Ethylene homopolymerized wax and preparation method thereof

Abstract

The invention relates to ethylene homopolymerized wax and a polymerization preparation method thereof. The invention relates to a polymerization preparation method of ethylene homopolymerized wax. The method comprises the following steps: under a catalytic system comprising one or more of a non-metallocene catalyst and a metallocene catalyst as a main catalyst and one or more of aluminoxane, boride, aluminum alkyl and aluminum alkyl chloride as a co-catalyst, carrying out a reaction on the main catalyst and the co-catalyst, ethylene is subjected to a polymerization reaction in the presence of hydrogen in an alkane solvent having a boiling point of 0-90 DEG C or a mixed alkane solvent having a saturated vapor pressure of 4-200 KPa at 20 DEG C as a polymerization solvent (preferably an alkane solvent having a boiling point of 25-82 DEG C or a mixed alkane solvent having a saturated vapor pressure of 30-160 KPa at 20 DEG C as a polymerization solvent). The ethylene homopolymer is narrow in molecular weight distribution, high in crystallinity, low in needle penetration, high in devolatilization efficiency and low in ash content, and the ethylene homopolymer wax shows excellent dispersity in the application of the color master batch and is excellent in processing performance.

Description

Technical Field

[0001] This invention relates to an ethylene homopolymer wax and its preparation method. Background Technology

[0002] Polyethylene wax, also known as low molecular weight polyolefin, is waxy at room temperature, with a weight-average molecular weight typically ranging from 500 to 10,000 g / mol. It is a representative synthetic wax produced from ethylene. In a narrow sense, polyethylene wax is a low relative molecular weight homopolymer polyethylene; in a broader sense, it also includes modified polyethylene wax and copolymerized polyethylene wax. Polyethylene wax has good chemical stability, is colorless, odorless, and non-toxic. Its chemical composition, saponification value, electrical properties, and density are similar to paraffin wax. It is completely insoluble in water and all aqueous solutions and is widely used in ink manufacturing polishing wax, high-grade floor paint, high-end car polishing wax, rubber release agent and anti-aging agent; textile softener and lubricant; gloss lubricant and release agent for polyvinyl chloride products; cable filler, diesel flow modifier, cable masterbatch additive, cardboard coating, glass bottle coating, hot melt adhesive, and special craft candles, etc.

[0003] Besides apparent factors such as whiteness and density, the molecular weight and molecular weight distribution of polyethylene wax also affect its price. The molecular weight of polyethylene wax determines its application, while the molecular weight distribution affects its performance. Homopolymer polyethylene wax is mainly used in polyolefin masterbatches, including polyethylene masterbatches, polypropylene masterbatches, and EVA masterbatches. Because masterbatches contain large quantities of pigments or fillers, and these pigments and fillers have very small particle sizes (0.01–1.0 μm), they are prone to agglomeration. By adding homopolymer polyethylene wax, within a certain temperature range, the polyethylene wax melts and wets the surface of the pigments or fillers, reducing particle agglomeration. It also increases the compatibility between the pigments or fillers and the matrix resin. Furthermore, the shear force of a twin-screw extruder or internal mixer ensures that the pigments and fillers are uniformly dispersed in the resin melt. In rigid PVC systems, the main purpose of adding homopolymer polyethylene wax is to reduce the adhesion between the molten plastic and processing equipment and molds, improve the surface smoothness and gloss of plastic products, and make PVC easier to process and improve processing efficiency. Adding external lubricants can also reduce the equipment load (such as mains current) during plastic product processing, reducing power consumption. The working principle of external lubricants is that they can precipitate from the inside to the surface during polymer melt processing and adhere to the contact surfaces of the equipment, forming a very thin "lubricating film." This prevents PVC from adhering to the surfaces of processing metal equipment and other contact materials, ensuring good roll release and demolding properties, and guaranteeing a smooth product surface. Therefore, adding appropriate lubricants can effectively improve the processing performance of rigid PVC, improve product quality, and increase equipment processing efficiency.

[0004] Polyethylene wax can usually be obtained through the following three methods: first, it is a byproduct of producing copolymer grades in slurry polyethylene production equipment; second, it is a product of polyethylene cracking or degradation; and third, it is obtained by polymerizing ethylene to obtain low molecular weight polyethylene.

[0005] There are different process routes for the synthetic production of polyethylene wax. High-pressure free radical polymerization can produce low-density polyethylene wax; low-pressure coordination polymerization has three processes: solution, slurry, and gas phase. It generally uses single-center metallocene or non-metallocene catalysts, and the product properties vary depending on the polymerization process. CN200780043554.8 discloses a method for preparing polyethylene wax by ethylene polymerization in the presence of a Ziegler-Natta catalyst system composed of titanium tetrachloride and dialkyl aluminum halides. The polymerization is carried out under conditions where there is virtually no solvent, and it is used to prepare synthetic polyethylene wax with high crystallinity and low viscosity. A dedicated high-hydrogen-adjusted Zn catalyst is used, with a high hydrogen-to-ethylene molar ratio and low catalyst activity. EP0367597A1 discloses a metallocene gas-phase polymerization method using silica gel supported on a narrow molecular weight distribution (less than 5) for preparing polyethylene wax. CN1 03554315A describes a slurry polymerization process using a supported metallocene catalyst as the main catalyst, alkylaluminum as a co-catalyst, hydrogen as a molecular weight regulator, and C2-C4 alkanes as solvents to catalyze the homopolymerization of ethylene or the copolymerization of ethylene with α-olefins selected from C3-C12, thereby preparing polyethylene wax. WO / 2013 / 027958 discloses a method for preparing polyethylene wax using a metallocene catalyst and a dual-loop reactor. According to the invention, a highly active polyethylene wax with a uniform and narrow molecular weight distribution can be polymerized. In this method, one or more comonomers selected from 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-octadecene, and their mixtures, can be further used during polymerization. The morphology of slurry polyethylene wax prepared based on the supported metallocene catalyst of the slurry loop is not easy to control in the reactor, and scaling and blockage of the loop may occur. The subsequent separation system is more difficult than that of ordinary polyethylene, which is not conducive to long-term operation.

[0006] CN1789292A relates to a method for applying a supported non-metallocene catalyst in a slurry polymerization process for ethylene. The slurry polymerization process utilizes a supported non-metallocene catalyst, which, together with a co-catalyst, forms a catalytic system directly used in the slurry polymerization of ethylene. Supported non-metallocene catalysts exhibit better hydrogen regulation sensitivity than Zn catalysts, but they also suffer from drawbacks such as low production efficiency at high hydrogen ratios and unsuitability for large-scale applications.

[0007] The main production methods for polyethylene wax include high-pressure polymerization, gas-phase polymerization, slurry polymerization, and solution polymerization. Among these, the homogeneous polymerization process for producing polyethylene wax is carried out through solution polymerization. The single-center catalyst solution method for preparing PEW (polyethylene wax) is relatively simple, has a wide range of adjustable products, and can produce homopolymer polyethylene wax products.

[0008] Hydrogen is a highly effective chain transfer agent in ethylene polymerization; however, the polymerization occurs in the presence of large amounts of hydrogen, leading to low yields in the polymerization of polyethylene waxes using Ziegler-Natta catalysts. This results in the production of large quantities of lower molecular weight oligomers and a broadened molecular weight distribution. Furthermore, the oligomer slurry is prone to scaling in the reactor, resulting in high ash content in the product. Using a single-center catalyst can solve these problems. Due to the single-center nature of the catalyst, each catalyst has the same polymerization active site, thus enabling the preparation of polyethylene waxes with a narrow molecular weight distribution using metallocene catalysts. Single-center polyethylene waxes differ from ordinary polyethylene waxes in that they have a narrow molecular weight distribution and high crystallinity.

[0009] To obtain the above-mentioned ethylene homopolymer wax product, the commonly used method is to use toluene solvent, the polymerization temperature needs to be above the melting point of polyethylene wax, and a high hydrogen concentration needs to be maintained.

[0010] The current state of affairs in this field is that there is still a desire to develop an ethylene homopolymer wax with adjustable and controllable weight-average molecular weight, narrow molecular weight distribution, high true density, high melting point, and high crystallinity. Summary of the Invention

[0011] Based on existing technology, the inventors, through in-depth research, discovered that using an alkane solvent with a boiling point of 0-90℃ or a mixed alkane solvent with a saturated vapor pressure of 4-200 kPa at 20℃ as the polymerization solvent, and employing a catalytic system containing one or more main catalysts selected from non-metallocene and metallocene catalysts, and one or more co-catalysts selected from alkylaluminum, aluminoxane, borides, and alkylaluminum chloride, under ethylene solution polymerization conditions, can prepare ethylene homopolymer wax with a narrow molecular weight distribution, high true density, high melting point, and high crystallinity. This solves the aforementioned problems, thus completing the present invention.

[0012] Specifically, the present invention provides an ethylene homopolymer wax with a weight-average molecular weight of 500-15000 g / mol, preferably 1000-10000 g / mol, a molecular weight distribution of 1.0-4.0, preferably 1.25-3.0, a crystallinity of 60-90%, preferably 65-80%, and a true density of 0.950-0.990 g / cm³. 3 The preferred concentration is 0.955–0.980 g / cm³. 3Crystallinity 60-90%, preferably 65-80%, melting point 120-130℃, preferably 122-128℃, penetration 0.1-1.5mm*10 -1 Preferred size: 0.5~1.0mm*10 -1 .

