Low metal content polyolefin filter membrane

Abstract

Certain polyolefin membranes are provided that are useful as components of filters for liquid purification. Advantageously, the filter membranes of the present disclosure are particularly useful for filtering liquids used in the manufacture of microelectronic devices because they have significantly reduced concentrations of certain trace metals. In one aspect, the present disclosure provides a filter membrane comprising a polyolefin, the polyolefin having less than about 4 ppm of a total of metals selected from titanium, aluminum, iron, zinc, and magnesium.

Description

[Technical Field]

[0001] This disclosure relates to a filter film containing a polyolefin, which is essentially free from metallic impurities typically found in polymers and filters containing such films. [Background technology]

[0002] Filter products are essential tools in modern industry, used to remove unwanted materials from the flow of useful fluids. Useful fluids processed using filters include water, liquid industrial solvents and processing fluids, industrial gases used in manufacturing or processing (e.g., in semiconductor manufacturing), and liquids with medical or pharmaceutical applications. Unwanted materials removed from fluids include impurities and contaminants such as particles, microorganisms, and dissolved chemical species. Specific examples of filter applications include their use with liquid materials in the manufacture of semiconductors and microelectronic devices.

[0003] To perform the filtration function, the filter may include a filter membrane that serves to remove unwanted materials from the fluid passing through the filter membrane. The filter membrane may be in the form of a flat sheet, wound up (e.g., spiral), flat, pleated, or disc-shaped, as needed. Alternatively, the filter membrane may be in the form of hollow fibers. The filter membrane may be housed within a housing, or otherwise supported, so that the fluid being filtered must pass through the filter membrane before passing through the filter outlet after entering through the filter inlet.

[0004] Filter membranes can consist of porous structures with average pore sizes that can be selected based on the use of the filter, i.e., the type of filtration performed by the filter. Typical pore sizes range from micrometers to submicrometers, e.g., about 0.001 micrometers to about 10 micrometers. Membranes with average pore sizes of about 0.001 to about 0.05 micrometers are sometimes classified as ultrafilter membranes. Membranes with pore sizes of about 0.05 to 10 micrometers are sometimes called microporous membranes.

[0005] Filter membranes having pore sizes in the micrometer or submicrometer range may be effective in removing undesirable materials from a fluid flow by either a sieving mechanism, a non-sieving mechanism, or both. A sieving mechanism is a mode of filtration that removes particles from a liquid flow by mechanically holding them on the surface of the filter membrane, which works by mechanically interfering with particle movement, holding particles within the filter, and mechanically preventing the flow of particles through the filter. Typically, the particles can be larger than the pores of the filter. A "non-sieving" filtration mechanism is a mode of filtration in which the filter membrane holds suspended particles or dissolved materials contained in the fluid flow through the filter membrane in a manner that is not necessarily mechanical, and includes, for example, an electrostatic mechanism in which fine particles or dissolved impurities are electrostatically attracted to and held on the filter surface and removed from the fluid flow, and the particles may be dissolved or solids having a particle size smaller than the pores of the filter material.

[0006] Many such filter membranes are composed of polyolefins, which are generally prepared using various metal-containing catalysts. For example, certain polyolefins, such as polyethylene, are prepared using the Ziegler-Natta catalyst and may contain metals such as titanium, aluminum, and magnesium. Other catalysts may contain chromium or silicon. Thus, such catalysts are present in small but potentially harmful amounts in the filter material prepared from such polyolefins. If used as is, the filter material can leach these metals when used to filter liquid compositions such as solvents. Therefore, these filter materials are typically washed to remove such metal contaminants from or near the surface of the polyolefin material. Thus, the metals not removed during such a process remain incorporated into the polymer matrix and can therefore leach under operating conditions. Removing ionic materials such as dissolved metal cations from solutions is important in many industries, such as the microelectronics industry, as even very low concentrations of cationic metal contaminants can ultimately adversely affect the quality and performance of microprocessors and memory devices. The ability to prepare positive and negative photoresists with low levels of metal ion impurities, or the ability to deliver isopropyl alcohol used in Maragoni drying for wafer cleaning with metal ion impurities at the level of parts per billion or parts per trillion, are highly desirable and are two very examples of the need for contamination control in semiconductor manufacturing. Therefore, improved methods for filtering liquid compositions that reduce or effectively eliminate the presence of such metal ions are still needed. [Overview of the Initiative]

[0007] In summary, the present disclosure provides certain polyolefin membranes useful as components of filters for liquid purification and / or filtration. In one embodiment, the polyolefin is selected from polyethylene and copolymers such as polyethylene and polyethylene-co-polybutylene. Advantageously, the filter membranes of the present disclosure are particularly useful for filtering liquids used in the manufacture of microelectronic devices because the concentrations of certain trace metals are significantly reduced. In one embodiment, the present disclosure provides a filter membrane comprising a polyolefin, where the total amounts of titanium, aluminum, iron, zinc, and magnesium in the polyolefin are less than about 4 ppm, as determined by the MARS6 Microwave Acid Digestion Method Note Compendium.

[0008] This disclosure may be better understood by considering the following description of various exemplary embodiments in relation to the attached drawings. [Brief explanation of the drawing]

[0009] [Figure 1] This figure shows an example of a filter product described herein (it is schematic and not necessarily to scale). [Modes for carrying out the invention]

[0010] This disclosure is open to various modifications and alternative forms, the details of which are shown in the drawings as examples and described in detail. However, it should be understood that the aspects of this disclosure are not intended to be limited to the specific exemplary embodiments described. Rather, the intention is to cover all modifications, equivalents, and alternatives that fall within the spirit and scope of this disclosure.

[0011] As used herein and in the appended claims, the singular forms "a," "an," and "the" refer to multiple subjects unless the context clearly indicates otherwise. As used herein and in the appended claims, the term "or" is generally used to mean "and / or" unless the context clearly indicates otherwise.

[0012] The term "approximately" generally refers to a range of numbers that are considered equivalent to a given value (e.g., having the same function or result). Often, the term "approximately" may include numbers rounded to the nearest significant figure.

[0013] A numerical range expressed using endpoints includes all numbers contained within that range (for example, 1-5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, and 5).

[0014] The amount of trace metals present in polyolefins is measured using the method described in "MARS 6 Microwave Acid Digestion Method Note Compendium," Microwave Digestion of polyethylene - High density, p. 511. CEM Corporation. October 1, 2019. Website: https: / / cem.com / media / contenttype / media / literature / MetNote_MARS6_Compendium_2.pdf. After microwave digestion, the sample was diluted approximately 50 times with deionized (DI) water, and the metal concentration was tested using inductively coupled plasma mass spectrometry (ICP-MS).

[0015] In a first embodiment, the Disclosure provides a filter film containing a polyolefin in which the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 4 ppm, as determined by the MARS6 Microwave Acid Digestion Method Note Compendium. This total level of metal is based on the total amount of metal in μg per gram of polyolefin resin. In other embodiments, the polyolefin has a total amount of metal selected from titanium, aluminum, iron, zinc, and magnesium of less than about 3.5 ppm, or less than about 3 ppm, or less than about 2 ppm, or less than about 1 ppm.

