CA2232456A1 - Copolymer of an olefinic monomer and 1,2-polybutadiene - Google Patents
Copolymer of an olefinic monomer and 1,2-polybutadiene Download PDFInfo
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- CA2232456A1 CA2232456A1 CA002232456A CA2232456A CA2232456A1 CA 2232456 A1 CA2232456 A1 CA 2232456A1 CA 002232456 A CA002232456 A CA 002232456A CA 2232456 A CA2232456 A CA 2232456A CA 2232456 A1 CA2232456 A1 CA 2232456A1
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- polybutadiene
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- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- 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
- C08F2420/00—Metallocene catalysts
- C08F2420/01—Cp or analog bridged to a non-Cp X neutral donor
-
- 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
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- 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
Abstract
The invention relates to a thermoplastic polyolefin which is a copolymer of at least one olefinic monomer and from 0.005 to 10 wt.% 1,2-polybutadiene referred to the copolymer and a process for producing a copolymer of at least one olefinic monomer and 1,2-polybutadiene under the influence of a cyclopentadienyl-containing transition metal complex.
Description
CA 022324~6 1998-03-17 W O 97/12920 PCT~NL96/00363 COPOLYMER OF AN OLEFINIC MONOMER AND 1,2-POLYBUTADIENE
The invention relates to a thermoplastic polyole~in which is a copolymer o~ at least one ole~inic monomer and ~rom 0.005 to 10 wt.% 1,2-polybutadiene.
One o~ the characterizing parameters o~
polyole~ins is their molecular weight distribution, expressed as the quotient o~ the weight average molecular weight, Mw, and the number average molecular weight, Mn.
This parameter has an in~luence on product properties, ~or instance, tensile strength and impact resistance. An important parameter which in~luences the processing behaviour o~ polyole~ins is the Melt Flow Ratio (MFR).
This is usually calculated as the quotient o~ the melt index (MI) determined according to ASTM D-1238 using a weight o~ 21.6 kg and the melt index determined using a weight o~ 2.16 kg. The MFR o~ common polyole~ins is known to increase with wider molecular weight distributions or, in other words, with increasing values o~ Mw/Mn. As a - consequence, in some applications a compromise needs to be sought when a particular MFR is desired ~or the processing properties and a particular Mw/Mn ratio ~or the desired product properties.
From WO-A-93/08221 it is known to produce thermoplastic polyole~ins with the aid o~ constrained-geometry catalysts. The disclosed process allows the MFR
to be varied while the width of the molecular weight distribution remains almost constant. However, the polyole~ins disclosed in the application mentioned all appear to possess a molecular weight distribution which is very near to 2. It is not taught how polyole~ins with other molecular weight distributions should be produced.
I CA 022324~6 1998-03-17 .,: . . ' '; ' - ' Enclosure 1.1 PCT/NL 96/00363; 8076WO
- Amended page 2 -However, to enable optimum mat~erial selection ~or more applications there is a need ~or thermoplastic polyole~ins with other combinations o~ MFR and molecular weight distribution than those according to the prior art.
The object o~ the invention is to provide such polyole~ins.
This object o~ the invention is achieved with a copolymer o~ ethylene, 0-50 wt.~ o~ a C4-C20 a-ole~in with respect to the total amount o~ ole~inic monomer present and ~rom 0.005 to 10 wt.~ 1,2-polybutadiene in which the number o~
1,2-vinyl unsaturations per polybutadiene chain is at least 3.
The 1,2-polybutadiene will hereina~ter also be re~erred to as (co)monomer. The amount o~ 1,2-polybutadiene is re~erred to the total o~ the copolymer.
From DE-A-2.123.911 it is known to copolymerize polybutadiene in the production o~ sulphur-crosslinkable ethylene-propylene-diene rubbers. In that application no mention is made o~ a possible in~luence o~ the 1,2-polybutadiene on the a~orementioned important properties o~
polyole~ins and, moreover, no distinction is made between the types o~ polybutadiene; as 1,4- or 1,2-polybutadiene.
In DE-A-1.151.941 and EP-A-0.253.752 EPR and EPDM
copolymer rubbers are disclosed containing 1,2-polybutadiene.
In these applications no mention is made on the a~orementioned important properties o~ copolymers containing ethylene, 0-50 wt.~ o~ a C4-C20 a-ole~in and 0.005-10 wt.~ 1,2-polybutadiene.
DE-A-2.917.403 discloses copolymers o~ propylene and polybutadiene containing ~rom 10 to 20 ~ 1,2-(vinyl)unsaturations and having a molecular weight o~ ~rom 105 to 106 g/mol. This application does not mention a di~erence between the types o~ polybutadiene, too. The described copolymers behave as a thermoplastic with elastomeric properties.
AMENDED SHEET
, CA 022324~6 1998-03-17 - ~ ....
- ;.'' ' ~-'~
Enclosure 1.2 PCT/NL 96/00363; 8076WO
- Amended page 2a -The polyole~in o~ the invention, in contrast, has essentially thermoplastic and no distinct elastomeric properties. The polyole~in o~ the invention contains at least one ole~inic monomer. As ole~inic monomer ethylene, optionally in combination with one or more o~ a C4 - C20 a-ole~in is used.
The ole~inic monomer can contain 0-50 wt.~ o~ a C4 - C20 a-ole~in with respect to the total amount o~ ole~inic monomer present in the polyole~in o~ the AMENDED SHEE~
CA 022324~6 1998-03-17 invention.
Pre~erably the a-ole~in combined with ethylene is a C4 -ClO ~-ole~in. Examples o~ such a-ole~ins are butene, hexene and octene.
It is known that in particular copolymers o~ ethylene with one or more a-ole~ins in which dienes are copolymerized as third monomer exhibit elastomeric properties. Since it possesses thermoplastic properties, the polyole~in o~ the invention does not contain any substantial amounts o~
diene-derived units other than those originating ~rom the 1,2-polybutadiene. It is pre~erred ~or at most 1 wt.~
re~erred to the total polymer o~ these other diene-derived units to be present but most pre~erably they are completely absent.
15The polyole~in o~ the invention does not contain substantial amounts o~ monomers other than the ole~inic monomer and the 1,2-polybutadiene as described be~ore.
The molecular weights, Mw and Mn o~ the polyole~in are determined by means o~ Size-Exclusion Chromatography in combination with a viscosity detector, with the polyethylene calibration samples being used as a re~erence.
For the purposes o~ the invention, 1,2-polybutadiene is understood to be a polymer o~ butadiene in which the number o~ t-CH2-CH-] units is XC=CH2 greater than the number o~ other butadiene-derived units such as t-CH2-CH=CH-CH2-] units and units in which there are no longer any unsaturations.
The length o~ the incorporated polybutadiene chains, expressed as the number o~ polymerized butadiene units, should be at least 4. Pre~erably, this length is at least 10, more pre~erably at least 25.
The number o~ 1,2-vinyl unsaturations per chain is at ~ CA 022324~6 1998-03-17 ~
A ~ 1- rl ~D ~D
- 4 - ~:
. ' ~ : .
least 3, pre~erably at least 6 and more pre~erably at least 13. I~ the requirements relating to the chain length and the number o~ vinyl unsaturations remain satis~ied, it is within the scope of the invention also permissible ~or the 1,2-polybutadiene to be partially saturated.
Saturation may be e~ected by, ~or instance, hydrogenation or copolymerization o~ butadiene with ~-ole~ins. The chain length o~ the polybutadiene pre~erably is not more than 5000~ Greater chain lengths result in deterioration o~ the normal properties o~ the polyole~in and the polyole~in begins to exhibit strongly inhomogeneous behaviour.
