Polymers of ethylene and monocyclic organosiloxanes

Abstract

The ethylene-based polymer composition comprises units derived from ethylene, units derived from a comonomer, and optionally units derived from a termonomer, wherein the comonomer is a monocyclic organosiloxane (MOCOS) of formula (I): [R 1 ,R 2 SiO 2 / 2 ] n In the formula, n is an integer of 3 or more, Each R 1 are independently (C2-C4) alkenyl or H2C=C(R 1a )-C(=O)-O-(CH2) m - and R 1a is H or methyl, m is an integer from 1 to 4, Each R 2 are independently H, (C1-C4) alkyl, phenyl, or R 1 is.

Description

Background Art

[0001] In ethylene-based polymers such as low density polyethylene (LDPE), the level of branching, for example, mainly depends on the reactor design (autoclave or tubular) and the polymerization conditions used to produce LDPE. Branching agents for improving the level of branching in LDPE are known. However, the process conditions required to achieve modified LDPE with a high level of branching often result in a final product with inferior properties, including a higher content of low molecular weight extractable fractions.

[0002] Therefore, in the art, there is a continuing need for LDPE having improved melt strength for an improved level of branching and for LDPE prepared under polymerization conditions that maintain good polymer properties.

Summary of the Invention

[0003] The present disclosure is directed to ethylene-based polymer compositions. In one embodiment, the ethylene-based polymer composition comprises units derived from ethylene, units derived from a comonomer, and optionally units derived from a terpolymer. The comonomer is a monocyclic organosiloxane (MOCOS) of formula (I), [R 1 ,R 2 SiO 2 / 2 n where n is an integer of 3 or more, each R 1 is independently (C2-C4) alkenyl or H2C=C(R 1a )-C(=O)-O-(CH2) m -, R 1a is H or methyl, m is an integer of 1 to 4, each R 2 is independently H, (C1-C4) alkyl, phenyl, or R​1 That is the case.

[0004] definition All references to the periodic table refer to the periodic table published by CRC Press, Inc., 1990–1991. The references to element groups in this table are based on a new notation for numbering groups.

[0005] For the purposes of U.S. patent practice, the content of any referenced patent, patent application, or publication, in particular with respect to the disclosure of definitions (to the extent that it does not conflict with any definitions specifically provided in this disclosure), is incorporated by reference in its entirety (or its corresponding U.S. version is incorporated by reference in this way).

[0006] 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 ranges that include explicit values ​​(e.g., 1 or 2, or 3 to 5, or 6 or 7), any sub-ranges between any two explicit values ​​are included (e.g., the above range of 1 to 7 includes sub-ranges such as 1 to 2, 2 to 6, 5 to 7, 3 to 7, 5 to 6, etc.).

[0007] Unless otherwise stated, implied by the context, or customary in the art, all parts and percentages are based on weight, and all test methods are current as of the filing date of this disclosure.

[0008] As used herein, "acrylate" refers to the following structure (A):

[0009] [ka] In the formula, R1 is a hydroxyl group or C1-C 18 It is a monomer containing an alkoxy group (where R2 is H or CH3). Examples of acrylate monomers include acrylates and methacrylates.

[0010] Alkanes are saturated hydrocarbons. Alkyl (or alkyl) is an alkane that has a bond value (typically monovalent).

[0011] An "alkene" is a hydrocarbon containing a carbon-carbon double bond. An "alkenyl" (or "alkenyl group") is an alkene with a bond value (typically monovalent).

[0012] The term "allyl" (or "allyl group") refers to a monovalent unsaturated C3H5 hydrocarbon. In other words, an allyl group is propene with one hydrogen atom removed.

[0013] As used herein, the terms “blend” or “polymer blend” refer to a mixture of two or more polymers. A blend may be miscible or not miscible (not phase-separated at the molecular level). A blend may be phase-separated or not. A blend may include or not include one or more domain configurations determined by transmission electron spectroscopy, light scattering, X-ray scattering, and other methods known in the art. A blend may be made by physically mixing two or more polymers at a macro level (e.g., melt blend or compounding of resins) or at a micro level (e.g., simultaneous formation in the same reactor).

[0014] The term "composition" refers to a mixture of materials containing the composition, as well as reaction 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, steps, or procedures, whether or not they are specifically disclosed. To avoid doubt, all compositions claimed through the use of the term “comprising” may include any additional additives, adjuvants, or compounds, whether polymers or otherwise, unless otherwise stated. In contrast, the term “essentially consisting of” excludes any other components, steps, or procedures from the scope of any subsequent description, except those not essential to the operability. The term “consisting of” excludes any components, steps, or procedures not explicitly described or enumerated. The term “or” refers to the enumerated members individually and in any combination, unless otherwise specified. The use of the singular includes the use of the plural, and vice versa.

[0016] An "ethylene-based polymer" is a polymer that contains more than 50 weight percent (wt%) of polymerizable ethylene monomers (based on the total amount of polymerizable monomers) and may optionally contain at least one comonomer. Ethylene-based polymers include ethylene monopolymers and ethylene copolymers (meaning units derived from ethylene and one or more comonomers). The terms "ethylene-based polymer" and "polyethylene" may be used synonymously.

[0017] As used herein, the terms "ethylene monomer" or "ethylene" refer to a chemical unit having two carbon atoms with a double bond between them, and each carbon atom being bonded to two hydrogen atoms, which polymerizes with other such chemical units to form an ethylene-based polymer composition.

