Waterproof moisture permeable film

Abstract

The invention provides a waterproof moisture permeable film. The waterproof moisture permeable film comprises a polyurethane. The polyurethane includes a hard segment, a first soft segment, and a second soft segment, the first soft segment including an aromatic polyester-polyether group. The modulus of the waterproof moisture permeable film is greater than about 50 kgf / cm2, and the moisture permeability of the waterproof moisture permeable film is greater than about 30000 g / m2 * 24 hr. When the first soft segment is about 1 mole, the hard segment is equal to or greater than about 4.5 mole.

Description

Technical Field The present disclosure relates to a waterproof and breathable membrane. Background Art Polyurethane is a common polymer material in life. It is widely used in foam products (such as sponges), shock-absorbing elastic materials (such as shoe soles), coatings (such as stainless steel tank coatings), adhesives, and waterproof and breathable films. Polyurethane can be widely used in different fields because polyurethane with different properties can be produced by selecting polyurethane compositions with different combinations of ingredients. Generally speaking, polyurethane compositions mainly include isocyanate, polyol, chain extender, etc., and the composition of the polyurethane composition used can be adjusted according to the properties required by different application fields of polyurethane. The polyurethane composition may contain a variety of polyols, generally polyester polyols or polyether polyols, and recycled polyols may also be used. For example, US4469823 discloses that recycled polyethylene terephthalate (PET) is reacted with C2-C4 dibasic acid and aliphatic diol (alkylene glycol) to obtain aromatic polyester polyol, and then the above aromatic polyester polyol is reacted with polyisocyanate to synthesize polyurethane foaming material. For another example, US9458354 discloses that recycled PET is reacted with C2-C4 dibasic acid and neopentyl glycol to obtain aromatic polyester polyol, and then the above aromatic polyester polyol is reacted with polyisocyanate to synthesize polyurethane material. In addition, the type of chain extender in the polyurethane composition will also affect its properties. For example, US4540768 discloses the use of a chain extender with an amine group to prepare a polyurethane material. Since the amine group structure has a higher modulus, it can be used in injection molding materials. The above technologies all use aromatic polyester polyols made from recycled polyester as one of the polyol formulas, which has the advantage of making the product more environmentally friendly and reducing carbon emissions. If these formulas can be applied to other fields, such as waterproof and breathable membranes, they should be more environmentally friendly. However, the formulas of the above technologies cannot be directly used for waterproof and breathable membranes. For example, the polyurethane with aliphatic dibasic acid group structure disclosed in US4469823 has a high hardness. When used for waterproof and breathable membranes, it will make the hand feel more rigid and reduce wearing comfort. For example, the polyurethane with neopentyl glycol polyurethane structure disclosed in US9458354 has a high hydrophobicity. When used for polyurethane waterproof and breathable membranes, it will reduce the moisture permeability. In addition, TWI766384 discloses the use of derivatives of recycled PET bottles as a formula for making polyurethane. However, there are many types of structures of derivatives of recycled PET bottles, and not all derivatives can produce waterproof and breathable films with soft touch, high moisture permeability and water pressure resistance. The polyurethane synthesized in the previous case TWI766384 has a different structure from that of the present case. The polyurethane in the previous case mainly uses 2-hydroxyethylaminobenzoic acid hydroxyethyl ester (BHETTA) recycled PET bottle derivatives for polyurethane synthesis. Although it can improve the strength of polyurethane, it fails to take into account sufficient moisture permeability. From the above description, it can be seen that in order to achieve a waterproof and breathable membrane that is environmentally friendly and carbon-reducing, has a soft feel, and has both moisture permeability and water pressure resistance, further research and development of the chemical structure of polyurethane suitable for making waterproof and breathable membranes is needed. The present disclosure is to develop a polyurethane composition that has good wearing comfort and meets the physical property requirements of waterproof and breathable membranes (water pressure resistance and high moisture permeability). Summary of the invention In some embodiments, the present disclosure provides a