JP6948405B2 - Linear ethylene cyclic olefin polymer - Google Patents

Description

Field of Invention The present invention relates to linear poly (ethylene / cyclic olefin) copolymers and linear poly (ethylene / α-olefin / cyclic olefin) terpolymers having improved processability and strain hardening.

Cross-reference to related applications This application is incorporated herein by reference in both US Provisional Application License Nos. 62 / 483,713, filed April 10, 2017, and filed June 1, 2017. Claims the benefit of the priority of EP Application No. 17173985.7.

Background Linear low density polyethylene (LLDPE) is a copolymer of ethylene and a small amount of comonomer, typically an acyclic C _3- C ₈ α-olefin. Elsewhere, the short-chain branches of the polymer in the linear skeleton are high-branched low-density polyethylene (LDPE) produced by a high-pressure radical process, and non-branched high-density polyethylene (HDPE) made from a low-pressure metal-catalyzed process. Gives LLDPE unique mechanical properties and processing properties compared to. Due to its relatively low cost and its good overall mechanical properties, LLDPE is widely used as the main component of films. However, the lack of some rheological properties such as shear fluidization, strain hardening, and melt strength is processed when LLDPE is made into film by techniques such as blown bubble extrusion, or when foamed products are manufactured. Brings difficulty. Typically, LDPE is added to LLDPE to improve its melt strength and foam stability, but at the same time some mechanical properties such as impact toughness are impaired.

Various methods based on the combination and optimization of long-chain branched structures and composition / molecular weight distributions have been explored, but it is difficult to obtain increasing benefits for commercial implementation. Previously, norbornene comonomer methods were explored at US 5,942,587 to make poly (ethylene / α-olefin / cyclic olefin) terpolymers, or “cyclic olefin copolymers” (COCs). The COC produced by the vapor phase process and the heterogeneous catalyst had significantly improved tensile strength and coefficient and Elmendorf tearing properties, but reduced spear impact properties. The gas phase COC had a relatively wide composition and molecular weight distribution, but it is not clear from this document whether the COC is linear or branched. Gas phase COC also showed minimal to moderate improvement in shear fluidization and melt strength. Therefore, the gas phase COC did not show the ideal balance of mechanical properties. What is needed is polyethylene, which has a better balance of properties when it comes to useful films and other articles, while having improved workability.
Other references include US 5,087,677; US 5,635,573; US 5,629,398; US 6,222,019; US 9,321,911; and US 2003/0130452.

Summary In the present specification, cyclic olefin-derived units in the range of 0.5, 1 or 2, or 4 wt% to 10, or 15, or 20 wt%, 0, or 1 wt% to 10, or 15 wt%. Containing (or essentially consisting of or consisting of) C4-C12α olefin-derived units in the range, the rest are ethylene-derived units; and less than 2.5 Mw / Mn; in the range of 80,000-300,000 g / mol. Provided are polymers obtained by a solution polymerization process having a mass average molecular weight (Mw); and a g'value greater than 0.95.
Also a polymer forming process involving (or essentially consisting of or consisting of) cyclic olefins, ethylene, hydrogen and optionally C4-C12α olefins mixed with a single site catalyst in solution to form a polymer. offer. Here, the single-site catalyst is preferably selected from Group 4 metallocenes, most preferably asymmetric Group 4 bis-bridged cyclopentadienyl metallocenes.

^{Invention Example 1, 1} H NMR of ethylene-norbornene-hexcenter polymer. Invention Example 2, ¹ H NMR of ethylene-norbornene copolymer. Gel Permeation Chromatogram (GPC) and Viscosity Profile of Examples of the Invention. Gel Permeation Chromatogram (GPC) and Viscosity Profile of Examples of the Invention. Complex viscosity as a function of shear rate data for invented polyethylene and comparative polyethylene. It is a complex viscosity plot of comparative polyethylene from US 5,942,587. It is an extension rheology profile of comparative polyethylene and invention polyethylene. It is an extension rheology profile of comparative polyethylene and invention polyethylene. It is an extension rheology profile of comparative polyethylene and invention polyethylene. It is an extension rheology profile of comparative polyethylene and invention polyethylene. Atomic force microscopy (AFM) of comparative polyethylene. Invention An atomic force microscope (AFM) of polyethylene 1. Invention An atomic force microscope (AFM) of polyethylene 2.

Detailed Description The inventors were surprised to find that the process used to make polyethylene, particularly preferably a single selected from Group 4 metallocenes, most preferably asymmetric Group 4 bis-bridged cyclopentadienyl metallocenes. We have found that processes using site catalysts can affect the structure of the final product. The polyethylene forming process disclosed herein is a solution process which will be further described later. The process is characterized in that the catalyst, the monomer, and the resulting polymer are dissolved in an inert hydrocarbon and / or a reaction solvent which can be one or more monomers.
As used herein, "Group 4" refers to the new notation of the Periodic Table of the Elements in the Hawley Practical Chemistry Dictionary, 13th Edition (John Wiley & Sons, Inc. 1997).
Similarly, as used herein, "mixing" refers to a chemical reaction between one or more monomers, typically catalyzed by the presence of catalyst precursors and activators, for example in a polymerization reactor. It means that the specified components are brought together and brought into contact with each other under causative temperature, pressure, solvent conditions, and other environmental conditions.

In any embodiment, the cyclic olefin monomer mixed with the ethylene monomer in the polymerization process is an olefin from C5 to C8, or C12, or C16, or C20 containing at least one C5-C8 cyclic structure, eg, a bicyclo compound. , For example bicyclo-(2,3,1) -heptene-2. Preferably the cyclic olefin is a cyclic olefin from C5, or C6 to C8, or C10, or C12, or C20, more preferably the whole, such as bicyclo- (2,3,1) -heptene-2 (norbornene). It is selected from bicyclic olefins, which are cyclic olefins containing crosslinked hydrocarbon moieties that form two rings in the structure. Most preferably, the cyclic olefin is selected from norbornene, tetracyclododecene, and substitutional forms thereof. In order to trigger the polymerization process during mixing, not only do they mix at the desired temperature, but at least 0.8, or 1, or 2, or 3 MPa; or 0.8, or 1, or 2, or 3 MPa to 4, 6, or 8 Or, it is preferable to mix at a pressure within the range of up to 10 MPa. This pressure can be derived from the addition of ethylene and / or other gases in the polymerization reactor and is naturally affected by the temperature of the reactor. The levels of ethylene and cyclic olefins are adjusted to obtain the desired catalytic activity as well as the desired levels of cyclic olefin comonomer incorporated into the polyethylenes described herein. In any embodiment, the mixing of the monomer and the catalyst can occur at a reaction temperature, which is the average temperature in the vessel or reactor used to mix the components and cause polymerization. This temperature is in the range of 80, 85, or 90, or 100 ° C to 120, or 130, or 140, or 150 ° C.

More specifically, it is preferred to mix the various monomers and catalyst precursors and activators in a polymerization reactor capable of reacting at the desired monomer concentration, catalyst concentration, temperature and pressure. In any embodiment, contact occurs in a polymerization reactor having an inlet for supplying the monomer and / or catalyst and an outlet for the outflow of the polymerization reaction. Here, the amount of polyethylene in the effluent is in the range of 2 or 4 or 6 wt% to 12 or 14 or 16 or 20 wt% based on the mass of the components in the solvent of the effluent stream. The polymerization reaction may be any type of polymerization useful for the formation of polyolefins, such as so-called gas phase reactions, solution reactions or slurry reactions, preferably continuous solution, slurry or gas phase reactions.
In any embodiment, polyethylene is made by a process commonly known as the "solution" process. For example, it is preferred to carry out copolymerization in one or more single-phase liquid-filled agitator reactors with a continuous feed stream to the system and continuous recovery of the product under steady state. When using multiple reactors, the reactors may be operated in series or parallel arrangements that produce essentially the same or different polymer components. Advantageously, the reactor can produce polymers with different properties, such as different molecular weights, or different monomer compositions, or different levels of long chain branching, or any mixture thereof. All polymerizations are non-coordinating hoe separate as soluble metallocene catalysts or other single-site catalysts and co-catalysts in systems with solvents containing any one or more C4-C12 alkanes and / or olefin monomers. This can be done using an acid anion. A homogeneously diluted solution of tri-n-octylaluminum in a suitable solvent can be used as a scavenger at a concentration suitable for maintaining the reaction. The molecular weight can be controlled by adding a chain transfer agent such as hydrogen. The polymerization can, if desired, the high temperature and high conversion rates described above to maximize the reinsertion of macromers creating long chain branches. This combination of uniform continuous solution processes helps the polymer product to have a narrow composition and sequence distribution.

