Polyolefin blend containing amorphous polyalphaolefin

Abstract

The present invention provides a blend comprising at least two different polyolefins, and as a further component an amorphous poly-α-olefin based on the monomers ethene, propene and 1-butene and having a viscosity at 190°C of 200 mPa·s to 200,000 mPa·s, the at least two different polyolefins being polyethylene and polypropylene, wherein the polyethylene has a melt flow index [MFI 2.16 kg @ 190°C] measured according to the method of ISO 1133 described herein of less than 10 g / 10 min, preferably 0.01 to 2 g / 10 min, and the polypropylene has a melt flow index [MFI 2.16 kg @ 230°C] measured according to the method described herein of 50 g / 10 min, preferably 0.01 to 25 g / 10 min; a method for producing such a formulation; Its use and Regarding.

Description

[Technical Field]

[0001] The present invention provides a blend comprising at least two different polyolefins, the blend comprising as a further component an amorphous poly-α-olefin based on the monomers ethene, propene and 1-butene and having a viscosity at 190°C of 200 mPa·s to 200,000 mPa·s measured according to the method described herein, the at least two different polyolefins being polyethylene and polypropylene, the polyethylene having a melt flow index [MFI 2.16 kg @ 190°C] measured according to the method described herein of less than 10 g / 10 min, preferably 0.01 to 2 g / 10 min, and the polypropylene having a melt flow index [MFI 2.16 kg @ 230°C] measured according to the method described herein of 50 g / 10 min, preferably 0.01 to 25 g / 10 min; a method for producing such a formulation; Its use and Regarding. [Background technology]

[0002] Polyolefins, particularly homopolymers and copolymers of the polyethylene, polypropylene, and polybutene groups, form the largest group of commonly used plastics and are the most widely produced worldwide. Substantial applications for these materials include films, packaging, and a wide variety of injection-molded parts, such as those used in automotive manufacturing. In particular, it is important to produce these injection-molded parts with the right balance of strength and impact resistance to ensure maximum everyday usability.

[0003] To achieve this balance, it is common to use a blend of one component (usually crystalline polypropylene) for strength and another (often polyethylene-rich) for impact resistance. The latter component is often rubbery and sticky, so the proportion of this component in the manufacturing process cannot be increased as desired because parts of the equipment become sticky and can no longer process the mixture.

[0004] To improve the quality of heterophasic polymer blends, especially those consisting of polyethylene and polypropylene, additives are often used to compatibilize the polypropylene matrix, which has the crystalline structure responsible for strength, with the soft, impact-absorbing polyethylene-rich fraction.

[0005] Patent Document 1 describes a synergistic composite composition comprising a random ethylene / propylene copolymer and a low- to very-low-density random ethylene / α-olefin copolymer, where the α-olefin has at least 4 carbon atoms. It also relates to a polyolefin composition, particularly a polypropylene composition, containing the composite composition. The MFI of the random ethylene / α-olefin copolymer is 0.1 to 30 dg / min.

[0006] US Pat. No. 5,629,493 describes the use of a C3-C2-block copolymer with an MFI of 30 dg / min or less and a styrene-ethylene-butylene-styrene (SEBS) rubber component.

[0007] Patent document 3 describes a polymer composition containing 1 to 30% by weight of a copolymer obtained by reacting ethylene with an α-olefin having 3 to 10 carbon atoms. The copolymer has an MFI of 100 to 2000 dg / min and a molecular weight distribution (MWD) of 1 to 5.

[0008] US Pat. No. 5,629,493 describes the production of polyolefin (PP or HDPE) based "impact-modified" blends using ethylene-α-olefin copolymers with an MWD well below 5.

[0009] Patent Document 5 describes a gas phase process for producing C2-C3 copolymers with a maximum MFI of 500, and mentions the fact that the material is obtained in a "non-sticky" state downstream of the gas phase reactor. Furthermore, it mentions that the high rubber content in the process is a problem.

