Use of biomass for the production of polyoxymethylene copolymers

Abstract

This disclosure provides a method for producing polyoxymethylene polymers or paraformaldehyde in an environmentally friendly and sustainable manner. [Solution] Polyoxymethylene polymers or paraformaldehyde can be manufactured to achieve carbon neutrality or carbon negativity. In one embodiment, the polyoxymethylene polymer or paraformaldehyde is formed from biogas or recycled gas. The biogas and recycled gas are used to produce the components required for polymer formation.

Description

[Technical Field]

[0001]

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 065,767, filed on 14 August 2020, which is incorporated herein by reference.

[0002] Polyacetal polymers, commonly known as polyoxymethylene polymers, are established as particularly useful engineering materials for a variety of applications. For example, due to their excellent mechanical properties, fatigue resistance, abrasion resistance, chemical resistance, and moldability, polyoxymethylene polymers are widely used in the composition of polymer articles, such as those used in the automotive, electrical, home appliance, and medical industries.

[0002]

[0003] Polyoxymethylene polymers can be compounded with various additives that alter and / or improve a range of properties. For example, polyoxymethylene polymers can be combined with tribological modifiers in applications where a low-friction surface is desired. In other embodiments, reinforcing fillers and reinforcing fibers can be incorporated into the polymer to enhance strength and toughness properties. In yet another embodiment, impact modifiers can be added to the polymer to improve impact resistance.

[0003]

[0004] Polyoxymethylene polymers are typically manufactured from formaldehyde monomers derived from fossil fuels. The production of polyoxymethylene polymers can even result in carbon emissions. However, in recent years, many companies, large and small, have pledged to achieve carbon neutrality within a certain timeframe. For example, Microsoft has pledged to achieve carbon negativity by 2030, while Amazon has pledged to achieve carbon neutrality by 2040. Unilever, which manufactures tens of thousands of consumer goods, has also pledged to achieve carbon neutrality by 2039.

[0004]

[0005] To achieve carbon neutrality, companies must remove the same amount of carbon dioxide they emit into the atmosphere, thus achieving net-zero carbon emissions. Conversely, carbon-negative companies remove more carbon from the atmosphere than they emit.

[0005]

[0006] As companies worldwide make tremendous efforts to achieve carbon neutrality or carbon negativity, there is a need for more sustainable methods and processes for producing polymers. From this perspective, there is a need for processes and methods for producing carbon-neutral or carbon-negative polyoxymethylene polymers. [Overview of the project] [Means for solving the problem]

[0006]

[0007] This disclosure relates, as a whole, to the production of polyoxymethylene polymers, particularly polyoxymethylene copolymers, that result in carbon offsetting.

[0008] One aspect of the present disclosure relates to a method for producing a polyoxymethylene polymer. The method comprises the step of forming a cyclic acetal from at least one carbon-negative component. A comonomer is also formed from at least one carbon-negative component. The cyclic acetal and comonomer are then polymerized in the presence of a catalyst to form a polyoxymethylene copolymer. According to the present disclosure, the carbon-negative component may include biogas or recycled gas, which may be collected from industrial processes, for example. Biogas may be a gas such as methane formed from organic waste using anaerobic digestion or gasification technology. Alternatively, the gas may be a recycled gas such as carbon dioxide or carbon monoxide, which is collected from industrial processes without being released into the environment.

[0007]

[0009] In one aspect, the carbon negative component can be used in the production of methanol. Methanol can then be converted into cyclic acetals and / or comonomers. Methanol can be produced from biomass or from the aforementioned carbon negative gases such as biogas or recycled gas.

[0008]

[0010] In one embodiment, the method further includes forming a chain transfer agent from at least one carbon negative component and polymerizing a cyclic acetal, a comonomer, and the chain transfer agent in the presence of a catalyst to form a polyoxymethylene copolymer. The chain transfer agent can include, for example, methylal. Alternatively, the chain transfer agent can be a glycol. On the other hand, the cyclic acetal can be trioxane, and the comonomer can include dioxolane. In one aspect, the polyoxymethylene copolymer contains the comonomer in an amount from about 0.1% to about 5 mol%.

[0009]

[0011] The polyoxymethylene copolymers produced according to the methods of the present disclosure can include a variety of different end groups. For example, in one embodiment, terminal hydroxyl groups can be present in the polymer in an amount from about 5 mmol / kg to about 150 mmol / kg, such as from about 25 mmol / kg to about 150 mmol / kg.

[0010]

[0012] Other end groups that may be present in the polyoxymethylene polymer include alkoxys such as methoxy or ethoxy groups. The polymer may also include formate groups and hemiacetal groups.

[0011]

[0013] In one aspect, more than about 80 wt%, such as more than about 90 wt%, and even, for example, 100 wt% of the carbon contained in the polyoxymethylene copolymer can be derived from one or more carbon negative components.

[0012]

[0014] In another aspect, the present disclosure relates to a method of manufacturing paraformaldehyde. The method includes forming formaldehyde from at least one carbon-negative component. For example, the carbon-negative component can include biogas or recycled gas that can be collected from industrial processes, for example. The biogas or recycled gas can first be converted to methanol. The methanol can then be used in the production of formaldehyde. The formaldehyde is then polymerized in the presence of a catalyst to form paraformaldehyde. Paraformaldehyde has the structure of HO(CH2O) n H, where n is from about 8 to about 100. The purity of the paraformaldehyde depends on the degree of polymerization n and can be between 90 and 99%, and the remainder is bound water or free water. The paraformaldehyde can then be used in the synthesis of phenol, urea, furfural alcohol, resorcinol resin, melamine resin, and formaldehyde resin. These products can be used in industrial coatings, wood products, textile products, casting resins, oil well additives, lubricant additives, adhesive resins, and molding materials for electrical components.

[0013]

[0015] Other features and aspects of the present disclosure are described in detail below.

[0016] The complete and enabling disclosure of the present disclosure is described more specifically in the remainder of the specification, including reference to the accompanying drawings.