In any embodiment, hydrogen is also mixed with the monomer and catalyst, most preferably hydrogen is 4, or 5 to 20, 25, or 30, or 40, or 50, or 100, or 200 cm ³ / min. It exists within the range up to (SCCM).
In any embodiment, the contact (or polymerization) occurs under one step or one set of conditions, even when performed in two or more reactors, to produce polyethylene.
In any embodiment, the reactor can be maintained at a pressure above the vapor pressure of the reactant mixture to keep the reactant in the liquid phase. In this mode, the reactor can operate at full liquid in a uniform single-phase state. A feed of ethylene and cyclic olefins (as well as any propylene, C4-C12α olefin and / or diene) can be mixed into a single stream before mixing with a precooled hexane stream. Just before the mixed solvent and stream of monomers enters the reactor, a solution of tri-n-octylaluminum nascavenger in the desired solvent can be added to further reduce the concentration of either catalytic venom. Mixtures of catalyst components (catalytic precursors and / or activators) in the solvent may be pumped separately into the reactor and delivered through separate ports. In another embodiment, a cooling isothermal reactor that does not require supply cooling can be used.

Any "diene" may be added to the polymerization medium, including so-called "dual-polymerizable dienes" and "non-conjugated dienes". In any embodiment, the "double polymerizable diene" is a vinyl-substituted strain bicyclic and non-conjugated diene, and both insatiable sites can be polymerized by a polymerization catalyst (eg, Ziegler-Natta, vanadium, metallocene, etc.). From α-ω linear dienes; more preferably selected from non-conjugated vinyl norbornene and C8-C12 α-ω linear dienes (eg, 1,7-heptadiene and 1,9-decadien), most preferably 5-vinyl-. 2-Norbornene. In any embodiment, the molar percentage of the double polymerizable diene that is mixed (ie, present in the feedstock leading to the polymerization reactor) is 0.30, or 0.28, or less than 0.26 mol% with respect to the other monomers. Or in the range of 0.05 to 0.26 or 0.28 or 0.30 mol%. The polyethylene formed from it contains a "double polymerizable diene-derived monomer unit".
In any embodiment, the "non-conjugated diene" is selected from cyclic and linear alkanes in which only one of the double bonds is activated by a polymerization catalyst and, as a non-limiting example thereof, 1,5-cyclo. Included are octadiene, unconjugated diene (and other structures in which each double bond is separated by two carbon atoms from the other), norbornadiene, and other strained bicyclic and unconjugated diene, as well as dicyclopentadiene. More preferably, the non-conjugated diene is selected from the C7-C30 cyclic non-conjugated diene. The most preferred non-conjugated diene is 5-ethylidene-2-norbornene. The polyethylene formed from it contains a "non-conjugated diene-derived monomer unit".
Most preferably, there is no diene in the polymerization process. That is, the diene is not intentionally mixed with the cyclic olefins, ethylene, and catalytic components at any stage of the polyethylene forming process described herein.

The solution reaction mixture can be vigorously agitated by any of the technically well-known means to achieve a thorough mixing over a wide range of solution viscosities. The flow rate can be set to maintain an average residence time in the reactor of 5 to 10 or 20 minutes. Once out of the reactor, the copolymer mixture is exposed to quenching, a series of concentration steps, heating and vacuum stripping and pelleting, or another reactor, such as propylene, which will be copolymerized with the next reactor. Or a solution or slurry (or a combination of both) in which close mixing can occur may be supplied to the line containing the polyolefin. The water or water / alcohol mixture is then fed to quench the polymerization reaction. Otherwise, the polymerization reaction may continue in the presence of residual catalyst, unreacted monomers, and elevated temperatures. The polymerization reaction can also be quenched with an antioxidant.

Polyethylene can be recovered from the effluent by separating the polymer from the other components of the effluent using conventional separation means. The polymer can be recovered from any effluent by, for example, liquid-liquid separation or coagulation with a non-solvent such as methanol, isopropyl alcohol, acetone, or n-butyl alcohol, or a solvent or other medium with heat or steam. The polymer can be recovered by stripping. After removal of the solvent and monomer, the pelleted polymer can be removed from the plant and physically braided with the polyolefin. If in-situ blending is preferred, solvent removal is performed after close mixing with the solution or slurry phase polyolefin.
The dilute phase and volatiles removed downstream of the liquid phase separation can be recirculated to form part of the polymerization feedstock. In this process, the degree of separation and purification is done to remove polar impurities or internally unsaturated olefins that can impair the activity of the catalyst. Otherwise, any internally unsaturated olefin that is difficult to polymerize will gradually accumulate in the dilute phase and the recirculation stream. Any adverse effect on polymerization activity can be mitigated by removing these olefins from the recirculation stream and / or encouraging them to incorporate them into polymers that are endowed with high polymerization temperatures.

As mentioned above, the solution polymerization process involves (or essentially consists of, or consists of) mixing cyclic olefins, ethylene, hydrogen and optionally C4-C12α olefins with a single site catalyst to form polyethylene. ) Provide a polyethylene forming process. Many organic metal compounds are useful single site catalysts such as metallocene (MN), pyridiyldiamide transition metal catalysts, alkoxides and / or amide transition metal catalysts, bis (imino) pyridyl transition metal catalysts, and technically well known polyolefins. Many other organic metal compounds and the like that are useful as catalysts are known. These compounds are accompanied by activating compounds such as methylaluminoxane or boron activators, especially total fluorine substituted aryl compounds. Together, these and other technically well-known organometallic compounds form "single-site catalysts", for example as outlined below (H. Kaneyoshi et al., "Non-metallosensing catalysts for polyolefins (" Nonmetallocene single-site catalysts for compounds) ”, Research Review (McGraw Hill, 2009); C. De Rosa et al.,“ Single site metalorganic polymerization catalysis as as a method for exploring the properties of polyolefins. a method to probe the properties of polyolefins) ”, 2 Polym. Chem. 2155 (2012); IE Sedov et al.“ Single-site catalysts in the industrial production of polyolefins, ”4 (2) Catalysis in Industry 129-140 (2012); and GW Coates, “Precise control of chemically stereochemistry using single-site metal catalysts,” 100 Chem. Rev. . 1223 (2000)). Most preferably, the single-site catalyst used to make the ssPP useful herein involves, for example, any type of activating compound as described in US 8,318,875; US 8,143,353; and US 7,524,910. It is a metallocene.

Thus, in any embodiment, the single site catalyst is selected from Group 4 metallocenes, most preferably asymmetric Group 4 bis-bridged cyclopentadienyl metallocenes.
More preferably, in any embodiment, the Group 4 metallocene or Group 4 bis-bridged cyclopentadienyl metallocene is isolobal to the two cyclopentadienyl ligands and / or cyclopentadienyl groups. Ligs, such as indenyl, benzoindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentadienyltrenyl, its hydrogenated or partially hydrided form, its substituted form, and its heterocyclic form. It includes (or consists of) one selected from (preferably substitution of ring carbon with nitrogen, oxygen, sulfur, silicon, and / or phosphorus).
What is meant by "asymmetry" is that the two cyclopentadienyl ligands differ from each other, at least by substitution pattern and uniqueness, but most preferably by the ring structure itself.

As used herein with respect to hydrocarbons, "substituted" or "substituted" means that the designated hydrocarbon moiety is C1-instead of one or more hydrogens, preferably one or two hydrogens. C6 alkyl, preferably methyl or ethyl, phenyl or other C7-C20 aromatic hydrocarbons (or "aryl"), aniline, imidazole or other nitrogen heterocycles, halogens, hydroxyls, carboxylates, succinates, glycols, and / Or it means that it may also contain mercaptan.
In any embodiment, at least one of the two ligands is a C1-C12 alkyl, C3-C16 isoalkyl, C6-C24 aryl, C9-C24 fused polycyclic aryl, C5-C20 nitrogen and / or sulfur heterocycle. , And the groups selected from the mixture are mono- or di-substituted. More preferably, at least one of the two ligands is mono- or di-substituted with a group selected from isopropyl, isobutyl, tert-butyl, phenyl, alkylphenyl, and dialkylphenyl. Also, in any embodiment, the cross-linking group that covalently binds any of the two ligands described herein comprises at least one phenyl group, an alkyl-substituted phenyl group, or a silyl-substituted phenyl group.

