WO2025190814A1 - Polymeres de diènes conjugués solubles dans des solvants organiques - Google Patents

Polymeres de diènes conjugués solubles dans des solvants organiques

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Publication number
WO2025190814A1
WO2025190814A1 PCT/EP2025/056321 EP2025056321W WO2025190814A1 WO 2025190814 A1 WO2025190814 A1 WO 2025190814A1 EP 2025056321 W EP2025056321 W EP 2025056321W WO 2025190814 A1 WO2025190814 A1 WO 2025190814A1
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Prior art keywords
polymers
group
conjugated dienes
carbon atoms
polymer chains
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PCT/EP2025/056321
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English (en)
Inventor
Gilbert Bouquet
Rudi Veraart
Pascal E.R.E.J. Lakeman
Elroy EEKMAN
Abidin Balan
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Trinseo Europe GmbH
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Trinseo Europe GmbH
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Publication of WO2025190814A1 publication Critical patent/WO2025190814A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/08—Depolymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2269—Heterocyclic carbenes
    • B01J31/2273—Heterocyclic carbenes with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/085—Devulcanisation
    • 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
    • C08F279/04—Vinyl aromatic monomers and nitriles as the only monomers
    • 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
    • C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
    • C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • 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
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles

Definitions

  • compositions containing polymers of conjugated dienes having polymer chains of conjugated dienes and chains of vinylidene aromatic monomers which are soluble in organic solvents Disclosed are methods for preparing the disclosed polymers. Disclosed are compositions containing such polymers.
  • Polymers prepared from vinylidene aromatic monomers such as polymers of styrene, are used in several polymeric systems, including foams, packaging (food packaging), medical, electronic, optical, appliance and automotive applications.
  • Polymers containing vinylidene substituted aromatic monomers and co-polymers of vinylidene substituted aromatic monomers and acrylonitrile were developed to provide polymers with increased glass transition temperatures and use temperatures which can be transparent or opaque. Such polymers may not exhibit great impact properties and modified polymers have been developed to improve the impact resistance.
  • Such modified polymers may contain impact modifiers, such as polymers of conjugated dienes such as butadiene-based rubbers, for example copolymers of styrene and acrylonitrile modified with polybutadiene rubber, acrylonitrile-butadiene-styrene (ABS), and high impact polystyrene (HIPS).
  • impact modifiers such as polymers of conjugated dienes such as butadiene-based rubbers, for example copolymers of styrene and acrylonitrile modified with polybutadiene rubber, acrylonitrile-butadiene-styrene (ABS), and high impact polystyrene (HIPS).
  • ABS acrylonitrile-butadiene-styrene
  • HIPS high impact polystyrene
  • a number of polymer producers desire to reduce the disposal of post-consumer polymer systems in landfills and by incineration. Such polymer producers desire to recycle the polymer systems and use them to prepare additional products. Processes to recover and reuse post-consumer used polymers have been developed see for example, WO2022/144158 wherein polymers of vinylidene aromatic monomers, such as of styrene, are recovered for recycling. In the disclosed process the polymers of vinylidene aromatic monomers are separated from the polybutadiene particles. The polybutadiene particles have been typically disposed of in landfills or by incineration. There is a need to develop uses for the recovered polybutadiene polymers.
  • compositions comprising polymers of conjugated dienes, containing polymer chains of conjugated dienes and polymer chains of vinylidene aromatic monomers, wherein the polymers are soluble in an organic solvent wherein soluble means at least 1 percent by weight, 5 percent by weight or 10 percent by weight of the polymers of conjugated diene dissolve in the organic solvent at about 25 ° C.
  • the composition may contain polymers of conjugated dienes consisting of polymer chains of conjugated dienes wherein the polymers are soluble in an organic solvent wherein soluble means at least 1 percent by weight, 5 percent by weight or 10 percent by weight of the polymers of conjugated dienes dissolve in the organic solvent at about 25 ° C.
  • the polymer chains of vinylidene aromatic monomers are disposed between polymer chains of conjugated dienes and optionally at the end of polymer chains of conjugated dienes.
  • the composition may contain polymers of conjugated diene containing polymer chains of conjugated dienes and polymer chains of vinylidene aromatic monomers and conjugated diene polymers having only polymer chains of conjugated dienes.
  • the polymer chains of vinylidene aromatic monomers may be homopolymers of vinylidene aromatic monomers or copolymers of two or more vinylidene aromatic monomers.
  • the polymer chains of vinylidene aromatic monomers may be copolymers of one or more vinylidene aromatic monomers with one or more monomers copolymerizable with the one or more vinylidene aromatic monomers.
  • the one or more monomers copolymerizable with the one or more vinylidene aromatic monomers may be one or more unsaturated nitriles, for instance acrylonitrile.
  • the conjugated dienes may be isoprene and/or butadiene.
  • the polymers of conjugated diene may exhibit a weight average molecular weight determined by gel permeation chromatography using polystyrene standards of from 20,000 to 200,000 atomic mass units.
  • the polymers of conjugated dienes may be dissolved in an organic solvent.
  • the organic solvent may comprise one or more of aromatic hydrocarbons, aliphatic hydrocarbons, ketones and the like.
  • the organic solvent may comprise one or more of aromatic hydrocarbons.
  • transition metal carbenes may be those corresponding to one of the formulas wherein:
  • M is a transition metal of the 8th transition group of the Periodic Table, exemplary transition metals are ruthenium or osmium; X and X 1 are each independently an anionic ligand; L is a neutral electron donor ligand; and,
  • R, R 1 R 2 , R 3 , R 4 , and R 5 are each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, Ci-C 20 alkoxy, C2 -C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2 -C20 alkoxycarbonyl, C1-C20 alkylthiol, arylthiol, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C1-C10 alkyl, Ci- C alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester,
  • the disclosed method may be conducted at a temperature of greater than 0°C to about 60°C.
  • the method may be conducted in the absence of oxygen.
  • the polymers of conjugated dienes utilized in the disclosed process may be virgin polymers of conjugated dienes or recycled polymers of conjugated diene such as those recovered according to WO2022/144158, incorporated herein by reference for all purposes in its entirety.
  • the polymers conjugated diene formed in the disclosed process may be contacted with polymers prepared from vinylidene aromatic monomers, and optionally monomers polymerizable with the vinylidene aromatic monomers, to form compositions comprising both. This may be achieved by blending the materials utilizing a known process, for example melt blending.
  • the polymers of conjugated dienes formed may be contacted with one or more vinylidene aromatic monomers, and optionally monomers polymerizable with the vinylidene aromatic monomers, during the polymerization of such monomers to form polymer compositions of conjugated dienes and polymers of vinylidene aromatic monomers, and optionally monomers polymerizable with the vinylidene aromatic monomers.
  • the polymers of conjugated dienes formed in the disclosed process which may contain polymers chains of vinylidene aromatic monomers, and optionally monomers polymerizable with the vinylidene aromatic monomers, may be contacted with other polymer systems containing polymers of conjugated dienes and polymers of one or more vinylidene aromatic monomers, and optionally monomers polymerizable with the vinylidene aromatic monomers,
  • the polymers of conjugated dienes formed in the disclosed process may be added to such systems either neat or in organic solvents.
