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WO1997011098A1 - Polymeres olefiniques contenant des groupes polaires et leur procede de production - Google Patents

Polymeres olefiniques contenant des groupes polaires et leur procede de production Download PDF

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Publication number
WO1997011098A1
WO1997011098A1 PCT/FI1996/000494 FI9600494W WO9711098A1 WO 1997011098 A1 WO1997011098 A1 WO 1997011098A1 FI 9600494 W FI9600494 W FI 9600494W WO 9711098 A1 WO9711098 A1 WO 9711098A1
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WO
WIPO (PCT)
Prior art keywords
polymerization
zrcl
ethylene
olefin
bis
Prior art date
Application number
PCT/FI1996/000494
Other languages
English (en)
Inventor
Barbro LÖFGREN
Päivi Aaltonen
Pekka Knuuttila
Original Assignee
Borealis A/S
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 Borealis A/S filed Critical Borealis A/S
Priority to AU69899/96A priority Critical patent/AU6989996A/en
Publication of WO1997011098A1 publication Critical patent/WO1997011098A1/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
    • 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
    • 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

  • Olefin polymers which contain polar groups, and a method for their manufacture
  • the invention relates to novel olefin copolymers which contain functional groups and to a method for their manufacture.
  • the linking of monomers which contain functional groups to a hydrocarbon polymer chain signifies the creating of a usable method for the modification of the chemical and physical properties of olefins.
  • monomers containing functional groups it is possible to improve properties such as adhesion, dyeability, printability and permeability.
  • a functional group provides a possibility for graft polymerization and thereby for uses such as compatibilization of blends containing polyolefins.
  • the Ziegler-Natta catalyst system is commonly used in the polymerization and copolymerization of olefins, but one of the major limitations of these conventional catalysts is that they are not suited for use in conjunction with monomers containing polar groups. Ziegler-Natta catalysts rather form a complex with the electron pair of a heteroatom, and thus in polymerization they rapidly deactivate the active centers by forming a stable complex with the functional group.
  • a polar monomer resembles alpha-olefin, the greater is its potential for becoming polymerized by the same active centers as olefins.
  • the inventors have shown that comonomers which contain heteroatoms can be used for the polymerization of polyolefin. It is known that Lewis acid components (Zr, Al) present in the catalyst tend to form a complex with the unbound electron pairs of heteroatoms, thus causing deactivation of the catalyst.
  • this non-desirable interaction can be minimized by certain methods, such as (a) by isolating the double bond from the heteroatoms by means of a longer hydrocarbon chain; (b) by adding a steric barrier around the heteroatom; (c) by decreasing the electron donor character of the heteroatom, for example, by linking to it or in its vicinity a group which attracts electrons; (d) by selecting catalyst components which are inert to functional groups; (e) by precomplexing the functional monomer by using a Lewis acid; or (f) by using a polar solvent which becomes polarized with the active center but allows the polymerization of the vinyl monomer.
  • US patent publication 5, 286, 800 discloses the polymerization, with alpha-olefins, of comonomers containing functional groups. In these polymerizations there are used borane monomers which are converted, by reactions after the polymerization step, into polyolefins which contain functional groups.
  • An object of the present invention is to provide novel copolymers of olefins and monomers containing functional groups. Furthermore, one object of the invention is a method in which the catalyst system has as high an activity as possible in the presence of a polar group. One object of the invention is also to provide for the copolymerization of olefins a method in which the copolymerization with a polar comonomer takes place in one step, without any pretreatment or postmodif ication. A further object according to the invention is to provide functional polyolefins in which the molar masses remain relatively high and the molar mass distributions are wide. In the Applicant's previous application FI 951970, this object was achieved by using as the functional monomer 2-methyl-3-buten-l-ol, 3-methyl-3-buten-l-ol and 5- hexen-1-ol.
  • the olefin copolymer according to the invention prepared by polymerizing an olefin which contains 2—5 carbon atoms with a monomer which contains a functional group, is characterized in that the functional monomer is 9-methyl decenoate.
  • the olefin used in the manufacture of copolymers according to the invention consists of olefins containing 2—6 carbon atoms.
  • ethylene or propylene is used, but olefins having a longer carbon chain, such as l-butene, pentene and 1 -hexene, may be used just as well.
  • the catalyst used is a metallocene-type catalyst.
  • the metallocene may be a metallocene of any type.