In any embodiment, the single-site catalyst is composed of the following structure (I):

(Here, M is a Group 4 metal, preferably zirconium or hafnium; Q is silicon or carbon; R'and R'are independently selected from phenyl, alkyl-substituted phenyl, and silyl-substituted phenyl, respectively. Each X is independently selected from C1-C10 alkyl, phenyl, and halogen; R ^{1 to} R ⁸ are independently selected from hydrogen, C1-C10 alkyl, phenyl, and alkyl phenyl, respectively; and R ^{1 'to} R ^6' are selected independently hydrogen, C1-C10 alkyl, and phenyl)
Is selected from.

(II) More preferably, the single-site catalyst is composed of the following structure (II) :.

(II)

(Here, M is a Group 4 metal, preferably zirconium or hafnium, most preferably hafnium; Q is silicon or carbon, most preferably carbon; R'and R'are independently phenyl, respectively. Alkyl-substituted phenyl and silyl-substituted phenyl, most preferably C1-C4 or C1-C6 alkyl-silyl-substituted phenyl; each X is independently selected from C1-C10 alkyl, phenyl, and halogen; R ¹ to R ⁸ is independently selected from hydrogen, C1-C10 alkyl, phenyl, and alkylphenyl, most preferably R ² and R ⁷ are C2-C6 linear or branched alkyl, with the remaining R groups being hydrogen. be atomic;. and R ^{1 '~R 6'} are each independently hydrogen, C1-C10 alkyl, and phenyl, in any embodiment is most preferably selected from hydrogen, M of the arbitrary structure Hafnium, and R'and R'are phenyl-p-tri- (C1-C6) -silyl groups, respectively)
Is selected from.

Also, the catalyst precursor must be mixed with at least one activator to cause polymerization of the cyclic olefin monomer and ethylene, the activator being preferably a non-coordinating borate anion and a bulky organic. Contains cations. In any embodiment, the non-coordinating borate anion comprises a tetra (total fluorine-substituted C6-C14 aryl) borate anion and its substituted form; most preferably the non-coordinating borate anion is a tetra (penta). Includes fluorophenyl) borate anion or tetra (perfluoronaphthyl) borate anion. Preferably, the bulky organic cations are the following structures (IIIa) and (IIIb):

(Here, each R group is independently selected from hydrogen, C6-C14 aryl (eg, phenyl, naphthyl, etc.), C1-C10 or or C1-C20 alkyl, or a substituted form thereof; more preferably at least one. The R group is C6-C14 aryl or a substituted form thereof)
Is selected from.
In any embodiment, the bulky organic cation is a reducible Lewis acid, particularly a trityl-type cation capable of deriving a ligand from a catalytic precursor (each "R" group in (IIIa) is an aryl). Each "R" group is a C6-C14 aryl group (phenyl, naphthyl, etc.) or a substituted C6-C14 aryl, preferably the reducible Lewis acid is triphenylcarbenium and its substituted forms.
Also, in any embodiment, the bulky organic cation is a Bronsted acid capable of donating protons to the catalyst precursor, and at least one "R" group in (IIIb) is hydrogen. Generally, typical bulky organic cations of this type are ammonium, oxonium, phosphonium, silylium, and mixtures thereof; preferably methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, Ammonium of N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, and p-nitro-N, N-dimethylaniline; phosphonium from triethylphosphine, triphenylphosphine, and diphenylphosphine Includes oxonium from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane; and sulfonium from thioethers such as diethyl thioether and tetrahydrothiophene, and mixtures thereof.

The catalyst precursor, preferably when mixed with the activator, can react with the activator to form a "catalyst" or "activation catalyst", resulting in the polymerization of the monomer. The catalyst can be formed before mixing with the monomer, after mixing with the monomer, or at the same time as the monomer.
In any embodiment, the result of the polymerization reaction by mixing the components is 0.5, or 1, or 2, or 4 to 10, or 15, or 20 wt% cyclic olefin-derived units, 0, or 1 wt%. Polyethylene, which contains (or consists essentially of, or consists of) C4-C12α olefin-derived units in the range from 10 to 10 or 15 wt%, the rest being ethylene-derived units. Most preferably, it contains (or consists essentially of, or consists of) cyclic olefin-derived units in the range of 0.5, or 1, or 2, or 4 to 10, or 15, or 20 wt%, with the rest derived from ethylene. The unit is polyethylene.

In any embodiment, the cyclic olefin-derived unit is selected from C5-C20 olefin-derived units that include at least one C5-C8 cyclic structure. In any embodiment, the cyclic olefin-derived unit is norbornene or a C1-C10 alkyl-substituted norbornene-derived unit. Most preferably, polyethylene consists of cyclic olefin-derived units and ethylene-derived units.
The branching level and molar mass of polyethylene can be controlled by any known means, such as adding hydrogen to the polymerization reactor when the monomer is mixed with the catalyst to cause polymerization. In any embodiment, the number average molecular weight (Mn) of polyethylene described herein ranges from 20, or 30 kg / mol to 60, or 80, or 100, or 140 kg / mol. In any embodiment, the mass average molecular weight (Mw) of polyethylene is in the range of 80, or 100 kg / mol to 120, or 140, or 160, or 200, or 300 kg / mol. In any embodiment, z average molecular weight (Mz) greater than 180 kg / mol or in the range of 180, or 200, or 210 kg / mol to 250, or 280, or 300 kg / mol. In any embodiment, polyethylene is Mw / Mn less than 2.5, 2.3, or 2.2, or Mw / Mn in the range of 1, or 1.1, or 1.2 to 1.8, or 2, or 2.2, 2.3, or 2.5. Has an Mn value. In any embodiment, the polyethylene described herein has Mz / Mw in the range of 2.5, or less than 2, or 1.2, or 1.5 to 2 or 2.5.

In any embodiment, polyethylene is substantially linear, which means that there are no long chain (chains longer than 6-10 carbon atoms) branches. Most preferably, polyethylene has a g'(or _g'vis ) value greater than 0.95, or 0.96, or 0.97. A value of "1" reflects the ideal linear polyethylene.
Polyethylene surprisingly exhibits improved shear fluidization, as reflected, for example, in having a relatively high complex viscosity at low shear rates and a relatively low complex viscosity at high shear rates. This behavior results in a plot of complex viscosity vs. shear rate that is nearly linear or linear with a negative gradient, for example as shown in FIG. Thus, in any embodiment, polyethylene is at least 70, 80, or 90 kPa · seconds, or 70, or 80, or 90 kPa · seconds to 120, or 140, at a shear rate ^{of 0.01 seconds-1 at 190 ° C.} Alternatively, it has a complex viscosity in the range of up to 160 kPa · sec. Also, in any embodiment, polyethylene is used at 190 ° C. for 100 seconds- ¹ shear rate of 40, 30, or 20, or less than 10 kPa · sec, or 40, 30, or 20, or 10 to 5 kPa. -Has a complex viscosity in the range up to seconds.

Polyethylene surprisingly exhibits improved strain hardening as reflected in having a viscosity that increases over time at various shear rates, for example as demonstrated in FIG. 6d. Preferably polyethylene exhibits a detectable extensional viscosity that exceeds the peak extensional viscosity and does not drop to zero viscosity after reaching the peak. Thus, in any embodiment, polyethylene is at least 600, or 700, or 800, or 900 kPa · sec (above the linear viscoelastic limit, or "LVE") at a strain rate ^{of 0.1 sec-1 at 150 ° C.} It has a peak extensional viscosity in the range of 600, 700, or 800, or 900 kPa · sec to 1000, 1500, or 2000 kPa · sec. Also, in any embodiment, polyethylene is ^{strained at 150 ° C. at a strain rate of 0.1 seconds-1} greater than 3, or 3.2, or in the range of 3, or 3.2 to 4, 5, or 6. Has a cure rate (SHR).
In any embodiment, polyethylene exhibits rod-like morphology as demonstrated by atomic force microscopy and has dimensions in the range of 1-10 nm wide and 50-1000 nm long below solidification temperature.