It has been ~ound that the MFR is relatively strongly dependent on the amount o~ incorporated 1,2-polybutadiene in that the MFR increases with increasing amounts o~ polybutadiene, whereas the Mw/Mn ratio appears to be relatively less sensitive. However, the ~w/Mn ratio does tend to increase with increasing 1,2-polybutadiene content, especially with copolymers incorporating ~
di~erent a-ole~inic monomeric units, so that this content can be used to control this ratio as well.
- In general, the Mw/Mn ratio o~ the polyole~in o~
the invention is higher than that o~ a ~co)polymer produced under otherwise equal conditions but not incorporating any 1,2-polybutadiene. It is pre~erred ~or this increaso to amount to not more than a ~actor o~ 3.5.
Any higher increases involve the risk o~ gel ~ormation in the copolymer. On being processed, especially on being processed into ~ilms, such a copolymer yields products whose appearance is less attractive. In view o~ the requirement o~ a limited increase in the Mw/Mn ratio, the amount o~ 1,2-polybutadiene is pre~erably at most 10 wt.
i~ the chain length o~ the 1,2-polybutadiene is at least 4, more pre~erably this amount is at most 5 wt.~ when the chain length is 10 or more, most pre~erably this amount is at most 3 wt.~ when the chain length is 25 or more. The AMENDED SHEET
. _ _ e~ect o~ the 1,2-polybutadiene is very readily appreciable even at an amount o~ 1,2-polybutadiene o~ at most 5 wt.~ at a chain length o~ 10 or more. Polyole~ins containing a larger amount o~ 1,2-polybutadiene than 10 may exhibit increased susceptibility to oxidation.
Furthermore, it has been ~ound that the presence o~ partially saturated 1,2-polybutadiene brings about an increase in the Mw/Mn ratio in that the Mw/Mn ratio increases as the number o~ double bonds in the polybutadiene decreases. In addition, in this case as well the MFR increases with increasing amounts o~ partially saturated 1,2-polybutadiene.
~ he polyole~ins o~ the invention possess good processability and melt strength and are suited to application in a wider range o~ products, both thin-walled objects, ~or instance ~ilms, and thick-walled objects.
The invention also relates to a process ~or the manu~acture o~ a thermoplastic polyole~in by contacting ethylene and optionally one or more C4 - C20 a-ole~ins with a cyclopentadienyl-containing transition metal complex as catalyst under conditions whereby the monomers polymerize in the presence o~ the catalyst.
It is generally known to produce polyole~ins with the aid o~ catalysts containing non-cyclopentadiene-derived ligands, such as Phillips and Ziegler catalysts.The molecular weight distribution, Mw/Mn, and the Melt Flow Ratio o~ polyole~ins so produced appear to be interdependent. Given a certain value o~ the Mw/Mn ratio, the MFR is virtually ~ixed so that when a polymer with a particular desired Mw/Mn ratio is to ~e produced, there is no more scope ~or selecting a particular MFR.
From WO-A-93/08221 it is known to produce polymers o~ ethylene and copolymers thereo~ with ~-ole~ins under the in~luence o~ a cyclopentadienyl-containing transition metal compound as catalyst. The process CA 022324~6 1998-03-17 WO 97/12920 PCT~L~6/0036 - 6 - .
disclosed in that application yields polyole~ins with an Mw/Mn ratio of~ 1. 86--2.32 and with values o~ 5.6--16~or a quantity equivalent to the MFR. It is not taught how polyole~ins having other molecular weight distributions can be produced.
Thus, there is a need ~or a process ~or producing thermoplastic polyole~ins having other combinations o~ Mw/Mn ratio and MFR than the known polyole~ins.
This need is met by the invention in that polymerization takes place in the presence o~ 1,2-polybutadiene.
It has been ~ound that the MFR and the Mw/Mn ratio can be controlled by the amount and type o~ 1,2-polybutadiene present in the polymerization medium. The manner in which this amount in~luences the properties mentioned is indicated in the discussion o~ the polyole~ins in the ~oregoing.
The amount o~ copolymerized 1,2-polybutadiene is 20 at most 10 wt.~, pre~erably at most 5 wt.95, more pre~erably at most 3 wt.~ too much 1,2-polybutadiene is copolymerized, this is at the expense o~ the thermoplastic properties o~ the polyole~in obtained. It is surprising that a clearly measurable e~ect on the polymer structure and end-product properties obtained is observed even when very small amounts o~ 1,2-polybutadiene are added as comonomer and/or termonomer. The permissible amounts depend on the chain length o~ the 1,2-polybutadiene as indicated in the above description o~ the polyole~ins o~ the invention.
The amount o~ 1,2-polybu'adiene that must be present in the reaction mixture in order ~or polyole~in having the desired amount o~ copolymerized 1,2-polybutadiene to be obtained depends on, inter alia, the activity o~ the catalyst used and can easily be determined CA 022324~6 1998-03-17 WO 97/12920 PCTANL96/00363-- 7 -- .
experimentally. The e~ect o~ ~or instance the 1,2-polybutadiene content on ~or instance the MFR will be apparent ~rom the ~oregoing and ~rom the examples. Those skilled in the art can determine this relationship ~rom a - 5 ~ew experiments under the reaction conditions chosen and subsequently determine the right amount and/or the right molecular weight ~or a copolymer having the desired properties.
The 1,2-polybutadiene appears to be incorporated in a highly e~icient manner. This is surprising because the vinyl-unsaturated side groups may be regarded as y-substituted ole~ins, which have an alkyl group substituent on the 3-site. Such substituents are known to strongly suppress the reactivity o~ an ole~in in catalytic polyole~in processes due to what is known as steric hindering around the ole~inic bond. Such a y-substituted ole~in is there~ore not an obvious choice as comonomer ~or e~ecting a high degree o~ incorporation o~ the 1,2-polybutadiene with a high degree o~ conversion in a catalyzed polyole~in process.
Furthermore, incorporation o~ only a minor amount o~ 1,2-polybutadiene appears to have a signi~icant e~ect on the MFR. Minor here means: in an amoun~ at which the detectable number o~ unsaturations in the polyole~in o~
the invention is in the same range as the number o~
unsaturations o~ an otherwise similar thermoplastic polyole~in in which no 1,2-polybutadiene is copolymerized.
A ~urther advantage o~ the process o~ the invention is the ~ollowing. In W0-A-93/08221 the variation in the MFR is e~ected by suitably choosing the amount o~
catalyst. This entails that the reaction conditions must be adapted also. The process o~ the invention, in contrast, can be practised with a constant amount o~
catalyst and otherwise equal conditions because the amount o~ 1,2-polybutadiene in the reaction mixture is in CA 022324~6 1998-03-17 principle the determining parameter.
For the de~initions o~ the copolymers to which the process o~ the invention relates and ~or the requirements ~or the 1,2-polybutadiene to be copolymerized, see the ~oregoing.
The polymerization is e~ected by contacting ethylene and optionally one or more C4-C20 ~-ole~ins with a cyclopentadienyl-containing transition metal complex as catalyst.
This metal complex contains a transition metal pre~erably ~rom group 3 or 4 o~ the Periodic System o~
Elements in the new IUPAC version as shown in the cover o~
Handbook o~ Chemistry and Physics, 70th Edition CRC Press, 1989-1990. If the valency o~ the metal is 3', the complex can be represented as RlMXlX2 or RlR2MXl. I~ the valency o~
the metal is 4+ the complex can be represented as RlR2MXlX2 or RlMXlX2X3 In the ~ormulae given, Rl is a substituted or unsubstituted cyclopentadienyl ligand, ~or instance indenyl, ~luorenyl, methyl-cyclopentadienyl, pentamethylcyclopentadienyl or a heteroatom-containing derivative o~ the cyclopentadienyl ligand. In the group last mentioned, the heteroatom may be an element ~rom group 15 or 16 o~ the Periodic System o~ Elements, ~or instance N, P, As, O or S. The heteroatom may ~orm part o~
the cyclopentadienyl ring or may be located outside thereo~. R2 may be a Cp derivative as de~ined ~or Rl but may also be a substituent containing an element ~rom group 15 or 16 o~ the Periodic System, ~or instance N, P, As, 0 or S, which element is linked to the metal via a covalent or coordinate bond. Rl and R2 may be linked to one another by an -Si(R)2 group, where R represents an aliphatic or aromatic group, by an aliphatic or aromatic group or by a group which contains an element ~rom group 15 or 16 o~ the Periodic System.