waterproof and breathable membrane comprising polyurethane, wherein the polyurethane comprises a hard segment, a first soft segment and a second soft segment, the first soft segment comprises an aromatic polyester-polyether group, and the modulus of the waterproof and breathable membrane is greater than about 50 kgf / cm 2 , and the moisture permeability of the waterproof and breathable membrane is greater than about 30000g / m 2 *24hr. When the first soft segment is about 1 mol, the hard segment is equal to or greater than about 4.5 mol. The first soft segment comprises a structure shown in the following formula (I): -X1-Y1-formula (I); Wherein X1 comprises at least one aromatic isocyanate group, and Y1 comprises an aromatic polyester-polyether group, wherein Y1 comprises a structure represented by the following formula (IA) or formula (IB): -[(CO)-R-(CO)-O-R'-O] n - Formula (IA); and -[(CO)-R-(CO)-O-R'-O-(CO)-OR”-O] n -Formula (IB); wherein R is an aromatic group, R' is a polyether group, R" is a C2-C4 aliphatic hydrocarbon, which may be the same or different, the CO groups attached to R are ortho, meta or para to each other, and n is an integer equal to or greater than 1; The second soft segment comprises a structure shown in the following formula (II): -X2-Y2-formula (II); Wherein X2 comprises at least one aromatic isocyanate group, Y2 comprises an aliphatic polyether group, the number average molecular weight of the aliphatic polyether group is equal to or greater than about 3000 g / mol, and Y2 comprises a structure as shown in the following formula (IIA): -[OR 1 ] m1 -O-formula (IIA); Where R 1 is a C2-C4 aliphatic hydrocarbon, m1 is an integer equal to or greater than 1, and when m1 is an integer equal to or greater than 2, R 1 Each occurrence may be the same or different. DETAILED DESCRIPTION The following disclosure provides many different embodiments or examples. Each aspect and each embodiment disclosed in the present disclosure can be individually combined with other aspects and embodiments disclosed in the present disclosure and combined into all possible combinations. In this specification and patent application, unless the context clearly dictates otherwise, the singular forms "a", "an" and "the" include plural forms. Unless otherwise claimed, any and all examples provided in this disclosure or exemplary language used (e.g., "such as") are only used to better illustrate the disclosure and are not intended to limit the scope of the disclosure. Here, the terms "about", "approximately", and "generally" generally mean within 20% of a given value or range, preferably within 10%, and more preferably within 5%, or within 3%, or within 2%, or within 1%, or within 0.5%. It should be noted that the quantities provided in the specification are approximate quantities, that is, in the absence of specific description of "about", "approximately", and "generally", the meanings of "about", "approximately", and "generally" can still be implied. The embodiments disclosed herein provide a polyurethane, a waterproof and breathable film, and a method for manufacturing a polyurethane. The first soft segment of the polyurethane has both an aromatic structure and a polyether structure. The aromatic structure can improve the strength of the polyurethane, and the polyether structure can improve the hydrophilicity of the polyurethane, that is, to compensate for the hydrophobic properties of the aromatic structure, so that the polyurethane can have both good strength and hydrophilicity, and is beneficial for being used to make a waterproof and breathable film with good modulus and moisture permeability. Furthermore, when the molar ratio of the hard segment of the polyurethane to the first soft segment meets the conditions disclosed herein (for example, equal to or greater than 4.5), a higher structural strength can be provided for the polyurethane, so that the polyurethane product (for example, a waterproof and breathable film) can have a relatively high modulus (for example, at least about 50kgf / cm 2 modulus). In some embodiments, the present disclosure provides a polyurethane, which includes at least one hard segment and one or more soft segments. The soft segment (or "first soft segment") of the polyurethane may include at least one aromatic polyester-polyether group. The aromatic polyester-polyether group may also be called an "aromatic polyether ester group". The first soft segment of the polyurethane may also be called an "aromatic polyester-polyether segment". According to some embodiments of the present disclosure, the soft segment (or "first soft segment") in the polyurethane has both an aromatic structure and a polyether structure. The aromatic structure can improve the strength of the polyurethane, and the polyether structure can improve the hydrophilicity of the polyurethane, that is, the hydrophobic properties of the aromatic structure