  • the polymers of conjugated dienes formed in the disclosed process may compatibilize the components of systems to which they are added.
  • Such polymer systems may be acrylonitrile butadiene styrene based polymer systems (ABS), styrene acrylonitrile based polymer systems (SAN) or high impact polystyrene based polymer systems (HIPS).
  • ABS acrylonitrile butadiene styrene based polymer systems
  • SAN styrene acrylonitrile based polymer systems
  • HIPS high impact polystyrene based polymer systems
  • the polymers of conjugated dienes formed in the disclosed process may be added to Mass ABS systems to enhance the gloss of such systems.
  • Polymers and polymer chains formed from recited monomers refer to polymers or polymer chains containing monomer units derived from the recited monomer systems. Those skilled in the art understand the monomer units formed.
  • Figure 1 shows a diagram of the starting polymers of conjugated dienes with conjugated diene chains and vinylidene monomer chains and a diagram of where polymers of conjugated diene chains could undergo chain scission.
  • Figure 2 shows a diagram of the produced polymers of conjugated dienes
  • Figures 4 to 6 are curves showing analytical results for a number of samples of soluble polymers of conjugated dienes disclosed herein.
  • Figure 7 is a plot of the viscosity versus time as the process proceeds for the metathesis of the polymer of the conjugated diene in example 2.
  • Hydrocarbyl refers to a group containing one or more carbon atom backbones and hydrogen atoms, which may optionally contain one or more heteroatoms. Where the hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups well known to one skilled in the art. Hydrocarbyl groups may contain cycloaliphatic, aliphatic, aromatic or any combination of such segments. The aliphatic segments can be straight or branched. The aliphatic and cycloaliphatic segments may include one or more double and/or triple bonds.
  • hydrocarbyl groups include alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, alkaryl and aralkyl groups. Cycloaliphatic groups may contain both cyclic portions and noncyclic portions.
  • Hydrocarbylene means a hydrocarbyl group or any of the described subsets having more than one valence, such as alkylene, alkenylene, alkynylene, arylene, cycloalkylene, cycloalkenylene, alkarylene and aralkylene.
  • Valence means a covalent bond between a hydrocarbyl or hydrocarbylene group and another group such as a carbonyl, oxygen, nitrogen or sulfur containing group or atom, or the referenced base compound.
  • percent by weight or parts by weight refer to, or are based on, the weight of the compositions unless otherwise specified.
  • Polymers and polymer chains formed from recited monomers refer to polymers or polymer chains containing monomer units derived from the recited monomer systems. Those skilled in the art understand the monomer units formed.
  • Molecular weight as used herein refers to weight average molecular weight determined by gel permeation chromatography using narrow polystyrene (Polydispersity ⁇ 1.2) tetra hydrofuran solvent performed at ambient temperature. Glass transition temperature as described herein is determined using differential scanning calorimetry, according to test procedure ASTM D3418-15.
  • polymers of conjugated dienes containing polymer chains of conjugated dienes and polymer chains of vinylidene aromatic monomers.
  • Other polymer chains as used in this context refers to other polymer chains of conjugated dienes or polymer chains of vinylidene aromatic monomers, such as polymers of styrene.
  • the polymers of conjugated dienes are soluble in organic solvents.
  • Disclosed is a process for preparing the polymers of conjugated dienes which are soluble in organic solvents.
  • the process comprises contacting polymers of conjugated dienes in any form with one or more metathesis catalysts, for instance a transition metal carbene compound commonly referred to as a Grubbs catalyst, in an organic solvent under conditions to break some of the crosslinks of the conjugated diene to form the conjugated diene polymers having the defined solubility.
  • the product formed may be dissolved in an organic solvent.
  • the product formed may be in the form of polymers dissolved in organic solvents.
  • the product formed may contain polymer chains based on one or more vinylidene aromatic monomers wherein the polymer chains of vinylidene aromatic monomers are disposed between polymer chains of conjugated dienes.
  • a portion of the polymer chains of vinylidene aromatic monomers may be disposed at the end of polymer chains of conjugated dienes
  • the product formed may be dissolved in an organic solvent, dispersed in an organic solvent or may be in neat form, that is not dissolved or dispersed in a solvent.
  • the product disclosed and formed may be blended with one or more other polymers as disclosed herein., either neat or in an organic solvent.
  • compositions comprising polymers of conjugated dienes which have polymer chains which can entangle with other polymer chains as disclosed herein and which are soluble in organic solvents.
  • the polymers of conjugated dienes may have bonded thereto polymer chains prepared from one or more vinylidene aromatic monomers, and optionally one or more monomers copolymerizable with vinylidene aromatic monomers.
  • the polymer chains prepared from one or more vinylidene aromatic monomers may be grafted to the backbone of the polymers of conjugated dienes.
  • the polymers of conjugated dienes can have any morphology which allows them to be soluble in organic solvents.
  • the polymers of conjugated dienes, containing polymer chains of conjugated dienes and polymer chains of vinylidene aromatic monomers may be blended with one or more polymers prepared from one or more vinylidene aromatic monomers.
  • the polymers of conjugated dienes disclosed herein may exhibit a weight average molecular weight sufficient to form entanglements between polymer chains of the conjugated dienes.
  • the polymers of conjugated dienes disclosed herein may exhibit a molecular weight sufficient such that the polymers are soluble in an organic solvent. Polymers which meet these criteria can have polymer chains of one or more vinylidene aromatic monomers bonded thereto.
  • the polymers of conjugated dienes may have a weight average molecular weight of about 20,000 atomic mass units (amu) or greater or about 30,000 amu or greater.
  • the polymers of conjugated dienes may have a weight average molecular weight of about 200,000 atomic mass units (amu) or less, about 150,000 amu or less or about 100,000 amu or less.
  • the molecular weight includes the polymer chains of the one or more vinylidene aromatic monomers.
  • the organic solvents which the polymers of conjugated dienes may be dissolved in may be any organic solvent capable of dissolving the polymers of conjugated dienes, containing polymer chains of conjugated dienes and polymer chains of vinylidene aromatic monomers.
  • exemplary organic solvents may be one or more of aromatic hydrocarbons, aliphatic hydrocarbons, ketones and the like.
  • the organic solvents may be one or more of aromatic hydrocarbons or aliphatic hydrocarbons.
  • the one or more of aromatic hydrocarbons may be ethyl benzene, and the like.
  • compositions disclosed herein may comprise the polymers of conjugated dienes which include the polymer chains of conjugated dienes and polymer chains of vinylidene aromatic monomers dissolved or dispersed in an organic solvent.
  • concentration of the polymers of conjugated dienes containing polymer chains of conjugated dienes and polymer chains of vinylidene aromatic monomers in an organic solvent may be any concentration which forms a solution or stable dispersion.