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

[0019] As used herein, the term "linear low-density polyethylene" (LLDPE) comprises units derived from ethylene and at least one C3-C 10 LLDPE refers to linear ethylene / α-olefin copolymers containing a heterogeneous short-chain branching distribution with units derived from α-olefins or C4-C8 α-olefin comonomers. In contrast to conventional LDPE, LLDPE is characterized by the presence of only a small amount of long-chain branching, if any. LLDPE has a density of less than 0.910 g / cc to 0.940 g / cc. Non-limiting examples of LLDPE include TUFLIN® linear low-density polyethylene resin (available from The Dow Chemical Company), DOWLEX® polyethylene resin (available from the Dow Chemical Company), and MARLEX® polyethylene (available from Chevron Phillips).

[0020] As used herein, the term “low-density polyethylene” (or LDPE) refers to polyethylene having a density of 0.910 g / cc to less than 0.940 g / cc or 0.918 g / cc to 0.930 g / cc, and long-chain branching with a broad molecular weight distribution (MWD), i.e., a “broad MWD” of 4.0 to 20.0.

[0021] "Olefins" are unsaturated aliphatic hydrocarbons that have a carbon-carbon double bond.

[0022] The term "phenyl" (or "phenyl group") refers to a C6H5 aromatic hydrocarbon ring with a bond value (typically monovalent).

[0023] As used herein, the terms “polymer” or “polymer material” refer to compounds prepared by polymerizing monomers, whether of the same or different types, providing multiple and / or repeating “units” or “mer units” that constitute the polymer in a polymeric form. Thus, the general term polymer encompasses the term homopolymer, which is typically used to refer to polymers prepared from only one type of monomer, and the term copolymer, which is typically used to refer to polymers 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” refer to the aforementioned copolymers prepared by polymerizing ethylene or propylene with one or more additional polymerizable α-olefin monomers, respectively. Polymers are often described as “made from” one or more specific monomers, “based on” a specific monomer or monomer type, “containing” a specific monomer content, etc., but it should be noted that in this context, the term “monomer” is understood to refer to the polymerized residue of a specific monomer and not to the non-polymerized species. In general, polymers as used herein refer to those based on "units," which are the polymerized forms of the corresponding monomers.

[0024] Test method Density is measured according to ASTM D792, Method B. Results are reported in grams per cubic centimeter (g / cc).

[0025] Fourier Transform Infrared Analysis (FTIR) The amount of terminal and internal trans double bonds per 1000 carbon atoms ("1000C") was determined by Fourier transform infrared analysis ("FTIR"). Sample films (approximately 250-300 microns thick) used for FTIR analysis were compressed by pressing approximately 0.5 g of sample pellets in a Carver hydraulic press equipped with a heated platen set to 190°C. The amounts of terminal and internal alkenes per 1000 carbon atoms were measured following a procedure similar to that outlined in ASTM method D6248. FTIR measures internal alkene bonds in the trans configuration; internal alkene bonds in the cis configuration cannot be detected by FTIR.

[0026] Gel Permeation Chromatography (GPC) The chromatography system consisted of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5), and a 4-capillary viscometer (DV) coupled with a Precision Detectors (now Agilent Technologies) 2-angle laser light scattering (LS) detector Model 2040. A 15-degree angle was used for all absolute light scattering measurements. The autosampler oven compartment was set to 160 degrees Celsius, and the column compartment to 150 degrees Celsius. The columns used were four Agilent "Mixed A" 30 cm, 20 micrometer linear mixed-bed columns. The chromatography solvent used was 1,2,4-trichlorobenzene (CAS 120-82-1, HPLC grade, manufactured by Fisher Scientific) 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.

[0027] Calibration of the GPC column set was performed using polystyrene standards with a narrow molecular weight distribution of at least 20, ranging from 580 to 8,400,000, arranged in six “cocktail” mixtures with at least 10 intervals 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 greater than 1,000,000, and 0.05 grams in 50 ml of solvent for molecular weights less than 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 Equation 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 (Equation 1) In the formula, M is the molecular weight, A has a value of 0.4315, and B is equal to 1.0.

[0028] A polynomial between the third and fifth orders was used to fit the respective polyethylene equivalent calibration points. A was slightly adjusted (to approximately 0.375 to 0.440) to compensate for column resolution and band broadening effects so that the homopolymer polyethylene standard has a molecular weight of 120,000.

[0029] The total plate count of the GPC column set was performed using Eicosane (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 equations:

[0030]

number

[0031]

number

[0032] Samples were 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 pre-nitrogen-spurged, septa-capped vial via a PolymerChar high-temperature autosampler. The samples were dissolved at 160°C for 2 hours under "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 4-6, using the PolymerChar GPCOne® software, the IR chromatogram with the baseline subtracted at each equally spaced data retrieval point (i), and the polyethylene equivalent molecular weight obtained from the narrow standard material calibration curve for point (i) in equation 1.

[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. Using this flow rate marker (FM), the pump flow rate (apparent flow rate) for each sample was linearly corrected by RV matching between the respective decane peaks in the sample (RV(FM sample)) and those in the narrow standard calibration (RV(FM calibrated)). It was then assumed that any temporal changes in the decane marker peaks corresponded to a linear shift in the flow rate (effective flow rate) throughout the run. To facilitate the highest accuracy of RV measurement of the flow rate marker peaks, a least-squares fitting routine was used to fit the peaks of the flow rate marker concentration chromatogram to a quadratic equation. The true peak location was then solved using the first derivative of the quadratic equation. After calibrating the system based on the flow rate marker peaks, the effective flow rate (relative to the narrow standard calibration) was calculated as equation 7. The processing of the flow rate marker peaks was performed via PolymerChar GPCOne® software. An acceptable flow rate correction is one that ensures the effective flow rate is within + / - 2% of the apparent flow rate. Effective flow rate = Apparent flow rate * (RV(FM calibrated) / RV(FM sample))(Equation 7)

[0036] Triple detector GPC (TDGPC) The chromatography system, analytical conditions, column set, column calibration, and conventional molecular weight moment calculations and distributions were performed according to the methods described for gel permeation chromatography (GPC).

