Method for producing branched polyolefins

Abstract

This disclosure provides a process. In embodiments, the process comprises contacting a single polymerization catalyst and co-catalyst in a single reactor with (i) an ethylene monomer and an optional C3-C8α-olefin comonomer, (ii) an alkyl-aluminum chain transfer agent, and (iii) an alkyl-zinc chain transfer agent under polymerization conditions at a temperature of 160°C to 250°C. The process is greater than 8.0 10 This involves forming an ethylene-based polymer having a / I2 value and a vinyl content exceeding 50 / 1,000,000C.

Description

Technical Field

[0001] An olefin polymer having long chain branching (LCB) is an olefin polymer containing one or more side chain branches whose length is comparable to or longer than the critical entanglement length. It is known that when long chain branching (LCB) is incorporated, the processability is improved and the melt strength is increased in olefin polymers.

[0002] Compared with a linear olefin polymer having the same molecular weight, an olefin polymer having LCB exhibits higher shear sensitivity, higher zero-shear viscosity, greater melt elasticity, greater impact strength, and higher melt strength ( "melt strength" is the resistance to stretching during the elongation of a molten olefin polymer). High melt strength is a desirable mechanical property in thermoforming, extrusion coating, and blow molding processes including olefin polymers.

[0003] Also, an olefin polymer having LCB shows a higher viscosity at a low shear rate and a lower viscosity at a high shear rate compared to a linear olefin polymer having the same molecular weight. Shear thinning is advantageous in polymer processing such as under high shear conditions.

[0004] Regarding linear low density polyethylene (LLDPE), the general mechanism by which long chain branches (LCBs) are formed during the coordination polymerization of olefins (a form of addition polymerization mediated by transition metal catalysts) is due to the insertion of vinyl-terminated polymer chains generated by thermal arrest at the transition metal catalyst sites. The level of LCBs formed by this mechanism is usually low due to the small population of vinyl-terminated polymer chains. In contrast, low density polyethylene (LDPE) produced by free radical polymerization is known for its excellent processability due to its unique "dendritic" branch-on-branch structure. It is known that an α,ω-diene such as decadiene is added during olefin polymerization to crosslink two polymer chains. The α,ω-diene approach is disadvantageous as it increases the risk of gelation in the reactor system and imposes a logistical burden due to the limited availability and high cost of industrial scale quantities of α,ω-diene.

[0005] In the art, there is a recognized need for alternative processes for generating long chain branches in olefin polymers. In particular, there is a need for a process for generating long chain branches in olefin polymers (especially ethylene polymers) by the coordination polymerization of olefins. SUMMARY OF THE INVENTION

[0006] The present disclosure provides a process. In an embodiment, the process comprises contacting a single polymerization catalyst and a cocatalyst in a single reactor under polymerization conditions at a temperature of 160°C to 250°C with (i) ethylene monomer and an optional C3 - C8 α-olefin comonomer, (ii) an alkyl-aluminum chain transfer agent, and (iii) an alkyl-zinc chain transfer agent. This process includes forming an ethylene polymer having an I / I2 value greater than 8.0 and a vinyl content greater than 50 / 1,000,000 C. 10 / I2 value and a vinyl content greater than 50 / 1,000,000 C. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] [Figure 1] This chart shows the chemical structures of different types of carbon-carbon double (unsaturated in polymer chains) bonds in vinylene, trisubstituted, vinyl, and vinylidene. [Figure 2] This is a schematic diagram of the polymerization process according to an embodiment of the present disclosure. [Figure 3] This graph shows the GPC curves and Mark-Houwink plots for comparative sample 1 and Example 1 of the present invention. [Figure 4] This graph shows the GPC curves and g' values ​​for comparative sample 1 and example 1 of the present invention. [Figure 5] This graph shows the DMS viscosity overlays for comparative sample 6 and examples 6-13 of the present invention. [Figure 6] This graph shows the DMS tan-delta overlay for comparative sample 6 and examples 6-13 of the present invention.

[0008] definition Any reference to the periodic table refers to the version published by CRC Press, Inc., 1990–1991. References to element groups in this table refer to a new notation for numbering groups.

[0009] For the purposes of U.S. patent practice, the content of any referenced patent, patent application, or publication is incorporated herein by reference in its entirety, particularly with respect to the disclosure of definitions and general knowledge in the art (to the extent that it does not contradict any definitions specifically provided herein) (or the corresponding U.S. patent application of the publication is incorporated by reference in the same way).

[0010] Numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit (including the lower and upper limits). In the case of a range that includes an explicit value (e.g., 1 or 2, or 3 to 5, or 6 or 7), any sub-range between any two explicit values ​​is included (e.g., in the case of the range 1 to 7 above, this includes sub-ranges such as 1 to 2, 2 to 6, 5 to 7, 3 to 7, 5 to 6, etc.).

[0011] Unless otherwise objected, and unless implied by the context, all parts and percentages are based on weight, and all test methods are current as of the filing date of this disclosure.

[0012] As used herein, "alkyl group" refers to a saturated hydrocarbonyl group.