  • the polymers of conjugated dienes containing polymer chains of conjugated dienes and polymer chains of vinylidene aromatic monomers may be present in the organic solvent up to the amount at which the solution becomes saturated or the dispersion becomes unstable.
  • the polymers of conjugated dienes containing polymer chains of conjugated dienes and polymer chains of vinylidene aromatic monomers may be present in an organic solvent in and amount of about 1 percent by weight of the solution or dispersion or greater, 5 percent by weight or greater or 10 percent by weight or greater.
  • the polymers of conjugated dienes which may include the polymer chains of one or more vinylidene aromatic monomers may be present in an organic solvent in and amount of about 40 percent by weight of the solution or dispersion or less, 30 percent by weight or less or 20 percent by weight or less.
  • the amount of the polymer chains of vinylidene aromatic monomers in the composition comprising polymers of conjugated dienes and the polymer chains of one or more of vinylidene aromatic monomers is that amount which provides the advantages of the compositions as disclosed herein.
  • the amount of the polymer chains of the one or more of vinylidene aromatic monomers in the composition comprising polymers chains of conjugated dienes and the polymer chains of one or more of vinylidene aromatic monomers may be about 2 percent by weight or greater, about 5 percent by weight or greater, or about 10 percent by weight or greater.
  • the amount of the polymer chains of the one or more vinylidene aromatic monomers in the composition comprising polymers of conjugated dienes and the polymer chains of one or more of vinylidene aromatic monomers may be about 50 percent by weight or less, about 30 percent by weight or less, or about 20 percent by weight or less.
  • the polymers of conjugated dienes containing polymer chains of conjugated dienes and polymer chains of vinylidene aromatic monomers utilized to form the disclosed polymers may exhibit any morphology wherein a portion of the conjugated double bonds can be broken.
  • Such starting polymers of conjugated dienes may be in the form of polymers or particles. If in the form of particles, the particle size may be any particle size wherein a portion of the double bonds can be broken in the disclosed process. Particles sizes which allow such composition to dissolve or form stable dispersions in a non-polar solvent may be advantageous.
  • the particle size of such particles may be about 0.1 micrometers or greater, about 1 micrometers or greater or about 5 micrometers or greater.
  • the particle size of such particles may be about 15.0 micrometers or less, about 10.0 micrometers or less or about 8 micrometers or less.
  • the average particle size of a rubber particle will, refer to the volume average diameter. In most cases, the volume average diameter of a group of particles is the same as the weight average diameter.
  • the average particle diameter measurement generally includes the polymer grafted to the rubber particles and occlusions of polymer within the particles.
  • the rubber particle sizes disclosed and claimed herein are determined on a Coulter Multisizer II or II e with the ACCUCOMPTM Software Version 2.01 by the following method: about 3 granules of polymer samples (30-70 mg) are dissolved in 5 milliliters (ml) of Dimethyl Formamide (DMF), using an ultrasonic bath for agitation for approximately 15 to 20 minutes. 10 ml of an electrolyte solution (1 percent of NH4SCN in DMF) is mixed with 0.2 ml of the sample solution. The coulter measuring stand is used with 20 micrometer Coulter tube and a 1.16 micrometer calibration material. The coincidence level indicator of the apparatus should read between 5 and 10 percent.
  • DMF Dimethyl Formamide
  • the volumetric mean particle size is reported. The particle sizes may be determined according to light scattering techniques well known to those skilled in the art.
  • Conjugated dienes useful in the disclosed compositions are any containing the described group wherein the conjugated diene group is capable of homopolymerizing and polymerizing with one or more vinylidene aromatic monomers.
  • Exemplary conjugated dienes include butadiene, isoprene, and the like. Many conjugated dienes and polymers thereof are commercially available.
  • Vinylidene aromatic monomers comprise vinylidene, alkenyl groups, bonded directly to aromatic structures.
  • the vinylidene aromatic monomers may contain one or more aromatic rings, may contain one or two aromatic rings, or may contain one aromatic ring.
  • the aromatic rings can be unsubstituted or substituted with a substituent that does not interfere with polymerization of the vinylidene aromatic monomers, or the fabrication of the polymers formed into desired structures.
  • the substituents may be halogens or alkyl groups, such as bromine, chlorine or Ci to C4 alkyl groups; or a methyl group.
  • Alkenyl groups comprise straight or branched carbon chains having one or more double bonds, or one double bond.
  • the alkenyl groups useful for the vinylidene aromatic monomers may include those that when bonded to an aromatic ring are capable of polymerization to form homopolymers or copolymers.
  • the vinylidene groups may have 2 to 10 carbon atoms, 2 to 4 carbon atoms or 2 carbon atoms.
  • Exemplary vinylidene aromatic monomers include styrene, alpha methyl styrene, N-phenyl-maleimide and chlorinated styrenes; or alpha-methyl styrene and styrene.
  • the vinylidene aromatic monomers may be mono-vinylidene aromatic monomers, which contain one unsaturated group. Vinylidene aromatic monomers include but are not limited to those described in U.S.
  • the monomer may correspond to the formula: wherein R 11 is separately in each occurrence hydrogen or methyl; an Ar is separately in each occurrence an aromatic group.
  • Ar may contain one or more aromatic rings, may contain one or two aromatic rings, or may contain one aromatic ring, n is separately in each occurrence 1 to 3, 1 to 2, or 1.
  • the aromatic rings can be unsubstituted or substituted with a substituent that does not interfere with polymerization of the vinylidene aromatic monomers, or the fabrication of the polymers formed into desired structures.
  • the substituents may be halogens or alkyl groups, such as bromine, chlorine or Ci to C4 alkyl groups; or a methyl group.
  • the vinylidene aromatic monomers may be present in the copolymers in a sufficient amount such that the polymer exhibits the advantageous properties associated with polymers of vinylidene aromatic monomers, for instance polystyrene.
  • the advantageous properties of polymers of vinylidene substituted monomers include processability, stiffness, and thermal stability.
  • Polymers or polymer chains prepared from vinylidene aromatic monomers may further comprise one or more ethylenically unsaturated monomers which copolymerize with vinylidene aromatic monomers.
  • exemplary ethylenically unsaturated monomers which copolymerize with vinylidene aromatic monomers include conjugated 1,3 dienes (for example butadiene, isoprene, etc.); alpha- or beta-unsaturated monobasic acids and derivatives thereof (for example, acrylic acid, methacrylic acid, etc.); vinyl halides such as vinyl chloride, vinyl bromide, etc.; vinylidene chloride, vinylidene bromide, etc.; vinyl esters such as vinyl acetate, vinyl propionate, etc.; ethylenically unsaturated dicarboxylic acids and anhydrides and derivatives thereof, such as maleic acid, fumaric acid, maleic anhydride, dialkyl maleates or fumarates, such as dimethyl maleate, diethyl
  • Exemplary ethylenically unsaturated monomers which copolymerize with vinylidene substituted aromatic monomers include conjugated 1 ,3 dienes; alpha- or beta-unsaturated monobasic acids and derivatives thereof; ethylenically unsaturated dicarboxylic acids and anhydrides and derivatives thereof; acrylates; and unsaturated nitriles.
