WO2020152326A1 - Compositions de polymère aromatique de monovinylidène et leur procédé de fabrication - Google Patents

Compositions de polymère aromatique de monovinylidène et leur procédé de fabrication Download PDF

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WO2020152326A1
WO2020152326A1 PCT/EP2020/051738 EP2020051738W WO2020152326A1 WO 2020152326 A1 WO2020152326 A1 WO 2020152326A1 EP 2020051738 W EP2020051738 W EP 2020051738W WO 2020152326 A1 WO2020152326 A1 WO 2020152326A1
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elastomer
reactor
weight
monovinylidene aromatic
aromatic hydrocarbon
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PCT/EP2020/051738
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English (en)
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Armelle SIGWALD
Fanni SYPASEUTH
Aurélien Vantomme
Alexandre WELLE
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Total Research & Technology Feluy
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Publication of WO2020152326A1 publication Critical patent/WO2020152326A1/fr

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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
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/02—Monomers containing only one unsaturated aliphatic radical
    • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F12/06—Hydrocarbons
    • C08F12/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0838—Copolymers of ethene with aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • 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
    • C08F2420/07—Heteroatom-substituted Cp, i.e. Cp or analog where at least one of the substituent of the Cp or analog ring is or contains a heteroatom

Definitions

  • the present invention relates to a monovinylidene aromatic polymer composition, and a method of making such a composition. More in particular, the monovinylidene aromatic polymer composition comprises an elastomer, preferably a rubber-like elastomer.
  • Blending is typically done by melt blending, wherein both polymers are melted, after which they are kneaded to form the blend, where after said blend is extruded and pelletized.
  • Other methods of blending involve twin-screw extrusion, solution mixing, latex blending, some methods providing more homogeneous blends than others. These blending techniques are herein referred to as“physical blending”. All these methods involve high energy consumption, time and/or use of large volumes of solvents.
  • the invention provides in at least one of the above named needs by using the same catalyst system in both the formation of the elastomer, preferably the rubber-like elastomer, and in the formation of the monovinylidene aromatic polymer.
  • the monovinylidene aromatic polymer composition can be obtained as a chemical blend.
  • the term“chemical blend” as used herein refers to a composition comprising at least two components, wherein the second component is formed from a reagent mixture comprising already the first component.
  • Such production processes may provide highly uniform compositions, and/or compositions that upon solidification and/or compacting have nodules of one component highly homogeneous distributed in a matrix of the other component.
  • said nodules are highly homogeneous in size.
  • the nodules comprise and/or are formed by the elastomer, preferably the rubber-like elastomer.
  • the matrix comprises and/or is formed by monovinylidene aromatic polymer.
  • the chemical blending avoids the need for a physical blending step to obtain a monovinylidene aromatic polymer composition.
  • a polymer fluff is obtained, which may be precipitated and compacted.
  • the same catalyst in the formation reaction of the elastomer, preferably the rubber-like elastomer, and the monovinylidene aromatic polymer preferably allows for using a single reaction vessel in both formation reactions.
  • the same reaction vessel comprising the reaction product from the formation of the elastomer, preferably the rubber-like elastomer is used as reaction vessel in the formation of the monovinylidene aromatic polymer; such a process can be seen as a one-pot-two-step reaction for the provision of monovinylidene aromatic polymer composition.
  • the present invention provides a process for manufacturing a monovinylidene aromatic polymer composition in a reactor, comprising the steps of:
  • a1) providing a monomer mixture to the reactor, wherein said monomer mixture comprises an a-olefin or diene, and preferably wherein said monomer mixture further comprises at least one first vinyl aromatic hydrocarbon monomer;
  • the present invention provides a process for manufacturing a monovinylidene aromatic polymer composition in a reactor, comprising the steps of:
  • c2) polymerizing at least part of the second vinyl aromatic hydrocarbon monomer with the catalyst system under polymerization conditions in the reactor to form a monovinylidene aromatic polymer; a1) providing a monomer mixture to the reactor, wherein said monomer mixture comprises an a-olefin or diene, and preferably wherein said monomer mixture further comprises at least one first vinyl aromatic hydrocarbon monomer; and,
  • the process comprises the step of at least partially removing the a- olefin or diene from the reactor after step a2) and preferably before step c2), preferably before step c1).
  • the first vinyl aromatic hydrocarbon monomer is the same as the second vinyl aromatic hydrocarbon monomer.
  • the first and/or the second vinyl aromatic hydrocarbon monomer is styrene.
  • the a-olefin or diene is ethylene.
  • the catalyst system comprises a rare earth element, preferably a light rare earth element.
  • At least 60.0 %, preferably at least 80.0 %, preferably at least 90.0 %, preferably at least 95.0 %, preferably at least 99.0 %, preferably at least 99.5 %, preferably at least 99.9 % of the metallic centres in the catalyst system are rare earth elements, preferably a light rare earth elements. These metallic centres result in a more random type of elastomer compared to the titanium, zirconium, hafnium, or vanadium metallic centres. Hence, such catalyst systems leave a typical microstructure. It has been found that a more random type of elastomer provides a better compatibility with other polymers, preferably when said other polymer is a polyolefin or a polydiene.
  • the catalyst system comprises an element selected from the list comprising neodymium (Nd), yttrium (Y), scandium (Sc), lanthanum (La), samarium (Sm), praseodymium (Pr); preferably the catalyst system comprises Nd and/or Y; preferably the catalyst system comprises Nd.
  • At least 60.0 %, preferably at least 80.0 %, preferably at least 90.0 %, preferably at least 95.0 %, preferably at least 99.0 %, preferably at least 99.5 %, preferably at least 99.9 % of the metallic centres in the catalyst system are metals selected from the list comprising neodymium (Nd), yttrium (Y), scandium (Sc), lanthanum (La), samarium (Sm), and praseodymium (Pr); preferably selected from Nd and/or Y; preferably Nd. These metallic centres result in a more random type of elastomer compared to the titanium, zirconium, hafnium, or vanadium metallic centres.
  • At most 10.0 %, preferably at most 5.0 %, preferably at most 2.0 %, preferably at most 1.0 %, preferably at most 0.5 % of the metallic centres in the catalyst system are titanium, zirconium, hafnium, and vanadium. In some embodiments, at most 10.0 %, preferably at most 5.0 %, preferably at most 2.0 %, preferably at most 1.0 %, preferably at most 0.5 % of the metallic centres in the catalyst system are titanium. These metallic centres result in a more blocky type of elastomer compared to the rare earth metallic centres.