The polyethylene described herein is a fairly large number of articles, such as films (average thickness less than 200 μm), sheets (average thickness greater than 200 μm), molded products (eg, thermoformed products, blow molded products, extrusion molding). (Products, etc.), and pipes, pipes, etc., all of which may be foamed or non-foamed, with polyethylene as the main polymer component alone or with other polymers such as propylene-based impact copolymers (propylene-based). Impact copolymer), ethylene-propylene-diene rubber (EPDM), high density polyethylene (HDPE), other linear low density polyethylene (LLDPE), polypropylene, polystyrene, butyl base polymer, aryl polyester carbonate, polyethylene terephthalate, poly With butylene terephthalate, amorphous polyacrylate, nylon-6, nylon-6,6, additional polyamides, polyaramids, polyether ketones, polyoxymethylene, polyoxyethylene, polyurethanes, polyethersulfone, polyvinylidene fluoride, etc. Include in combination. For films, sheets and the like, polyethylene is preferably used alone or as a main component, that is, by mass of the article, 50, 60, or 70, or more than 80 wt% of the article.

The polyethylenes described herein are useful for films, especially blow films. In any embodiment, an intrinsic Tear containing (or essentially consisting of, or consisting of) the polyethylene described herein, greater than 500, or 550, or 600 g / mil (kg / 25 mm). , 800, or 850, or 900%, and MD 1% Second Flexural Modulus, greater than 150, 200, or 250, or 300 MPa. The film may be single layer, two layers, three or more layers, and one or more layers contain one or more polyethylenes or consist essentially of one or more polyethylenes.
The various descriptive elements and numerical ranges disclosed herein with respect to the polyethylene described herein and the methods thereof are combined with other descriptive elements and numerical ranges to describe polyethylene and the desired composition comprising it. In addition, for a given element, any upper limit value can be combined with any lower limit value described herein, including examples within jurisdiction that allow the combination. The characteristics of polyethylene will be demonstrated in the following non-limiting examples.

Test method Chemical structure. 120 scans at 120 ° C in 500 MHz NMR instrument, TCE-d2 solvent. NMR data of the olefin block copolymer was measured by dissolving a 20 ± 1 mg sample in 0.7 ml of d-solvent. Dissolve the sample in TCE-d2 at 120 ° C. in a 5 mm NMR tube until the sample dissolves. No standard substance is used. TCE-d2 appeared as a peak at 5.98 ppm and was used as a reference peak for the sample.
Molecular weight properties and branching. Mw, Mn and Mw / Mn using three in-line detectors, namely a high temperature GPC (Agilent PL-220) equipped with a differential index detector (DRI), a light scattering (LS) detector and a viscometer. Decided. Details of the experiment, including detector calibration, can be found in the paper by T. Sun, P. Brant, RR Chance, and WW Graessley, 34 (19) Macromolecules, 6812-6820 (2001) and references therein. ing. Three Agilent PLgel 10 μm Mixed-B LS columns were used. The nominal flow rate is 0.5 mL / min and the nominal injection volume is 300 μL. Various transfer lines, columns, viscometers and differential refractometers (DRI detectors) were housed in ovens maintained at 145 ° C. The experimental solvent is prepared by dissolving 6 grams of butylated hydroxytoluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.1 μm Teflon® filter. Then degas the TCB with an online degasser before entering the GPC. The polymer solution was prepared by placing the dry polymer in a glass container, adding the desired amount of TCB, and then heating the mixture at 160 ° C. for about 2 hours with continuous shaking. All quantities were measured by the gravimetric method. The TCB density used to express the polymer concentration in mass / volume units is 1.463 g / ml at room temperature and 1.284 g / ml at 145 ° C. The injection concentration is 0.5 to 2.0 mg / ml, and the larger the molecular weight of the sample, the lower the concentration used. The DRI detector and viscometer were purged before each sample was run. The flow rate of the device is then increased to 0.5 ml / min, the DRI is stabilized for 8 hours and then the first sample is injected. Turn on the LS laser at least 1-1.5 hours before running the sample. The concentration c at each point on the chromatogram is _{calculated from the baseline subtraction DRI signal, I DRI} , using the following equation.
c ＝ K _DRI I _DRI ／ (dn / dc)
In the equation, K _DRI is a constant determined by calibrating the DRI and (dn / dc) is the index index increment of the system. Refractive index of TCB at 145 ° C and y = 690 nm, n = 1.500. The unit for parameters throughout this description is ^{expressed in g / cm 3} , the molecular weight is expressed in kg / mol or g / mol, and the intrinsic viscosity is expressed in dL / g.

The LS detector is Wyatt Technology High Temperature DAWN HELEOS. The molecular weight M at each point on the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (MB Huglin, Light Scattering from Polymer Solutions, Academic Press, 1971).

Here, ΔR (Θ) is the excess Rayleigh scattering intensity measured at the scattering angle Θ, “c” is the polymer concentration determined from the DRI analysis, and A ₂ is the second virial coefficient. .. P (Θ) is the shape factor of the monodisperse random coil and _Ko is the optical constant of the system.

In the equation, N _A is Avogadro's number and (dn / dc) is the index index increment of the system, which takes the same value as obtained from the DRI method. Refractive index of TCB at 145 ° C and y = 657 nm n = 1.500.
The specific viscosity is determined using a high temperature Viscotek Corporation viscometer with four capillaries arranged in a Wheatstone bridge structure with two pressure transducers. One transducer measures the total pressure drop across the detector and the other transducer located between both sides of the bridge measures the differential pressure. From those outputs, calculate _{the specific viscosity η s of the} solution flowing through the viscometer. Calculate the intrinsic viscosity [η] of each point on the chromatogram from the following equation.
η _s = c [η] + 0.3 (c [η]) ²
In the formula, c is the concentration, determined from the DRI output.

_{The branch index (g'vis} ) is calculated using the output of the GPC-DRI-LS-VIS method as follows. As a model, Example 2 below was analyzed to analyze as EPDM with 0 wt% propylene in EP and 5.9 wt% ENB; Example 1 was analyzed as 6.7 wt% propylene in EP (hexene substitution). Analyzed as EPDM with (as a minute) and 9.3 wt% ENB (as a substitution of NB). The average intrinsic viscosity [η] _avg of the sample is calculated by the following formula.

In the equation, the sum spans all chromatographic slices, i, between integration limits.

M_vは、LS解析によって決まる分子量に基づく粘度平均分子量である。データ処理のために、使用したマルク・ホウインク(Mark-Houwink)定数はK=0.000579及びa=0.695だった。Mnの値は±50g/モル、Mwの値は±100g/モル、Mzの値は±200である。
ひずみ硬化。Anton-Paar MCR 501又はTA機器DHR-3でSER Universal Testing Platform (Xpansion Instruments, LLC)、モデルSER2-P又はSER3-Gを用いて伸長レオメトリーを行なった。SER(Sentmanat伸長レオメーター)試験プラットフォームは、US 6,578,413及びUS 6,691,569に記載されている。過渡的一軸伸長粘度測定の概要は、例えば、“一軸伸長流れにおける種々のポリオレフィンのひずみ硬化(Strain hardening of various polyolefins in uniaxial elongational flow),” 47(3) The Society of Rheology, Inc., J. Rheol., 619-630 (2003)；及び“SER汎用試験プラットフォームを用いるポリエチレン溶融物の過渡的伸長レオロジーの測定(Measuring the transient extensional rheology of polyethylene melts using the SER universal testing platform),” 49(3) The Society of Rheology, Inc., J. Rheol., 585-606 (2005)に提供されている。ポリマーが一軸伸長を受けるとひずみ硬化が起こり、過渡的伸長粘度は、線形粘弾性理論から予測されるものより増大する。ひずみ硬化は、過渡的伸長粘度対時間のプロットにおいて伸長粘度の急激な上昇として観察される。ひずみ硬化率(SHR)は、伸長粘度の上昇を特徴づけるために使用され、同一ひずみにおける過渡的ゼロずり速度粘度の値の3倍と比べた最大過渡的伸長粘度の比と定義される。この比が1より大きい場合に該材料にひずみ硬化が存在する。SER機器は、シャーシ内に収容され、交差反転式ギアによって機械的に連結されたベアリングに取り付けられた対の主動及び従動巻取ドラムから成る。駆動軸の回転が、装着された主ドラムの回転と、従動ドラムの等しいが反対の回転をもたらし、ポリマーサンプルの末端を探ってドラムに押し上げさせ、結果としてサンプルを引き伸ばす。ほとんどの場合、固定クランプを用いてサンプルをドラムに取り付ける。伸長試験に加えて、過渡的定常ずり条件を利用してもサンプルを調べ、3という相関係数を用いて伸長データと一致させた。これは線形粘弾性包絡線(LVE)を与える。概算寸法が長さ18.0mm×幅12.70mmの矩形サンプル片をSER治具に載せた。一般的に3つのヘンキー(Hencky)ひずみ速度：0.01秒^-1、0.1秒^-1及び1秒^-1でサンプルを試験した。試験温度は150℃である。ポリマーサンプルは以下のように調製した：サンプル片を190℃でホットプレスし、治具に取り付け、150℃で平衡化した。 The branching index g'(or _g'vis ) is defined as follows.