[0037] Regarding the determination of viscometer and light scattering detector offsets from an IR5 detector, a systematic method for determining multiple detector offsets was implemented in a manner consistent with that published by Balke, Mourey et al. (Mourey and Balke, Chromatography Polym. Chpt 12, (1992)) (Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, (1992)). Using PolymerChar GPCOne™ software, the results of triple detector logs (MW and IV) from a broad homopolymer polyethylene standard (Mw / Mn>3) were optimized for the results of narrow standard column calibration from a narrow standard calibration curve.

[0038] Absolute molecular weight data were obtained using PolymerChar GPCOne® software in a format consistent with that published by Zimm (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratochvil (Kratochvil, P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY (1987)). The total injection concentration used in determining the molecular weight was obtained from the mass detector area and mass detector constant derived from one of a suitable linear polyethylene homopolymer or a polyethylene standard material with a known weight-average molecular weight. The molecular weight calculated (using GPCOne®) was obtained using the light scattering constant and the refractive index concentration coefficient of 0.104, dn / dc, derived from one or more of the polyethylene standards described below. Generally, the mass detector response (IR5) and light scattering constant (determined using GPCOne®) should be determined from linear standards having a molecular weight greater than approximately 50,000 g / mol. Viscometer calibration (determined using GPCOne®) can be achieved using the method described by the manufacturer, or alternatively, by using published values ​​of suitable linear standards such as Standard Reference Material (SRM) 1475a (available from the National Institute of Standards and Technology, NIST). The viscometer constant (obtained using GPCOne®) is calculated by relating the specific viscosity area (DV) and injected mass of the calibration standard to its intrinsic viscosity. The chromatographic concentration is assumed to be low enough to eliminate the second viral coefficient effect (concentration effect on molecular weight).

[0039] Absolute weight average molecular weight (MW) (Abs)) is obtained from a light scattering (LS) area integrated chromatogram (factorized by the light scattering constant) (using GPCOne®) by dividing the mass recovered from the mass constant by the mass detector (IR5) area. The molecular weight and intrinsic viscosity response are linearly extrapolated (using GPCOne®) at the edge of the chromatography where the signal-to-noise ratio is low. Other respective moments Mn (Abs) and Mz (Abs) This is calculated according to equations 8-9 as follows.

[0040]

number

[0041] GPCBR branch index obtained using Triple Detector GPC (3D-GPC) The gpcBR branching index is determined by first calibrating the light scattering, viscosity, and concentration detectors, as described above. The baseline is then subtracted from the light scattering, viscometer, and concentration chromatograms. Next, an integration window is set to ensure integration of the entire low molecular weight retention volume range of the light scattering and viscometer chromatograms that indicate the presence of detectable polymers from the infrared (IR5) chromatogram. Then, the Mark-Houwink constants for polyethylene and polystyrene are established using linear polyethylene standards. After obtaining the constants, a conventional calibration method using two linear references for polyethylene molecular weight and polyethylene intrinsic viscosity as functions of elution volume is constructed using the two values, as shown in equations (10) and (11). M PE =(K PS / K PE ) 1 / α PE +1 ·M PS αPS+1 / αPE+1 (Equation 10) [η] PE =K PS ·M PS α+1 / M PE (Equation 11)

[0042] The gpcBR branching index is a robust method for characterizing long-chain branching, as described in Yau, Wallace W., "Examples of Using 3D-GPC-TREF for Polyolefin Characterization," Macromol.Symp., 2007, 257, 29-45. This index prioritizes the entire polymer detector area, avoiding the "per-slice" 3D-GPC calculations conventionally used in determining g' values ​​and calculating branching frequencies. From the 3D-GPC data, the bulk absolute weight-average molecular weight (Mw,Abs) of the sample can be obtained using a light scattering (LS) detector with a peak area method. This method avoids the "per-slice" ratio of the light scattering detector signal to the concentration detector signal, as required in conventional g' determination.

[0043] 3D-GPC allows for the independent acquisition of the sample's intrinsic viscosity using equation (8). Area calculations in equations (5) and (8) provide greater accuracy because they are far less affected by detector noise and variations caused by 3D-GPC settings at the baseline and integration limits for the overall sample area. More importantly, peak area calculations are unaffected by detector volume offset. Similarly, the intrinsic viscosity (IV) of the sample can be obtained with high accuracy using the area method shown in equation (12).

[0044]

number

[0045] To determine the gpcBR branching index, the molecular weight of the sample is determined using the light scattering elution area of ​​the sample polymer. The intrinsic viscosity (IV or [η]) of the sample is determined using the elution area of ​​a viscosity detector for the sample polymer.

[0046] First, the molecular weight and intrinsic viscosity of a linear polyethylene standard sample, such as SRM1475a or its equivalent, are determined using conventional calibration ("conventional calibration, cc") for both molecular weight and intrinsic viscosity as a function of elution.