  • suitable metallocene compounds include compounds having the formula (Cp) m R n MR' 0 X p , where Cp is an unsubstituted or substituted and/or fused homo- or heterocyclopentadienyl, R is a group containing 1-4 carbon atoms and serving as a bridge between two Cp rings, M is a transition metal belonging to group 4A, 5A or 6A (Hubbard), R' is a C j -C 2 hydrocarbyl or hydroxy- carbyl group, and X is a halogen, m being 1—3, n being 0 or p being 0—3, and the sum m+n+p corresponding to the state of oxidation of the transition metal M.
  • the transition metal is preferably zirconium or hafnium, most preferably zirconium.
  • metallocene compounds include bis(n-butylcyclopentadienyl) zirconium dichloride, 1 ,2-ethylene-bis(indenyl) zirconium dichloride, and 1,2- ethylene-bis(indenyl) hafnium dichloride.
  • the polymerization activity of the catalyst can also be increased by using activators such as alumoxane.
  • activators such as alumoxane.
  • One method is to add the alumoxane to the metallocene compo ⁇ nent either before, simultaneously or after the metallocene.
  • Another method is to add the activator directly into the polymerization reactor.
  • Suitable activators include alumoxane compounds having the formula R-(Al(R)-O) n - A1R2 or (-Al(R)-O-) m ,where n is 1-40, m is 3-40, and R is a C r C 8 alkyl group.
  • R is a methyl group.
  • the support used may be any porous or inert support, such as silica or alumina or mixtures thereof.
  • the polymerization may be carried out by any method, for example by slurry polymerization or gas phase polymerization.
  • the polymerization may be carried out, for example, at a temperature of 60-100 °C and under a pressure of 1-100 bar.
  • the partial pressure of olefin in the reactor may vary within the range 1-3 bar and the amount of comonomer within the range 0.5—10 mmol.
  • n-butylcyclopentadienyl) zirconium dichloride (n-butCp) 2 )ZrCl 2 dicyclopenta- dienyl zirconium dichloride Cp 2 ZrCl 2 , l,2-ethylene-bis(indenyl) zirconium di ⁇ chloride Et(Ind) 2 ZrCl 2 , (dimethylsilyl-bis(lH-indenyl)) zirconium dichloride Me Si(Ind) 2 ZrCl 2 and methylalumoxane (MAO) were of a commercial grade and were not purified separately.
  • n-butCp) 2 )ZrCl 2 dicyclopenta- dienyl zirconium dichloride Cp 2 ZrCl 2 , l,2-ethylene-bis(indenyl) zirconium di ⁇ chloride Et(Ind) 2 ZrCl 2 , (dimethylsilyl-bis(lH-in
  • Polymerization-grade ethylene and propylene and the n-heptane and toluene serving as the medium were purified by feeding them through a column series to eliminate any moisture and oxygen residues.
  • the comonomer methy 1-9-decenoate was of own production.
  • Ethylene copolymerizations were carried out in a 0.5 dm 3 autoclave at a temperature of 60 °C for 40 minutes, and the reaction medium used was n-heptane.
  • the medium n-heptane (350 cm 3 ) was fed into a vacuumized reactor, blanketed with nitrogen and equipped with a stirrer. The rotation velocity of the stirrer was con ⁇ stantly 400 rotations per minute.
  • ethylene was monitored by means of a mass flow controller. After equilibrium had been reached, polymerization was started by pumping the catalyst into the reactor. The partial pressure of ethylene or propylene was maintained constant (2.5 bar ethylene overpressure) by means of an electronic pressure controller and a solenoid valve, and the reactor temperature was maintained constant ( ⁇ 0.1 °C). The conver ⁇ sion was maintained low in order that it could be assumed that the concentration in the reactor remained constant. At 40 minutes, reactor pressure was released and the obtained polymer product was washed with a solution of ethanol and hydrochloric acid, and was dried.
  • Propylene copolymerizations were carried in the same manner as ethylene copolymerizations except that the medium used was toluene in an amount of 300 cm 3 , the polymerization time was 60 minutes and the polymerization tempera- ture was 30 °C, and the propylene overpressure was 3.0 bar.
  • the catalyst used was l,2-ethylene-bis(indenyl) zirconium dichloride.
  • compositions of the copolymers of ethylene and the functional monomer were determined by using a Jeol NMR spectrometer.
  • the melting points and enthalpies were determined from the peak of the DSC curve by using a Perkin Elmer DSC-7 instrument.
  • the DSC measurements were carried out by reheating the sample to 180 °C at heating rates of 2 and 10 °C/min.
  • the molar masses and the molar mass distributions were measured using a Waters- type ALC/GPC 150 instrument in which there had been installed 3 TOSOH mixed- bed columns in which the polystyrene barrier limit was 4 x 10 8 at a temperature of 135 °C.
  • the solvent used was 1,2,4-trichlorobenzene having a flow rate of 1.0 ml/min.
  • Ethylene was copolymerized with methyl-9-decenoate.
  • the catalysts used were combinations (n-butCp) 2 ZrCl 2 /MAO, Cp 2 ZrCl 2 /MAO, Et(Ind) 2 ZrCl 2 /MAO and Me 2 Si(Ind) 2 ZrCl 2 /MAO.
  • the polymerization conditions and some product properties are shown in Table 1.
  • Copolymerizations of propylene and methyl-9-decenoate were carried out by using the combination l ,2-ethylene-bis(indenyl) zirconium chloride/MAO.
  • the polymerization conditions and some properties of the product are shown in Table 2.