M _v is the viscosity average molecular weight based on the molecular weight determined by LS analysis. The Mark-Houwink constants used for data processing were K = 0.000579 and a = 0.695. The value of Mn is ± 50 g / mol, the value of Mw is ± 100 g / mol, and the value of Mz is ± 200.
Strain hardening. Elongation rheometry was performed on the Anton-Paar MCR 501 or TA instrument DHR-3 using the SER Universal Testing Platform (Xpansion Instruments, LLC), model SER2-P or SER3-G. SER (Sentmanat Elongation Rheometer) test platforms are described in US 6,578,413 and US 6,691,569. For an overview of transient uniaxial elongational viscosity measurements, see, for example, “Strain hardening of various polyolefins in uniaxial elongational flow,” 47 (3) The Society of Rheology, Inc., J. et al. Rheol., 619-630 (2003); and “Measuring the transient extensional rheology of polyolefin melts using the SER universal testing platform,” 49 (3). Provided in The Society of Rheology, Inc., J. Rheol., 585-606 (2005). Strain hardening occurs when the polymer undergoes uniaxial elongation, and the transient extensional viscosity increases more than predicted by linear viscoelasticity theory. Strain hardening is observed as a sharp increase in extensional viscosity in the transient extensional viscosity vs. time plot. Strain cure rate (SHR) is used to characterize an increase in extensional viscosity and is defined as the ratio of maximum transient extensional viscosity compared to three times the value of transient zero shear rate viscosity at the same strain. If this ratio is greater than 1, strain hardening is present in the material. The SER equipment consists of a pair of driven and driven take-up drums housed in the chassis and mounted on bearings mechanically connected by intermesh gears. The rotation of the drive shaft results in the same but opposite rotation of the driven drum as the rotation of the mounted main drum, searching for the end of the polymer sample and pushing it up to the drum, resulting in stretching of the sample. In most cases, a fixed clamp is used to attach the sample to the drum. In addition to the elongation test, the sample was examined using the transient steady-state shear condition and matched with the elongation data using a correlation coefficient of 3. This gives a linear viscoelastic envelope (LVE). A rectangular sample piece with approximate dimensions of 18.0 mm in length and 12.70 mm in width was placed on the SER jig. Samples were generally tested at three Hencky strain rates: 0.01 s- ¹ , 0.1 s- ¹ and 1 s- ¹ . The test temperature is 150 ° C. Polymer samples were prepared as follows: Sample pieces were hot pressed at 190 ° C., mounted on a jig and equilibrated at 150 ° C.

Sliding fluidization. Small Angle Oscillatory Spectroscopy (SAOS) was performed on the invention samples and samples B21-B25, as well as the US 5,942,587 (“Arjunan”) “ECD” LLDPE (ECD-103) samples. Polymer samples prepared using a hot press (Carver Press or Wabash Press) were disks 25 mm in diameter and 2.5 mm thick. Rheometer ARES-G2 (TA Instruments) was used to characterize the shear fluidization behavior and small-angle vibration shear measurements were performed at 190 ° C. at frequencies in the range 0.01-500 radians / sec and 10% fixed strain. .. Next, the data is converted to viscosity as a function of shear rate. Strain sweep measurements were made (at an angular frequency of 100 Hz) to ensure that the selective strain gave measurements within the linear deformation range. Data was processed using Trios software.
Morphology. Atomic force microscopy (AFM) is a morphological imaging technique performed using an Asylum Research Cypher atomic force microscope. Samples were cryo-microtomed prior to scanning to create a smooth surface at -120 ° C. After the microtome, the sample was purged under _{N 2 in a desiccator and then evaluated.} Imaging was performed according to the following: the instrument was put into the basic (first) mode of the cantilever, the amplitude was set to 1.0V, and the drive frequency was set about 5% below the free air resonance frequency of the cantilever. When running in multi-frequency mode, a higher mode (2nd, 3rd, or 4th depending on the cantilever and holder) was selected, the amplitude was set to 100 mV, and the drive frequency at resonance was set. The set point was set to 640 mV, the scan speed was set to 1 Hz, and the scan angle was set to 90 °. Asylum Research standard samples (10 micron x 10 micron pitch grid x 200 nm deep pits) were used for AFM SQC and X, Y, and Z calibration. The instrument was calibrated to be within 2% or more of the true value for XY and within 5% or more for Z. A typical scan size was 500 x 500 nm.

Table 1 shows all other test methods used herein.

Examples All invention polymers were prepared using a solution process in a 1.0 liter continuous stirrer reactor (autoclave reactor). The autoclave reactor was equipped with a stirrer, a water cooling / steam heating element with a temperature controller, and a pressure controller. Purification was performed by first passing the solvent and monomer through a purification column. Purified columns were regenerated on a regular basis (twice a year) or whenever there was evidence of low catalytic activity. Isohexane was used as the polymerization solvent. The solvent was supplied to the reactor using a Pulsa pump and its flow rate was controlled by a mass flow controller. The purified ethylene feedstock was supplied to the manifold upstream of the reactor, and its flow rate was also adjusted by a mass flow controller. A mixture of isohexane and tri-n-octylaluminum (TNOAL) and comonomer (1-hexene, norbornene, or a mixture of both) is added to the same manifold through another line, and the mixture of monomer and solvent is added in a single tube. Was supplied to the reactor using. The molecular weight was controlled by adding the amounts of hydrogen shown in Table 1 to achieve the branching level of polyethylene. The reaction temperature was also controlled to 110 ° C. for both polymerization examples, but the reaction temperature can be changed to achieve the molecular weight and branching of polyethylene.

First, the collected polymer was placed on a boiling steam table in the hood to evaporate most of the solvent and unreacted monomers, and then dried in a vacuum oven at a temperature of 90 ° C. for about 12 hours. Vacuum oven dried samples were weighed to give yields. The 1-hexene content of the polymer was determined by FTIR and / or NMR, whereas the norbornene content of the polymer was determined by NMR. Monomer conversion was calculated using the yield, composition and amount of monomer supplied to the reactor. Catalytic activity (also called catalytic productivity) was calculated based on yield and catalyst feed rate. All reactions were carried out at a gauge pressure of about 2.2 MPa.
The single-site catalyst used for the polymerization was p-triethylsilylphenylcarbylbis (cyclopentadienyl) (2,7-di-t-butylfluorenyl) hafnium dimethyl, and the activators used were N, N. -Dimethylanilinium tetrakis (pentafluorophenyl) borate. Both the catalyst and the activator were first dissolved in toluene and the solution was maintained in an inert atmosphere. The catalyst and activator solutions were premixed and fed to the reactor using an ISCO syringe pump. The supply ratio (molar ratio) of the catalyst and the activator was set to 0.98. A tri-n-octyl aluminum (TNOAL) solution (available from Sigma Aldrich, Milwaukee, WI) was further diluted with isohexane and used as a scavenger.