  • Exemplary ethylenically unsaturated monomers polymerizable with the vinylidene aromatic monomers may be one or more of conjugated dienes, unsaturated nitriles, (meth)acrylics, maleic anhydrides and maleic imides.
  • Exemplary ethylenically unsaturated monomers which copolymerize with vinylidene substituted aromatic monomers include conjugated 1 ,3 dienes; and unsaturated nitriles, or unsaturated nitriles.
  • Polymers or polymer chains prepared from vinylidene substituted aromatic monomers may contain vinylidene aromatic monomers in an amount of about 10 percent by weight of the polymers or polymer chains or greater, about 15 percent by weight or greater, about 20 percent by weight or greater, about 30 weight percent of greater, 40 weight percent or greater or about 50 weight percent or greater.
  • the polymers or polymer chains disclosed herein may contain vinylidene aromatic monomers in an amount of about 100 percent by weight of the polymers or polymer chains or less, about 90 percent by weight or less, about 85 percent by weight or less, or about 80 percent by weight or less.
  • the amount of such ethylenically unsaturated comonomers may be about 50 weight percent or less, about 40 weight percent or less, about 30 weight percent or less, about 20 weight percent or less or about 10 weight percent or less based on the weight of the polymers or polymer chains.
  • Such co-monomers may be present in an amount of about 1 percent by weight or greater, 10 weight percent or greater or about 20 weight percent or greater based on the weight of the polymers or polymer chains.
  • the copolymers or copolymer chains of vinylidene aromatic monomers disclosed herein may comprise one or more (meth)acrylates.
  • (Meth) acrylate as used herein refers to compounds having a vinyl group bonded to the carbonyl moiety of an alkyl ester wherein the carbon of the vinyl group bonded to the carbonyl group further has a hydrogen or a methyl group bonded thereto.
  • the term (meth) as used in this context refers to compounds having either of a hydrogen or methyl group on the carbon of the vinyl group bonded to the carbonyl group.
  • Acrylate refers to compounds having a vinyl group bonded to the carbonyl moiety of an alkyl ester wherein the carbon of the vinyl group bonded to the carbonyl group further has a hydrogen bonded thereto.
  • the use of alkyl acrylate means the compound referred to does not have a methyl group on the carbon adjacent to the carbonyl group, that is R a is hydrogen.
  • the alkyl groups of the (meth)acrylates may have one or greater, two or greater, three or greater or four carbons in the alkyl group.
  • the alkyl groups of the (meth)acrylates may have 30 or less, 10 or less, 6 or less or 4 or less carbons in the alkyl group.
  • (Meth)acrylates useful include those that correspond to the formula: wherein R a is separately in each occurrence H or — CH3; and
  • R b is separately in each occurrence an alkyl group that allows the (meth)acrylate form a homopolymer having a glass transition temperature of about 100 °C or greater.
  • R b may be a C 1 to C-3o alkyl group or C 1-10 alkyl group.
  • R b may be a C 2 to C-30 alkyl group, C 2-10 alkyl group, C 2-6 alkyl group or C 3-4 alkyl group.
  • the (meth)acrylates may contain a mixture of (meth)acrylates such that for one (meth)acrylate R b is Ci and for one or more the other R b may be a C 2-30 alkyl group, C 2-10 alkyl group, C 2-6 alkyl group or C 3-4 alkyl group.
  • the one or more (meth)acrylates may include methyl (meth)acrylate and one or more of ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)(acrylate) and hexyl (meth) acrylate.
  • the one or more (meth)acrylates include lower alkyl (meth) acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)(acrylate) and hexyl (meth) acrylate.
  • the (meth)acrylates may be one or more straight chain Cs to C16 alkyl acrylates based on the weight of the copolymers.
  • the one or more (meth)acrylates may include include methyl (meth)acrylate and one or more of ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)(acrylate) and hexyl (meth) acrylate.
  • the one or more (meth)acrylates may include methyl (meth)acrylate and butyl (meth)acrylate.
  • the copolymers or copolymer chains of vinylidene aromatic monomers disclosed herein may contain one or more unsaturated nitriles in an amount of about 0 percent by weight of the copolymers or copolymer chains or greater, about 1 percent by weight or greater, about 2 percent by weight or greater, about 5 percent by weight or greater or about 10 percent by weight or greater.
  • the copolymers and copolymer chains disclosed herein may contain one or more unsaturated nitriles in an amount of about 40 percent by weight of the polymer chains or copolymers or less, about 35 percent by weight or less, about 30 percent by weight or less, about 25 percent by weight or less or about 20 percent by weight or less.
  • the method comprises comprising contacting compositions comprising polymers of conjugated dienes with a metathesis catalyst, such as a transition metal carbene, in an organic solvent under conditions such that a portion of the double bonds in the polymers conjugated dienes are broken wherein polymers of conjugated dienes prepared wherein the conjugated diene polymers are soluble in an organic solvent wherein soluble means at least 1 percent by weight, 5 percent by weight or 10 percent by weight of the polymers of conjugated dienes dissolve in an organic solvent at about 25° C.
  • a metathesis catalyst such as a transition metal carbene
  • Transition metal carbenes are commonly known as Grubbs catalysts.
  • Exemplary transition metal carbenes include imidazolidine based metal carbenes, which are among what are known as Grubbs 2 carbenes.
  • useful transition metal carbenes are imidazolidine based metal carbenes which include those corresponding to the formula: wherein: M is a transition metal, exemplary transition metals are ruthenium or osmium; the transition metal may be ruthenium; X and X’ are each independently an anionic ligand; L is a neutral electron donor ligand; and, R, R 1 R 2 , R 3 , R 4 , and R 5 are each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, Ci-C 20 alkoxy, C2 -C20 alkenyloxy, C2-C20 alkynyloxy,
  • L is a neutral two-electron donor; which may be one or more of amines, imines, phosphines, phosphites, stibines, arsines, CO, carbonyl compounds, nitrites, alcohols, thiols, ethers and thioethers.
  • L may each independently selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, and thioether.
  • L may be a phosphine of the formula PR 6 R 7 R 8 , where R 6 , R 7 , and R 8 are each independently aryl, C1-C10 alkyl, or cycloalkyl.
  • L may be-P(cyclohexyl)3, - P(cyclopentyl)3, - P(isopropyl)3, and -P(phenyl)3.
  • R 6 , R 7 , and R 8 are independently in each occurrence methyl, ethyl, cyclopentyl, cyclohexyl or phenyl.
  • X and X’ may be the same or different and are each an anionic ligand from the group of halides, pseudohalides, hydroxides, alkoxides, carboxylates and sulphonates.
  • X and X 1 may each independently be hydrogen, halide, or a substituent selected from the group consisting of C1-C20 alkyl, aryl, C1- C20 alkoxide, aryloxide, C3 -C20 alkyldiketonate, aryldiketonate, C1-C20 carboxylate, arylsulfonate, C1-C20 alkylsulfonate, C1-C20 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl, and C1- C20 alkylsulfinyl, the substituent optionally may be substituted with one or more moieties selected from the group consisting of C1-10 alkyl, C1-C
  • X and X’ may be the same and are each halide.