[0013] The present invention also provides a method for preparing ethylene homopolymer wax by polymerization, wherein ethylene is polymerized in the presence of hydrogen in a catalytic system comprising one or more of a non-metallocene catalyst and a metallocene catalyst as the main catalyst and one or more of aluminoxane, boride, alkylaluminum, and alkylaluminum chloride as the co-catalyst, and in an alkane solvent with a boiling point of 0-90°C or a mixed alkane solvent with a saturated vapor pressure of 4-200 kPa at 20°C as the polymerization solvent (preferably an alkane solvent with a boiling point of 25-82°C or a mixed alkane solvent with a saturated vapor pressure of 30-160 kPa at 20°C as the polymerization solvent), wherein the molar ratio of ethylene to hydrogen is 35-0.5:1, preferably 30-1:1.

[0014] Technical effect

[0015] The ethylene homopolymer wax of the present invention has an adjustable molecular weight, a narrow molecular weight distribution, and high crystallinity, which can improve the dispersion, hardness, and wear resistance when the ethylene homopolymer wax is used in color masterbatch.

[0016] The polymerization preparation method of this invention requires low amounts of main catalyst and co-catalyst, has a stable polymerization process, stable real-time ethylene consumption, and high ethylene solution polymerization activity, and can obtain ethylene homopolymer wax products at higher polymerization temperatures.

[0017] Furthermore, the polymerization method of this invention allows for a wide range of solvent choices, including alkane solvents with boiling points between 0 and 90°C or mixed alkane solvents with saturated vapor pressures between 4 and 200 kPa at 20°C. This provides greater flexibility in selecting the heat removal method for the polymerization reaction and the post-treatment method for the resulting ethylene homopolymer wax solution. Moreover, the post-treatment of the obtained ethylene homopolymer wax is easy to perform.

[0018] In addition, when ethylene homopolymer wax is prepared by the polymerization method of the present invention, the resulting ethylene homopolymer wax has excellent processing performance, the metal content as impurities is further reduced, the VOCs content is low, and the odor is minimal. Attached Figure Description

[0019] Figure 1 NMR spectrum of ethylene homopolymer wax in Example 1.

[0020] Figure 2 GPC curve of ethylene homopolymer wax in Example 1.

[0021] Figure 3DSC curve of ethylene homopolymer wax in Example 1. Detailed Implementation

[0022] The specific embodiments of the present invention will be described in detail below. However, it should be noted that the scope of protection of the present invention is not limited to these specific embodiments, but is determined by the claims in the appendix.

[0023] In the context of this invention, unless otherwise explicitly defined or the meaning is beyond the understanding of those skilled in the art, hydrocarbon or hydrocarbon derivative groups with three or more carbon atoms (such as propyl, propoxy, butyl, butane, butene, butenyl, hexane, etc.) have the same meaning when not prefixed with "n-" as when prefixed with "n-". For example, propyl is generally understood as n-propyl, and butyl is generally understood as n-butyl, unless otherwise explicitly stated.

[0024] In order to avoid complexity, this specification does not explicitly state whether the valence of each substituent or group in the compound is monovalent, divalent, trivalent, or tetravalent. Those skilled in the art can make specific judgments based on the position or substitution of these substituents or groups (such as groups G, D, B, A, and F as described or defined in this specification) in the structural formula of the corresponding compound, and select the appropriate definition for the valence at that position or substitution from the definitions given for these substituents or groups in this specification.

[0025] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0026] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0027] In the context of this specification, except where expressly stated, any matters or issues not mentioned herein shall apply directly to those known in the art without any modification. Furthermore, any implementation described herein may be freely combined with one or more other implementations described herein, and any resulting technical solutions or concepts shall be considered part of the original disclosure or original record of this invention, and should not be regarded as new content not disclosed or anticipated herein, unless those skilled in the art consider such combination to be clearly unreasonable.

[0028] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this specification are based on weight, unless being based on weight would not be in accordance with the common understanding of those skilled in the art.

[0029] In the context of this invention, unless otherwise specified, the physical properties of substances (such as boiling point) are measured at room temperature (25°C) and normal pressure (101325 Pa).

[0030] In this invention, ethylene homopolymer wax is also called homopolymer polyethylene wax, or polyethylene wax, and is sometimes simply referred to as polyethylene.

[0031] This invention provides a method for preparing ethylene homopolymer wax by polymerization, wherein ethylene is polymerized in the presence of hydrogen in a catalytic system comprising one or more of a non-metallocene catalyst and a metallocene catalyst as the main catalyst and one or more of aluminoxane, boride, alkylaluminum, and alkylaluminum chloride as the co-catalyst, and in an alkane solvent with a boiling point of 0-90°C or a mixed alkane solvent with a saturated vapor pressure of 4-200 kPa at 20°C as the polymerization solvent (preferably an alkane solvent with a boiling point of 25-82°C or a mixed alkane solvent with a saturated vapor pressure of 30-160 kPa at 20°C as the polymerization solvent), wherein the molar ratio of ethylene to hydrogen is 35-0.5:1, preferably 30-1:1.

[0032] Through in-depth research, the inventors of this invention discovered that, by using metallocene and / or non-metallocene catalysts as the main catalyst and one or more selected from aluminoxanes, borides, alkylaluminum, and alkylaluminum chlorides as co-catalysts, ethylene homopolymer wax can be prepared by solution polymerization of ethylene in the presence of hydrogen using a specific polymerization solvent. The ethylene homopolymer wax of this invention has a low molecular weight and a narrow molecular weight distribution; furthermore, it has a low VOC content and minimal odor, while the content of metal impurities in the resulting wax is further suppressed. Furthermore, the obtained ethylene homopolymer wax exhibits excellent performance when used in various processing aids.

[0033] In this invention, the weight-average molecular weight of the ethylene homopolymer wax is 500-15000 g / mol, preferably 1000-10000 g / mol.

[0034] In this invention, in the solution polymerization preparation method of ethylene homopolymer wax, the polymerization solvent is selected from alkane solvents with boiling points of 0-90℃ or mixed alkane solvents with saturated vapor pressure of 4-200KPa at 20℃, preferably alkane solvents with boiling points of 25-82℃ or mixed alkane solvents with saturated vapor pressure of 30-160KPa at 20℃.

[0035] Among them, the alkane solvent with a boiling point of 0-90℃ is preferably an alkane solvent with a boiling point of 25-82℃, such as 2,2-dimethylpropane (also known as neopentane, boiling point 9.5℃), 2-methylbutane (also known as isopentane, boiling point 27.83℃), n-pentane (boiling point 36.1℃), cyclopentane (boiling point 49.26℃), n-hexane (boiling point 68.73℃), cyclohexane (boiling point 80.7℃), 2-methylpentane (also known as isohexane, boiling point 60.3℃), 3-methylpentane (boiling point 64.0℃), 2,3-dimethylbutane (boiling point 58.7℃), and 2,2-dimethylbutane (boiling point 58.7℃). It is preferably selected from n-pentane, isopentane, cyclopentane, n-hexane, and cyclohexane, and more preferably selected from n-pentane, isopentane, and cyclopentane.

[0036] As a mixed alkane solvent with a saturated vapor pressure of 4-200 kPa at 20°C, preferably a mixed alkane solvent with a saturated vapor pressure of 30-160 kPa at 20°C, it refers to a mixed solvent formed by mixing different alkane solvents in a certain proportion, such as a solvent obtained by mixing solvents of hexane and its isomers, or solvents of pentane and its isomers. It can also be a mixture of alkanes obtained by cutting according to the distillation range in a solvent distillation unit, such as n-pentane and isopentane, isopentane and neopentane, n-pentane and cyclopentane, n-pentane and neopentane, isopentane and cyclopentane, neopentane and cyclopentane, n-hexane and 3-methylpentane, n-hexane and 2,2-dimethylbutane, n-hexane and 2,3-dimethylbutane, n-hexane and cyclohexane, n-hexane and isohexane, isohexane and cyclohexane, n-pentane-isopentane-cyclopentane, n-hexane-isohexane-cyclohexane, etc.

[0037] In one embodiment of the present invention, the polymerization solvent may be selected from n-pentane, isopentane, neopentane, and cyclopentane, or may be a mixed alkane solvent composed of two or more alkanes selected from n-pentane, isopentane, neopentane, and cyclopentane. Preferably, it may be selected from a combination of n-pentane and isopentane, a combination of isopentane and neopentane, a combination of n-pentane and cyclopentane, a combination of n-pentane and neopentane, a combination of isopentane and cyclopentane, a combination of neopentane and cyclopentane, a combination of n-hexane and n-pentane, and a combination of n-pentane-isopentane-cyclopentane.

[0038] In this invention, there are no particular limitations on the polymerization temperature and polymerization pressure; the conventional polymerization temperature and polymerization pressure used in the field for preparing ethylene homopolymer wax can be adopted.

[0039] In one embodiment of the present invention, the polymerization temperature is 90-160°C, preferably 100-150°C.

[0040] In one embodiment of the present invention, the polymerization pressure is 1.5-6.0 MPa, preferably 2.0-5.0 MPa.

[0041] In this invention, ethylene is polymerized in a polymerization solvent in the presence of hydrogen within a catalytic system comprising a main catalyst and a co-catalyst to obtain ethylene homopolymer wax; at this time, the molar ratio of ethylene to hydrogen is 35–0.5:1, preferably 30–1:1. In this invention, no other comonomers besides ethylene are used to form the ethylene homopolymer wax.

[0042] It is known to those skilled in the art that all the foregoing method steps are preferably carried out under substantially anhydrous and oxygen-free conditions. "Substantially anhydrous and oxygen-free" here means that the water and oxygen content in the system is consistently less than 100 ppm. Furthermore, the catalyst of the present invention, after preparation, typically needs to be stored under sealed conditions in the presence of a slightly positive pressure inert gas (such as nitrogen, argon, helium, etc.) for later use.