  • the catalyst system comprises a metallocene catalyst component of the general formula (II),
  • Cp is a cyclopentadienyl, optionally substituted with one or more substituents each independently selected from the group consisting of halogen, hydrosilyl, a hydrocarbyl having 1 to 20 carbon atoms, and SiR” 3 wherein R” is a hydrocarbyl having 1 to 20 carbon atoms; and wherein said hydrocarbyl optionally contains one or more atoms selected from the group comprising B, Si, S, O, F, Cl, and P;
  • Flu is a fluorenyl, optionally substituted with one or more substituents each independently selected from the group consisting of halogen, hydrosilyl, a hydrocarbyl having 1 to 20 carbon atoms, and SiR’” 3 wherein R’” is a hydrocarbyl having 1 to 20 carbon atoms; and wherein said hydrocarbyl optionally contains one or more atoms selected from the group comprising B, Si, S, O, F, Cl, and P;
  • M is a rare earth metal
  • ether is a donor solvent molecule
  • R" is a structural bridge between Cp and Flu (9-position) imparting stereorigidity to the component
  • each R' is the same or different, and is hydrogen or a hydrocarbyl having from 1 to 20 carbon atoms;
  • n 0, 1 or 2.
  • the catalyst system comprises a compound according to formula (III):
  • the monovinylidene aromatic polymer is a syndiotactic monovinylidene aromatic polymer having at least 70% rrrrr hexads, preferably at least 75% rrrrr hexads, preferably at least 80% rrrrr hexads, preferably at least 85% rrrrr hexads, preferably at least 90% rrrrr hexads, preferably at least 95% rrrrr hexads, determined by 13C ⁇ 1 H ⁇ NMR.
  • the invention provides in a monovinylidene aromatic polymer composition comprising:
  • an elastomer preferably a rubber-like elastomer, which is preferably the polymerization product of vinyl aromatic hydrocarbon monomer and an a-olefin or a diene; and,
  • composition is a chemical blend of the elastomer, preferably the rubber-like elastomer and the monovinylidene aromatic polymer, preferably a chemical blend of the elastomer, preferably the rubber-like elastomer, the monovinylidene aromatic polymer and a third polymer;
  • the invention provides in a monovinylidene aromatic polymer composition comprising:
  • an elastomer preferably a rubber-like elastomer, which is preferably the polymerization product of vinyl aromatic hydrocarbon monomer and an a-olefin or a diene;
  • a third polymer preferably a homopolymer of the a-olefin or the diene.
  • the invention provides in a process for manufacturing the monovinylidene aromatic polymer composition according to an embodiment of the invention, said process being a process according to an embodiment of the invention, further comprising the step of physical blending a third polymer in the monovinylidene aromatic polymer composition.
  • the invention provides in the use of hemi-metallocene catalyst, a metallocene catalyst or post-metallocene catalyst in a catalyst system in at least two different polymerization reactions carried out in the same reactor, wherein:
  • At least one polymerization reaction is the polymerization of vinyl aromatic hydrocarbon monomer to form a monovinylidene aromatic polymer
  • At least one polymerization reaction is the polymerization of a monomer mixture, said monomer mixture comprises vinyl aromatic hydrocarbon monomer and an a- olefin or a diene;
  • Preferred embodiments of one aspect of the invention are preferred embodiments of the other aspects of the invention.
  • FIG. 1 shows the different chemical shifts in a 13 C ⁇ 1 H ⁇ NMR spectra for a styrene-ethylene copolymer.
  • FIG. 2a depicts a SEM image of a physical blend of syndiotactic polystyrene with a styrene- ethylene copolymer.
  • FIG. 2b depicts a SEM image of a monovinylidene aromatic polymer composition according to an embodiment of the invention.
  • FIG. 2c depicts a SEM image of a monovinylidene aromatic polymer composition according to an embodiment of the invention.
  • FIG. 3 depicts a detail of the NMR spectrum of a styrene homopolymer.
  • a polymer means one polymer or more than one polymer.
  • the terms “comprising”, “comprises” and “comprised of as used herein are synonymous with “including”, “includes” or “containing”, “contains”, and are inclusive or open-ended and do not exclude additional, non-recited members, elements or method steps.
  • the terms “comprising”, “comprises” and “comprised of” also include the term“consisting of”.
  • endpoints includes all integer numbers and, where appropriate, fractions subsumed within that range (e.g. 1 to 5 can include 1 , 2, 3, 4 when referring to, for example, a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when referring to, for example, measurements).
  • the recitation of end points also includes the end point values themselves (e.g. from 1.0 to 5.0 includes both 1.0 and 5.0). Any numerical range recited herein is intended to include all sub-ranges subsumed therein.
  • a process for manufacturing a monovinylidene aromatic polymer composition in a reactor comprising the steps of: a1) providing a monomer mixture to the reactor, wherein said monomer mixture comprises an a-olefin or diene, and preferably wherein said monomer mixture further comprises at least one first vinyl aromatic hydrocarbon monomer;
  • a process for manufacturing a monovinylidene aromatic polymer composition in a reactor comprising the steps of:
  • a1) providing a monomer mixture to the reactor, wherein said monomer mixture comprises at least one first vinyl aromatic hydrocarbon monomer and an a-olefin or diene;
  • a process for manufacturing a monovinylidene aromatic polymer composition in a reactor comprising the steps of:
  • a process for manufacturing a monovinylidene aromatic polymer composition in a reactor comprising the steps of:
  • a1) providing a monomer mixture to the reactor, wherein said monomer mixture comprises at least one first vinyl aromatic hydrocarbon monomer and an a-olefin or diene;
  • step b1) can be performed before, during, or after step a1) or d); whichever step a1) or d) is performed first.
  • step b1) the catalyst system is provided to the reactor comprising already at least part of the monomer mixture or vinyl aromatic hydrocarbon monomer.
  • step a2) the partial pressure of the a-olefin and/or diene in the reaction mixture is maintained.
  • step a2) the pressure in the reactor is maintained by controlling the amount of a- olefin and/or diene in the reaction mixture.
  • the process comprises the step of at least partially removing the a-olefin or diene from the reactor after step a2) and preferably before step c2), preferably before step d).
  • a third polymer is formed in step a2), preferably a homopolymer, preferably a homopolymer of the a-olefin or the diene.
  • R is hydrogen or an alkyl group having from 1 to 4 carbon atoms
  • Ar is an aromatic radical of at least 6 to at most 14 carbon atoms, preferably 6 to 10 carbon atoms, preferably wherein the first and the second vinyl aromatic hydrocarbon monomer are the same.
  • first and/or the second vinyl aromatic hydrocarbon monomer is selected from the list comprising: styrene, alpha-methylstyrene, ortho-methylstyrene, meta-methylstyrene, para-methylstyrene, vinyl toluene, para-t-butylstyrene, vinyl naphthalene, divinylbenzene, para-chlorostyrene, meta-chlorostyrene, ortho-chlorostyrene, 2,4-dimethylstyrene, 4- vinylbiphenyl, and vinylanthracene, preferably wherein the first and the second vinyl aromatic hydrocarbon monomer are the same.
  • the catalyst system comprises a rare earth element, preferably a light rare earth element.
  • the catalyst system comprises an element selected from the list comprising neodymium (Nd), yttrium (Y), scandium (Sc), lanthanum (La), samarium (Sm), praseodymium (Pr); preferably wherein the catalyst system comprises Nd and/or Y; preferably wherein the catalyst system comprises Nd.
  • the catalyst system comprises a hemi-metallocene catalyst, a metallocene catalyst, or a post-metallocene catalyst, preferably a metallocene catalyst or a hemi-metallocene catalyst, preferably a hemi-metallocene catalyst.