[0016] In another embodiment, the polyolefin contains less than 1 ppm of ruthenium. In one embodiment, the total amount of titanium, aluminum, silicon, chromium, and magnesium in the polyolefin is greater than 0.1 ppm, and the amount of ruthenium is greater than 0.1 ppm but less than the amount described above.

[0017] In one embodiment, the polyolefin is selected from polyethylene and polyethylene copolymers. Exemplary polyolefins include polyethylene and polyethylene-co-polybutylene copolymers. The physical properties of copolymers such as polyethylene-co-polybutylene are similar to those of commercially available polyethylene. In one embodiment, the polyolefin is polyethylene. In another embodiment, polyethylene-co-polybutylene has a number-average molecular weight of about 330,000 to 2,200,000 daltons. In yet another embodiment, polyethylene and polyethylene-co-polybutylene have a number-average molecular weight of about 700,000 to about 1,500,000 daltons. In yet another embodiment, the polyolefin is ultra-high molecular weight polyethylene.

[0018] The filter film of the first embodiment can be made of polyethylene that can be prepared by a ring-opening metathesis polymerization (ROMP) reaction between 1-octene and a ruthenium II catalyst. For example, the following scheme is followed. TIFF0007926987000001.tif23170

[0019] In the above reaction, the ruthenium(II) catalyst is used in the ring-opening metathesis polymerization (ROMP) reaction to provide the unsaturated polymer of formula (A) (i.e., polyethylene). The reaction is generally carried out in a non-polar aprotic solvent such as hexane, dichloromethane, chloroform, toluene, diethyl ether, ethyl acetate, etc., and can be carried out at room temperature or a slightly elevated temperature, for example, from about 23°C to about 70°C. In one embodiment, the Ru II catalyst has a functional group that renders the catalyst soluble or water-dispersible, thus facilitating its removal during post-treatment of the product using conventional aqueous extraction. Such functional groups include, for example, ammonium groups, quaternary ammonium groups, amines, polyalkylene glycols and other functional groups that allow effective removal of the catalyst from the organic solution of the polymer of formula (A) by aqueous extraction (at acidic or basic pH), continuous precipitation, Soxhlet extraction, or adsorption onto silica, or removal of the catalyst by adsorption onto ion exchange or chelating resins. Alternatively, the ruthenium(II) catalyst can be anchored to a solid support as an alternative means for separating the catalyst from the reaction product mixture, thus reducing or effectively eliminating ruthenium contamination of the resulting polyolefin.

[0020] Examples of suitable ruthenium(II) catalysts include those known as Grubbs catalysts and Hoveyda-Grubbs second-generation catalysts. Suitable metathesis catalysts include those available from Apeiron Synthesis. Specific catalysts include i. (1,3-Bis(2,6-diisopropylphenyl)-4-((4-ethyl-4-methylpiperazin-1-ium-1-yl)methyl)imidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(II) chloride dihydrate; ("FixCat"); ii. (1,3-Dimethyl-4-((trimethylammonio)methyl)imidazolidin-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II) chloride; ("StickyCat Cl"); iii. (4-((4-ethyl-4-methylpiperazine-1-ium-1-yl)methyl)-1,3-dimethylimidazolidined-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II) chloride ("AquaMet") iv. (1,3-Dimethyl-4-((trimethylammonio)methyl)imidazolidin-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II)hexafluorophosphate; ("StickyCat PF6"); and v. (1,3-Dimethyl-4-((trimethylammonio)methyl)imidazolidine-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II)tetrafluoroborate; ("StickyCat BF4") It includes.

[0021] The reaction typically takes place over a period of 0.3 to 4 hours, after which chain cleavage is performed using a vinyl ether such as ethyl vinyl ether, ethylene glycol vinyl ether, di(ethylene glycol) vinyl ether, or di(ethylene glycol) divinyl ether.

[0022] A purified solution of the unsaturated polymer of formula (A) can be reduced in the presence of an amine such as tripropylamine using a hydrazine-type or hydrazide-type reducing agent such as p-toluenesulfonyl hydrazide to provide a saturated polyethylene compound represented by formula (B). TIFF0007926987000002.tif21170

[0023] Therefore, in another embodiment, the present disclosure provides the above film, and the polyolefin is A. After contacting cis or trans cyclooctene with a Ru II catalyst, B. Removal or extraction of the Ru II catalyst, followed by C. Hydrogenation using hydrazine-type or hydrazide-type reducing agents It is prepared by [method].

[0024] Alternatively, the polyolefin of the first embodiment can be prepared by reducing commercially available polybutadiene (CAS number 9003-17-2). Such reduction (i.e., hydrogenation) can be achieved by using a hydrazine-type or hydrazide-type reducing agent such as p-toluenesulfonyl hydrazide (available from Sigma-Aldrich, CAS number 576-35-8) in the presence of an amine such as tributylamine. Other suitable reducing agents include benzenesulfonyl hydrazide; 2,4,6-triisopropylbenzenesulfonyl hydrazide; 2,4,6-trimethylbenzenesulfonohydrazide; and N,N'-bis(p-toluenesulfonyl)hydrazine. Thus, the compound of formula (C) can be prepared according to the following scheme. The compound of formula (C) is called polyethylene-co-polybutylene. TIFF0007926987000003.tif27170

[0025] Therefore, in another embodiment, the present disclosure provides the above-mentioned film, the polyolefin being prepared by contacting polybutadiene with hydrogen in the presence of a hydrazide-type or hydrazine-type reducing agent.

[0026] The polyolefins of formulas (B) and (C) have, in one embodiment, a number molecular weight (M) of about 330 K daltons to about 2.2 M daltons, or about 700 K daltons to about 1.5 M daltons, or about 1.1 M daltons. n ) has.

[0027] Subsequently, the polyolefins of formulas (B) and (C) can be used to manufacture filter membranes for use in various filter structures. A suitable process for preparing porous filter membranes as described may be an extrusion melt-cast process or a method sometimes called “thermal-induced liquid-liquid phase separation”. In this type of process, the polymer is dissolved at a high temperature (“extrusion temperature”) in a combination of two or more solvents to form a heated polymer solution that can be processed and molded, for example, by an extruder. The heated polymer solution can be molded into the form of a sheet membrane or the like by passing through an extruder and an extrusion die. The heated polymer solution passes through the die and is distributed onto a molding surface at a temperature much lower than the extrusion temperature, i.e., the “cooling temperature”. When the extruded heated polymer solution comes into contact with the cold molding surface, the polymer and solvent in the heated polymer solution undergo one or more phase separations to form the polymer in the porous filter membrane described herein. An example of an equivalent process for producing porous polymer molding material is described, for example, in U.S. Patent No. 6,497,752, which is incorporated herein by reference in whole.