[0043] In this invention, there is no particular limitation on the amount of the main catalyst; conventional catalyst amounts in the art can be used. In one embodiment of this invention, the concentration of the main catalyst in the polymerization solvent is 0.1 × 10⁻⁶ atoms, calculated based on the central metal atom. -5 mol / L~50×10 -5 mol / L, preferably 0.5×10 -5 mol / L~20×10 -5 mol / L, more preferably 1×10 -5 mol / L~15×10 -S mol / L.

[0044] In this invention, the main catalyst is at least one selected from metallocene catalysts and non-metallocene catalysts. More specifically, the main catalyst can be selected from metallocene catalysts, non-metallocene catalysts, or a mixture of metallocene catalysts and non-metallocene catalysts.

[0045] In this invention, when the main catalyst is selected from metallocene catalysts, there is no particular limitation on the type of metallocene catalyst; catalysts conventionally used in ethylene polymerization in the art can be used. There is also no particular limitation on the form of the catalyst; it can be a supported metallocene catalyst or an unsupported metallocene catalyst. An unsupported metallocene catalyst is preferred.

[0046] More specifically, as metallocene catalysts, such as those described in invention patents CN201110247347.2, CN201110080343.X, CN201010518904.5, CN201010519660.2, CN201210289014.0, CN200910078596.6, CN201310090758.4, CN201310090736.8, CN201310521768.9, and CN20141058. 9467.4, CN201410590067.5, CN201610835700.1, CN201610944191.6, CN201710959423.X, CN201110247349.1, CN201110080294.X、CN201110080395.7、CN201210289017.4、CN201210289031.4、CN201310091192.7、CN20131 0540973.X, CN201510724626.1, CN200410086283.2, CN200610137777.8, CN2 01610944182.7, CN201710312720.5, CN201110080422.0,, CN201110080394. 2. CN201010519406.2, CN201010519715.X, CN201010519174.0, CN201010519 429.3, CN201210289004.7, CN201310090847.9, CN201310091209.9, CN20131 0540975.9, CN201410554709.6, CN201410513506.2, CN00130388.0, CN200710176589.0, CN201610944083.9, CN 201110246705.8, CN201110247085.X, CN2011102914899, CN201010521674.8, CN201310090752.7, CN2013100908 48.3, CN2013100908483, CN201510624502.6, CN201710166709.2, CN20171031225.2, CN201110246710.9, CN2011 10080374.5, CN201010519797.8, CN201210289012.1, CN201210418645.8, CN201310090998.4, CN201410252254.2. Metallocene catalysts described in CN201610393399.3, CN201610956141.X, CN201710958837.0, etc.

[0047] In one embodiment of the present invention, when the main catalyst comprises a metallocene catalyst, a single metallocene catalyst may be used, or a combination of multiple metallocene catalysts may be used.

[0048] According to the present invention, the term "non-metallocene catalyst" is a single-center olefin polymerization catalyst, as opposed to a metallocene catalyst, which does not contain cyclopentadienyl groups or their derivatives such as cyclopentadienyl, fluorene, or indene rings in its structure, and is an organometallic compound that can exhibit olefin polymerization catalytic activity when combined with a co-catalyst (such as those described below). (Therefore, the non-metallocene catalyst is sometimes also referred to as a non-metallocene olefin polymerization complex.) The compound comprises a central metal atom and at least one polydentate ligand (preferably a tripentate or more dental ligands) coordinated to the central metal atom, and the term "non-metallocene ligand" refers to the aforementioned polydentate ligand.

[0049] In this invention, when the main catalyst is selected from non-metallocene catalysts, there is no particular limitation on the type of non-metallocene catalyst; catalysts conventionally used in ethylene polymerization in the art can be used. There is also no particular limitation on the form of the catalyst; it can be a supported non-metallocene catalyst or an unsupported non-metallocene catalyst. An unsupported non-metallocene catalyst is preferred.

[0050] Specifically, as non-metallocene catalysts, such as those specified in invention patents CN200310106156.X, CN200310106157.4, CN2004 1 0066068.6, CN200510119401.X, CN200610107651.6, CN200710162677.5, CN200710162667.1, CN200710162672.2, CN200710162675.6, CN200710162676.0, CN200710162666.7, CN2009 1 0180100.6, CN200910180607.1, CN200910180601.4, CN2009 1 0180606.7, CN200910180602.9, CN200910180605.2, CN200910180603.3, CN200910180604.8, CN2009102109 88.3, ​​CN200910210984.5, CN200910210989.8, CN200910210986.4, CN200910210985.X, CN200910210990.0, CN200910210987.9, CN200910210991.5, CN201010286008.0, CN201010286012.7, CN201010284870.8, CN201 010285982.5, CN201010284856.8, CN201010285970.2, CN201010285956.2, CN201010285969.X, CN201010285 958.1, CN201010285967.0, CN201010285994.8, CN201110259336.6, CN201110259219.X, CN201110259330.9 , CN201110259327.7, CN201110259367.1, CN201110259289.5, CN201110259359.7, CN201110259282.3, CN201 110259318.8, CN201110259258.X, CN201110259300.8, CN201110259254.1,, CN201110259245.2, CN2011102 59296.5, CN201110259338.5, CN201110259370.3, CN201110259339.X, CN201110259293.1, CN201110259356.3. CN201210063756.1, CN201210063777.3, CN20121 0063788.1, CN201210063818.9, CN201210063824.4, CN201210063843.7, CN201210063854.5, CN201210063876.1, CN20121 0063878.0, CN201210063891.6, CN201210063894.X, CN201210063907.3, CN201210063909.2, CN201210063935.5, CN20121 The non-metallocene catalysts described in CN201210063945.9, CN201310189677.X, CN201310227368.7, CN201310227370.4, CN201310227830.3, CN201310227393.5, CN201310452714.1, CN201710814678.7, CN201710814595.8, CN201710814594.3, CN201710814593.9, CN201710814592.4, CN201710814591.X, and CN201310091208.4 are examples of such catalysts.

[0051] In one embodiment of the present invention, when the main catalyst comprises a non-metallocene catalyst, one non-metallocene catalyst may be used, or a combination of multiple non-metallocene catalysts may be used.

[0052] According to the present invention, the non-metallocene catalyst is selected from compounds represented by formula (I) or mixtures thereof in any proportion:

[0053]

[0054] In equation (I), R1, R2, R3, and R4 are each independently selected from hydrogen and C. 1-6 Straight-chain or branched hydrocarbon groups, preferably each independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups, more preferably each independently selected from hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, and tert-butyl;

[0055] R6, R7, R8, and R9 are each independently selected from hydrogen and C. 1-6 Straight-chain or branched hydrocarbon groups, preferably each independently selected from hydrogen and C. 1-6 Straight-chain or branched alkyl groups, more preferably each independently selected from hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, and tert-butyl;

[0056] R5 represents hydrogen or C. 1-12 Straight-chain or branched hydrocarbon groups, preferably hydrogen or C 1-6 Straight-chain or branched alkyl or C 6-10 Aryl, more preferably hydrogen, C 1-3 Straight-chain or branched alkyl or phenyl, more preferably hydrogen, methyl, ethyl, n-propyl, isopropyl or phenyl;

[0057] R 10 Each is independently selected from hydrogen or C. 1-6 Straight-chain or branched hydrocarbon groups, preferably hydrogen or C 1-6 Straight-chain or branched alkyl, more preferably hydrogen, methyl and ethyl, more preferably hydrogen; p indicates 1 or 2;

[0058] Group Y is O or S, preferably O; group A is S or O, preferably S;

[0059] M is selected from Group IVB metallic elements, preferably titanium, zirconium and hafnium, and more preferably titanium;

[0060] X is selected from fluorine, chlorine, bromine and iodine, with chlorine or bromine being preferred;

[0061] Indicates a single bond or a double bond, where when When it is a single bond, then p is a hydrogen atom present at 2 and N. When it is a double bond, then p is 1 and the hydrogen on N is absent; Represents a coordinate bond;

[0062] n depends on the valence state of atom M, for example, it can be 1, 2, 3, 4 or 5.

[0063] In one embodiment of the present invention, in formula (I), R1, R2, R3, and R4 are each independently selected from hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, and tert-butyl, preferably each independently selected from hydrogen and tert-butyl.

[0064] In one embodiment of the invention, in formula (I), R9 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, preferably selected from hydrogen.

[0065] In one embodiment of the invention, in formula (I), R7 is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, preferably selected from hydrogen and tert-butyl.

[0066] In one embodiment of the present invention, in formula (I), R6 and R8 are each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl, preferably each independently selected from hydrogen and tert-butyl.

[0067] In one embodiment of the present invention, in formula (I), R5 represents hydrogen or C. 1-12 Straight-chain or branched hydrocarbon groups, preferably hydrogen or C 1-6 Straight-chain or branched alkyl or C 6-10 Aryl, more preferably hydrogen, C 1-3 Straight-chain or branched alkyl or phenyl, more preferably hydrogen, methyl, ethyl, n-propyl, isopropyl or phenyl.

[0068] In one embodiment of the present invention, in formula (I), R 10 Each is independently selected from hydrogen or C. 1-6 Straight-chain or branched hydrocarbon groups, preferably hydrogen or C 1-6 Straight-chain or branched alkyl, more preferably hydrogen, methyl or ethyl, more preferably hydrogen.

