Foamable branched polypropylene compositions and foamed products produced therefrom

Abstract

The foamable composition may include a branched polypropylene copolymer having a g 'vis value of about 0.93 or less, and a blowing agent blended with the branched polypropylene copolymer. The branched polypropylene copolymer comprises the polymerization reaction product of propylene and an alpha, omega-diene having five or more carbon atoms. The foamed product may include a foamable composition converted to a foamed form. In some cases, the branched polypropylene copolymer may have a g 'vis value of about 0.8 or less.

Description

Technical Field

[0001] The present disclosure relates to polymer foams, and more particularly, polymer foams comprising branched polypropylene copolymers. Background Art

[0002] Polymer foams can be produced by introducing a physical or chemical foaming agent into a molten polymer stream, blending the foaming agent with the polymer, and extruding the resulting mixture in a relatively low pressure environment while being molded into a desired product form. Exposure of the molten extrudate to a relatively low pressure environment causes the foaming agent to gasify (either by chemical reaction or by simple expansion after undergoing decompression), thereby forming cells in the polymer to define the polymer foam. Depending on the conditions, the cells may be open or closed in form. Due to their generally excellent mechanical properties, such as high compressive strength and relatively light weight, polymer foams are commonly used in various industrial applications and consumer products. Thus, polymer foams may be useful in, for example, automotive, aerospace, insulation, and packaging industries.

[0003] Polyurethane, polystyrene and polyethylene are polymers that have traditionally been used in polymer foams. Polypropylene is a relatively new entry into the field of polymer foams. Properties of polypropylene that make such polymers desirable for incorporation into foams include, for example, excellent heat resistance, chemical resistance and impact resistance, as well as thermal and electrical insulation properties. For example, impact resistance can make expanded polypropylene particularly desirable for use in automotive manufacturing.

[0004] Not every polypropylene is suitable for foaming. Linear polypropylene can exhibit low melt strength, which can make the cell walls produced during foaming susceptible to rupture during continued cell growth, resulting in inefficient foam production. Blends of linear polypropylene with other polymers having higher melt strength can improve cell structure and foaming performance. Chemical changes can also be made to enhance the melt strength and foaming performance of as-formed linear polypropylene.

[0005] Compared to their linear counterparts, long-chain branched polymers can exhibit increased tensile hardening, which can improve their melt strength and foaming properties. Conventionally, linear polypropylenes are converted to branched polypropylenes by post-synthesis modification (such as by free radical-mediated methods). Although free radical-mediated branching can provide branched polypropylenes with properties suitable for foaming, the degree of branching may be lower than desired, and additional processing operations for introducing branching may increase production costs. Summary of the invention

[0006] The present disclosure relates to foamable compositions and foamed products made by converting the foamable compositions into a foamed form. In various aspects, the foamable compositions comprise a g′ having a g′ of about 0.93 or less.vis A branched polypropylene copolymer having a high carbon value, the branched polypropylene copolymer comprising a polymerization reaction product of propylene and an α,ω-diene having five or more carbon atoms, and a blowing agent blended with the branched polypropylene copolymer.

[0007] In various other aspects, the present disclosure provides a polymer foaming method comprising introducing a blowing agent into a polymer having a g′ of about 0.93 or less. vis The invention relates to a branched polypropylene copolymer having a certain molecular weight and a certain molecular weight, wherein the branched polypropylene copolymer comprises a polymerization reaction product of propylene and an α,ω-diene having five or more carbon atoms to form a foamable composition, and inducing foam formation in the foamable composition to produce a foamed product comprising the foamable composition in a foamed form.

[0008] These and other features and properties of the disclosed foamable compositions and foamed products of the present disclosure and their advantageous applications and / or uses will be apparent from the following detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The following drawings are included to illustrate certain aspects of the disclosure and should not be considered an exclusive configuration. The disclosed subject matter is capable of considerable modification, alteration, combination, and equivalents in form and function as will occur to those skilled in the art and having the benefit of this disclosure.

[0010] To assist one of ordinary skill in the relevant art in making and using the subject matter of this document, reference is made to the accompanying drawings.

[0011] Figure 1 is a plot of the small amplitude oscillatory shear (SAOS) data of branched polypropylene copolymers fitted to the Winter-Chambon model.

[0012] Figure 2 is a graph of the expansion ratio as a function of temperature for various branched polypropylene copolymers and comparative commercial polypropylenes.

[0013] Figure 3 is a graph of cell density as a function of temperature for various branched polypropylene copolymer foams and comparative commercial polypropylene foams.

[0014] Figures 4A-4D is a graph of the average cell diameter of various branched polypropylene copolymer foams as a function of temperature. DETAILED DESCRIPTION

[0015] The present disclosure relates to polymer foams, and more particularly, polymer foams comprising branched polypropylene copolymers.

[0016] As discussed above, polymer foams containing branched polypropylene can be used in many industries due to the high melt strength of these types of polymers. Branching is typically introduced into substantially linear polypropylene after its reactor production (such as by free radical mediated processes). Polypropylene branching introduced in this manner can significantly increase production costs, and in some cases, the amount of branching introduced may be insufficient.

[0017] Compared to conventional polypropylene foams and foamable compositions produced from polypropylene that has been modified after synthesis to introduce branching, the present disclosure provides polypropylene foams and foamable compositions in which a large amount of long chain branching is introduced during the polymerization process to form branched polypropylene copolymers. Such branched polypropylene copolymers may be referred to herein as "in-reactor" branched polypropylene copolymers and / or as being produced "in-reactor". In particular, branched polypropylene copolymers may be produced in-reactor by copolymerization of propylene and α,ω-diene to form long chain branches produced by α,ω-diene. As further discussed herein, such copolymerization processes may be promoted by catalysts that tolerate and promote the ready polymerization of α,ω-diene. Due to its in-reactor production, branched polypropylene copolymers may provide an enhanced and economical method for producing foamable compositions containing polypropylene for use in batch, extrusion, blow molding, and injection molding based manufacturing processes.

[0018] Branched polypropylene copolymers produced by in-situ processes in reactors can have several advantages over linear polypropylenes that have undergone post-synthesis modification (such as by free radical-mediated modification) to introduce branching and provide increased melt strength values. Branched polypropylenes with higher melt strength can provide polymer foams with higher cell counts, and thus smaller cell sizes, compared to linear polypropylenes. These features can provide foamable compositions comprising branched polypropylenes that exhibit high expansion ratios over a wide temperature range. As further described herein, in-situ production of branched polypropylene copolymers in reactors can also be less costly and less labor-intensive than introducing branching by post-synthesis modification.

[0019] definition

[0020] All numerical values ​​within the detailed description and claims herein are modified by "about" or "approximately" with respect to the indicated value, and take into account experimental error and deviation that would be expected by one of ordinary skill in the art. Room temperature is approximately 23°C unless otherwise indicated.

[0021] Unless the context clearly indicates otherwise, as used in the present disclosure and claims, the singular forms "a / an" and "the" include plural forms. The term "and / or" as used herein in phrases such as "A and / or B" is intended to include "A and B", "A or B", "A" as well as "B".

[0022] For the purposes of this disclosure, a new numbering scheme for the groups of the periodic table of the elements is used. In the numbering scheme, the groups (columns) are numbered sequentially from left to right from 1 to 18, except for the f-block elements (lanthanides and actinides). According to this scheme, the term "transition metal" refers to any atom from Groups 3-12 of the periodic table of the elements, including lanthanides and actinides. For example, Ti, Zr, and Hf are Group 4 transition metals.

[0023] "Linear polypropylene" or "linear polypropylene" comprises a polymer backbone derived from the polymerization of propylene and optionally one or more additional ethylenically unsaturated monomers, and at least methyl branches extending from the polymer backbone, wherein the methyl branches are derived from propylene. "Branched polypropylene" contains additional branches in addition to the methyl branches. The branched polypropylene of the present disclosure may have a g' vis The branching index measured by the propylene copolymerization method is lower than the branching index obtained by homopolymerization of propylene under similar conditions. As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, and Mz is the z-average molecular weight, wt% is the weight percentage, and mol% is the mole percentage. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn. Unless otherwise indicated, all molecular weight units (e.g., Mw, Mn, and Mz) are expressed in g / mol (g·mol -1 The procedure used to determine the molecular weight of a polymer is set forth below.

[0024] For the purposes of this disclosure, and unless otherwise specified, a "catalyst system" is a combination of at least one catalyst compound, at least one activator, an optional co-activator, and an optional support material. The catalyst compound may contain a transition metal. When "catalyst system" is used to describe such a pairing before activation, it refers to an unactivated catalyst complex (precatalyst) together with an activator and an optional co-activator. When the term is used to describe such a pairing after activation, it refers to an activated complex and an activator or other charge balancing structural part. The transition metal compound may be neutral as in a precatalyst, or a charged substance with a counter ion as in an activated catalyst system. For the purposes of this disclosure, and unless otherwise specified, when a catalyst system is described as comprising a neutral stable form of a component, it is fully understood by those of ordinary skill in the art that the ionic form of the component is a form that reacts with a monomer to produce a polymer. A polymerization catalyst system is a catalyst system that can polymerize a monomer into a polymer. In addition, the catalyst compound and activator represented by the formula herein include both the neutral and ionic forms of the catalyst compound and the activator.

[0025] For the purposes of this disclosure, and unless otherwise specified, "olefins", alternatively referred to as "alkenes", are linear, branched, or cyclic compounds of carbon and hydrogen with at least one double bond. For the purposes of this disclosure, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such a polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have a "propylene" content of 35wt% to 55wt%, based on the weight of the copolymer, it is understood that the monomer units in the copolymer are derived from propylene in the polymerization reaction, and the derived units are present at 35wt% to 55wt% based on the weight of the copolymer. A "polymer" has two or more identical or different monomer units. A "homopolymer" is a polymer having the same monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. A "terpolymer" is a polymer having three monomer units that are different from each other. Therefore, as used herein, the definition of a copolymer includes a terpolymer. "Different" as used to refer to monomer units indicates that the monomer units differ from each other by at least one atom or are isomerically different. A "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50 mol% propylene derived units, and so forth.

[0026] For the purposes of this disclosure, and unless otherwise specified, the term “ n” refers to one or more hydrocarbons having n carbon atoms per molecule, where n is a positive integer. The term “hydrocarbon” refers to a class of compounds containing hydrogen bonded to carbon, and encompasses (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds having different values ​​of n. Similarly, “C m -C y "A group or compound refers to a group or compound containing carbon atoms whose total number is in the range of m to y. Therefore, C1-C 50 The alkyl group refers to an alkyl group containing carbon atoms whose total number ranges from 1 to 50.

[0027] For the purposes of this disclosure, and unless otherwise specified, the terms "group," "radical," and "substituent" may be used interchangeably.

[0028] For the purposes of this disclosure, and unless otherwise specified, the terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" are used interchangeably and are defined to mean a radical consisting solely of hydrogen and carbon atoms. Suitable hydrocarbyl radicals are C1-C 100 The term "group" refers to a group which may be straight chain, branched or cyclic and may be aromatic or non-aromatic when cyclic. Examples of such groups include, but are not limited to, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and aryl groups such as phenyl, benzyl and naphthyl.

[0029] For the purposes of this disclosure, and unless otherwise specified, the terms "alkyl radical" and "alkyl" are used interchangeably throughout this disclosure. For the purposes of this disclosure, "alkyl" is defined as a C1-C ... 100 Examples of such groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including substituted analogs thereof.

[0030] The term "α-olefin" refers to an olefin having a structure ((R 1 R 2 )-C=CH2, where R 1 and R 2 can be independently hydrogen or any hydrocarbon group; preferably R 1 is hydrogen and R2 A "linear alpha-olefin" is an alpha-olefin as defined in this paragraph, wherein R 1 is hydrogen, and R 2 is hydrogen or a straight chain alkyl group.

[0031] For the purposes of this disclosure, and unless otherwise specified, ethylene shall be considered an alpha-olefin.

[0032] For the purposes of this disclosure, and unless otherwise specified, the term "alkoxy" or "alkoxide" means an alkyl or aryl group bonded to an oxygen atom, such as an alkyl ether or aryl ether group (group / radical) attached to an oxygen atom, and may include alkyl groups / radicals in which the alkyl / aryl group is C1-C 10 The hydrocarbon group may be a straight chain, a branched chain, or a cyclic group. The hydrocarbon group may be a saturated or unsaturated group. Examples of suitable hydrocarbon oxy groups may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and phenoxy.

[0033] For the purposes of this disclosure, and unless otherwise specified (such as for "substituted hydrocarbyl", etc.), the term "substituted" means that at least one hydrogen atom has been replaced by at least one non-hydrogen group, such as a hydrocarbyl, a heteroatom, or a heteroatom-containing group, such as a halogen (such as Br, Cl, F or I), or at least one functional group, such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -ASR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, -(CH2) q -SiR*3, wherein q is 1 to 10 and each R* is independently hydrogen, a hydrocarbon group or a halocarbyl group, or two or more R* may be linked together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted into the hydrocarbon ring.

[0034] For the purposes of the present disclosure, the term "substituted hydrocarbyl" means a hydrocarbyl group in which at least one of the hydrogen atoms of the hydrocarbyl group has been replaced by at least one heteroatom (such as a halogen, e.g., Br, Cl, F, or I) or a heteroatom-containing group (such as a functional group, e.g., -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*2, -SR*, -BR*2, -SiR*3, -GeR*3, -SnR*3, -PbR*3, -(C) qSiR*3, etc., wherein q is 1 to 10 and each R* is independently hydrogen, a hydrocarbon group or a halogenated hydrocarbon group, and two or more R* may be linked together to form a substituted or unsubstituted saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure), or wherein at least one heteroatom has been inserted into the hydrocarbon ring.

[0035] For the purposes of this disclosure, and unless otherwise specified, the term "ring atom" refers to an atom that is part of a ring structure. For purposes of this definition, benzyl has six ring atoms and tetrahydrofuran has five ring atoms.

[0036] For the purposes of this disclosure, and unless otherwise specified, the term "aryl" or "aryl group" refers to an aromatic ring, such as phenyl, naphthyl, xylyl, etc. Likewise, heteroaryl refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom such as N, O, or S. As used herein, the term "aromatic" also refers to pseudoaromatic heterocycles, which are heterocyclic substituents that have similar properties and structure (almost planar) to aromatic heterocyclic ligands, but are not aromatic by definition.

[0037] For the purposes of this disclosure, and unless otherwise specified, the term "substituted aryl" means an aryl group having one or more hydrogen groups replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0038] For the purposes of this disclosure, and unless otherwise specified, the term "substituted heteroaryl" means a heteroaryl group having one or more hydrogen groups replaced with a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group.