[0013] As used herein, the terms “blend” or “polymer blend” refer to a blend of two or more polymers. Such a blend may or may not be miscible (i.e., not phase-separated at the molecular level). Such a blend may or may not be phase-separated. Such a blend may or may not contain one or more domain configurations as determined by transmission electron spectroscopy, light scattering, X-ray scattering, and other methods well known in the art.

[0014] The term "composition" refers to a mixture of materials that constitute a composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0015] The terms “comprising,” “including,” and “having,” and their derivatives, are not intended to exclude the existence of any additional components, processes, or procedures, whether or not they are specifically disclosed. To avoid any doubt, all compositions claimed through the use of the term “comprising” may, unless otherwise stated, include any additional additives, adjuvants, or compounds, whether polymers or otherwise. In contrast, the term “consisting essentially of” excludes any other components, processes, or procedures from the scope of any prior description, except those not essential to operability. The term “consisting of” excludes any components, processes, or procedures that are not specifically described or enumerated. The term “or” refers to the enumerated members individually and in any combination, unless otherwise stated. The use of the singular includes the use of the plural, and vice versa.

[0016] The term "ethylene-based polymer" and similar terms refer to polymers that, based on the total weight of the polymer, contain a majority by weight percentage of ethylene-derived units in polymeric form. Non-limiting examples of ethylene-based polymers include low-density polyethylene (or ethylene homopolymer, or long-chain branching with a density of 0.915 g / cc to 0.940 g / cc and a broad MWD, typically produced by high-pressure free radical polymerization) and at least one C3-C 10 α-olefins, preferably ethylene / α-olefin copolymers containing C3-C4 (and optionally selected polar ter monomers), which are "LDPE" (linear low-density polyethylene) (or "LLDPE"), units derived from ethylene and at least one C3-C4 10Examples include linear ethylene / α-olefin copolymers containing a heterogeneous short-chain branching distribution that includes units derived from α-olefin comonomers, or at least one C4-C8 α-olefin comonomer, or at least one C6-C8 α-olefin comonomer, wherein LLDPE is characterized in that, in contrast to conventional LDPE, long-chain branching is present, if any, minimal. LLDPE has densities of 0.880 g / cc, 0.890 g / cc, 0.900 g / cc, 0.910 g / cc, 0.915 g / cc, 0.920 g / cc, 0.925 g / cc to 0.930 g / cc, 0.935 g / cc, or 0.940 g / cc, and is classified as very low density polyethylene (VLDPE), ultra low density polyethylene (ULDPE), medium density polyethylene (or "medium density polyethylene, MDPE") - ethylene homopolymer, or has a density of 0.926 g / cc to 0.940 g / cc, and contains at least one C3-C 10 α-olefins or ethylene / α-olefin copolymers containing C3-C4 α-olefins), high-density polyethylene (or "high-density polyethylene, HDPE") are ethylene homopolymers, or at least one C4-C 10 (An α-olefin comonomer or a C4-C8 α-olefin comonomer, and an ethylene / α-olefin copolymer having a density of up to 0.94 g / cc, 0.945 g / cc, 0.95 g / cc, 0.955 g / cc to 0.96 g / cc, 0.97 g / cc, or 0.98 g / cc).

[0017] A "heteroatom" is an atom other than carbon and hydrogen. Heteroatoms can be non-carbon atoms from groups IV, V, VI, and VII of the periodic table. Non-restrictive examples of heteroatoms include F, N, O, P, B, S, and Si.

[0018] A "hydrocarbon" is a compound containing only hydrogen and carbon atoms. A "hydrocarbonyl" (or "hydrocarbonyl group") is a hydrocarbon with a bonding value (typically monovalent). Hydrocarbons can have linear, cyclic, or branched structures.

[0019] An "interpolymer" is a polymer prepared by the polymerization of at least two different monomers. This general term includes polymers prepared from two different monomers, and copolymers, which are commonly used to refer to polymers prepared from more than two different monomers, such as terpolymers, tetrapolymers, etc.

[0020] The terms "long-chain branching," "LCB," and similar terms refer to branched chains extending from the polymer backbone, each containing more than one carbon atom. If the polymer is a copolymer (e.g., ethylene / α-olefin copolymer), the LCB contains one more carbon atom and two less carbon atoms than the total length of the longest comonomer copolymerized with ethylene. For example, in ethylene / octene copolymer, the LCB is at least seven carbon atoms long. In practice, the LCB is longer than the side chains resulting from the incorporation of comonomers into the polymer backbone. The polymer backbone of HPLDPE contains bonded ethylene units.

[0021] An "olefin polymer" or "polyolefin" is a polymer containing more than 50 weight percent of polymerizable olefin monomers (based on the total amount of polymerizable monomers), and may optionally contain at least one comonomer. Non-limiting examples of olefin polymers include ethylene polymers or propylene polymers.