[0069] In one embodiment of the present invention, in formula (I), R5 represents hydrogen or C. 1-12 Straight-chain or branched hydrocarbon groups, preferably hydrogen, C1-6 straight-chain or branched alkyl groups, or C6... 6-10 Aryl, more preferably hydrogen, C1-3 straight-chain or branched alkyl or phenyl, more preferably hydrogen, methyl, ethyl, n-propyl or isopropyl.

[0070] In one embodiment of the invention, in formula (I), the group Y is O or S, preferably O.

[0071] In one embodiment of the invention, in formula (I), group A is S or O, preferably S.

[0072] In one embodiment of the present invention, in formula (I), the group M is selected from group IVB metals of the periodic table, such as titanium, zirconium and hafnium, more preferably titanium.

[0073] In one embodiment of the invention, in formula (I), group X is a halogen, including fluorine, chlorine, bromine and iodine, wherein chlorine or bromine is preferred.

[0074] In one embodiment of the present invention, in formula (I), the symbol ------ represents a coordinate bond.

[0075] In one embodiment of the invention, in formula (I), n is 1, 2, 3, 4 or 5, depending on the valence state of the central metal atom M, where n is the valence state of atom M-1, preferably n is 2, 3 or 4.

[0076] In one embodiment of the present invention, the compound represented by formula (I) is selected from titanium trichloride of 3-tert-butylsalicylene-2-methylthioaniline, titanium trichloride of salicylene-2-methylthioaniline, titanium trichloride of salicylene-2-phenylthioaniline, titanium trichloride of 3,5-di-tert-butylsalicylene-2-propylthioaniline, titanium trichloride of 3-tert-butylsalicylene-2-propylthioaniline, titanium trichloride of 3,5-di-tert-butylsalicylene-2-mercaptoaniline, titanium trichloride of salicylene-2-mercaptoaniline, titanium trichloride of 3,5-di-tert-butylsalicylene-2-mercaptoaniline, titanium trichloride of 3,5-di-tert-butylsalicylene-2-mercaptoaniline, titanium trichloride of 2-mercaptoaniline. At least one of the following: salicyl-2-methylthioaniline titanium trichloride, salicyl-2-propylthioaniline titanium trichloride, 3,5-di-tert-butylsalicyl-2-methylthioaniline titanium trichloride, 3,5-di-tert-butylsalicyl-2-methylthioaniline titanium trichloride, 3,5-di-tert-butylsalicyl-2-propylthioaniline titanium trichloride, 4-tert-butylsalicyl-2-methylthioaniline titanium trichloride, and 5-tert-butylsalicyl-2-methylthioaniline titanium trichloride.

[0077] In one embodiment of the present invention, the compound represented by formula (I) is at least one selected from 3-tert-butylsalicyl-2-methylthioaniline titanium trichloride, salicyl-2-phenylthioaniline titanium trichloride, 3,5-di-tert-butylsalicyl-2-propylthioaniline titanium trichloride, 4-tert-butylsalicyl-2-methylthioaniline titanium trichloride, and 5-tert-butylsalicyl-2-methylthioaniline titanium trichloride.

[0078] In this invention, the metallocene catalyst is selected from one of the compounds shown in formula (II) and formula (III) below, or a mixture thereof in any proportion.

[0079]

[0080] In formula (II), R1 is a C1-C8 straight-chain or branched alkylene group, or a di-C6-C2 alkylene group. 10 arylalkylene, diC1-C8 alkylsilylene or diC6-C 10 Arylmethylenesilyl, preferably C1-C4 straight-chain or branched alkylene, diphenylmethylene, diphenylethylene, diC1-C4 alkylsilyl or diphenylsilyl, more preferably methylene, ethylene, isopropylene, diphenylmethylene, dimethylsilyl or diphenylsilyl;

[0081] R2 and R3 are each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, or C6-C 10 aryl; or R2 together with its bonded cyclopentadienyl group, and R3 together with its bonded cyclopentadienyl group, each independently forming a fluorenyl, indene, benzoindene, tetrahydroindene, and benzodihydroindene group substituted by 1 to 5 substituents independently selected from halogen, C1-C4 alkyl, C1-C4 haloalkyl, or phenyl.

[0082]

[0083] In formula (iii), R6 and R7 are each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, or C6-C 10 Aryl;

[0084] R4 and R5 are each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, or C6-C 10 Aryl; or R4 together with its bonded cyclopentadienyl group, and R5 together with its bonded cyclopentadienyl group, each independently forming a fluorenyl, indene, benzo[a]indene, tetrahydroindene, and benzo[a]dihydroindene group substituted by 1 to 5 substituents independently selected from halogen, C1-C4 alkyl, C1-C4 haloalkyl, or phenyl.

[0085] In one embodiment of the present invention, the metallocene catalyst is selected from one of dimethylsilyl(cyclopentadienyl)(1-indenyl)zirconia, diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconia, isopropyl(cyclopentadienyl)(4,5-benzo-1-indenyl)zirconia, dimethylsilyl(cyclopentadienyl)(4,5-benzo-1-indenyl)zirconia, or a mixture thereof in any proportion.

[0086] It should be noted that the aforementioned non-metallocene and metallocene catalysts can be used alone or mixed in any proportion. When used in combination, the ratio of non-metallocene to metallocene catalysts is not particularly limited. Based on the number of central active metal atoms in each catalyst, the molar ratio can be 1:100 to 100:1, or 1:50 to 50:1, or 1:10 to 10:1, for example, 1:1.

[0087] In this invention, the co-catalyst is selected from one or more of aluminoxanes, borides, alkylaluminums, or haloalkylaluminums. For each of the various co-catalysts—aluminoxanes, borides, alkylaluminums, and haloalkylaluminums—it can be selected from one or more of the following: for example, one or more alkylaluminums, one or more aluminoxanes, one or more borides, or one or more haloalkylaluminums.

[0088] Examples of aluminum oxanes include linear aluminum oxanes represented by the following general formula (IV-1) and cyclic aluminum oxanes represented by the following general formula (IV-2).

[0089]

[0090] In the aforementioned general formulas (IV-1) and (IV-2), the groups R are the same or different from each other (preferably the same), and are each independently selected from C1-C8 alkyl groups, preferably methyl, ethyl, isobutyl, or isohexyl; n is any integer in the range of 1-50, preferably any integer in the range of 10-30.

[0091] The aluminum oxane is preferably selected from at least one of methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and n-butylaluminoxane, more preferably from at least one of methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane, and most preferably from at least one of methylaluminoxane and ethylaluminoxane.

[0092] In this invention, the aluminum oxane can be further modified and used as a modified aluminum oxane. Examples of modified aluminum oxanes include modified methyl aluminum oxane (MMAO), triisobutylaluminum-modified methyl aluminum oxane, or tri-n-hexylaluminum-modified methyl aluminum oxane.

[0093] These aluminum oxanes can be used alone or in combination in any proportion.

[0094] Examples of alkylaluminum compounds include those represented by the general formula (V):

[0095] Al(R)3(V)

[0096] In general formula (V), the groups R are the same or different from each other (preferably the same) and are each independently selected from C1-C8 alkyl groups, preferably methyl, ethyl and isobutyl, with methyl being the most preferred.

[0097] Specifically, examples of alkylaluminum include trimethylaluminum (Al(CH3)3), triethylaluminum (Al(CH3CH2)3), tri-n-propylaluminum (Al(C3H7)3), triisopropylaluminum (Al(i-C3H7)3), triisobutylaluminum (Al(i-C4H9)3), tri-n-butylaluminum (Al(C4H9)3), and triisopentylaluminum (Al(i-C5H)3). 11 )3) Tri-n-pentyl aluminum (Al(C5H) 11 )3) Tri-n-hexyl aluminum (Al(C6H) 13 )3) Triisohexylaluminum (Al(i-C6H) 13 3) Diethylmethylaluminum (Al(CH3)(CH3CH2)2) and dimethylethylaluminum (Al(CH3CH2)(CH3)2), etc., wherein trimethylaluminum, triethylaluminum, tripropylaluminum, dimethylethylaluminum, triisobutylaluminum, dimethylethylaluminum and triisohexylaluminum are preferred, and triethylaluminum, triisobutylaluminum, dimethylethylaluminum and triisohexylaluminum are most preferred.

[0098] These alkylaluminums can be used alone or in combination in any proportion.

[0099] Examples of such haloalkylaluminum compounds include those represented by the general formula (V′):

[0100] Al(R) n X 3-n (V′)

[0101] In the general formula (V′), the groups R are the same or different from each other (preferably the same) and are each independently selected from C1-C8 alkyl groups, preferably methyl, ethyl, propyl, butyl and isobutyl, with methyl being the most preferred; X represents fluorine, chlorine, bromine and iodine; n represents 1 or 2.

[0102] Specifically, examples of the aforementioned alkyl halogenated aluminum include, for instance, dichlorodimethylaluminum (Al(CH3)2Cl), dichloromethylaluminum (Al(CH3)Cl2), dichlorodiethylaluminum (Al(CH3CH2)2Cl), dichloroethylaluminum (Al(CH3CH2)Cl2), dichlorodipropylaluminum (Al(C3H7)2Cl), dichloropropylaluminum (Al(C3H7)Cl2), dichlorodi-n-butylaluminum (Al(C4H9)2Cl), dichlorodi-n-butylaluminum (Al(C4H9)Cl2), dichlorodiisobutylaluminum (Al(i-C4H9)2Cl), dichloroisobutylaluminum (Al(i-C4H9)Cl2), and dichlorodi-n-pentylaluminum (Al(C5H9)Cl2). 11 )2Cl), dichloro-n-pentyl aluminum (Al(C5H) 11 )Cl2), monochlorodiisopentylaluminum (Al(i-C5H11)2Cl), dichloroisopentylaluminum (Al(i-C5H11)2Cl) 11 Cl2), di-n-hexyl aluminum chloride (Al(C6H) 13 )2Cl), dichloro-n-hexyl aluminum (Al(C6H) 13 Cl2), aluminum monochlorodiisohexyl (Al(i-C6H) 13 )2Cl), dichloroisohexylaluminum (Al(i-C6H) 13The preferred materials are diethylaluminum chloride (Al(CH3)(CH3CH2)Cl), diethylaluminum chloride (Al(CH3)(C3H7)Cl), diethylaluminum chloride (Al(CH3)(C4H9)Cl), diethylaluminum chloride (Al(CH3)(i-C4H9)Cl), diethylaluminum chloride (Al(CH2CH3)(C3H7)Cl), diethylaluminum chloride (AlCH2CH3)(C4H9)Cl), diethylaluminum chloride (Al(CH2CH3)(i- ...