[0039] For the purposes of this disclosure, and unless otherwise specified, a "halohydrocarbyl" is a halogen-substituted hydrocarbyl group, which may be bonded to another substituent through a carbon atom or a halogen atom.

[0040] For the purposes of this disclosure, and unless otherwise specified, in the presence of isomers of named alkyl, alkenyl, alkoxy, or aryl (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), a reference to one member of a group (e.g., n-butyl) should explicitly disclose the remaining isomers in the family (e.g., isobutyl, sec-butyl, and tert-butyl). Similarly, reference to an alkyl, alkenyl, alkoxy, or aryl without specifying a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0041] The following abbreviations may be used herein: Me is methyl, Ft is ethyl, Pr is propyl, cPR is cyclopropyl, nPr is n-propyl, iPr is isopropyl, Bu is butyl, nBu is n-butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, Oct is octyl, Ph is phenyl, MAO is methylaluminoxane, dme is 1,2-dimethoxyethane, p-tBu is p-tert-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, p-Me is p-methyl, Bz and Bn are benzyl (i.e., CH2Ph), THF (also known as thf) is tetrahydrofuran, RT is room temperature (and is 23°C unless otherwise indicated), tol is toluene, EtOAc is ethyl acetate, Cbz is carbazole, and Cy is cyclohexyl.

[0042] In the description herein, a catalyst may be described as a catalyst, a catalyst precursor, a precatalyst compound, a catalyst compound, or a transition metal compound. These terms may be used interchangeably. The terms "cocatalyst" and "activator" are used interchangeably herein.

[0043] For purposes of this disclosure, and unless otherwise specified, an "anionic ligand" is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A "neutral donor ligand" is a neutrally charged ligand that donates one or more pairs of electrons to a metal ion.

[0044] For the purposes of this disclosure, and unless otherwise specified, a heterocycle is a ring having a heteroatom in the ring structure, as opposed to a heteroatom-substituted ring in which a hydrogen on a ring atom is replaced by a heteroatom. For example, tetrahydrofuran is a heterocycle, while 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring.

[0045] For purposes of this disclosure, and unless otherwise specified, a scavenger is a compound typically added to promote polymerization by scavenging impurities. Some scavengers may also act as activators and may be referred to as co-activators. Co-activators that are not scavengers may also be used in conjunction with an activator to form an active catalyst. In at least one embodiment, the co-activator may be premixed with the transition metal compound to form an alkylated transition metal compound.

[0046] For the purposes of this disclosure, and unless otherwise specified, a "metallocene" catalyst compound is a transition metal catalyst compound having one, two or three, typically one or two, substituted or unsubstituted cyclopentadienyl ligands bound to a transition metal, typically a metallocene catalyst is an organometallic compound containing at least one p-bound cyclopentadienyl moiety (or substituted cyclopentadienyl moiety). Substituted or unsubstituted cyclopentadienyl ligands include substituted or unsubstituted indenyl, fluorenyl, indacenyl, benzindenyl, and the like.

[0047] For purposes of this disclosure, and unless otherwise specified, the term "continuous" refers to a system that operates without interruption or stopping. For example, a continuous process to produce a polymer would be one in which reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

[0048] For the purposes of this disclosure, and unless otherwise specified, the term "in-reactor in-situ polypropylene" or "in-reactor in-situ branched polypropylene" means a polypropylene polymer or copolymer produced in one or more polymerization stages without post-polymerization synthetic modification of the polypropylene chain. Although the various polymerization stages may be carried out in different polymerization zones, i.e., in different reactors or different parts of the same reactor, the stages may alternatively be carried out sequentially in the same polymerization zone. A polymerization zone is defined as the zone where the activated catalyst and monomer are contacted and the polymerization reaction occurs. When multiple reactors are used in a series or parallel configuration, each reactor is considered a separate polymerization zone.

[0049] For the purposes of this disclosure, and unless otherwise specified, a composition being "foamable" means that foam formation has not yet occurred, but the composition is capable of forming foam once exposed to suitable conditions. In contrast, a "foamable composition" or "foamed product" means that foam formation has occurred to introduce a plurality of cells within the polymer within the composition.

[0050] For purposes of this disclosure, and unless otherwise specified, the term "α,ω-diene" refers to an olefinic compound having two terminal olefin groups located at opposite ends of the hydrocarbon chain.

[0051] Unless otherwise specified, the branching index herein is defined as g′ vis Value. Given g′ vis The value can be determined by gel permeation chromatography (GPC)-4D.

[0052] Branched polypropylene copolymers, polymerization methods and catalyst compounds

[0053] The branched polypropylene copolymer suitable for use in the present disclosure may comprise the polymerization product of propylene and an α,ω-diene having five or more carbon atoms. The branched polypropylene copolymer may have a g′ of about 0.93 or less, preferably about 0.9 or less or about 0.8 or less. vis A value which is characteristic of the amount of branching. A foamable composition can be produced by blending a branched polypropylene copolymer with a blowing agent.

[0054] Branched polypropylene copolymers suitable for use herein can be produced by a polymerization process in which propylene is copolymerized with at least one additional comonomer. More specifically, the polymerization process can copolymerize propylene with at least one α, ω-diene, and optionally with at least one additional comonomer. Propylene and one or more additional comonomers can be introduced into a catalyst system (or contacted with) comprising an activator and at least one catalyst compound described herein, wherein the at least one catalyst compound is suitable for polymerizing α, ω-diene. The catalyst compound and the activator can be combined to form a catalyst system before contacting the monomer. Alternatively, the catalyst compound and the activator can be introduced separately into a polymerization reactor, wherein they react to form a catalyst system afterwards.

[0055] The branched polypropylene copolymer disclosed herein may contain propylene in an amount of about 50 wt% or more, or about 55 wt% or more, or about 60 wt% or more, or about 65 wt% or more, or about 70 wt% or more, or about 75 wt% or more, or about 80 wt% or more, or about 85 wt% or more, or about 90 wt% or more, or about 99 wt% or more, or about 99.5 wt% or more, provided that the α,ω-diene is present in a non-zero amount in the branched polypropylene copolymer. In some embodiments, the at least one α,ω-diene may account for the mass balance in the branched polypropylene copolymer, and in other embodiments, in addition to the at least one α,ω-diene, at least one additional comonomer may also be present. In a specific embodiment, the branched polypropylene copolymer may comprise or consist essentially of about 90 wt% or more propylene and a non-zero amount of the at least one α,ω-diene, based on the total mass of the branched polypropylene copolymer, preferably about 99 wt% or more propylene and a non-zero amount of the at least one α,ω-diene, based on the total mass of the branched polypropylene copolymer. In some embodiments, the non-zero amount of the at least one α,ω-diene may range from about 0.001 wt% to about 10 wt%, or about 0.01 wt% to about 9.99 wt%, or about 0.1 wt% to about 9.9 wt%, or about 0.5 wt% to about 99.5 wt%, or about 0.1 wt% to about 10 wt%, or any subrange thereof, based on the total mass of the branched polypropylene copolymer.

[0056] Specific examples of suitable α,ω-dienes may include, but are not limited to, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1,13-tetradecadiene, 2-methyl-1,6-heptadiene, 2-methyl-1,7-octadiene, 2-methyl-1,8-nonadiene, 2-methyl-1,9-decadiene, 2-methyl-1,10-undecadiene, 2-methyl-1,11-dodecadiene, 2-methyl-1,12-tridecadiene, and 2-methyl-1,13-tetradecadiene.

[0057] In addition to the α,ω-dienes, the branched polypropylene copolymer may also include at least one additional comonomer, such as one or more α-olefins and / or a plurality of diene monomers. Suitable diene monomers may include any type of diene except α,ω-dienes. Suitable α-olefins may include ethylene or substituted or unsubstituted C4-C 40 α-olefins, such as C4-C 20 α-olefins or C4-C 12 α-Olefins such as 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and isomers thereof, including branched isomers. Other illustrative monomers that may be present in the branched polypropylene copolymer may include, for example, norbornene, ethylidene norbornene, vinyl norbornene, norbornadiene, dicyclopentadiene, cyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, divinylbenzene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof and isomers thereof such as cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, butadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, and their respective homologs and derivatives.

[0058] When present, in addition to α, one or more dienes other than ω-dienes can be present in the branched polypropylene copolymer in an amount of up to about 10wt% or up to about 1wt% based on the total mass of the branched polypropylene copolymer, such as about 0.00001wt% to about 1.0wt% based on the total mass of the branched polypropylene copolymer, or about 0.002wt% to about 0.5wt%, or about 0.003wt% to about 0.2wt%. In at least one embodiment, 500ppm or less of diene can be added to the polymerization reactor, such as 400ppm or less, such as 300ppm or less. In other embodiments, at least 50ppm, or 100ppm or more, or 150ppm or more of diene can be added to the polymerization. Alternatively, one or more dienes can be present with 0.1mol% to 1mol%, such as 0.5mol%.

[0059] The in-situ polymerization method in the reactor disclosed herein can be carried out in any manner known in the art that can appropriately produce branched polypropylene copolymers. Any suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization method known in the art can be used. Such methods can be operated in batch, semi-batch, or continuous modes. Homogeneous polymerization methods and slurry methods can be used. Homogeneous polymerization methods refer to methods in which at least 90wt% of the product is soluble in the reaction medium. Homogeneous polymerization methods can be bulk homogeneous methods. Bulk methods refer to methods in which the monomer concentration in all feeds entering the reactor is 70 volume % or greater. Alternatively, there is no or no solvent or diluent (except a small amount used as a carrier for the catalyst system or other additives, or the amount typically present with the monomer; for example, propane in propylene) in the reaction medium. In another embodiment, the method is a slurry method. As used herein, the term "slurry polymerization method" refers to a polymerization method in which a supported catalyst is used and the monomer is polymerized on supported catalyst particles. At least 95 wt% of the polymer product derived from the supported catalyst is in the form of pellets which are solid particles (not dissolved in the diluent).

[0060] Suitable diluents / solvents for the polymerization process include non-coordinating inert liquids. Examples include straight chain and branched hydrocarbons such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof, such as those commercially available (ISOPAR TM fluid); fully halogenated hydrocarbons, such as fully fluorinated C4-C 10Alkanes, chlorobenzenes, and aromatic and alkyl-substituted aromatic compounds such as benzene, toluene, mesitylene and xylene. Suitable solvents also include liquid olefins that can be used as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene and mixtures thereof. In at least one embodiment, aliphatic hydrocarbon solvents are used as solvents, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof. In another embodiment, the solvent is not aromatic, such as aromatic compounds are present in the solvent in an amount of less than 1wt%, such as less than 0.5wt%, or even 0wt% based on the weight of the solvent.

[0061] In at least one embodiment, the feed concentration of monomers and comonomers for polymerization may comprise 60 volume % solvent or less, or 40 volume % or less, or 20 volume % or less, based on the total volume of the feed stream.

[0062] Polymerization can be carried out at any temperature and / or pressure suitable for obtaining the desired branched polypropylene copolymer. Suitable temperature and / or pressure can include a temperature in the range of about 0°C to about 300°C, such as about 20°C to about 200°C, or about 35°C to about 150°C, or about 40°C to about 120°C, or about 45°C to about 80°C; and a pressure in the range of about 0.35MPa to about 10MPa, or about 0.45MPa to about 6MPa, or about 0.5MPa to about 4MPa.

[0063] In suitable polymerizations, the run time of the reaction may be up to 300 minutes, such as in the range of about 5 minutes to about 250 minutes, or about 10 minutes to about 120 minutes. In a continuous process, the run time may be the average residence time of the reactor.

[0064] In at least one embodiment, hydrogen can be present in the polymerization reactor at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa), such as 0.01 psig to 25 psig (0.07 kPa to 172 kPa), or 0.1 psig to 10 psig (0.7 kPa to 70 kPa).

[0065] In some embodiments, the activity of the catalyst can be at least 50 g / mmol / hour, such as 1,000 g / mmol / hour or greater, 5,000 g / mmol / hour or greater, or 50,000 g / mmol / hour or greater, or 100,000 g / mmol / hour or greater, or 500,000 g / mmol / hour or greater. In alternative embodiments, the conversion of the olefin monomer can be at least 10%, such as 20% or greater, or 30% or greater, or 50% or greater, or 80% or greater, based on the polymer yield and the weight of the monomer entering the reaction zone.

[0066] In some embodiments, the branched polypropylene copolymers produced herein can have an Mw of about 5,000 to about 1,000,000 g / mol, such as about 25,000 to about 750,000 g / mol, or about 50,000 to about 500,000 g / mol, or about 80,000 to about 300,000 g / mol, or about 80,000 to about 200,000 g / mol), as determined by GPC-4D. In some embodiments, the branched polypropylene copolymers produced herein may have an Mn of about 1,000 to about 100,000 g / mol, such as about 10,000 to about 100,000 g / mol, or about 20,000 to about 80,000 g / mol, or about 30,000 to about 75,000 g / mol, or about 25,000 to about 85,000 g / mol), as determined by GPC-4D. In some embodiments, the branched polypropylene copolymers may have a molecular weight distribution (MWD) (Mw / Mn) greater than about 1, such as about 1 to about 40, or about 1.5 to about 20, or about 2 to about 10, as determined by GPC-4D. Preferably, Mw / Mn is about 9 or less, such as about 1 to about 9, or about 2 to about 8, or about 3 to about 7.

[0067] In some embodiments, the branched polypropylene copolymers produced herein can have an Mz of about 100,000 to about 10,000,000 g / mol, such as about 100,000 to about 5,000,000 g / mol, or about 200,000 to about 1,000,000 g / mol, or about 1,000,000 to about 3,000,000 g / mol, or about 1,500,000 to about 3,000,000 g / mol, as determined by GPC-4D. In some embodiments, the branched polypropylene copolymers can have an Mz / Mw of about 6 or less, such as about 1 to about 6, or about 2 to about 5, or about 3 to about 6, or about 1 to about 3.

[0068] In some embodiments, the branched polypropylene copolymer may have a g′ of 0.5 or greater and less than 0.8, or less than 0.85, or less than 0.9, or less than 0.93, such as from about 0.5 to about 0.93, or from about 0.5 to about 0.8, or from about 0.5 to about 0.75, or from about 0.5 to about 0.7, or from about 0.5 to about 0.65, or from about 0.5 to about 0.6, or from about 0.6 to about 0.8, or from about 0.65 to about 0.8, or from about 0.7 to about 0.8, or from about 0.75 to about 0.93, or from about 0.8 to about 0.9. vis , as determined by GPC-4D.

[0069] In some embodiments, the branched polypropylene copolymer can have a melt flow rate (MFR) of about 0.4 dg / min to about 56 dg / min, or about 0.4 dg / min to about 30 dg / min, or about 0.4 dg / min to about 10 dg / min, or about 0.4 dg / min to about 3.6 dg / min, or about 0.6 dg / min to about 3.0 dg / min, or about 1 dg / min to about 2.5 dg / min, as measured by ASTM D1238 (230° C., 2.16 kg).