Brief Description of the Drawings

[0014] [Figure 1] FIG. shows an embodiment of a coffee maker device including a composition prepared according to the present disclosure. [Figure 2] FIG. shows an embodiment of a component of a coffee maker device including a composition prepared according to the present disclosure. [Figure 3] FIG. shows an embodiment of a medical device including a composition prepared according to the present disclosure. [Figure 4] FIG. shows another embodiment of a medical device including a composition prepared according to the present disclosure. [Figure 5]This figure shows one embodiment of a conveying device comprising a composition prepared in accordance with this disclosure. [Figure 6] This figure shows one embodiment of a cosmetic closure device comprising a composition prepared in accordance with this disclosure. [Modes for carrying out the invention]

[0015]

[0017] It will be understood by those skilled in the art that this disclosure is merely a description of exemplary embodiments and is not intended to limit broader embodiments of this disclosure.

[0018] This disclosure relates, as a whole, to a method for producing polyoxymethylene polymers or paraformaldehyde in a more sustainable manner. According to this disclosure, polyoxymethylene polymers or paraformaldehyde are formed from carbon-negative components. The raw materials used in the production of polyoxymethylene polymers or paraformaldehyde may be biogas and / or recycled gases, rather than fossil-derived gases such as natural gas. Biogas or recycled gases may be used, for example, to produce methanol. Methanol may then be used in the production of formaldehyde. Formaldehyde may then be converted to trioxane or other monomers. Methanol may also be used in the production of comonomers, chain transfer agents, etc. These components may then be polymerized with each other to form polyoxymethylene polymers formed from biogas and / or recycled gases as described above. Alternatively, paraformaldehyde may be formed directly from formaldehyde. Therefore, the resulting polyoxymethylene polymers or paraformaldehyde have a much smaller carbon footprint and can even be manufactured to achieve carbon neutrality or carbon negativity overall. Further reductions in the carbon footprint can be achieved by using renewable energy, or by using renewable energy in combination with other energy sources.

[0016]

[0019] Polyoxymethylene polymers or paraformaldehyde manufactured in accordance with this disclosure can satisfy the sustainability needs of many manufacturers and consumers. Polyoxymethylene polymers or paraformaldehyde can be used in the manufacture of various types of products and articles in a wide range of fields. For example, polyoxymethylene polymers can be used in the manufacture of molded parts and articles used in the automotive, electrical, and medical fields. Manufacturers can incorporate polyoxymethylene polymers into their products to achieve renewable or bio-content targets. Overall, polyoxymethylene polymers or paraformaldehyde manufactured in accordance with this disclosure can help manufacturers reduce their carbon footprint without sacrificing quality or mechanical properties for any reason.

[0017]

[0020] Ultimately, polyoxymethylene polymers or paraformaldehyde manufactured in accordance with this disclosure may be certified according to any appropriate standard. One such certification is the International Sustainability and Carbon Certification (ISCC). ISCC is a globally applicable sustainability certification system covering all sustainable raw materials, including agricultural and forest biomass, circular biomaterials, and renewable energy. ISCC follows a mass balance scheme that allows for verification of the renewable content of polymers. In the mass balance, renewable raw materials are attributed to products selected according to their individual composition, taking into account all yields and losses. Only raw material substances used as raw materials for manufacturing (not for energy purposes) are considered in the mass balance. Key criteria used in applying the mass balance scheme include raw material qualification, control of the processing and distribution process, and product claims. It is possible.

[0018]

[0021] In contrast to other methods that may calculate the bio-content in the actual product, the mass balance method has become a popular preferred method for certifying sustainable products in the chemical industry over the past few years. The mass balance method makes it possible to track the quantity and sustainable characteristics of recycled and / or bio-based materials throughout the value chain and attribute them to the final product in a verifiable manner.

[0019]

[0022] For illustrative purposes only, for example, in a mass balance model, the formation of methanol from fossil fuels such as natural gas generates a greenhouse gas footprint and is carbon positive. The amount of carbon released into the environment can be calculated considering production, combustion, and transport. If methanol is not burned, combustion emissions are not considered, and the carbon footprint is approximately 16 gCO2eq / MJ for production and approximately 1.4 gCO2eq / MJ for transport. On the other hand, if methanol is produced from biogas or recycled gas (e.g., recycled gas from industrial processes), using methanol for chemical applications can make the final product carbon natural or carbon negative. Using biogas or recycled gas for methanol production can be considered, for example, a carbon sink. The carbon sink may be calculated to be approximately 40 gCO2eq / MJ. The carbon sink is then subtracted from the production and transport carbon footprints calculated as described above. As a result, according to this calculation example, the use of methanol derived from biogas or recycled gas results in a negative carbon footprint of approximately -30 g CO2eq / MJ to approximately -45 g CO2eq / MJ, and the carbon sink could reach as high as -0.860 KG CO2 / kg.

[0020]

[0023] To produce polyoxymethylene polymers in accordance with this disclosure, methanol is first formed from biogas or recycled gas. Methanol is, for example, a primary raw material in the production of polyoxymethylene polymers. Conventionally, methanol has been produced from fossil natural gas to form methanol, which is known in the art as "gray" methanol. Generally, about 1.1 kg to about 1.3 kg of methanol is required to produce 1 kg of polyoxymethylene polymer. Methanol is first used to form formaldehyde, which is then used to form a cyclic acetal such as trioxane, which is then polymerized to form a polyoxymethylene polymer. When producing polyoxymethylene copolymers, the polyoxymethylene polymer may typically contain about 0.1 mol% to about 5 mol% of comonomers. In one embodiment, the comonomer is 1,3-dioxolane. The comonomer may also be produced from methanol via formaldehyde and ethylene glycol.

[0021]

[0024] According to this disclosure, methanol is produced from biogas or recycled gas. In one embodiment, biogas is methane produced from solid waste landfills and anaerobic digesters. The use of biogas has been found to be far more efficient than other biosources such as glycerin.

[0022]

[0025] The conversion of methane biogas to methanol can be carried out using a variety of processes and steps. In one embodiment, for example, methane can be directly converted to methanol via partial oxidation of methane in the presence of a metal-containing zeolite catalyst. In this embodiment, 1 mole of methane reacts with 0.5 moles of oxygen molecules to produce methanol.