  • X X 1 may each be independently selected from the group consisting of halide, CF3CO2, CH3CO2, CFH2CO2, (CH 3 ) 3 CO, (CF 3 )2(CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate.
  • X and X 1 may each be chloride.
  • R may be hydrogen.
  • R 1 may be phenyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of C1-C5 alkyl, C1-C5 alkoxy, phenyl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.
  • R 6 and R 7 may together form a cycloalkyl or an aryl; a cyclopentyl or a cyclohexyl moiety.
  • R 6 and R 7 may the same and are hydrogen or phenyl.
  • R 8 and R 9 are each independently a substituted or unsubstituted aryl or are the same and are phenyl.
  • R 8 and R 12 are each independently of the formula; wherein R 12 is independently in each occurrence hydrogen, C i- lkyl, C 1-10 alkoxy, aryl, or a functional group selected from hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.
  • R 12 may independently be hydrogen, methyl or isopropyl.
  • transition metal carbenes are metal carbenes which include those wherein X, X’, L and M are as described hereinbefore; and R 9 , is independently in each occurrence are each hydrogen, with the proviso that at least one radical R 9 is different from hydrogen, or are each cyclic, straight-chain or branched alkyl radicals having 1 to 50 carbon atoms or aryl radicals having 6 to 30 carbon atoms, at least one hydrogen atom in the radicals mentioned optionally being replaced by an alkyl group or a functional group, and at least one R 9 is halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ce-C -aryloxy, cyano, Ci-C4-alkoxy- carbonyl, Ce-Cw-aryloxycarbonyl or aliphatic or aromatic Ci-C -acyloxy; and/or two adjacent R 9 s may be part of a cyclic system which consists of a carbon framework having 3 to 20 carbon
  • R 10 is hydrogen or a cyclic, straight-chain or branched alkyl radical having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms, at least one hydrogen atom in the radicals mentioned optionally being replaced by an alkyl group or a functional group, and the R 9 ’s opposite the five membered ring may not be part of a cyclic, aromatic system having 4 carbon atoms, not including the carbon atoms, when R 10 is at the same time methyl.
  • R 9 may independently be in each occurrence hydrogen, with the proviso that at least one R 9 is different to hydrogen, or are each cyclic, straight-chain or branched alkyl radicals having 1 to 20 carbon atoms or aryl radicals having 6 to 20 carbon atoms, at least one hydrogen atom in the alkyl and aryl radicals mentioned optionally being replaced by a functional group, and at least one of R 9 is halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ce-Cw-aryloxy, cyano, C1-C4- alkoxycarbonyl, Ce-Cw-aryloxycarbonyl or aliphatic or aromatic Ci-Cw-acyloxy.
  • All R 9 ’s may be each hydrogen except the R 9 adjacent to the carbon bonded to the oxygen is a cyclic, straight-chain or branched alkyl radical having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms, at least one hydrogen atom in the radicals mentioned optionally being replaced by an alkyl group or a functional group, or is halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ce-Cw-aryloxy, cyano, Ci-C4-alkoxycarbonyl, Ce-Cw-aryloxycarbonyl or aliphatic or aromatic Ci-Cw-acyloxy, or all R 9 ’s may be each hydrogen except the R 9 adjacent to the carbon bonded to indirectly to M which is a cyclic, straight-chain or branched alkyl radical having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms, at least one hydrogen atom in the radicals mentioned optionally being replaced by an al
  • All R 9 ’s may be each hydrogen except the R 9 bonded to the second carbon from the carbon adjacent to the carbon bonded to indirectly to M which is a cyclic, straight-chain or branched alkyl radical having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms, at least one hydrogen atom in the radicals mentioned optionally being replaced by an alkyl group or a functional group, or is halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ce-Cw-aryloxy, cyano, Ci-C4-alkoxycarbonyl, Ce-Cw- aryloxy-carbonyl or aliphatic or aromatic Ci-Cw-acyloxy.
  • All R 9 ’s may be each hydrogen except the R 9 bonded to the second carbon from the carbon bonded to the oxygen which is a cyclic, straight-chain or branched alkyl radical having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms, at least one hydrogen atom in the radicals mentioned optionally being replaced by an alkyl group or a functional group, or is halogen, C1-C4- haloalkyl, Ci-C4-alkoxy, Ce-Cw-aryloxy, cyano, Ci-C4-alkoxycarbonyl, Ce-Cw-aryloxy-carbonyl or aliphatic or aromatic Ci-Cw-acyloxy.
  • the R 9 ’s on the carbon atoms adjacent to the carbons of the five membered ring are each hydrogen or an aryl radical having 6 to 20 carbon atoms, at least one hydrogen atom in the aryl radical optionally being replaced by an alkyl group or a functional group, or are each
  • the two R 9 ’s on carbons closest to the carbon of the five membered ring not bonded to the oxygen atom are the same or different and are each hydrogen or an aryl radical having 6 to 20 carbon atoms, at least one hydrogen atom in the aryl radical optionally being replaced by an alkyl group or a functional group, or are each halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ce-C - aryloxy, cyano, Ci-C4-alkoxycarbonyl, Ce-Cw-aryloxy-carbonyl or aliphatic or aromatic C1-C10- acyloxy and the two R 9 ’s on carbons closest to the carbon of the five membered ring bonded to the oxygen atom are part of a cyclic aromatic system having 4 to 14 carbon atoms, at least one hydrogen atom optionally being replaced by an alkyl group or a functional group.
  • transition metal carbenes include the following:
  • PCya is -P(cyclohexyl)3
  • Imidazolidine based metal carbenes are commercially available and may be synthesized by the methods disclosed in W02000/071554, incorporated herein by reference for all purposes in its entirety.
  • the starting polymers of conjugated dienes may be any conjugated diene polymers as described herein.
  • the polymers of conjugated dienes may contain polymer chains of vinylidene aromatic monomers, optionally containing monomers copolymerizable with the vinylidene aromatic monomers.
  • a portion of the polymers of the starting conjugated dienes may have grafted to the backbone of the polymer chains of the conjugated dienes, polymer chains of vinylidene aromatic monomers, optionally containing monomers copolymerizable with the vinylidene aromatic monomers.
  • the monomers copolymerizable with the vinylidene aromatic monomers may be any one or more of the one or more monomers copolymerizable with the vinylidene aromatic monomers as described herein.
  • the starting polymers of conjugated dienes may be in the form of polymers or the polymers may be in the form of particles.
  • the starting polymers or particles may be virgin polymers or particles, recycled polymers or particles, or a mixture thereof.
  • the polymers of conjugated dienes utilized in the disclosed process may be virgin conjugated diene polymers or recycled conjugated diene polymers such as those recovered according to WO2022/144158, incorporated herein by reference for all purposes in its entirety.