[0028] The filter membranes described may be housed within larger filter structures, such as filter cartridges used in multilayer filter assemblies or filtration systems. The filtration system may position the filter membrane within a filtration housing, for example as part of a multilayer filtration assembly or as part of a filter cartridge, exposing the filter membrane to the flow path of the chemical solution, allowing at least a portion of the chemical solution flow to pass through the filter membrane, so that the filter membrane removes a certain amount of impurities or contaminants from the chemical solution. The structure of the multilayer filter assembly or filter cartridge may include one or more additional materials and structures that support a composite filter membrane within the filter assembly or filter cartridge, allowing fluid to flow from the filter inlet through the composite membrane (including the filter layer) and through the filter outlet, thereby passing through the composite filter membrane as it passes through the filter. The filter membrane supported by the filter assembly or filter cartridge may, among other things, be any useful shape, such as a pleated cylinder, a cylindrical pad, one or more non-pleated (flat) cylindrical sheets, or a pleated sheet.

[0029] An example of a filter structure including a filter membrane in the form of a pleated cylinder may be prepared to include the following component parts: a rigid or semi-rigid core supporting the pleated cylindrical coated filter membrane at the internal opening of the pleated cylindrical coated filter membrane; a rigid or semi-rigid cage supporting or surrounding the outside of the pleated cylindrical coated filter membrane on the outside of the filter membrane; optional end pieces or "packs" located at each of the two opposing ends of the pleated cylindrical coated filter membrane; and a filter housing including an inlet and an outlet, any of which may be included in the filter structure but may not be essential. The filter housing may have any useful and desired size, shape, and material, and may preferably be made from a suitable polymer material.

[0030] The following detailed description should be read with reference to the drawings, which number similar elements in different drawings. The detailed description and drawings are not necessarily to scale and illustrate exemplary embodiments, and are not intended to limit the scope of the invention. The illustrated exemplary embodiments are intended for illustrative purposes only. Unless otherwise explicitly stated, selected features of any exemplary embodiment may be incorporated into additional embodiments.

[0031] As an example, Figure 1 shows a filter component 30 which is a product of a pleated cylindrical forming element 10 and an end piece 22 and other optional components. The cylindrical forming element 10 is pleated and includes a filter membrane 12, as described herein. The end piece 22 is attached to one end of the cylindrical filter component 10 (e.g., “potted”). The end piece 22 may be made of a melt-workable polymer material, preferably. A core (not shown) may be placed in the internal opening 24 of the pleated cylindrical forming element 10, and a cage (not shown) may be placed around the outside of the pleated cylindrical forming element 10. A second end piece (not shown) may be attached to the second end of the pleated cylindrical forming element 30 (“potted”). The resulting pleated cylindrical forming element 30 having two opposing potted ends and an optional core and cage may then be placed in a filter housing which includes an inlet and an outlet and is configured such that the entire amount of fluid entering the inlet must pass through the filter membrane 12 before exiting the filter at the outlet. [Examples]

[0032] material: All materials were used as received. Alfa Aesar dichloromethane 99.6%, cis-cyclooctene 95%. Merck KgaA chloroform 99.8%. Sigma Aldrich (4-((4-ethyl-4-methylpiperazine-1-ium-1-yl)methyl)-1,3-dimethylimidazolidine-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II) chloride (AquaMet) >99%, ((1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(o-isopropoxyphenylmethylene)ruthenium, Hoveyda-Grubbs Catalyst® M72 > 97%, cis and trans decahydronaphthalene mixture, anhydrous > 99%, 1,4-bis(3-isocyanopropyl)piperazine (SnatchCat) > 95%, 2,6-di-tert-butyl-4-methylphenol > 99.0%, ethyl vinyl ether, 99%, ethylene glycol vinyl ether, 97%, hydrochloric acid (HCl) 37%, p-toluenesulfonyl hydrazide > 97%, tripropylamine > 98%, xylene > 98.5%. Isopropyl alcohol (IPA) gigabit grade KMG from VWR, hexane 98.5%. ([1,3-bis(2,4,6-trimethylphenyl)-4-[(trimethylammonio)methyl]imidazolidin-2-ylidene]-(2-i-propoxybenzylidene)dichlororuthenium(II) chloride from Strem Chemicals) (StickyCat) Cl)>99%. Polybutadiene (P10053-Bd, M) from Polysource. n(=1200k Dalton, D=1.18). Tetramethylammonium hydroxide (25% in H2O) manufactured by JTBaker. Silica gel for column chromatography, 40um-60um, average pore size 60Å manufactured by Acros Organics. SiliaMetS thiol (SH) Metal Scavenger (R51030B) manufactured by Silicycle (pore size 60Å). Puromet MTS9100 (amido oxime) manufactured by Purolite and NRW160 resin manufactured by Purolite. Cellulose filter paper No. 42 ashless circle 90mm manufactured by Whatman. (Trademark) PTFE-based beakers, separatory funnels and vials.

[0033] Analysis method: The samples were analyzed according to the method described in "MARS 6 Microwave Acid Digestion Method Note Compendium," Microwave Digestion of polyethylene-High density p 511. CEM Corporation. October 1, 2019. Website: https: / / cem.com / media / contenttype / media / literature / MetNote_MARS6_Compendium_2.pdf.

[0034] After microwave digestion, the sample was diluted approximately 50 times with deionized (DI) water, and the metal concentration was tested using inductively coupled plasma mass spectrometry (ICP-MS).

[0035] Polymer molecular weight was determined using gel permeation chromatography (GPC) combined with an Agilent 1260 refractive index detector. Data acquisition and processing were performed using Jordi GPC software. Data was obtained under the following conditions: Solvent: Chloroform. Column: Jordi Resolve DVB MB+ 500Å, 300x7.8mm, calibrated with polystyrene standards 6.57M, 3.152M, 885K, 479.2K, 194.5K, 75.05K, 22.29K, 10.33K, 4.88K, 1.21K, 580 & 162Da. Flow rate: 1.0 mL / min.

[0036] The sample was placed in a Bruker 75MHz 13 Analysis was performed using 14C molten state NMR at 150°C and a MAS frequency of 2.5 kHz. Each experiment lasted 18 hours. The exponential window function of the spectrum was 3 Hz (S / N > 1000).

[0037] Elemental analysis was performed using a Perkin-Elmer 2400 equipped with an oxygen accessory kit.

[0038] The melting temperature was determined using a Perkin Elmer diamond differential scanning calorimeter (DSC).

[0039] Example 1: This example demonstrates the synthesis of polyoctene and the expected M n = 2200k Daltons.

[0040] In a typical experiment, 11.8 mL of cis-cyclooctene solution in 180 mL of chloroform was added dropwise to 3.3 mg of Stickycat Cl solution in 3 mL of chloroform over 60 minutes.

[0041] Next, 100 mL of chloroform was added, and the solution was heated at 40°C for 4 hours. Then, 2.5 mL of ethyl vinyl ether was added all at once, and the mixture was stirred at 40°C for 0.5 hours.