[0047]

number

[0048] All statistical values ​​with the subscript "cc" are determined using the respective elution amount, the corresponding conventional calibration described above, and the concentration (Ci). Values ​​without a subscript are measurements based on the mass detector, LALLS, and viscometer area. K PE The value of is adjusted iteratively until the linear reference sample has a gpcBR measurement of zero. For example, the final values ​​of α and Log K for determining the gpcBR in this particular case are 0.725 and -3.391 for polyethylene and 0.722 and -3.993 for polystyrene, respectively. These polyethylene coefficients were then entered into Equation 13.

[0049] Once the K and α values ​​have been determined using the procedure described above, the procedure is repeated using branched samples. The branched samples are analyzed using the final Mark-Houwink constants obtained from the linear reference, when the best "cc" calibration value is applied.

[0050] The interpretation of gpcBR is straightforward. For linear polymers, the values ​​measured by LS and viscometers are close to the conventional calibration standard, so the gpcBR calculated from equation (14) will be close to zero. For branched polymers, the measured polymer molecular weight will be higher than the calculated Mw,cc, and the calculated IVcc will be higher than the measured polymer IV, so gpcBR will be greater than zero, especially if the level of long-chain branching is high. In fact, the gpcBR value represents the fractional change in IV due to the molecular size contraction effect resulting from polymer branching. A gpcBR value of 0.5 or 2.0 means a molecular size contraction effect of IV at levels of 50% and 200%, respectively, for equivalent weight linear polymer molecules.

[0051] In these specific embodiments, the advantage of using gpcBR compared to conventional "g' index" and branching frequency calculations lies in the higher accuracy of gpcBR. All parameters used in determining the gpcBR index are obtained with high accuracy and are not adversely affected by the low 3D-GPC detector response at high molecular weights from the concentration detector. Errors in detector volume alignment also do not affect the accuracy of gpcBR index determination.

[0052] Melting force Melting force is measured using a D-MELT apparatus (available from Goettfert GmbH Buchen, Germany). D-MELT apparatuses include commercially available plastometers and digital scales incorporating custom weighted samples. A weighted piston is used to extrude the molten polymer strand from a standard plastometer barrel at a constant temperature (190°C) through a standard ASTM D1238 MFR die (orifice height [8.000 ± 0.025 mm] and diameter [2.0955 ± 0.005 mm]). In the D-MELT apparatus, the extruded material is pulled onto a drum driven by a stepping motor, through two free-rotating rollers, which tilt over a speed range during analysis. The force of the polymer strand being pulled onto tension rollers mounted on a force sensor platform is recorded by an integrated control computer within the D-MELT apparatus. From the curve fitting function of the acquired force data, the final reported value is determined based on a constant speed ratio of polymer strand speed to die exit speed (the exact speed ratio depends on the product group). The measurement results are reported as melt elasticity ("ME") in centi-Newtons (cN) or melt force ("MF") in milli-Newtons (mN), depending on the type of rheometer. Immediately after the force measurement, the melt index ("MI") is measured under ASTM conditions using the same filler.

[0053] Melt Index As used herein, the terms “Melt Index” or “MI” refer to a measure of how easily a thermoplastic polymer flows when in a molten state. The Melt Index, or I2, is measured according to ASTM D1238, conditions 190°C / 2.16 kg, and reported as grams of elution per 10 minutes (g / 10 min). I10 is measured according to ASTM D1238, conditions 190°C / 10 kg, and reported as grams of elution per 10 minutes (g / 10 min).

[0054] Melt strength As used herein, the term “melt strength” refers to a measure of the maximum tension that can be applied to a molten polymer before it breaks. Melt strength is measured at 190°C using Goettfert Rheotens 71.97 (Goettfert Inc.; Rock Hill, SC). A Goettfert Rheotester 2000 capillary rheometer, 30 mm long and 2 mm in diameter, with a flat inlet angle (180 degrees), is fed into the molten sample (25–50 grams). The sample is fed into a barrel (L=300 mm, diameter=12 mm), compressed, and melted for 10 minutes, followed by a constant piston speed of 0.265 mm / s (which is 38.2 s for a given die diameter). -1 The extruded material is pushed out at a rate equivalent to the wall shear rate. The extruded material passes through a rheoten wheel located 100 mm below the die exit at 2.4 mm / square second (mm / s). 2 The strand is pulled downward by the wheel at an accelerating speed of ). The force acting on the wheel (measured in centinewtons, cN) is recorded as a function of the wheel's velocity (mm / s). The sample is repeated at least twice until the two curves of force (cN) as a function of strand velocity (mm / s) coincide. Then, the curve showing the highest velocity at the time of strand severance is reported. The melting strength is reported in centinewtons (cN) as the plateau force before the strand is severed.

[0055] Nuclear magnetic resonance ( 1 (H NMR) As used herein, the terms “nuclear magnetic resonance” or “NMR” or “proton NMR” refer to the spectral analysis of a material or compound that provides information about the chemical composition and structure of the material or compound. Proton NMR samples were prepared using 0.1–0.2 g of the sample in 3.25 g of 30 / 70 wt / wt o-dichlorobenzene-d4 / perchloroethylene (ODCB-d4 / PCE) containing 0.001 M chromium(III) acetylacetonate, Cr(AcAc)3, prepared in a 10 mm tube. To ensure homogeneity, the samples were heated and vortexed at 115°C. Single-pulse proton spectra were acquired using a Bruker AVANCE 600 MHz spectrometer with a Bruker high-temperature CryoProbe and a sample temperature of 120°C. Spectra were acquired with a ZG pulse, P1=20us (90°PW), 64 scans, AQ 1.82 sec, D 115 sec.