[0070] In some embodiments, the branched polypropylene copolymer may have a g' of about 0.8 or less. vis and an MFR of about 0.4 dg / min to about 3.6 dg / min as measured by ASTM D1238 (230° C., 2.16 kg).

[0071] In some embodiments, the branched polypropylene copolymer may have a Tm greater than about 145°C, such as about 150°C to about 165°C, or about 155°C to about 162°C, or about 158°C to about 160°C, as determined by differential scanning calorimetry as described below. In some embodiments, the branched polypropylene copolymer may have a Tm of about 148°C to about 159°C.

[0072] In some embodiments, the branched polypropylene copolymer can have a shear thinning ratio (STR) of about 0.15 to about 0.007, or about 0.1 to about 0.01, or about 0.075 to about 0.025, as measured as the shear viscosity ratio between radial frequencies of 100 rad / s and 0.1 rad / s. Alternatively, the branched polypropylene copolymer can have a shear thinning ratio of about 0.007 to about 0.12.

[0073] Shear thinning can be described by the following parameters: power law index (slope of viscosity with respect to frequency in the power law regime), transition index (parameter describing the transition between the Newtonian plateau and the power law region), consistency (characteristic relaxation time of the polymer, as opposed to the frequency corresponding to the transition from the Newtonian to the power law regime), infinite rate viscosity, zero shear viscosity as defined by the Carreau-Yasuda model by fitting the dependence of the complex viscosity on the angular frequency data. These parameters can be calculated using Equation 1:

[0074]

[0075] where η0 is the zero shear viscosity, η ∞ is the infinite viscosity, k is the consistency, η is the power law exponent, and a is the transition exponent.

[0076] In at least one embodiment, the branched polypropylene copolymers produced herein may have one or more of the following as measured at 190°C and at a radial frequency between 0.1 and 628 rad / s:

[0077] a. A power law exponent η of about -1.0 to about 0.25, such as about -1.1 to about 0.23 CY ;

[0078] b. A transition index a of about 0.09 to about 0.3, such as about 0.1 to about 0.2 CY ;

[0079] c. Such as about 1.0e -4 s to about 17.0, such as about 1.2e -4 s to a consistency k of about 16.3 CY ;

[0080] d. An infinite rate viscosity η of about -140 Pa·s to about 42 Pa·s, such as about -132.6 Pa·s to about 31.9 Pa·s ∞CY ; and / or

[0081] e. A zero shear viscosity η of about 14 kPa·s to about 3,200 kPa·s, such as about 16 kPa·s to about 3000 kPa·s 0CY , defined by fitting the dependence of the complex viscosity on the angular frequency data by the Carreau-Yasuda model using TA Instruments Trios v3.3.1.4246 software, with a high quality fit as indicated by the high value of the parameter R2 (>0.9999).

[0082] In at least one embodiment, the branched polypropylene copolymer may have a strain hardening ratio (SHR) of about 25 or less, or about 20 or less, such as about 15 to about 5, as measured using 1 sec -1 The first strain rate, 0.1sec -1 The strain hardening ratio was determined as described below with a second strain rate of 1.5 s and a time of 2.5 s for both rates.

[0083] In at least one embodiment, the branched polypropylene copolymer can have a complex viscosity of 140 Pa·s to 2,000 Pa·s, or about 180 Pa·s to 1,600 Pa·s, or about 240 Pa·s to about 1,400 Pa·s, or about 25 Pa·s to about 500 Pa·s, or about 50 Pa·s to about 350 Pa·s, as measured by oscillatory shear at a radial frequency of 100 rad / s.

[0084] In at least one embodiment, the branched polypropylene copolymer may have a complex viscosity of about 1,000 Pa·s to about 80,000 Pa·s, or about 1,500 Pa·s to about 70,000 Pa·s, or about 2,000 Pa·s to about 60,000 Pa·s as measured by oscillatory shear at a radial frequency of 0.1 rad / s.

[0085] In at least one embodiment, the branched polypropylene copolymer can have a 1% secant flexural modulus of about 1,300 MPa to about 2,300 MPa, or about 1,500 MPa to about 2,200 MPa, or about 1,700 MPa to about 2,130 MPa. The 1% secant flexural modulus is measured according to ASTM D 790 (A, 1.0 mm / min) using an Instron machine, using an ISO 37-3 type rod, with a crosshead speed of 1.0 mm / min and a support span of 30.0 mm.

[0086] In at least one embodiment, the branched polypropylene copolymer may have a Hencky strain of 2.5 and a -1 The composite material has an extensional viscosity of about 700 kPa·s or less, or about 400 kPa·s to about 650 kPa·s, or about 450 kPa·s to about 600 kPa·s, measured at 190° C. at a Hencky strain rate of .

[0087] In at least one embodiment, the branched polypropylene copolymer can have a unimodal or multimodal molecular weight distribution as determined by gel permeation chromatography (GPC). "Unimodal" means that the GPC trace has one peak or inflection point. "Multimodal" means that the GPC trace has at least two peaks or inflection points. An inflection point is a point where the sign of the second derivative of the curve changes (e.g., from negative to positive, or vice versa).

[0088] The branched propylene copolymers may have a certain level of isotacticity and may be isotactic or highly isotactic. As used herein, "isotactic" is defined as 13 C NMR analysis has at least 10% isotactic pentads, as described in US 2008 / 0045638. As used herein, "highly isotactic" is defined as 13 C NMR analysis has at least 60% isotactic pentads. In another embodiment, the branched polypropylene copolymer produced can be random. Random polypropylene is defined as polypropylene that is branched according to 13 C NMR analysis showed less than 10% isotactic or syndiotactic pentads.

[0089] Suitable catalyst compounds for producing branched polypropylene copolymers may have a structure represented by Formula 1:

[0090]

[0091]

[0092] Where M is a transition metal atom; T is a bridging group; X 1 and X 2 Each of X is a monovalent anionic ligand, or X 1 and X 2 Connect to form a metal ring; R 1 is hydrogen, halogen, unsubstituted C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl; R 3 It is an unsubstituted C4-C62 Cycloalkyl, substituted C4-C 62 Cycloalkyl, unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, or substituted C4-C 62 Heteroaryl; R 2 and R 4 Each of the 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl; R 5 , R 6 , R 7 and R 8 Each of the 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon, unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl, or R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 One or more pairs of these may be linked to form a substituted or unsubstituted C4-C 62 a saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; and J 1 and J 2 Each of the C4-C 62(Alternatively C5-C 62 , alternatively C5-C 40 , alternatively C6 to C 30 , alternatively C6 to C 20 ) an unsaturated cyclic or polycyclic ring structure, or a combination thereof, provided that J 1 and J 2 Together with the two carbon atoms to which they are attached on the indenyl group, they form at least one saturated ring. 1 and J 2 Together with the two carbon atoms to which they are attached on the indenyl group, they form at least one 5- or 6-membered saturated ring.

[0093] As a non-limiting illustration, in Formula 1, the phrase "J 1 and J 2 Together with the two carbon atoms to which they are attached on the indenyl group, "means that in the following formula 2, J in the box 1 and J 2 Preferably, the atoms in the box form a 5-membered or 6-membered saturated ring, indacene and hexahydrobenzo[f]indenyl.

[0094]

[0095] The unsaturated ring in the indacenyl or hexahydrobenzo[f]indenyl group may be substituted or unsubstituted and may be part of a polycyclic group in which the other cyclic groups may be saturated or unsaturated and substituted or unsubstituted. Typical substituents on the unsaturated ring include C1 to C 40 A hydrocarbon group (which may be substituted or unsubstituted), a heteroatom (such as a halogen, such as Br, F, Cl), a heteroatom-containing group (such as a halogenated hydrocarbon group), or two or more substituents linked together to form a cyclic or polycyclic ring structure (which may contain saturated and / or unsaturated rings), or a combination thereof.

[0096] In some embodiments, J 1 and J 2 Each of the can be linked to form an unsubstituted C4-C 30 (Alternatively C5-C 30 , alternatively C6-C 20 ) cyclic or polycyclic ring structure, any of which can be saturated, partially saturated, aromatic, or unsaturated. In some embodiments, each J is connected to form a substituted C4-C 20 Cyclic or polycyclic rings, any one of which may be saturated or unsaturated. Examples include structures represented by the following formulas 3-5:

[0097]

[0098] Where R 1 , R 2 , R 3 and R 4 As defined in Formula 1 above, and the wavy lines indicate the relationship between M (such as Hf or Zr) and T (such as Me 2 Si) connection.

[0099] In some embodiments, M is a transition metal, such as a transition metal of Group 3, 4, or 5 of the Periodic Table of Elements, such as a Group 4 metal, for example, Zr, Hf, or Ti.

[0100] In some embodiments, X 1 and X 2 Each of which is independently unsubstituted C1-C 40 Hydrocarbyl (such as unsubstituted C2-C 20 Hydrocarbon), substituted C1-C 40 Hydrocarbyl (such as substituted C2-C 20 Hydrocarbon), unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 Heteroaryl, hydride, amino, alkoxy, sulfhydryl, phosphorus, halogen, diene, amine, phosphine, ether and combinations thereof, such as X 1 and X 2 Each of X is independently halo or C1-C5 alkyl, such as methyl. 1 and X 2 Each of X is independently chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl. In some embodiments of the present disclosure, X 1 and X 2 Forming part of a fused ring or ring system.

[0101] In some embodiments, T is represented by the formula (R*2G)g, wherein each G is C, Si, or Ge, g is 1 or 2, and each R* is independently hydrogen, halogen, unsubstituted C1-C20 hydrocarbon group (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), substituted C1-C 20The hydrocarbon group, or the two or more R* may be linked to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. In some embodiments of the present disclosure, T is a bridging group and is represented by: R'2C, R'2Si, R'2Ge, R'2CCR'2, R'2CCR'2CR'2, R'2CCR'2CR'2CR'2, R'C=CR', R'C=CR'CR'2, R'2CCR'=CR'CR'2, R'C=CR'CR'=CR', R'C=CR'CR'2CR'2, R'2CSiR'2, R'2SiSiR'2, R2CSiR'2CR'2, R'2SiCR'2SiR'2, R'C=CR'SiR'2, R'2CGeR'2, R'2GeGeR'2, R'2CGeR'2CR'2, R'2GeCR'2GeR'2, R'2SiGeR'2, R'C=CR'GeR'2 , R'B, R'2C-BR', R'2C-BR'-CR'2, R'2C-0-CR'2, R'2CR'2C-O-CR'2CR'2, R'2C-O-CR'2 CR'2, R'2C-O-CR'=CR', R'2C-S-CR'2, R'2CR'2C-S-CR'2CR'2, R'2C-S-CR'2CR'2, R'2 C-S-CR'=CR', R'2C-Se-CR'2, R'2CR'2C-Se-CR'2CR'2, R'2C-Se-CR2CR'2, R'2C-Se-C R'=CR', R'2C-N=CR', R'2C-NR'-CR'2, R'2C-NR'-CR'2CR'2, R'2C-NR'-CR'=CR'R'CR'C NR'CR'CR'R'C P CR', or R'2C-PR'-CR'2, wherein each R' is independently hydrogen or unsubstituted C1-C 20 hydrocarbon groups (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), substituted C1-C 20 Hydrocarbon, C1-C 20 Halogenated hydrocarbon, C1-C 20 Silylcarbyl, or C1-C 20Germylcarbyl substituents, or two or more adjacent R's are connected to form substituted or unsubstituted saturated, partially unsaturated or aromatic, cyclic or polycyclic substituents. In some embodiments of the present disclosure, T is a bridging group including carbon or silicon, such as a dialkylsilyl group; for example, T can be CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, or Si(CH2)4.

[0102] In some embodiments, R 1 is hydrogen, substituted C1-C 20 Hydrocarbon, or unsubstituted C1-C 20 Hydrocarbyl, such as substituted C1-C 12 Hydrocarbon or unsubstituted C1-C 12 Hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), for example, hydrogen, substituted C1-C6 hydrocarbyl, or unsubstituted C1-C6 hydrocarbyl.

[0103] In some embodiments, R 2 and R 4 Each of which is independently hydrogen, substituted C1-C 20 Hydrocarbon, or unsubstituted C1-C 20 Hydrocarbyl, such as substituted C1-C 12 Hydrocarbon or unsubstituted C1-C 12 Hydrocarbyl (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), for example, hydrogen, substituted C1-C6 hydrocarbyl, or unsubstituted C1-C6 hydrocarbyl.

[0104] In some embodiments, R 5 , R 6 , R 7 and R 8 Each of which is independently hydrogen, substituted C1-C 20 Hydrocarbon, or unsubstituted C1-C 20 Hydrocarbyl, such as substituted C1-C 12 Hydrocarbon or unsubstituted C1-C 12 a hydrocarbon group (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as a substituted C1-C6 hydrocarbon group, or an unsubstituted C1-C6 hydrocarbon group (such as methyl, ethyl, propyl, butyl, pentyl, or hexyl), or R 5 and R 6 , R6 and R 7 , or R 7 and R 8 One or more pairs of these may be linked to form a substituted or unsubstituted C4-C 20 Saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof.

[0105] In some embodiments, R 5 and R 6 , R 6 and R 7 , or R 7 and R 8 One or more pairs of may be linked to form a substituted or unsubstituted C5-C8 saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof.

[0106] In some embodiments, R 3 It is an unsubstituted C4-C 20 Cycloalkyl (e.g., cyclohexane, cyclopentane, cyclooctane, adamantane), or substituted C4-C 20 Cycloalkyl.

[0107] In some embodiments, R 3 It is a substituted or unsubstituted phenyl group, benzyl group, carbazolyl group, naphthyl group, or fluorenyl group.

[0108] In some embodiments, R 3 is a substituted or unsubstituted aryl group represented by Formula 6:

[0109]

[0110] Where R 9 , R 10 , R 11 , R 12 and R 13 Each of which is independently hydrogen, unsubstituted C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbon group, a heteroatom, a group containing a heteroatom, or R 9 , R 10 , R 11 , R 12 and R 13 Two or more of these are linked together to form C4-C 62 Cyclic or polycyclic ring structures, or combinations thereof.