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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 a trait à un copolymère oléfinique préparé par la polymérisation d'une oléfine comprenant de 2 à 5 atomes de carbone au moyen d'un monomère comportant un groupe fonctionnel, le monomère fonctionnel étant un 9-méthyl décénoate.
PCT/FI1996/000494 1995-09-21 1996-09-19 Polymeres olefiniques contenant des groupes polaires et leur procede de production WO1997011098A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU69899/96A AU6989996A (en) 1995-09-21 1996-09-19 Olefin polymers which contain polar groups, and a method for their manufacture

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI954475A FI954475L (fi) 1995-09-21 1995-09-21 Olefiinipolymeerit, jotka sisältävät polaarisia ryhmiä, ja menetelmä niiden valmistamiseksi
FI954475 1995-09-21

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WO1997011098A1 true WO1997011098A1 (fr) 1997-03-27

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1186619A2 (fr) * 2000-09-07 2002-03-13 Mitsui Chemicals, Inc. Copolymère d'oléfines contenant des groupes polaires, procédé pour sa préparation, composition thermoplastique de résine contenant le copolymère et son utilisation
US7279536B2 (en) 2002-09-20 2007-10-09 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US7319125B2 (en) 2002-09-20 2008-01-15 Exxonmobil Chemical Patents Inc. Supercritical polymerization process and polymers produced therefrom
WO2009123663A1 (fr) 2007-12-20 2009-10-08 Exxonmobil Chemical Patents Inc. Polypropylène isotactique produit à partir d'un procédé de polymérisation en milieu supercritique
US7741420B2 (en) 2004-07-14 2010-06-22 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US7910679B2 (en) 2007-12-20 2011-03-22 Exxonmobil Research And Engineering Company Bulk homogeneous polymerization process for ethylene propylene copolymers
US7910637B2 (en) 2007-09-13 2011-03-22 Exxonmobil Research And Engineering Company In-line blending of plasticizers with a base polymer
US7928162B2 (en) 2007-09-13 2011-04-19 Exxonmobil Research And Engineering Company In-line process for producing plasticized polymers and plasticized polymer blends
US8080610B2 (en) 2007-03-06 2011-12-20 Exxonmobil Research And Engineering Company Monomer recycle process for fluid phase in-line blending of polymers
US8138269B2 (en) 2007-12-20 2012-03-20 Exxonmobil Research And Engineering Company Polypropylene ethylene-propylene copolymer blends and in-line process to produce them
US8143352B2 (en) 2006-12-20 2012-03-27 Exxonmobil Research And Engineering Company Process for fluid phase in-line blending of polymers
US20120277133A1 (en) * 2011-03-24 2012-11-01 Dibiase Stephen A Functionalized polymers
US9012385B2 (en) 2012-02-29 2015-04-21 Elevance Renewable Sciences, Inc. Terpene derived compounds
US9315748B2 (en) 2011-04-07 2016-04-19 Elevance Renewable Sciences, Inc. Cold flow additives
US9464255B2 (en) 2013-03-12 2016-10-11 Elevance Renewable Sciences, Inc. Maleinized ester derivatives
US9481850B2 (en) 2013-03-12 2016-11-01 Elevance Renewable Sciences, Inc. Maleinized ester derivatives

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4518757A (en) * 1983-12-23 1985-05-21 Exxon Research & Engineering Co. Drag reduction agent for hydrocarbon liquid
US4523929A (en) * 1983-12-23 1985-06-18 Exxon Research & Engineering Co. Antimisting system for hydrocarbon fluids
EP0356692A2 (fr) * 1988-07-29 1990-03-07 Idemitsu Kosan Company Limited Procédé de préparation de produits de moulage étirés