can be improved, so that the polyurethane can have both good strength and moisture permeability and hydrophilicity. According to some embodiments of the present disclosure, in addition to the need for a proper proportion of soft segments and hard segments in the polyurethane, the aromatic structure and the polyether structure need to be well matched so that the recycled polyol can be applied to the polyurethane waterproof and breathable membrane. In some embodiments, when the first soft segment is about 1 mole, the hard segment is equal to or greater than about 4.5 moles. In other words, the molar ratio of the hard segment of the polyurethane relative to the first soft segment (or aromatic polyester-polyether segment) may be equal to or greater than about 4.5. In some embodiments, the molar ratio of the hard segment of the polyurethane relative to the first soft segment may be equal to or greater than about 4.8, 5, 5.3, 6, 7, 7.5, 8, 8.5, or 8.8. In some embodiments, the molar ratio of the hard segment of the polyurethane relative to the first soft segment may be equal to or less than about 10. In some embodiments, the molar ratio of the hard segment of the polyurethane relative to the first soft segment may be equal to or less than about 9.8, 9.5, 9.3, or 8.9. In some embodiments, the first soft segment may comprise a structure as shown in the following formula (I): -X1-Y1-formula (I); Wherein X1 may include at least one aromatic isocyanate group. In some embodiments, X1 may include an aromatic diisocyanate group. For example, X1 may include the following structure: -[(CO)N-Rx-N(CO)]-, wherein Rx may be an aromatic group. In some embodiments, Y1 may include a structure as shown in Formula (IA) or Formula (IB): -[(CO)-R-(CO)-O-R'-O] n - Formula (IA); and -[(CO)-R-(CO)-O-R'-O-(CO)-OR”-O] n -Formula (IB); Wherein R may be an aromatic group, R' may be a polyether group, R" may be a C2-C4 aliphatic hydrocarbon, which may be the same or different, the CO groups connected to R are in ortho, meta or para positions to each other, and n may be an integer equal to or greater than 1. In some embodiments, Y1 may include the aforementioned formula (IA) and the structure shown in the following formula (IA-1). In some embodiments, Y1 may include the aforementioned formula (IB) and the structure shown in the following formula (IB-1). -[(CO)-R-(CO)-OR”-O] n - Formula (IA-1); and -[(CO)-R-(CO)-OR”-O-(CO)-OR”-O] n -Formula (IB-1). In some embodiments, the number-average molecular weight (Mn) of the aromatic polyester-polyether groups in the first soft segment is equal to or greater than about 450 g / mol. In some embodiments, the number-average molecular weight of the aromatic polyester-polyether groups is equal to or greater than about 900 g / mol, 1200 g / mol, 1600 g / mol, or 1900 g / mol. In some embodiments, the number-average molecular weight of the aromatic polyester-polyether groups is equal to or less than about 2000 g / mol. In some embodiments, the aromatic polyester-polyether group may include repeating units of polyethylene terephthalate (PET), poly(trimethylene terephthalate) (PTT), poly(butylene terephthalate) (PBT), or the like. In some embodiments, the aromatic polyester-polyether group may include aromatic polyester-polyether repeating units of polyethylene terephthalate-polyether repeating units, polytrimethylene terephthalate-polyether repeating units, polybutylene terephthalate-polyether repeating units, or the like. In some embodiments, the aromatic polyester-polyether group may include aromatic polyester-polyether repeating units of polyethylene terephthalate-polyether-polyester repeating units, polytrimethylene terephthalate-polyether-polyester repeating units, polybutylene terephthalate-polyether-polyester repeating units, or the like. In some embodiments, the aromatic polyester-polyether group may be or include a depolymerization product derived from a polyester. In some embodiments, the depolymerization product of the aforementioned polyester is obtained by depolymerizing a polyester with a polyether polyol. The aforementioned polyester may be or include, for example, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), or the like. In some embodiments, the aromatic polyester-polyether group may be or include a depolymerization product derived from the reaction of a polyester with a polyether polyol. In some embodiments, the aromatic polyester-polyether group may be or include a depolymerization product derived from, for example, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), or the like with a polyether polyol. In some embodiments, the number average molecular weight of the aforementioned polyether polyol is equal to or greater than 130 g / mol. In some embodiments, the aforementioned polyether polyol comprises an aliphatic polyol. In some embodiments, the aforementioned polyether polyol comprises diethylene glycol (DEG), triethylene glycol (TEG), or a combination thereof. In some embodiments, the depolymerization product may include a structure as shown in the following formula (A), formula (B) and / or formula (C): Here, nA, nB, nC, mA, mB, and mC are each an integer equal to or greater than 1. In some embodiments, the aromatic polyester-polyether group may be or include a depolymerization product derived from a polyester and a polyether polyol, a polymer obtained by reacting a depolymerization product of a polyester and a polyether polyol with a carbonate, or a combination thereof. In some embodiments, the aromatic polyester-polyether group may be or include a depolymerization product derived from, for example, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), or the like with a polyether polyol. In some embodiments, the aromatic polyester-polyether group may be or include a polymer obtained by further reacting the depolymerization product with a carbonate. In some embodiments, the number average molecular weight of the aforementioned polyether polyol is equal to or greater than about 130 g / mol. In some embodiments, the aforementioned carbonate includes dimethyl carbonate (DMC), ethylene carbonate (EC), propylene carbonate (PC), and diphenyl carbonate (DPC). Since polyester (e.g., polyethylene terephthalate (PET)) has the characteristics of high strength and long life, it is widely used in the production of daily necessities such as PET bottles and textile fibers. However, the disposal of the large amount of polyester waste generated has also become a major problem. With the international attention paid to environmental protection measures in recent years, the industry has gradually developed various technologies for recycling and reusing plastic waste (e.g., polyester waste). How to efficiently recycle polyester waste and reuse it in polyester products has become one of the goals that the industry is committed to research and development. According to some embodiments of the present disclosure, the aromatic polyester-polyether group is or contains a depolymerization product derived from polyester, which can be directly used as one of the raw materials for polymerization reaction to make polyurethane, and therefore has the advantages of environmental protection and reduced energy consumption. Furthermore, the depolymerization product of polyester includes an aromatic polyester polyol group. Since the aromatic polyester polyol group has a relatively high hydrophobicity, the polyurethane used to make the waterproof and breathable film requires a high hydrophilicity. Therefore, the depolymerization product of polyester is generally not used as a raw material for preparing the polyurethane. In contrast, according to some embodiments of the present disclosure, since the aromatic polyester-polyether group is or includes a depolymerization product derived from the reaction of polyester and at least one polyether polyol, the depolymerization product has both a polyether structure and an aromatic structure, and is therefore a flowing liquid at room temperature, which is conducive to the feeding of the polymerization reaction, thereby improving the processability and convenience of the process steps for the polymerization reaction. Furthermore, the polyether structure can improve the hydrophilicity, which helps to improve the moisture permeability of the polyurethane and its products (e.g., waterproof and breathable films). In some embodiments, the first soft segment does not include aliphatic dibasic acid groups and neopentyl glycol groups. In some embodiments, the first soft segment does not include products derived from the reaction of polyester depolymerization products and aliphatic dibasic acids (e.g., C2-C4 dibasic acids). In some embodiments, the first soft segment does not include products derived from the reaction of polyester and neopentyl glycol. According to some embodiments of the present disclosure, the first soft segment of the polyurethane does not include aliphatic dibasic acid groups and / or products derived from the reaction of polyester and aliphatic dibasic acid. Since the structure of the aliphatic dibasic acid group may induce partial crystallization and have a higher hardness, the polyurethane and its products (e.g., waterproof and breathable membranes) used in the present disclosure will make the hand feel more rigid and reduce the wearing comfort. Therefore, the polyurethane and its products (e.g., waterproof and breathable membranes) disclosed in the present disclosure have a softer hand feel, and the made clothing has better wearing comfort. Furthermore, according to some embodiments of the present disclosure, the first soft segment of the polyurethane does not include neopentyl glycol groups and / or products derived from the reaction of polyester and neopentyl glycol. Since the neopentyl glycol structure has a higher