[0111] In some embodiments of the present disclosure, R 9 , R 10 , R 11 , R 12 and R 13Each of the 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbon, unsubstituted C4-C 62 Aryl (such as unsubstituted C4-C 20 aryl, such as phenyl), substituted C4-C 62 Aryl (such as substituted C4-C 20 Aryl), unsubstituted C4-C 62 Heteroaryl (such as unsubstituted C4-C 20 Heteroaryl), substituted C4-C 62 Heteroaryl (such as substituted C4-C 20 heteroaryl), -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl. For example, R 9 , R 10 , R 11 , R 12 and R 13 Each of which is independently hydrogen, substituted C1-C 20 Hydrocarbon, or unsubstituted C1-C 20 Hydrocarbyl, such as substituted C1-C 12 Hydrocarbon or unsubstituted C1-C 12 a hydrocarbon group (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as a substituted C1-C6 hydrocarbon group, or an unsubstituted C1-C6 hydrocarbon group (such as methyl, ethyl, propyl, butyl, pentyl, or hexyl), or R 9 , R 10 , R 11 , R 12 and R 13 Two or more of the can be linked to form a substituted or unsubstituted C4-C 20 Saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof.

[0112] In some embodiments of the present disclosure, R 9 , R 10 , R 11 , R 12 and R 13 At least one of the groups is phenyl or substituted phenyl.

[0113] In some embodiments, a suitable catalyst compound may have a structure represented by Formula 7

[0114]

[0115] Among them, M, T, J 1 , J 2 , X 1 , X 2 , R 1 , R 2 , R 4 , R 5 , R 6 , R 7 and R 8 As described in Formula 1, and R 9 , R 10 , R 11 , R 12 and R 13 As described in Eq. 6.

[0116] In some embodiments, a suitable catalyst compound may have a structure represented by Formula 8:

[0117]

[0118] Where R 14 , R 15 , R 16 , R 17 , R 18 and R 19 Each of which is independently hydrogen, unsubstituted C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbon group, a heteroatom, a group containing a heteroatom, or R 14 , R 15 , R 16 , R 17 , R 18 and R 19 Two or more of are connected together to form a cyclic or polycyclic ring structure, or a combination thereof; and wherein M, T, J 1 , J 2 , X 1 , X 2 , R 1 , R 2 , R 4 , R 5 , R 6 , R 7 and R 8 As described in Formula 1, and R 9 , R 10 , R 11 , R 12 and R 13 As described in Eq. 6.

[0119] In some embodiments, R 14 , R 15 , R 16 , R 17 , R 18 and R 19 Each of the 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbon, unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl. For example, R 14 , R 15 , R 16 , R 17 , R 18 and R 19 Each of which is independently hydrogen, substituted C1-C 20 Hydrocarbon, or unsubstituted C1-C 20 Hydrocarbyl, such as substituted C1-C 12 Hydrocarbon or unsubstituted C1-C 12 a hydrocarbon group (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as a substituted C1-C6 hydrocarbon group, or an unsubstituted C1-C6 hydrocarbon group (such as methyl, ethyl, propyl, butyl, pentyl, or hexyl), or R 14 , R 15 , R 16 , R 17 , R 18 and R 19 Two or more of the can be linked to form a substituted or unsubstituted C4-C 20 Saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof.

[0120] In some embodiments of the present disclosure, a suitable catalyst compound may have a structure represented by Formula 9:

[0121]

[0122] Where R 20 , R 21 , R 22, R 23 , R 24 , R 25 , R 26 , R 27 Each of which is independently hydrogen, unsubstituted C1-C 40 Hydrocarbyl, substituted C1-C 40 A hydrocarbon group, a heteroatom, a group containing a heteroatom, or R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 Two or more of are connected together to form a cyclic or polycyclic ring structure, or a combination thereof; and wherein M, T, J 1 , J 2 , X 1 , X 2 , R 1 , R 2 , R 4 , R 5 , R 6 , R 7 and R 8 As described in Formula 1, and R 9 , R 10 , R 11 , R 12 and R 13 As described in Eq. 6.

[0123] In some embodiments, R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 Each of the 40 Hydrocarbyl, substituted C1-C 40 Hydrocarbon, unsubstituted C4-C 62 Aryl, substituted C4-C 62 Aryl, unsubstituted C4-C 62 Heteroaryl, substituted C4-C 62 heteroaryl, -NR'2, -SR', -OR, -SiR'3, -OSiR'3, -PR'2, or -R"-SiR'3, wherein R" is C1-C 10 Alkyl and each R' is hydrogen, halogen, C1-C 10 Alkyl, or C6-C 10 Aryl. For example, R20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 Each of which is independently hydrogen, substituted C1-C 20 Hydrocarbon, or unsubstituted C1-C 20 Hydrocarbyl, such as substituted C1-C 12 Hydrocarbon or unsubstituted C1-C 12 a hydrocarbon group (such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl), such as a substituted C1-C6 hydrocarbon group, or an unsubstituted C1-C6 hydrocarbon group (such as methyl, ethyl, propyl, butyl, pentyl, or hexyl), or R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 Two or more of the can be linked to form a substituted or unsubstituted C4-C 20 Saturated or unsaturated cyclic or polycyclic ring structures, or combinations thereof.

[0124] In a non-limiting example, a suitable catalyst compound may have a structure represented by the following formula.

[0125]

[0126]

[0127]

[0128] In at least one embodiment, the polymerization can be carried out 1) at a temperature of about 0°C to about 300°C, or about 25°C to about 150°C, or about 40°C to 120°C, or about 45°C to about 80°C; 2) at a pressure of atmospheric pressure to about 10 MPa, or about 0.35 MPa to about 10 MPa, or about 0.45 MPa to about 6 MPa, or about 0.5 MPa to about 4 MPa; 3) in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane and mixtures thereof; such as wherein the aromatic compound may be present in the solvent at less than 1 wt %, such as less than 0.5 wt %, such as 0 wt % based on the weight of the solvent); 4) wherein the catalyst system used in the polymerization comprises less than 0.5 mol %, such as 0 mol % of aluminoxane, alternatively aluminoxane is present in an aluminoxane ratio of less than 500:1, such as less than 300:1, or less than 100:1, or less than 1:1. 5) the polymerization is carried out in one reaction zone; 6) the productivity of the catalyst compound is at least 80,000 g / mmol / hour (such as at least 150,000 g / mmol / hour, or at least 200,000 g / mmol / hour, or at least 250,000 g / mmol / hour, or at least 300,000 g / mmol / hour); 7) optionally, there is no scavenger (such as a trialkylaluminum compound) (e.g., present at 0 mol%, alternatively The scavenger is present in a molar ratio of scavenger metal to transition metal of less than 100: 1, such as less than 50: 1, or less than 15: 1, or less than 10: 1); and / or 8) optionally hydrogen may be present in the polymerization reactor at a partial pressure of 0.001 psig to 50 psig (0.007 kPa to 345 kPa) (such as 0.01 psig to 25 psig (0.07 kPa to 172 kPa), or 0.1 psig to 10 psig (0.7 kPa to 70 kPa)). In at least one embodiment, the catalyst system used in the polymerization comprises no more than one catalyst compound. A "reaction zone", also referred to as a "polymerization zone", is a container in which polymerization occurs, such as a batch reactor. When multiple reactors are used in a series or parallel configuration, each reactor is considered to be a separate polymerization zone. For multi-stage polymerization in both batch reactors and continuous reactors, each polymerization stage is considered to be a separate polymerization zone. In at least one embodiment, polymerization is carried out in one reaction zone.

[0129] As desired, other additives discussed herein may also be used in the polymerization, such as one or more scavengers, promoters, modifiers, reducing agents, oxidizing agents, hydrogen, alkyl aluminums, silanes, or chain transfer agents (such as alkyl aluminoxanes, compounds represented by the formula AlR3 or ZnR2 (wherein each R is independently a C1-C8 aliphatic group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof) or combinations thereof, such as diethyl zinc, methyl aluminoxane, trimethyl aluminum, triisobutyl aluminum, trioctylaluminum, or combinations thereof).

[0130] The catalyst system described herein may include a catalyst and an activator as described above, such as aluminoxane or a non-coordinating anion, and may be formed by combining the catalyst components described herein with an activator in any suitable manner (including combining them with a carrier such as silica). The catalyst system may also be added to a solution polymerization or bulk polymerization (in a monomer) or generated therein. The catalyst system of the present disclosure may have one or more activators and one, two, or more catalyst components. An activator is defined as any compound that can activate any of the catalyst compounds described above by converting a neutral metal compound into a catalytically active metal compound cation. Non-limiting activators may include, for example, aluminoxanes, alkyl aluminums, ionizing activators (which may be neutral or ionic) and conventional types of cocatalysts. Suitable activators may include aluminoxane compounds, modified aluminoxane compounds, and ionizing anion precursor compounds that capture metal ligands to make the metal compound a cation and provide a non-coordinating or weakly coordinating anion, for example, a non-coordinating anion, for charge balance.

[0131] In at least one embodiment, the catalyst system may include an activator and a catalyst compound as defined above.

[0132] Aluminoxane activators can be used as activators in the catalyst systems described herein. Aluminoxanes are typically oligomeric compounds containing -Al(Ra)-O- subunits, where Ra is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, such as when the extractable ligand is an alkyl, halide, alkoxy or amino group. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. It can be appropriate to use visually clear methylaluminoxane. Turbid or gelled aluminoxanes can be filtered to produce a clear solution or a clear aluminoxane can be decanted from a turbid solution. A useful aluminoxane is modified methylalumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name ModifiedMethylalumoxane type 3A, covered in patent number US 5,041,584, which is incorporated herein by reference). Another useful aluminoxane is a solid polymethylaluminoxane as described in US 9,340,630, US 8,404,880 and US 8,975,209, which are incorporated herein by reference.

[0133] When the activator is an aluminoxane (modified or unmodified), at least one embodiment selects a maximum amount of activator at up to a 5,000-fold molar excess of Al / M relative to the catalyst compound (per metal catalytic site). The minimum activator to catalyst compound ratio may be a 1:1 molar ratio. Alternative ranges may include 1:1 to 500:1, or 1:1 to 200:1, or 1:1 to 100:1, or 1:1 to 50:1.

[0134] In alternative embodiments, little or no alumoxane is used in the polymerization methods described herein. For example, the alumoxane may be present at 0 mol%, alternatively the alumoxane may be present at a molar ratio of aluminum to the catalyst compound transition metal of less than 500:1, such as less than 300:1, or less than 100:1, or less than 1:1.

[0135] The term "non-coordinating anion" (NCA) means an anion that does not coordinate with a cation or only weakly coordinates with a cation so as to remain sufficiently unstable to be displaced by a Lewis base. "Compatible" non-coordinating anions are those that do not degrade to neutrality when the initially formed complex decomposes. In addition, the anion will not transfer anionic substituents or fragments to the cation, thereby causing it to form a neutral transition metal compound and neutral byproducts from the anion. Non-coordinating anions useful according to the present disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge with +1 and still remain sufficiently unstable to allow displacement during polymerization. Suitable ionizing activators can include NCAs, such as compatible NCAs.

[0136] It is within the scope of the present disclosure to use neutral or ionic ionizing activators. It is also within the scope of the present disclosure to use neutral or ionic activators alone or in combination with aluminoxane or modified aluminoxane activators. Suitable activators are described in US 8,658,556 and US 6,211,105.

[0137] The catalyst system of the present disclosure may include at least one non-coordinating anion (NCA) activator. In at least one embodiment, a boron-containing NCA activator represented by Formula 10 may be used:

[0138] Z d+ (A d- )

[0139] Formula 10

[0140] wherein Z is (LH) or a reducible Lewis acid; L is a Lewis base; H is hydrogen; (LH) is a Bronsted acid; A d - is a non-coordinating boron-containing anion having a charge of d-; and d is 1, 2, or 3.

[0141] Cationic component Z d+ A Bronsted acid may be included, such as a proton or protonated Lewis base or a reducible Lewis acid, which is capable of protonating or abstracting a moiety (such as an alkyl or aryl group) from a bulky ligand transition metal catalyst precursor, generating a cationic transition metal species.

[0142] Activated cation Z d+ It can also be a structural part, such as silver, onium, carbonium, ferrocenium and mixtures such as carbonium and ferrocenium. d+ The reducible Lewis acid may be a triphenylcarbonium. The reducible Lewis acid may be a triarylcarbonium (wherein the aryl group may be substituted or unsubstituted, such as those represented by the following formula: (Ar3C + ), wherein Ar is an aromatic group or is substituted by a heteroatom, C1 to C 40Hydrocarbyl, or substituted C1 to C 40 Hydrocarbyl-substituted aryl), such as a reducible Lewis acid "Z" may include those represented by the formula: (Ph3C), wherein Ph is a substituted or unsubstituted phenyl, such as substituted with C1 to C 40 Hydrocarbyl or substituted C1 to C 40 Hydrocarbon groups, such as C1 to C 20 Alkyl or aromatic compounds or substituted C1 to C 20 Alkyl or aromatic compounds, such as Z is triphenylcarbonium.

[0143] When Z d+ Is the activating cation (LH) d When the catalytic precursor is oxidized to a catalytic reaction product, it may be a Bronsted acid capable of donating a proton to the transition metal catalytic precursor to produce a transition metal cation, including ammonium, oxonium, phosphonium, silylium and mixtures thereof, such as ammonium from methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, di-octadecylmethylamine, phosphonium from triethylphosphine, triphenylphosphine and diphenylphosphine, oxonium from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, sulfonium from sulfide ethers such as diethyl sulfide, tetrahydrothiophene and mixtures thereof.

[0144] Anionic component A d- Including having the formula [M k+ Q n ] d- Those wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (such as 1, 2, 3, or 4); nk = d; M is an element selected from Group 13 of the Periodic Table of Elements, such as boron or aluminum, and Q is independently hydrogen, bridged or non-bridged dialkylamido, halo, alkoxy, aryloxide, hydrocarbon, substituted hydrocarbon, halohydrocarbon, substituted halohydrocarbon, and halogen-substituted hydrocarbon, wherein Q has up to 50 (such as up to 20) carbon atoms, optionally with the proviso that Q is halo in no more than 1 occurrence. Each Q may be a fluorinated hydrocarbon having 1 to 50 (such as 1 to 20) carbon atoms, such as each Q is a fluorinated aryl, and such as each Q is a pentafluoroaryl. Suitable A d- Examples also include diboron compounds as disclosed in US 5,447,895 (which is incorporated herein by reference in its entirety).

[0145] Illustrative but non-limiting examples of boron compounds that can be used as activating co-catalysts are the compounds described as activators in US 8,658,556, which is incorporated herein by reference.

[0146] Ionic stoichiometric activator Z d+ (A d- ) can be one or more of N,N-dimethylanilinium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, dioctadecylmethylammonium tetrakis(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbonium tetrakis(perfluoronaphthyl)borate, triphenylcarbonium tetrakis(perfluorobiphenyl)borate, triphenylcarbonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, or triphenylcarbonium tetrakis(perfluorophenyl)borate.