[0103] These alkyl halogenated aluminum halide can be used alone or in combination in any proportion.

[0104] In this invention, the boride may be at least one selected from alkylboron, arylboron, and borates.

[0105] In this invention, the alkylboron and arylboron can be compounds having the following general formula (B-1):

[0106] B(R)3(B-1)

[0107] In general formula (B-1), each of the three R groups may be the same as or different from each other, and each R is independently selected from C1-C6 straight-chain or branched alkyl groups and C6-C6 branched alkyl groups. 10 The aryl group is optionally substituted with one or more halogen atoms, halogenated C1-C6 straight-chain or branched alkyl groups, or phenoxy groups. The R group is preferably selected from methyl, ethyl, propyl, butyl, isobutyl, phenyl, tolyl, trifluoromethylphenyl, and pentafluorophenyl. Specific examples of alkylboron include trimethylboron, triethylboron, triisobutylboron, tripropylboron, or tributylboron. Specific examples of arylboron include tris(pentafluorophenyl)boron and tris[3,5-bis(trifluoromethyl)phenyl]boron.

[0108] In this invention, the borate can be a compound having the following general formula (B-2):

[0109] [L] + [BE4] m - (B-2)

[0110] Where L is a cationic group, and each E can be the same or different, and each is independently selected from halogen atoms, C6-C 10The aryl group is optionally substituted with one or more halogen atoms, a C1-C6 straight-chain or branched alkyl group, a halogenated C1-C6 straight-chain or branched alkyl group, a C1-C6 straight-chain or branched alkoxy group, or a phenoxy group. The ethyl group is preferably selected from fluorine, phenyl, trifluoromethylphenyl, and pentafluorophenyl. m represents the numerical value of the valence of the group in the L portion.

[0111] [L] + Some of these can be cations common in borates, for example, Li can be listed. + Na + K + Ca 2+ Mg 2+ [Fe(C5H5)2] + (Ferrocene group), etc. Additionally, the L moiety can also be an organic amine, in which case the L moiety can be represented as N(R′)3, where each R′ is independently selected from H, C1-C6 straight-chain or branched alkyl groups, and C6-C6... 10 Aryl, but not simultaneously H; or two R′ and N may be bonded together to form a 5-7 membered nitrogen-containing heterocycle optionally substituted with a C1-C6 straight-chain or branched alkyl group, preferably each R′ independently selected from H, C1-C4 straight-chain or branched alkyl, and phenyl, but not simultaneously H; or two R′ and N may be bonded together to form a 5-7 membered nitrogen-containing heteroaromatic ring or heterocyclic hydrocarbon optionally substituted with a C1-C4 straight-chain or branched alkyl group. Examples include methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, N,N-dimethylaniline, N,N-diethylaniline, imidazole, 1-butyl-3-methylimidazolium, pyridine, piperidine, etc. [L] + Some can also be groups carrying carbocations, such as triphenylmethyl carbocations.

[0112] Specific examples of borates include trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, tripropylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o-,p-dimethylphenyl)borate, triethylammonium tetra(o-,p-dimethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(pentafluorophenyl)borate, N,N-diethylphenylammonium tetraphenylborate, N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate, N,N-diethylphenylammonium tetrapentafluorophenylborate, diethylammonium tetrapentafluorophenylborate, triphenylmethyl tetra(pentafluorophenyl)borate, 1-butyl-3-methylimidazolium tetrafluoroborate, and ferrocene tetrafluoroborate.

[0113] Furthermore, according to the present invention, the co-catalyst can be used alone, or multiple co-catalysts can be used in combination in any proportion as needed, without any particular limitation.

[0114] In this invention, unless otherwise specified, the amount of the co-catalyst is expressed as the content of Al and / or B elements.

[0115] In this invention, the concentration of the boride, calculated as B, in the polymerization solvent is 0.1 × 10⁻⁶. 5 mol / L~100×10 -5 mol / L, preferably 0.5 × 10⁻⁶ -5 mol / L~100×10 -5 mol / L.

[0116] In this invention, the concentration of the co-catalyst (aluminoxane, alkylaluminum, haloalkylaluminum) in the polymerization solvent, calculated as Al, is 0.5 × 10⁻⁶. -4 mol / L~2500×10 -4 mol / L, preferably 10×10 -4 mol / L~300×10 -4 mol / L.

[0117] In one embodiment of the present invention, the molar ratio of the total amount of co-catalyst (aluminoxane, alkylaluminum, haloalkylaluminum) based on Al to the total amount of main catalyst (metallocene catalyst and / or non-metallocene catalyst) based on the central metal atom is 20 to 2000:1, preferably 50 to 1500:1, and more preferably 100 to 1000:1.

[0118] In one embodiment of the present invention, the molar ratio of the boride, calculated as B, to the total amount of the main catalyst (metallocene catalyst and / or non-metallocene catalyst), calculated as the central metal atom, is (1-20):1, preferably (2-10):1.

[0119] In the preparation of the ethylene homopolymer wax of the present invention, a chain transfer agent may or may not be used, preferably without a chain transfer agent. As the chain transfer agent, other metal alkyl compounds besides the co-catalysts listed above in the present invention can be included, for example, one or more of n-butyllithium, diethylzinc, dipropylzinc, dibutylzinc, diisobutylzinc, diethylmagnesium, dibutylmagnesium, or n-butylethylmagnesium. In one embodiment of the present invention, when a chain transfer agent is used, the molar ratio of the amount of chain transfer agent (based on its metal content) to the total amount of the main catalyst (non-metallocene catalyst and / or metallocene catalyst) (based on the central metal atoms) is 1-300:1, preferably 10-200:1.

[0120] Furthermore, the co-catalyst is generally used in solution form. There are no particular limitations on the solvent used in preparing the co-catalyst solution, as long as it can dissolve / disperse the co-catalyst. The solvent is generally selected from alkane solvents, such as n-pentane, isopentane, cyclopentane, neopentane, etc., or aromatic solvents, such as toluene, ethylbenzene, xylene, etc. According to the present invention, for ease of subsequent separation, it is preferable to use the same solvent as the polymerization solvent; or the same solvent as one of the solvents in the mixed solvents used for polymerization.

[0121] In the preparation method of the ethylene homopolymer wax of the present invention, ethylene is polymerized under the polymerization reaction conditions of the present invention, specifically under ethylene solution polymerization conditions. Specifically, if ethylene solution polymerization is carried out at a higher polymerization temperature, a solvent with a higher boiling point and a lower polymerization pressure can be selected; conversely, if ethylene solution polymerization is carried out at a lower polymerization temperature, a solvent with a lower boiling point and a higher polymerization pressure can be selected. It is known that, under ethylene solution polymerization conditions, and with similar and comparable conditions such as polymerization pressure, main catalyst, co-catalyst, and solvent, within the polymerization temperature range described in the present invention, as the polymerization temperature and the hydrogen-to-ethylene ratio increase, the weight-average molecular weight of the resulting ethylene homopolymer wax decreases accordingly. Therefore, according to the present invention, the weight-average molecular weight of the ethylene homopolymer wax can be controlled by the polymerization temperature, the ethylene solution polymerization, and different hydrogen-to-ethylene ratios.

[0122] Using alkane solvents with boiling points of 0-90℃ or mixed alkane solvents with saturated vapor pressures of 4-200 kPa at 20℃ as polymerization solvents, this invention provides opportunities and choices for preparing ethylene homopolymer waxes of different weight-average molecular weights via ethylene solution polymerization. For example, using alkane solvents with lower boiling points (such as n-pentane, isopentane, or cyclopentane) or mixed alkane solvents with higher saturated vapor pressures at 20℃ (such as n-pentane and neopentane, isopentane and neopentane) facilitates heat removal from the ethylene solution polymerization reaction, allowing it to be carried out at higher polymerization pressures and lower polymerization temperatures. Conversely, using alkane solvents with higher boiling points (such as n-hexane, cyclohexane, or 3-methylpentane) or mixed alkane solvents with lower saturated vapor pressures at 20℃ (such as n-hexane and cyclohexane, n-hexane and 3-methylpentane, cyclohexane and 2-methylpentane) allows for effective heat removal from the polymerization reaction, enabling it to be carried out at lower polymerization pressures and higher polymerization temperatures.

[0123] In the polymerization preparation method of ethylene homopolymer wax of the present invention, the ethylene solution polymerization reactor is not limited to any type, as long as it can achieve mutual contact between ethylene and the main catalyst and co-catalyst in the solvent within the polymerization pressure and temperature range described in the present invention, and can effectively avoid material adhesion and aggregation. The reactor is a batch-type ethylene slurry stirred tank reactor, and its stirring rate is not particularly limited, as long as it can ensure that the solution in the reactor can be properly dispersed. The stirring speed is related to the reactor volume. Generally speaking, the smaller the reactor volume, the higher the required stirring speed. The stirring speed is 10-1000 rpm, preferably 20-500 rpm.

