WO1986005794A1 - Production de terpolymeres - Google Patents

Production de terpolymeres Download PDF

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Publication number
WO1986005794A1
WO1986005794A1 PCT/US1985/002016 US8502016W WO8605794A1 WO 1986005794 A1 WO1986005794 A1 WO 1986005794A1 US 8502016 W US8502016 W US 8502016W WO 8605794 A1 WO8605794 A1 WO 8605794A1
Authority
WO
WIPO (PCT)
Prior art keywords
ethylene
stage
terpolymer
butene
slurry
Prior art date
Application number
PCT/US1985/002016
Other languages
English (en)
Inventor
Raymond J. Ehrig
John J. Godfrey
Original Assignee
Uss Engineers And Consultants, Inc.
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 Uss Engineers And Consultants, Inc. filed Critical Uss Engineers And Consultants, Inc.
Publication of WO1986005794A1 publication Critical patent/WO1986005794A1/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
    • 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
    • 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

  • Terpolymers comprising 90% or more propylene having a DSC melting point lower than 140-145°C cannot be prepared in hexane slurry at 60°C because the polymer particles swell by absorbing the hexane diluent, become very sticky, and thereby cause agglomeration and reactor fouling.
  • 1-butene as a termonomer along with small amounts of ethylene is not new, its advantage over ethylene of not increasing the solubility of the polymer as much as ethylene has not been fully utilized in the past because a satisfactory method of manufacturing the polymer has not been conceived to take advantage of the unique contributions of 1-butene while also benefiting from the use of ethylene to modify a basically polypropylene product.
  • the reader may also be interested in Shirai et al 3,642,951, Saito et al 4,066,718, Furutachi et al 4,128,606, and particularly Scoggin 3,525,781, which teaches preparing block copolymers continuously by feeding batch prepolymers into a continuous polymerization zone, Baba et al 4,433,110, which provides propylene and 1-butene polymerization in a first stage and propylene and ethylene polymerization in a second stage, and particularly Frese et al 3,959,409, which discloses the production of crystalline propylene/ethylene/butene-1 terpolymers in series-connected reactors, the ethylene being introduced only in the second or subsequent reactors. See also the large number of examples of terpolymer production in Suzuki et al US Patent 4,304,890. The feed of ethylene is increased, compared to propylene, after the first stage in Sennari et al 3,670,053.
  • the two-stage process may be operated conveniently on a commercial scale by using two continuous reactors in series.
  • the following examples demonstrating the process use, for convenience, the process equivalent of two reactors in series, namely a single batch reactor wherein the batch is treated in a first and a second stage. Concentrations of the termonomers are maintained in the first and second stages of the batch reactor at levels equivalent to those in two reactors in series operating continuously and at steady-state conditions.
  • hexane slurry polymerization system where the first reactor is charged with hexane or other solvent for propylene, about one-half percent to about one percent of a titanium tetrachlor ide catalyst supported on magnesium chloride and about 2.5-3.0% of a solution of 10% tr iethylaluminum in hexane. Temperature is preferably maintained at about 35oC and pressure is about 150 psig.
  • the termonomer composition in the reactor to produce a product melting in the range of 130o to 140°C is typically the following as determined by sampling the reactor gas cap and analyzing for the weight ratio of monomers by vapor-phase chromatography: First Stage Second Stage
  • the ethylene component of the termonomer mixture is maintained at a higher level than in the first stage by supplementing the liquid termonomer feed with ethylene typically in 3 psig increments.
  • Product melt flows in the range of 5 to 55 are produced by maintaining levels of hydrogen in the reactor of 0.025 and 0.25 weight percent in stages 1 and 2, respectively, in the gas cap, by vapor-phase chromatography.
  • This process with variations in the content of ethylene and 1-butene of plus or minus five percent and consequent possible variations in content of propylene, will produce a terpolymer having a DSC melting point of about 135 oC, typically about 130o to 140oC, and containing about 3.1 weight percent ethylene and about 4.3 weight percent 1-butene.
  • Our invention includes products recovered from the above process containing from about 3% to about 4% ethylene and about 3% to about 5.6% 1-butene and having a melting point between 130o and 140oC., according to the formula:
  • C 2 and C 4 are the concentrations of ethylene and 1-butene in weight percent.
  • C 2 and C 4 are the concentrations of ethylene and 1-butene in weight percent.
  • the product slurry is in the form of small particles dispersed in the hexane diluent.
  • the size of the terpolymer particles is determined primarily by the size of the original catalyst particles.
  • the terpolymer particles isolated from the reactor slurry have a size ranging from 200 to 2,000 microns diameter,
  • terpolymer product having an ethylene content in the lower part of its range and a 1-butene content in the higher part of its range, in order to minimize the portion of product which is undesirable because it is soluble in hexane.
  • the reactor was loaded with hexane and catalyst components, and 1 psig was maintained in the reactor gas caps for one hour at 35°C by feeding propylene.
  • the catalyst used was a commercial Montedison FTlSS catalyst.
  • the initial reactor charge at 35°C is carried out as indicated in the table of examples.
  • a stirred, jacketed reactor of 300 psig maximum operating pressure was used to make up and feed the termonomer mixtures to the polymerization reactor.
  • 1-butene, propylene, and ethylene were charged in that order to give the liquid-phase feed composition indicated in the table of examples below.
  • the termonomer mixture was then heated to 30°C to raise its pressure above 150 psig so that it could be metered by way of a needle valve to the polymerization reactor, on demand, to maintain 150 psig.
  • the termonomer feed mixture of the compositions indicated in the table of examples was fed to the polymerization reactor, on demand, to maintain the "First Stage" gas cap composition shown above at 150 psig. Demand is manifested immediately when the reaction begins.
  • the second-stage was started by supplementing the termonomer feed with 3 psig incremental additions of ethylene to elevate the ethylene content of the reactor gas cap to 2-4 wt.% ethylene.
  • the more desirable products for our purposes are those of examples 12 and 13, having good or excellent processability with a melting point between 130°C and 140°C, providing good heat sealability.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (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)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Des terpolymères comprenant du propylène et de petites quantités d'éthylène et de butène-1 sont produits par un procédé en deux étapes. Un terpolymère aléatoire à point de fusion relativement élevé est obtenu pendant une première étape et un terpolymère aléatoire à point de fusion relativement bas présentant une teneur en éthylène plus élevée est produit pendant une deuxième étape de manière à être dispersé dans le produit de la première étape. Les deux étapes du traitement peuvent être exécutées dans un seul réacteur à charge discontinue ou dans deux réacteurs continus en série.
PCT/US1985/002016 1985-04-01 1985-10-15 Production de terpolymeres WO1986005794A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US71859185A 1985-04-01 1985-04-01
US718,591 1985-04-01