[0022] A "polymer" is a compound prepared by polymerizing monomers that provide a plurality of and / or repeating "units" or "mer units" that constitute the polymer, whether of the same type or different types. Thus, the general term "polymer" encompasses the term "homopolymer", which is commonly used to refer to a polymer prepared from only one type of monomer, and the term "copolymer", which is commonly used to refer to a polymer prepared from at least two types of monomers. It also encompasses all forms of copolymers, such as random, block, etc. The terms "ethylene / α-olefin polymer" and "propylene / α-olefin polymer" each denote the above-mentioned copolymers prepared by polymerizing ethylene or propylene with one or more additional polymerizable α-olefin monomers. Polymers are often referred to as being "made of", "based on", "containing" a specified monomer or type of monomer, etc., but in this context, it should be noted that the term "monomer" is understood to refer to the specified monomer of the polymerization residue and not to non-polymerized species. Generally, polymers herein are based on "units" that are the polymerized form of the corresponding monomers.

[0023] Test Method 1 1H NMR. 1 1H nuclear magnetic resonance 1 1H nuclear magnetic resonance, 1¹H NMR detects the following types of carbon-carbon double bonds ("unsaturated") in polymers: "Vinylen" is a carbon-carbon double bond having the formula R1-CH=CH-R2 (wherein R1 and R2 are each a carbon atom, an alkyl group, or a heteroatom selected from N, O, P, B, S, and Si). "Trisubstituted" is a carbon-carbon double bond in which the carbon of the double bond is bonded to a total of three carbon atoms, where R1, R2, and R3 (in Figure 1) are each carbon atoms. "Vinyl" is a carbon-carbon double bond having the formula R-CH=CH2 (wherein R is a carbon atom or a heteroatom selected from N, O, P, B, S, and Si). "Vinylidene" is a carbon-carbon double bond having the formula C=CH2. "Total unsaturated" (or "total") is the sum of vinylene, trisubstituted, vinyl, and vinylidene in the polymer. The chemical structures of vinylene, trisubstituted vinyl, and vinylidene are shown in Figure 1.

[0024] 1 Polymer samples for 1H NMR analysis were prepared by adding 130 mg of the sample to 3.25 g of 50 / 50 wt tetrachloroethane-d2 / perchloroethylene containing 0.001 M Cr(AcAc)3 in a 10 mm NMR tube. To prevent oxidation, the sample was purged by passing N2 through the solvent for approximately 5 minutes using a pipette inserted into the tube, then the tube was capped and sealed with Teflon tape. To ensure homogeneity, the sample was heated to 115°C and vortexed.

[0025] Using a Bruker AVANCE 400 / 600MHz spectrometer equipped with a Bruker high-temperature CryoProbe, at a sample temperature of 120°C, 11H NMR was performed. To obtain spectra, two experiments were performed: a control spectrum to quantify total polymer protons, and a double pre-saturation experiment to suppress strong polymer backbone peaks and enable a highly sensitive spectrum for quantification of end groups. The control was performed with a ZG pulse, 4 scans, SWH 10,000 Hz, AQ 1.64 s, D 114 s. The double pre-saturation experiment was performed with a modified pulse sequence, lc1prf2.zz1, TD32768, 100 scans, DS4, SWH 10,000 Hz, AQ 1.64 s, D 11 s, D 13 The test was performed in 13 seconds. The results are reported as the number of vinyl groups per 1,000,000 carbon atoms, i.e., per 1,000,000 C (and the number of vinylene, trisubstituted, vinylidene, and total).

[0026] Density is measured according to ASTM D792, Method B. The results are recorded in grams per cubic centimeter (g / cc).

[0027] Triple Detector GPC (TD-GPC). The chromatography system for triple detector gel permeation chromatography (TD-GPC) consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5). The autosampler's oven compartment was set to 160°C, and the column compartment to 150°C. The columns used were four Agilent "Mixed A" 30 cm, 20 micron linear mixed-bed columns and a 20 μm pre-column. The chromatography solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was spurged with nitrogen. The injection volume used was 200 microliters, and the flow rate was 1.0 ml / min.

[0028] Calibration of the GPC column set was performed using 21 polystyrene standards with narrow molecular weight distributions ranging from 580 to 8,400,000, placed in six "cocktail" mixtures with at least a 10-fold gap between individual molecular weights. The standards were purchased from Agilent Technologies. Polystyrene standards were prepared using 0.025 grams in 50 ml of solvent for molecular weights above 1,000,000, and 0.05 grams in 50 ml of solvent for molecular weights below 1,000,000. The polystyrene standards were dissolved at 80 degrees Celsius for 30 minutes with gentle stirring. The peak molecular weights of the polystyrene standards were converted to polyethylene molecular weights using Formula 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M ポリエチレン =A×M ポリスチレン B (Formula 1) In the formula, M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0029] A quintic polynomial was used to fit the respective polyethylene equivalent calibration points. A slight adjustment (approximately 0.375 to 0.445) was made for A to correct the column resolution and band expansion effect so that linear monopolymer polyethylene standards could be obtained at 120,000 Mw.