[0124] In the polymerization preparation method of narrow molecular weight distribution ethylene homopolymer wax of the present invention, there is no particular limitation on the polymerization reaction time. Within a certain polymerization time, as long as the catalytic activity of ethylene polymerization in solution exceeds 10,000 g of ethylene homopolymer wax / g of main catalyst, based on the active metal content in the main catalyst as described in the present invention, the polymerization activity is higher than 10,000 g of ethylene homopolymer wax / g of main catalyst. According to the present invention, the homogeneous single-center catalyst as the main catalyst and one or more mixtures of aluminoxane, boride, alkylaluminum, or haloalkylaluminum as the co-catalyst can be added to the polymerization reaction system in the following ways: first add the main catalyst and then add the co-catalyst, or first add the co-catalyst and then add the main catalyst, or the two can be mixed together and then added together, or they can be added separately and simultaneously. When the main catalyst and co-catalyst are added separately, they can be added sequentially in the same feeding pipeline or sequentially in multiple feeding pipelines. When the two are added separately and simultaneously, multiple feeding pipelines should be selected.

[0125] The polymerization method of the present invention can polymerize ethylene in a continuous manner or in a batch manner.

[0126] In this invention, there is no limitation on the polymerization time; those skilled in the art can select the appropriate polymerization time as needed.

[0127] Following the polymerization method of the present invention, ethylene homopolymer wax can be recovered from the polymerization solvent using conventional techniques in the art. For example, after the polymerization reaction is complete, the polymerization solvent can be removed by flash evaporation, and the ethylene homopolymer wax can be further refined as needed.

[0128] The present invention further provides an ethylene homopolymer wax with a weight-average molecular weight of 500-15000 g / mol, a molecular weight distribution of 1.0-4.0, and a true density of 0.950-0.990 g / cm³. 3 Crystallinity 60-90%, melting point 120-130℃, penetration 0.1-1.5mm*10 -1 .

[0129] In one embodiment of the present invention, the ethylene homopolymer wax of the present invention has a weight-average molecular weight of 1000-10000 g / mol, a molecular weight distribution of 1.25-3.0, a crystallinity of 65-80%, and a true density of 0.955-0.980 g / cm³. 3 It has a crystallinity of 65-80%, a melting point of 122-128℃, and a penetration of 0.4-1.0 mm. -1 .

[0130] The ethylene homopolymer wax described in this invention is obtained by the polymerization preparation method of the ethylene homopolymer wax described above.

[0131] Ethylene homopolymer wax has a narrow molecular weight distribution, high crystallinity, and low total ash content. This ethylene homopolymer wax can improve the dispersion, hardness, and wear resistance in color masterbatches, and can be used as a high-grade material in color masterbatches, PVC release agents, asphalt, hot melt adhesives, and other fields.

[0132] Example

[0133] The present invention will be further described in detail below with reference to the embodiments, but the present invention is not limited to these embodiments.

[0134] In the following examples, the ethylene homopolymer wax was polymerized using the following method.

[0135] Atmospheric pressure polymerization

[0136] After the dried flask was replaced with ethylene three times, the solvent, co-catalyst and catalyst solution were added successively under a gas pressure of 0.1 MPa. The reaction was carried out for 15 min, the ethylene was stopped, acidified ethanol was added to the polymer solution, the mixture was filtered and washed with distilled water and ethanol, and the resulting product was dried and weighed.

[0137] High-pressure reactor polymerization

[0138] After the stainless steel stirred polymerization reactor is heated to the set temperature, it is replaced three times with ethylene. Solvent, co-catalyst and catalyst are added in sequence, the temperature is raised and ethylene is introduced. The total pressure is kept constant. After polymerization for a period of time, the polymer solution is released, dried and the resulting product is weighed after drying.

[0139] Continuous solution polymerization

[0140] Solvent, main catalyst solution, and co-catalyst solution are fed into the polymerization reactor from the bottom via metering pumps, where ethylene undergoes polymerization. The materials in the reactor flow out from the top. A discharge control system is used to ensure continuous discharge and stable reaction in the polymerization reactor. The discharged material goes directly into a receiving tank. The entire process requires a closed system and nitrogen protection, and the purity of the raw materials is also relatively high.

[0141] The structure of the ethylene homopolymer wax was determined using nuclear magnetic resonance (NMR). Specifically, the degree of branching of the sample was determined using a Bruker Avance 600M NMR spectrometer at 120°C. The copolymer sample was dissolved in deuterated o-dichlorobenzene to prepare a solution of approximately 20 wt%, and the solution was scanned 6000 times at 120°C to obtain the sample's structure. 13 C10 NMR spectrum.

[0142] The molecular weight and molecular weight distribution of ethylene homopolymer wax were determined according to GB / T 21864-2005 standard using a Polymer Laboratories PL-220 gel permeation chromatograph. 1,2,4-trichlorobenzene was used as the mobile phase, polystyrene was used as the standard, a differential detector was used, the flow rate was 1.0 mL / min, the measurement temperature was 150 ℃, and the sample concentration was 2.0 mg / mL.

[0143] Determination of melting point and crystallinity of ethylene homopolymer wax: The properties were determined using a differential scanning calorimeter (Perkin-Elmer DSC 7) according to GB / T 28724-2012 and GB / T19466.3-2004 standards. The sample size was 3-5 mg, and the atmosphere was nitrogen. The sample was first heated from 30℃ to 180℃ at a rate of 20℃ / min, held for 3 min, then cooled to 20℃ at a rate of 20℃ / min, held for 3 min, and then heated back to 180℃ at a rate of 20℃ / min. The second heating curve was used for analysis.

[0144] The density of ethylene homopolymer wax was tested using an Anton Paar DMA 4500M densitometer at 23°C, in accordance with ISO 1183 standard.

[0145] Color Masterbatch Color Evaluation

[0146] HDPE5000S was used as the carrier resin, and phthalocyanine blue pigment accounted for 20% by mass. Ethylene homopolymer wax of this invention was added as a dispersant at a mass fraction of 3% in each phthalocyanine blue pigment masterbatch. Raw materials were prepared according to the formula and co-extruded using a twin-screw extruder to obtain blue masterbatch. The prepared blue masterbatch was then added to PE for blow molding to prepare a film with a pigment content of 0.4 wt%. The number of coloring spots has a significant impact on the tinting strength of the pigment. The various physical properties of the film were determined according to the requirements of GB / T 4456-2008 "Polyethylene Blown Film for Packaging".

[0147] Thin film transmittance evaluation method: The sample was tested according to the spectrophotometer method of GB / T 2410-2008, and the transmittance was recorded.

[0148] Masterbatch particle size: The particle size of pigments in the matrix was studied using a polarizing microscope.

[0149] Specifically, for the thin film, three regions are randomly divided at the center and edge locations, with each region being 1 mm thick. 2 The particle sizes of the pigments within the field of view were statistically analyzed, and the average value was taken.

[0150] The wetting improvement effect of the polymer on the masterbatch can be demonstrated by testing the film transmittance and pigment particle size. That is, the higher the transmittance and the smaller the pigment particles, the better the wetting improvement effect of the polymer on the masterbatch.

[0151] Method for determining metal content (method for determining ash content): Inductively coupled plasma atomic emission spectrometry (ICP-AES) is used to detect metal content. The polymer sample solution is carried into the nebulization system by a carrier gas and then atomized. It enters the axial channel of the plasma in the form of an aerosol. It is fully evaporated, atomized, ionized and excited in the high temperature and inert gas. The characteristic spectral lines of the contained elements emitted are sent to the spectrometer by the spectrometer. The spectrometer performs qualitative and quantitative analysis based on the characteristic spectra of the elements.

[0152] The method for determining VOC content: VOC content was detected by gas chromatography. Based on the set parameters of the gas chromatograph, solutions of different concentrations of polymerization solvent-toluene were first prepared. A 10 μl microsyringe was used to repeatedly draw the solution to be tested to remove air bubbles. Then, 0.1 μl of the solution was injected into the gas chromatograph. After the components of the sample were fully displayed in the chromatogram, the peak areas of the polymerization solvent-toluene solutions were recorded. A curve was plotted between the peak areas and the corresponding concentrations of the polymerization solvent standard solutions. The ethylene homopolymer wax from each example and comparative example was dissolved in toluene. The polymerization solvent content in the polymer was tested by comparing it with the curve of the polymerization solvent standard solution, and this was taken as the VOC content.

[0153] Penetration determination method: The penetration of ethylene homopolymer wax is tested using a NORMLAB penetration meter according to ASTM D 1321D / DIN 51579 standards.

[0154] PVC application evaluation

[0155] The test was conducted using a torque rheometer (model CTR-300, Shanghai Changkai Electromechanical Technology Co., Ltd.). The melt torque was used as the basis for quantitative data, while qualitative results such as the surface gloss (roughness) and adhesion to the equipment were observed during the experiment to represent the processing performance of ethylene homopolymer wax.

[0156] Examples 1-18, Comparative Examples 1-3

[0157] Following the polymerization method described above, and in accordance with the conditions in Table 1 below, Examples 1-18 and Comparative Examples 1-3 were carried out to prepare various ethylene homopolymer waxes.

[0158] The properties of the polymers obtained in Examples 1-18 and Comparative Examples 1-3 were measured according to the above-described measurement method. The results are shown in Table 2 below.