  • Cp is a cyclopentadienyl, optionally substituted with one or more substituents each independently selected from the group consisting of halogen, hydrosilyl, a hydrocarbyl having 1 to 20 carbon atoms, and SiR” 3 wherein R” is a hydrocarbyl having 1 to 20 carbon atoms; and wherein said hydrocarbyl optionally contains one or more atoms selected from the group comprising B, Si, S, O, F, Cl, and P;
  • Flu is a fluorenyl, optionally substituted with one or more substituents each independently selected from the group consisting of halogen, hydrosilyl, a hydrocarbyl having 1 to 20 carbon atoms, and SiR’”3 wherein R’” is a hydrocarbyl having 1 to 20 carbon atoms; and wherein said hydrocarbyl optionally contains one or more atoms selected from the group comprising B, Si, S, O, F, Cl, and P;
  • M is a rare earth metal
  • ether is a donor solvent molecule
  • R" is a structural bridge between Cp and Flu (9-position) imparting stereorigidity to the component
  • each R' is the same or different, and is hydrogen or a hydrocarbyl having from 1 to 20 carbon atoms;
  • n 0, 1 or 2.
  • M is a rare earth element, preferably a light rare earth element, for example wherein M is selected from the list comprising neodymium (Nd), yttrium (Y), scandium (Sc), lanthanum
  • La samarium
  • Pr praseodymium
  • the catalyst system comprises a cocatalyst.
  • the cocatalyst is an alkylmagnesium of formula MgR b 2, wherein each R b can be the same or different independently selected from halogens, alkoxy or alkyl.
  • alkylmagnesium of formula MgR b 2 is selected from the group comprising: di-iso-butyl magnesium, di-ethyl magnesium, di-methyl magnesium, and methyl-ethyl magnesium, preferably wherein said alkylmagnesium of formula MgR b 2 is di-butyl -magnesium.
  • the monovinylidene aromatic polymer is a syndiotactic monovinylidene aromatic polymer having at least 70% rrrrr hexads, preferably at least 75% rrrrr hexads, preferably at least 80% rrrrr hexads, preferably at least 85% rrrrr hexads, preferably at least 90% rrrrr hexads, preferably at least 95% rrrrr hexads, determined by 13C ⁇ 1 H ⁇ NMR.
  • the weight average molecular weight of the monovinylidene aromatic polymer is at least 10,000 Da, preferably at least 50,000 Da, preferably at least 100,000 Da, preferably at least 150,000 Da, preferably at least 175,000 Da, preferably at least 200,000 Da, determined by high temperature gel permeation chromatography (GPC).
  • the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the monovinylidene aromatic polymer is at least 1.0 to at most 15.0, preferably at least 1.1 to at most 10.0, preferably at least 1.5 to at most 7.5, preferably at least 1.7 to at most 5.0, preferably at least 2.0 to at most 3.0, determined by high temperature gel permeation chromatography (GPC).
  • GPC high temperature gel permeation chromatography
  • the melting temperature (Tm) of the monovinylidene aromatic polymer is at least 150°C to at most 270°C, preferably at least 200°C to at most 265°C, preferably at least 220°C to at most 260°C, preferably at least 240°C to at most 255°C, preferably around 250°C, determined by differential scanning calorimetry (DSC) with a heating and cooling rate of 10°C/min in the range 30°C to + 300°C in the second heating cycle.
  • DSC differential scanning calorimetry
  • the glass transition temperature (Tg) of the elastomer, preferably the rubber-like elastomer is at most -10°C, preferably at most -15°C, preferably at most -18°C, preferably at most -20°C, preferably at most -25°C, preferably at most -27°C, preferably at most - 30°C, determined by differential scanning calorimetry (DSC) with a heating and cooling rate of 10°C/min in the range -85°C to + 300°C.
  • DSC differential scanning calorimetry
  • the vinyl aromatic hydrocarbon monomer content of the elastomer, preferably the rubber like elastomer is at least 5.0% by weight, preferably at least 10.0% by weight, preferably at least 20.0% by weight, preferably at least 30.0% by weight, preferably at least 35.0% by weight, wherein the % by weight is based on the total weight of the elastomer, preferably the rubber-like elastomer.
  • the vinyl aromatic hydrocarbon monomer content of the elastomer, preferably the rubber like elastomer is at least 5.0% by weight to at most 75.0% by weight, preferably at least 10.0% by weight to at most 65.0% by weight, preferably at least 20.0% by weight to at most 60.0% by weight, preferably at least 35.0% by weight to at most 55.0% by weight, preferably at least 25.0% by weight to at most 50.0% by weight, wherein the % by weight is based on the total weight of the elastomer, preferably the rubber-like elastomer.
  • a-olefin monomer content together with the diene monomer content, which ever one is present, of the elastomer, preferably the rubber-like elastomer is at least 25.0% by weight, preferably at least 35.0% by weight, preferably at least 45.0% by weight, preferably at least 55.0% by weight, preferably at least 60.0% by weight, wherein the % by weight is based on the total weight of the elastomer, preferably the rubber-like elastomer.
  • a-olefin monomer content together with the diene monomer content, which ever one is present, of the elastomer, preferably the rubber-like elastomer is at most 95.0% by weight, preferably at most 90.0% by weight, preferably at most 80.0% by weight, preferably at most 75.0% by weight, preferably at most 65.0% by weight, wherein the % by weight is based on the total weight of the elastomer, preferably the rubber-like elastomer.
  • the a-olefin monomer content together with the diene monomer content, which ever one is present, of the elastomer, preferably the rubber-like elastomer is at least 25.0% by weight to at most 90.0% by weight, preferably at least 35.0% by weight to at most 85.0% by weight, preferably at least 45.0% by weight to at most 80.0% by weight, preferably at least 55.0% by weight to at most 75.0% by weight, preferably at least 60.0% by weight to at most 65.0% by weight, wherein the % by weight is based on the total weight of the elastomer, preferably the rubber-like elastomer.
  • the monovinylidene aromatic polymer composition comprises at least 70.0% by weight of the monovinylidene aromatic polymer, preferably at least 75.0% by weight of the monovinylidene aromatic polymer, preferably at least 80.0% by weight of the monovinylidene aromatic polymer, preferably at least 85.0% by weight of the monovinylidene aromatic polymer, preferably at least 90.0% by weight of the monovinylidene aromatic polymer, preferably at least 95.0% by weight of the monovinylidene aromatic polymer, preferably at least 99.0% by weight of the monovinylidene aromatic polymer, wherein the % by weight is based on the total weight of the monovinylidene aromatic polymer composition.
  • the monovinylidene aromatic polymer composition comprises at most 75.0% by weight of the monovinylidene aromatic polymer, preferably at most 80.0% by weight of the monovinylidene aromatic polymer, preferably at most 85.0% by weight of the monovinylidene aromatic polymer, preferably at most 90.0% by weight of the monovinylidene aromatic polymer, preferably at most 95.0% by weight of the monovinylidene aromatic polymer, preferably at most 99.0% by weight of the monovinylidene aromatic polymer, preferably at most 99.5% by weight of the monovinylidene aromatic polymer, wherein the % by weight is based on the total weight of the monovinylidene aromatic polymer composition.