hydrophobicity, the polyurethane and its products (e.g., waterproof and breathable membranes) used in the present disclosure will reduce the moisture permeability. Therefore, the polyurethane and its products (e.g., waterproof and breathable membranes) disclosed in the present disclosure have a higher hydrophilicity, thereby having a better moisture permeability. In some embodiments, the polyurethane may further include another soft segment different from the aforementioned first soft segment (or referred to as a "second soft segment"). In some embodiments, the second soft segment may include an aliphatic polyether group. The second soft segment of the polyurethane may also be referred to as an "aliphatic polyether segment." In some embodiments, the molar ratio of the first soft segment (or aromatic polyester-polyether segment) of the polyurethane relative to the second soft segment (or aliphatic polyether segment) may be equal to or greater than about 3. In some embodiments, the molar ratio of the first soft segment of the polyurethane relative to the second soft segment may be about 3.5 to 8.5, about 3.8 to 8, or about 4 to 7.8. In some embodiments, when the first soft segment is about 1 mole, the second soft segment is about 0.1 to 1 mole. In some embodiments, when the first soft segment is about 1 mole, the second soft segment is about 0.11 mole, about 0.3 mole, about 0.4 mole, about 0.5 mole, about 0.6 mole, about 0.7 mole, or about 0.8 mole. In some embodiments, the second soft segment may comprise a structure as shown in the following formula (II): -X2-Y2-formula (II); Wherein X2 may include at least one aromatic isocyanate group, and Y2 may include an aliphatic polyether group. In some embodiments, X2 may include an aromatic diisocyanate group. For example, X2 may include the following structure: -[(CO)N-Rx-N(CO)]-, wherein Rx may be an aromatic group. In some embodiments, Y2 may comprise a structure as shown in the following formula (IIA): -[OR 1 ] m1 -O-formula (IIA); Where R 1 is a C2-C4 aliphatic hydrocarbon, m1 is an integer equal to or greater than 1, and when m1 is an integer equal to or greater than 2, R 1 Each occurrence may be the same or different. In some embodiments, the number average molecular weight of the aliphatic polyether groups in the second soft segment is equal to or greater than 3000 g / mol. In some embodiments, the number average molecular weight of the aliphatic polyether groups is 3000 g / mol to 9000 g / mol. In some embodiments, the number average molecular weight of the aliphatic polyether groups is equal to or greater than about 3000 g / mol, 3400 g / mol, 6000 g / mol, or 9000 g / mol. In some embodiments, the number average molecular weight of the aliphatic polyether groups is equal to or less than about 10000 g / mol. In some embodiments, the aliphatic polyether group may include a polyglycol group repeating unit. In some embodiments, the aliphatic polyether group may include a polyethylene glycol (PEG) group repeating unit, a polypropylene glycol (PPG) group repeating unit, a polytetramethylene ether glycol (PTMEG) group repeating unit, or a block copolymer of any combination thereof. In some embodiments, the aliphatic polyether group may include a PEG group, a co-PEG-PPG group, a co-PEG-PTMEG group, or the like. In some embodiments, the aliphatic polyether group can be or include a repeating unit prepared from a polyether polyol. In some embodiments, the aliphatic polyether group can be or include a group or repeating unit prepared from polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether glycol (PTMEG), or any combination thereof. In some embodiments, the hard segment may comprise a structure as shown in the following formula (III): -X3-Y3-formula (III); Wherein X3 may include at least one aromatic isocyanate group. In some embodiments, X3 may include an aromatic diisocyanate group. For example, X3 may include the following structure: -[(CO)N-Rx-N(CO)]-, wherein Rx may be an aromatic group. In some embodiments, Y3 may comprise a structure as shown in Formula (IIIA): -OR a -O-formula (IIIA); Where R ais an aliphatic hydrocarbon. In some embodiments, in some embodiments, R a It is a C2-C4 aliphatic hydrocarbon. According to some embodiments of the present disclosure, the polyurethane further comprises a first soft segment (or an aromatic polyester-polyether segment). In addition to the polyether structure being able to improve the hydrophilicity of the polyurethane, the aromatic structure is able to improve the strength of the polyurethane, thereby providing the polyurethane with a higher structural strength, so that the polyurethane product (e.g., a waterproof and breathable membrane) can have a strength of at least about 50 kgf / cm 2 The modulus. Furthermore, according to some embodiments of the present disclosure, the polyurethane further comprises a second soft segment (or aliphatic