[0056] The amounts of Si-CH3 and Si-CH=CH2 groups (also interchangeably referred to as "Si-vinyl") per 1000 carbon atoms were obtained as described above. 1 The values ​​were determined by 1H NMR spectroscopy. Total polymer protons were quantified by integrating from approximately -0.5 ppm to 3 ppm, with this integral set to a value of 2000, thus representing 1000 carbons. The signals from the three Si-vinyl protons appear as three distinct multiplets from approximately 5.8 ppm to 6.1 ppm. The closest value is (D) at 5.8 ppm. Vi The 4-multiterm partially overlaps with one of the LDPE chain-terminal vinyl protons at approximately 5.76 ppm. Therefore, we integrate only the two multiplets at approximately 5.92 ppm and 6.02 ppm and average to obtain the number of moles of Si-vinyl per 1000 carbon atoms. [Brief explanation of the drawing]

[0057] [Figure 1] This graph shows the melting force (MF) relative to the weight percentage of MOCOS present in the formant ethylene / MOCOS copolymer according to embodiments of the present disclosure. [Modes for carrying out the invention]

[0058] This disclosure relates to ethylene-based polymer compositions. In one embodiment, the ethylene-based polymer composition comprises units derived from ethylene, units derived from comonomers, and optionally units derived from termonomers. The comonomer is a monocyclic organosiloxane (MOCOS) of formula (I), [R 1 ,R 2 SiO 2 / 2 ] n In the formula, n is an integer greater than or equal to 3. Each R 1 These are independently (C2~C4) alkenyls or H2C=C(R 1a )-C(=O)-O-(CH2) m -and, R 1a is H or methyl, m is an integer between 1 and 4. Each R 2 These are independently H, (C1-C4) alkyl, phenyl, or R 1 That is the case.

[0059] The ethylene-based polymer composition contains (i) units derived from ethylene, (ii) units derived from comonomers (hereinafter interchangeably referred to as "ethylene / MOCOS copolymer"), and (iii) optionally units derived from ter monomers (hereinafter interchangeably referred to as "ethylene / MOCOS / ter polymer"), wherein the ethylene units constitute the majority of the amount (weight %) of monomers present in the polymer. In other words, the ethylene-based polymer composition contains ethylene monomers, MOCOS comonomers (and optionally selected ter monomers), and each of the two monomers (or each of the three monomers if ter monomers are present) polymerizes to form the polymer backbone. Thus, this ethylene-based polymer is structurally different from polyethylene, which contains functional additives grafted onto the polymer chain in a pendant-like manner.

[0060] The ethylene-based polymer composition contains units derived from comonomers in addition to ethylene. The comonomer is a monocyclic organosiloxane of formula (I) [R 1 ,R 2 SiO 2 / 2 ] n (Interchangeably referred to as "MOCOS" or "MOCOS comonomer"), formula (I) is a molecule comprising a monocyclic substructure composed of alternating silicon and oxygen atoms, wherein formula (I) comprises an unsaturated organo(hydrocarbonyl) group and optionally a hydrogen ("H"), a saturated substituent, or an aromatic substituent. Each of at least two unsaturated organic groups and at least two silicon atoms in the cyclic substructure has at least one unsaturated organic group bonded to it, and after being occupied by the unsaturated organic groups and the oxygen atom, any remaining bond value of the silicon atom is bonded to a hydrogen atom, a saturated substituent, or an aromatic substituent, or to an aggregate of such molecules.

[0061] MOCOS is a 6-membered ring (n=3), 8-membered ring (n=4), 10-membered ring (n= 5 ), or it may be a monocyclic organosiloxane composed of a 12-membered ring (n=6). The substructure of the ring is composed of units of formula (I), [R 1 ,R 2 SiO 2 / 2 ] n In the formula, n is an integer greater than or equal to 3, or n is 3, 4-5, or 6, and each R 1 These are independently (C2~C4) alkenyls or H2C=C(R 1a )-C(=O)-O-(CH2) m - and R 1a is H or methyl, and each R 2 These are independently H, (C1-C4) alkyl, phenyl, or R 1 (As defined above). Each [R 1 ,R 2 SiO 2 / 2 In units, R 1 Base and R 2 The group is bonded to each of its silicon atoms. The unit is simply D, using the conventional abbreviation for organosiloxane.R1,R2 It may also be represented as, and as a result, formula (I) is [D R1,R2 n and R 1 and R 2 may be the same or different.

[0062] Non-limiting examples of compounds suitable for the MOCOS of formula (I) include the following: When the abbreviation of MOCOS is D Vi,Et (where Vi is vinyl and Et is ethyl), R 1 is vinyl and R 2 is ethyl; when the abbreviation of MOCOS is D アリル,Et , R 1 is allyl and R<� 2 is ethyl; when the abbreviation of MOCOS is D ブテニル,Et , R 1 is butenyl (H2C=C(H)CH2CH2-) and R 2 is ethyl; when the abbreviation of MOCOS is D Vi,Vi , R 1 is vinyl and R 2 is vinyl; when the abbreviation of MOCOS is D アリル,アリル , R 1 is allyl and R 2 is allyl; when the abbreviation of MOCOS is D ブテニル,ブテニル , R 1 is butenyl (H2C=C(H)CH2CH2-) and R 2 is butenyl; when the abbreviation of MOCOS is D Vi,Ph (where Ph is phenyl), R[[ID=,,52]] 1 is vinyl and R 2 is phenyl; when the abbreviation of MOCOS is D アリル,Ph , R 1 is allyl and R 2 is phenyl; when the abbreviation of MOCOS is D ブテニル,Ph , R 1 is butenyl (H2C=C(H)CH2CH2-) and R 2 is phenyl.

