link
EP (1) EP1090044A1 (fr)
JP (1) JP2002513048A (fr)
KR (1) KR20010034822A (fr)
CN (1) CN1298414A (fr)
BR (1) BR9909845A (fr)
DE (1) DE19818216A1 (fr)
HU (1) HUP0101834A3 (fr)
WO (1) WO1999055738A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10006900A1 (de) 2000-02-16 2001-08-23 Basell Polyolefine Gmbh Verfahren zur radikalischen Ethylen-Hochdruckpolymerisation unter Vermeidung unerwünschter Polymerablagerungen
EP2325229A1 (fr) * 2009-11-13 2011-05-25 Cytec Surface Specialties, S.A. Polyesters pour revêtements

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0121755A2 (fr) * 1983-03-12 1984-10-17 BASF Aktiengesellschaft Procédé de préparation de polymères d'éthylène à une pression supérieure à 500 bar dans un réacteur tubulaire à deux zones
EP0717054A2 (fr) * 1994-12-14 1996-06-19 Xerox Corporation Procédé de polymérisation utilisant des radicaux libres stables et matières thermoplastiques ainsi obtenues

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0121755A2 (fr) * 1983-03-12 1984-10-17 BASF Aktiengesellschaft Procédé de préparation de polymères d'éthylène à une pression supérieure à 500 bar dans un réacteur tubulaire à deux zones
EP0717054A2 (fr) * 1994-12-14 1996-06-19 Xerox Corporation Procédé de polymérisation utilisant des radicaux libres stables et matières thermoplastiques ainsi obtenues

Also Published As

Publication number Publication date
KR20010034822A (ko) 2001-04-25
EP1090044A1 (fr) 2001-04-11
DE19818216A1 (de) 1999-10-28
CN1298414A (zh) 2001-06-06
HUP0101834A3 (en) 2002-05-28
JP2002513048A (ja) 2002-05-08
BR9909845A (pt) 2000-12-19
HUP0101834A2 (hu) 2001-09-28

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