[0010] Recently, there has been an additional need to be able to process polypropylene and / or polyethylene-containing recyclates into blends that, after processing, have material properties similar to those obtained using virgin polyethylene and / or polypropylene. [Prior art documents] [Patent documents]

[0011] [Patent Document 1] European Patent Publication No. 0884353A1 [Patent Document 2] U.S. Patent Publication No. 2018134884A1 [Patent Document 3] U.S. Patent Publication No. 2019218383A1 [Patent Document 4] International Publication No. 2011 / 119486A1 [Patent Document 5] Canadian Patent Publication No. 2102542A1 Summary of the Invention [Problem to be solved by the invention]

[0012] The problem that the present invention sought to solve was therefore to provide a polyolefin formulation that solves one or more of the above problems. [Means for solving the problem]

[0013] It has surprisingly been found that one or more of the above-mentioned problems can be solved by a formulation comprising at least two different polyolefins and, as an additional component, an amorphous poly-α-olefin based on the monomers ethene, propene and 1-butene and having a viscosity at 190°C of 200 mPa·s to 200 000 mPa·s.

[0014] Therefore, the present invention provides comprising at least two different polyolefins, as a further component an amorphous poly-α-olefin (APAO) based on the monomers ethene, propene and 1-butene and having a viscosity at 190°C of 200 mPa·s to 200,000 mPa·s, measured according to the method described below in the Measurement Methods section, A blend containing polyethylene and polypropylene as at least two different polyolefins, The polyethylene has a melt flow index [MFI 2.16 kg @ 190°C] measured according to the method of ISO 1133 described in the specification of less than 10 g / 10 min, preferably 0.01 to 2 g / 10 min; The polypropylene is a compound having a melt flow index [MFI 2.16 kg @ 230°C] measured according to the method described in the specification of 50 g / 10 min, preferably 0.01 to 25 g / 10 min. This provides:

[0015] The present invention further provides processes for the preparation of the formulations according to the invention and their uses, as defined in the claims and more particularly as described below.

[0016] The compounds according to the invention have the advantage of having improved material properties: they show good / improved impact resistance and good / improved expansion behavior, especially when the tensile strength is moderately reduced. A further advantage of the blends according to the invention is that they exhibit good compatibility of polyethylene and polypropylene when these are present as different polyolefins.

[0017] The use of APAOs also allows the formulations of the present invention to contain higher amounts of recycled material, particularly polyethylene and / or propylene recycled material, without deteriorating the material properties to the extent that the material can no longer be used for its intended purpose.

[0018] Since separation of polymer waste cannot currently be performed using a single method, for example, PE recycled materials still contain small amounts of PP polymers, and PP recycled materials still contain small amounts of PE polymers, the use of the APAO according to the present invention is particularly advantageous for blends containing such non-single-type recycled materials.

[0019] The formulations according to the present invention, the methods according to the present invention, and the uses of the formulations according to the present invention are illustrated by the following examples, without intending that the present invention be limited to these exemplary embodiments. When ranges, general formulas, or groups of compounds are specified below, these are intended to include not only the corresponding ranges or groups of compounds explicitly mentioned, but also all subranges and subgroups of compounds obtained by excluding individual values ​​(ranges) or compounds. When documents are cited in the context of this specification, their contents fully form part of the disclosure of the present invention, with respect to the matters specifically mentioned. When numerical values ​​are reported below as percentages, these values ​​are by weight unless otherwise specified. When averages, e.g., molar mass averages, are reported below, these are numerical averages unless otherwise specified. When material properties, e.g., viscosity, are reported below, these are material properties at 25°C unless otherwise specified. When chemical (empirical) formulas are used in the present invention, the reported indices may be either absolute numbers or average values. For polymeric compounds, the indices preferably represent average values.

[0020] The formulations according to the invention comprising at least two different polyolefins are characterized in that they contain, as a further constituent, an amorphous poly-α-olefin based on the monomers ethene, propene and 1-butene and having a viscosity at 190°C of 200 mPa·s to 200 000 mPa·s, preferably 1 000 to 150 000 mPa·s, more preferably 2 000 to 100 000 mPa·s, particularly preferably 3 000 to 50 000 mPa·s, measured according to the method reported in the Measurement Methods section below. The amorphous poly-α-olefin includes at least two different polyolefins: polyethylene and polypropylene; the polyethylene has a melt flow index [MFI 2.16 kg @ 190°C] of less than 10 g / 10 min, preferably 0.01 to 2 g / 10 min, measured according to the method of ISO 1133 reported herein; and the polypropylene has a melt flow index [MFI 2.16 kg @ 230°C] of less than 50 g / 10 min, preferably 0.01 to 25 g / 10 min, measured according to the method reported herein.