[0030] The total plate count of the GPC column set was performed using decane (prepared at 0.04 g in 50 ml of TCB and dissolved for 20 minutes with gentle agitation). Plate count (Equation 2) and symmetry (Equation 3) were measured using 200 microliter injections according to the following formulas:

[0031]

number

[0032] The sample was prepared semi-automatically using PolymerChar "Instrument Control" software, with a target weight of 2 mg / mL. The solvent (containing 200 ppm BHT) was added to a vial with a pre-nitrogen-spurged septum cap via a PolymerChar high-temperature autosampler. The sample was dissolved at 160°C for 2 hours with "low-speed" shaking.

[0033] Mn (GPC) , Mw (GPC) , and Mz (GPC) The calculations were based on GPC results using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, according to Equations 4 to 6, using PolymerChar GPCOne® software, IR chromatograms with baselines subtracted at each equally spaced data acquisition point (i), and the narrow standard calibration curve for point (i) in Equation 1, and IR5 detector (measurement channel).

[0034]

number

[0035] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (apparent flow rate) for each sample by matching the RV (RV(FM sample)) of each decane peak in the sample with the RV (RV(FM calibrated)) of the calibrated decane peak in the narrow standard material. It was assumed that any temporal changes in the decane marker peak were related to a linear shift in the flow rate (effective flow rate) over the entire run. To facilitate the highest accuracy of RV measurements of the flow marker peaks, the least-squares fitting method was used to fit the peaks of the flow marker concentration chromatogram to a quadratic equation. The first derivative of the quadratic equation was then used to solve for the true peak location. After calibrating the system based on the flow rate marker peaks, the effective flow rate (relative to the narrow standard calibration) was calculated as shown in Equation 7. The processing of the flow rate marker peaks was performed via PolymerChar GPCOne® software. The acceptable flow rate correction should be such that the effective flow rate is within ±1% of the apparent flow rate. Effective flow rate = Apparent flow rate × (RV (FM calibrated) / RV (FM sample)) (Equation 7)

[0036] Meltflow index (I2, I 10 ) were measured according to ASTM method D1238. I2 and I 10 The measurements were taken at 190°C / 2.16 kg and 190°C / 10 kg, respectively. The results are reported as grams of elution per 10 minutes, i.e., g / 10 min.

[0037] Dynamic mechanical analysis (DMS) was performed using an ARES-G2 rheometer with two parallel plates of 25 mm diameter. The tests were conducted at 190°C, using a 1.8 mm gap, with a frequency interval ranging from 0.1 to 100 rad / s and a 10% strain. By applying this deformation and measuring the resulting torque with a transducer, parameters such as complex viscosity, storage modulus, and loss modulus at specific shear conditions were determined. [Modes for carrying out the invention]

[0038] This disclosure provides a process. In an embodiment, under polymerization conditions at a temperature of 160°C to 250°C, a single polymerization catalyst and co-catalyst in a single reactor are brought into contact with (i) ethylene monomer and an optional C3-C8α-olefin comonomer, (ii) alkyl-aluminum chain transfer agent, and (iii) alkyl-zinc chain transfer agent, and a greater than 8.0 10 A process is provided for forming an ethylene copolymer having a / I2 value and a vinyl content exceeding 50 / 1,000,000C.

[0039] The process involves contacting a single polymerization catalyst and co-catalyst with (i) an ethylene monomer and an optional C3-C8α-olefin comonomer, (ii) an alkyl-aluminum chain transfer agent, and (iii) an alkyl-zinc chain transfer agent under polymerization conditions at a temperature of 160°C to 250°C. As used herein, the term “polymerization conditions” refers to process parameters for copolymerization of ethylene (and an optional C3-C8α-olefin comonomer) in the presence of the catalyst system. Polymerization conditions include, for example, those that affect polymerization reactor conditions (reactor type), reactor pressure, reactor temperature, reagent and polymer concentrations, solvent, support, residence time and distribution, molecular weight distribution, and polymer structure. As used herein, the term polymerization conditions include a single polymerization reaction and a polymerization reactor temperature of 160°C to 250°C, or 180°C to 250°C, or 182°C to 240°C, or 190°C to 240°C, or 192°C to 230°C, or 200°C to 220°C.

[0040] A single polymerization catalyst exhibits resilience to ethylene polymerization at high temperatures, or at temperatures of 160°C to 250°C or 180°C to 250°C. The single polymerization catalyst shows efficient chain transfer with alkyl-zinc and good ability to incorporate vinyl-terminated polymeryl chains. In embodiments, the polymerization catalyst is of formula (1)

[0041] [ka] It has, in the formula, M is titanium, zirconium, hafnium, or scandium. Each Y 1 and Y 2 (C1~C 40 ) Hydrocarbyl, (C1~C 40 ) independently selected from the group consisting of trihydrocarbylsilylhydrocarbyl, halogen, alkoxide, or amine, or two Y groups together are a divalent hydrocarbylene, hydrocarbadiyl, or trihydrocarbylsilyl group. Each Ar 1 and Ar 2 (C6~C 40 ) Aryl, substitution (C6~C 40 )Aaryl, (C3~C 40 ) Heteroaryls, and substitutions (C3~C 40 ) Selected from the group consisting of heteroaryls, T 1 It is a divalent bridging group of 2 to 20 carbon atoms, independently containing heteroatoms containing Si, Ge, O, N, S, and P in each occurrence, at arbitrary selection. Each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12, R 13 , and R 14 These are, independently, hydrogen, halogens, (C1~C 40 ) Hydrocarbyl substitution (C1~C 40 ) Hydrocarbyl, (C1~C 40 ) Heterohydrocarbyl, substitution (C1~C 40 ) Heterohydrocarbyl, (C6~C 40 ) Aryl, substitution (C6~C 40 )Aaryl, (C3~C 40 ) Heteroaryls, and substitutions (C3~C 40 ) Selected from the group consisting of heteroaryls and nitro (NO2).