[0063] R 2 ​If is methyl (CH3), the unit is [D R1 ] n To make it simpler, D R1 This can be shown. Further non-limiting examples of compounds suitable for MOCOS in formula (I) include: MOCOS is abbreviated as D Vi In the case of R 1 It is vinyl, R 2 It is methyl; the abbreviation for MOCOS is D アリル In the case of R 1 is an allele, R 2 It is methyl; the abbreviation for MOCOS is D ブテニル In the case of R 1 It is butenyl (H2C=C(H)CH2CH2-), and R 2 It is methyl.

[0064] In one embodiment, each R of MOCOS in formula (I) 1 These are independent of H2C=C(R 1a )-C(=O)-O-(CH2) m - and in the formula, R 1a is H or methyl, and the subscript m is an integer from 1 or 2 to 3 or 4, and any range or individual value therein. In further embodiments, each R 2 Each R is independently either an (C1-C2) alkyl or an (C2-C3) alkenyl, or each R 2 Each R is independently either (C1~C2) alkyl or 2 It is independently methyl.

[0065] In one embodiment, MOCOS of formula (I) has the following structure (B):

[0066] [ka] 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, which has "(D Vi )3" (CAS number 3901-77-7).

[0067] In one embodiment, MOCOS of formula (I) has the following structure (C):

[0068] [ka] 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, which has "(D Vi )4" (CAS number 2554-06-5).

[0069] In one embodiment, MOCOS of formula (I) is 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentavinylcyclopentasiloxane, (D Vi )5.

[0070] The MOCOS comonomer of formula (I) is present in the ethylene-based polymer in amounts of 0.01% to 2% by weight, or 0.01% to 0.5% by weight, or 0.05% to 0.45% by weight, or 0.1% to 0.40% by weight, or 0.15% to 0.30% by weight, or 0.05% to 0.15% by weight. The weight percentage is based on the total weight of the ethylene-based polymer composition.

[0071] In addition to ethylene and MOCOS comonomers, the ethylene-based polymer composition contains units derived from optionally selected ter monomers. If present, ter monomers are olefins, unsaturated esters, functionalized alkenes, silanes, and combinations thereof. Non-limiting examples of suitable ter monomers (if present) include propylene, C4-C8α-olefins, acrylates, (meth)acrylates, vinyl acetate, vinyltrimethoxysilane, and combinations thereof. When ter monomers are present in the ethylene-based polymer, they are present in amounts of 0.5% to 20% by weight, or 1% to 15% by weight, 3% to 12% by weight, or 5% to 10% by weight. The weight percentages are based on the total weight of the ethylene-based polymer composition.

[0072] In one embodiment, the ethylene polymer composition comprises the ethylene / MOCOS copolymer of formula (I) and also comprises the ter monomer of formula (II). Formula (II) [R 1 ,R 2 SiO 2 / 2 ] n In the formula, n is an integer greater than or equal to 3. Each R 1 These are independently a methyl group, a (C2-C4) alkenyl, or H2C=C(R 1a )-C(=O)-O-(CH2) m - and, however, at least two R 1 It is not a methyl group, R 1a is H or methyl, m is an integer between 1 and 4. Each R 2 These are independently H, (C1-C4) alkyl, phenyl, or R 1 That is the case.

[0073] The ethylene polymer composition may contain one or more optional additives. If additives are present, non-limiting examples of suitable additives include stabilizers, light stabilizers, UV absorbers, antioxidants, plasticizers, antistatic agents, pigments, dyes, nucleating agents, fillers, slip agents, flame retardants, processing aids, smoke suppressants, peroxides, crosslinking aids and vulcanization retarders, viscosity modifiers, and anti-blocking agents. The ethylene polymer composition may, for example, contain, a total weight of one or more additives less than 10 percent based on the weight of the ethylene polymer composition.

[0074] In one embodiment, the ethylene polymer composition is treated with one or more stabilizers, such as antioxidants like IRGANOX1010, IRGANOX1076, and IRGAFOS168. Generally, the ethylene polymer composition is treated with one or more stabilizers before extrusion or other melting processes.

[0075] In one embodiment, the ethylene polymer composition is an ethylene / MOCOS copolymer, comprising (i) ethylene and (ii) 0.05% to 0.5% by weight of (D Vi )3, (D Vi )4, and (D Vi This is an ethylene / MOCOS copolymer comprising a MOCOS copolymer selected from 5, having an Mw / Mn ratio of 7.5 to 9.5, a vinyl content of 0.3600 / 1000 carbon atoms to 0.6200 / 1000 carbon atoms, a trans content of 0.1000 / 1000 carbon atoms to 0.3100 / 1000 carbon atoms, an MI of 2.0 g / 10 min to 5.0 g / 10 min, and a melt strength of 5.0 cN to 8.5 cN.