[0147] Bulk activators may also be used as NCAs herein. As used herein, "bulky activators" refer to anionic activators represented by Formulas 11 and 12:

[0148]

[0149] Each R A Ar is independently a halogen group, such as a fluoro group; Ar is a substituted or unsubstituted aryl group (such as a substituted or unsubstituted phenyl group), such as a substituted C1 to C 40 Hydrocarbon groups, such as C1 to C 20 Alkyl or aromatic compound; each R B are independently halogen, C6 to C 20 Substituted aromatic hydrocarbon or -O-Si-R D silyloxy, where R D C1 to C 20 Hydrocarbyl or hydrocarbyl silyl (such as R B is a fluoro group or a perfluorinated phenyl group); each R C Is a halogen, C6 to C 20 Substituted aromatic hydrocarbon or -O-Si-R D silyloxy, where R D C1 to C 20 Hydrocarbyl or hydrocarbyl silyl (such as R D is a fluoro group or a C6 perfluorinated aromatic hydrocarbon group); wherein R B and R C One or more saturated or unsaturated, substituted or unsubstituted rings (such as R B and R C forming a perfluorinated phenyl ring); L is a Lewis base; (LH) +is a Bronsted acid; d is 1, 2, or 3; wherein the anion has a molecular weight greater than 1,020 g / mol; and wherein at least three of the substituents on the B atom each have a molecular weight greater than Alternatively, greater than or alternatively greater than The molecular volume of .

[0150] For example, (Ar3C) d Can be (Ph3C) d , wherein Ph is a substituted or unsubstituted phenyl group, such as substituted with C1 to C 40 Hydrocarbyl substituted or substituted C1 to C 40 Hydrocarbon groups, such as C1 to C 20 Alkyl or aromatic compounds or substituted C1 to C 20 Alkyl or aromatic compounds.

[0151] "Molecular volume" is used herein as an approximation of the spatial volume of the activator molecule in solution. Comparison of substituents having different molecular volumes allows a substituent having a smaller molecular volume to be considered "less bulky" than a substituent having a larger molecular volume. Conversely, a substituent having a larger molecular volume can be considered "more bulky" than a substituent having a smaller molecular volume.

[0152] Molecular volume can be calculated as reported in Girolami, GS, "A Simple "Back of the Envelope" Method for Estimating the Densities and Molecular Volumes of Liquids and Solids," Journal of Chemical Education, Vol. 71(11), November 1994, pp. 962-964, which is incorporated herein by reference. Molecular volume (MV), in cubic A, is calculated using the following formula: MV = 8.3 V S , where V S is the scaled volume. S is the sum of the relative volumes of the constituent atoms and is calculated from the molecular formula of the substituents using the following table of relative volumes.

[0153] For fused rings, V of each fused ring S Reduced by 7.5%.

[0154] element Relative volume H 1 The first short period, Li to F 2 Second short cycle, Na to Cl 4 The first long cycle, K to Br 5 The second long cycle, Rb to I 7.5 3rd long period, Cs to Bi 9

[0155] Suitable bulky activators are further described in US 8,658,556, which is incorporated herein by reference.

[0156] In another embodiment, one or more of the NCA activators are selected from the activators described in US 6,211,105.

[0157] In at least one embodiment, the activator is selected from one or more of triarylcarbeniums such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate.

[0158] In at least one embodiment, the activator is selected from one or more of the following: trialkylammonium tetrakis (pentafluorophenyl) borate, N,N-dialkylanilinium tetrakis (pentafluorophenyl) borate, di-octadecylmethylammonium tetrakis (pentafluorophenyl) borate, di-octadecylmethylammonium tetrakis (perfluoronaphthyl) borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trialkylammonium tetrakis - (2,3,4,6-tetrafluorophenyl) borate, N,N-dialkylanilinium tetrakis - (2,3,4,6-tetrafluorophenyl) borate, trialkylammonium tetrakis (perfluoronaphthyl) borate , N,N-dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N,N-dialkylanilinium tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, N,N-dialkyl-(2,4,6-trimethylanilinium)tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(isopropyl)ammonium tetrakis(pentafluorophenyl)borate, (wherein the alkyl group is methyl, ethyl, propyl, n-butyl, sec-butyl, or tert-butyl).

[0159] In particularly useful embodiments, the activator is soluble in a non-aromatic hydrocarbon solvent such as an aliphatic solvent.

[0160] In one or more embodiments, a 20 wt % mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25°C, preferably a 30 wt % mixture of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25°C.

[0161] In at least one embodiment, little or no alumoxane is used in the process for producing the polymer. The alumoxane may be present at 0 mol%, alternatively the alumoxane may be present at a molar ratio of aluminum to transition metal of less than 500:1, such as less than 300:1, or less than 100:1, or less than 1:1.

[0162] In at least one embodiment, little or no scavenger is used in the process for producing ethylene polymers. For example, the scavenger (such as a trialkylaluminum) can be present at 0 mol%, alternatively the scavenger can be present at a molar ratio of scavenger metal to transition metal of less than 100: 1, such as less than 50: 1, or less than 15: 1, or less than 10: 1.

[0163] In one or more embodiments, the activators described herein have a solubility of greater than 10 mM, or greater than 20 mM, or greater than 50 mM in methylcyclohexane at 25°C (stirring for 2 hours) and / or a solubility of greater than 1 mM, or greater than 10 mM, or greater than 20 mM in isohexane at 25°C (stirring for 2 hours).

[0164] In a preferred embodiment, the activator is a non-aromatic hydrocarbon soluble activator compound.

[0165] Non-aromatic hydrocarbon-soluble activator compounds useful herein include those represented by Formula 13:

[0166] [R 1 'R 2 'R 3 'EH] d+ [Mt k+ Q n ] d-

[0167] Formula 13

[0168] wherein E is nitrogen or phosphorus; d is 1, 2 or 3; k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6; nk = d (preferably d is 1, 2 or 3; k is 3; n is 4, 5 or 6); R 1 '、R 2 ' and R 3 ' is independently a C1 to C12 group optionally substituted by one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups 50 Hydrocarbyl, where R 1 , R 2 and R 3together contain 15 or more carbon atoms; Mt is an element selected from Group 13 of the Periodic Table of Elements, such as B or Al, preferably boron; and each Q is independently hydrogen, a bridged or non-bridged dialkylamido, a halo, an alkoxy, an aryloxy, a hydrocarbon, a substituted hydrocarbon, a halohydrocarbon, a substituted halohydrocarbon, or a halogen-substituted hydrocarbon.

[0169] Non-aromatic hydrocarbon soluble activator compounds useful herein include those represented by Formulas 14 and 15:

[0170]

[0171] N is nitrogen; R 2 ' and R 3 ' is independently a C6-C6 group optionally substituted by one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups 40 Hydrocarbyl, where R 2 ' and R 3 ' (if present) together contain 14 or more carbon atoms; R 8 '、R 9 ' and R 10 'Independently C4-C 30 Hydrocarbon or substituted C4-C 30 hydrocarbon group; B is boron; and R 4 '、R 5 '、R 6 ' and R 7 ' is independently hydrogen, bridged or non-bridged dialkylamido, halo, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, or halo-substituted hydrocarbyl.

[0172] Optionally, R 4 '、R 5 '、R 6 ' and R 7 ' can be pentafluorophenyl or pentafluoronaphthyl.

[0173] Optionally, R 8 ' and R 10 ' is a hydrogen atom and R 9 ' is a C4-C ... 30 Optionally, R 9 ' is a C8-C8 group optionally substituted by one or more alkoxy groups, silyl groups, halogen atoms, or halogen-containing groups 22 Optionally, R 2 ' and R 3 'Independently is C 12 -C 22Hydrocarbon.

[0174] Optionally, R 1 '、R 2 ' and R 3 'Together contain 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms).

[0175] Optionally, R 2 ' and R 3 'Together contain 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms).

[0176] Optionally, R 8 '、R 9 ' and R 10 'Together contain 15 or more carbon atoms (such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 38 or more carbon atoms, such as 40 or more carbon atoms, such as 15 to 100 carbon atoms, such as 25 to 75 carbon atoms).

[0177] Optionally, when Q is fluorophenyl, then R 2 'Not C1-C 40 Straight chain alkyl (alternatively R 2 ' is not optionally substituted C1-C 40 Straight chain alkyl).

[0178] Optionally, R 4 '、R 5 '、R 6 ' and R 7 ' is an aryl group (such as phenyl or naphthyl), wherein R 4 '、R 5 '、R 6 ' and R 7 ' is substituted by at least one fluorine atom, preferably R 4 '、R5 '、R 6 ' and R 7 Each of ' is a perfluoroaryl group (such as a perfluorophenyl group or a perfluoronaphthyl group).

[0179] Optionally, each Q is an aryl group (such as phenyl or naphthyl), wherein at least one Q is substituted with at least one fluorine atom, and preferably each Q is a perfluoroaryl group (such as perfluorophenyl or perfluoronaphthyl).

[0180] Optionally, R 1 ' is methyl; R 2 'It is C6-C 50 aryl; and R 3 'Independently C1-C 40 Straight chain alkyl or C5-C 50 -Aryl.

[0181] Optionally, R 2 ' and R 3 Each of ' is independently unsubstituted or substituted with halogen, C1-C 35 Alkyl, C5-C 15 Aryl, C6-C 35 Arylalkyl, C6-C 35 At least one substituted alkylaryl group, wherein R 2 ' and R 3 'together contain 20 or more carbon atoms.

[0182] Optionally, each Q is independently hydrogen, bridged or non-bridged dialkylamido, halo, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl, or halo-substituted hydrocarbyl, provided that when Q is fluorophenyl, then R 2 'Not C1-C 40 Straight chain alkyl, preferably R 2 ' is not optionally substituted C1-C 40 Straight chain alkyl (alternatively when Q is substituted phenyl, then R 2 'Not C1-C 40 Straight chain alkyl, preferably R 2 ' is not optionally substituted C1-C 40 Optionally, when Q is fluorophenyl (alternatively when Q is substituted phenyl), then R 2 ' is a meta- and / or para-substituted phenyl group, wherein the meta- and para-substituents are independently optionally substituted C1 to C 40 Hydrocarbyl (such as C6 to C 40 Aryl or linear alkyl, C 12 To C 30 Aryl or linear alkyl, or C 10To C 20 aryl or linear alkyl), optionally substituted alkoxy, or optionally substituted silyl. Optionally, each Q is a fluorinated hydrocarbon group having 1 to 30 carbon atoms, more preferably each Q is a fluorinated aryl group (such as phenyl or naphthyl), and most preferably each Q is a perfluorinated aryl group (such as phenyl or naphthyl). Suitable [Mt k+ Q n ] d- Examples of also include diboron compounds as disclosed in U.S. Patent No. 5,447,895 (which is incorporated herein by reference in its entirety). Optionally, at least one Q is not substituted phenyl. Optionally, all Q are not substituted phenyl. Optionally, at least one Q is not perfluorophenyl. Optionally, all Q are not perfluorophenyl.

[0183] In some embodiments, R 1 'Not methyl, R 2 'Not C 18 Alkyl and R 3 'Not C 18 Alkyl, alternatively R 1 'Not methyl, R 2 'Not C 18 Alkyl and R 3 'Not C 18 alkyl, and at least one Q is not substituted phenyl, optionally all Q are not substituted phenyl.

[0184] Usable cationic components include those represented by the following formulae.

[0185]

[0186]

[0187] The anionic component of the activator described herein preferably comprises a k+ Q n ] -Those represented by , wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4), (preferably k is 3; n is 4, 5, or 6, preferably when M is B, n is 4); Mt is an element selected from Group 13 of the Periodic Table of Elements, preferably boron or aluminum, and Q is independently hydrogen, bridged or non-bridged dialkylamido, halo, alkoxy, aryloxy, hydrocarbon, substituted hydrocarbon, halohydrocarbon, substituted halohydrocarbon and halogen-substituted hydrocarbon, said Q having up to 20 carbon atoms, provided that Q is halo in no more than 1 occurrence. Preferably, each Q is a fluorinated hydrocarbon optionally having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl, and most preferably each Q is a perfluorinated aryl. Preferably at least one Q is not substituted phenyl, such as perfluorophenyl, preferably all Q are not substituted phenyl, such as perfluorophenyl.

[0188] Particularly useful activators include N-methyl-4-nonadecyl-N-octadecylanilinium tetrakis(pentafluorophenyl)borate, N-methyl-4-nonadecyl-N-octadecylanilinium tetrakis(perfluoronaphthyl)borate, and those disclosed in US2019 / 0330139 and US2019 / 0330392.

[0189] All NCA activator to catalyst ratios may be about a 1:1 molar ratio. Alternative ranges include 0.1:1 to 100:1, or 0.5:1 to 200:1, or 1:1 to 500:1, or 1:1 to 1000:1. A suitable range may be 0.5:1 to 10:1, such as 1:1 to 5:1.

[0190] It is also within the scope of the present disclosure that the catalyst compound may be combined with a combination of aluminoxane and NCA (see, for example, US 5,153,157; ​​US 5,453,410; EP 0573120 Bl; WO 1994 / 007928; and WO 1995 / 014044, which discuss the use of aluminoxanes in combination with ionizing activators).

[0191] Useful chain transfer agents may include hydrogen, alkylaluminoxanes, compounds represented by the formula AlR3, ZnR2 (wherein each R is independently a C1-C8 aliphatic group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or an isomer thereof) or combinations thereof, such as diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or combinations thereof.

[0192] Additionally, the catalyst system of the present disclosure may include a metal hydrocarbenyl chain transfer agent represented by Formula 16:

[0193] Al(R') 3-v (R”)v

[0194] Formula 16

[0195] Where each R' can independently be C1-C 30 hydrocarbon group, and / or each R" may independently be a C4-C 20 hydrocarbenyl; and v may be from 0.1 to 3.

[0196] In addition to these activator compounds, scavengers or co-activators may also be used. Alkyl aluminum or aluminoxane compounds that may be used as scavengers or co-activators may include, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diisobutyl aluminum hydride, methylaluminoxane (MAO), modified methylaluminoxane (MMAO), MMAO-3A, ​​and diethyl zinc.

[0197] The catalyst system may include an inert support material. The support material may be a porous support material, for example, talc and an inorganic oxide. Other support materials include zeolites, clays, organoclays, or other organic or inorganic support materials, or mixtures thereof.

[0198] The support material can be an inorganic oxide in finely divided form. Suitable inorganic oxide materials for the catalyst system herein can include metal oxides of Groups 2, 4, 13 and 14, such as silica, alumina and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina can be magnesium oxide, titanium dioxide, zirconium oxide. However, other suitable support materials can be used, for example, finely divided functionalized polyolefins, such as finely divided polyethylene. Examples of suitable supports can include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, phyllosilicate, zeolite, talc, clay. In addition, combinations of these support materials can be used, for example, silica-chromium, silica-alumina, silica-titania. In at least one embodiment, the support material is selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, SiO2 / TiO2, silica clay, silica / clay, or a mixture thereof.