polyether segment) having a relatively high number average molecular weight. Since the aliphatic polyether segment having a relatively high number average molecular weight is equivalent to having a long carbon chain polyether structure, the moisture permeability of the polyurethane product (e.g., a waterproof and breathable film) can be further improved. In addition, according to some embodiments of the present disclosure, the molar ratio of the first soft segment (or aromatic polyester-polyether segment) of the polyurethane to the second soft segment (or aliphatic polyether segment) meets the aforementioned conditions, so that the polyurethane can further have both good strength and hydrophilicity. In some embodiments, "S1" represents the molar number of the first soft segment (or aromatic polyester-polyether segment), "S2" represents the molar number of the second soft segment, "H1" represents the molar number of the hard segment, "M1" represents the molar ratio of the first soft segment (or aromatic polyester-polyether segment) to the sum of the hard segment, the first soft segment and the second soft segment (M1 = (S1 / (H1+S1+S2))*100), and M1 is equal to or less than about 20. In some embodiments, M1 is equal to or less than about 18, 17.5, or 17. In some embodiments, M1 is equal to or greater than about 9. In some embodiments, M1 is equal to or greater than about 9.2 or 9.5. In some embodiments, the present disclosure provides a waterproof and breathable membrane, which comprises the aforementioned polyurethane. In some embodiments, the modulus of the waterproof and breathable membrane is greater than about 50 kgf / cm 2 In some embodiments, the modulus of the waterproof and breathable membrane is greater than about 52 kgf / cm 2 、53kgf / cm 2 , or 54kgf / cm 2 In some embodiments, the modulus of the waterproof and breathable membrane is equal to or less than about 80 kgf / cm 2 In some embodiments, the modulus of the waterproof and breathable membrane is equal to or less than about 75 kgf / cm 2 、70kgf / cm 2 、65kgf / cm 2 , or 60kgf / cm 2In some embodiments, the moisture permeability of the waterproof and breathable membrane is greater than about 30,000 g / m 2 *24hr. The "modulus (also called "100% modulus")" mentioned in this disclosure is the secant modulus at 100% elongation, and its test method is based on ASTMD638 specification (Load Cell: 50N, Crosshead Speed: 200mm / min). The "moisture permeability" mentioned in this disclosure is the moisture permeability of the sample at a temperature of 30°C and a humidity of 65%RH, and its unit is g / m 2 *24hr, measured according to JIS L1099B1 standard test method. In some embodiments, the present disclosure provides a method for producing polyurethane. The method for producing polyurethane may include at least the following steps: providing isocyanate, linear diol, aliphatic polyol (e.g., long carbon chain polyether polyol), and aromatic polyester-polyether polyol, mixing the isocyanate, linear diol, aliphatic polyol, and aromatic polyester-polyether polyol into a mixture, and then heating the mixture to perform a polymerization reaction to obtain polyurethane. In some embodiments, the isocyanate comprises an organic isocyanate, such as an aliphatic isocyanate and / or an aromatic isocyanate. In some embodiments, the isocyanate comprises a diisocyanate. In some embodiments, the isocyanate comprises an aromatic diisocyanate. In some embodiments, the isocyanate may comprise trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate and / or octamethylene diisocyanate, 2-methylpentamethylene-1,5-diisocyanate, 2-ethylbutylene-1,4-diisocyanate, pentamethylene-1,5-diisocyanate, butylene-1,4-diisocyanate, isophorone diisocyanate, cyanate (IPDI), 1,4-bis(isocyanatomethyl)cyclohexane and / or 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate and / or 1-methyl-2,6-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate and / or 2,2'-dicyclohexylmethane diisocyanate 1,5-naphthylene diisocyanate (NDI), 2,4-toluene diisocyanate and / or 2,6-toluene diisocyanate (TDI), o-toluene diisocyanate (TODI), p-phenylene diisocyanate (PPDI), 1,2-diphenylethane diisocyanate and / or phenylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate (H12MDI), 2,4'-dicyclohexylmethane diisocyanate (H12MDI), 2,2'-dicyclohexylmethane diisocyanate (H12MDI), 2,4-p-phenylene diisocyanate (PPDI), 2,4-tetramethylene xylene diisocyanate (TMXDI), or any combination thereof. In some embodiments, the aliphatic polyol comprises an aliphatic polyether polyol. In some embodiments, the number average molecular weight of the aliphatic polyether polyol is equal to or greater than about 3000 g / mol. In some embodiments, the number average molecular weight of the aliphatic polyether polyol is equal to or greater than about 3000 g / mol, 3400 g / mol, 6000 g / mol, or 9000 g / mol. In some embodiments, the aliphatic polyether