[0042] In the embodiment, the monopolymerization catalyst has formula (2)

[0043] [ka]

[0044] Polymerization conditions include providing a co-catalyst. Non-limiting examples of suitable co-catalysts include boron compounds that can be used as activating co-catalysts in the preparation of the improved catalysts of this disclosure, which include trisubstituted ammonium salts, such as trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, Tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2 ,3,5,6-tetrafluorophenyl) borate, N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl) borate, dimethyloctadecylammonium tetrakis(pentafluorophenyl) borate, methyldioctadecylammonium tetrakis(pentafluorophenyl) borate; many dialkylammonium salts, for example, Di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, methyloctadecylammonium tetrakis(pentafluorophenyl)borate, methyloctadodecylammonium tetrakis(pentafluorophenyl)borate, and dioctadecylammonium tetrakis(pentafluorophenyl)borate; various trisubstituted phosphonium salts, e.g., triphenylphosphonium tetrakis(pentafluorophenyl)borate, methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate, and tri(2,6-dimethyl Examples include phenyl)phosphonium tetrakis(pentafluorophenyl)borate; disubstituted oxonium salts, such as diphenyloxonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)oxonium tetrakis(pentafluorophenyl)borate, and di(octadecyl)oxonium tetrakis(pentafluorophenyl)borate; and disubstituted sulfonium salts, such as di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate and methyloctadecylsulfonium tetrakis(pentafluorophenyl)borate.

[0045] (i) an ethylene monomer and (ii) an optional C3-C8α-olefin comonomer are polymerized under polymerization conditions. Non-limiting examples of preferred optional C3-C8α-olefin comonomers include α-olefins having 3 to 8 carbon atoms or 4 to 8 carbon atoms. In embodiments, the C3-C8α-olefin comonomer is selected from propylene, butene, hexene, and octene. In further embodiments, a C4-C8α-olefin comonomer exists, and the C4-C8α-olefin monomer is selected from butene, hexene, and octene.

[0046] In embodiments, the process involves contacting a single polymerization catalyst and co-catalyst with only (i) an ethylene monomer and (ii) one or more C4-C8 olefin comonomers under polymerization conditions at a temperature of 160°C to 250°C to eliminate the diene and / or branching agent.

[0047] The process involves contacting a single polymerization catalyst and co-catalyst with (i) an ethylene monomer and an optional C3-C8α-olefin comonomer, (ii) an alkyl-aluminum chain transfer agent, and (iii) an alkyl-zinc chain transfer agent under polymerization conditions at a temperature of 160°C to 250°C. As used herein, “chain transfer agent” refers to a compound in which an alkyl or polymeryl group in the chain transfer agent can be exchanged with a growing polymer chain in the catalyst, resulting in the cessation of polymer chain growth under polymerization conditions. As used herein, “alkyl-aluminum chain transfer agent” refers to a compound of formula R 1 AlR 2 R 3 (In the formula, R 1 , R 2 , and R 3 Each of these is independent of C1~C 20 , or C2~C 10 The chain transfer agent is a compound having (or a C2-C4 alkyl group). The "alkyl-zinc chain transfer agent" as used herein is a compound of formula R 4 ZnR 5 (In the formula, R 4 and R 5 Each of these is independent of C1~C 20 , or C2~C 10 The chain transfer agent is a compound having (or a C2-C4 alkyl group). Non-limiting examples of alkylaluminum chain transfer agents include trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, triisobutylaluminum, trihexylaluminum, triisohexylaluminum, trioctylaluminum, and triisooctylaluminum. Non-limiting examples of alkyl-zinc chain transfer agents include dialkylzinc such as dimethylzinc, diethylzinc, dipropylzinc, dibutylzinc, diisobutylzinc, dihexylzinc, diisohexylzinc, dioctylzinc, and diisooctylzinc.