  • the polymers prepared by the disclosed method may comprise any of the disclosed polymers of conjugated dienes optionally containing polymer chains of vinylidene aromatic monomers, optionally containing monomers copolymerizable with the vinylidene aromatic monomers, which may be disposed between two or more conjugated dienes polymer chains.
  • the polymers or particles prepared by the disclosed method may comprise any of the disclosed polymers of conjugated dienes, optionally containing polymer chains of vinylidene aromatic monomers, which polymer chains may optionally contain monomers copolymerizable with the vinylidene aromatic monomers, which may be disposed at the end of conjugated diene polymer chains.
  • the polymers prepared by the method disclosed meet the criteria of being soluble in an organic solvent wherein soluble means at least 1 percent by weight, 5 percent by weight or 10 percent by weight of the polymers of conjugated dienes dissolve in the organic solvent at about 25° C.
  • the polymers prepared may have only a portion of the original conjugated double bonds broken and thus have a significant amount of conjugated double bonds in the final product.
  • the disclosed method may be conducted at a temperature of greater than 0°C, about 10°C or greater or about 20°C or greater.
  • the disclosed method may be conducted at a temperature of about 60°C or less, about 50°C or less or about 40°C or less
  • the process may be conducted at ambient temperatures within the recited ranges.
  • the metathesis catalyst such as a transition metal carbene, may be present in the reaction mixture in any amount that catalyzes the breaking of unsaturated bonds of the conjugated diene polymer.
  • the amount of transition metal carbene present in the reaction mixture may be about 10 ppm (parts per million) or greater based on the amount of conjugated diene polymer present, about 50 ppm or greater or about 100 ppm or greater.
  • the amount of transition metal carbene present in the reaction mixture may be about 1000 ppm or less based on the amount of conjugated diene polymer present, about 500 ppm or less or about 300 ppm or less.
  • the method may be conducted for a sufficient period of time to prepare polymers of conjugated dienes as described herein meeting the criteria of being soluble in an organic solvent wherein soluble means at least 1 percent by weight, 5 percent by weight or 10 percent by weight of the polymers of conjugated dienes dissolve in the non-polar organic solvent at about 25° C.
  • the method may be conducted for about 1 minute or greater, 5 minutes or greater or about 10 minutes or greater.
  • the method may be conducted for about 120 minutes or less, 60 minutes or less or about 30 minutes or less.
  • the method may be conducted in the absence of oxygen.
  • the formed polymers may be remain dissolved in the organic solvent or may be separated therefrom by common separation techniques including filtration, centrifugation and the like.
  • the polymers of conjugated diene formed may be blended with one or more other polymers such as polymers of one or more vinylidene aromatic monomers, and optionally monomers polymerizable with the vinylidene aromatic monomers as disclosed herein, polyamides, polymers of conjugated dienes, and the like.
  • the blending may utilize the polymers of conjugated diene as dissolved in organic solvents or in neat form.
  • compositions comprising the conjugated diene polymers disclosed herein and one or more other polymers.
  • the compositions may be a blend of the polymers.
  • the blends may comprise two or more polymers having significantly different polarities, one being polar and the other being apolar.
  • the blends may comprise one or more other polymers such as polymers of vinylidene aromatic monomers, and optionally monomers polymerizable with the vinylidene aromatic monomers, polyamides, conjugated dienes, and the like.
  • the blending may utilize the conjugated diene polymers as dissolved in organic solvents or in neat form.
  • [41] Disclosed is a method of compatabilizing different polymers utilizing the polymers of conjugated dienes prepared as disclosed herein. This is achieved by blending the polymers of conjugated dienes with two or more polymers, such as particles of polymers of conjugated dienes and a polymer prepared from one or more vinylidene aromatic monomers, and optionally monomers polymerizable with the vinylidene aromatic monomers as disclosed herein.
  • the polymers of conjugated dienes as disclosed herein may be introduced into the process of preparing impact modified polymers of vinylidene aromatic monomers, such as by mass polymerization. Such modified polymers of vinylidene aromatic monomers may exhibit improved gloss.
  • Figure 1 shows a diagram of the starting polymers of conjugated dienes 1 and a diagram of the starting polymers of conjugated dienes and where chain scission can take place 2. Shown are conjugated diene chains 3, vinylidene aromatic polymer chains 4 and where the crosslinks are broken 5.
  • Figure 2 shows soluble fragments of chains polymers of conjugated dienes and fragments of polymers of conjugated diene chains 3 bonded to fragments of polymer chains of vinylidene aromatic monomers 4.
  • a composition comprising polymers of conjugated dienes, containing polymer chains of conjugated dienes and polymer chains of vinylidene aromatic monomers, wherein the polymers are soluble in an organic solvent wherein soluble means at least 1 percent by weight, 5 percent by weight or 10 percent by weight of the polymers of conjugated diene dissolved in the organic solvent at about 25 ° C.
  • a composition according to Embodiment 1 comprising polymers of conjugated dienes wherein the polymers are soluble in an organic solvent wherein soluble means at least 1 percent by weight, 5 percent by weight or 10 percent by weight of the polymers of conjugated dienes dissolve in the organic solvent at about 25 ° C.
  • a composition according to any one of the preceding Embodiments which comprise polymers chains of one or more vinylidene aromatic monomers and one or more monomers polymerizable with the one or more vinylidene aromatic monomers.
  • [50] 7. A composition according to any one of the preceding Embodiments which comprise polymers chains of one or more vinylidene aromatic monomers and one or more unsaturated nitriles.
  • composition according to any one of the preceding Embodiments which comprise polymers chains comprising styrene and acrylonitrile.
  • a composition according to any one of the preceding Embodiments comprising the polymers of conjugated dienes have grafted polymer chains prepared from one or more vinylidene aromatic monomers.
  • [59] 16 A composition according to any one of the preceding Embodiments comprising the polymers of conjugated dienes blended with polymers comprising vinylidene aromatic monomers.
  • a method comprising contacting polymers of conjugated dienes containing polymer chains of conjugated dienes and polymer chains of vinylidene aromatic monomers with a metathesis catalyst in an organic solvent under conditions such that a portion of the double bonds in the polymers of conjugated dienes are broken wherein polymers of conjugated dienes containing polymer chains of conjugated dienes and polymer chains of vinylidene aromatic monomers are prepared wherein the polymers of conjugated dienes are soluble in an organic solvent wherein soluble means at least 1 percent by weight, 5 percent by weight or 10 percent by weight of the polymers of conjugated dienes dissolve in the organic solvent at about 25° C.