  • the monovinylidene aromatic polymer composition comprises at least 70.0% by weight to at most 99.5%by weight of the monovinylidene aromatic polymer, preferably at least 75.0% by weight to at most 99.0% by weight of the monovinylidene aromatic polymer, preferably at least 80.0% by weight to at most 95.0% by weight of the monovinylidene aromatic polymer, preferably at least 85.0% by weight to at most 90.0% by weight of the monovinylidene aromatic polymer, wherein the % by weight is based on the total weight of the monovinylidene aromatic polymer composition.
  • the monovinylidene aromatic polymer composition comprises at least 1.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at least 5.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at least 10.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at least 15.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at least 20.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at least 25.0% by weight of the r elastomer, preferably the rubber-like elastomer, preferably at least 30.0% by weight of the elastomer, preferably the rubber-like elastomer, wherein the % by weight is based on the total weight of the monovinylidene aromatic polymer, preferably at least 5.0% by weight of the elastomer,
  • the monovinylidene aromatic polymer composition comprises at most 45.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at most 40.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at most 35.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at most 30.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at most 25.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at most 20.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at most 15.0% by weight of the elastomer, preferably the rubber-like elastomer, wherein the % by weight is based on the total weight of the monovinylidene aromatic poly
  • the monovinylidene aromatic polymer composition comprises at least 1.0% by weight to at most 45.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at least 5.0% by weight to at most 40.0% by weight of the elastomer, preferably the rubber like elastomer, preferably at least 10.0% by weight to at most 35.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at least 15.0% by weight to at most 30.0% by weight of the elastomer, preferably the rubber-like elastomer, preferably at least 20.0% by weight to at most 25.0% by weight of the elastomer, preferably the rubber-like elastomer, wherein the % by weight is based on the total weight of the monovinylidene aromatic polymer composition.
  • the monovinylidene aromatic polymer composition may comprise from at least 0.0% by weight to at most 10.0% by weight third polymer, preferably from at least 0.1 % by weight to at most 8.0% by weight third polymer, preferably from at least 0.2% by weight to at most 2.0% by weight third polymer, preferably from at least 0.3% by weight to at most 5.0% by weight third polymer, preferably from at least 0.4% by weight to at most 2.0% by weight third polymer, preferably from at least 0.5% by weight to at most 1.0% by weight third polymer, based on the total weight of the composition.
  • the melting temperature (Tm) of the third polymer is at most 150°C, preferably at most 140°C, preferably at most 130°C, preferably at most 125°C, preferably at most 120°C, determined by differential scanning calorimetry (DSC) with a heating and cooling rate of 10°C/min in the range -85°C to + 300°C in the second heating cycle.
  • DSC differential scanning calorimetry
  • the melting temperature (Tm) of the elastomer, preferably the rubber-like elastomer is at least 100°C, preferably at least 105°C, preferably at least 1 10°C, preferably at least 1 15°C, preferably at least 120°C, determined by differential scanning calorimetry (DSC) with a heating and cooling rate of 10°C/min in the range -85°C to + 300°C in the second heating cycle.
  • DSC differential scanning calorimetry
  • the melting temperature (Tm) of the third polymer is at least 100°C to at most 150°C, preferably at least 105°C to at most 140°C, preferably at least 1 10°C to at most 130°C, preferably at least 1 15°C to at most 125°C, preferably around 120°C, determined by differential scanning calorimetry (DSC) with a heating and cooling rate of 10°C/min in the range -85°C to + 300°C in the second heating cycle.
  • DSC differential scanning calorimetry
  • the monovinylidene aromatic polymer composition may comprise from at least 0.5% by weight to at most 25.0% by weight rubber-like elastomer, preferably from at least 1.0% by weight to at most 20.0% by weight rubber-like elastomer, preferably from at least 2.0% by weight to at most 15.0% by weight rubber-like elastomer, preferably from at least 3.0% by weight to at most 12.0% by weight rubber-like elastomer, preferably from at least 4.0% by weight to at most 10.0% by weight rubber-like elastomer, preferably from at least 5.0% by weight to at most 7.0% by weight rubber-like elastomer, based on the total weight of the composition.
  • the monovinylidene aromatic polymer composition comprises nodules formed by the elastomer, preferably the rubber-like elastomer.
  • Monovinylidene aromatic polymer composition comprising:
  • an elastomer preferably a rubber-like elastomer, which is preferably the polymerization product of vinyl aromatic hydrocarbon monomer and an a-olefin or a diene; and,
  • a monovinylidene aromatic polymer which is the polymerization product of vinyl aromatic hydrocarbon monomer
  • composition is a chemical blend of the elastomer, preferably the rubber-like elastomer and the monovinylidene aromatic polymer, preferably a chemical blend of the elastomer, preferably the rubber-like elastomer, the monovinylidene aromatic polymer and a third polymer.
  • Monovinylidene aromatic polymer composition comprising: an elastomer, preferably a rubber-like elastomer, which is preferably the polymerization product of vinyl aromatic hydrocarbon monomer and an a-olefin or a diene;
  • a third polymer preferably a homopolymer of the a-olefin or the diene.
  • Monovinylidene aromatic polymer composition comprising:
  • a third polymer preferably a homopolymer of the a-olefin or the diene; and, a chemical blend of:
  • an elastomer preferably a rubber-like elastomer, which is preferably the polymerization product of vinyl aromatic hydrocarbon monomer and an a- olefin or a diene; and,
  • a monovinylidene aromatic polymer which is the polymerization product of vinyl aromatic hydrocarbon monomer.
  • step of physical blending comprises co-extrusion and/or melt blending.
  • At least one polymerization reaction is the polymerization of a monomer mixture, said monomer mixture comprising vinyl aromatic hydrocarbon monomer, and an a-olefin or a diene.
  • At least one polymerization reaction is the polymerization of vinyl aromatic hydrocarbon monomer to form a monovinylidene aromatic polymer; and, wherein at least one polymerization reaction is the polymerization of a monomer mixture, said monomer mixture comprises vinyl aromatic hydrocarbon monomer and an a-olefin or a diene.
  • the invention relates to a process for manufacturing a monovinylidene aromatic polymer composition in a reactor, comprising the steps of:
  • a1) providing a monomer mixture to the reactor, wherein said monomer mixture comprises an a-olefin or diene, and preferably wherein said monomer mixture further comprises at least one first vinyl aromatic hydrocarbon monomer;
  • the same inventive concept provides for a process for manufacturing a monovinylidene aromatic polymer composition in a reactor, comprising the steps of:
  • c1) providing at least a second vinyl aromatic hydrocarbon monomer to the reactor; b1) providing a catalyst system to the reactor; c2) polymerizing at least part of the second vinyl aromatic hydrocarbon monomer with the catalyst system under polymerization conditions in the reactor to form a monovinylidene aromatic polymer;
  • a1) providing a monomer mixture to the reactor, wherein said monomer mixture comprises an a-olefin or diene, and preferably wherein said monomer mixture further comprises at least one first vinyl aromatic hydrocarbon monomer; and, a2) polymerizing at least part of the monomer mixture with the same catalyst system under polymerization conditions in the reactor to form an elastomer, preferably a rubber-like elastomer;
  • first vinyl aromatic hydrocarbon monomer and “second vinyl aromatic hydrocarbon monomer” do not necessarily denote the order in which they are used.