CA 022324~6 1998-03-17 W O 97/12920 PCT~NL96/00363 _ g _ .
I~ R2 is neutral and is not a cyclopentadiene-derived compound and, also, is linked to Rl in one o~ the a~orementioned manners, this combination o~ Rl and R2 is considered a heteroatom-containing derivative o~ the - 5 cyclopentadienyl ligand as meant in the description o~ Rl.
Xl, x2 and X3 may or may not be the same and are chosen ~rom the group o~:
- halogens - aliphatic or aromatic substituents - substituents which contain an element ~rom group 15 or 16 o~ the Periodic System such as oR3, NR3 and the like, where R3 may be an aliphatic or aromatic substituent which may optionally contain silicon.
As catalyst a cyclopentadienyl-containing transition metal complex with the ~ormula R4MXlX2 is pre~erably used, where M is a transition metal ~rom Group 4 o~ the Periodic System, not having the highest valency, pre~erably Ti3+, where Xl and x2 have the same meaning as in the ~oregoing and where R4 is equal to [Cp'-Y-Z(R5) n ] -where Cp'is a cyclopentadienyl derivative substituted with aliphatic or aromatic groups or with groups containing a heteroatom, Y is an aliphatic or aromatic group or a group containing silicon or a heteroatom, Z is an element ~rom group 15 or 16 o~ the Periodic System, pre~erably N or P, Rs is an aliphatic, aromatic or silicon-containing group and n is equal to the valency o~ Z minus 1.
As a rule, the metal complex is employed as catalyst in conjunction with an activator. As activator use may be made o~ substances known to be suitable ~or the purpose, ~or instance methylaluminoxane (MAO) or possibly (per)~luorinated boron compounds, ~or instance tris-penta~luorophenylborane and tetrakispenta~luoro-CA 022324~6 1998-03-17 phenylborate compounds. In addition, organometal compounds with a metal ~rom group 1, 2, 12 or 13, pre~erably aluminium-alkyl compounds or magnesium-alkyl compounds, may be applied in the catalyst system, ~or instance trimethylaluminium, triethylaluminium, triisobutylaluminium, trioctylaluminium, diethylaluminiumethoxide, diethylmagnesium, dibutylmagnesium, ethyl-butylmagnesium and butyl-octylmagnesium. The activity o~ the catalyst system can be increased ~urther by adding these main-group-metal/alkyl compounds.
The ole~inic monomers are contacted with the catalyst under conditions at which the monomers polymerize in the presence o~ the catalyst. The polymerization o~
ole~ins with the aid o~ metal catalysts, ~or instance classical Ziegler-Natta or Phillips catalysts and the conditions to be chosen ~orm a technique known per se which may also be employed ~or the polymerization o~
ole~ins with the aid o~ catalysts as prescribed ~or the process o~ the invention.
The polymerization reaction may ~or instance be e~ected in the gas phase, in suspension or in solution, either (semi)continuously or batchwise. Furthermore, it is also possible to apply a plurality o~ reactors arranged in parallel, in series or in a combination thereo~.
Pre~erably, a solution process is used, since this process is eminently suitable ~or the production o~ very low-crystalline polymers which at least to some extent are soluble in hydrocarbons.
As dispersant or solvent ~or the polymerization reaction any liquid that does not have an adverse e~ect on the activity o~ the catalyst system may be used.
Saturated, linear or branched aliphatic hydrocarbons, ~or instance butanes, pentanes, heptanes, pentamethylheptane or petroleum ~ractions, ~or instance light or regular CA 022324~6 1998-03-17 gasoline, naphtha, kerosene or gas oil or mixtures o~ the a~orementioned substances may be used there~or.
Aromatic hydrocarbons, ~or instance benzene and toluene, are suitable but are not pre~erred ~or reasons o~ cost and 5 sa~ety. For plant-scale polymerization, the aliphatic hydrocarbons or mixtures thereo~ supplied by the petrochemical industry are pre~erably used as dispersant or solvent a~ter drying and puri~ication.
The polymer obtained by the process o~ the 10 invention can be worked up by methods known per se. In general, the catalyst is deactivated in a manner known per se at some point in this working-up phase o~ the polymer.
The polymerization may be e~ected at atmospheric pressure but also at increased pressure. I~
15 the polymerization is e~ected at increased pressure, the polymer yield per unit time can be increased still ~urther. It is pre~erred ~or the polymerization to take place at pressures between 0.1 and 60 MPa, particularly between 1 and 30 MPa. Higher pressures o~ 100 MPa and 20 above may be used when the polymerization takes place in so-called autoclaves.
The molecular weight o~ the polymer may be controlled in the usual manner, ~or instance by adding hydrogen or other chain terminating agents or by adjusting 25 the polymerization conditions.
The 1,2-polybutadiene is pre~erably added as a solution in a suitable dispersant that has no adverse e~ect on the polymerization process. In a continuous process, the 1,2-polybutadiene is pre~erably added to the 30 polymerization reactor on a continuous basis. In a system employing a plurality o~ reactors it also possible to add - the 1,2-polybutadiene to only some o~ the reactors employed. In batch polymerization, the 1,2-polybutadiene J may be added prior to or during polymerization. The 35 amounts to be used and the molecular weights o~ the 1,2-CA 022324~6 1998-03-17 W O 97/1~920 PCT~NL96/00363 - 12 -polybutadiene are described in the ~oregoing.
The invention will be illustrated by the ~ollowing examples without being limited thereto.
The density D23 was determined in accordance with ASTM Standard D 792-66. The melt index MI was determined in accordance with ASTM Standard D1238 using a weight o~ 2.16 kg. The Melt Flow Ratio, MFR, was determined as the quotient o~ the melt indices determined to ASTM D1238 using weights o~ 21.6 and 2.16 kg, respectively. The Mw/Mn ratio was determined with the aid o~ a Waters M150C Gel Permeation Chromatograph with DRI-detector as Size Exclusion Chromatograph in combination with a Viscotek type 502 viscometer as viscosity detector and using polyethylene calibration samples as re~erence.
ExamPles I-IV
A number o~ polyole~ins o~ the invention were produced as ~ollows.
An autoclave with a capacity o~ 2 litres was ~illed with special boiling point spirit (boiling range ~rom 65 to 70~C) and kept at a temperature o~ 160~C. A
mixture o~ special boiling point spirit (5.5 kg/h) and ethylene (1.2 kg/h) was continuously added to the autoclave. Also, in some cases, hydrogen was added in order to obtain the desired molar mass. The supply to the autoclave was adjusted so that the autoclave remained completely ~illed with the reaction medium. A solution o~
a catalyst, a suspension o~ an activator and a solution o~
triethylaluminium was also continuously added to the autoclave. The ethylene conversion was controlled by means o~ the amounts o~ catalyst and activator and amounted to approximately 95~ in each experiment.
Ethylene-dimethylamino-tetramethyl-cyclopentadienyl-titanium-dimethyl, Cp (CH2CH2)N(CH3)2Ti(CH3)2, was added as catalyst ~or the CA 022324~6 1998-03-17 W O 97/12920 PCT~NL96/00363 preparation o~ a copolymer o~ ethylene and 1,2-polybutadiene. A concentration o~ the catalyst o~ approx.