  • M is a transition metal of the 8th transition group of the Periodic Table
  • X and X 1 are each independently an anionic ligand
  • L is a neutral electron donor ligand
  • R and R 1 are each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, C1-C 20 alkoxy, C2 -C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2 -C20 alkoxycarbonyl, C1-C20 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C1-C10 alkyl, C1- C10 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide
  • M is a transition metal of the 8th transition group of the Periodic Table
  • X and X 1 are each independently an anionic ligand
  • L is a neutral electron donor ligand
  • R, R 1 R 2 , R 3 , R 4 and R 5 are each independently hydrogen or a substituent selected from the group consisting of C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, aryl, C1-C20 carboxylate, C1-C 20 alkoxy, C2 -C20 alkenyloxy, C2-C20 alkynyloxy, aryloxy, C2 -C20 alkoxycarbonyl, C1-C20 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl and C1-C20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C1-C10 alkyl, C1- C10 alkoxy, aryl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, este
  • M is ruthenium or osmium
  • L and L are each independently selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, and thioether; and,
  • X and X 1 are each independently hydrogen, halide, or a substituent selected from the group consisting of C1-C20 alkyl, aryl, C1-C20 alkoxide, aryloxide, C3 -C20 alkyldiketonate, aryldiketonate, C1-C20 carboxylate, arylsulfonate, C1-C20 alkylsulfonate, C1-C20 alkylthiol, aryl thiol, C1-C20 alkylsulfonyl, and C1-C20 alkylsulfinyl, the substituent optionally substituted with one or more moieties selected from the group consisting of C1-10 alkyl, C1-C10 alkoxy, aryl and halide.
  • X and X 1 are each independently selected from the group consisting of halide, CF3CO2, CH3CO2, CFH2CO2, (CH 3 ) 3 CO, (CF 3 )2(CH 3 )CO, (CF 3 )(CH 3 ) 2 CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate;
  • L is a phosphine of the formula PR 6 R 7 R 8 , where R 6 , R 7 , and R 8 are each independently aryl, C1-C10 alkyl, or cycloalkyl;
  • R is hydrogen
  • R 1 is phenyl or vinyl, optionally substituted with one or more moieties selected from the group consisting of Ci-Csalkyl, C1-C5 alkoxy, phenyl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, carbamate, and halogen.
  • moieties selected from the group consisting of Ci-Csalkyl, C1-C5 alkoxy, phenyl, and a functional group selected from the group consisting of hydroxyl, thiol, thioether, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide
  • X and X’ are the same or different and are each an anionic ligand
  • R 9 is independently in each occurrence are each hydrogen, with the proviso that at least one radical R 9 is different from hydrogen, or are each cyclic, straight-chain or branched alkyl radicals having 1 to 50 carbon atoms or aryl radicals having 6 to 30 carbon atoms, at least one hydrogen atom in the radicals mentioned optionally being replaced by an alkyl group or a functional group, and at least one R 9 is halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ce-C - aryloxy, cyano, Ci-C4-alkoxy-carbonyl, Ce-Cw-aryloxycarbonyl or aliphatic or aromatic C1-C10- acyloxy; and/or two adjacent R 9 ’s may be part of a cyclic system which consists of a carbon framework having 3 to 20 carbon atoms, not including the carbon atoms in formula (I), at least one hydrogen atom optionally being replaced by an alkyl group or a functional
  • R 10 is hydrogen or a cyclic, straight-chain or branched alkyl radical having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms, at least one hydrogen atom in the radicals mentioned optionally being replaced by an alkyl group or a functional group, and the R 9 ’s opposite the five membered ring may not be part of a cyclic, aromatic system having 4 carbon atoms, not including the carbon atoms, when R 10 is at the same time methyl, and,
  • L is a neutral two-electron donor; from the group of amines, imines, phosphines, phosphites, stibines, arsines, CO, carbonyl compounds, nitrites, alcohols, thiols, ethers and thioethers.
  • M is ruthenium or osmium
  • X and X’ are the same or different and are each an anionic ligand from the group of halides, pseudohalides, hydroxides, alkoxides, carboxylates and sulphonates;
  • R 9 is independently in each occurrence hydrogen, with the proviso that at least one R 9 is different to hydrogen, or are each cyclic, straight-chain or branched alkyl radicals having 1 to 20 carbon atoms or aryl radicals having 6 to 20 carbon atoms, at least one hydrogen atom in the alkyl and aryl radicals mentioned optionally being replaced by a functional group, and at least one of R 9 is halogen, Ci-C4-haloalkyl, Ci-C4-alkoxy, Ce-Cw-aryloxy, cyano, C1-C4- alkoxycarbonyl, Ce-Cw-aryloxycarbonyl or aliphatic or aromatic Ci-Cw-acyloxy, or all R 9 ’s are each hydrogen except the R 9 adjacent to the carbon bonded to the oxygen is a cyclic, straight-chain or branched alkyl radical having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms, at least one hydrogen atom in the radical
  • R 10 is a straight-chain or branched alkyl radical having 1 to 20 carbon atoms, and the R 9 ’s not bonded to carbon atoms bonded to carbon atoms on the five membered ring may not be part of a cyclic, aromatic system having 4 carbon atoms, when R 5 is at the same time methyl.
  • M is ruthenium
  • X and X’ are the same and are each halide
  • R 9 are each hydrogen except the R 9 bonded to the carbon bonded to the oxygen atom is a phenyl or naphthyl radical, at least one hydrogen atom optionally being replaced by an alkyl group or a functional group, or is a radical from the group of F, Cl, Br, trifluoromethyl, methoxy, ethoxy, isopropoxy, tert-butoxy, phenoxy, cyano, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, acetoxy, propionyloxy and pivaloyloxy, or, all R 9 ’s are each hydrogen except the R 9 bonded to the second carbon from the carbon on the five membered ring bonded to the oxygen is a radical from the group of F, Cl, Br, trifluoromethyl, methoxy, ethoxy, isopropoxy, tert-butoxy, phenoxy, cyano, methoxy carbonyl, ethoxycarbonyl, e
  • R 10 is a branched alkyl radical from the group of isopropyl, isobutyl, sec-butyl, tert-butyl, branched pentyl, branched hexyl, and,
  • L is a phosphine of the formula PR 6 R 7 R 8 , where R 6 , R 7 , and R 8 are each independently aryl, C1-C10 alkyl, or cycloalkyl.
  • [70] 27 A method according to any one of Embodiments 17 to 26 wherein, the method is conducted at a temperature of greater than 0°C to about 60°C, or about 20°C to about 50°C.
  • [73] 30 A method according to any one of Embodiments 17 to 29 wherein the conjugated dienes polymers formed comprise the polymer chains of vinylidene aromatic monomers disposed between polymer chains of conjugated dienes.
  • [74] 31 A method according to any one of Embodiments 17 to 30 wherein, the starting polymers of conjugated dienes are in the form of particles having grafted thereto polymer chains of one or more vinylidene aromatic monomers.
  • [75] 32 A method according to Embodiment 31 wherein the particles of the polymers of conjugated dienes are virgin particles of the polymers of conjugated dienes having grafted thereto polymer chains of one or more vinylidene aromatic monomers.
  • [76] 33 A method according to Embodiments 32 wherein, the particles of the polymers of conjugated dienes are recycled particles of the polymers of conjugated dienes.
  • [77] 34 A method according to any one of Embodiments 17 to 33 wherein, a portion of the polymers of conjugated dienes have grafted to the backbone of the polymer chains of the polymers of conjugated dienes polymer chains of one or more vinylidene aromatic monomers.