[0021] The blend of the present invention preferably contains polyethylene and polypropylene as the at least two different polyolefins. The proportion of the minor polyolefin in the blend is preferably 1% to 45% by weight, more preferably 2% to 30% by weight, and particularly preferably 5% to 20% by weight, based on the total mass of the at least two different polyolefins present in the blend. The proportion of the major polyolefin in the blend is preferably 55% to 99% by weight, more preferably 70% to 98% by weight, and particularly preferably 80% to 95% by weight. The above proportions are particularly preferred when some or all of the at least two different polyolefins are recycled.

[0022] It may be advantageous if at least one of the two different polyolefins is at least partially, preferably to an extent of more than 50% by weight, more preferably entirely recycled. It is preferred if both of the at least two different polyolefins are at least partially, preferably to an extent of more than 50% by weight, more preferably entirely recycled.

[0023] The proportion of amorphous poly-α-olefins in the formulation according to the invention is preferably from 1% to 25% by weight, more preferably from 2% to 15% by weight, particularly preferably from 3% to 10% by weight, very particularly preferably from 5% to 7.5% by weight, relative to the total mass of the formulation.

[0024] The amorphous poly-α-olefins preferably have a polydispersity (Mw / Mn) of 5 to 10 and / or a glass transition temperature of −45° C. to −25° C., in each case measured according to the measurement methods reported in the Measurement Methods section below.

[0025] The amorphous poly-α-olefin preferably has a melt flow index [MFI 2.16 kg @ 140°C] of 40 to 10,000, preferably 50 to 5,000, more preferably 100 to 2,000, measured according to the measurement method reported in the measurement method section below.

[0026] In amorphous poly-α-olefins based on the monomers ethylene, propylene, and 1-butene, the proportion of the monomer propylene or 1-butene exceeds 50% by weight, preferably 51 to 98% by weight, and the total proportion of the remaining monomers ethylene and 1-butene, or ethylene and propene, is less than 50% by weight, in either case relative to the total proportions of ethylene, propylene, and 1-butene. The proportion of ethylene is preferably 1 to 15% by weight relative to the total proportion of the monomers ethylene, propylene, and 1-butene.

[0027] It may be advantageous if the amorphous poly-α-olefin has, with respect to the isotacticity of the 1-butene or propene block, an mmmm-pentad fraction of less than 80%, measured according to the measurement method reported herein.

[0028] The blend is preferably a mixture of the listed components, more preferably a pellet mixture of pellets of the listed components. It may be advantageous if the blend is in the form of a mixed pellet material, each pellet containing all the components. Such a mixed pellet material has the following advantages: processing the material, for example by injection molding, can provide a more uniform distribution of the constituent components, resulting in better material properties.

[0029] The formulations of the present invention may contain additional components, such as additives, fillers, and / or pigments (organic or inorganic). The formulations of the present invention preferably contain fibers, more preferably glass fibers, mineral fibers, wood fibers, or other fibrous components, as fillers. This increases the strength of the formulations of the present invention. As a result, the formulations of the present invention can be employed or used in applications that impose high mechanical demands on the materials used, such as when used as or for the manufacture of compounds or composites. The formulations preferably contain 0.01% to 3% by weight of at least one antioxidant, based on the total weight of the APAO and the antioxidant. Usable antioxidants include all substances known as antioxidants and / or inhibitors, i.e., substances that stop the propagation of free radical reactions. The formulations of the present invention preferably contain sterically hindered amines (e.g., piperidine derivatives), more preferably sterically hindered phenols (e.g., Irganox 1010, Naugard XL1, Songnox 1035). This prevents or reduces the decomposition and / or yellowing of the APAO.

[0030] The formulation may preferably contain 0.01% to 3% by weight of at least one free radical former decomposition product relative to the total of the APAO and the free radical former decomposition products. The formulation according to the present invention preferably contains benzoic acid, methanol, butanol, tert-butanol, propionic acid, and / or, preferably, 2,5-dimethylhexanol as free radical former decomposition products.

[0031] The formulations according to the invention may be produced by known formulation production methods, preferably by the formulation production method described below, which is characterized by mixing the components of the formulation.