[0199] Support materials, such as inorganic oxides, may have a surface area of ​​about 10 m 2 / g to about 700m 2 / g surface area, about 0.1cm 3 / g to about 4.0cm 3 / g pore volume and an average particle size of about 5 mm to about 500 mm. The surface area of ​​the support material can be about 50 m 2 / g to about 500m 2 / g, about 0.5cm 3 / g to about 3.5cm 3 / g pore volume and an average particle size of about 10 pm to about 200 mm. For example, the surface area of ​​the support material can be about 100 m 2 / g to about 400m 2 / g, the pore volume can be about 0.8cm 3 / g to about 3.0cm 3 / g and the average particle size may be from about 5 pm to about 100 pm. The average pore size of the support material may be to Such as to about or to about In at least one embodiment, the support material can be a high surface area amorphous silica (surface area = 300 m 2 / gm; 1.65cm 3 For example, suitable silicas are available from the Davison Chemical Division of WR Grace and Company under the trade name DAVISON TM 952 or DAVISON TM 955. In other embodiments, DAVISON TM 948. Alternatively, the silica may be, for example, ES-70 which has been calcined (such as at 875°C). TM Silica (PQ Corporation, Malvern, Pennsylvania).

[0200] The support material may be dry, i.e., free of absorbed water. Drying of the support material may be achieved by heating or calcining at about 100°C to about 1,000°C, such as at least about 600°C. When the support material is silica, the silica may be heated to at least 200°C, such as about 200°C to about 850°C, and such as at about 600°C; and for a period of about 1 minute to about 100 hours, about 12 hours to about 72 hours, or about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl groups (OH) to produce the supported catalyst system of the present disclosure. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0201] The carrier material with reactive surface groups such as hydroxyl groups can be slurried in a non-polar solvent, and the resulting slurry can be contacted with a solution of a catalyst compound and an activator. In at least one embodiment, the slurry of the carrier material is first contacted with an activator for a period of about 0.5 hour to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. Then the solution of the catalyst compound is contacted with the carrier / activator separated. In at least one embodiment, the supported catalyst system can be generated in situ. In an alternative embodiment, the slurry of the carrier material is first contacted with a catalyst compound for a period of about 0.5 hour to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. Then the slurry of the supported catalyst compound is contacted with an activator solution.

[0202] The mixture of catalyst, activator and support can be heated from about 0° C. to about 70° C., such as from about 23° C. to about 60° C., such as at room temperature. The contact time can be about 0.5 hours to about 24 hours, such as about 2 hours to about 16 hours, or about 4 hours to about 8 hours.

[0203] Suitable non-polar solvents are materials in which all reactants used herein (e.g., activators and catalyst compounds) are at least partially soluble and are liquid at the reaction temperature. Non-polar solvents can include alkanes such as isopentane, hexane, n-heptane, octane, nonane, and decane, but a variety of other materials can also be used, including cycloalkanes such as cyclohexane, aromatic compounds such as benzene, toluene, and ethylbenzene.

[0204] Foamable composition, foaming agent, foaming product and foaming method

[0205] The present disclosure describes a foamable composition comprising: having a g′ of about 0.93 or less, or about 0.8 or less. vis A branched polypropylene copolymer; and a blowing agent blended with the branched polypropylene copolymer, wherein the branched polypropylene copolymer comprises a polymerization reaction product of propylene and an α,ω-diene having five or more carbon atoms. The foamed product can be produced by converting the foamable composition into a foamed form. Any of the aforementioned branched polypropylene copolymers may be present therein.

[0206] The foamable composition, foamed product and foaming method disclosed in the present invention can utilize a foaming agent to cause expansion of the branched polypropylene copolymer by foaming under specified conditions.

[0207] Suitable blowing agents may include both physical blowing agents and chemical blowing agents. Chemical blowing agents include, but are not limited to, azodicarbonamide, azobisisobutyronitrile, benzenesulfonylhydrazide, 4,4-oxybenzenesulfonylsemicarbazide, p-toluenesulfonylsemicarbazide, barium azodicarboxylate, N,N′-dimethyl-N,N′-dinitrosoterephthalamide, trihydrazinotriazine, nitroso compounds such as N,N′-dimethyl-N,N′-dinitrosoterephthalamide and N,N′-dinitrosopentamethylenetetramine; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexanecarbonitrile, azodiaminobenzene and barium azodicarboxylate; sulfonylhydrazide compounds such as benzenesulfonylhydrazide, toluenesulfonylhydrazide, p,p′-oxybis(benzenesulfonylhydrazide) and diphenylsulfone-3,3′-disulfonylhydrazide; and azide compounds such as calcium azide, 4,4′-diphenyldisulfonyl azide and p-toluenesulfonyl azide.

[0208] Suitable chemical blowing agents also include organic blowing agents, which include aliphatic hydrocarbons having 1-9 carbon atoms, halogenated aliphatic hydrocarbons having 1-4 carbon atoms, and aliphatic alcohols having 1-3 carbon atoms. Aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, isobutylene, n-pentane, isopentane, neopentane, etc. Chemical blowing agents also include halogenated hydrocarbons, such as chlorofluorocarbons, hydrochlorofluorocarbons, and preferably, fluorinated hydrocarbons. Examples of fluorinated hydrocarbons include fluoromethane; perfluoromethane; fluoroethane; 1,1-difluoroethane (HFC-152a); 1,1,1-trifluoroethane (HFC-143a); 1,1,1,2-tetrafluoro-ethane (HFC-134a); pentafluoroethane; perfluoroethane; 2,2-difluoropropane; 1,1,1-trifluoropropane; perfluoropropane; perfluorobutane; and perfluorocyclobutane. Partially halogenated chlorocarbons and chlorofluorocarbons for use in the present invention include methyl chloride; methylene chloride; ethyl chloride; 1,1,1-trichloroethane; 1,1-dichloro-1-fluoroethane (HCFC-141b); 1-chloro-1,1-difluoroethane (HCFC-142b); 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123); and 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124). Fully halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC-11); dichlorodifluoromethane (CFC-12); trichlorotrifluoroethane (CFC-113); dichlorotetrafluoroethane (CFC-114); chloroheptafluoropropane; and dichlorohexafluoropropane. Fully halogenated chlorofluorocarbons are not preferred. Aliphatic alcohols useful as blowing agents include methanol, ethanol, n-propanol and isopropanol.

[0209] Suitable inorganic blowing agents include, but are not limited to, carbon dioxide, nitrogen, argon, water, air, nitrogen and helium and combinations thereof. Inorganic blowing agents also include sodium bicarbonate; sodium carbonate; ammonium bicarbonate; ammonium carbonate; and ammonium nitrite. Preferably, the foamable composition may contain nitrogen, n-butane, isobutane, n-pentane, isopentane, carbon dioxide, or any combination thereof in a suitable amount as a blowing agent.

[0210] The amount of blowing agent incorporated into the foamable composition may range from about 0.01 wt% to about 10 wt% and preferably from about 0.1 wt% to about 5 wt% based on the total mass of the foamable composition. The amount of blowing agent may be varied to obtain a desired foam density and / or cell size.

[0211] A foaming aid can be used together with a foaming agent. The simultaneous use of a foaming agent and a foaming aid can help reduce the decomposition temperature of the foaming agent, accelerate decomposition, and homogenize bubbles. Examples of foaming aids may include organic acids such as salicylic acid, phthalic acid, stearic acid, and nitric acid, urea, and derivatives thereof. Based on the total mass of the foamable composition, the amount of the foaming aid incorporated into the foamable composition may be in the range of about 0.01 wt % to about 10 wt %, and preferably about 0.1 wt % to about 5 wt %, more preferably about 0.5 wt % to about 3 wt %.

[0212] The foamed products described herein may have a foaming capacity of at least about 0.02 kg / cm 3 The density of the foam is determined according to ASTM D1622-08.

[0213] The foamed product may comprise a foamed form having open cells, closed cells, or any combination thereof. The percentage of open or closed cells in the foamed product may be determined according to ASTM D2856-A.

[0214] According to ASTM D3576-04, foamed products produced using the blends described herein typically have an average cell diameter of about 75 μm or less, preferably about 10 μm to about 75 μm, or about 15 μm to about 70 μm.

[0215] The foamed products described herein have a thermal conductivity of about 10 at a temperature of about 120°C to about 180°C as measured by ASTM D1622-08. 7 Up to 10 8 Cells / cm 3 The foamed form may have a cell density of about 0.1 g / cm 3 The bulk density.

[0216] In other cases, the foamed products described herein can have an expansion ratio of about 30 to about 40 in a temperature range of about 110° C. to about 180° C. as determined according to ASTM D792-13. The expansion ratio can be measured by dividing the density of the foamed form by the density of the polypropylene from which it is derived. The foamed product can have a maximum expansion ratio in a temperature range of about 130° C. to about 155° C.

[0217] Polyolefin foams are typically made by an extrusion process. Preferably, the extruder is longer than standard types, typically with an overall L / D (length to diameter) ratio > 40 in a single extruder or tandem extruder configuration. Melt temperature is one parameter that may affect foam extrusion. Preferably, the melt temperature is in the range of about 130°C to 180°C.

[0218] Foamed products can be produced by a foamable composition by a variety of methods such as compression molding, injection molding, and mixing of extrusion and molding. These methods may include mixing the branched polypropylene copolymer under heating to form a melt, together with a foaming agent and other typical additives, to obtain a uniform or non-uniform blend. These ingredients can be mixed and blended by any means known in the art (such as with Banbury, a powerful mixer, a double-roll mill, an extruder, etc.). Time, temperature, and shear rate can be adjusted to ensure optimal dispersion without premature foaming. For example, too high a mixing temperature may lead to premature foaming due to the decomposition of the foaming agent or to cell collapse due to lack of stabilization of the structure. In contrast, when the melt temperature is too low, foaming may be limited because the material solidifies before the cell is likely to expand completely. Sufficient temperature is expected to promote good mixing of polymers and dispersion of other ingredients. The upper temperature limit for safe operation may depend on the initial decomposition temperature of the foaming agent used. The decomposition temperature of some foaming agents is lower than the melt temperature of the polymer. In this case, the polymer can be melt blended before being mixed with one or more other ingredients. The resulting mixture can then be mixed with these ingredients. An extruder with graded cooling / heating can also be used. The latter half of the foam extruder is dedicated to melt cooling and intimate mixing of the polymer-foaming agent system. After mixing, molding can be performed. Sheeting rollers or calendering rollers are generally used to make sheets of appropriate size for foaming. An extruder can be used to mold the composition into pellets. Foaming can be performed in a compression mold at a certain temperature and time to complete the decomposition of the foaming agent. Pressure, molding temperature and heating time can be controlled. Foaming can also be performed in an injection molding device by using a foam composition in the form of pellets. The resulting foam can be further molded into the size of the finished product by any means known in the art (such as by thermoforming and compression molding).

[0219] Optionally, a nucleating agent may be blended in the polymer melt.The feed rates of the blowing agent and the nucleating agent may be adjusted to achieve a relatively low density foam and a small cell size, which results in a foam with thin cell walls.

[0220] In a non-limiting embodiment, the in-situ branched polypropylene copolymers in the reactor can be used to produce injection molded parts for automobiles, such as door panels, consoles, armrests, instrument panels, seats, and headliners; especially where the parts include a foamed core covered by a soft-touch but scratch-resistant skin. Such parts can be formed by producing the core and skin using separate injection molding operations, or can be produced in a single injection molding operation using a commercially available multi-shot injection molding machine.

[0221] Those skilled in the art will appreciate that the steps outlined above may vary depending on the desired results. For example, the foamable compositions of the present disclosure may be directly thermoformed or blow molded without cooling, thereby skipping the cooling step. Other parameters may also be varied in order to obtain a foamed product with desired characteristics.

[0222] Additional embodiments

[0223] Embodiments disclosed herein include:

[0224] A. A foamable composition. The foamable composition comprises: a g′ having a g′ of about 0.93 or less vis A branched polypropylene copolymer; and a blowing agent blended with the branched polypropylene copolymer; wherein the branched polypropylene copolymer comprises a polymerization reaction product of propylene and an α,ω-diene having five or more carbon atoms. Optionally, the foamable composition comprises: a g′ having a g′ of about 0.8 or less vis A branched polypropylene copolymer; and a blowing agent blended with the branched polypropylene copolymer; wherein the branched polypropylene copolymer comprises a polymerization reaction product of propylene and an α,ω-diene having five or more carbon atoms. Optionally, the foamable composition comprises: a g′ having a g′ of about 0.8 or less vis Branched polypropylene copolymer.

[0225] B. Foamed product. The foamed product comprises the foamable composition of A converted into a foamed form.

[0226] C. A polymer foaming method using the foamable composition of A. The polymer foaming method comprises: inducing foam formation using the foamable composition of A to produce a foamed product comprising the foamable composition of A in a foamed form.

[0227] C1. A polymer foaming method comprising: introducing a blowing agent having a g' of about 0.93 or less vis8 or less; wherein the branched polypropylene copolymer comprises a polymerization reaction product of propylene and an α,ω-diene having five or more carbon atoms; and inducing foam formation in the foamable composition to produce a foamed product comprising the foamable composition in a foamed form. Optionally, the foamable composition comprises: a g′ having a g′ of about 0.8 or less vis Branched polypropylene copolymer.

[0228] Embodiments A, B, C and C1 can have one or more of the following elements in any combination.

[0229] Element 1: wherein the branched polypropylene copolymer has an Mz / Mw of about 6 or less.

[0230] Element 2: wherein the branched polypropylene copolymer has a Mw / Mn of about 9 or less.

[0231] Element 3: wherein the branched polypropylene copolymer has a melt flow rate of about 0.4 dg / min to about 56 dg / min as measured by ASTM D1238-20 (2.16 kg, at 230° C.). Optionally, the branched polypropylene copolymer has a melt flow rate of about 0.4 dg / min to about 3.6 dg / min as measured by ASTM D1238-20 (2.16 kg, at 230° C.).

[0232] Element 4: wherein the blowing agent comprises carbon dioxide, n-butane, isobutane, n-pentane, isopentane, nitrogen, or any combination thereof.

[0233] Element 5: wherein the foamable composition contains about 0.1 wt % to about 10 wt % of the foaming agent based on the total mass of the foamable composition.

[0234] Element 6: wherein the branched polypropylene copolymer comprises about 99 wt% or about propylene based on the total mass of the branched polypropylene copolymer and a non-zero amount of α,ω-diene.

[0235] Element 7: wherein the branched polypropylene copolymer comprises about 0.0001 wt% to about 1 wt% of the α,ω-diene based on the total mass of the branched polypropylene copolymer.