[0023]

[0026] In an alternative embodiment, biogas methane can be converted into synthesis gas produced by steam reforming of methane. The synthesis gas may contain, for example, carbon monoxide or carbon dioxide. The reaction scheme is then as follows: CO + 2H2 → CH3OH CO2 + 3H2 → CH3OH + H2O Methanol can be produced from carbon monoxide or carbon dioxide by this process.

[0024]

[0027] The above reaction can be carried out using a copper-based catalyst.

[0028] In addition to the use of methane biogas, methanol may also be produced using regenerated gases as stipulated in this disclosure. Regenerated gases may, for example, be obtained from industrial processes. Regenerated gases represent, for example, carbon-containing gases that are normally released into the atmosphere. By collecting these gases and using them for methanol production, the carbon footprint of the resulting polymers is significantly reduced.

[0025]

[0029] The regenerated gas may include, for example, carbon dioxide, carbon monoxide, or a combination of carbon dioxide and carbon monoxide. The reaction scheme described above can then be used to convert the regenerated gas to methanol.

[0026]

[0030] Through the methods described above, methanol products are produced from entirely sustainable resources. To produce polyoxymethylene polymers, methanol can be converted to formaldehyde, and then to cyclic acetal monomers such as trioxane. Methanol can also be used in the production of comonomers and chain transfer agents.

[0027]

[0031] The preparation of formaldehyde from methanol can also be carried out using various processes and techniques. In one embodiment, for example, the formation of formaldehyde is carried out at 300°C to 450°C under a catalyst containing iron oxide and molybdenum oxide, using the following reaction scheme: CH3OH + 1 / 2O2 → CH2O + H2O This is carried out by oxidation by [a specific agent]. In another embodiment, at 600°C to 720°C, the following reaction scheme is used: CH3OH → CH2O + H2 H2 + 1 / 2O2 → H2O Oxidative dehydrogenation according to the following method is used in the production of methanol.

[0028]

[0032] In yet another embodiment, formaldehyde is given by the following formula:

[0029] [ka]

[0030] It can be produced from methanol by dehydrogenation in a non-oxidative process according to [the relevant regulations].

[0033] Suitable catalysts are known, for example, in the literature (see, e.g., Chem.Eng.Technol. 1994, 17, 34).

[0031]

[0034] Suitable metals include, for example, Li, Na, K, Cs, Mg, Al, In, Ga, Ag, Cu, Zn, Fe, Ni, Co, Mo, Ti, Pt, or compounds thereof. Transition metal phosphates such as S, Se, V, and Fe, as well as heteropoly acids such as molybd phosphate, are also suitable.

[0032]

[0035] Specific examples of catalysts are: Sodium or sodium compounds (DE-A-37 19 055 and DE-A-38 19 509) Aluminum oxide, alkali metal aluminates, and / or alkaline earth metal aluminum Salt (EP-A04 05 348) Silver oxide (JP-A60 / 089 441, Derwent Report 85-15 68 91 / 26) Catalyst containing copper, zinc, and sulfur (DE-A-25 25 174) Catalyst containing copper, zinc, and selenium (U.S. Patent No. 4,054,609) Catalyst containing zinc and / or indium (EP-A 0 130 068) Silver (US Patent No. 2,953,602) Silver, copper, and silicon (U.S. Patent No. 2,939,883) Compounds containing zinc, cadmium, selenium, tellurium, or indium That is the case.

[0033]

[0036] a) Sodium alkoxide, b) Sodium carboxylate, c) Sodium salts of CH acid compounds, and d) Sodium oxide, sodium hydroxide, sodium nitride, sodium acetylide, sodium carbide, sodium hydride, and sodium carbonyl A sodium compound selected from the group consisting of the following is particularly preferred.

[0034]

[0037] Once formaldehyde is produced from methanol, it can then be used to produce monomers, comonomers, and any other components used in the polymerization of polyoxymethylene polymers. In one embodiment, formaldehyde is used to produce a cyclic acetal as a primary monomer for the production of a polyoxymethylene polymer. To produce a cyclic acetal, the formaldehyde source is reacted with or transformed in the presence of a catalyst. The catalyst may be a cationic catalyst such as a Brønsted acid or a Lewis acid.

[0035]

[0038] The catalyst is for the conversion (reaction) of a formaldehyde source to cyclic acetals, particularly trioxanes and / or tetroxanes.

[0039] This section concerns cyclic acetals derived from formaldehyde. A typical representative example is shown in the following formula:

[0036] [ka]

[0037] This shows that a is an integer in the range of 1 to 3.

[0040] Preferably, the cyclic acetal produced by this method is trioxane (a=1) and / or tetroxane (a=2). Trioxane and tetroxane typically constitute the majority (at least 80% by weight, preferably at least 90% by weight) of the cyclic acetal formed by this method.

[0038]

[0041] The weight ratio of trioxane to tetroxane varies depending on the catalyst used. Typically, the weight ratio of trioxane to tetroxane ranges from about 3:1 to about 40:1, preferably from about 4:1 to about 20:1.

[0039]

[0042] In one embodiment, the above reaction may occur in the presence of an aprotic compound, such as that described in U.S. Patent No. 9,604,956, which is incorporated herein by reference. The aprotic compound may be, for example, a cyclic or alicyclic organosulfoxide, alicyclic or ring This could be a sulfone or the like. In one embodiment, the aprotic compound is a sulfolane. The presence of an aprotic compound can significantly improve the conversion rate.

[0040]

[0043] In addition to the production of primary monomers, methanol of the Disclosure derived from biogas or recycled gas may also be used to produce one or more comonomers. One or more comonomers may include cyclic ethers or acetals. In one embodiment, the comonomer is a dioxolane, such as 1,3-dioxolane. Particularly useful, the comonomer may also be produced from methanol of the Disclosure produced from biogas or recycled gas. In one embodiment, the comonomer may be produced from or via formaldehyde obtained from such methanol. In addition to formaldehyde, glycols, such as ethylene glycol, may also be used to produce comonomers. Ethylene glycol may be produced from one or more carbon-negative components.