[0076] In one embodiment, the ethylene polymer composition comprises (i) ethylene and (ii) 0.05% to 0.5% by weight of (D Vi )4 is an ethylene / MOCOS copolymer, and the ethylene / MOCOS copolymer composition has one, some, or all of the following properties: (i) Mw / Mn in 7.5-9.5, and / or (ii) Vinyl content of 0.3600 / 1000 carbon atoms to 0.6200 / 1000 carbon atoms; and / or (iii) Trans content of 0.1000 / 1000 carbon atoms to 0.3100 / 1000 carbon atoms, and / or (iv) MI of 2.0g / 10 min to 5.0g / 10 min, or 2.5g / 10 min to 4.7g / 10 min, and / or (v) Melt elasticity of 2.5 cN to 5.0 cN, or 2.7 cN to 4.8 cN, and / or (vi) Melting force of 20mN to 40mN, or 22mN to 37mN, and / or (vii) Melt strength of 5.0 cN to 8.5 cN, or 5.5 cN to 8.5 cN.

[0077] In one embodiment, the ethylene polymer composition is an ethylene / MOCOS copolymer, comprising (i) ethylene and (ii) 0.1% to 0.5% by weight of (D ViThis is an ethylene / MOCOS copolymer comprising a MOCOS copolymer selected from 4, having an Mw / Mn ratio of 7.0 to 7.5, a vinyl content of 0.5800 / 1000 carbons to 0.6200 / 1000 carbons, a trans content of 0.2000 / 1000 carbons to 0.2500 / 1000 carbons, and an MI of 35.0 g / 10 mins to 42.0 g / 10 mins.

[0078] In one embodiment, the ethylene-based polymer composition is an ethylene / MOCOS / MA terpolymer comprising (i) ethylene, (ii) 0.1% to 0.5% by weight of MOCOS, and (iii) 8% to 12% by weight of MA.

[0079] Purpose The ethylene polymer compositions of this disclosure may be used in a variety of conventional thermoplastic manufacturing processes to produce useful articles, including, but not limited to, single-layer and multi-layer films; agricultural films; molded articles, such as blow-molded articles, injection-molded articles, or rotationally molded articles; coatings; fibers; and woven or nonwoven fabrics; cables; pipes; greenhouse films; silo bag films; collation shrink films; food packaging films; and foams. The ethylene polymer compositions are particularly suitable for applications requiring crosslinking by free radical methods such as organic peroxides, including, but not limited to, insulators for power cables.

[0080] This ethylene-based polymer composition can be used in a variety of films, including but not limited to transparent shrink films, agricultural films, collated shrink films, cast stretch films, silage films, stretch hoods, sealants, and diaper backsheets. Other suitable applications include, but are not limited to, wire insulators, cable insulators, gaskets and profiles, adhesives; footwear components and automotive interior components. This ethylene-based polymer composition can be used as part of a blend with LLDPE for agricultural films (large inflation films).

[0081] Without limiting ourselves to any particular example, several embodiments of this disclosure will be described in detail in the following examples. [Examples]

[0082] The materials used in the examples are described in Table 1 below.

[0083] [Table 1]

[0084] The amounts of each material used in the embodiment of the invention and the comparative sample (control) are provided in Table 2 below. In a 545 ml stirring autoclave, ethylene, MOCOS((D Vi 4) A mixture of propylene (as a chain transfer agent) and methyl acrylate (as a ter monomer in comparative sample 6 and inventive examples 7-8) is charged. An organic peroxide (Luperox 26) is added to the mixture as a polymerization initiator in a solution of 0.5% by weight, 1% by weight, or 2% by weight in odorless mineral spirits, and this mixture is heated to approximately 28,000 psi (1,969 kg / cm³). 2 The reactor was subjected to the set pressure. The reactor temperature was set to a target temperature of 220°C. Under the polymerization conditions shown in Table 2, ethylene / MOCOS copolymers were continuously synthesized and then converted into pellet form by melt extrusion. The conditions listed in Table 2 are averages over the length of time samples were collected. The experimental reactor copolymers thus formed "autoclave-produced" were found to have the characteristics described in Table 3.

[0085] [Table 2] Control = Comparison sample IE = Invention Examples

[0086] The properties of the obtained ethylene / MOCOS copolymer and ethylene / MOCOS / MA terpolymer are shown in Table 3 below.

[0087] [Table 3] Control = Comparison sample IE = Invention Examples MA = Methyl acrylate, ME = Melt elasticity (cN), MF = Melt force (mN), MI = Melt index (g / 10 min), MS = Melt strength (cN) NM=Not measured * (D) Based on the total weight of the ethylene polymer composition Vi ) 4% by weight and % by weight of MA + Vinyl and transformer are expressed in mole percent.

[0088] [Table 4] * ID = Identification information, the first value in closing parentheses is (D Vi ) is a weight percentage of 4, and the second value is MI.

[0089] Using proton NMR, (D) in the selected sample Vi The degree of incorporation / conversion of )4 was characterized. Proton NMR detects the presence of Si-CH3 and Si-vinyl. On average, D Vi 2.5 double bonds are incorporated into the polyethylene backbone per 41 molecules (Table 5). Although not bound by any particular theory, (D Vi The copolymerization of 4 with ethylene and the incorporation of two double bonds are thought to create an H-branched structure, resulting in an unexpected increase in melt strength.

[0090] [Table 5]

[0091] Figure 1 shows the melting force pairs (D) for control 1, IE11, IE2, IE3, and IE4 from Table 3. Vi )4 shows the weight percentage (from left to right). As shown in Figure 1, (D Vi Even at low levels of 4 (from 0.5 wt% IE4 to 0.08 wt% IE11), the melting force dramatically increases compared to the comparative sample LDPE, control 1. The linear regression line passing through the present invention in Figure 1 shows a very good linear fit among the invention examples (correlation coefficient R = 0.9989). 2 ), on the other hand, the y-intercept of the linear regression line (19.4 mN), which is much higher than that of the comparative example (12.8 mN), is at a very low level (D Vi )4 suggests extremely nonlinear behavior. In other words, (D Vi Even at very low levels of )4, the melting force increases surprisingly rapidly. For example, 0.08 wt% of IE11 with a corresponding MF of 2.07 mN (D Vi )4, and IE2 0.15 wt% (D) having the corresponding MF25.03mN Vi See 4. When increasing the melting force at these low levels (D Vi The degree of effectiveness of )4 is an unexpected result.