For Example 1, the norbornene monomer was dissolved in isohexane and purified by flowing the solution through a basic alumina bed while whipping nitrogen gas in the solution. Purified norbornene was then premixed with isohexane and 1-hexene and then the mixture was fed to the manifold upstream of the reactor using a comonomer feeding system. For Invention Example 2, norbornene was dissolved in toluene and purified in the same manner as in Invention Example 1. This solution was premixed with isohexane and fed to the upstream manifold of the reactor using a comonomer feeding system.
A summary of process conditions (Table 2) and product properties (Table 3) are as follows. Ethylene-derived units (“C2”), 1-hexene-derived units (“C6”) and norbornene-derived units (“NB”) are expressed as mass percent based on the total mass of polyethylene.

Polymer characterization by NMR. The polymer product was characterized by proton nuclear magnetic resonance ( ¹ H NMR) spectroscopy. ¹ H NMR spectra of terpolymer invention example 1 (terpolymer) and invention example 2 (copolymer) are shown in FIGS. 1 and 2, respectively. Peaks in the 1.92 to about 2.4 ppm region were assigned to norbornene, which were used to calculate the norbornene concentration in the polymer. Peaks in the 0.85 to about 1.05 ppm region were assigned to the terminal methyl groups of the 1-hexencomonomer, which were used to calculate the hexene-derived unit concentration in the polymer.
Narrow MW distribution and linearity by GPC. The GPC traces of Invention Example 1 and Invention Example 2 are shown in FIG. Both polymers exhibit a monomodal and narrow molecular weight distribution (Mw / Mn <1.9) and a g'value close to 1. The molecular weight is comparable to that of Exceed ™ 1018 LLDPE (Mw approx. 108 kg / mol).
Slip fluidization of polyethylene copolymer. The invented copolymer exhibits stronger shear fluidization compared to Exceed 1018 LLDPE (Fig. 4). For reference, a plot of complex viscosity vs. shear rate of some previous gas phase copolymers disclosed in US 5,942,587 (“Arjunan”) is shown in Figure 5. Substantial shear fluidization was not observed in the patent (at low shear rates, the viscosity remained flat without increasing).

Strain hardening. Figure 6 shows the extensional viscosity of the polymer melt at 150 ° C. Exceed 1018 LLDPE is essentially non-strain hardened (Figure 6a). The post-reactor blending technique (addition of low levels of hypercyclic polyethylene) results in moderate strain hardening, but the melt breaks easily upon elongation (Figure 6b). Exceed 1018 LLDPE contains 8 wt% hexencomonomer and Topas ™ 5013 Cyclic Olefin Copolymer (COC) contains 78 wt% norbornene monomer, so the Exceed 1018 LLDPE blend with 10 wt% Topas 5013 COC is 7 wt%. Contains hexene and 8 wt% norbornene. Invention Example 1, which has a comonomer content similar to that of this blend, exhibits excellent strain hardening (Fig. 6c). Furthermore, Invention Example 2 also has much improved strain hardening (Fig. 6d). The SHR calculated for Exceed 1018 LLDPE at 150 ° C. and ^{a strain rate of 0.1 sec-1} is 1.6, for Exceed 1018 with 10 wt% Topas 5018 is 2.9, in Invention Example 1 is 3.4, and inventive Example 2 is SHR. It was 4.
Mechanical properties. Invention Polyethylene and Exceed 1018 LLDPE resin were compression molded and the resulting film was subjected to tensile and tear tests. The data are summarized in Table 4. Exceed 1018 LLDPE and vapor phase COC terpolymer blow films are also included for comparison purposes. Gas-phase COC terpolymer blow films are typically 3-5 mils (76.2-127 μm) thick. The Exceed 1018 blow film is approximately 1 mil (25.4 μm) thick. All compression molded films are approximately 2 mils (50.8 μm) thick. Normalize all data to thickness. "GP" is a gas phase-forming LLDPE terpolymer blow-molded into a film.

Invented polyethylene (Invention Copolymer 2) has twice the tensile modulus of Exceed 1018, demonstrating an improvement over previous vapor phase terpolymers made according to US 5,942,587. Yield strength is 35% higher than Exceed 1018 LLDPE and higher than vapor phase terpolymer. Break point elongation is better than that of the similarly machined Exceed 1018 LLDPE. The tear properties of the invented polyethylene are twice the intrinsic tear strength of Exceed 1018 LLDPE, three times the MD tear strength of Exceed 1018 LLDPE, and 70% higher than the MD tear strength of vapor-phase terpolymer.
Morphological properties of solution-forming polyethylene. Invention Polyethylene also has a unique morphology that differs from Exceed 1018 LLDPE (Fig. 7a). As shown in the bimodal AFM images in Figures 7b and 7c, the polyethylenes of both inventions are insects with a width of several nanometers and a length of 50-about 500 nm, probably due to the aggregate of norbornene-rich segments of the polymer chain. It shows a similar structure. These worm-like structures are very different from the shish-kabob aggregates of polyethylene crystallites in Figure 7a, which instead have alternating light-dark segments and show sparsely distributed norbornene monomer content. .. The worm-like aggregates are mainly present in the amorphous phase. As a result, they weave and reinforce the polymer matrix. Longer worm-like aggregates are seen in the Invention Copolymer 2 samples, as they do not have additional hexencomonomers and perhaps higher order continuity aggregates can be achieved without interruption of the hexenecomonomers. The morphological properties are consistent with the observed improvements of the invention copolymer 2 samples in shear fluidization, strain hardening, and mechanical properties.

These results demonstrate the surprising difference in invention polyethylene when made in solution process compared to gas phase processes such as US 5,942,587. Invention Polyethylene exhibits strain hardening and shear fluidization greater than the gas relative resistance. Thus, the polyethylene of invention maintains or enhances the mechanical properties of the resulting film while having improved processability and productivity in the film blow process. The polyethylene invention will also provide the improved melt strength required for extrusion coatings and coatings such as foams.

（ここで、
Mは、4族金属であり；
Qは、ケイ素又は炭素であり；
R’及びR”は、それぞれフェニル、アルキル置換フェニル、及びシリル置換フェニルから選択され；
各Xは、独立にC1-C10アルキル、フェニル、及びハロゲンから選択され；
R ¹ 〜R ⁸ は、それぞれ独立に水素、C1-C10アルキル、フェニル、及びアルキルフェニルから選択され；かつ
R ^1’ 〜R ^6’ は、それぞれ独立に水素、C1-C10アルキル、及びフェニルから選択される）
から選択される、付記14に記載のポリマー。
［付記１６］
前記シングルサイト触媒が、下記：

（ここで、
Mは、4族金属であり；
Qは、ケイ素又は炭素であり；
R’及びR”は、それぞれ独立にフェニル、アルキル置換フェニル、及びシリル置換フェニルから選択され；
各Xは、独立にC1-C10アルキル、フェニル、及びハロゲンから選択され；
R ¹ 〜R ⁸ は、それぞれ独立に水素、C1-C10アルキル、フェニル、及びアルキルフェニルから選択され；かつ
R ^1’ 〜R ^6’ は、それぞれ独立に水素、C1-C10アルキル、及びフェニルから選択される）
から選択される、付記14に記載のポリマー。
［付記１７］
付記1〜16のいずれか1項に記載のポリマーを含み、500g/ミルより大きい固有引裂、800%より大きい伸び、及び150MPaより大きいMD 1%セカント曲げ弾性率を有する、フィルム。
［付記１８］
付記1〜16のいずれか1項に記載のポリマーを含む、熱成形品、発泡品、又は押出被覆品。
［付記１９］
溶液中で環状オレフィン、エチレン、水素及び場合によりC4-C12αオレフィンをシングルサイト触媒と混ぜ合わせてポリマーを形成することを含む、ポリマーの形成プロセスであって、前記シングルサイト触媒が、下記構造体：

（ここで、
Mは、4族金属であり；
Qは、ケイ素又は炭素であり；
R’及びR”は、それぞれフェニル、アルキル置換フェニル、及びシリル置換フェニルから選択され；
各Xは、独立にC1-C10アルキル、フェニル、及びハロゲンから選択され；
R ¹ 〜R ⁸ は、それぞれ独立に水素、C1-C10アルキル、フェニル、及びアルキルフェニルから選択され；かつ
R ^1’ 〜R ^6’ は、それぞれ独立に水素、C1-C10アルキル、及びフェニルから選択される）
から選択され；
前記ポリマーは、0.95より大きいg’値を有する、
前記プロセス。
［付記２０］
前記シングルサイト触媒が、下記：