[0042] Subsequently, the organic phase was extracted five times with 50 mL of HCl (10%) acid solution prepared from 68.2 mL of HCl (37%) in 181 mL of DI water. After each extraction, 0.2 mL of ethyl vinyl ether was added to the organic phase, and the solution was stirred for 20 minutes after each extraction.

[0043] After extraction, the solution was poured into 200 mL of isopropyl alcohol. A white polymer precipitated. The mother liquor was decanted, and the polymer was dried in a convection oven at room temperature for 16 hours (9.90 g, 99.0% yield). The metal concentration was determined using microwave digestion and ICP-MS. Al=0.0ppm, Mg=0.0ppm, Ti=0.0ppm, Zn=0.0ppm, Fe=0.0ppm, Ru=5.4ppm. Therefore, the total concentration of titanium, aluminum, iron, zinc, and magnesium is 0.0 ppm.

[0044] In subsequent experiments conducted under the same conditions, the amount of polymer after drying was 5.6 g, with a yield of 56.0%. Metal concentrations were determined using microwave digestion and ICP-MS. Al=0.00 ppm, Mg=0.00 ppm, Ti=0.28 ppm, Zn=0.00 ppm, Fe=0.05 ppm, Ru=10.39 ppm. Therefore, the total concentration of titanium, aluminum, iron, zinc, and magnesium is 0.33 ppm.

[0045] Example 2: This example demonstrates the synthesis of polyoctene by purification using serial precipitation, and predicts the M n = 2200k Daltons.

[0046] In a typical experiment, 11.8 mL of cis-cyclooctene solution in 180 mL of chloroform was added dropwise to 3.3 mg of Stickycat Cl solution in 3 mL of chloroform over 60 minutes.

[0047] Next, 100 mL of chloroform was added, and the solution was heated at 40°C for 4 hours. Then, 2.5 mL of ethyl vinyl ether was added all at once, and the mixture was stirred at 40°C for 0.5 hours.

[0048] The organic solution was poured into 300 mL of IPA, and a white polymer precipitated.

[0049] The liquid was decanted, and the white polymer was dried in a convection oven at room temperature for 10 hours. The polymer was then redissolved in 180 mL of dichloromethane at 30°C and reprecipitation three times using the indicated amount of IPA.

[0050] Next, the polymer was dried in a convection oven at room temperature for 16 hours (9.20 g, 92% yield). The metal concentrations were determined using microwave digestion and ICP-MS. Al=0.0 ppm, Mg=0.0 ppm, Ti=0.4 ppm, Zn=0.1 ppm, Fe=0.1 ppm, Ru=0.6 ppm. Therefore, the total concentration of titanium, aluminum, iron, zinc, and magnesium is 0.6 ppm.

[0051] In subsequent experiments conducted under the same conditions, the amount of polymer after drying was 4.2 g, with a yield of 42%. Metal concentrations were determined using microwave digestion and ICP-MS. After the first precipitation, the metal concentrations were Al=0.00 ppm, Mg=0.00 ppm, Ti=0.00 ppm, Zn=0.00 ppm, Fe=11.46 ppm, and Ru=3.88 ppm. After the second precipitation, the metal concentrations were Al=0.00 ppm, Mg=0.00 ppm, Ti=0.00 ppm, Zn=0.00 ppm, Fe=0.00 ppm, and Ru=2.98 ppm. Therefore, the total concentration of titanium, aluminum, iron, zinc, and magnesium is 0.00 ppm.

[0052] Example 3: This example demonstrates the synthesis of polyoctene and the expected M n = 330k Daltons.

[0053] In a typical experiment, 177 mL of cis-cyclooctene solution in 2950 mL of chloroform was added dropwise to 333 mg of Stickycat Cl solution in 43 mL of chloroform over 35 minutes.

[0054] The solution was heated to 40°C for 6 hours. Then, 8 mL of ethylene glycol vinyl ether was added all at once, and the mixture was stirred at room temperature for 4 hours.

[0055] The viscous solution was extracted five times with 3 L of DI water. 8 mL of ethylene glycol vinyl ether was added to the organic phase, and the solution was stirred for 20 minutes after each extraction.

[0056] After extraction, the solution was poured into 6 L of IPA. A white polymer precipitated. The mother liquor was decanted, and the polymer was dried in a convection oven at room temperature for 16 hours (146 g, 97% yield). Metal concentrations were determined using microwave digestion and ICP-MS. Al = 2.7 ppm, Mg = 0.3 ppm, Ti = 0.0 ppm, Zn = 0.3 ppm, Fe = 0.0 ppm, Ru = 42.1 ppm. Therefore, the total concentration of titanium, aluminum, iron, zinc, and magnesium is 3.3 ppm.

[0057] In subsequent experiments conducted under the same conditions, the amount of polymer after drying was 129 g, with a yield of 86%. GPC (Mn=132.2kDaltons, Mw=202.8kDaltons, D=1.5).

[0058] Example 4: This example demonstrates the synthesis of polyoctene and the expected M n = 1100k Daltons.

[0059] In a typical experiment, a solution of 5.9 mL of cis-cyclooctene in 50 mL of dichloromethane was added dropwise to a solution of 3.5 mg of Aquamet in 2 mL of dichloromethane over a period of 4 minutes.

[0060] The solution was heated to 36°C for 30 minutes to obtain a viscous solution. Next, 200 mL of hexane was added and the mixture was heated to 50°C for 3 hours. Then, 2 mL of ethylene glycol vinyl ether was added all at once and the mixture was stirred at room temperature for 4 hours.

[0061] The organic solution was poured into 200 mL of IPA, and a white polymer precipitated.

[0062] The liquid was decanted, and the white polymer was dried in a convection oven at room temperature for 10 hours. The polymer was then redissolved in 300 mL of dichloromethane at 30°C.

[0063] The viscous solution was extracted five times with 20 mL of DI water. After extraction, the solution was poured into 200 mL of IPA. A white to light brown polymer precipitated. The mother liquor was decanted, and the polymer was dried in a convection oven at room temperature for 16 hours (4.5 g, 90% yield). Metal concentrations were determined using microwave digestion and ICP-MS. Al=0.9 ppm, Mg=0.7 ppm, Ti=0.0 ppm, Zn=0.0 ppm, Fe=0.0 ppm, Ru=2.4 ppm. Therefore, the total concentration of titanium, aluminum, iron, zinc, and magnesium is 1.6 ppm.

[0064] In subsequent experiments conducted under the same conditions, the amount of polymer after drying was 3.5 g, with a yield of 70%. The metal concentrations were determined using microwave digestion and ICP-MS, and were Al=0.00 ppm, Mg=0.00 ppm, Ti=0.00 ppm, Zn=0.00 ppm, Fe=0.00 ppm, and Ru=11.62 ppm. Therefore, the total concentration of titanium, aluminum, iron, zinc, and magnesium is 0.00 ppm.

[0065] Example 5: (Prediction) This example demonstrates the synthesis of polyoctene by purification using silica gel adsorption, and predicts the M n = 5500k Daltons.