[0048] Figure 2 is a schematic diagram of the process for producing branched polymers. Under polymerization conditions in a single polymerization reactor at a temperature of 160°C to 250°C, a single polymerization catalyst, a co-catalyst, an ethylene monomer (and an optional C3-C8α-olefin comonomer), an alkyl-aluminum chain transfer agent, and an alkyl-zinc chain transfer agent are brought into contact to form one or more grown polymer chains 12 from the ethylene monomer (and an optional C3-C8α-olefin comonomer), or polymerize in another manner. At the transition metal (M) of the single polymerization catalyst (M is Hf, Zr, Ti, or Sc), the grown polymer chains 12 undergo a chain transfer reaction with the alkyl-zinc chain transfer agent to form one or more zinc-terminated polymer chains 14. The process includes converting one or more zinc-terminated polymer chains 14 into aluminum-terminated polymer chains 16. The process includes converting the multiple aluminum-terminated polymer chains 16 into one or more vinyl-terminated polymer chains 18 by beta-hydride elimination. The vinyl-terminated polymeryl chain 18 is incorporated into the growing polymer chain 12 to form the growing branched polymer chain 12a. The growing branched polymer chain 12a moves to the zinc-terminated polymer chain, then to aluminum again, by repeating the three steps described above, to form the aluminum-terminated branched polymer chain 16a, and subsequently, beta-hydride elimination forms the vinyl-terminated branched polymer chain 18a, which is incorporated into the growing polymer chain 12a or 12 to form the branch-on-branched polymer chain 12b or 12c. In other words, the growing polymer chain 12 first moves from M to alkyl-zinc to form the zinc-terminated polymer chain 14, and then moves again from the zinc-terminated polymer chain to aluminum to form the aluminum-terminated polymer chain 16. Although not bound by any particular theory, it is thought that catalytic transfer by zinc increases the overall transfer rate to aluminum, and that the transfer from zinc to aluminum occurs rapidly. In this way, the presence of the alkyl-zinc chain transfer agent increases (i.e. shortens) the transfer rate compared to the transfer rate of alkyl-aluminum alone, and facilitates the chain transfer process.

[0049] As the polymerization and repeated migration / desorption / integration processes of the growing branched chain continue, the process exceeds 8.0 I 10 It forms a highly branched ethylene-based polymer having an I2 value and a vinyl content exceeding 50 / 1,000,000C.

[0050] In the embodiment, the process involves polymerization under polymerization conditions at a temperature of 160°C to 250°C or 180°C to 240°C, using a single polymerization catalyst and co-catalyst in a single polymerization reactor. (i) Ethylene monomer, (ii) Alkyl-aluminum chain transfer agent or TEA, (iii) Alkyl-zinc chain transfer agent or DEZ To bring it into contact with, I above 8.0 10 This includes forming an ethylene homopolymer having a / I2 value and a vinyl content exceeding 50 / 1,000,000C.

[0051] In the embodiment, the process involves polymerization under polymerization conditions at a temperature of 160°C to 250°C or 180°C to 240°C, using a single polymerization catalyst and co-catalyst in a single polymerization reactor. (i) Ethylene monomers and propylene comonomers, (ii) Alkyl-aluminum chain transfer agent or TEA, (iii) Alkyl-zinc chain transfer agent or DEZ To bring it into contact with, This includes forming an ethylene / propylene copolymer having a vinyl content of more than 50 / 1,000,000C, or 200 / 1,000,000C to 3,000 / 1,000,000C, or 250 / 1,000,000C to 2,500 / 1,000,000C, or 275 / 1,000,000C to 2,100 / 1,000,000C.

[0052] In the embodiment, the process involves polymerization under polymerization conditions at a temperature of 160°C to 250°C or 180°C to 240°C, using a single polymerization catalyst and co-catalyst in a single polymerization reactor. (i) Ethylene monomers and octencomonomers, (ii) Alkyl-aluminum chain transfer agent or TEA, (iii) Alkyl-zinc chain transfer agent or DEZ To bring it into contact with, I 10 This includes forming an ethylene / octen copolymer having a / I2 value and a vinyl content of over 50 / 1,000,000C, or 60 / 1,000,000C to 300 / 1,000,000C, or 70 / 1,000,000C to 250 / 1,000,000C, or 80 / 1,000,000C to 200 / 1,000,000C.

[0053] This process enables the formation of vinyl-terminated polymeryl chains by rapid chain transfer to aluminum (relative to alkyl-zinc), followed by beta-hydride elimination of the aluminum-terminated polymer chain. While not bound by any specific theory, polymerization conditions, including the polymerization catalyst and polymerization temperature of 160°C–250°C, are thought to promote improved chain transfer ability and efficient beta-hydride elimination, allowing for the insertion of significantly large amounts of vinyl-terminated polymeryl chains into the growing polymer chain for the formation of long-chain branching and the generation of branch-on-branch structures.

[0054] Some embodiments of this disclosure are described in detail below, without limitation, as examples. [Examples]

[0055] Table 1 below provides the catalysts, co-catalysts, and chain transfer agents used to prepare Comparative Samples (CS) A to C and Inventive Examples (IE) 1 to 5 of the present invention.