[0032] In the method according to the present invention, the components are preferably used and mixed as powders or pellets. It may be advantageous to process the pellet mixture thus obtained into a mixed pellet material, for example by extruding the pellet mixture. Therefore, before subjecting this additive pellet material to further processing, the pellet mixture may be applied, for example, by a mixing drum or using a hopper, and the pellets may be introduced using a mixing funnel and uniformly sent to a mixing extruder for further pelletization. Alternatively, a series of extruders may be used to meter the components as a molten stream into the extruder leading to the molding process. Furthermore, one of these processes may be used to directly produce the final processed object (workpiece) by extrusion or injection molding, without the need for granules.

[0033] It may be advantageous if the method according to the invention comprises the step of producing packaging, films, injection moulded parts, pipes, hoses, fibres, fibers, bottles, plastic housings, masterbatch compounds for improving pigment dispersion, plastic articles in the automotive or transport sector.

[0034] The formulations according to the invention / the formulations produced according to the invention may be used in all applications in which polyolefin formulations are usually used. It is preferred if the formulations according to the invention / the formulations produced according to the invention are employed as or used to produce packaging, films, injection molded parts, pipes, hoses, textiles, fibers, bottles, plastic housings, masterbatch compounds to improve pigment dispersion, plastic articles in the automotive or transport sector.

[0035] Without further details, it is assumed that a person skilled in the art can utilize the above description to the fullest extent possible. Accordingly, the preferred embodiments and examples should be construed as merely an illustrative disclosure and are in no way limiting.

[0036] The subject matter of the present invention is more particularly explained by FIGS. 1 and 2, but is not intended to be limited thereto. [Brief explanation of the drawings]

[0037] [Figure 1] FIG. 1 shows a scanning electron micrograph of the fracture edge of a specimen according to Example 1.11, prepared and recorded as described in Example 2. [Figure 2] FIG. 2 shows a scanning electron micrograph of the fracture edge of a specimen according to Example 1.12, prepared and recorded as described in Example 2. [Example]

[0038] The subject matter of the present invention will be explained more specifically in the following examples, but it is not intended that the subject matter of the present invention be limited thereto.

[0039] Measurement method Notch Impact Resistance: Notch impact resistance was measured according to IZOD ISO 180 / 1A using a Zwick 5102.100 / 00 testing machine.

[0040] Tensile testing: Tensile tests were prepared and carried out according to EN ISO 527-1. A Zwick BT1-FB010TH.D30 testing machine was used.

[0041] Optical determination of area: The analytical instruments used were an Epson V850 ProScanner and a JEOL SM IT300 Scanning Electron Microscope (SEM).

[0042] Glass transition temperature [Tg]: Thermal analysis was performed according to DIN EN ISO 11357 using a Mettler Toledo DSC1 instrument, with evaluation performed using Stare 10.0 software. For semicrystalline polymer samples, the influence of thermal history was removed only when the entire sample was melted. Therefore, separate heating steps are required for Tg measurements to obtain reproducible results at specified heating and cooling rates. A uniform heating rate of 10 K / min to Tg + 50°C and a uniform cooling rate of 20 K / min to Tg - 50°C should preferably be used. The glass transition temperature is the sample temperature at which half the change in specific heat capacity [0.5 ΔcP] is achieved. This is the temperature at which the measured curve intersects with the center line between the extrapolated baselines before and after the glass transition.

[0043] Molecular weight determination: Mw represents the weight-average molecular weight, and Mn represents the number-average molecular weight. Molecular weights Mw and Mn were determined by HT-GPC (high-temperature gel permeation chromatography) as described in DIN 55 672. Specifically, analytical HT-GPC was performed at 150 °C using a PL220 oven (Agilent, Waldbronn) with an integrated isocratic pump. 1,2,4-trichlorobenzene (TCB) (Merck, Darmstadt) spiked with approximately 1 g / L of butylhydroxytoluene (BHT) was used as the mobile phase with a flow rate of 1 mL / min. One Agilent PLgel Olexis Guard (50 × 7.5 mm, precolumn) and three Agilent PLgel Olexis (300 × 7.5 mm) columns were used as the stationary phase. Detection was performed using an IR detector (model IR4, PolymerChar, Valencia, Spain). The data sets were evaluated using polystyrene calibration (EasiCal PS-1, Agilent) using WinGPC software (Polymer Standards Service, Mainz). The polydispersity (Mw / Mn), also known as the molecular weight distribution, is obtained by dividing the weight average molecular weight by the number average molecular weight.