[0066] In a typical experiment, 11.8 mL of cis-cyclooctene solution in 170 mL of chloroform is added dropwise to 1.3 mg of Stickycat Cl solution in 3 mL of chloroform over 60 minutes.

[0067] Next, add 100 mL of chloroform and heat the solution at 40°C for 4 hours. Then, add 2.5 mL of ethyl vinyl ether all at once and stir at 40°C for 0.5 hours.

[0068] Next, add 2 g of silica gel and stir the solution for 30 minutes. Then, filter the silica using filter paper under reduced pressure (approximately 150 mbar). Wash the silica with 150 mL of dichloromethane at 36°C. Repeat the addition of silica gel and filtration.

[0069] Next, the viscous solution is extracted three times with 100 mL of HCl (10%) acid solution prepared from 81 mL of HCl (37%) in 219 mL of DI water.

[0070] After extraction, the solution is poured into 300 mL of isopropyl alcohol to precipitate the white polymer. Then, the mother liquor is decanted, and the precipitate is dried in a convection oven at room temperature for 16 hours.

[0071] Example 5A This example demonstrates the synthesis of polyoctene and its purification using silica gel adsorption.

[0072] In a typical experiment, 11.8 mL of cis-cyclooctene solution was added dropwise over 30 minutes to 3 mL of chloroform solution containing 1.3 mg of Stickycat Cl.

[0073] Next, 280 mL of chloroform was added, and the solution was heated at 60°C for 12 hours. Then, 2.5 mL of ethyl vinyl ether and 10 mg of Snatchcat were added all at once. The solution was then stirred at 40°C for 0.5 hours.

[0074] Subsequently, 2.0 g of silica gel was added to the solution and stirred at 40°C for 2 hours. The silica was filtered under reduced pressure (approximately 150 mbar) using filter paper. The silica was washed with chloroform at room temperature. The addition of 2.0 g of silica and filtration were repeated using the filtrate.

[0075] Next, the organic phase was extracted three times with 100 mL of HCl (10%) acid solution prepared from 81 mL of HCl (37%) in 219 mL of DI water.

[0076] After extraction, the organic solution is poured into 300 mL of isopropyl alcohol to precipitate a polymer. The liquid is then decanted. The solid is collected and dried in a convection oven at room temperature for 16 hours. (3.5 g, 35.0% yield). GPC (Mn=486.1 kDa, Mw=1311.2 kDa, Đ=2.7). Metal concentration was determined using microwave digestion and ICP-MS. Al=0.83 ppm, Ti=0.32 ppm, Zn=0.37 ppm, Fe=2.42 ppm, Ru=2.40 ppm. Therefore, the total amount of titanium, aluminum, iron, zinc, magnesium and other metals is 3.94 ppm.

[0077] Example 6: (Predicted) This example demonstrates the synthesis of polyoctene via purification using basic extraction with tetramethylammonium hydroxide, and the expected M n n is 1100 kDa.

[0078] In a representative experiment, a solution of 11.8 mL of cis-cyclooctene in 180 mL of chloroform is added dropwise over 60 minutes to a solution of 6.7 mg of Stickycat Cl in 3 mL of chloroform.

[0079] 100 mL of chloroform is then added, and the solution is heated to 40°C for 4 hours. 2.5 mL of ethyl vinyl ether is then added in one portion, and the mixture is stirred at 40°C for 0.5 hours.

[0080] A solution of 5% NCH4OH is prepared with 30 mL of NCH4OH (25% in water) in 120 mL of DI water. The organic phase is then extracted three times with 50 mL of the 5% NCH4OH solution alternating with 50 mL of DI water.

[0081] After extraction, the solution is poured into 200 mL of IPA to precipitate a white polymer. The liquid is then decanted, and the polymer is dried in a convection oven at room temperature for 16 hours.

[0082] Example 6A This example demonstrates the synthesis of polyoctene by purification using basic extraction with tetramethylammonium hydroxide, and predicts the M n = 1100k Daltons.

[0083] In a typical experiment, 11.8 mL of cis-cyclooctene solution in 180 mL of chloroform was added dropwise to 6.7 g of Stickycat Cl solution in 3 mL of chloroform over 60 minutes.

[0084] Next, 100 mL of chloroform was added, and the solution was heated at 60°C for 4 hours. Then, 2.5 mL of ethyl vinyl ether and 10 mg of Snatchcat were added all at once, and the solution was stirred at 40°C for 0.5 hours.

[0085] Subsequently, a 5% NCH4OH solution was prepared by adding 30 mL of NCH4OH (25% in H2O) to 120 mL of DI water. Then, the organic phase was extracted three times alternately with 50 mL of DI water and 50 mL of the 5% NCH4OH solution.

[0086] After extraction, the organic solution was poured into 200 mL of IPA, and a white polymer precipitated. The liquid was then decanted. The solid was collected and dried in a convection oven at room temperature for 16 hours (4.13 g, yield 41.3%).

[0087] Metal concentrations were determined using microwave digestion and ICP-MS. Al = 2.96 ppm, Mg = 0.00 ppm, Ti = 0.00 ppm, Zn = 0.00 ppm, Fe = 0.78 ppm, Ru = 4.03 ppm. Therefore, the total concentration of titanium, aluminum, iron, zinc, and magnesium was 3.74 ppm.

[0088] Example 7: (Prediction) This example demonstrates the synthesis of polyoctene by purification using Soxhlet extraction in IPA, and predicts the M n = 2200k Daltons.

[0089] In a typical experiment, 11.8 mL of cis-cyclooctene solution in 180 mL of chloroform is added dropwise to 3.3 mg of Stickycat Cl solution in 3 mL of chloroform over 60 minutes.

[0090] Next, add 100 mL of chloroform and heat the solution at 40°C for 4 hours. Then, add 2.5 mL of ethyl vinyl ether all at once and stir at 40°C for 0.5 hours.

[0091] Pour the organic solution into 300 mL of IPA and allow the white polymer to precipitate.

[0092] The liquid is decanted, and the white polymer is dried in a convection oven at room temperature for 10 hours. The polymer is then placed in a Soxhlet apparatus covered with a nonwoven film and extracted continuously with IPA for 72 hours.

[0093] Next, the polymer is dried in a convection oven at room temperature for 16 hours.

[0094] Example 7A This example demonstrates the synthesis of polyoctene by purification using Soxhlet extraction in IPA, and predicts the M n = 2200k Daltons.

[0095] In a typical experiment, 11.8 mL of cis-cyclooctene solution in 180 mL of chloroform was added dropwise to 3.2 g of Stickycat Cl solution in 3 mL of chloroform over 60 minutes.

[0096] Next, 100 mL of chloroform was added, and the solution was heated at 60°C for 4 hours. Then, 2.5 mL of ethyl vinyl ether was added all at once, and the solution was stirred at 40°C for 0.5 hours.

[0097] Subsequently, the organic solution was poured into 200 mL of IPA, and a white polymer precipitated. The liquid was then decanted. The solid was collected, covered with a nonwoven film, and introduced into a Soxhlet apparatus. The polymer was then extracted using the Soxhlet apparatus with continuous use of IPA for 72 hours.