[0056] [Table 1-1]

[0057] [Table 1-2]

[0058] Example 1 (IE1) of the present invention - Ethylene polymerization in a batch reactor Approximately 1.3 kg of Isopar® E mixed alkane solvent was added to a single 1-gallon stirred autoclave reactor. The reactor was heated to 180°C, and triethylaluminum (1 mmol), diethylzinc (0.25 mmol), and ethylene (20 g) were added. The catalyst composition of formula (2) and co-catalyst (a mixture of 1.2 equivalents of borate activator and 10 equivalents of modified methylaluminoxane (MMAO-3A)) was prepared in a dry box under an inert atmosphere by mixing with 0.5 mL of toluene, and the mixture was injected into the autoclave reactor to initiate polymerization. During polymerization, ethylene was supplied, and the reactor pressure and temperature were kept constant by cooling the reactor as needed. After 10 minutes, the supply of ethylene was stopped, and the solution was transferred to a nitrogen-purged plastic kettle. A phosphorus stabilizer and a phenolic antioxidant (Irgafos in toluene at a weight ratio of 2:1) were added. * 168 and Iganox * An additive solution containing 10¹⁰ was added to obtain a total additive content of approximately 0.1% in the polymer. The polymer was completely dried in a vacuum oven.

[0059] Comparative Sample 1 (CS1) The procedure was the same as that described in Example 1 (IE1) of the present invention, except that hydrogen (20 mmol) was added instead of triethylaluminum and diethylzinc.

[0060] The results of Example 1 and Comparative Sample 1 of the present invention are compared in Table 2.

[0061] [Table 2]

[0062] The polymer of Example 1 of the present invention contains a significantly larger amount of terminal vinyl groups compared to comparative sample 1, demonstrating that polymer chain transfer to aluminum and subsequent beta-hydride elimination were effective. The vinyl unsaturation formed in the batch reactor indicates the amount of vinyl-terminated polymer available for insertion and is therefore a good indicator of the ability to form long-chain branches. The formation of several long-chain branches is evident from the GPC Mark-Houwink plot (Figure 3) and g' values ​​(Figure 4). The Mark-Houwink plot is created by plotting molecular weight (MW) against intrinsic viscosity (IV) on a log-log graph. In the presence of long-chain branches, the intrinsic viscosity (IV) is lower, and the plot deviates from those of linear structures with the same composition. As shown in Figure 3, the Mark-Houwink plot of IE1 deviates from CS1, indicating the presence of more long-chain branches in IE1. The g' value is also used to characterize the amount of long-chain branching in the polymer and is the ratio of the intrinsic viscosity of the polymer, determined using a calibrated viscometer and concentration detector, to the calculated intrinsic viscosity of an ethylene homopolymer having the same weight-average molecular weight. The intrinsic viscosity of an ethylene homopolymer is given by the Mark-Houwink equation, IV=k * Mw α It is calculated using and the k value is 4.06 × 10 -4 The α value is 0.725 (Th.G.Scholte, NLJMeijerink, HMSchoffeleers, and AMGBrands, J.Appl.Polym.Sci., 29, 3763-3782 (1984)). As shown in Table 2 and Figure 4, IE1 has a lower g' value, which is consistent with the presence of more long-chain branches.

[0063] Examples 2-5 of the present invention: Ethylene-propylene copolymerization Approximately 1.3 kg of Isopar® E mixed alkane solvent was added to a single 1-gallon stirred autoclave reactor and heated to 180°C. Triethylaluminum (1 mmol), diethylzinc (0.25 mmol), propylene (30 g) (labeled "P" in Table 3), and ethylene (30 g) were added in sequence. Various catalyst compositions were prepared in a dry box under an inert atmosphere by mixing catalysts of formulas (2), (3), (4), and (5) and co-catalysts (a mixture of 1.2 equivalents of borate activator and 10 equivalents of modified methylaluminoxane (MMAO-3A)) with 0.5 mL of toluene, and these were injected into the reactor to initiate polymerization. Only one catalyst was used for each polymerization. Reactor pressure and temperature were kept constant by supplying ethylene during polymerization and cooling the reactor as needed. After 10 minutes, the supply of ethylene was stopped, and the solution was transferred to a nitrogen-purged plastic kettle. Phosphorus stabilizer and phenolic antioxidant (Irgafos in toluene at a weight ratio of 2:1) * 168 and Iganox * An additive solution containing 10¹⁰ was added to obtain a total additive content of approximately 0.1% in the polymer. The polymer was completely dried in a vacuum oven.

[0064] Comparative samples 2-5 The polymerization procedure was the same as that described in Examples 2-5 of the present invention, except that hydrogen (20 mmol) was added instead of triethylaluminum and diethylzinc.

[0065] The results of Examples 2-5 of the present invention and the corresponding comparative samples 2-5 are provided in Table 3 below.

[0066] [Table 3] P-Propylene

[0067] In comparative samples 2-5, terminal unsaturation in the polymer was formed via beta-hydride elimination or chain transfer to monomer at the transition metal center, whereas in Examples 2-5 of the present invention, the unsaturation value included contributions from thermal termination reactions in the catalyst and beta-hydride elimination in the aluminum metal. Two findings were obtained: (1) For all catalysts, Examples 2-5 of the present invention generated significantly more vinyl terminal chains compared to their respective comparative samples 2-5, reflecting the effectiveness of chain transfer to the aluminum metal and subsequent beta-hydride elimination; (2) Examples 2-5 of the present invention showed a higher vinyl / vinylidene ratio, suggesting that chain transfer from the catalyst to aluminum occurred when ethylene was the final unit. This demonstrates branching formation, because only vinyl groups can be inserted into the growing polymeric chain.