Publications (1)

Publication Number Publication Date
WO1986005794A1 true WO1986005794A1 (fr) 1986-10-09

Family

ID=24886667

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1985/002016 WO1986005794A1 (fr) 1985-04-01 1985-10-15 Production de terpolymeres

Country Status (3)

Country Link
EP (1) EP0217803A1 (fr)
JP (1) JPS62502405A (fr)
WO (1) WO1986005794A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5516866A (en) * 1987-11-27 1996-05-14 Montell Technology Company Bv Crystalline copolymers of propylene
WO1998058971A1 (fr) * 1997-06-24 1998-12-30 Borealis A/S Terpolymeres de propylene et leur procede de fabrication
EP3257877A1 (fr) * 2016-06-16 2017-12-20 Borealis AG Terpolymères propylène-éthylène-butylène nucléés et articles moulés faits à partir de ceux-ci

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959409A (en) * 1973-10-23 1976-05-25 Chemische Werke Huls Aktiengesellschaft Process for the production of crystalline propene-ethene-butene-1 terpolymers
US4304890A (en) * 1976-04-19 1981-12-08 Chisso Corporation Method for producing propylene copolymers using a catalyst activated prior to copolymerization
GB2116989A (en) * 1982-03-23 1983-10-05 Mitsubishi Petrochemical Co Block copolymers of propylene butene-1 and optionally ethylene

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959409A (en) * 1973-10-23 1976-05-25 Chemische Werke Huls Aktiengesellschaft Process for the production of crystalline propene-ethene-butene-1 terpolymers
US4304890A (en) * 1976-04-19 1981-12-08 Chisso Corporation Method for producing propylene copolymers using a catalyst activated prior to copolymerization
GB2116989A (en) * 1982-03-23 1983-10-05 Mitsubishi Petrochemical Co Block copolymers of propylene butene-1 and optionally ethylene

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5516866A (en) * 1987-11-27 1996-05-14 Montell Technology Company Bv Crystalline copolymers of propylene
US6355758B1 (en) 1987-11-27 2002-03-12 Basell Technology Company Bv Crystalline copolymers of propylene
WO1998058971A1 (fr) * 1997-06-24 1998-12-30 Borealis A/S Terpolymeres de propylene et leur procede de fabrication
AU726669B2 (en) * 1997-06-24 2000-11-16 Borealis As Propylene terpolymers and a process for the production thereof
US6365682B1 (en) 1997-06-24 2002-04-02 Borealis Technology Oy Process for the production of propylene terpolymers
EP3257877A1 (fr) * 2016-06-16 2017-12-20 Borealis AG Terpolymères propylène-éthylène-butylène nucléés et articles moulés faits à partir de ceux-ci
WO2017216091A3 (fr) * 2016-06-16 2018-03-22 Borealis Ag Nouveaux terpolymères de propylène-éthylène-butylène nucléés et articles moulés fabriqués à partir de ceux-ci
CN109689706A (zh) * 2016-06-16 2019-04-26 博里利斯股份公司 新型成核丙烯-乙烯-丁烯三元共聚物以及由其制成的成型制品
RU2701732C1 (ru) * 2016-06-16 2019-10-01 Бореалис Аг Новые нуклеированные пропилен-этилен-бутиленовые терполимеры и изготовленные из них литые изделия
US10982028B2 (en) 2016-06-16 2021-04-20 Borealis Ag Nucleated propylene-ethylene-butylene terpolymers and moulded articles made thereof
CN109689706B (zh) * 2016-06-16 2022-02-18 博里利斯股份公司 成核丙烯-乙烯-丁烯三元共聚物以及由其制成的成型制品

Also Published As

Publication number Publication date
EP0217803A1 (fr) 1987-04-15
JPS62502405A (ja) 1987-09-17

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