[0098] Next, the polymer was dried in a convection oven at room temperature for 16 hours (3.6 g, 36% yield). The metal concentrations were determined using microwave digestion and ICP-MS. Al = 0.00 ppm, Mg = 0.00 ppm, Ti = 0.26 ppm, Zn = 0.00 ppm, Fe = 0.00 ppm, Ru = 24.24 ppm. Therefore, the total concentration of titanium, aluminum, iron, zinc, and magnesium was 0.26 ppm.

[0099] Example 8: This example demonstrates the synthesis of polyethylene by reduction of polyoctene in Example 4.

[0100] In a typical experiment, 1.00 g of polyoctene (M n (1100k Dalton) was dissolved in 110 mL of xylene. The mixture was then heated to 110°C.

[0101] 6.78 g of p-toluenesulfonyl hydrazide was added to the reaction mixture all at once. Then, 4.7 mL of tripropylamine was added all at once. The reaction mixture was heated to 150°C and stirred under reflux for 7 hours.

[0102] Next, it was cooled to 135°C and poured all at once into 300 mL of IPA. A white precipitate formed. The polymer was filtered through filter paper and washed with 40 mL of acetone.

[0103] The polymer was dried in a convection oven for 24 hours (0.93 g, 89% yield). Melting point: 130.2°C to 134.5°C.

[0104] At 150℃ 13¹¹C molten state NMR determined the double bond concentration of 2.72% in the sample. Elemental analysis determined the composition to be C=83.68% and H=14.79% (molar ratio of H to C=2.11).

[0105] Example 9: This example demonstrates the purification of polybutadiene by acid extraction.

[0106] In a typical experiment, 1.00 g of polybutadiene (M n (=1200k Dalton, D=1.18) was dissolved in 100 mL of hexane. The organic solution was extracted five times with 100 mL of HCl (10%) acid solution prepared with 137 mL of HCl (37%) in 363 mL of DI water.

[0107] The solution was precipitated in 100 mL of IPA. The polymer was precipitated from the solution and filtered through filter paper. The polymer was dried in a convection oven at room temperature for 24 hours.

[0108] Polybutadiene contained a total metal concentration of <100 ppb, including titanium, aluminum, iron, zinc, and magnesium.

[0109] Example 10: This example demonstrates the synthesis of polyethylene copolymers such as polyethylene-co-polybutylene resin by reduction of the double bond of polybutadiene.

[0110] In a typical experiment, after the purification described in Example 9, 1.00 g of polybutadiene (M) was added. n (1200k Dalton, D=1.18) was dissolved in 50 mL of xylene, and then 10 mg of 2,6-di-tert-butyl-4-methylphenol was added. The mixture was then heated to 110°C.

[0111] 12.03 g of p-toluenesulfonyl hydrazide was added to the reaction mixture all at once. Then, 8.5 mL of tripropylamine was added all at once. The reaction mixture was heated to 150°C and stirred under reflux for 6 hours.

[0112] The reaction mixture was cooled to 135°C and poured all at once into 50 mL of IPA. A white precipitate formed. The polymer was filtered using filter paper. The solid was dried in a convection oven for 24 hours (0.83 g, 83% yield).

[0113] The polymer was redissolved in 50 mL of decahydronaphthalene at 150°C and poured into 200 mL of IPA at room temperature. Precipitation was repeated twice. The polymer was filtered using filter paper and dried in a convection oven for 24 hours.

[0114] At 150℃ 13 3.48% double bond concentration in the sample was determined by 3.48% ¹¹C molten state NMR. Elemental analysis determined C = 81.71% and H = 13.65% (molar ratio of H to C = 1.99). Melting point = 109.0°C.

[0115] Example 11: (Prediction) This example demonstrates the synthesis of polyethylene by reduction of polyoctene and the expected M n = 5600k Daltons.

[0116] In a typical experiment, 10 mg of 2,6-di-tert-butyl-4-methylphenol was mixed with 1.00 g of polyoctene (M) in 100 mL of xylene. n It is added to a solution of 5500k Daltons. Then the mixture is heated to 110°C.

[0117] Add 6.8 g of p-toluenesulfonyl hydrazide to the reaction mixture all at once. Then add 4.8 mL of tripropylamine all at once. Heat the reaction mixture to 150°C and stir under reflux for 6 hours.

[0118] The reaction mixture is then cooled to 135°C and poured into 100 mL of IPA all at once to precipitate the polymer. The polymer is then filtered using filter paper, and the solid is dried in a convection oven for 24 hours.

[0119] Example 12: This example demonstrates the synthesis of polyoctene and its purification using silica gel adsorption.

[0120] In a typical experiment, 11.8 mL of cis-cyclooctene solution in 180 mL of chloroform was added dropwise over 60 minutes to 3 mL of Stickycat Cl solution in 3 mL of chloroform.

[0121] Next, 100 mL of chloroform was added, and the solution was heated at 60°C for 4 hours. Then, 2.5 mL of ethyl vinyl ether and 10 mg of Snatchcat were added all at once, and the solution was stirred at 40°C for 0.5 hours.

[0122] Subsequently, 5.0 g of silica gel was added to the solution and stirred at 40°C for 2 hours. The silica was filtered under reduced pressure (approximately 150 mbar) using filter paper. The silica was washed with chloroform at room temperature.

[0123] Next, the organic phase was extracted three times with 100 mL of HCl (10%) acid solution prepared from 81 mL of HCl (37%) in 219 mL of DI water.

[0124] After extraction, the organic solution was poured into 300 mL of isopropyl alcohol, and a white polymer precipitated. The liquid was then decanted. The solid was collected and dried in a convection oven at room temperature for 16 hours (3.56 g, yield 35.6%). GPC (Mn=212.0 kDaltons, Mw=430.3 kDaltons, D=2.0). Metal concentrations were determined using microwave digestion and ICP-MS. Al=1.01 ppm, Mg=0.00 ppm, Ti=0.22 ppm, Zn=0.36 ppm, Fe=1.54 ppm, Ru=0.19 ppm. Therefore, the total concentration of titanium, aluminum, iron, zinc, and magnesium was 3.13 ppm.

[0125] Example 13: This example demonstrates the synthesis of polyoctene using Stickycat Cl, which is immobilized on silica gel before polymerization.

[0126] In typical experiments, Stickycat Cl was immobilized on silica gel before the reaction. The silica gel was dried in a convection oven at 150°C for 12 hours and then cooled to room temperature in a reduced-pressure chamber before use.

[0127] A solution of 3.2 mg of Stickycat Cl in 2 mL of CHCl3 was added to 0.64 g of dry silica gel. The silica gel was then dried in a rotating evaporator.

[0128] Next, 11.8 mL of cis-cyclooctene solution in 180 mL of chloroform was added dropwise to immobilized Stickycat Cl on silica gel for 60 minutes. The heterogeneous reaction mixture was vigorously stirred.