group may include a polyglycol group repeating unit. In some embodiments, the aliphatic polyether polyol may include polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether glycol (PTMEG), or a copolymer of any combination thereof. In some embodiments, the aliphatic polyether polyol may include PEG, co-PEG-PPG, co-PEG-PTMEG, or the like. In some embodiments, the method for producing an aromatic polyester-polyether polyol may include at least the following steps: providing a polyester, then adding a polyether polyol to the polyester, and performing a depolymerization step on the polyester to obtain an aromatic polyester-polyether polyol. In some embodiments, the alcohol value of the prepared aromatic polyester-polyether polyol is equal to or less than about 37.4 mg KOH / g. In some embodiments, the alcohol value of the prepared aromatic polyester-polyether polyol is equal to or less than about 37 mg KOH / g, 30 mg KOH / g, 20 mg KOH / g, 13 mg KOH / g, or 12.5 mg KOH / g. The "alcohol value" described in the present disclosure represents the number of milligrams (mg) of KOH required to neutralize the OH functional groups in each gram (g) of sample, and its unit is "mg KOH / g", which is determined based on the standard method of ASTM E1899-16. In some embodiments, the number average molecular weight of the polyether polyol used for depolymerizing polyester is equal to or greater than about 130 g / mol. In some embodiments, the polyether polyol comprises an aliphatic polyol. In some embodiments, the polyether polyol comprises diethylene glycol ether (DEG). Providing the aromatic polyester-polyether polyol further comprises: during the depolymerization step, when the alcohol value of the intermediate product of the depolymerization step reaches 245-255 mg KOH / g, adding a carbonate compound to the intermediate product and performing a polymerization reaction until the alcohol value reaches about 56 mg KOH / g, thereby terminating the reaction and obtaining the product. In some other embodiments, the aromatic polyester-polyether polyol can also be prepared by polymerization. In some embodiments, the aromatic polyester-polyether polyol can be prepared by polymerization of terephthalic acid (TPA), ethylene glycol (EG) and polyethylene glycol (PEG). In some embodiments, the method for manufacturing polyurethane may use a chain extender, and the aforementioned chain extender may include aliphatic compounds and / or aromatic compounds. In some embodiments, the chain extender may include diamines and / or alkanediols, for example, C2-C10 alkylene and / or C3-C8 alkanediol, or only primary hydroxyl groups. In some embodiments, a straight-chain diol is used as a chain extender for the polymerization reaction. In some embodiments, the chain extender may include 1,2-ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, neopentyl glycol, hydroquinone bis (β-hydroxyethyl) ether (HQEE), or any combination thereof. In some embodiments, the chain extender includes an amine compound, so that the prepared polyurethane has a higher modulus. In some embodiments, the chain extender may not include an amine compound. This is because the first soft segment of the polyurethane (or the aromatic polyester-polyether segment) already includes an aromatic structure, which helps to increase the modulus of the polyurethane. In some embodiments, the mixture can then be heated to perform a polymerization reaction to obtain a polyurethane. In some embodiments, the group of the aforementioned chain extender and isocyanate (e.g., aromatic diisocyanate) form a hard segment of the polyurethane via a polymerization reaction. In some embodiments, the aforementioned aromatic polyester-polyether polyol and isocyanate (e.g., aromatic diisocyanate) form a first soft segment (or aromatic polyester-polyether segment) of the polyurethane via a polymerization reaction. In some embodiments, the aforementioned aliphatic polyol and isocyanate (e.g., aromatic diisocyanate) form a second soft segment (or aliphatic polyether segment) of the polyurethane via a polymerization reaction. At this point, the polyurethane disclosed herein is formed. The present disclosure will be further described with reference to the following examples and comparative examples. However, it should be understood that the following examples are only for illustrative purposes and should not be construed as limiting the implementation of the present disclosure. [raw material] <Isocyanate>: 4,4'-diphenylmethane diisocyanate (MDI), a product of Tosoh Millionate MT of Japan. <Aliphatic polyol>: as shown in Table 1 below. Table 1 Product Name PEG9000 PEG3400 PEG2000 company Donglian Chemical Donglian Chemical Donglian Chemical Functionality 2 2 2 Number average molecular weight (g / mol) 9000 3400 2000 Alcohol value (mg KOH / g) 12.5 33 56

[0001] <Aromatic polyester-polyether polyol>: as shown in Table 2 below.