20 ~mol per litre was needed ~or attaining 95% ethylene conversion.
Dimethylaniliniumtetrakispenta~luorophenylborate was applied as activator. A concentration o~ the activator o~
approx. 40 ~mol per litre was needed ~or attaining 95%
ethylene conversion. The concentration o~
triethylaluminium applied in the autoclave amounted to approx. 40 ~mol per litre. In a seperate vessel a mixture o~ 1,2-polybutadiene (1,2-polybutadiene) with a Mn o~
approx. 3000 g/mol, containing approx. 50 vinyl groups per molecule chain ~grade B-- 3000 ~rom Messrs NISSOH IWAI) and special boiling point spirit was prepared. A certain amount o~ 1,2-polybutadiene solution was continuously pumped ~rom this vessel to the autoclave. The desired rate at which 1,2-polybutadiene was added was adjusted by suitably choosing the concentration o~ 1,2-polybutadiene in the solution. Here, 1 g/h o~ 1,2-polybutadiene corresponded to 0.088 wt.% re~erred to converted ethylene.
The properties o~ the copolymers obtained with various rates o~ addition o~ 1,2-polybutadiene are shown in Table 1.
CA 022324~6 1998-03-17 example addition o~ MI MFR Mw/Mn D23 1,2-polybutadiene g/h I 0 6.1 25.8 2.5 958.9 II 0.25 4.7 27.8 2.5 959.6 III 2.5 4.7 30.2 2.6 959.1 IV 5 4.1 33.0 2.8 959.1 These results indicate that the MFR can be controlled by means o~ the rate at which 1,2-polybutadiene is added.
Exam~les V-IX
Terpolymerizations o~ ethylene, l-octene and 1,2-polybutadiene:
Analogously to Examples I-IV, polymerizations were carried out in which 0.2 kg/hour o~ octene-l was added to the autoclave as extra monomer.
The properties o~ the copolymers obtained with various rates o~ addition o~ 1,2-polybutadiene are shown in Table 2. The polymers contained 15 wt.~ octene.
CA 022324~6 l998-03-l7 W O 97/12920 PCT~NL9 example addition o~ MI MFR Mw/Mn DZ3 1,2-polybutadiene g/h S V 0 4.2 29.1 2.5 914.9 VI 1.0 2. 8 33.4 2. 6 915.4 VII 5 2.4 39.8 3.2 91S.6 VIII 15 0.6 56.7 5.0 916.2 IX 25 0.1 79.4 8. 2 917.7 lQ
The process o~ the invention proves suitable ~or producing terpolymers also. The MFR shows a distinct increase when as little as 1 g/h o~ 1,2--polybutadiene, corresponding to 0.088 wt.~ re~erred to the converted ethylene, is added.
ExamPles X-XIII
Analogously to the previous examples, terpolymers o~ ethylene, 1-octene and 1,2-polybutadiene were produced using two di~erent 1,2-polybutadiene grades in order to study the e~ect o~ the molar mass o~ the 1,2-polybutadiene on the MFR in the terpolymerization o~
ethylene, octene and 1,2-polybutadiene. Use was made o~
grade B-3000 and grade B-2000 already mentioned in Examples V-IX, ~rom the same supplier, with a Mn o~ 2000 g/mol, containing approx. 33 vinyl unsaturations per molecule chain. The results are shown in Table 3.
CA 022324S6 1998-03-17 ~~
5 ~Dr~
example 1,2- MI MFR Mw/Mn D23 1,2-polybuta- poly-diene buta-diene grade g/h X 0 4.2 29.1 2.4 914.9 XI 2.5 4.1 31.1 2.7 917.0 B-2000 XII 5.0 2.2 38.6 3.0 915.6 B-2000 XIII 2.5 2.3 36.5 2.8 917.0 B-3000 VlI 5.0 2.4 39.8 3.2 915.6 B-3000 ExamPles XIV-XVIII
Polymerizations were carried out analogously to Examples I-IV exce;~t that diphenylmethylene-~luorenyl-cyclopentadienyl- -dimethyl {[(C6H5)2CJFluCpZrMe2}
was used as catalyst.
As 1,2-polybutadiene a grade supplied by Messrs Aldrich with a Mn o~ approx. 1300 g/mol, approx. 99~ unsaturated and with a vinyl:trans unsaturations o~ 40:30 (designated grade A) and a grade ~rom the same company with a Mn o~
1800 g/mol, approx. 60~ unsaturations and with the distribution o~ the unsaturations among the various possibilities given by vinyl:trans:cis = 45:10:5 (designated grade B) were used. The results are shown in AMEN~ED SHEE'r W O 97/12920 PCT~L96/~0 Table 4.
Exam--addition MI MFR Mw/Mn D23 grade ple oi~ 1,2-polybuta-diene ~ m/m XIV 0 12 n.d. 3.5 956.7 XV 0.30 2.5 52 5.6 951.5 B
XVI 0.60 0.5 98 4.6 949.7 B
XVII 0.09 42 n.d. 3.8 955.8 A
XVIII 0.19 9.6 38 3.8 956.7 A
-n.d. : not determined
The invention relates to a thermoplastic polyole~in which is a copolymer o~ at least one ole~inic monomer and ~rom 0.005 to 10 wt.% 1,2-polybutadiene.
One o~ the characterizing parameters o~
polyole~ins is their molecular weight distribution, expressed as the quotient o~ the weight average molecular weight, Mw, and the number average molecular weight, Mn.
This parameter has an in~luence on product properties, ~or instance, tensile strength and impact resistance. An important parameter which in~luences the processing behaviour o~ polyole~ins is the Melt Flow Ratio (MFR).
This is usually calculated as the quotient o~ the melt index (MI) determined according to ASTM D-1238 using a weight o~ 21.6 kg and the melt index determined using a weight o~ 2.16 kg. The MFR o~ common polyole~ins is known to increase with wider molecular weight distributions or, in other words, with increasing values o~ Mw/Mn. As a - consequence, in some applications a compromise needs to be sought when a particular MFR is desired ~or the processing properties and a particular Mw/Mn ratio ~or the desired product properties.
From WO-A-93/08221 it is known to produce thermoplastic polyole~ins with the aid o~ constrained-geometry catalysts. The disclosed process allows the MFR
to be varied while the width of the molecular weight distribution remains almost constant. However, the polyole~ins disclosed in the application mentioned all appear to possess a molecular weight distribution which is very near to 2. It is not taught how polyole~ins with other molecular weight distributions should be produced.
I CA 022324~6 1998-03-17 .,: . . ' '; ' - ' Enclosure 1.1 PCT/NL 96/00363; 8076WO
- Amended page 2 -However, to enable optimum mat~erial selection ~or more applications there is a need ~or thermoplastic polyole~ins with other combinations o~ MFR and molecular weight distribution than those according to the prior art.
The object o~ the invention is to provide such polyole~ins.
This object o~ the invention is achieved with a copolymer o~ ethylene, 0-50 wt.~ o~ a C4-C20 a-ole~in with respect to the total amount o~ ole~inic monomer present and ~rom 0.005 to 10 wt.~ 1,2-polybutadiene in which the number o~
1,2-vinyl unsaturations per polybutadiene chain is at least 3.
The 1,2-polybutadiene will hereina~ter also be re~erred to as (co)monomer. The amount o~ 1,2-polybutadiene is re~erred to the total o~ the copolymer.
From DE-A-2.123.911 it is known to copolymerize polybutadiene in the production o~ sulphur-crosslinkable ethylene-propylene-diene rubbers. In that application no mention is made o~ a possible in~luence o~ the 1,2-polybutadiene on the a~orementioned important properties o~
polyole~ins and, moreover, no distinction is made between the types o~ polybutadiene; as 1,4- or 1,2-polybutadiene.