  • [78] 35 A method according to any one of Embodiments 17 to 34, wherein the polymer chains of one or more vinylidene aromatic monomers comprise one or more styrene based monomers.
  • [79] 36 A method according to any one of Embodiments 17 to 34, wherein the polymer chains of one or more vinylidene aromatic monomers comprise one or more styrene based monomers and one or more monomers polymerizable with the one or more styrene based monomers.
  • [80] 37 A method according to Embodiment 36, wherein the polymer chains comprising one or more vinylidene aromatic monomers comprise one or more styrene based monomers and acrylonitrile.
  • [81] 38 A method according to any one of Embodiments 17 to 37 wherein, the prepared conjugated diene polymers have the polymer chains of one or more vinylidene aromatic monomers grafted to their backbone.
  • [84] 41 A method according to Embodiment 38 or 39, wherein the conjugated diene polymers prepared contain polymer chains of one or more vinylidene aromatic monomers which comprise one or more styrene based monomers and acrylonitrile.
  • the organic solvent comprises one or more of aromatic hydrocarbons, aliphatic hydrocarbons and ketones.
  • [90] 47 A method for compatibilizing i) a polymer prepared from one or more vinylidene aromatic monomers and ii) particles comprising one or more polymers of conjugated dienes by contacting i) and ii) with a composition according to any one of Embodiments 1 to 16.
  • Polybutadiene 1 polybutadiene rubber which is not crosslinked or grafted.
  • Polybutadiene 2 is a grafted rubber concentrate consisting of styrene acrylonitrile and grafted and crosslinked rubber wherein the graft rubber concentrate comprises 50 weight percent polybutadiene.
  • a reaction mixture is formed from ethyl benzene, styrene and acrylonitrile in the amounts recited in Table 1.
  • the mixture is dissolved in tetrahydrofuran at 0.25 weight percent, 35 mg solids in 10 milliliters.
  • the C949 Grubbs catalyst, Catalyst 1 is added to the mixture at the amounts listed in Table 1.
  • Polybutadiene 1 is mixed into tetra hydrofuran at a 5 percent by weight amount, 500 mg per 10 milliliters.
  • the polybutadiene mixture is feed to the first mixture and the mixture formed is heated for 24 hours at 50 °C.
  • a comparison mixture is formed and reacted without the catalyst. Samples of the product mixtures are analyzed using gel permeation chromatography.
  • Figure 3 is the DAD (Diode Array detector measuring at a wavelength of 245 nm) signal for each of the samples prepared without catalyst.
  • Figure 4 is the RID (refractive index detector) signal which is the signal from the polybutadiene for each of the samples without catalyst.
  • Figure 5 is DAD signal of the three samples where catalyst is used.
  • Figure 6 is the RID signal of the three samples where catalyst is used. The data demonstrates that without the catalyst there is no rubber decomposition.
  • 6 is the curve for samples without acrylonitrile
  • 7 is the curve for samples with 10 percent acrylonitrile
  • 8 is the curve with 20 percent acrylonitrile.
  • acrylonitrile inhibits decomposition at 10 percent as there is little reaction and at 20 percent there is no reaction.
  • acrylonitrile feed using high impact polystyrene, double bonds are broken and styrene endcaps the chains where the double bonds are broken.
  • FIG. 7 is a plot of the viscosity versus time as the process proceeds for the metathesis of the polymer of the conjugated diene in example 2. The figure shows that viscosity increases initially as the graft rubber concentrate becomes soluble and then drops as the Mw of the soluble graft rubber concentrate is reduced.

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Abstract

L'invention divulgue des compositions contenant des polymères de diènes conjugués possédantant des chaînes polymères de diènes conjugués et des chaînes de monomères aromatiques de vinylidène qui sont solubles dans des solvants organiques. L'invention divulgue également des procédés de préparation des polymères divulgués. L'invention divulgue en outre des compositions contenant de tels polymères.
PCT/EP2025/056321 2024-03-11 2025-03-07 Polymeres de diènes conjugués solubles dans des solvants organiques Pending WO2025190814A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4572819A (en) 1983-08-24 1986-02-25 The Dow Chemical Company Apparatus for anionic polymerization wherein the molecular weight of the polymer is closely controlled
US4585825A (en) 1983-09-30 1986-04-29 The Dow Chemical Company Monovinylidene aromatic polymer resins having added amounts of high molecular weight polymer
US4666987A (en) 1985-02-22 1987-05-19 The Dow Chemical Company In-mold polymerization of vinyl aromatic compound
US5446102A (en) * 1994-08-10 1995-08-29 Bridgeston, Corporation Olefin metathesis catalysts for degelling polymerization reactors
WO2000071554A2 (fr) 1999-05-24 2000-11-30 California Institute Of Technology Catalyseurs de metathese de carbene metallique a base d'imidazolidine
EP1740632A1 (fr) * 2004-04-21 2007-01-10 Dow Global Technologies Inc. Composition polymere aromatique amelioree de monovinylidene modifiee au caoutchouc par polymerisation en masse
EP4019576A1 (fr) * 2020-12-28 2022-06-29 Trinseo Europe GmbH Procédé de recyclage de polymères thermoplastiques renforcés par des élastomères

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4572819A (en) 1983-08-24 1986-02-25 The Dow Chemical Company Apparatus for anionic polymerization wherein the molecular weight of the polymer is closely controlled
US4585825A (en) 1983-09-30 1986-04-29 The Dow Chemical Company Monovinylidene aromatic polymer resins having added amounts of high molecular weight polymer
US4666987A (en) 1985-02-22 1987-05-19 The Dow Chemical Company In-mold polymerization of vinyl aromatic compound
US5446102A (en) * 1994-08-10 1995-08-29 Bridgeston, Corporation Olefin metathesis catalysts for degelling polymerization reactors
WO2000071554A2 (fr) 1999-05-24 2000-11-30 California Institute Of Technology Catalyseurs de metathese de carbene metallique a base d'imidazolidine
EP1740632A1 (fr) * 2004-04-21 2007-01-10 Dow Global Technologies Inc. Composition polymere aromatique amelioree de monovinylidene modifiee au caoutchouc par polymerisation en masse
EP4019576A1 (fr) * 2020-12-28 2022-06-29 Trinseo Europe GmbH Procédé de recyclage de polymères thermoplastiques renforcés par des élastomères
WO2022144158A1 (fr) 2020-12-28 2022-07-07 Trinseo Europe Gmbh Procédé de recyclage de polymères thermoplastiques renforcés par élastomère

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
SADAKA FATEN ET AL: "Telechelic oligomers obtained by metathetic degradation of both polyisoprene and styrene-butadiene rubbers. Applications for recycling waste tyre rubber", POLYMER DEGRADATION AND STABILITY, BARKING, GB, vol. 98, no. 3, 28 December 2012 (2012-12-28), pages 736 - 742, XP028577456, ISSN: 0141-3910, DOI: 10.1016/J.POLYMDEGRADSTAB.2012.12.018 *

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