[0041]

[0044] During the polymerization of polyoxymethylene polymers, chain transfer agents are commonly used to control the molecular weight and / or the composition of end groups. Particularly useful, the chain transfer agents used in this method can also be formed from biogas or recycled gas via methanol. For example, methylal, one type of chain transfer agent, can be formed by the oxidation of methanol or by the reaction of formaldehyde with methanol.

[0042]

[0045] After polymer building blocks are produced from biogas and / or recycled gas, polyoxymethylene polymers can be produced using other components.

[0046] The preparation of polyoxymethylene polymers can be carried out by polymerization of polyoxymethylene-forming monomers, such as trioxane or a mixture of trioxane and a cyclic acetal such as dioxolane, in the presence of molecular weight modifiers such as glycol or methylal. The polyoxymethylene polymers used in polymer compositions may include homopolymers or copolymers. While homopolymers can be produced, this disclosure primarily relates to the production of polyoxymethylene copolymers containing at least 50 mol%, for example, at least 75 mol%, for example, at least 90 mol%, and even, for example, at least 97 mol%, of -CH2O- repeating units.

[0043]

[0047] In one embodiment, a polyoxymethylene copolymer is used. The copolymer may contain repeating units comprising saturated or ethylenically unsaturated alkylene or cycloalkylene groups having at least two carbon atoms, which have a sulfur atom or oxygen atom in the chain and may contain one or more substituents selected from the group consisting of alkylcycloalkyl, aryl, aralkyl, heteroaryl, halogen, or alkoxy, in an amount of about 0.01 mol% to about 20 mol%, particularly about 0.5 mol% to about 10 mol%. In one embodiment, a cyclic ether or acetal that can be introduced into the copolymer via a ring-opening reaction is used.

[0044]

[0048] A preferred cyclic ether or acetal is given by formula:

[0045] [ka]

[0046] This is represented by , where x is 0 or 1, and R 2 This is a C2-C4 alkylene group having, as appropriate, one or more substituents that are C1-C4 alkyl groups or C1-C4 alkoxy groups and / or halogen atoms, preferably chlorine atoms. Examples include, but are limited to, ethylene oxide, propylene 1,2-oxide, and butylene. Examples of cyclic ethers include 1,2-oxide, butylene 1,3-oxide, 1,3-dioxane, 1,3-dioxolane, and 1,3-dioxepane, while examples of comonomers include linear oligonucleotides or polyformals such as polydioxolane or polydioxepane. It is particularly advantageous to use copolymers consisting of 99.5 to 95 mol% trioxane and 0.01 to 5 mol%, for example, 0.5 to 4 mol%, of one of the aforementioned comonomers. In one embodiment, the polyoxymethylene polymer contains relatively small amounts of comonomers. For example, the comonomer may be present in amounts of less than about 2 mol%, for example, less than about 1.5 mol%, for example, less than about 1 mol%, for example, less than about 0.8 mol%, for example, less than about 0.6 mol%.

[0047]

[0049] Polymerization is achieved by precipitation polymerization or melt polymerization. By appropriately selecting polymerization parameters such as polymerization time or the amount of molecular weight modifier, the molecular weight and, consequently, the MVR value of the resulting polymer can be adjusted.

[0048]

[0050] In one embodiment, the polyoxymethylene polymer used in the polymer composition may contain a relatively large amount of reactive or functional groups at its terminal positions. The reactive groups may include, for example, -OH or -NH2 groups.

[0049]

[0051] In one embodiment, a polyoxymethylene polymer may have terminal hydroxyl groups, such as hydroxyethyl terminal groups and / or hemiformal terminal groups, in an amount exceeding at least about 50% of the total terminal sites on the polymer. For example, of the terminal groups of a polyoxymethylene polymer, at least 70%, for example at least about 80%, or for example at least about 85%, may be hydroxyl groups, based on the total number of terminal groups present. It should be understood that the total number of terminal groups present includes all terminal and side-terminal groups.

[0050]

[0052] In one embodiment, the terminal hydroxyl group content of the polyoxymethylene polymer is at least 15 mmol / kg, for example, at least 18 mmol / kg, for example, at least 20 mmol / kg. In one embodiment, the terminal hydroxyl group content varies in the range of 18 to 50 mmol / kg. In an alternative embodiment, the polyoxymethylene polymer may contain terminal hydroxyl groups in amounts less than 20 mmol / kg, for example, less than 18 mmol / kg, for example, less than 15 mmol / kg. For example, the polyoxymethylene polymer may contain terminal hydroxyl groups in amounts from about 5 mmol / kg to about 20 mmol / kg, for example, from about 5 mmol / kg to about 15 mmol / kg. For example, a polyoxymethylene polymer with a lower terminal hydroxyl group content may be formed.

[0051]

[0053] In addition to, or instead of, terminal hydroxyl groups, polyoxymethylene polymers may also have other terminal groups. Examples include alkoxy groups, formate groups, acetate groups, or aldehyde groups. According to one embodiment, the polyoxymethylene is a homopolymer or copolymer containing at least 50 mol%, for example, at least 75 mol%, for example, at least 90 mol%, for example, even more than 95 mol%, of -CH2O- repeating units.

[0052]

[0054] In one embodiment, the polyoxymethylene polymer can be produced using a cationic polymerization process followed by solution hydrolysis to remove any unstable end groups. In cationic polymerization, a glycol such as ethylene glycol or methylal can be used as a chain terminating agent. A heteropolyacid, trifluoromethanesulfonic acid, or a boron compound may be used as a catalyst.

[0053]

[0055] The polyoxymethylene polymer can have any suitable molecular weight. The molecular weight of the polymer can be, for example, from about 4,000 grams per mole to about 20,000 g / mol. However, in other embodiments, the molecular weight can exceed 20,000 g / mol and can be, for example, from about 20,000 g / mol to about 100,000 g / mol.