  • the first vinyl aromatic hydrocarbon monomer is used to prepare an elastomer, while the second vinyl aromatic hydrocarbon monomer is used to prepare a monovinylidene aromatic polymer.
  • the “first vinyl aromatic hydrocarbon monomer” and “second vinyl aromatic hydrocarbon monomer” may be different or the same, preferably the same.
  • Such processes provide a monovinylidene aromatic polymer composition
  • a monovinylidene aromatic polymer composition comprising monovinylidene aromatic polymer and elastomer, preferably rubber-like elastomer.
  • the direct result of using the same catalyst system for both polymerization steps a2) and c2) is a chemical blend of the formed polymers, as the first formed polymer is present when the second polymer is formed.
  • the monovinylidene aromatic polymer in the composition may form a matrix, with nodules embedded in said matric, the nodules being formed by the elastomer.
  • the term“providing” means“adding”.
  • a solid is obtained at the end of the process, possible after a solidification step, e.g. cooling, precipitation or solvent evaporation.
  • the solid obtained at the end of the process may be grinded and extruded.
  • the solid can be compacted and/or extruded. Is some embodiments, the solid does not have to undergo a physical blend step to form a composition with homogeneously distributed nodules dispersed in a matrix.
  • steps a2) and c2) are performed in the same reactor or reaction vessel.
  • reactor or“reaction vessel” as used herein refers to any reactor suitable for polymerisation reactions. Examples of reactors are batch containers, pipe reactors, two or more serially connected reactors, preferably batch type reactors, continuous reactor, continuous stirred-tank reactors, plug flow reactors, fluidized bed reactors and the like.
  • the reactor is a batch reactor.
  • step a2) is performed in a first reactor vessel reactor
  • step c2) is performed in the second reactor vessel, wherein the first reactor vessel and the second reactor vessel are serially connected to each other.
  • step a1) b1) and/or d) involves providing a solvent to the reactor.
  • tall the solvent is added to the reactor in step a1) and b1), but preferably, solvent is provided to the reactor in step a1) and in step d).
  • Suitable solvents comprise but are not limited to hydrocarbon solvents such as aliphatic, cycloaliphatic and aromatic hydrocarbon solvents, or halogenated versions of such solvents.
  • Preferred solvents are C12 or lower, straight chain or branched chain, saturated hydrocarbons, C5 to C9 saturated alicyclic or aromatic hydrocarbons or C2 to C6 halogenated hydrocarbons.
  • Non-limiting illustrative examples of solvents are butane, isobutane, pentane, hexane, heptane, cyclopentane, cyclohexane, isohexane, cycloheptane, methyl cyclopentane, methyl cyclohexane, isooctane, benzene, toluene, xylene, chloroform, chlorobenzenes, tetrachloroethylene, dichloroethane and trichloroethane, preferably isohexane.
  • polymer composition refers to an assembly of at least two different polymers.
  • the polymers may differ in
  • rubber-like elastomer is an elastomer with have a tensile strength of at most 300 MPa, preferably at most 200 MPa, preferably at most 100 MPa, preferably at most 50 MPa, preferably at most 20 MPa, preferably at most 10 MPa, preferably at most 5 mPa, measured according to ISO 37 (2017).
  • the rubber like elastomer has an elongation at break of at least 200%, preferably at least 400%, preferably at least 500%, preferably at least 600%, preferably at least 700% preferably at least 800%, according to ASTM D412-16.
  • the step b1) can be performed before, during, or after step a1) or d); whichever step a1) or d) is performed first. This might provide some flexibility to the process in the order of adding compounds to the reactor. It may also save time.
  • step a2) the partial pressure of the a-olefin and/or diene in the reaction mixture is maintained.
  • step a2) the pressure in the reactor is maintained by controlling the amount of a-olefin and/or diene in the reaction mixture.
  • the process comprises the step of at least partially, preferably completely, removing the a-olefin or diene from the reactor after step a2) and preferably before step c2), preferably before step d). This avoids formation of copolymers with various degrees of incorporation of a-olefin or diene in the polymeric backbone. This may provide more control over the properties of the composition.
  • the process comprises a single catalyst activation step, preferably before step a2) or step c2), whichever is performed first.
  • a third polymer is formed in step a2), preferably a homopolymer, preferably a homopolymer of the a-olefin or the diene.
  • the catalyst system in step a2) provides:
  • a chemical blend comprising at least three different polymers, i.e. the elastomer, the monovinylidene aromatic polymer, and the third polymer, preferably homopolymer.
  • the presence of the third polymer, preferably a homopolymer may provide a better compatibility between the elastomer and the monovinylidene aromatic polymer, or better compatibility when the monovinylidene aromatic polymer composition is further blended with other polymers, for example polyolefins or polydienes, for example polyethylene.
  • the first vinyl aromatic hydrocarbon monomer is the same as the second vinyl aromatic hydrocarbon monomer. This may provide a good compatibility between the elastomer and the monovinylidene aromatic polymer. This might avoid repulsion at interfaces between the elastomer and the monovinylidene aromatic polymer. This might also favor the formation of more small nodules instead of fewer big nodules.
  • the vinyl aromatic hydrocarbon monomer is a monomer according to formula (IV):
  • R1 is H, a halogen or a C1-C10 hydrocarbon chain.
  • the vinyl aromatic hydrocarbon monomer is a monomer according to formula (V):
  • R1 is H, a halogen or a C1-C10 hydrocarbon chain
  • R2 is H, a halogen or a C1-C10 hydrocarbon chain.
  • R 1 is H. In some embodiments, R 2 is H.
  • the vinyl aromatic hydrocarbon monomer is selected from the list comprising styrene, divinyl-benzene, alpha-methyl-styrene, para-methyl-styrene, ethyl-vinyl- benzene, vinyl-naphthalene, para-chloro-styrene and or mixtures thereof.
  • the vinyl aromatic hydrocarbon is styrene, meaning both R 1 and R 2 are H.
  • the first and/or the second vinyl aromatic hydrocarbon monomer is styrene.
  • Styrene is easily available, cheap, and has no functional groups after being built into the polymer backbone, therefore the obtained polymer is chemically rather non-reactive.
  • the first and the second vinyl aromatic hydrocarbon monomer is styrene, and the a-olefin is ethylene. Both monomers are easily available, cheap, and have no functional groups after being built into the polymer backbone, therefore the obtained polymer is chemically rather non-reactive. This combination may also provide a good compatibility between the elastomeric nodules and the styrene matrix.
  • the catalyst system comprises a rare earth element, preferably a light rare earth element.