[0236] Element 8: wherein the branched polypropylene copolymer has a molecular weight of about 50 Pa·s n or greater gel stiffness.

[0237] Element 9: wherein the foamable composition has an expansion ratio of about 20 to about 40 within a temperature range of about 120°C to about 170°C.

[0238] Element 10: wherein the foamable composition has a maximum expansion ratio in a temperature range of about 130°C to about 155°C.

[0239] Element 11: wherein the foamed product has an average cell size of about 10 μm to about 75 μm.

[0240] Element 12: wherein the foamed product has about 10 7 Cells / cm 3 to about 10 8 Cells / cm 3 The average cell density.

[0241] Element 13: wherein inducing foam formation comprises batch foaming, extrusion foaming, injection molding, blow molding, or any combination thereof.

[0242] Element 14: wherein the branches are introduced into the branched polypropylene copolymer during a polymerization process for producing the branched polypropylene copolymer.

[0243] The present disclosure further relates to the following non-limiting embodiments:

[0244] Embodiment 1. A foamable composition comprising: having a g′ of about 0.93 or less vis A branched polypropylene copolymer; and a blowing agent blended with the branched polypropylene copolymer; wherein the branched polypropylene copolymer comprises a polymerization reaction product of propylene and an α,ω-diene having five or more carbon atoms.

[0245] Embodiment 2. The foamable composition of Embodiment 1, wherein the branched polypropylene copolymer has an Mz / Mw of about 6 or less.

[0246] Embodiment 3. The foamable composition of Embodiment 1 or Embodiment 2, wherein the branched polypropylene copolymer has a Mw / Mn of about 9 or less.

[0247] Embodiment 4. A foamable composition as described in any of Embodiments 1 to 3, wherein the branched polypropylene copolymer has a melt flow rate of about 0.4 dg / min to about 56 dg / min as measured by ASTM D1238-20 (2.16 kg, at 230°C).

[0248] Embodiment 5. The foamable composition of any one of Embodiments 1 to 4, wherein the blowing agent comprises carbon dioxide, n-butane, isobutane, n-pentane, isopentane, nitrogen, or any combination thereof.

[0249] Embodiment 6. A foamable composition as described in any of Embodiments 1 to 5, wherein the foamable composition comprises about 0.1 wt% to about 10 wt% of the blowing agent based on the total mass of the foamable composition.

[0250] Embodiment 7. The foamable composition of any one of Embodiments 1 to 6, wherein the branched polypropylene copolymer comprises about 99 wt% or more propylene and a non-zero amount of α,ω-diene based on the total mass of the branched polypropylene copolymer.

[0251] Embodiment 8. The foamable composition of any one of Embodiments 1 to 7, wherein the branched polypropylene copolymer comprises from about 0.0001 wt% to about 1 wt% of the α,ω-diene based on the total mass of the branched polypropylene copolymer.

[0252] Embodiment 9. A foamable composition as described in any one of Embodiments 1 to 8, wherein the branched polypropylene copolymer has a g' of about 0.8 or less. vis .

[0253] Embodiment 10. The foamable composition of any one of Embodiments 1 to 9, wherein the branched polypropylene copolymer has a melt flow rate of about 0.4 dg / min to about 3.6 dg / min as measured by ASTM D1238-20 (2.16 kg, at 230°C).

[0254] Embodiment 11. A foamed product comprising a foamable composition according to any one of embodiments 1 to 10 converted into a foamed form.

[0255] Embodiment 12. The foamed product of embodiment 11, wherein the foamable composition of any one of embodiments 1 to 10 has an expansion ratio of about 20 to about 40 in a temperature range of about 120°C to about 170°C.

[0256] Embodiment 13. The foamed product of embodiment 11 or embodiment 12, wherein the foamable composition of any one of embodiments 1 to 10 has a maximum expansion ratio in a temperature range of about 130°C to about 155°C.

[0257] Embodiment 14. The foamed product of any one of Embodiments 11 to 13, wherein the foamed product has an average cell size of about 10 μm to about 75 μm.

[0258] Embodiment 15. The foamed product of any one of Embodiments 11 to 14, wherein the foamed product has about 10 7 Cells / cm 3 to about 108 Cells / cm 3 The average cell density.

[0259] Embodiment 16: A foamed product as described in any one of Embodiments 11 to 15, wherein the branched polypropylene copolymer has a g' of about 0.8 or less. vis value.

[0260] Embodiment 17. A method of foaming a polymer, comprising: introducing a blowing agent into a polymer having a g′ of about 0.93 or less. vis The invention relates to a branched polypropylene copolymer having a certain carbon content of propylene and an α,ω-diene having five or more carbon atoms to form a foamable composition; wherein the branched polypropylene copolymer comprises a polymerization reaction product of propylene and an α,ω-diene having five or more carbon atoms; and inducing foam formation in the foamable composition to produce a foamed product comprising the foamable composition in a foamed form.

[0261] Embodiment 18. The polymer foaming method as described in Embodiment 17, wherein inducing foam formation includes intermittent foaming, extrusion foaming, injection molding, blow molding, or any combination thereof.

[0262] Embodiment 19. The polymer foaming method of Embodiment 17 or Embodiment 18, wherein the branched polypropylene copolymer has an Mz / Mw of about 6 or less.

[0263] Embodiment 20. The polymer foaming method of any one of Embodiments 17 to 19, wherein the branched polypropylene copolymer has a Mw / Mn of about 9 or less.

[0264] Embodiment 21. The polymer foaming method of any one of Embodiments 17 to 20, wherein the branched polypropylene copolymer has a melt flow rate of about 0.4 dg / min to about 56 dg / min as measured by ASTM D1238-20 (2.16 kg, at 230°C).

[0265] Embodiment 22. A polymer foaming method as described in any one of Embodiments 17 to 21, wherein the blowing agent comprises carbon dioxide, n-butane, isobutane, n-pentane, isopentane, nitrogen, or any combination thereof.

[0266] Embodiment 23. A polymer foaming method as described in any of Embodiments 17 to 22, wherein the foamable composition contains about 0.1 wt% to about 10 wt% of the blowing agent based on the total mass of the foamable composition.

[0267] Embodiment 24. The polymer foaming method of any one of Embodiments 17 to 23, wherein the branched polypropylene copolymer comprises about 99 wt% or more propylene and a non-zero amount of α,ω-diene based on the total mass of the branched polypropylene copolymer.

[0268] Embodiment 25. The polymer foaming method of any one of Embodiments 17 to 24, wherein the branched polypropylene copolymer comprises from about 0.0001 wt% to about 1 wt% of the α,ω-diene based on the total mass of the branched polypropylene copolymer.

[0269] Embodiment 26. The polymer foaming method of any one of Embodiments 17 to 25, wherein the foamable composition has an expansion ratio of about 20 to about 40 within a temperature range of about 120°C to about 170°C.

[0270] Embodiment 27. The polymer foaming method of any one of Embodiments 17 to 26, wherein the foamed product has an average cell size of about 10 μm to about 75 μm and / or about 10 7 Cells / cm 3 to about 10 8 Cells / cm 3 The average cell density.

[0271] Embodiment 28. The polymer foaming method of any one of Embodiments 17 to 27, wherein the branches are introduced into the branched polypropylene copolymer during the polymerization process for producing the branched polypropylene copolymer.

[0272] Embodiment 29. The polymer foaming method of any one of Embodiments 17 to 28, wherein the branched polypropylene copolymer has a g' of about 0.8 or less. vis .

[0273] Embodiment 30. The polymer foaming method of any one of Embodiments 17 to 29, wherein the branched polypropylene copolymer has a melt flow rate of about 0.4 dg / min to about 3.6 dg / min as measured by ASTM D1238-20 (2.16 kg, at 230°C).

[0274] In order to facilitate a better understanding of the embodiments of the present disclosure, the following examples of preferred or representative embodiments are given. The following examples should in no way be read as limiting or defining the scope of the present invention.

[0275] Example

[0276] Batch Polymerization Process. Polypropylene copolymers were prepared under the general batch conditions specified in WO 2021 / 034459, which is incorporated herein by reference. Briefly, the following procedure was used.

[0277] A 1L autoclave reactor equipped with a mechanical stirrer was used for polymer preparation. Prior to operation, the reactor was placed under a nitrogen purge while maintaining a temperature of 90°C for 30 minutes. After cooling back to ambient temperature, propylene feed (500 mL), scavenger (0.2 mL of 1M TIBAL, triisobutylaluminum), 1,7-octadiene (0.05–0.5 mL, pure) and hydrogen (0.5–15 mmol) were introduced into the reactor and mixed for 5 minutes. Then, a predetermined amount of catalyst slurry (5 wt% in mineral oil) was rinsed from the catalyst tube with 100 mL of liquid propylene, and the desired amount of supported catalyst (typically 12.5–25.0 mg) was introduced into the reactor. The reactor was kept at room temperature for 5 minutes, and then the temperature was raised to 70°C. The reaction was allowed to proceed for the desired period of time (typically 30 min) at this temperature. After a given time, the temperature was reduced to 25°C, excess propylene was discharged, and the polymer particles were collected and dried overnight. Additional reaction conditions are given in Table 1 below.

[0278] Continuous Polymerization Process. Polypropylene copolymers were produced in a pilot scale, continuous, bulk liquid system using a 50 gallon stirred tank reactor equipped with a jacket for removal of polymerization heat. Polymerizations were conducted at a constant temperature of 70°C under bulk conditions with varying levels of 1,7-octadiene and scavenger (triisobutylaluminum, TIBAL) as further specified in Table 2 below. The catalyst was added at 13-17 cm 3 The feed rate was 10 wt% / hour as a 10 wt% slurry in oil.

[0279] Polymer Characterization. Unless otherwise stated, the molecular weight distribution and moments (Mw, Mn, Mz, Mw / Mn, etc.), comonomer content and branching index (g' vis ) was measured by using a high temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with a multi-channel bandpass filter-based infrared detector IR5 and a multi-channel bandpass filter-based infrared detector integrated body IR5 (having a coverage area of ​​about 2,700 cm -1 To about 3,000cm -1(band area representing saturated CH stretching vibrations), 18-angle light scattering detector and viscometer. Three Agilent PLgel 10-mm mixed-B LS columns are used to provide polymer separation. Reagent grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) containing ~300ppm antioxidant BHT is used as the mobile phase, with a nominal flow rate of ~1.0mL / min and a nominal injection volume of ~200mL. The entire system including the transfer line, column and detector is contained in an oven maintained at ~145°C. A given amount of sample is weighed and sealed in a standard vial to which a -10mL flow marker (heptane) is added. After the vial is loaded into the autosampler, the oligomer or polymer can be automatically dissolved in an instrument with ~8mL TCB solvent added at ~160°C under continuous shaking. The sample solution concentration is ~0.2 to ~2.0mg / ml, with lower concentrations used for higher molecular weight samples. The concentration c at each point in the chromatogram was calculated from the baseline-subtracted IR5 broadband signal l using the following equation: c = αl, where α is a mass constant determined with polyethylene or polypropylene standards. The mass recovery was calculated from the ratio of the integrated area of ​​the concentration chromatography over the elution volume to the injected mass equal to the predetermined concentration multiplied by the injection loop volume. The conventional molecular weight (IR MW) was determined by combining a universal calibration relationship with a column calibration with a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 M gm / mole. The MW at each elution volume was calculated using Equation 2:

[0280]

[0281] The variables with the subscript "PS" represent polystyrene, while the variables without the subscript represent the test sample. PS =0.67 and K PS =0.000175, α and K for other materials are calculated as described in the published literature (e.g., Sun, T. et al. (2001) Macromolecules, Vol. 34, p. 6812), except that for the purposes of the present disclosure and claims, for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, α=0.705 and K=0.0000229; for linear ethylene polymers, α=0.695 and K=0.000579; for linear propylene polymers, α=0.705 and K=0.0002288; and for linear butane polymers, α=0.695 and K=0.000181. Unless otherwise stated, concentrations are in g / cm 3 denoted by , molecular weight is expressed in g / mole, and intrinsic viscosity (and hence K in the Mark-Houwink equation) is expressed in dL / g.

[0282] The comonomer composition is determined by the ratio of the IR5 detector intensities corresponding to the CH2 and CH3 channels, which are calibrated with a series of PE and PP homopolymer / copolymer standards whose nominal values ​​are predetermined by NMR or FTIR. In particular, this provides the methyl groups / 1,000 total carbons (CH3 / 1000TC) as a function of molecular weight. The short chain branching (SCB) content / 1,000TC (SCB / 1000TC) is then calculated as a function of molecular weight by applying a chain end correction to the CH3 / 1000TC function, assuming that each chain is linear and terminated at each end by a methyl group. The weight % of the comonomer is then obtained by equation 3, where f is 0.3, 0.4, 0.6, 0.8, etc. for comonomers such as C3, C4, C6, C8, etc., respectively:

[0283] w2=f×SCB / 1000TC

[0284] Equation 3

[0285] The overall composition of the polymer was obtained from GPC-IR and GPC-4D analysis by considering the entire signal of the CH3 and CH2 channels between the integration limits of the concentration chromatogram. First, the following ratio in Eq. 4 was obtained

[0286]

[0287] Then, as mentioned previously in obtaining CH3 / 1000TC as a function of molecular weight, the same calibration of the ratio of CH3 and CH2 signals is applied to obtain bulk CH3 / 1000TC. As shown in Equations 5 and 5, the bulk methyl chain ends / 1000 total carbons (bulk CH3 ends / 1000TC) is obtained by weighted averaging the chain end corrections over the molecular weight range.

[0288] w2b=f×body CH3 / 1000TC

[0289] Equation 5

[0290] Main body SCB / 1000TC = main body CH3 / 1000TC - main body CH3 end / 1000TC

[0291] Equation 6

[0292] The body SCB / 1000TC is then converted to body w2 in the same manner as described above.

[0293] The LS detector was an 18-angle Wyatt Technology high temperature DAWN HELEOS II. The LS molecular weight (M) at each point in the chromatogram was determined by analyzing the LS output using the Zimm model for static light scattering (Light Scattering from Polymer Solutions; Huglin, MB, ed.; Academic Press, 1972.) using Equation 7:

[0294]

[0295] Here, ΔR(θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, c is the polymer concentration determined by IR5 analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coil, and K o is the optical constant of the system, as in Equation 8:

[0296]

[0297] Where N A is the Avogadro number, and (dn / dc) is the refractive index increment of the system. At 145°C and λ=665nm, the refractive index n of TCB is 1.500. For the analysis of polyethylene homopolymers, ethylene-hexene copolymers and ethylene-octene copolymers, dn / dc=0.1048 ml / mg and A2=0.0015; for the analysis of ethylene-butene copolymers, dn / dc=0.1048*(1-0.00126*w2)ml / mg and A2=0.0015, where w2 is the weight percent of butene comonomer.