[0129] Next, 100 mL of chloroform was added, and the solution was heated at 60°C for 4 hours. Then, 2.5 mL of ethyl vinyl ether and 10 mg of Snatchcat were added all at once, and the suspension was stirred at 40°C for 0.5 hours. Next, the silica gel was filtered under reduced pressure (approximately 150 mbar) using filter paper. The silica gel was washed with chloroform at room temperature.

[0130] Next, the organic phase was extracted three times with 100 mL of HCl (10%) acid solution prepared from 81 mL of HCl (37%) in 219 mL of DI water.

[0131] After extraction, the organic solution was poured into 300 mL of isopropyl alcohol, and a white polymer precipitated. The liquid was then decanted. The solid was collected and dried in a convection oven at room temperature for 16 hours (2.10 g, yield 21.0%). GPC (Mn=591.2kDaltons, Mw=1703.9kDaltons, D=2.9).

[0132] Example 14: (Prediction) This example demonstrates the synthesis of polyoctene using Stickycat Cl immobilized on silica gel (SiliaMetS Thiol(SH)Metal Scavenger(R51030B)) before polymerization, and predicts the M n= 2300k Daltons.

[0133] In typical experiments, Stickycat Cl is immobilized on silica gel (SiliaMetS Thiol (R51030B)) before the reaction.

[0134] Next, 3.2 mg of StickyCat Cl solution in 2 mL of CHCl3 is added to 0.64 g of silica gel (SiliaMetS Thiol (R51030B)). Then, the silica gel is dried in a rotating evaporator.

[0135] Next, 11.8 mL of cis-cyclooctene solution in 180 mL of chloroform is added dropwise to Stickycat Cl immobilized on silica gel (SiliaMetS Thiol (R51030B)) for 60 minutes, and the mixture is vigorously stirred.

[0136] Next, add 280 mL of chloroform and heat the solution at 40°C for 4 hours. Then, add 2.5 mL of ethyl vinyl ether all at once and stir at 40°C for 0.5 hours.

[0137] Next, the silica is filtered under reduced pressure (approximately 150 mbar) using filter paper. The silica is then washed with 150 mL of dichloromethane at room temperature.

[0138] Next, the viscous solution is extracted three times with 100 mL of HCl (10%) acid solution prepared from 81 mL of HCl (37%) in 219 mL of DI water.

[0139] After extraction, the solution is poured into 300 mL of isopropyl alcohol to precipitate the white polymer. Then, the mother liquor is decanted, and the precipitate is dried in a convection oven at room temperature for 16 hours.

[0140] Example 15: (Prediction) This example demonstrates the synthesis of polyoctene and its purification using a chelate resin (Puromet MTS9100), and predicts the M n = 5500k Daltons.

[0141] In a typical experiment, 11.8 mL of cis-cyclooctene solution is added dropwise to 3 mL of chloroform solution containing 1.3 mg of Stickycat Cl over 60 minutes.

[0142] Next, add 100 mL of chloroform and heat the solution at 60°C for 12 hours. Then, add 2.5 mL of ethyl vinyl ether all at once and stir at 40°C for 0.5 hours.

[0143] Then, take 6 mL, aliquot it, add it to 0.2 g of resin (Puromet MTS9100), and stir for 24 hours.

[0144] Next, the liquid is decanted into another vial with 20 mL of isopropyl alcohol. The vial is stirred to precipitate the polymer. Then, the liquid is decanted and the solid is dried in a convection oven at room temperature.

[0145] Example 16: (Prediction) This example demonstrates the synthesis of polyoctene and its purification using an ion exchange resin (NRW160), and predicts the M n = 5500k Daltons.

[0146] In a typical experiment, 11.8 mL of cis-cyclooctene solution is added dropwise to 3 mL of chloroform solution containing 1.3 mg of Stickycat Cl over 60 minutes.

[0147] Next, add 100 mL of chloroform and heat the solution at 60°C for 12 hours. Then, add 2.5 mL of ethyl vinyl ether all at once. Next, stir the solution at 40°C for 0.5 hours.

[0148] Then, take 6 mL, aliquot it, add it to 0.2 g of resin (NRW160), and stir for 24 hours.

[0149] Next, the liquid is decanted into another vial with 20 mL of isopropyl alcohol. The vial is stirred to precipitate the polymer. Then, the liquid is decanted and the solid is dried in a convection oven at room temperature.

[0150] Example 17: This example demonstrates the synthesis of polyoctene using the Hoveyda-Grubbs M720 initiator.

[0151] In a typical experiment, 11.8 mL of cis-cyclooctene solution in 180 mL of chloroform was added dropwise over 60 minutes to 2.8 mg of Hoveyda-Grubbs M720 initiator solution in 3 mL of chloroform.

[0152] Next, 100 mL of chloroform was added, and the solution was heated at 60°C for 4 hours. Then, 2.5 mL of ethyl vinyl ether was added all at once, and the solution was stirred at 40°C for 0.5 hours.

[0153] Next, the organic phase was extracted three times with 100 mL of HCl (10%) acid solution prepared from 81 mL of HCl (37%) in 219 mL of DI water.

[0154] After extraction, the organic solution was poured into 300 mL of isopropyl alcohol, and a white polymer precipitated. The liquid was then decanted. The solid was collected and dried in a convection oven at room temperature for 16 hours (0.75 g, yield 7.5%). GPC (Mn=31.2kDaltons, Mw=76.4kDaltons, D=2.5).

[0155] manner In a first aspect, the disclosure provides a filter film comprising a polyolefin, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than approximately 4 ppm, as determined by the MARS6 Microwave Acid Digestion Method Note Compendium.

[0156] In a second aspect, the disclosure provides a film of the first aspect, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 3.5 ppm.

[0157] In a third aspect, the disclosure provides a film of the first aspect, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 3 ppm.

[0158] In a fourth aspect, the disclosure provides a film of the first aspect, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 2 ppm.

[0159] In a fifth aspect, the disclosure provides a film of the first aspect, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 1 ppm.

[0160] In a sixth aspect, the disclosure provides a film of the first aspect, wherein the polyolefin has less than 1 ppm of ruthenium, as determined by the MARS6 Microwave Acid Digestion Method Note Compendium.

[0161] In a seventh aspect, the disclosure provides a film of any one of the first to sixth aspects, wherein the polyolefin is selected from polyethylene and polyethylene-co-polybutylene.

[0162] In the eighth aspect, the disclosure provides a film according to any one of the first to sixth aspects, wherein the polyolefin is ultra-high molecular weight polyethylene.

[0163] In the ninth embodiment, the disclosure provides a film of any one of the first to eighth embodiments, wherein the polyolefin has a number-average molecular weight of about 330,000 to 2,200,000 daltons.

[0164] In a tenth embodiment, the disclosure provides a film of any one of the first to eighth embodiments, wherein the polyolefin has a number-average molecular weight of about 700,000 daltons to about 1,500,000 daltons.