In DE-A-1.151.941 and EP-A-0.253.752 EPR and EPDM
copolymer rubbers are disclosed containing 1,2-polybutadiene.
In these applications no mention is made on the a~orementioned important properties o~ copolymers containing ethylene, 0-50 wt.~ o~ a C4-C20 a-ole~in and 0.005-10 wt.~ 1,2-polybutadiene.
DE-A-2.917.403 discloses copolymers o~ propylene and polybutadiene containing ~rom 10 to 20 ~ 1,2-(vinyl)unsaturations and having a molecular weight o~ ~rom 105 to 106 g/mol. This application does not mention a di~erence between the types o~ polybutadiene, too. The described copolymers behave as a thermoplastic with elastomeric properties.
AMENDED SHEET
, CA 022324~6 1998-03-17 - ~ ....
- ;.'' ' ~-'~
Enclosure 1.2 PCT/NL 96/00363; 8076WO
- Amended page 2a -The polyole~in o~ the invention, in contrast, has essentially thermoplastic and no distinct elastomeric properties. The polyole~in o~ the invention contains at least one ole~inic monomer. As ole~inic monomer ethylene, optionally in combination with one or more o~ a C4 - C20 a-ole~in is used.
The ole~inic monomer can contain 0-50 wt.~ o~ a C4 - C20 a-ole~in with respect to the total amount o~ ole~inic monomer present in the polyole~in o~ the AMENDED SHEE~
CA 022324~6 1998-03-17 invention.
Pre~erably the a-ole~in combined with ethylene is a C4 -ClO ~-ole~in. Examples o~ such a-ole~ins are butene, hexene and octene.
It is known that in particular copolymers o~ ethylene with one or more a-ole~ins in which dienes are copolymerized as third monomer exhibit elastomeric properties. Since it possesses thermoplastic properties, the polyole~in o~ the invention does not contain any substantial amounts o~
diene-derived units other than those originating ~rom the 1,2-polybutadiene. It is pre~erred ~or at most 1 wt.~
re~erred to the total polymer o~ these other diene-derived units to be present but most pre~erably they are completely absent.
15The polyole~in o~ the invention does not contain substantial amounts o~ monomers other than the ole~inic monomer and the 1,2-polybutadiene as described be~ore.
The molecular weights, Mw and Mn o~ the polyole~in are determined by means o~ Size-Exclusion Chromatography in combination with a viscosity detector, with the polyethylene calibration samples being used as a re~erence.
For the purposes o~ the invention, 1,2-polybutadiene is understood to be a polymer o~ butadiene in which the number o~ t-CH2-CH-] units is XC=CH2 greater than the number o~ other butadiene-derived units such as t-CH2-CH=CH-CH2-] units and units in which there are no longer any unsaturations.
The length o~ the incorporated polybutadiene chains, expressed as the number o~ polymerized butadiene units, should be at least 4. Pre~erably, this length is at least 10, more pre~erably at least 25.
The number o~ 1,2-vinyl unsaturations per chain is at ~ CA 022324~6 1998-03-17 ~
A ~ 1- rl ~D ~D
- 4 - ~:
. ' ~ : .
least 3, pre~erably at least 6 and more pre~erably at least 13. I~ the requirements relating to the chain length and the number o~ vinyl unsaturations remain satis~ied, it is within the scope of the invention also permissible ~or the 1,2-polybutadiene to be partially saturated.
Saturation may be e~ected by, ~or instance, hydrogenation or copolymerization o~ butadiene with ~-ole~ins. The chain length o~ the polybutadiene pre~erably is not more than 5000~ Greater chain lengths result in deterioration o~ the normal properties o~ the polyole~in and the polyole~in begins to exhibit strongly inhomogeneous behaviour.
It has been ~ound that the MFR is relatively strongly dependent on the amount o~ incorporated 1,2-polybutadiene in that the MFR increases with increasing amounts o~ polybutadiene, whereas the Mw/Mn ratio appears to be relatively less sensitive. However, the ~w/Mn ratio does tend to increase with increasing 1,2-polybutadiene content, especially with copolymers incorporating ~
di~erent a-ole~inic monomeric units, so that this content can be used to control this ratio as well.
- In general, the Mw/Mn ratio o~ the polyole~in o~
the invention is higher than that o~ a ~co)polymer produced under otherwise equal conditions but not incorporating any 1,2-polybutadiene. It is pre~erred ~or this increaso to amount to not more than a ~actor o~ 3.5.
Any higher increases involve the risk o~ gel ~ormation in the copolymer. On being processed, especially on being processed into ~ilms, such a copolymer yields products whose appearance is less attractive. In view o~ the requirement o~ a limited increase in the Mw/Mn ratio, the amount o~ 1,2-polybutadiene is pre~erably at most 10 wt.
i~ the chain length o~ the 1,2-polybutadiene is at least 4, more pre~erably this amount is at most 5 wt.~ when the chain length is 10 or more, most pre~erably this amount is at most 3 wt.~ when the chain length is 25 or more. The AMENDED SHEET
. _ _ e~ect o~ the 1,2-polybutadiene is very readily appreciable even at an amount o~ 1,2-polybutadiene o~ at most 5 wt.~ at a chain length o~ 10 or more. Polyole~ins containing a larger amount o~ 1,2-polybutadiene than 10 may exhibit increased susceptibility to oxidation.
Furthermore, it has been ~ound that the presence o~ partially saturated 1,2-polybutadiene brings about an increase in the Mw/Mn ratio in that the Mw/Mn ratio increases as the number o~ double bonds in the polybutadiene decreases. In addition, in this case as well the MFR increases with increasing amounts o~ partially saturated 1,2-polybutadiene.
~ he polyole~ins o~ the invention possess good processability and melt strength and are suited to application in a wider range o~ products, both thin-walled objects, ~or instance ~ilms, and thick-walled objects.
The invention also relates to a process ~or the manu~acture o~ a thermoplastic polyole~in by contacting ethylene and optionally one or more C4 - C20 a-ole~ins with a cyclopentadienyl-containing transition metal complex as catalyst under conditions whereby the monomers polymerize in the presence o~ the catalyst.
It is generally known to produce polyole~ins with the aid o~ catalysts containing non-cyclopentadiene-derived ligands, such as Phillips and Ziegler catalysts.The molecular weight distribution, Mw/Mn, and the Melt Flow Ratio o~ polyole~ins so produced appear to be interdependent. Given a certain value o~ the Mw/Mn ratio, the MFR is virtually ~ixed so that when a polymer with a particular desired Mw/Mn ratio is to ~e produced, there is no more scope ~or selecting a particular MFR.
From WO-A-93/08221 it is known to produce polymers o~ ethylene and copolymers thereo~ with ~-ole~ins under the in~luence o~ a cyclopentadienyl-containing transition metal compound as catalyst. The process CA 022324~6 1998-03-17 WO 97/12920 PCT~L~6/0036 - 6 - .
disclosed in that application yields polyole~ins with an Mw/Mn ratio of~ 1. 86--2.32 and with values o~ 5.6--16~or a quantity equivalent to the MFR. It is not taught how polyole~ins having other molecular weight distributions can be produced.
Thus, there is a need ~or a process ~or producing thermoplastic polyole~ins having other combinations o~ Mw/Mn ratio and MFR than the known polyole~ins.
This need is met by the invention in that polymerization takes place in the presence o~ 1,2-polybutadiene.
It has been ~ound that the MFR and the Mw/Mn ratio can be controlled by the amount and type o~ 1,2-polybutadiene present in the polymerization medium. The manner in which this amount in~luences the properties mentioned is indicated in the discussion o~ the polyole~ins in the ~oregoing.