[0044] Viscosity at 190°C: The viscosity is measured at 190°C by measuring in a rotational viscometer according to DIN 53 019. The measurement is carried out using a Brookfield CAP 2000+ cone-plate viscometer with a viscosity-dependent shear rate according to Table a below.

[0045] [Table a]

[0046] The Brookfield viscometer was calibrated using a 500,000 BW Newtonian standard sample. This was obtained from Zentrum fur Messen und Kalibrieren&Analytik GmbH and comes with the accompanying calibration certificate. Calibration of the instrument is only performed when the DKD oil is replaced with DKD oil from ZMK&ANALYTIK GmbH. This is done using cone 7. An initial measurement of the new DKD oil is performed first. The instrument is then calibrated. The Newtonian standard sample is weighed directly onto the spindle. This involves placing the sample upside down in a 100 mL Erlenmeyer flask and weighing the appropriate amount. The spindle is then attached to the viscometer and lowered. After preheating for at least 3 minutes, press "Spindle" on the control panel and confirm with "Enter." The prompt "Calibrate YES / NO" appears. Selecting "Yes" starts the calibration mode. Next, enter and confirm the desired temperature and dynamic viscosity of the fluid (see the latest calibration certificate). The viscosity value must be entered in cP (cP = mPa·s). At the prompt "SPEED", enter 10s-1 and confirm with "Enter". Then press "Run" to start the calibration. After calibration, save the calibration value with "Enter".

[0047] Melt Flow Index (MFI): MFI of 2.16 kg @ 230°C and 2.16 kg @ 190°C were measured using a Zwick MFlow instrument in accordance with ISO 1133-1:2011. Melt mass flow rate (MFR) and melt volume flow rate (MVR) are measured by extruding molten material from a plastometer barrel through an extrusion die of a specific length and diameter under specific temperature and load conditions. If the MFI value exceeds 1000 at 190°C and a load of 2.16 kg, the measurement temperature should be reduced to 140°C (MFI 2.16 @ 140°C) to obtain a reliable measurement.

[0048] To measure the MFR (Method A), the area extruded from a specified time is weighed and used to calculate the extrusion rate (g / 10 min). To measure MVR (Method B), plot the path length traveled by the piston in a specified time, or the time required for the piston to travel a specified path length, and calculate the extrusion rate (cm 3 / 10 minutes).

[0049] If the density of the material melt at the test temperature is known, the MVR may be converted to MFR, or vice versa.

[0050] Isotactic The polymer composition and isotacticity [mmmm-pentad fraction (%)] were determined by high-temperature 13 Measured by C-NMR. A. Zambelli et al.: Macomolecules, 8, 687 (1975) and A. Filho, G. Galland: J. Appl. Polym. Sci., 80, 1880 (2001).

[0051] Experimental Example

[0052] [Table 0]

[0053] [Table b]

[0054] [Table c]

[0055] Experimental Example 1 The pellet mixture was made using the raw materials and amounts reported in Table 1. Mixing was performed manually by adding all ingredients to a PE bag, and then the contents were poured into the funnel of the gravimetric system. The pellet mixture was then processed into a mixed pellet material in an extruder (Leistritz ZSE 27 MAXXX 44LD) at 210 °C and a speed of 300 rpm.

[0056] [Table 1]

[0057] This mixed pellet material was then used to prepare tensile test specimens (tensile test dumbbells) in accordance with DIN EN ISO 527-2 in an injection molding machine (Engel ES200 / 50HL) at an injection temperature of 230°C, an injection pressure of 600 bar, and a cycle time of 45 seconds.

[0058] One half of the tensile test dumbbells was used to measure the notch impact resistance according to IZOD ISO 180 / 1A, and the other half was used for tensile testing according to EN ISO 527-1. The test results are shown in Table 2. In the table, E T = tensile modulus, σ M = tensile strength, σ Y = yield stress, ε Y = yield elongation, ε tB = nominal elongation at break, ε B = elongation at break.