[0054]

[0054]

[0056] Typically, the melt flow index (MFI) of the polyoxymethylene polymer present in the composition, measured at 190 °C and 2.16 kg according to ISO 1133, can vary in the range of about 0.1 to about 120 cm 3 / 10 minutes. In one embodiment, the melt flow index of the polyoxymethylene polymer exceeds about 1 cm 3 / 10 minutes, for example exceeds about 2 cm 3 / 10 minutes, for example exceeds about 5 cm 3 / 10 minutes, for example exceeds about 10 cm 3 / 10 minutes, for example exceeds about 20 cm 3 / 10 minutes, for example exceeds about 30 cm 3 / 10 minutes. In some cases, the melt flow index of the polymer is less than about 55 cm 3 / 10 minutes, for example less than about 45 cm 3 / 10 minutes, for example less than about 35 cm 3 / 10 minutes, for example less than about 25 cm 3 / 10 minutes, for example less than about 15 cm 3 / 10 minutes, for example less than about 10 cm 3 / 10 minutes, for example less than about 5 cm 3 / 10 minutes.

[0055]

[0057] In addition to polyoxymethylene polymers, this disclosure also relates to a method for producing paraformaldehyde. The method includes the step of forming formaldehyde from at least one carbon-negative component. For example, the carbon-negative component may include biogas or recycled gas, which may be collected from, for example, industrial processes. The biogas or recycled gas may first be converted to methanol. As previously stated, methanol may then be used to produce formaldehyde. The formaldehyde is then polymerized in the presence of a catalyst to form paraformaldehyde. Paraformaldehyde is HO(CH2O) n It has a structure represented by H, where n is approximately 8 to approximately 100. The purity of paraformaldehyde depends on the degree of polymerization n and can be between 90 and 99%, with the remainder being bound water or free water. Paraformaldehyde can then be used in the synthesis of phenol, urea, furfural alcohol, resorcinol resin, melamine resin, and formaldehyde resin. These products can be used in industrial coatings, wood products, textile products, casting resins, oil well additives, lubricant additives, adhesive resins, and electrical component molding materials.

[0056]

[0058] The polyoxymethylene polymers of this disclosure may be used in pure form or in combination with various additives and components. For example, in one embodiment, the polyoxymethylene polymer may be combined with a tribological modifier.

[0057]

[0059] For example, ultra-high molecular weight silicones (UHMW-Si) may be used to prepare polyoxymethylene polymers. Generally, the average molecular weight of UHMW-Si can be greater than 100,000 g / mol, e.g., greater than about 200,000 g / mol, e.g., greater than about 300,000 g / mol, e.g., greater than about 500,000 g / mol, and less than about 3,000,000 g / mol, e.g., less than about 2,000,000 g / mol, e.g., less than about 1,000,000 g / mol, e.g., less than about 500,000 g / mol, e.g., less than 300,000 g / mol. Generally, the kinematic viscosity of UHMW-Si at 40°C, as measured according to DIN 51562, is 100,000 mm². 2 s -1 For example, exceeding approximately 200,000 mm 2 s -1 For example, exceeding approximately 1,000,000 mm 2 s -1 For example, exceeding approximately 5,000,000 mm 2 s -1 For example, exceeding approximately 10,000,000 mm 2 s -1 For example, exceeding approximately 15,000,000 mm 2 s -1 Exceeding and approximately 50,000,000 mm 2 s -1 Less than, for example, approximately 25,000,000 mm 2 s -1 Less than, for example, approximately 10,000,000 mm 2 s -1 Less than, for example, approximately 1,000,000 mm 2 s -1 Less than, for example, approximately 500,000 mm 2 s -1 Less than, for example, approximately 200,000 mm 2 s -1 It can be less than.

[0058]

[0060] In yet another embodiment, the tribological modifier is polytetrafluoroethylene It may contain ethylene. Polytetrafluoroethylene may be in powder form and may be present in the polymer composition in an amount of about 1% to about 10% by weight.

[0059]

[0061] In accordance with this disclosure, various other tribological modifiers may be incorporated into the polyoxymethylene polymer composition. Examples of these tribological modifiers include calcium carbonate particles, ultra-high molecular weight polyethylene (UHMW-PE) particles, stearyl stearate particles, silicone oil, polyethylene wax, amide wax, wax particles including aliphatic ester waxes consisting of fatty acids and monohydric alcohols, graft copolymers with olefin polymers as graft stems, or combinations thereof. These tribological modifiers include the following:

[0060]

[0062] (1) Calcium carbonate particles, such as calcium carbonate (chalk) powder, in an amount of 0.1 to 50% by weight, for example, 1 to 25% by weight.

[0063] (2) Ultra-high molecular weight polyethylene (UHMW-PE) powder in amounts of 0.1 to 50% by weight, e.g., 1 to 25% by weight, e.g., 2.5 to 20% by weight, e.g., 5 to 15% by weight. UHMW-PE can be used as a powder, especially as a micropowder. Typical average particle size D (by volume, as measured by light scattering) of UHMW-PE. 50 The thickness is in the range of 1 to 5000 μm, preferably 10 to 500 μm, particularly preferably 10 to 150 μm, for example 30 to 130 μm, for example 80 to 150 μm, for example 30 to 90 μm.

[0061]

[0064] The average molecular weight of UHMW-PE, as determined by viscosity measurement, is 1.0·10. 6 Exceeding g / mol, for example 2.0·10 6 If it exceeds g / mol, for example 4.0·10 6 Exceeding g / mol, for example 1.0·10 6 g / mol to 15.0·10 6 Range of g / mol, e.g., 3.0-10 6 From g / mol to 12.0·10 6The viscosity can be in the range of g / mol. Preferably, the viscosity number of UHMW-PE is greater than 1000 ml / g, for example greater than 1500 ml / g, and varies in the range of, for example, 1800 ml / g to 5000 ml / g, or for example, 2000 ml / g to 4300 ml / g (determined according to ISO 1628-3, concentration in decahydronaphthalene: 0.0002 g / ml).

[0062]

[0065] (3) 0.1 to 10% by weight, for example 0.1 to 5% by weight, for example 0.5 to 3% by weight of stearyl stearate.