[0068] Examples 6-14 and comparative sample 6 of the present invention - Ethylene / octen copolymer in a continuous reactor

[0069] Polymerization was carried out in a single, continuous, well-mixed reactor using formula (2) as the sole catalyst, with a borate activator (indicated as "co-catalyst 1" in Table 4) and the MMAOs listed in Table 1 as co-catalysts. The process conditions and results are shown in Tables 4 and 5 below.

[0070] [Table 4]

[0071] [Table 5]

[0072] Comparative sample 6 was prepared under conventional conditions using hydrogen as a molecular weight modifier, and yielded 7.7 I 10 / I2A linear ethylene / octen copolymer having was produced. Examples 6-14 of the present invention were carried out with the addition of triethylaluminum and diethylzinc. 7.7 at CS6 10 Compared to / I2, I is significantly higher at 12.3-18.1. 10 A / I2 value was observed, which indicates the formation of long-chain branching.

[0073] DMS analysis is shown in Figures 5-6. Examples 6-14 of the present invention exhibit significantly different rheological behavior compared to the ethylene / octen copolymer produced from comparative sample 6, e.g., higher shear viscosity reduction and lower tan-delta values.

[0074] This disclosure is not limited to the embodiments and examples contained herein, but is specifically intended to include some embodiments and modified forms of those embodiments, including combinations of elements of different embodiments, to the extent that they fall within the scope of the following claims.

Claims

1. It is a process, Under polymerization conditions at temperatures of 160°C to 250°C, a single polymerization catalyst and co-catalyst in a single reactor, (i) Ethylene monomer and an optional C ３ ~C ８ α-olefin comonomer, (ii) Alkyl-aluminum chain transfer agent, and (iii) Alkyl-zinc chain transfer agent To bring it into contact with, I above 8.0 １０ / I ２ A process comprising forming an ethylene-based polymer having a vinyl content exceeding 50 / 1,000,000C.

2. The polymerization catalyst is of formula (1) 【Chemistry 1】 It has, in the formula, M is titanium, zirconium, hafnium, or scandium. Each Y １ and Y ２ is independently selected from the group consisting of (C １ ~C ４０ ) hydrocarbyl, (C １ ~C ４０ ) trihydrocarbylsilyl hydrocarbyl, halogen, alkoxide, or amine, or two Y groups together are a divalent hydrocarbylene, hydrocarbyldiyl or trihydrocarbylsilyl group, Each Ar １ and Ar ２ (C ６ ~C ４０ ) Aryl, substitution (C ６ ~C ４０ ) Aryl, (C ３ ~C ４０ ) heteroaryl and substituted (C ３ ~C ４０ ) Selected from the group consisting of heteroaryls, T １ It is a divalent bridging group of 2 to 20 carbon atoms, independently containing, at any choice, a heteroatom containing Si, Ge, O, N, S, and P in each occurrence. Each R １ , R ２ , R ３ , R ４ , R ５ , R ６ , R ７ , R ８ , R ９ , R １０ , R １１ , R １２ , R １３ , and R １４ These are, independently, hydrogen, halogen, (C １ ~C ４０ ) Hydrocarbyl, substitution (C １ ~C ４０ ) Hydrocarbyl, (C １ ~C ４０ ) Heterohydrocarbyl, substitution (C １ ~C ４０ ) Heterohydrocarbyl, (C ６ ~C ４０ ) Aryl, substitution (C ６ ~C ４０ ) Aryl, (C ３ ~C ４０ ) heteroaryl and substituted (C ３ ~C ４０ ) heteroaryl and nitro(NO ２ The process according to claim 1, selected from the group consisting of ).

3. The process according to claim 1 or 2, wherein the polymerization catalyst has formula (2). 【Chemistry 2】

4. Under polymerization conditions at a temperature of 180°C to 250°C, the polymerization catalyst of formula (2) 【Transformation 3】 and co-catalysts, (i) Ethylene monomer and C ３ ~C ８ α-olefin comonomer, (ii) Alkyl-aluminum chain transfer agent, and (iii) Alkyl-zinc chain transfer agent To bring it into contact with, I above 8.0 １０ / I ２ The process according to any one of claims 1 to 3, comprising forming an ethylene copolymer having a value and a vinyl content greater than 50 / 1,000,000C.

5. Under polymerization conditions at a temperature of 180°C to 250°C, the polymerization catalyst of formula (2) 【Chemistry 4】 and co-catalysts, (i) Ethylene monomers, and olefin comonomers selected from the group consisting of propylene, 1-butene, 1-hexene, 1-octene, and combinations thereof, (ii) Triethylaluminum chain transfer agent, and (iii) Diethylzinc chain transfer agent To bring it into contact with, I above 8.0 １０ / I ２ Ethylene / C having a vinyl content exceeding 50 / 1,000,000C ３ ~C ８ The process according to any one of claims 1 to 4, comprising forming an α-olefin copolymer.

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