  • the catalyst system comprises an element selected from the list comprising neodymium (Nd), yttrium (Y), scandium (Sc), lanthanum (La), samarium (Sm), praseodymium (Pr); preferably the catalyst system comprises Nd and/or Y; preferably the catalyst system comprises Nd.
  • the catalyst system comprises a constrained geometry metallocene or a bridged metallocene.
  • the catalyst system comprises a cocatalyst.
  • cocatalyst refers to a compound which can activate a catalyst.
  • the monovinylidene aromatic polymer is a syndiotactic monovinylidene aromatic polymer.
  • “syndiotactic polymer” as used herein refers to a polymer having preferably at least 70% rrrrr hexads, preferably at least 75% rrrrr hexads, preferably at least 80% rrrrr hexads, preferably at least 85% rrrrr hexads, preferably at least 90% rrrrr hexads, preferably at least 95% rrrrr hexads, determined by 13C ⁇ 1 H ⁇ NMR.
  • the composition comprises at least one homopolymer and at least one copolymer.
  • copolymer as used herein is intended to encompass polymers which consist essentially of repeat units deriving from at least two monomers or at least two co-monomers.
  • interpolymer and“copolymer” as used herein, are synonyms and can be used interchangeably.
  • homopolymer as used herein is intended to encompass polymers which consist essentially of repeat units deriving from the same monomer. Homopolymers may, for example, comprise at least 99.8 % preferably 99.9 % by weight of repeats units derived from of that same monomer, the rest can be regarded as unavoidable imperfections. In some embodiments, the composition comprises at least one syndiotactic homopolymer and at least one copolymer.
  • the composition comprises at least one syndiotactic homopolymer and at least one copolymer, wherein the copolymer comprises the same monomer residue as the syndiotactic homopolymer.
  • the elastomer preferably the rubber-like elastomer, is a copolymer, preferably a random copolymer.
  • the elastomer preferably the rubber-like elastomer is a thermoplastic elastomers, preferably selected from the list comprising polybutadiene, polyisoprene, polyisobutylene, styrene/butadiene rubber (SBR), styrene/isoprene rubber (SIR), styrene/isoprene/butadiene rubber (SIBR), styrene-butadiene-styrene block copolymer (SBS) preferably having a butadiene/styrene weight ratio of about 90/10 to about 40/60, a styrene- butadiene block copolymer (SB), hydrogenated styrene-butadiene-styrene block copolymer (SEBS), hydrogenated styrene-butadiene block copolymer (SEB), styrene-isoprene
  • SBR
  • the elastomer preferably the rubber like elastomer include hydrogenated styrene-butadiene-styrene block copolymer (SEBS), and random copolymers of styrene/butadiene (SBR), block copolymers containing a-olefin and vinyl substituted aromatic hydrocarbons contributed units or hydrogenated versions thereof or block copolymers containing conjugated diene monomers and vinyl substituted aromatic hydrocarbons contributed units or hydrogenated versions thereof.
  • SEBS hydrogenated styrene-butadiene-styrene block copolymer
  • SBR random copolymers of styrene/butadiene
  • the elastomer preferably the rubber-like elastomer, is a block copolymer comprising blocks of a-olefin residues and vinyl substituted aromatic hydrocarbons contributed units or hydrogenated versions thereof.
  • the elastomer preferably the rubber-like elastomer, is a copolymer comprising:
  • a-olefin and/or diene residues a-olefin and/or diene residues; and, optionally vinyl aromatic hydrocarbon residues, e.g. styrene residues.
  • the elastomer preferably the rubber-like elastomer, is a copolymer comprising:
  • a-olefin residues e.g. ethylene residues, propylene residues, butene residues, preferably ethylene residues;
  • vinyl aromatic hydrocarbon residues e.g. styrene residues.
  • the elastomer preferably the rubber-like elastomer, is a block copolymer comprising:
  • At least one first block wherein the first block comprises:
  • vinyl aromatic hydrocarbon residues e.g. styrene residues
  • the second block comprises:
  • vinyl aromatic hydrocarbon residues e.g. styrene residues; wherein preferably at least 90.0% of the residues in the second block are vinyl aromatic hydrocarbon residues, preferably at least 95.0% of the residues in the second block are vinyl aromatic hydrocarbon residues, preferably at least 98.0% of the residues in the second block are vinyl aromatic hydrocarbon residues, preferably at least 99.0% of the residues in the second block are vinyl aromatic hydrocarbon residues, preferably at least 99.9% of the residues in the second block are vinyl aromatic hydrocarbon residues.
  • the elastomer preferably the rubber-like elastomer, is a block copolymer comprising:
  • At least one first block wherein the first block comprises:
  • a-olefin residues e.g. ethylene residues, propylene residues, butene residues, preferably ethylene residues;
  • vinyl aromatic hydrocarbon residues e.g. styrene residues
  • the second block comprises:
  • vinyl aromatic hydrocarbon residues e.g. styrene residues; wherein preferably at least 90.0% of the residues in the second block are vinyl aromatic hydrocarbon residues, preferably at least 95.0% of the residues in the second block are vinyl aromatic hydrocarbon residues, preferably at least 98.0% of the residues in the second block are vinyl aromatic hydrocarbon residues, preferably at least 99.0% of the residues in the second block are vinyl aromatic hydrocarbon residues, preferably at least 99.9% of the residues in the second block are vinyl aromatic hydrocarbon residues.
  • the at least one first block comprises a random copolymer of:
  • vinyl aromatic hydrocarbon residues e.g. styrene residues
  • the at least one first block comprises a random copolymer of:
  • vinyl aromatic hydrocarbon residues e.g. styrene residues
  • the at least one second block comprises:
  • vinyl aromatic hydrocarbon residues e.g. styrene residues; wherein preferably at least 90.0% of the residues in the second block are vinyl aromatic hydrocarbon residues, preferably at least 95.0% of the residues in the second block are vinyl aromatic hydrocarbon residues, preferably at least 98.0% of the residues in the second block are vinyl aromatic hydrocarbon residues, preferably at least 99.0% of the residues in the second block are vinyl aromatic hydrocarbon residues, preferably at least 99.9% of the residues in the second block are vinyl aromatic hydrocarbon residues.
  • the elastomer preferably the rubber-like elastomer, comprises from at least 20.0% to at most 85.0% by weight a-olefin residues and/or diene residues, preferably from at least 25.0% to at most 75.0% by weight a-olefin residues and/or diene residues preferably from at least 30.0% to at most 65.0% by weight a-olefin residues and/or diene residues, preferably from at least 35.0% to at most 55.0% by weight a-olefin residues and/or diene residues, preferably from at least 35.0% to at most 45.0% by weight a-olefin residues and/or diene residues, compared to the total weight of the elastomer, preferably the rubber like elastomer.
  • the elastomer preferably the rubber-like elastomer comprises from at least 80.0% to at most 15.0% by weight vinyl aromatic hydrocarbon residues, preferably from at least 75.0% to at most 25.0% by weight vinyl aromatic hydrocarbon residues, preferably from at least 70.0% to at most 35.0% by weight vinyl aromatic hydrocarbon residues, preferably from at least 65.0% to at most 50.0% by weight vinyl aromatic hydrocarbon residues, preferably from at least 65.0% to at most 55.0% by weight vinyl aromatic hydrocarbon residues, compared to the total weight of the elastomer, preferably the rubber-like elastomer.