[0066] (4) 0.1 to 10% by weight of silicone oil, for example 0.5 to 5% by weight, for example 0.8 to 2% by weight. Alternatively, in one embodiment, the composition may be substantially free of silicone oil, for example, in an amount of less than about 0.1% by weight, for example less than about 0.05% by weight, for example less than about 0.01% by weight, for example about 0% by weight.

[0063]

[0067] (5) A polyethylene wax such as 0.1 to 5% by weight, for example, 0.5 to 3% by weight of polyethylene oxide wax.

[0068] (6) 0.1 to 5% by weight, for example, 0.2 to 2% by weight of amide wax.

[0064]

[0069] (7) 0.1 to 5% by weight, for example, 0.5 to 3% by weight, of an aliphatic ester wax consisting of a fatty acid and a monohydric alcohol.

[0070] The polymer compositions of this disclosure may also contain other known additives, such as antioxidants, formaldehyde scavengers, acid scavengers, UV stabilizers or heat stabilizers, and reinforcing fibers. In addition, the compositions may contain processing aids, such as adhesion promoters, lubricants, nucleating agents, demolding agents, fillers, or antistatic agents, and additives that impart desired properties to the composition and its articles or parts.

[0065]

[0071] In one embodiment, a UV stabilizer may be present. The UV stabilizer may include benzophenone, benzotriazole, or benzoic acid ester. UV light absorber If present, it may be present in the polymer composition in an amount of at least about 0.01% by weight, e.g., at least about 0.05% by weight, e.g., at least about 0.075% by weight, and less than about 1% by weight, e.g., less than about 0.75% by weight, e.g., less than about 0.5% by weight, where weight is based on the total weight of each polymer composition.

[0066]

[0072] In one embodiment, formaldehyde scavengers such as nitrogen-containing compounds may be present. Most of these are heterocyclic compounds having at least one nitrogen atom adjacent to an amino-substituted carbon atom or carbonyl group as a heteroatom, such as pyridine, pyrimidine, pyrazine, pyrrolidone, aminopyridine, and compounds derived therefrom. Other particularly useful compounds include triamino-1,3,5-triazine (melamine) and its derivatives such as melamine-formaldehyde condensates and methylolmelamine. In principle, oligomeric polyamides are also suitable for use as formaldehyde scavengers. Formaldehyde scavengers may be used individually or in combination.

[0067]

[0073] Furthermore, the formaldehyde scavenger may be a guanamine compound that may include aliphatic guanamine compounds, alicyclic guanamine compounds, aromatic guanamine compounds, heteroatom-containing guanamine compounds, and the like. The formaldehyde scavenger may be present in the polymer composition in an amount of at least about 0.01% by weight, for example at least about 0.05% by weight, for example at least about 0.075% by weight, and less than about 1% by weight, for example less than about 0.75% by weight, for example less than about 0.5% by weight, where the weight is based on the total weight of each polymer composition.

[0068]

[0074] In one embodiment, an acid scavenger may be present. The acid scavenger may include, for example, an alkaline earth metal salt. For example, the acid scavenger may include a calcium salt such as calcium citrate. The acid scavenger may be present in an amount of at least about 0.001% by weight, for example at least about 0.005% by weight, for example at least about 0.0075% by weight, and less than about 1% by weight, for example less than about 0.75% by weight, for example less than about 0.5% by weight, where the weight is based on the total weight of each polymer composition.

[0069]

[0075] In one embodiment, a nucleating agent may be present. The nucleating agent may be an agent that enhances crystallinity and may include an oxymethylene terpolymer. In a particular embodiment, for example, the nucleating agent may include a terpolymer of butanediol diglycidyl ether, ethylene oxide, and trioxane. The nucleating agent may be present in the composition in an amount of at least about 0.01% by weight, e.g., at least about 0.05% by weight, e.g., at least about 0.1% by weight, and less than about 2% by weight, e.g., less than about 1.5% by weight, e.g., less than 1% by weight, where the weight is based on the total weight of each polymer composition.

[0070]

[0076] In one embodiment, antioxidants such as sterically hindered phenols may be present. Examples of commercially available antioxidants include pentaerythrityltetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 3,3'-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate hydrazide], and hexamethylene glycol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]. The antioxidant may be present in the polymer composition in an amount of at least about 0.01% by weight, e.g., at least about 0.05% by weight, e.g., at least about 0.075% by weight, and less than about 1% by weight, e.g., less than about 0.75% by weight, e.g., less than about 0.5% by weight, where weight is based on the total weight of each polymer composition.

[0071]

[0077] In one embodiment, in addition to the UV stabilizer, a photostabilizer such as a sterically hindered amine may be present. Examples of sterically hindered amine photostabilizers that may be used include N-methylated olivine. Examples include sterically hindered amine compounds. For example, sterically hindered amine photostabilizers may include high molecular weight sterically hindered amine stabilizers. If present, the photostabilizer may be present in the polymer composition in an amount of at least about 0.01% by weight, e.g., at least about 0.05% by weight, e.g., at least about 0.075% by weight, and less than about 1% by weight, e.g., less than about 0.75% by weight, e.g., less than about 0.5% by weight, where the weight is based on the total weight of each polymer composition.

[0072]

[0078] In one embodiment, a lubricant that does not contain the aforementioned tribological modifier may be present. The lubricant may include a polymer wax composition. Furthermore, in one embodiment, a polyethylene glycol polymer (processing aid) may be present in the composition. The molecular weight of the polyethylene glycol may be, for example, about 1000 to about 5000, for example, about 3000 to about 4000. In one embodiment, for example, PEG-75 may be present. In another embodiment, a fatty acid amide such as ethylenebis(stearamide) may be present. The lubricant may generally be present in the polymer composition in an amount of at least about 0.01% by weight, for example at least about 0.05% by weight, for example at least about 0.075% by weight, and less than about 1% by weight, for example less than about 0.75% by weight, for example less than about 0.5% by weight, where the weight is based on the total weight of each polymer composition.