The amount o~ copolymerized 1,2-polybutadiene is 20 at most 10 wt.~, pre~erably at most 5 wt.95, more pre~erably at most 3 wt.~ too much 1,2-polybutadiene is copolymerized, this is at the expense o~ the thermoplastic properties o~ the polyole~in obtained. It is surprising that a clearly measurable e~ect on the polymer structure and end-product properties obtained is observed even when very small amounts o~ 1,2-polybutadiene are added as comonomer and/or termonomer. The permissible amounts depend on the chain length o~ the 1,2-polybutadiene as indicated in the above description o~ the polyole~ins o~ the invention.
The amount o~ 1,2-polybu'adiene that must be present in the reaction mixture in order ~or polyole~in having the desired amount o~ copolymerized 1,2-polybutadiene to be obtained depends on, inter alia, the activity o~ the catalyst used and can easily be determined CA 022324~6 1998-03-17 WO 97/12920 PCTANL96/00363-- 7 -- .
experimentally. The e~ect o~ ~or instance the 1,2-polybutadiene content on ~or instance the MFR will be apparent ~rom the ~oregoing and ~rom the examples. Those skilled in the art can determine this relationship ~rom a - 5 ~ew experiments under the reaction conditions chosen and subsequently determine the right amount and/or the right molecular weight ~or a copolymer having the desired properties.
The 1,2-polybutadiene appears to be incorporated in a highly e~icient manner. This is surprising because the vinyl-unsaturated side groups may be regarded as y-substituted ole~ins, which have an alkyl group substituent on the 3-site. Such substituents are known to strongly suppress the reactivity o~ an ole~in in catalytic polyole~in processes due to what is known as steric hindering around the ole~inic bond. Such a y-substituted ole~in is there~ore not an obvious choice as comonomer ~or e~ecting a high degree o~ incorporation o~ the 1,2-polybutadiene with a high degree o~ conversion in a catalyzed polyole~in process.
Furthermore, incorporation o~ only a minor amount o~ 1,2-polybutadiene appears to have a signi~icant e~ect on the MFR. Minor here means: in an amoun~ at which the detectable number o~ unsaturations in the polyole~in o~
the invention is in the same range as the number o~
unsaturations o~ an otherwise similar thermoplastic polyole~in in which no 1,2-polybutadiene is copolymerized.
A ~urther advantage o~ the process o~ the invention is the ~ollowing. In W0-A-93/08221 the variation in the MFR is e~ected by suitably choosing the amount o~
catalyst. This entails that the reaction conditions must be adapted also. The process o~ the invention, in contrast, can be practised with a constant amount o~
catalyst and otherwise equal conditions because the amount o~ 1,2-polybutadiene in the reaction mixture is in CA 022324~6 1998-03-17 principle the determining parameter.
For the de~initions o~ the copolymers to which the process o~ the invention relates and ~or the requirements ~or the 1,2-polybutadiene to be copolymerized, see the ~oregoing.
The polymerization is e~ected by contacting ethylene and optionally one or more C4-C20 ~-ole~ins with a cyclopentadienyl-containing transition metal complex as catalyst.
This metal complex contains a transition metal pre~erably ~rom group 3 or 4 o~ the Periodic System o~
Elements in the new IUPAC version as shown in the cover o~
Handbook o~ Chemistry and Physics, 70th Edition CRC Press, 1989-1990. If the valency o~ the metal is 3', the complex can be represented as RlMXlX2 or RlR2MXl. I~ the valency o~
the metal is 4+ the complex can be represented as RlR2MXlX2 or RlMXlX2X3 In the ~ormulae given, Rl is a substituted or unsubstituted cyclopentadienyl ligand, ~or instance indenyl, ~luorenyl, methyl-cyclopentadienyl, pentamethylcyclopentadienyl or a heteroatom-containing derivative o~ the cyclopentadienyl ligand. In the group last mentioned, the heteroatom may be an element ~rom group 15 or 16 o~ the Periodic System o~ Elements, ~or instance N, P, As, O or S. The heteroatom may ~orm part o~
the cyclopentadienyl ring or may be located outside thereo~. R2 may be a Cp derivative as de~ined ~or Rl but may also be a substituent containing an element ~rom group 15 or 16 o~ the Periodic System, ~or instance N, P, As, 0 or S, which element is linked to the metal via a covalent or coordinate bond. Rl and R2 may be linked to one another by an -Si(R)2 group, where R represents an aliphatic or aromatic group, by an aliphatic or aromatic group or by a group which contains an element ~rom group 15 or 16 o~ the Periodic System.
CA 022324~6 1998-03-17 W O 97/12920 PCT~NL96/00363 _ g _ .
I~ R2 is neutral and is not a cyclopentadiene-derived compound and, also, is linked to Rl in one o~ the a~orementioned manners, this combination o~ Rl and R2 is considered a heteroatom-containing derivative o~ the - 5 cyclopentadienyl ligand as meant in the description o~ Rl.
Xl, x2 and X3 may or may not be the same and are chosen ~rom the group o~:
- halogens - aliphatic or aromatic substituents - substituents which contain an element ~rom group 15 or 16 o~ the Periodic System such as oR3, NR3 and the like, where R3 may be an aliphatic or aromatic substituent which may optionally contain silicon.
As catalyst a cyclopentadienyl-containing transition metal complex with the ~ormula R4MXlX2 is pre~erably used, where M is a transition metal ~rom Group 4 o~ the Periodic System, not having the highest valency, pre~erably Ti3+, where Xl and x2 have the same meaning as in the ~oregoing and where R4 is equal to [Cp'-Y-Z(R5) n ] -where Cp'is a cyclopentadienyl derivative substituted with aliphatic or aromatic groups or with groups containing a heteroatom, Y is an aliphatic or aromatic group or a group containing silicon or a heteroatom, Z is an element ~rom group 15 or 16 o~ the Periodic System, pre~erably N or P, Rs is an aliphatic, aromatic or silicon-containing group and n is equal to the valency o~ Z minus 1.
As a rule, the metal complex is employed as catalyst in conjunction with an activator. As activator use may be made o~ substances known to be suitable ~or the purpose, ~or instance methylaluminoxane (MAO) or possibly (per)~luorinated boron compounds, ~or instance tris-penta~luorophenylborane and tetrakispenta~luoro-CA 022324~6 1998-03-17 phenylborate compounds. In addition, organometal compounds with a metal ~rom group 1, 2, 12 or 13, pre~erably aluminium-alkyl compounds or magnesium-alkyl compounds, may be applied in the catalyst system, ~or instance trimethylaluminium, triethylaluminium, triisobutylaluminium, trioctylaluminium, diethylaluminiumethoxide, diethylmagnesium, dibutylmagnesium, ethyl-butylmagnesium and butyl-octylmagnesium. The activity o~ the catalyst system can be increased ~urther by adding these main-group-metal/alkyl compounds.
The ole~inic monomers are contacted with the catalyst under conditions at which the monomers polymerize in the presence o~ the catalyst. The polymerization o~
ole~ins with the aid o~ metal catalysts, ~or instance classical Ziegler-Natta or Phillips catalysts and the conditions to be chosen ~orm a technique known per se which may also be employed ~or the polymerization o~
ole~ins with the aid o~ catalysts as prescribed ~or the process o~ the invention.
The polymerization reaction may ~or instance be e~ected in the gas phase, in suspension or in solution, either (semi)continuously or batchwise. Furthermore, it is also possible to apply a plurality o~ reactors arranged in parallel, in series or in a combination thereo~.
Pre~erably, a solution process is used, since this process is eminently suitable ~or the production o~ very low-crystalline polymers which at least to some extent are soluble in hydrocarbons.
As dispersant or solvent ~or the polymerization reaction any liquid that does not have an adverse e~ect on the activity o~ the catalyst system may be used.