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4518757A (en) * 1983-12-23 1985-05-21 Exxon Research & Engineering Co. Drag reduction agent for hydrocarbon liquid
US4523929A (en) * 1983-12-23 1985-06-18 Exxon Research & Engineering Co. Antimisting system for hydrocarbon fluids
EP0356692A2 (fr) * 1988-07-29 1990-03-07 Idemitsu Kosan Company Limited Procédé de préparation de produits de moulage étirés

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7393907B2 (en) 2000-09-07 2008-07-01 Mitsui Chemicals, Inc. Polar group-containing olefin copolymer, process for preparing the same, thermoplastic resin composition containing the copolymer, and uses thereof
EP1186619A3 (fr) * 2000-09-07 2003-10-29 Mitsui Chemicals, Inc. Copolymère d'oléfines contenant des groupes polaires, procédé pour sa préparation, composition thermoplastique de résine contenant le copolymère et son utilisation
US7714087B2 (en) 2000-09-07 2010-05-11 Mitsui Chemicals, Inc. Polar group-containing olefin copolymer, process for preparing the same, thermoplastic resin composition containing the copolymer, and uses thereof
EP1186619A2 (fr) * 2000-09-07 2002-03-13 Mitsui Chemicals, Inc. Copolymère d'oléfines contenant des groupes polaires, procédé pour sa préparation, composition thermoplastique de résine contenant le copolymère et son utilisation
US7319125B2 (en) 2002-09-20 2008-01-15 Exxonmobil Chemical Patents Inc. Supercritical polymerization process and polymers produced therefrom
US7354979B2 (en) 2002-09-20 2008-04-08 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US7279536B2 (en) 2002-09-20 2007-10-09 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US7807769B2 (en) 2002-09-20 2010-10-05 Exxonmobil Chemical Patents Inc. Isotactic polypropylene produced from supercritical polymerization process
US7741420B2 (en) 2004-07-14 2010-06-22 Exxonmobil Chemical Patents Inc. Polymer production at supercritical conditions
US8143352B2 (en) 2006-12-20 2012-03-27 Exxonmobil Research And Engineering Company Process for fluid phase in-line blending of polymers
US8080610B2 (en) 2007-03-06 2011-12-20 Exxonmobil Research And Engineering Company Monomer recycle process for fluid phase in-line blending of polymers
US7910637B2 (en) 2007-09-13 2011-03-22 Exxonmobil Research And Engineering Company In-line blending of plasticizers with a base polymer
US7928162B2 (en) 2007-09-13 2011-04-19 Exxonmobil Research And Engineering Company In-line process for producing plasticized polymers and plasticized polymer blends
WO2009123663A1 (fr) 2007-12-20 2009-10-08 Exxonmobil Chemical Patents Inc. Polypropylène isotactique produit à partir d'un procédé de polymérisation en milieu supercritique
US8138269B2 (en) 2007-12-20 2012-03-20 Exxonmobil Research And Engineering Company Polypropylene ethylene-propylene copolymer blends and in-line process to produce them
US7910679B2 (en) 2007-12-20 2011-03-22 Exxonmobil Research And Engineering Company Bulk homogeneous polymerization process for ethylene propylene copolymers
US20120277133A1 (en) * 2011-03-24 2012-11-01 Dibiase Stephen A Functionalized polymers
WO2012129490A3 (fr) * 2011-03-24 2012-11-08 Elevance Renewable Sciences Polymères fonctionnalisés
US8846587B2 (en) 2011-03-24 2014-09-30 Elevance Renewable Sciences, Inc. Functionalized monomers and polymers
US9334347B2 (en) 2011-03-24 2016-05-10 Elevance Renewable Sciences, Inc. Functionalized monomers and polymers
US9738618B2 (en) 2011-03-24 2017-08-22 Elevance Renewable Sciences, Inc. Malienated derivatives
US10294210B2 (en) 2011-03-24 2019-05-21 Elevance Renewable Sciences, Inc. Maleinated derivatives
US9315748B2 (en) 2011-04-07 2016-04-19 Elevance Renewable Sciences, Inc. Cold flow additives
US9012385B2 (en) 2012-02-29 2015-04-21 Elevance Renewable Sciences, Inc. Terpene derived compounds
US9464255B2 (en) 2013-03-12 2016-10-11 Elevance Renewable Sciences, Inc. Maleinized ester derivatives
US9481850B2 (en) 2013-03-12 2016-11-01 Elevance Renewable Sciences, Inc. Maleinized ester derivatives

Also Published As

Publication number Publication date
FI954475L (fi) 1997-03-22
FI954475A0 (fi) 1995-09-21
AU6989996A (en) 1997-04-09

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