[0298] The specific viscosity is determined using a high temperature Agilent (or Viscotek Corporation) viscometer with four capillaries arranged in a Wheatstone bridge configuration and two pressure sensors. One sensor measures the total pressure drop across the detector, while the other sensor between the two sides of the bridge measures the pressure difference. The specific viscosity η of the solution flowing through the viscometer is calculated from their outputs. s The intrinsic viscosity [η] at each point in the chromatogram is given by the equation [η] = η s / c is calculated, where c is the concentration and is determined from the IRS broadband channel output. The viscosity MW at each point is calculated using Equation 9

[0299]

[0300] where α PS is 0.67 and K PS It is 0.000175.

[0301] Branching index (g' vis ) is calculated using the output of the GPC-IRS-LS-VIS method as follows. The average intrinsic viscosity [η] of the sample avg Calculated by equation 10:

[0302]

[0303] where the sum is taken over all chromatographic slices i between the integration limits. Branching index g' vis Defined in Equation 11:

[0304]

[0305] Among them, M V is the viscosity average molecular weight based on the molecular weight determined by LS analysis, K and α are for reference linear polymers, which for the purposes of this disclosure and claims thereof, for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, α=0.705 and K=0.0000229; for linear ethylene polymers, α=0.695 and K=0.000579; for linear propylene polymers, α=0.705 and K=0.000228; for linear butene polymers, α=0.695 and K=0.000181. Unless otherwise stated, concentrations are in g / cm 3 denoted by , molecular weight in g / mole, and intrinsic viscosity (and hence K in the Mark-Houwink equation) in dL / g. The calculation of w2b values ​​is as discussed above.

[0306] T. Sun, P. Brant, RR Chance, and WW Graessley (Macromolecules, 2001, Vol. 34(19), pp. 6812-6820) further describe experimental and analytical details not described above, including how to calibrate the detector and how to calculate the composition dependence of the Mark-Houwink parameters and the second virial coefficient.

[0307] Table 1 summarizes the reaction conditions for producing branched polypropylene copolymers under batch conditions and is further characterized below (entries 1-6). Table 2 summarizes the reaction conditions for producing branched polypropylene copolymers under continuous conditions and is further characterized below (entries 7-14). Table 3 summarizes the physical properties of the branched polypropylene copolymers produced according to the above procedure and is further specified in Tables 1 and 2.

[0308] Table 1

[0309]

[0310] Table 2

[0311]

[0312]

[0313] Table 3

[0314]

[0315] As shown, lower branching index and higher molecular weight were obtained under the batch conditions tested. With increasing loading of 1,7-octadiene under continuous polymerization, molecular weight and g' vis The values ​​begin to approach those obtained under batch conditions.

[0316] Small amplitude oscillatory shear (SAOS) data are collected. Dynamic shear melt rheology data are measured in a nitrogen atmosphere in dynamic mode using an advanced rheology expansion system (ARES-G2) from a thermal analysis instrument company (TA Instruments) using parallel plates (diameter = 25 mm). For all experiments, the rheometer is thermally stabilized at 190 ° C for at least 30 minutes, and then the compression molded sample (prepared at 190 ° C) is inserted into the parallel plate. In order to determine the viscoelastic behavior of the sample, a frequency sweep in the range of 0.01 to 628rad / s is performed at a temperature of 190 ° C under constant strain. Depending on the molecular weight and temperature, strains within the linear deformation range verified by strain sweep tests are used. A nitrogen flow is circulated through the sample furnace to minimize chain extension or crosslinking during the experiment. If the strain amplitude is small enough so that the sample behaves linearly, a sinusoidal shear strain is applied to the sample. It can be shown that the resulting steady-state stress will also oscillate sinusoidally at the same frequency, but will be offset relative to the strain wave by a phase angle δ. Stress leads strain δ. For purely elastic materials, δ = 0° (stress is in phase with strain), and for purely viscous materials, δ = 90° (although stress is in phase with the strain rate, stress leads strain by 90°). For viscoelastic materials, 0<δ<90.

[0317] The rheological properties of polypropylene were fitted to the Winter-Chambon model using Equation 12,

[0318] η * (ω)=SΓ(1-n)ω n-1 ,

[0319] Equation 12

[0320] where η * represents the complex viscosity (Pa·s), ω represents the frequency, Γ is the gamma function, S is the gel stiffness, and n is the critical network relaxation index. The results are shown in Table 4. Based on the rheological properties, the polypropylene can be characterized as having a "gel-like" behavior.

[0321] Table 4

[0322]

[0323]

[0324] Figure 1 is a plot of the small amplitude oscillatory shear (SAOS) data of the branched polypropylene copolymer of entry 2 fitted to the Winter-Chambon model. As shown, the polymer samples produced under continuous polymerization conditions have rheological parameters that are different from those produced under batch polymerization conditions. As the loading of 1,7-octadiene in the continuous polymerization reaction increases under the conditions tested, the rheological parameters of the polymer samples produced under continuous polymerization conditions become closer to those values ​​obtained under batch polymerization conditions.

[0325] Intermittent foaming method. The foaming apparatus used herein consists of a chamber in which the temperature is precisely controlled by a band heater with proportional integral differential feedback control. A CO2 cylinder is connected to the chamber by a pipeline, and a syringe pump is used to supply a metered flow of gas to maintain the internal CO2 pressure at a constant 2000psi. After the chamber is preheated to 210°C, a branched polypropylene copolymer (0.1–0.2g) is loaded and sealed in the chamber. CO2 is injected into the chamber to saturate the branched polypropylene copolymer at 210°C for a certain period of time, depending on the specified foaming temperature. After CO2 is saturated, the heat supply is turned off, and the chamber is cooled at a constant rate of 5.5°C / min until the specified foaming temperature is reached. After a total of 18 minutes of CO2 saturation and cooling, the chamber is rapidly decompressed and quenched. Expansion ratio data are collected within the range of foaming temperature. Figure 2 is a graph of the expansion ratio of a branched polypropylene copolymer as a function of temperature compared to various commercial polypropylenes. As shown, the branched polypropylene copolymer exhibits ready foamability over a range of temperatures.

[0326] Cell morphology data of the foamed polypropylene were collected via scanning electron microscopy (SEM) in order to determine the cell diameter and other relevant properties. Figure 3 is a graph of the average cell density as a function of temperature for various foamed polypropylenes compared to several commercial polypropylenes having high melt strength.

[0327] Figures 4A-4D is a graph of the average cell diameter of various expanded polypropylenes as a function of temperature. As shown, within the temperature range of 120°C to 160°C, the average cell size is relatively constant at a level below 100 mm.

[0328] For the purpose of all jurisdictions that allow such practice, all documents described herein are incorporated herein by reference, including any priority documents and / or testing procedures, as long as they are not inconsistent with this article. As is apparent from the general description and specific embodiments above, although the form of the present disclosure has been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Therefore, it is not intended to limit the present disclosure thereby. For example, the composition described herein may not contain any component or composition that is not explicitly listed or disclosed herein. Any method may lack any step that is not listed or disclosed herein. Similarly, the term "comprising" is considered to be synonymous with the term "including". Whenever there is a transitional phrase "comprising / including" before a method, composition, element or element group, it should be understood that we also contemplate the same composition or element group with a transitional phrase "substantially consisting of...", "consisting of...", "selected from a group consisting of...", or "is" before the narration of the composition, one or more elements, and vice versa.

[0329] Unless otherwise indicated, all numerical values ​​used in this specification and the related claims to represent the amount of ingredients, properties such as molecular weight, reaction conditions, etc., should be understood as being modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters set forth in the following specification and the appended claims are approximate values, which may vary depending on the desired properties sought to be obtained by one or more embodiments described herein. At least, without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in accordance with the number of reported significant figures and by applying ordinary rounding techniques.

[0330] Whenever a numerical range with a lower limit and an upper limit is disclosed, any value and any included range falling within the range are specifically disclosed. In particular, each value range disclosed herein (in the form of "about a to about b", or equivalently, "about a to b", or equivalently, "about ab") should be understood to set forth each value and range covered within the broader value range. In addition, unless otherwise explicitly and clearly defined by the patentee, the terms in the claims have their straightforward, ordinary meanings. In addition, as used in the claims, the indefinite article "a / an" is defined herein to mean one / kind or more than one / kind of elements it introduces.

[0331] One or more illustrative embodiments are presented herein. For the sake of clarity, not all features of physical implementations are described or shown in the present application. It should be understood that in the development of the physical embodiments of the present disclosure, many implementation-specific decisions must be made to achieve the goals of developers, such as compliance with system-related, business-related, government-related and other constraints, which vary from implementation to implementation and vary over time. Although the efforts of developers may be time-consuming, however, for those of ordinary skill in the art who benefit from the present disclosure, such efforts will be routine tasks.

[0332] Therefore, the present disclosure is well adapted to achieve the objects and advantages mentioned and those inherent therein. The specific embodiments disclosed above are illustrative only, because the present disclosure can be modified and practiced in different but equivalent ways that are obvious to those of ordinary skill in the art who benefit from the teachings of this article. In addition, except as described in the following claims, it is not intended to limit the details of the construction or design shown herein. Therefore, it is obvious that the specific illustrative specific embodiments disclosed above can be changed, combined, or modified, and all such changes are considered to be within the scope and spirit of the present disclosure. The embodiments disclosed illustratively herein can be suitably practiced in the absence of any elements not specifically disclosed herein and / or any optional elements disclosed herein.

Claims

1. A foamable composition comprising: Having a g′ of about 0.93 or less vis A branched polypropylene copolymer of a blowing agent blended with the branched polypropylene copolymer; The branched polypropylene copolymer comprises a polymerization reaction product of propylene and an α,ω-diene having five or more carbon atoms.

2. The foamable composition according to claim 1, wherein The branched polypropylene copolymer has a Mz / Mw of about 6 or less.

3. A foamable composition according to any preceding claim, wherein The branched polypropylene copolymer has a Mw / Mn of about 9 or less.

4. A foamable composition according to any preceding claim, wherein The branched polypropylene copolymer has a melt flow rate of about 0.4 dg / min to about 56 dg / min as measured by ASTM D1238-20 (2.16 kg, at 230° C.).

5. A foamable composition according to any preceding claim, wherein The blowing agent comprises carbon dioxide, n-butane, isobutane, n-pentane, isopentane, nitrogen, or any combination thereof.

6. A foamable composition according to any preceding claim, wherein The foamable composition includes about 0.1 wt % to about 10 wt % of the foaming agent based on the total mass of the foamable composition.

7. A foamable composition according to any preceding claim, wherein The branched polypropylene copolymer comprises about 99 wt% or more propylene based on the total mass of the branched polypropylene copolymer and a non-zero amount of α,ω-diene.

8. The foamable composition according to claim 7, wherein The branched polypropylene copolymer comprises about 0.0001 wt% to about 1 wt% of the α,ω-diene based on the total mass of the branched polypropylene copolymer.

9. A foamable composition according to any preceding claim, wherein The branched polypropylene copolymer has a g′ of about 0.8 or less. vis .

10. The foamable composition according to claim 9, wherein The branched polypropylene copolymer has a melt flow rate of about 0.4 dg / min to about 3.6 dg / min as measured by ASTM D1238-20 (2.16 kg, at 230° C.).

11. A foamed product comprising the foamable composition according to claim 1 converted into a foamed form.

12. The foamed product according to claim 11, wherein The foamable composition has an expansion ratio of about 20 to about 40 within a temperature range of about 120°C to about 170°C.

13. The foamed product according to claims 11-12, wherein: The foamable composition has a maximum expansion ratio in a temperature range of about 130°C to about 155°C.

14. The foamed product according to claims 11-13, wherein: The foamed product has an average cell size of about 10 μm to about 75 μm.

15. The foamed product according to claims 11-14, wherein: The foamed product has about 10 7 Cells / cm 3 to about 10 8 Cells / cm 3 The average cell density.

16. The foamed product according to claims 11-15, wherein: The branched polypropylene copolymer has a g′ of about 0.8 or less. vis .

17. A polymer foaming method comprising: The blowing agent is introduced into the g′ of about 0.93 or less. vis A branched polypropylene copolymer having a value of 1:1 to form a foamable composition; wherein the branched polypropylene copolymer comprises the polymerization reaction product of propylene and an α,ω-diene having five or more carbon atoms; and Foam formation is induced in the foamable composition to produce a foamed product comprising a foamed form of the foamable composition.

18. The polymer foaming method according to claim 17, wherein: Inducing foam formation includes batch foaming, extrusion foaming, injection molding, blow molding, or any combination thereof.

19. The polymer foaming method according to claims 17-18, wherein: The branched polypropylene copolymer has a Mz / Mw of about 6 or less.

20. The polymer foaming method according to claims 17-19, wherein: The branched polypropylene copolymer has a Mw / Mn of about 9 or less.

21. The polymer foaming method according to claims 17-20, wherein: The branched polypropylene copolymer has a melt flow rate of about 0.4 dg / min to about 56 dg / min as measured by ASTM D1238-20 (2.16 kg, at 230° C.).

22. The polymer foaming method according to claims 17-21, wherein: The blowing agent comprises carbon dioxide, n-butane, isobutane, n-pentane, isopentane, nitrogen, or any combination thereof.

23. The polymer foaming method according to claims 17-22, wherein: The foamable composition includes about 0.1 wt % to about 10 wt % of the foaming agent based on the total mass of the foamable composition.

24. The polymer foaming method according to claims 17-23, wherein: The branched polypropylene copolymer comprises about 99 wt% or more propylene based on the total mass of the branched polypropylene copolymer and a non-zero amount of α,ω-diene.

25. The polymer foaming method according to claim 24, wherein: The branched polypropylene copolymer comprises about 0.0001 wt% to about 1 wt% of the α,ω-diene based on the total mass of the branched polypropylene copolymer.

26. The polymer foaming method according to claims 17-25, wherein: The foamable composition has an expansion ratio of about 20 to about 40 within a temperature range of about 120°C to about 170°C.

27. The polymer foaming method according to claims 17-26, wherein: The foamed product has an average cell size of about 10 μm to about 75 μm and / or about 10 7 Cells / cm 3 to about 10 8 Cells / cm 3 The average cell density.

28. The polymer foaming method according to claims 17 to 27, wherein: The branches are introduced into the branched polypropylene copolymer during the polymerisation process for producing the branched polypropylene copolymer.

29. The polymer foaming method according to claims 17-28, wherein: The branched polypropylene copolymer has a g′ of about 0.8 or less. vis .

30. The polymer foaming method according to claim 29, wherein: The branched polypropylene copolymer has a melt flow rate of about 0.4 dg / min to about 3.6 dg / min as measured by ASTM D1238-20 (2.16 kg, at 230° C.).

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