Saturated, linear or branched aliphatic hydrocarbons, ~or instance butanes, pentanes, heptanes, pentamethylheptane or petroleum ~ractions, ~or instance light or regular CA 022324~6 1998-03-17 gasoline, naphtha, kerosene or gas oil or mixtures o~ the a~orementioned substances may be used there~or.
Aromatic hydrocarbons, ~or instance benzene and toluene, are suitable but are not pre~erred ~or reasons o~ cost and 5 sa~ety. For plant-scale polymerization, the aliphatic hydrocarbons or mixtures thereo~ supplied by the petrochemical industry are pre~erably used as dispersant or solvent a~ter drying and puri~ication.
The polymer obtained by the process o~ the 10 invention can be worked up by methods known per se. In general, the catalyst is deactivated in a manner known per se at some point in this working-up phase o~ the polymer.
The polymerization may be e~ected at atmospheric pressure but also at increased pressure. I~
15 the polymerization is e~ected at increased pressure, the polymer yield per unit time can be increased still ~urther. It is pre~erred ~or the polymerization to take place at pressures between 0.1 and 60 MPa, particularly between 1 and 30 MPa. Higher pressures o~ 100 MPa and 20 above may be used when the polymerization takes place in so-called autoclaves.
The molecular weight o~ the polymer may be controlled in the usual manner, ~or instance by adding hydrogen or other chain terminating agents or by adjusting 25 the polymerization conditions.
The 1,2-polybutadiene is pre~erably added as a solution in a suitable dispersant that has no adverse e~ect on the polymerization process. In a continuous process, the 1,2-polybutadiene is pre~erably added to the 30 polymerization reactor on a continuous basis. In a system employing a plurality o~ reactors it also possible to add - the 1,2-polybutadiene to only some o~ the reactors employed. In batch polymerization, the 1,2-polybutadiene J may be added prior to or during polymerization. The 35 amounts to be used and the molecular weights o~ the 1,2-CA 022324~6 1998-03-17 W O 97/1~920 PCT~NL96/00363 - 12 -polybutadiene are described in the ~oregoing.
The invention will be illustrated by the ~ollowing examples without being limited thereto.
The density D23 was determined in accordance with ASTM Standard D 792-66. The melt index MI was determined in accordance with ASTM Standard D1238 using a weight o~ 2.16 kg. The Melt Flow Ratio, MFR, was determined as the quotient o~ the melt indices determined to ASTM D1238 using weights o~ 21.6 and 2.16 kg, respectively. The Mw/Mn ratio was determined with the aid o~ a Waters M150C Gel Permeation Chromatograph with DRI-detector as Size Exclusion Chromatograph in combination with a Viscotek type 502 viscometer as viscosity detector and using polyethylene calibration samples as re~erence.
ExamPles I-IV
A number o~ polyole~ins o~ the invention were produced as ~ollows.
An autoclave with a capacity o~ 2 litres was ~illed with special boiling point spirit (boiling range ~rom 65 to 70~C) and kept at a temperature o~ 160~C. A
mixture o~ special boiling point spirit (5.5 kg/h) and ethylene (1.2 kg/h) was continuously added to the autoclave. Also, in some cases, hydrogen was added in order to obtain the desired molar mass. The supply to the autoclave was adjusted so that the autoclave remained completely ~illed with the reaction medium. A solution o~
a catalyst, a suspension o~ an activator and a solution o~
triethylaluminium was also continuously added to the autoclave. The ethylene conversion was controlled by means o~ the amounts o~ catalyst and activator and amounted to approximately 95~ in each experiment.
Ethylene-dimethylamino-tetramethyl-cyclopentadienyl-titanium-dimethyl, Cp (CH2CH2)N(CH3)2Ti(CH3)2, was added as catalyst ~or the CA 022324~6 1998-03-17 W O 97/12920 PCT~NL96/00363 preparation o~ a copolymer o~ ethylene and 1,2-polybutadiene. A concentration o~ the catalyst o~ approx.
20 ~mol per litre was needed ~or attaining 95% ethylene conversion.
Dimethylaniliniumtetrakispenta~luorophenylborate was applied as activator. A concentration o~ the activator o~
approx. 40 ~mol per litre was needed ~or attaining 95%
ethylene conversion. The concentration o~
triethylaluminium applied in the autoclave amounted to approx. 40 ~mol per litre. In a seperate vessel a mixture o~ 1,2-polybutadiene (1,2-polybutadiene) with a Mn o~
approx. 3000 g/mol, containing approx. 50 vinyl groups per molecule chain ~grade B-- 3000 ~rom Messrs NISSOH IWAI) and special boiling point spirit was prepared. A certain amount o~ 1,2-polybutadiene solution was continuously pumped ~rom this vessel to the autoclave. The desired rate at which 1,2-polybutadiene was added was adjusted by suitably choosing the concentration o~ 1,2-polybutadiene in the solution. Here, 1 g/h o~ 1,2-polybutadiene corresponded to 0.088 wt.% re~erred to converted ethylene.
The properties o~ the copolymers obtained with various rates o~ addition o~ 1,2-polybutadiene are shown in Table 1.
CA 022324~6 1998-03-17 example addition o~ MI MFR Mw/Mn D23 1,2-polybutadiene g/h I 0 6.1 25.8 2.5 958.9 II 0.25 4.7 27.8 2.5 959.6 III 2.5 4.7 30.2 2.6 959.1 IV 5 4.1 33.0 2.8 959.1 These results indicate that the MFR can be controlled by means o~ the rate at which 1,2-polybutadiene is added.
Exam~les V-IX
Terpolymerizations o~ ethylene, l-octene and 1,2-polybutadiene:
Analogously to Examples I-IV, polymerizations were carried out in which 0.2 kg/hour o~ octene-l was added to the autoclave as extra monomer.
The properties o~ the copolymers obtained with various rates o~ addition o~ 1,2-polybutadiene are shown in Table 2. The polymers contained 15 wt.~ octene.
CA 022324~6 l998-03-l7 W O 97/12920 PCT~NL9 example addition o~ MI MFR Mw/Mn DZ3 1,2-polybutadiene g/h S V 0 4.2 29.1 2.5 914.9 VI 1.0 2. 8 33.4 2. 6 915.4 VII 5 2.4 39.8 3.2 91S.6 VIII 15 0.6 56.7 5.0 916.2 IX 25 0.1 79.4 8. 2 917.7 lQ
The process o~ the invention proves suitable ~or producing terpolymers also. The MFR shows a distinct increase when as little as 1 g/h o~ 1,2--polybutadiene, corresponding to 0.088 wt.~ re~erred to the converted ethylene, is added.
ExamPles X-XIII
Analogously to the previous examples, terpolymers o~ ethylene, 1-octene and 1,2-polybutadiene were produced using two di~erent 1,2-polybutadiene grades in order to study the e~ect o~ the molar mass o~ the 1,2-polybutadiene on the MFR in the terpolymerization o~
ethylene, octene and 1,2-polybutadiene. Use was made o~
grade B-3000 and grade B-2000 already mentioned in Examples V-IX, ~rom the same supplier, with a Mn o~ 2000 g/mol, containing approx. 33 vinyl unsaturations per molecule chain. The results are shown in Table 3.
CA 022324S6 1998-03-17 ~~
5 ~Dr~
example 1,2- MI MFR Mw/Mn D23 1,2-polybuta- poly-diene buta-diene grade g/h X 0 4.2 29.1 2.4 914.9 XI 2.5 4.1 31.1 2.7 917.0 B-2000 XII 5.0 2.2 38.6 3.0 915.6 B-2000 XIII 2.5 2.3 36.5 2.8 917.0 B-3000 VlI 5.0 2.4 39.8 3.2 915.6 B-3000 ExamPles XIV-XVIII
Polymerizations were carried out analogously to Examples I-IV exce;~t that diphenylmethylene-~luorenyl-cyclopentadienyl- -dimethyl {[(C6H5)2CJFluCpZrMe2}
was used as catalyst.