[0059] [Table 2]

[0060] As is evident from Tables 1 and 2, the addition of APAO as an additive to PE / PP pellet mixtures results in mixed pellet materials that have significantly better (higher) elongation behavior and better (higher) impact resistance, even at slightly reduced tensile strength, and that allow injection molding of molded articles. This is especially true for formulations that contain, in addition to APAO, at least one other amorphous or at least semi-crystalline polyolefin component.

[0061] Experimental Example 2 The specimens of Examples 1.11 and 1.12 were cooled in liquid nitrogen, fractured longitudinally and transversely in each case, sputtered with palladium, and then analyzed by SEM. Micrographs are shown in Figures 1 and 2.

[0062] For specimens from Examples 1.11 and 1.12, the images show many small areas that appear more homogeneous in Figure 2. Therefore, there appears to be improved bonding, as also indicated by the better mechanical properties of Example 1.12 (Table 2).

Claims

1. comprising at least two different polyolefins; as a further component an amorphous poly-α-olefin based on the monomers ethene, propene and 1-butene and having a viscosity at 190°C of 2000 mPa·s to 100000 mPa·s, A blend comprising polyethylene and polypropylene as the at least two different polyolefins, the proportion of the amorphous poly-α-olefin is between 2% and 15% by weight relative to the total mass of the blend, The polyethylene has a melt flow index [MFI 2.16 kg @ 190°C] of 0.01 g / 10 min or more and less than 10 g / 10 min, The polypropylene has a melt flow index [MFI 2.16 kg @ 230°C] of 0.01 to 25 g / 10 min, The amorphous poly-α-olefin has a melt flow index [MFI 2.16 kg @ 140°C] of 40 to 10,000 g / 10 min, the amorphous poly-α-olefin has a polydispersity of 5 to 10; A blend wherein the proportion of the least minority polyolefin in said blend is from 1% to 45% by weight and the proportion of the most major polyolefin in said blend is from 55% to 99% by weight, based on the total weight of said at least two polyolefins.

2. 10. The composition of claim 1, wherein the at least two different polyolefins comprise polyethylene and polypropylene.

3. 3. The blend of claim 1 or claim 2, wherein at least one of the two different polyolefins is at least partially, preferably completely recycled.

4. 4. The blend according to claim 1, wherein the proportion of said amorphous poly-α-olefin is between 3% and 10% by weight relative to the total mass of the blend.

5. 5. The blend of any one of claims 1 to 4, wherein the proportion of the least abundant polyolefin in the blend is from 2% to 30% by weight and the proportion of the most abundant polyolefin in the blend is from 70% to 98% by weight, relative to the total mass of the at least two polyolefins.

6. The formulation of any one of claims 1 to 5, wherein the amorphous poly-α-olefin has a glass transition temperature of -45°C to -25°C.

7. The amorphous poly-α-olefins are based on the monomers ethene, propene, and 1-butene; The proportion of the monomer propene or 1-butene is more than 50% by weight, the total proportion of the remaining monomers, ethene and 1-butene or ethene and propene, is in each case less than 50% by weight, 7. The blend according to any one of claims 1 to 6, in each case relative to the sum of ethene, propene and 1-butene.

8. The blend according to any one of claims 1 to 7, wherein the amorphous poly-α-olefin has an isotacticity of the 1-butene block or the propene block of less than 80% in terms of mmmm-pentad fraction.

9. A method for producing the blend according to any one of claims 1 to 8, comprising mixing the components that constitute the blend.

10. The method of claim 9, wherein the components that make up the blend are used and mixed as powders or pellets.

11. The method of claim 9, further comprising blending the components of said compound to obtain a pellet mixture, and then extruding said pellet mixture to obtain a mixed pellet material.

12. 12. The process according to any one of claims 9 to 11, comprising the step of producing packaging, films, injection moulded parts, pipes, hoses, fibres, textiles, bottles, plastic housings, masterbatch compounds to improve pigment dispersion, plastic products in the automotive or transport sector.

13. 10. Use of a formulation according to any one of claims 1 to 8 as or for the production of packaging, films, injection moulded parts, pipes, hoses, fibres, textiles, bottles, plastic housings, masterbatch compounds to improve pigment dispersion, plastic articles in the automotive or transport sector.

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