[0159]

[0160]

[0161]

[0162]

[0163] The embodiments of this invention demonstrate that, using the polymerization method of this invention, ethylene homopolymer waxes with high crystallinity, high transmittance, and low penetration can be efficiently prepared. Furthermore, the polymerization method of this invention is beneficial for improving the devolatilization efficiency of the polymer, resulting in a polymer with a VOC content below 50 ppm. It exhibits high polymerization activity and extremely low metal content (metal residue below 10 μg / g). The molecular weight of the ethylene homopolymer wax can be adjusted by changing the ratio of hydrogen to ethylene, and high polymerization activity is maintained even at a higher hydrogen ratio.

[0164] Finally, it should be noted that the above examples are merely some specific embodiments of the present invention. Obviously, the present invention is not limited to the above embodiments and many variations are possible. All variations that can be directly derived or conceived by those skilled in the art from the disclosure of the present invention should be considered within the scope of protection of the present invention.

Claims

1. A process for the polymerization preparation of an ethylene homopolymer wax, wherein, Ethylene is polymerized in the presence of hydrogen in an alkane solvent having a boiling point of 0 to 90°C or a mixed alkane solvent having a saturated vapor pressure of 4 to 200 KPa at 20°C as a polymerization solvent (preferably an alkane solvent having a boiling point of 25 to 82°C or a mixed alkane solvent having a saturated vapor pressure of 30 to 160 KPa at 20°C as a polymerization solvent) under a catalytic system comprising one or more selected from a non-metallocene catalyst and a metallocene catalyst as a main catalyst, one or more selected from an aluminoxane, a boron compound, an aluminum alkyl, and an aluminum alkyl chloride as a cocatalyst, wherein the molar ratio of ethylene to hydrogen is 35 to 0.5:1, preferably 30 to 1:

1.

2. The production method according to claim 1, wherein, The polymerization solvent is one selected from n-pentane, isopentane, and cyclopentane; or a mixed alkane solvent obtained by mixing two or more alkane selected from n-pentane, isopentane, neopentane, and cyclopentane, more preferably one selected from a combination of n-pentane and isopentane, a combination of isopentane and neopentane, a combination of n-pentane and cyclopentane, a combination of n-pentane and neopentane, a combination of isopentane and cyclopentane, a combination of neopentane and cyclopentane, a combination of n-hexane and n-pentane, and a combination of n-pentane-isopentane-cyclopentane.

3. The production method according to claim 1 or 2, wherein, The polymerization conditions satisfy: a polymerization temperature of 90 to 160°C, preferably 100 to 150°C; and / or a polymerization pressure of 1.5 to 6.0 MPa, preferably 2.0 to 5.0 MPa; and / or The concentration of the procatalyst in the polymerization solvent is 0.1 x 10 -5 mol / L to 50 x 10 -5 mol / L, preferably 0.5 x 10 -5 mol / L to 20 x 10 -5 mol / L, more preferably 1 x 10 5 mol / L to 15 x 10 -5 mol / L, based on the central metal atom.

4. The production process according to any one of claims 1 to 3, wherein, The non-metallocene catalyst is selected from a compound represented by the following formula (I) or a mixture thereof at any ratio: In formula (I), R1, R2, R3, R4are each independently selected from the group consisting of hydrogen and C 1-6 linear or branched alkyl, more preferably each independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl; 1-6 linear or branched alkyl, more preferably each independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl; R6, R7, R8, R9are each independently selected from the group consisting of hydrogen and C 1-6 linear or branched alkyl, more preferably each independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl; 1-6 linear or branched alkyl, more preferably each independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, butyl, isobutyl, sec-butyl, tert-butyl; R5represents hydrogen or C 1-12 linear or branched alkyl, preferably hydrogen, C 1-6 linear or branched alkyl or C 6-10 aryl, more preferably hydrogen, C 1-3 linear or branched alkyl or phenyl, more preferably hydrogen, methyl, ethyl, n-propyl, i-propyl or phenyl; R 10 each independently selected from hydrogen or C 1-6 linear or branched alkyl, preferably hydrogen or C 1-6 linear or branched alkyl, more preferably hydrogen, methyl or ethyl; p is selected from 1 or 2; group Y is O or S, preferably O; group A is S or O, preferably S; M is selected from a group IVB metal element, preferably selected from titanium, zirconium, and hafnium, more preferably titanium; X is selected from fluorine, chlorine, bromine, and iodine, preferably chlorine or bromine; represents a single or double bond, wherein when is a single bond, then p is 2, the hydrogen on N is present, when is a double bond, then p is 1, the hydrogen on N is absent; represents a coordination bond; n depends on the valence of the atom M, and can be 1, 2, 3, 4, or 5, for example.

5. The method of claim 4, wherein, In formula (I), R1, R2, R3, R4are each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl, preferably each independently selected from hydrogen and tert-butyl; R7is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl, preferably selected from hydrogen and tert-butyl; R9is selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl, preferably selected from hydrogen; R6, R8are each independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and tert-butyl, preferably each independently selected from hydrogen and tert-butyl.

6. The method of preparation according to claim 4 or 5, wherein, The compound represented by formula (I) is at least one selected from the group consisting of 3-tert-butylsulfoxalyl 2-methylthioaniline titanium trichloride, salicyl 2-methylthioaniline titanium trichloride, sulfoxalyl 2-phenylthioaniline titanium trichloride, 3,5-di-tert-butylsulfoxalyl 2-propylthioaniline titanium trichloride, 3-tert-butylsulfoxalyl 2-propylthioaniline titanium trichloride, 3,5-di-tert-butylsulfoxalyl 2-mercaptoaniline titanium trichloride, sulfoxalyl 2-mercaptoaniline titanium trichloride, sulfoxalyl 2-methylthioaniline titanium trichloride, sulfoxalyl 2-propylthioaniline titanium trichloride, 3,5-di-tert-butylsulfoxalyl 2-methylthioaniline titanium trichloride, 3,5-di-tert-butylsalicyl 2-methylthioaniline titanium trichloride, 3,5-di-tert-butylsalicyl 2-propylthioaniline titanium trichloride, 4-tert-butylsulfoxalyl 2-methylthioaniline titanium trichloride, 5-tert-butylsulfoxalyl 2-methylthioaniline titanium trichloride, preferably at least one selected from the group consisting of 3-tert-butylsulfoxalyl 2-methylthioaniline titanium trichloride, sulfoxalyl 2-phenylthioaniline titanium trichloride, 3,5-di-tert-butylsalicyl 2-propylthioaniline titanium trichloride, 4-tert-butylsulfoxalyl 2-methylthioaniline titanium trichloride, 5-tert-butylsulfoxalyl 2-methylthioaniline titanium trichloride.

7. The production process according to any one of claims 1 to 6, wherein The metallocene catalyst is one or a mixture thereof in any ratio selected from the group consisting of dimethylsilyl(cyclopentadienyl)(1-indenyl)zirconium dichloride, diphenylmethylenyl(cyclopentadienyl)(9-fluorenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(4,5-benzo-1-indenyl)zirconium dichloride, dimethylsilyl(cyclopentadienyl)(4,5-benzo-1-indenyl)zirconium dichloride. In formula (II), R1is a C1-C8straight-chain or branched alkylene, di-C6-C10arylene, di-C1-C8alkylsilylene or di-C6-C10arylsilylene, preferably a C1-C4straight-chain or branched alkylene, di-C1-C4alkylsilylene or di-C6-C10arylsilylene, more preferably methylene, ethylene, isopropylidene, diphenylmethylene, dimethylsilylene or diphenylsilylene, most preferably methylene, ethylene or isopropylidene. 10 In formula (II), R1is a C1-C8straight-chain or branched alkylene, di-C6-C10arylene, di-C1-C8alkylsilylene or di-C6-C10arylsilylene, preferably a C1-C4straight-chain or branched alkylene, di-C1-C4alkylsilylene or di-C6-C10arylsilylene, more preferably methylene, ethylene, isopropylidene, diphenylmethylene, dimethylsilylene or diphenylsilylene, most preferably methylene, ethylene or isopropylidene. 10 In formula (II), R1is a C1-C8straight-chain or branched alkylene, di-C6-C10arylene, di-C1-C8alkylsilylene or di-C6-C10arylsilylene, preferably a C1-C4straight-chain or branched alkylene, R2 and R3 are each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, or C6-C 10 aryl; or R2 together with its bonded cyclopentadienyl group, and R3 together with its bonded cyclopentadienyl group, each independently forming a fluorenyl, indene, benzoindene, tetrahydroindene, and benzodihydroindene group substituted by 1 to 5 substituents independently selected from halogen, C1-C4 alkyl, C1-C4 haloalkyl, or phenyl. In formula (III), R6 and R7 are each independently selected from hydrogen, halogen, C1-C4 alkyl, C1-C4 haloalkyl, or C6-C 10 Aryl; R4and R5are each independently selected from hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, or C6-C10aryl; or R4together with the cyclopentadienyl group to which it is bonded and R5together with the cyclopentadienyl group to which it is bonded each independently forms a fluorenyl, indenyl, benzindenyl, tetrahydroindenyl, and benzo dihydroindenyl group substituted with 1-5 substituents each independently selected from halogen, C1-C4alkyl, C1-C4haloalkyl, or phenyl. 10 R4and R5are each independently selected from hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, or C6-C10aryl; or R4together with the cyclopentadienyl group to which it is bonded and R5together with the cyclopentadienyl group to which it is bonded each independently forms a fluorenyl, indenyl, benzindenyl, tetrahydroindenyl, and benzo dihydroindenyl group substituted with 1-5 substituents each independently selected from halogen, C1-C4alkyl, C1-C4haloalkyl, or phenyl.