  • the a-olefin monomers are a C3-C20 alpha-olefins, preferably selected from the list comprising ethylene, propylene, 1 -butene, 1-pentene, 4-methyl-1-pentene, 1- hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
  • the elastomer, preferably the rubber-like elastomer has a glass transition temperature (Tg) of the elastomer, preferably the rubber-like elastomer, is at most 30°C, preferably at most 15°C, preferably at most 0°C, preferably at most -5°C, preferably at most -10°C, preferably at most -20°C, preferably at most -30°C, determined by differential scanning calorimetry (DSC) with a heating and cooling rate of 10°C/min in the range -85°C to + 300°C.
  • Tg glass transition temperature
  • the invention also relates to a monovinylidene aromatic polymer composition
  • a monovinylidene aromatic polymer composition comprising: an elastomer, preferably a rubber-like elastomer, which is preferably the polymerization product of vinyl aromatic hydrocarbon monomer and an a-olefin or a diene; and, a monovinylidene aromatic polymer, which is the polymerization product of vinyl aromatic hydrocarbon monomer;
  • composition is a chemical blend of the elastomer, preferably the rubber-like elastomer and the monovinylidene aromatic polymer, preferably a chemical blend of the elastomer, preferably the rubber-like elastomer, the monovinylidene aromatic polymer and a third polymer.
  • the chemical blend is obtained by a process disclosed herein. Preferred embodiments of the process above are also preferred embodiments of the polymer composition.
  • the monovinylidene aromatic polymer composition may comprise: from at least 0.5 weight % to at most 25.0 weight %, preferably from at least 1.0 weight % to at most 15.0 weight %, preferably from at least 2.0 weight % to at most 10.0 weight %, preferably from at least 4.0 weight % to at most 7.0 weight % of the elastomer, preferably the rubber-like elastomer; and,
  • weight % is relative to the total weight of the composition.
  • the amount of each polymer in the monovinylidene aromatic polymer composition is determined after chemical separation.
  • the composition may comprise a third polymer, which third polymer may comprise a-olefin and/or diene residues, wherein preferably at least 90.0% of the residues in the third polymer are a-olefin residues and/or diene residues, preferably at least 95.0% of the residues in the third polymer are a-olefin residues and/or diene residues, preferably at least 98.0% of the residues in the third polymer are a-olefin residues and/or diene residues, preferably at least 99.0% of the residues in the third polymer are a-olefin residues and/or diene residues, preferably at least 99.9% of the residues in the third polymer are a-olefin residues and/or diene residues.
  • the monovinylidene aromatic polymer composition may comprise from at least 0.0% by weight to at most 5.0% by weight third polymer, preferably from at least 0.1 % by weight to at most 4.0% by weight third polymer, preferably from at least 0.2% by weight to at most 2.0% by weight third polymer, preferably from at least 0.3% by weight to at most 1.0% by weight third polymer, preferably from at least 0.4% by weight to at most 0.8% by weight third polymer, preferably from at least 0.5% by weight to at most 0.7% by weight third polymer, based on the total weight of the composition.
  • the third polymer is a homopolymer, preferably a homopolymer of the a-olefin or the diene, preferably a polyolefin, preferably ethylene.
  • the monovinylidene aromatic polymer composition may comprise from at least 0.5% by weight to at most 25.0% by weight elastomer, preferably rubber-like elastomer, preferably from at least 1.0% by weight to at most 20.0% by weight elastomer, preferably rubber-like elastomer, preferably from at least 2.0% by weight to at most 15.0% by weight elastomer, preferably rubber-like elastomer, preferably from at least 3.0% by weight to at most 12.0% by weight elastomer, preferably rubber-like elastomer, preferably from at least 4.0% by weight to at most 10.0% by weight elastomer, preferably elastomer, preferably rubber-like elastomer, preferably from at least 5.0% by weight to at most 7.0% by weight elastomer, preferably rubber-like elastomer, based on the total weight of the composition.
  • the monovinylidene aromatic polymer composition may comprise: an elastomer, preferably a rubber-like elastomer, which is preferably the polymerization product of vinyl aromatic hydrocarbon monomer and an a-olefin or a diene;
  • a third polymer preferably a homopolymer of the a-olefin or the diene.
  • the monovinylidene aromatic polymer composition may comprise: from at least 0.5 weight % to at most 25.0 weight % rubber-like elastomer; from at least 70.0 weight % to at most 99.5 weight % monovinylidene aromatic polymer; and,
  • weight % is relative to the total weight of the composition.
  • the monovinylidene aromatic polymer composition may comprise:
  • a third polymer preferably a homopolymer of the a-olefin or the diene
  • an elastomer preferably a rubber-like elastomer, which is preferably the polymerization product of vinyl aromatic hydrocarbon monomer and an a-olefin or a diene; and,
  • the invention also relates to the use of hemi-metallocene catalyst, a metallocene catalyst or post-metallocene catalyst in a catalyst system in at least two different polymerization reactions carried out in the same reactor.
  • Such use allows for a two-step-one-pot polymerization of a monovinylidene aromatic polymer composition, comprising a monovinylidene aromatic polymer chemically blended with an elastomer, preferably a rubber-like elastomer.
  • the use results in a process disclosed herein. Preferred embodiments of the process above are also preferred embodiments of the use.
  • At least 60.0 %, preferably at least 80.0 %, preferably at least 90.0 %, preferably at least 95.0 %, preferably at least 99.0 %, preferably at least 99.5 %, preferably at least 99.9 % of the metallic centres in the catalyst system are rare earth elements, preferably a light rare earth elements.
  • At least one polymerization reaction is the polymerization of vinyl aromatic hydrocarbon monomer to form a monovinylidene aromatic polymer.
  • At least one polymerization reaction is the polymerization of a monomer mixture, said monomer mixture comprises vinyl aromatic hydrocarbon monomer and an a- olefin or a diene.
  • At least one polymerization reaction is the polymerization of vinyl aromatic hydrocarbon monomer to form a monovinylidene aromatic polymer; and, at least one polymerization reaction is the polymerization of a monomer mixture, said monomer mixture comprises vinyl aromatic hydrocarbon monomer and an a-olefin or a diene.
  • Equation 2 100 [wt%]
  • ATJ MEKS mass of MEK soluble fraction [g]
  • the microstructure of the copolymers was determined by 13 C ⁇ 1 H ⁇ NMR spectroscopy.
  • the samples were prepared by dissolving a sufficient amount of polymer in 1 ,2,4-trichlorobenzene (TCB 99% spectroscopic grade) at 130°C with occasional agitations to homogenize the sample followed by the addition of hexadeuterobenzene (C6D6, spectroscopic grade) and a minor amount of hexamethyldisiloxane (HMDS, 99.5+%), with HMDS serving as internal standard.