[0073]

[0079] In one embodiment, a colorant may be present. Possible colorants include any desired inorganic pigment such as titanium dioxide, ultramarine blue, or cobalt blue, as well as other organic pigments and dyes such as phthalocyanine and anthraquinone. Other colorants include carbon black or a variety of other polymer-soluble dyes. The colorant may be present in the composition in an amount of at least about 0.01% by weight, e.g., at least about 0.05% by weight, e.g., at least about 0.1% by weight, and less than about 5% by weight, e.g., less than about 2.5% by weight, e.g., less than 1% by weight, where weight is based on the total weight of each polymer composition.

[0074]

[0080] In one embodiment, reinforcing fibers may be present. Examples of reinforcing fibers that may be used according to the present invention include mineral fibers, polymer fibers such as glass fibers and aramid fibers, metallic fibers such as steel fibers, carbon fibers, or natural fibers. These fibers may be unmodified or modified, and may be sizing or chemically treated, for example, to improve adhesion to polymers. The fiber diameter may vary depending on the specific fiber used and whether the fiber is chopped or continuous. The fiber diameter may be, for example, about 5 μm to about 100 μm, for example about 5 μm to about 50 μm, or for example about 5 μm to about 15 μm. If present, each composition may contain reinforcing fibers in an amount of at least 1% by weight, e.g., at least 5% by weight, e.g., at least 7% by weight, e.g., at least 10% by weight, e.g., at least 15% by weight, and generally less than about 50% by weight, e.g., less than about 45% by weight, e.g., less than about 40% by weight, e.g., less than about 30% by weight, e.g., less than 20% by weight, where weight is based on the total weight of each polyoxymethylene polymer composition.

[0075]

[0081] The polymer composition may also include impact modifiers such as thermoplastic elastomers. Thermoplastic elastomers are materials that possess both thermoplastic and elastomeric properties. Thermoplastic elastomers include styrene block copolymers, polyolefin blends referred to as thermoplastic olefin elastomers, elastomer alloys, thermoplastic polyurethanes, thermoplastic copolyesters, and thermoplastic polyamides.

[0076]

[0082] Thermoplastic elastomers well suited for use in this disclosure are polyester elastomers (TPE-E), thermoplastic polyamide elastomers (TPE-A), and especially thermoplastic polyurethane elastomers (TPE-U).

[0077]

[0083] Alternatively, the impact modifier may be a core-shell type impact modifier. For example, the impact modifier may contain methacrylate-butadiene-styrene copolymer particles.

[0084] The amount of thermoplastic elastomer contained in a polymer composition can vary depending on various factors. For example, the thermoplastic elastomer may be present in an amount ranging from about 0.5% to about 50% by weight. In one embodiment, for example, the thermoplastic elastomer or impact modifier may be present in the composition in an amount of less than about 25% by weight, for example, less than about 15% by weight, or for example, less than 10% by weight. Generally, the thermoplastic elastomer or impact modifier is present in an amount greater than about 2% by weight, for example, more than about 5% by weight, for example, more than about 8% by weight, or for example, more than 10% by weight.

[0078]

[0085] The polymer compositions of this disclosure can be used in the manufacture of various molded parts. The parts can be molded by any suitable molding method, such as injection molding or blow molding. Examples of polymer articles that may be manufactured according to this disclosure include, but are not limited to, knobs, door handles, and automotive decorative trim pieces. Examples of other polymer articles that may be manufactured according to this disclosure include latches, levers, gears, pivot housings, and speaker grilles.

[0079]

[0086] In one specific embodiment, the polymer composition is used to manufacture a coffee maker 10 as shown in Figure 1. The coffee maker is designed to heat liquid very rapidly and produce heated beverages. Therefore, the operating environment of the coffee maker, particularly the internal operating environment, can change relatively quickly from room temperature to high temperatures. A coffee maker like the coffee maker 10 shown in Figure 1 also has many parts. According to this disclosure, various internal and external parts of the coffee maker, particularly parts exposed to high-temperature water, can be manufactured from the polymer composition of this disclosure.

[0080]

[0087] A coffee brewing apparatus typically includes a water heating unit, a coffee supply unit, and a coffee brewing assembly. To produce a heated beverage, coffee is supplied from the coffee supply unit and heated water from the water heating unit to the brewing assembly. A typical brewing assembly includes a brewing head, an upper closure element, a lower closure element, and at least one linear guide element.

[0081]

[0088] Referring to Figure 2, the coffee maker 10 may include a first component 22 and a second component 24. In one embodiment, the first component 22 and the second component 24 may be part of an extraction assembly or part of a coffee supply unit. For example, the components 22 and 24 may be components for receiving coffee and dispensing coffee into a designated area, such as a capsule, in order to produce a coffee beverage, because they are in close proximity to heated water. The components 22 and 24 may be subjected to operating environments above 30°C, for example above 40°C, for example above 50°C, or even above 60°C.

[0082]

[0089] Referring to Figure 3, an inhaler 30 which may be manufactured from a polyoxymethylene polymer is shown. The inhaler 30 includes a housing 32 which is attached to a mouthpiece 34. A plunger 36 for receiving a canister containing the composition to be inhaled works in cooperation with the housing 32. The composition includes a liquid atomizer or a powder.

[0083]

[0090] During use, the inhaler 30 administers a measured amount of medication, such as an asthma medication, to the patient. The asthma medication may be suspended or dissolved in a propellant, or contained in a powder. When the patient operates the inhaler and inhales the medication, a valve opens to expel the medication from the mouthpiece. According to this disclosure, the housing 32, mouthpiece 34, and plunger 36 may all be manufactured from the aforementioned polymer composition.

[0084]

[0091] Referring to Figure 4, another medical product that may be manufactured in accordance with this disclosure is shown. In Figure 4, a medical injector 40 is shown. The medical injector 40 includes a housing 42 that acts in conjunction with a plunger 44. The housing 42 may slide relative to the plunger 44. The medical injector 40 may be held in place by a spring. The medical injector is for injecting medication into a patient, usually in the thigh or buttocks. The medical injector may be needleless or may contain a needle. If it contains a needle, the needle tip is usually shielded within the housing before injection. Needleless injectors, on the other hand, may contain a pressurized gas cylinder that pushes medication through the skin without using a needle. In accordance with this disclosure, the housing 42 and / or the plunger 44 may be manufactured from the aforementioned polymer compositions.