8. The production method according to claim 7, wherein 9. The production method according to any one of claims 1 to 8, wherein the aluminoxane is at least one selected from the group consisting of linear aluminoxane represented by general formula (IV-1) below and cyclic aluminoxane represented by general formula (IV-2) below, The aluminoxane is at least one selected from the group consisting of linear aluminoxane represented by general formula (IV-1) below and cyclic aluminoxane represented by general formula (IV-2) below, In general formula (IV-1) and general formula (IV-2), the group R is the same or different (preferably the same) from each other, and each is independently selected from the group consisting of C1-C8 alkyl, preferably methyl, ethyl and isobutyl, most preferably methyl; n is any integer in the range of 1 to 50, preferably any integer in the range of 10 to 30; The aluminum alkyl is selected from the group consisting of compounds represented by general formula (V), Al(R)3(V) In general formula (V), the group R is the same or different (preferably the same) from each other, and each is independently selected from the group consisting of C1-C8 alkyl, preferably methyl, ethyl, isobutyl, isohexyl; The aluminum alkyl is selected from the group consisting of compounds represented by general formula (V), In general formula (V), the group R is the same or different (preferably the same) from each other, and each is independently selected from the group consisting of C1-C8 alkyl, preferably methyl, ethyl, isobutyl, isohexyl; Al(R) n X 3-n (V') ​ The boride is at least one selected from the group consisting of alkyl boron and aryl boron represented by the following general formula (B-1), borate represented by the following general formula (B-2), B(R)3(B-1) In general formula (B-1), each of the three R groups can be the same as or different from one another, and each R is independently selected from the group consisting of C1-C6 linear or branched alkyl groups and C6-C10 aryl groups, each group being optionally substituted with one or more halogen atoms, halogenated C1-C6 linear or branched alkyl groups, or phenoxy groups. 10 aryl, preferably selected from the group consisting of methyl, ethyl, propyl, butyl, isobutyl, phenyl, tolyl, trifluoromethylphenyl, and pentafluorophenyl, each group being optionally substituted with one or more halogen atoms, halogenated C1-C6 linear or branched alkyl groups, or phenoxy groups; [L] + [BE4] m - (B-2) In general formula (B-2), L is a cationic group, each E can be the same or different, and each is independently selected from a halogen atom, a C6-Ci2aryl group, a C6-Ci2aryl group optionally substituted with one or more halogen atoms, C1-C6linear or branched alkyl groups, halogenated C1-C6linear or branched alkyl groups, C1-C6linear or branched alkoxy groups, or phenoxy groups, preferably selected from fluorine, phenyl, trifluoromethylphenyl, and pentafluorophenyl, and m represents the number of valence of the group of the L moiety. 10 In general formula (B-2), L is a cationic group, each E can be the same or different, and each is independently selected from a halogen atom, a C6-Ci2aryl group, a C6-Ci2aryl group optionally substituted with one or more halogen atoms, C1-C6linear or branched alkyl groups, halogenated C1-C6linear or branched alkyl groups, C1-C6linear or branched alkoxy groups, or phenoxy groups, preferably selected from fluorine, phenyl, trifluoromethylphenyl, and pentafluorophenyl, and m represents the number of valence of the group of the L moiety.

10. The production process according to any one of claims 1 to 9, wherein, The aluminoxane is at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane and n-butyl aluminoxane, preferably at least one selected from the group consisting of methyl aluminoxane, ethyl aluminoxane and isobutyl aluminoxane, most preferably at least one selected from the group consisting of methyl aluminoxane and ethyl aluminoxane; The alkylaluminum is at least one selected from the group consisting of trimethylaluminum (Al(CH3)3), triethylaluminum (Al(CH3CH2)3), tri-n-propylaluminum (Al(C3H7)3), triisopropylaluminum (Al(i-C3H7)3), triisobutylaluminum (Al(i-C4H9)3), tri-n-butylaluminum (Al(C4H9)3), triisopentylaluminum (Al(i-C5H 11 )3), tri-n-pentylaluminum (Al(C5H 11 )3), tri-n-hexylaluminum (Al(C6H 13 )3), triisohexylaluminum (Al(i-C6H 13 )3), diethylmethylaluminum (Al(CH3)(CH3CH2)2), and dimethylethylaluminum (Al(CH3CH2)(CH3)2), preferably at least one selected from the group consisting of trimethylaluminum, triethylaluminum, tripropylaluminum, dimethylethylaluminum, triisobutylaluminum, dimethylethylaluminum, and triisohexylaluminum, most preferably at least one selected from the group consisting of triethylaluminum, triisobutylaluminum, dimethylethylaluminum, triisohexylaluminum; said halogenated aluminum alkyl is at least one selected from the group consisting of monochlorodi- methylaluminum (Al(CH3)2Cl), dichloromethylaluminum (Al(CH3)Cl2), monochlorodi- ethylaluminum (Al(CH3CH2)2Cl), dichloroethylaluminum (Al(CH3CH2)Cl2), monochlorodi- propylaluminum (Al(C3H7)2Cl), dichloropropylaluminum (Al(C3H7)Cl2), monochlorodi- n-butylaluminum (Al(C4H9)2Cl), dichloro-n-butylaluminum (Al(C4H9)Cl2), monochlorodi- iso-butylaluminum (Al(i-C4H9)2Cl), dichloroiso-butylaluminum (Al(i-C4H9)Cl2), monochlorodi-n-pentylaluminum (Al(C5H 11 )2Cl), dichloro-n-pentylaluminum (Al(C5H 11 )Cl2), monochlorodi-iso-pentylaluminum (Al(i-C5H 11 )2Cl), dichloroiso-pentylaluminum (Al(i-C5H 11 )Cl2), monochlorodi-n-hexylaluminum (Al(C6H 13 )2Cl), dichloro-n-hexylaluminum (Al(C6H 13 )Cl2), monochlorodi-iso-hexylaluminum (Al(i-C6H 13 )2Cl), dichloroiso-hexylaluminum (Al(i-C6H 13 )Cl2), monochloromethyl-ethylaluminum (Al(CH3)(CH3CH2)Cl), monochloromethyl- propylaluminum (Al(CH3)(C3H7)Cl), monochloromethyl-n-butylaluminum (Al(CH3)(C4H9)Cl), monochloromethyl-iso-butylaluminum (Al(CH3)(i-C4H9)Cl), monochloroethyl-propylaluminum (Al(CH2CH3)(C3H7)Cl), monochloroethyl-n-butylaluminum (Al(CH2CH3)(C4H9)Cl), monochloromethyl-iso-butylaluminum (Al(CH2CH3)(i-C4H9)Cl), preferably at least one selected from the group consisting of monochlorodiethylaluminum, dichloroethylaluminum, monochlorodi-n-butylaluminum, dichloro-n-butylaluminum, monochlorodi-iso-butylaluminum, dichloro-iso-butylaluminum, monochlorodi-n-hexylaluminum, dichloro-n-hexylaluminum, further preferred at least one of chlorodiethylaluminum, dichloroethylaluminum and monochlorodi-n-hexylaluminum, most preferred monochlorodiethylaluminum; The alkyl boron is at least one selected from the group consisting of trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron and tributyl boron; The aryl boron is at least one selected from the group consisting of tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron; The borate is at least one selected from the group consisting of trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tributylammonium tetraphenylborate, trimethylammonium tetra(p-tolyl)borate, tripropylammonium tetra(p-tolyl)borate, trimethylammonium tetra(o,p-dimethylphenyl)borate, triethylammonium tetra(o,p-dimethylphenyl)borate, trimethylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(p-trifluoromethylphenyl)borate, tributylammonium tetra(pentafluorophenyl)borate, N,N-diethylbenzenammonium tetraphenylborate, N,N-dimethylbenzenammonium tetra(pentafluorophenyl)borate, N,N-diethylbenzenammonium tetra(pentafluorophenyl)borate, diethylammonium tetra(pentafluorophenyl)borate, triphenylmethyl tetra(pentafluorophenyl)borate, 1-butyl-3-methylimidazolium tetrafluoroborate, ferrocenium tetrafluoroborate.

11. The production process according to any one of claims 1 to 10, wherein, The ratio of the total amount of the cocatalyst (aluminoxane, alkylaluminum, halogenated alkylaluminum) calculated as Al to the total amount of the main catalyst (metallocene catalyst and / or non-metallocene catalyst) calculated as central metal atom is a molar ratio of 20 to 2000:1, preferably 50 to 1500:1, further preferably 100 to 1000:1; and / or The ratio of the total amount of the boride calculated as B to the total amount of the main catalyst (metallocene catalyst and / or non-metallocene catalyst) calculated as central metal atom is a molar ratio of (1-20):1, preferably (2-10):

1.

12. Ethylene homopolymer wax prepared according to the process of any one of claims 1 to 11, wherein, The ethylene homopolymer wax has a weight average molecular weight of 500 to 15,000 g / mol, a molecular weight distribution of 1.0 to 4.0, a true density of 0.950 to 0.990 g / cm 3 , a crystallinity of 60 to 90%, a melting point of 120 to 130°C, and a penetration of 0.1 to 1.5 mm*10 -1 .

13. The ethylene homopolymer wax according to claim 12, wherein the ethylene homopolymer wax has a weight average molecular weight of 1000 to 10000 g / mol, a molecular weight distribution of 1.25 to 3.0, a true density of 0.955 to 0.980 g / cm3, a crystallinity of 65 to 80%, a melting point of 122 to 128°C, and a penetration of 0.5 to 1.0 mm*10. 3 -1 .​

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