[0165] In the eleventh embodiment, the present disclosure relates to polyolefins, A. After contacting cis or trans cyclooctene with a Ru II catalyst, B. Removal or extraction of the Ru II catalyst, followed by C. Hydrogenation using hydrazine-type or hydrazide-type reducing agents A film of the first embodiment, prepared by [method], is provided.

[0166] In a twelfth aspect, the present disclosure describes a Ru II catalyst, i. (1,3-bis(2,6-diisopropylphenyl)-4-((4-ethyl-4-methylpiperazine-1-ium-1-yl)methyl)imidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(II) chloride dihydrate; ii. (1,3-Dimethyl-4-((trimethylammonio)methyl)imidazolidin-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II) chloride; iii. (4-((4-ethyl-4-methylpiperazine-1-ium-1-yl)methyl)-1,3-dimethylimidazolidined-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II) chloride; iv. (1,3-Dimethyl-4-((trimethylammonio)methyl)imidazolidine-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II) hexafluorophosphate; and v.(1,3-Dimethyl-4-((trimethylammonio)methyl)imidazolidine-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II)tetrafluoroborate The present invention provides a film of an eleventh embodiment, selected from the following.

[0167] In a thirteenth aspect, the disclosure provides a film of the first aspect, wherein the polyolefin is polyethylene-co-polybutylene prepared by contacting polybutadiene with hydrogen in the presence of a hydrazide-type or hydrazine-type reducing agent.

[0168] In a fourteenth aspect, the disclosure provides a filter comprising a filter membrane containing a polyolefin, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 4 ppm, as determined by the MARS6 Microwave Acid Digestion Method Note Compendium.

[0169] In a 15th aspect, the disclosure provides a filter of a 14th aspect, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 3.5 ppm.

[0170] In a sixteenth aspect, the disclosure provides a filter of a fourteenth aspect, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 3 ppm.

[0171] In a 17th aspect, the disclosure provides a filter of a 14th aspect, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 2 ppm.

[0172] In the eighteenth aspect, the disclosure provides a filter of the fourteenth aspect, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 1 ppm.

[0173] In a 19th aspect, the disclosure provides a filter of a 14th aspect, wherein the polyolefin has less than 1 ppm of ruthenium, as determined by the MARS6 Microwave Acid Digestion Method Note Compendium.

[0174] In a 20th aspect, the disclosure provides a filter according to any one of the 14th to 18th aspects, wherein the polyolefin is selected from polyethylene and polyethylene-co-polybutylene.

[0175] In a 21st aspect, the disclosure provides a filter according to any one of the 14th to 18th aspects, wherein the polyolefin is ultra-high molecular weight polyethylene.

[0176] In a 22nd aspect, the disclosure provides a filter according to any one of the 14th to 18th aspects, wherein the polyolefin has a number-average molecular weight of about 330,000 to 2,200,000 daltons.

[0177] In a 23rd aspect, the disclosure provides a filter according to any one of the 14th to 18th aspects, wherein the polyolefin has a number-average molecular weight of about 700,000 daltons to about 1,500,000 daltons.

[0178] In a 24th aspect, the Disclosure provides a method for removing impurities from a liquid, the method comprising contacting the liquid with a filter according to any one of the 14th to 23rd aspects.

[0179] Having described several exemplary embodiments of this disclosure, those skilled in the art will readily understand that further embodiments can be created and used within the scope of the appended claims. Many of the advantages of this disclosure, which are covered herein, are described above. However, it will be understood that this disclosure is in many respects only illustrative. The scope of this disclosure is, naturally, defined in the language in which the appended claims are expressed.

Claims

1. A filter membrane for purifying and / or filtering a liquid, comprising a polyolefin, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 4 ppm.

2. The filter film according to claim 1, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 3.5 ppm.

3. The filter film according to claim 1, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 3 ppm.

4. The filter film according to claim 1, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 2 ppm.

5. The filter film according to claim 1, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 1 ppm.

6. The filter film according to claim 1, wherein the polyolefin has less than 1 ppm of ruthenium.

7. The filter membrane according to any one of claims 1 to 6, wherein the polyolefin is selected from polyethylene and polyethylene-copolybutylene.

8. The filter film according to any one of claims 1 to 6, wherein the polyolefin is ultra-high molecular weight polyethylene.

9. The filter film according to any one of claims 1 to 8, wherein the polyolefin has a number-average molecular weight of about 330,000 to 2,200,000 daltons.

10. The filter film according to any one of claims 1 to 8, wherein the polyolefin has a number-average molecular weight of about 700,000 daltons to about 1,500,000 daltons.

11. Polyolefins A. After contacting cis or trans-cyclooctene with the Ru II catalyst, B. Removal or extraction of Ru II catalyst, followed by C. Hydrogenation using hydrazine or hydrazide type reducing agents The filter membrane according to claim 1, wherein the polyethylene is prepared by [method].

12. Ru II catalyst, i. (1,3-bis(2,6-diisopropylphenyl)-4-((4-ethyl-4-methylpiperazine-1-ium-1-yl)methyl)imidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(II) chloride dihydrate; ii. (1,3-Dimethyl-4-((trimethylammonio)methyl)imidazolidine-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II) chloride; iii. (4-((4-ethyl-4-methylpiperazine-1-ium-1-yl)methyl)-1,3-dimethylimidazolidine-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II) chloride iv. (1,3-Dimethyl-4-((trimethylammonio)methyl)imidazolidine-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II) hexafluorophosphate; and v. (1,3-Dimethyl-4-((trimethylammonio)methyl)imidazolidine-2-ylidene)dichloro(2-isopropoxybenzylidene)ruthenium(II)tetrafluoroborate A filter film according to claim 11, selected from the above.

13. The filter membrane according to claim 1, wherein the polyolefin is polyethylene-copolybutylene obtained by contacting polybutadiene with hydrogen in the presence of a hydrazide-type or hydrazine-type reducing agent.

14. A filter comprising a filter membrane for purifying and / or filtering a liquid, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 4 ppm.

15. The filter according to claim 14, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 3.5 ppm.

16. The filter according to claim 14, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 3 ppm.

17. The filter according to claim 14, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 2 ppm.

18. The filter according to claim 14, wherein the total amount of titanium, aluminum, iron, zinc, and magnesium in the polyolefin is less than about 1 ppm.

19. The filter according to claim 14, wherein the polyolefin has less than about 1 ppm of ruthenium.

20. The filter according to any one of claims 14 to 18, wherein the polyolefin is selected from polyethylene and polyethylene-copolybutylene.

21. The filter according to any one of claims 14 to 18, wherein the polyolefin is ultra-high molecular weight polyethylene.

22. The filter according to any one of claims 14 to 18, wherein the polyolefin has a number-average molecular weight of about 330,000 to 2,200,000 daltons.

23. The filter according to any one of claims 14 to 18, wherein the polyolefin has a number-average molecular weight of about 700,000 daltons to about 1,500,000 daltons.

24. A method for removing impurities from a liquid, comprising contacting the liquid with a filter according to any one of claims 14 to 23.

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