[0085]

[0092] In one embodiment, polymer articles manufactured according to this disclosure may be used in the manufacture of transport system components. For example, a transport system typically includes a transport chain that moves on a truck. Such a transport system may be used for the transport of all kinds of products and goods. For example, in one embodiment, such a transport device is used for transporting food.

[0086]

[0093] Referring to Figure 5, for example, one embodiment of a portion of a transport chain 50 is shown. As shown, the transport chain 50 is made up of a plurality of transport components 52 or links. Each transport component 52 includes a top surface for receiving and transporting food. According to the present disclosure, the transport components 52 may be manufactured from the polymer compositions of the present disclosure. Particularly advantageous, the transport components 52 may include one or more colorants to give the component a desired appearance. Advantageously, components containing compositions prepared according to the present disclosure may emit and leach less formaldehyde when exposed to harsh cleaning conditions.

[0087]

[0094] In yet another embodiment of the present disclosure, the polymer composition may be coated with metal to produce a cosmetic closure. For example, Figure 6 shows one embodiment of a cosmetic closure 60 that may be produced according to the present disclosure.

[0088]

[0095] These and other improvements and modifications to the present invention can be implemented by those skilled in the art without departing from the spirit and scope of the invention as specifically described in the appended claims. It should also be understood that the various embodiments may be interchangeable in whole or in part. Furthermore, those skilled in the art will understand that the foregoing description is illustrative and not intended to limit the invention to those further described in such appended claims.

Claims

1. A method for producing polyoxymethylene polymers, A step of forming a cyclic acetal from at least one carbon-negative component including biogas or recycled gas, A step of forming a comonomer from at least one carbon-negative component, A method comprising the step of polymerizing the cyclic acetal with the comonomer in the presence of a catalyst to form a polyoxymethylene copolymer.

2. The method according to claim 1, further comprising the steps of forming a chain transfer agent from at least one carbon-negative component, and polymerizing the cyclic acetal with the comonomer and the chain transfer agent in the presence of the catalyst to form the polyoxymethylene copolymer.

3. The method according to claim 2, wherein the at least one carbon-negative component is used for forming an aqueous formaldehyde solution for producing the cyclic acetal, the comonomer, and the chain transfer agent.

4. The method according to any one of claims 1 to 3, wherein the carbon-negative component is first used for methanol formation.

5. The method according to any one of claims 1 to 4, wherein the cyclic acetal comprises trioxane.

6. The method according to any one of claims 1 to 5, wherein the comonomer comprises dioxolane.

7. The method according to any one of claims 1 to 6, wherein the polyoxymethylene copolymer contains 0.5 to 5 mol% of the comonomer.

8. The method according to claim 6, wherein the comonomer comprises 1,3-dioxolane.

9. The method according to claim 2 or 3, wherein the chain transfer agent comprises methylal or glycol.

10. The method according to any one of claims 1 to 9, wherein the chain transfer agent is used in an amount of 100 ppm to 1500 ppm relative to the weight of the polyoxymethylene polymer.

11. The method according to any one of claims 1 to 10, wherein the polyoxymethylene copolymer contains terminal hydroxyl groups, and the content of terminal hydroxyl groups of the polyoxymethylene copolymer is about 5 mmol / kg to about 150 mmol / kg, for example, about 25 mmol / kg to about 150 mmol / kg.

12. The method according to claim 11, wherein the polyoxymethylene polymer further comprises terminal groups composed of alkoxy groups.

13. The method according to any one of claims 1 to 12, wherein the polyoxymethylene copolymer comprises terminal groups, the terminal groups comprising a methoxy group, an ethoxy group, a formate group, and a hemiacetal group.

14. The method according to any one of claims 1 to 13, wherein more than 80% by weight of the carbon contained in the polyoxymethylene copolymer is derived from the carbon-negative component.

15. A method for producing polyoxymethylene polymers, The process of collecting carbon dioxide by-products from industrial processes, A process of combining carbon dioxide and a hydrogen source to form methanol, The process of forming a formaldehyde solution, The process involves forming a cyclic acetal from the formaldehyde solution, A method comprising the step of polymerizing the cyclic acetal in the presence of a catalyst to form a polyoxymethylene polymer.

16. The process of forming comonomers from carbon dioxide, The process further includes the step of polymerizing the cyclic acetal with the comonomer in the presence of a chain transfer agent and a catalyst to form a polyoxymethylene polymer. The method according to claim 15, wherein the polyoxymethylene polymer includes a polyoxymethylene copolymer.

17. The method according to claim 15 or 16, wherein the cyclic acetal comprises trioxane.

18. The method according to claim 16 or 17, wherein the comonomer comprises dioxolane.

19. The method according to claim 16, wherein the polyoxymethylene copolymer contains 0.5 to 5 mol% of the comonomer.

20. The method according to claim 19, wherein the comonomer comprises 1,3-dioxolane.

21. The method according to any one of claims 15 to 20, wherein the polyoxymethylene copolymer contains terminal hydroxyl groups, and the content of terminal hydroxyl groups of the polyoxymethylene copolymer is about 25 mmol / kg to about 150 mmol / kg, for example, about 40 mmol / kg to about 150 mmol / kg.

22. The method according to claim 21, wherein the polyoxymethylene polymer further comprises terminal groups composed of alkoxy groups.

23. The method according to any one of claims 15 to 22, wherein more than 50% by weight of the carbon contained in the polyoxymethylene copolymer is derived from carbon dioxide.

24. A method for producing paraformaldehyde, A process of forming formaldehyde from at least one carbon-negative component, including biogas or recycled gas, A method comprising the step of polymerizing the formaldehyde in the presence of a catalyst to form paraformaldehyde.

25. The method according to claim 24, wherein the carbon-negative component is first used for methanol formation.

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