[0092] This disclosure is not limited to the embodiments and examples contained herein, but is particularly 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. This application also relates to the following aspects. (1) Ethylene-based polymer composition, It includes units derived from ethylene, units derived from comonomers, and optionally units derived from termonomers. The comonomer is a monocyclic organosiloxane (MOCOS) of formula (I), [R 1 ,R 2 SiO 2 / 2 ] n In the formula, n is an integer greater than or equal to 3. Each R 1 However, independently, (C 2 ~C 4 ) Alkenyl or H 2 C=C(R 1a )-C(=O)-O-(CH 2 ) m -and, R 1a However, it is H or methyl, m is an integer between 1 and 4. Each R 2 However, independently, H, (C 1 ~C 4 ) alkyl, phenyl, or R 1 An ethylene-based polymer composition. (2) The ethylene-based polymer composition according to (1), comprising 0.01% to 0.5% by weight of the MOCOS comonomer. (3) The ethylene-based polymer composition according to (1) or (2) above, wherein the MOCOS comonomer is selected from the group consisting of 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentavinylcyclopentasiloxane, and combinations thereof. (4) The ethylene polymer is (i) Mw / Mn for 7.5 to 9.5, (ii) Vinyl content of 0.3600 / 1000 carbon to 0.6200 / 1000 carbon, and (iii) An ethylene-based polymer according to any one of (1) to (3) above, which is an ethylene / MOCOS copolymer having a trans content of 0.1000 / 1000 carbon atoms to 0.3100 / 1000 carbon atoms. (5) The ethylene / MOCOS copolymer is (iv) MI of 2.0g / 10 min to 5.0g / 10 min, and (v) An ethylene-based polymer according to any one of (1) to (4) above, having a melt strength of 5.0 to 8.5 cN. (6) The ethylene-based polymer composition according to (1), wherein the ter monomer is present and selected from the group consisting of olefins, unsaturated esters, functionalized alkenes, and combinations thereof. (7) The ethylene-based polymer is in an amount of 0.01% to 0.5% by weight of the MOCOS comonomer, The ethylene polymer according to (6), comprising 0.5% to 20% by weight of the ter monomer. (8) An article comprising the ethylene polymer composition described in any of (1) to (7) above.

Claims

1. An ethylene-based polymer composition, It includes a polymer backbone formed by polymerizing units derived from ethylene, units derived from comonomers, and optionally units derived from termonomers, The comonomer is a monocyclic organosiloxane (MOCOS) of formula (I) present in the ethylene polymer in an amount of 0.01% to 2.0% by weight, based on the total weight of the ethylene polymer composition. [R １ , R ２ SiO ２／２ ｎ Formula (I)​ In the formula, n is an integer of 3, 4, 5, or 6. Each R １ is independently (C ２ ~C ４ ) alkenyl or H ２ C=C(R １ａ )-C(=O)-O-(CH ２ ) ｍ - and R １ａ However, it is H or methyl, m is an integer between 1 and 4. Each R ２ However, independently, H, (C １ ~C ４ ) alkyl, phenyl, or R １ An ethylene-based polymer composition.

2. The ethylene-based polymer composition according to claim 1, comprising 0.01% to 0.5% by weight of the MOCOS comonomer.

3. The ethylene-based polymer composition according to claim 1 or 2, wherein the MOCOS comonomer is selected from the group consisting of 2,4,6-trimethyl-2,4,6-trivinyl-cyclotrisiloxane, 2,4,6,8-tetramethyl-2,4,6,8-tetravinyl-cyclotetrasiloxane, 2,4,6,8,10-pentamethyl-2,4,6,8,10-pentavinyl-cyclopentasiloxane, and combinations thereof.

4. The aforementioned ethylene polymer (i) Mw / Mn between 7.5 and 9.5, (ii) Vinyl content of 0.3600 / 1000 carbon to 0.6200 / 1000 carbon, and (iii) An ethylene-based polymer composition according to any one of claims 1 to 3, which is an ethylene / MOCOS copolymer having a trans content of 0.1000 / 1000 carbon atoms to 0.3100 / 1000 carbon atoms.

5. The ethylene / MOCOS copolymer is (iv) MI of 2.0 g / 10 min to 5.0 g / 10 min, and (v) Having a melt strength of 5.0 to 8.5 cN, The aforementioned MI was measured according to the conditions of 190°C / 2.16 kg. The aforementioned melt strength is measured at 190°C. The ethylene-based polymer composition according to claim 4.

6. The ethylene-based polymer composition according to claim 1, wherein the aforementioned ter monomer is present, and is selected from the group consisting of olefins, unsaturated esters, functionalized alkenes, and combinations thereof.

7. The ethylene-based polymer is present in an amount of 0.01% to 0.5% by weight of the MOCOS comonomer, The ethylene-based polymer composition according to claim 6, comprising 0.5% to 20% by weight of the ter monomer.

8. An article comprising the ethylene polymer composition according to any one of claims 1 to 7.

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