（ここで、
Mは、ジルコニウム又はハフニウムであり；
Qは、ケイ素又は炭素であり；
R’及びR”は、それぞれ独立にフェニル、アルキル置換フェニル、及びシリル置換フェニルから選択され；
各Xは、独立にC1-C10アルキル、フェニル、及びハロゲンから選択され；
R ¹ 〜R ⁸ は、それぞれ独立に水素、C1-C10アルキル、フェニル、及びアルキルフェニルから選択され；かつ
R ^1’ 〜R ^6’ は、それぞれ独立に水素、C1-C10アルキル、及びフェニルから選択される）
から選択される、
付記19に記載のプロセス。
［付記２１］
前記ポリマーが、0.5〜20wt%の範囲内の環状オレフィン由来単位、0wt%〜15wt%の範囲内のC4-C12αオレフィン由来単位を含み、残りはエチレン由来単位である、付記19又は20に記載のプロセス。
［付記２２］
前記ポリマーが、2.5未満のMw/Mn；及び80,000〜300,000g/モルの範囲内の質量平均分子量(Mw)を有する、付記19〜21のいずれか1項に記載のプロセス。
［付記２３］
前記シングルサイト触媒を80℃〜150℃の範囲内の温度でモノマーと混ぜ合わせる、付記19〜22のいずれか1項に記載のプロセス。
［付記２４］
シングルサイト触媒を用いて溶液重合プロセスによって得られるポリマーであって、0.5〜20wt%の範囲内の環状オレフィン由来単位、0wt%〜15wt%の範囲内のC4-C12αオレフィン由来単位を含み、残りはエチレン由来単位であり；かつ
2.5未満のMw/Mn；
80〜300kg/モルの範囲内の質量平均分子量(Mw)；
0.95より大きいg’値
を有する、前記ポリマー。
［付記２５］
凝固温度以下で幅1〜10nm及び長さ50〜1000nmの範囲内の寸法を有する棒状形態学を示す、付記24に記載のポリマー。
［付記２６］
190℃で0.01秒 ^-1 のずり速度にて少なくとも70kPa・秒の複素粘度；及び190℃で100秒 ^-1 のずり速度にて40kPa・秒未満の複素粘度を有する、付記24に記載のポリマー。
［付記２７］
500g/ミルより大きい固有引裂、800%より大きい伸び、及び150MPaより大きいMD 1%セカント曲げ弾性率を有するフィルムであって、0.5〜20wt%の範囲内の環状オレフィン由来単位、0wt%〜15wt%の範囲内のC4-C12αオレフィン由来単位を含み、残りはエチレン由来単位であるポリマーを含み；前記ポリマーは、
2.5未満のMw/Mn；
80〜300kg/モルの範囲内の質量平均分子量(Mw)；
0.95より大きいg’値；
190℃で0.01秒 ^-1 のずり速度にて少なくとも70kPa・秒の複素粘度；及び
190℃で100秒 ^-1 のずり速度にて40kPa・秒未満の複素粘度
を有する、前記フィルム。 The expression "consisting essentially of" in a polymeric composition or polymer component is that the composition or process referred to is free of other additives, monomers, and / or catalysts other than those listed. That, or if present, only to the level of 0.5, 1.0, or 2.0, or 4.0 wt% or less by mass of the composition; and also in the process, "the process is essential from ... "Consists of" means that there are no other major process steps that cause the formation of a covalent chemical bond between the two or more moieties, such as exposure to external radiation, addition of a reactive cross-linking agent, another polymerization step, etc. As meant, there may be minor process features and changes that result in covalent bond formation rates as required, such as changes in temperature or pressure or component concentration. "Additives" include common compounds such as antioxidants, acid scavengers, fillers, colorants, alkyl radical scavengers, UV absorbers, hydrocarbon resins, antislip agents, anti-adhesive agents and the like.
For all jurisdictions to which the principle of "incorporation by reference" applies, all test methods, patent publications, patents and reference articles are incorporated herein by reference in their entirety or the relevant parts to which they are referenced. Is done.
The present invention can also be regarded as including the following matters.
[Appendix 1]
Contains cyclic olefin-derived units in the range of 0.5-20 wt%, C4-C12α olefin-derived units in the range of 0 wt% to 15 wt%, and the rest are ethylene-derived units;
Mw / Mn less than 2.5;
Mass average molecular weight (Mw) in the range of 80-300 kg / mol;
G'value greater than 0.95;
Complex viscosity of at least 70 kPa · sec at 190 ° C. for 0.01 sec- ^{1 shear rate;}
Complex viscosity of less than 40 kPa · sec at 190 ° C for 100 seconds- ^{1 shear rate}
Has a polymer.
[Appendix 2]
The polymer according to Appendix 1, wherein the polymer is formed by mixing cyclic olefins, ethylene, and optionally C4-C12α olefins in a solution process.
[Appendix 3]
The polymer according to Appendix 1 or 2, which exhibits rod-like morphology having dimensions in the range of 1 to 10 nm in width and 50 to 1000 nm in length below the solidification temperature.
[Appendix 4]
The polymer according to any one of Appendix 1 to 3, which has a Mw / Mn value in the range of 1 to 2.5.
[Appendix 5]
The polymer according to any one of Appendix 1 to 4, which is larger than 180 kg / mol or has a z-average molecular weight in the range of 180 kg / mol to 300 kg / mol.
[Appendix 6]
The polymer according to any one of Appendix 1 to 5, which has a Mz / Mw of less than 2.5.
[Appendix 7]
The polymer according to any one of Appendix 1 to 6, having a complex viscosity in the range of 70 to 160 kPa · sec at a shear rate of 0.01 seconds- ^{1 at 190 ° C.}
[Appendix 8]
The polymer according to any one of Appendix 1 to 7, having a complex viscosity in the range of 40 to 5 kPa · sec at 190 ° C. for 100 seconds- ^{1 shear rate.}
[Appendix 9]
The polymer according to any one of Appendix 1 to 8, which has an extensional viscosity exceeding LVE by at least 600 kPa · sec at a strain rate of 0.1 sec- ^{1 at 150 ° C.}
[Appendix 10]
The polymer according to any one of Appendix 1 to 9, which has a strain curing rate (SHR) greater than 3 at a strain rate of 0.1 seconds- ^{1 at 150 ° C.}
[Appendix 11]
The polymer according to any one of Supplementary note 1 to 10, wherein the cyclic olefin-derived unit is selected from C5-C20 olefin-derived units containing at least one C5-C8 cyclic structure.
[Appendix 12]
The polymer according to any one of Supplementary note 1 to 11, wherein the cyclic olefin-derived unit is norbornene or a C1-C10 alkyl-substituted norbornene-derived unit.
[Appendix 13]
The polymer according to any one of Appendix 1 to 12, which comprises a cyclic olefin-derived unit and an ethylene-derived unit.
[Appendix 14]
The polymer according to Appendix 2, which is also mixed with a single-site catalyst.
[Appendix 15]
The single-site catalyst has the following structure:

(here,
M is a Group 4 metal;
Q is silicon or carbon;
R'and R'are selected from phenyl, alkyl-substituted phenyl, and silyl-substituted phenyl, respectively;
Each X is independently selected from C1-C10 alkyl, phenyl, and halogen;
R ^{1 to} R ⁸ are independently selected from hydrogen, C1-C10 alkyl, phenyl, and alkyl phenyl;
R ^{1 '~R 6'} are selected independently hydrogen, C1-C10 alkyl, and phenyl)
The polymer according to Appendix 14, which is selected from.
[Appendix 16]
The single-site catalyst is as follows:

(here,
M is a Group 4 metal;
Q is silicon or carbon;
R'and R'are independently selected from phenyl, alkyl-substituted phenyl, and silyl-substituted phenyl, respectively;
Each X is independently selected from C1-C10 alkyl, phenyl, and halogen;
R ^{1 to} R ⁸ are independently selected from hydrogen, C1-C10 alkyl, phenyl, and alkyl phenyl;
R ^{1 '~R 6'} are selected independently hydrogen, C1-C10 alkyl, and phenyl)
The polymer according to Appendix 14, which is selected from.
[Appendix 17]
A film comprising the polymer according to any one of Appendix 1 to 16 and having an intrinsic tear greater than 500 g / mil, elongation greater than 800%, and MD 1% secant modulus greater than 150 MPa.
[Appendix 18]
A thermoformed product, a foamed product, or an extruded coated product containing the polymer according to any one of Appendix 1 to 16.
[Appendix 19]
A polymer forming process comprising mixing cyclic olefins, ethylene, hydrogen and optionally C4-C12α olefins with a single site catalyst in solution to form a polymer, wherein the single site catalyst comprises the following structure:

(here,
M is a Group 4 metal;
Q is silicon or carbon;
R'and R'are selected from phenyl, alkyl-substituted phenyl, and silyl-substituted phenyl, respectively;
Each X is independently selected from C1-C10 alkyl, phenyl, and halogen;
R ^{1 to} R ⁸ are independently selected from hydrogen, C1-C10 alkyl, phenyl, and alkyl phenyl;
R ^{1 '~R 6'} are selected independently hydrogen, C1-C10 alkyl, and phenyl)
Selected from;
The polymer has a g'value greater than 0.95,
The process.
[Appendix 20]
The single-site catalyst is as follows:

(here,
M is zirconium or hafnium;
Q is silicon or carbon;
R'and R'are independently selected from phenyl, alkyl-substituted phenyl, and silyl-substituted phenyl, respectively;
Each X is independently selected from C1-C10 alkyl, phenyl, and halogen;
R ^{1 to} R ⁸ are independently selected from hydrogen, C1-C10 alkyl, phenyl, and alkyl phenyl;
R ^{1 '~R 6'} are selected independently hydrogen, C1-C10 alkyl, and phenyl)
To be selected from
The process described in Appendix 19.
[Appendix 21]
The polymer comprises a cyclic olefin-derived unit in the range of 0.5 to 20 wt%, a C4-C12α olefin-derived unit in the range of 0 wt% to 15 wt%, and the rest are ethylene-derived units, according to Appendix 19 or 20. process.
[Appendix 22]
The process according to any one of Appendix 19-21, wherein the polymer has a Mw / Mn of less than 2.5; and a mass average molecular weight (Mw) in the range of 80,000 to 300,000 g / mol.
[Appendix 23]
The process of any one of Appendix 19-22, wherein the single-site catalyst is mixed with the monomer at a temperature in the range of 80 ° C to 150 ° C.
[Appendix 24]
A polymer obtained by a solution polymerization process using a single-site catalyst, containing cyclic olefin-derived units in the range of 0.5-20 wt%, C4-C12α olefin-derived units in the range of 0 wt% to 15 wt%, and the rest. It is an ethylene-derived unit;
Mw / Mn less than 2.5;
Mass average molecular weight (Mw) in the range of 80-300 kg / mol;
G'value greater than 0.95
The polymer having.
[Appendix 25]
The polymer according to Appendix 24, which exhibits rod-like morphology having dimensions in the range of 1-10 nm wide and 50-1000 nm long below the solidification temperature.
[Appendix 26]
The polymer according to Appendix 24, having a complex viscosity of at least 70 kPa · sec at a shear rate of 0.01 seconds- ¹ at 190 ° C; and a complex viscosity of less than 40 kPa · sec at a shear rate ^{of 100 seconds-1 at 190 ° C.}
[Appendix 27]
Films with intrinsic tear greater than 500 g / mil, elongation greater than 800%, and MD 1% second flexural modulus greater than 150 MPa, cyclic olefin-derived units in the range 0.5-20 wt%, 0 wt% -15 wt%. Includes C4-C12α olefin-derived units within the range of, the rest contains polymers that are ethylene-derived units; said polymers
Mw / Mn less than 2.5;
Mass average molecular weight (Mw) in the range of 80-300 kg / mol;
G'value greater than 0.95;
Complex viscosity of at least 70 kPa · sec at 190 ° C. for 0.01 sec- ^{1 shear rate;}
Complex viscosity of less than 40 kPa · sec at 190 ° C for 100 seconds- ^{1 shear rate}
The film having.

Claims (10)

And 0.5-20% of a cyclic olefin-derived units, and C ₄ -C ₁₂ alpha-olefin derived units of 0 wt% 15 wt%, essentially consists of a 96～65Wt% of units derived from ethylene;
Mw / Mn less than 2.5;
Mass average molecular weight (Mw) in the range of 80-300 kg / mol;
G'value greater than 0.95;
A polymer having a complex viscosity of 70-160 kPa · sec at 190 ° C. for 0.01 seconds- ¹ shear rate; and a complex viscosity of 5-40 kPa · sec at 190 ° C. for 100 seconds- ^{1 shear rate.} The polymer according to claim 1, which has a z average molecular weight in the range of 180 kg / mol to 300 kg / mol and / or has an Mz / Mw of 1.1 to 2.5. It has a complex viscosity in the range of 70 to 140 kPa · sec at a shear rate of 0.01 seconds- ¹ at 190 ° C. and / or 30-5 kPa · sec at a shear rate ^{of 100 seconds-1 at 190 ° C.} The polymer according to claim 1 or 2, which has a complex viscosity within the range of. It has an extensional viscosity that exceeds LVE by at least 600 kPa · sec at a strain rate of 0.1 sec- ¹ at 150 ° C. and / or strain curing greater than 3 at a strain rate ^{of 0.1 sec-1 at 150 ° C.} The polymer according to any one of claims 1 to 3, which has a rate (SHR). Claimed that the cyclic olefin-derived unit is _{selected from C 5-} C _{20 olefin-derived units comprising at least one C 5-} C _8- cyclic structure, preferably norbornene or a C _1- C ₁₀ alkyl-substituted norbornene-derived unit. Item 8. The polymer according to any one of Items 1 to 4. A thermoformed product, a foamed product, or an extruded coated product containing the polymer according to any one of claims 1 to 5. In a solution polymerization process comprises forming a cyclic olefin, ethylene, alpha-olefin comonomer selected from the group consisting of C ₄ -C ₁₂ alpha-olefin with hydrogen and optionally, by mixing the single-site catalyzed polymers, claim The polymer forming process according to any one of 1 to 5, wherein the single-site catalyst has the following structure:

(here,
M is a Group 4 metal;
Q is silicon or carbon;
R'and R'are selected from phenyl, alkyl-substituted phenyl, and silyl-substituted phenyl, respectively;
Each X is selected C ₁ -C ₁₀ alkyl independently, phenyl, and halogen;
R ¹ to R ⁸ are each independently hydrogen, C ₁ -C ₁₀ alkyl, phenyl, and is selected from alkyl phenyl; and R ^{1 '~R 6'} are each independently hydrogen, C ₁ -C ₁₀ alkyl, And phenyl)
Selected from;
The polymer is made cycloolefin derived units 0.5-20%, and C ₄ -C ₁₂ alpha-olefin derived units of 0 wt% 15 wt%, essentially of 96～65Wt% of units derived from ethylene;
The polymer has a g'value greater than 0.95, Mw / Mn less than 2.5, mass average molecular weight (Mw) in the range of 80-300 kg / mol, 0.01 seconds- ¹ shear rate at 190 ° C. The process having a complex viscosity of 70-160 kPa · sec at 190 ° C. and a complex viscosity of ^{5-40 kPa · sec at a shear rate of 100 seconds-1 at 190 ° C.} The process of claim 7 , wherein the single-site catalyst is mixed with the monomer at a temperature in the range of 80 ° C to 150 ° C. A polymer obtained by a solution polymerization process using a single-site catalyst.
And 0.5-20% of a cyclic olefin-derived units, and C ₄ -C ₁₂ alpha-olefin derived units of 0 wt% 15 wt%, essentially consists of a 96～65Wt% of units derived from ethylene;
G'value greater than 0.95,
Mw / Mn less than 2.5,
Mass average molecular weight (Mw) in the range of 80-200 kg / mol,
A polymer having a complex viscosity of 70-160 kPa · sec at 190 ° C. for 0.01 seconds- ¹ shear rate; and a complex viscosity of 5-40 kPa · sec at 190 ° C. for 100 seconds- ^{1 shear rate.} Shows rod-like morphology with dimensions in the range of 1-10 nm wide and 50-1000 nm long below solidification temperature; complex viscosity of 70-140 kPa · sec at ^{190 ° C. for 0.01 seconds-1 shear rate;} The polymer according to claim 9 , which has a complex viscosity of 5 to 30 kPa · sec at 190 ° C. and ^{a shear rate of 100 sec-1.}

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