  • TCB 99% spectroscopic grade
  • C6D6 hexadeuterobenzene
  • HMDS hexamethyldisiloxane
  • about 200 to 300 mg of polymer was dissolved in 2.0 ml of TCB, followed by the addition of 0.5 ml of C6D6 and 2 to 3 drops of HMDS.
  • Decoupling sequence inverse-gated decoupling sequence to avoid NOE effect
  • the total amounts of incorporated styrene and ethylene were determined after considering the different chemical environment of the incorporated co-monomers in various sequences as shown in Figure 1.
  • the resonances of the different carbon atoms in the various styrene-ethylene co-monomer sequences are listed in Table 1.
  • C Arq ppm
  • CH 126.3 - 125.2 ppm
  • the total aliphatic region was considered from which the total amount of styrene previously determined by the aromatic resonances was subtracted.
  • Equation 3- Equation 14, where“Int” stands for integrated area of the peaks at given resonances.
  • the unit ⁇ 1” is a measure for the randomness of the copolymer, as it represents the amount of single ethylene monomers which are flanked by styrene monomers at either sides in the copolymer backbone. Equation 3
  • Table 1 13 NMR integrations zones in chemical shifts of different carbon atoms present in the microstructures of the ethylene / styrene copolymerization products.
  • sPS styrene homopolymerization samples
  • the tacticity of the monovinylidene aromatic polymer in the composition may be determined by synthesizing monovinylidene aromatic polymer in the absence of rubber-like elastomer, but under exact the same polymerization conditions as if the elastomer, preferably the rubber-like elastomer was present using the same catalyst.
  • An example of the relevant section of the spectrum styrene homopolymer is shown in Figure 3.
  • Table 2 13 C NMR integrations zones in chemical shifts of different carbon atoms present in the microstructures of styrene homopolymerization product sPS.
  • DSC Differential scanning calorimetry
  • DSC differential scanning calorimetry
  • Styrene-ethylene copolymer 1 (S/E 1)
  • the filtration was facilitated by pressure difference and the styrene was introduced to the reactor via a Teflon tube.
  • pressure difference of N2 150 mL of isohexane (/Ce) was added to the reactor from a solvent tank.
  • Styrene-ethylene copolymer 2 (S/E 2)
  • the filtration was facilitated by pressure difference and the styrene was introduced to the reactor via a Teflon tube.
  • the catalyst was added to a small addition funnel attached to the reactor. After the catalyst was added to the reactor the stirrer was started at 200 rpm. After 30 min polymerization the stirring speed was reduced to 100 rpm and the valve to the vent was opened to release any overpressure from the reactor.
  • the reaction was quenched by adding compressed air to the reactor. Then the mixture was cooled to room temperature.
  • the polymer slurry was poured into an iPrOH solution of Irganox 1010. The slurry was filtered and the fluff was dried in the vacuum oven. Further details are provided in Table 4.
  • the tacticity measured for this sPS may be used as the tacticity of the sPS component in the inventive examples, wherever similar polymerisation conditions are used.
  • the filtration was facilitated by pressure difference and the styrene was introduced to the reactor via a Teflon tube.
  • pressure difference of N2 150 ml_ of /Ce was added to the reactor from a solvent tank.
  • the catalyst was added to a small addition funnel attached to the reactor. After the catalyst was added to the reactor, 50 ml_ /Ce was used to wash the addition funnel and then stirrer was started at 200 rpm. After 90 min polymerization the stirring speed was reduced to 100 rpm and the valve to the vent was opened to release any overpressure from the reactor. Then the mixture was cooled to room temperature. The reaction was quenched by adding compressed air to the reactor.
  • the tacticity measured for this sPS may be used as the tacticity of the sPS component in the inventive examples, wherever similar polymerisation conditions are used. sPS1 sPS2
  • compositions (sPS + S/E)
  • This section relates to preparation of monovinylidene aromatic polymers compositions according to different embodiments of the invention.
  • the filtration was facilitated by pressure difference and the styrene was introduced to the reactor via a Teflon tube.
  • pressure difference of N2 150 ml_ of iCe was added to the reactor from a solvent tank.
  • the catalyst was added to a small addition funnel attached to the reactor. After the catalyst was added to the reactor, 60 ml_ /Ce was used to wash the addition funnel and then stirrer was started at 800 rpm. 60 bar of ethylene was added and maintained during the first polymerisation.
  • the reactor was flushed with N2. Afterwards 250 ml_ of styrene was added to the reactor passing through an alumina column. The temperature was kept at 100 °C for 60 min and the reaction mixture was stirred at 800 rpm. After 60 min the reaction was quenched by adding 40-80 ml_ of isopropanol (iPrOH) to the reactor. The reactor was left to cool down. The polymer slurry was poured into an iPrOH solution of Irganox 1010. The slurry was filtered and the fluff was dried in the vacuum oven. The fluff was melt-processed before carrying out the SEM experiments. Further details are provided in Table 5.
  • the filtration was facilitated by pressure difference and the styrene was introduced to the reactor via a Teflon tube.
  • pressure difference of N2 150 ml_ of iCe was added to the reactor from a solvent tank.
  • the catalyst was added to a small addition funnel attached to the reactor. After the catalyst was added to the reactor, 60 ml_ /Ce was used to wash the addition funnel and then stirrer was started at 200 rpm. 50 bar of ethylene was added and maintained during polymerisation.
  • the reactor was flushed with N2.
  • the filtration was facilitated by pressure difference and the styrene was introduced to the reactor via a Teflon tube.
  • pressure difference of N2 150 ml_ of iCe was added to the reactor from a solvent tank.
  • the catalyst was added to a small addition funnel attached to the reactor. After the catalyst was added to the reactor, 60 ml_ /Ce was used to wash the addition funnel and then stirrer was started at 200 rpm. 50 bar of ethylene was added and maintained during the first polymerisation.
  • the reactor was flushed with N2.
  • Figure 2a depicts a SEM image of a physical blend of syndiotactic polystyrene with a styrene- ethylene copolymer.
  • the physical blend comprises 10 wt% of S/E1 and 90 wt% of sPS1 and was prepared by extrusion using a MiniLab twin screw extruder by Haake at 270°C in con- rotatory configuration.
  • Figure 2b depicts a SEM image of Inventive Example 1 , showing a more homogeneous distribution of the E/S nodules in the sPS matrix then Figure 2a. The E/S nodules are also more homogeneous in size then in Figure 2a.
  • Figure 2c depicts a SEM image of Inventive Example 2, showing a more homogeneous distribution of the E/S nodules in the sPS matrix then Figure 2a.
  • the E/S nodules are also more homogeneous in size then in Figure 2a.

Abstract

La présente invention concerne une composition de polymère aromatique de monovinylidène, et un procédé de fabrication d'une telle composition. Plus particulièrement, la composition de polymère aromatique de monovinylidène comprend un élastomère, de préférence un élastomère de type caoutchouc.
PCT/EP2020/051738 2019-01-25 2020-01-24 Compositions de polymère aromatique de monovinylidène et leur procédé de fabrication WO2020152326A1 (fr)

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