As 1,2-polybutadiene a grade supplied by Messrs Aldrich with a Mn o~ approx. 1300 g/mol, approx. 99~ unsaturated and with a vinyl:trans unsaturations o~ 40:30 (designated grade A) and a grade ~rom the same company with a Mn o~
1800 g/mol, approx. 60~ unsaturations and with the distribution o~ the unsaturations among the various possibilities given by vinyl:trans:cis = 45:10:5 (designated grade B) were used. The results are shown in AMEN~ED SHEE'r W O 97/12920 PCT~L96/~0 Table 4.
Exam--addition MI MFR Mw/Mn D23 grade ple oi~ 1,2-polybuta-diene ~ m/m XIV 0 12 n.d. 3.5 956.7 XV 0.30 2.5 52 5.6 951.5 B
XVI 0.60 0.5 98 4.6 949.7 B
XVII 0.09 42 n.d. 3.8 955.8 A
XVIII 0.19 9.6 38 3.8 956.7 A
-n.d. : not determined
Claims (10)
1. Thermoplastic polyolefin which is a copolymer of ethylene, 0-50 wt% of a C4-C20 .alpha.-olefin with respect to the total amount of olefinic monomer present and from 0.005 to 10 wt.% 1,2-polybutadiene referred to the copolymer in which the number of 1,2-vinyl unsaturations per polybutadiene chain is at least 3.
2. Thermoplastic polymer according to claim 1 in which the olefinic monomer is ethylene.
3. Thermoplastic polymer according to claim 1, in which the .alpha.-olefin is a C4-C10 .alpha.-olefin.
4. Polyolefin according to any one of claims 1-3, in which the chain length of the 1,2-polybutadiene, expressed as the number of polymerized butadiene units, is not more than 5000.
5. Polyolefin according to any one of claims 1-4, which contains from 0.01 to 5 wt.% polybutadiene.
6. Polyolefin according to any one of claims 1-5, in which the chain length of the 1,2-polybutadiene is at least 10.
7. Process for producing a thermoplastic polyolefin of at least one olefinic monomer comprising contacting ethylene and optionally one or more C4-C20 .alpha.-olefins with a cyclopentadienyl-containing transition metal complex as catalyst under conditions at which the monomers polymerize in the presence of the catalyst, characterized in that polymerization takes place in the presence of 0.005 to 10 wt.% 1,2-polybutadiene in which the number of 1,2-vinyl unsaturations per polybutadiene chain is at least 3.
- Amended Set of Claims (continued) -
- Amended Set of Claims (continued) -
8. Process according to claim 7 in which a cyclopentadienyl-containing transition metal complex with the formula R4MX1X2 is used as catalyst, where M is a transition metal from Group 4 of the Periodic system, not of the highest valency, preferably Ti3+, where X1 and X2 may be the same or different and are chosen from the group of:
- halogens - aliphatic or aromatic substituents - substituents which contain an element from group 15 or 16 of the Periodic System such as OR3, NR3 and the like, where R3 may be an aliphatic or aromatic substituent which may optionally contain silicon, where R4 is equal to [Cp'-Y-Z(R5)n]-where Cp' is a cyclopentadienyl derivative substituted with an aliphatic or aromatic groups or groups containing a heteroatom, Y is an aliphatic or aromatic group or a silicon-containing or heteroatom-containing group, Z is an element from group 15 or 16 of the Periodic System, preferably N or P, R5 is an aliphatic, aromatic or silicon-containing group and n is equal to the valency of Z minus 1.
- halogens - aliphatic or aromatic substituents - substituents which contain an element from group 15 or 16 of the Periodic System such as OR3, NR3 and the like, where R3 may be an aliphatic or aromatic substituent which may optionally contain silicon, where R4 is equal to [Cp'-Y-Z(R5)n]-where Cp' is a cyclopentadienyl derivative substituted with an aliphatic or aromatic groups or groups containing a heteroatom, Y is an aliphatic or aromatic group or a silicon-containing or heteroatom-containing group, Z is an element from group 15 or 16 of the Periodic System, preferably N or P, R5 is an aliphatic, aromatic or silicon-containing group and n is equal to the valency of Z minus 1.
9. Process according to any one of claims 7-8 in which polymerization takes place in the presence of 0.01-10 wt.% 1,2-polybutadiene.
10. Process according to any one of claims 7-8 in which polymerization takes place in the presence of 0.01-5 wt.%
1,2-polybutadiene.
1,2-polybutadiene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1001237 | 1995-09-19 | ||
| NL1001237A NL1001237C2 (en) | 1995-09-19 | 1995-09-19 | Copolymer of an olefinic monomer and 1,2-polybutadiene. |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2232456A1 true CA2232456A1 (en) | 1997-04-10 |
Family
ID=19761595
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002232456A Abandoned CA2232456A1 (en) | 1995-09-19 | 1996-09-18 | Copolymer of an olefinic monomer and 1,2-polybutadiene |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0851878A1 (en) |
| KR (1) | KR19990045746A (en) |
| CN (1) | CN1202180A (en) |
| AU (1) | AU7146296A (en) |
| CA (1) | CA2232456A1 (en) |
| EA (1) | EA199800311A1 (en) |
| NL (1) | NL1001237C2 (en) |
| NO (1) | NO981219L (en) |
| WO (1) | WO1997012920A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6479424B1 (en) | 1998-12-14 | 2002-11-12 | Bp Corporation North America Inc. | Fluxional catalysts and related ligands containing bulky substituents |
| EP1930353A1 (en) * | 2006-12-07 | 2008-06-11 | Borealis Technology Oy | Olefin copolymer, a process for preparing an olefin copolymer and the use of same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE615768A (en) * | 1961-03-29 | |||
| JPS6323946A (en) * | 1986-07-15 | 1988-02-01 | ヒュ−ズ・ツ−ル・カンパニ− | Synthetic elastomer and its production |
| US5055438A (en) * | 1989-09-13 | 1991-10-08 | Exxon Chemical Patents, Inc. | Olefin polymerization catalysts |
| US5349100A (en) * | 1991-01-02 | 1994-09-20 | Exxon Chemical Patents Inc. | Chiral metallocene compounds and preparation thereof by creation of a chiral center by enantioselective hydride transfer |
-
1995
- 1995-09-19 NL NL1001237A patent/NL1001237C2/en not_active IP Right Cessation
-
1996
- 1996-09-18 WO PCT/NL1996/000363 patent/WO1997012920A1/en not_active Application Discontinuation
- 1996-09-18 EP EP96932849A patent/EP0851878A1/en not_active Ceased
- 1996-09-18 CA CA002232456A patent/CA2232456A1/en not_active Abandoned
- 1996-09-18 CN CN96198385A patent/CN1202180A/en active Pending
- 1996-09-18 AU AU71462/96A patent/AU7146296A/en not_active Abandoned
- 1996-09-18 KR KR1019980701989A patent/KR19990045746A/en not_active Application Discontinuation
- 1996-09-18 EA EA199800311A patent/EA199800311A1/en unknown
-
1998
- 1998-03-18 NO NO981219A patent/NO981219L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| NO981219D0 (en) | 1998-03-18 |
| NL1001237C2 (en) | 1997-03-20 |
| KR19990045746A (en) | 1999-06-25 |
| EA199800311A1 (en) | 1998-10-29 |
| CN1202180A (en) | 1998-12-16 |
| EP0851878A1 (en) | 1998-07-08 |
| AU7146296A (en) | 1997-04-28 |
| NO981219L (en) | 1998-05-13 |
| WO1997012920A1 (en) | 1997-04-10 |
| MX9802137A (en) | 1998-05-31 |
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