[0002] Table 2 Product Name rPET201 rPET041 PCrP201 company Donglian Chemical Donglian Chemical Donglian Chemical Functionality 2 2 2 Number average molecular weight (g / mol) 2000 450 2000 Alcohol value (mg KOH / g) 56.1 250 56.1 The preparation steps of "rPET041" are as follows: PET (100 g, 0.52 mol), DEG (138 g, 1.30 mol) and zinc acetate (0.1 g, 0.1 wt% relative to PET) are placed in a 500 mL round-bottom bottle, the reactants are heated to 200°C under a nitrogen environment and a depolymerization reaction is started, and the alcohol value of the reactants is continuously tracked. When the alcohol value reaches 250±5 mg KOH / g, the reaction is terminated to obtain an aromatic polyester-polyether polyol "rPET041". The preparation steps of "rPET201" are as follows: PET (100 g, 0.52 mol), DEG (138 g, 1.30 mol) and zinc acetate (0.1 g, 0.1 wt% relative to PET) are placed in a 500 mL round-bottom bottle, the reactants are heated to 200°C under a nitrogen environment and a depolymerization reaction is started, and the alcohol value of the reactants is continuously tracked. When the alcohol value reaches 250±5 mg KOH / g, the pressure of the reaction environment in the round-bottom bottle is adjusted to 2 torr, and then the reaction is continued until the alcohol value of the reactants reaches 56.1±3 mgKOH / g, at which time the reaction is terminated to obtain aromatic polyester-polyether polyol "rPET201". In some embodiments, the reaction process of depolymerizing PET into "rPET201" and "rPET041" can be represented by the reaction formula shown in the following formula (IV): Wherein n1 and n2 are integers equal to or greater than 1, and n1>n2, "rPET201" and "rPET041" have the same structure, but have different n2 values ​​and number average molecular weights. The preparation steps of "PCrP201" are as follows: PET (100g, 0.52mol), DEG (138g, 1.30mol) and zinc acetate (0.1g, 0.1wt% relative to PET) are placed in a 500mL round-bottom bottle, the reactants are heated to 200°C under a nitrogen environment and a depolymerization reaction is started, and the alcohol value of the reactants is continuously tracked. When the alcohol value reaches 250±5mg KOH / g, dimethyl carbonate (37.47g, 0.42mol) is further added to the reactants, the reaction temperature is adjusted to 150°C, and the pressure of the reaction environment in the round-bottom bottle is adjusted to 30torr. The reaction is then continued until the alcohol value of the reactants reaches 56.1±3mg KOH / g, when the reaction is terminated, an aromatic polyester-polyether polyol "PCrP201" is obtained. In some embodiments, the reaction process of further reacting the depolymerization product of PET with dimethyl carbonate (DMC) to form "PCrP201" can be represented by the reaction formula shown in the following formula (V): Wherein n3 is an integer equal to or greater than 1, preferably 2-10, more preferably 3-6. <Chain extender>: Ethylene glycol (EG), a product of Donglian Chemical. <Solvent>: dimethylacetamide (DMAc), Acros product. [Polymerization reaction] [Examples 1 to 7 and Comparative Examples 1 to 7] Weigh 16.283g of PEG9000, 16.397g of aromatic polyester-polyether polyol "rPET201", 2.477g of aromatic polyester-polyether polyol "rPET041", 4.151g of EG, and 56g of solvent DMAc, and place the above compounds in a glass reaction tank and react under nitrogen, with a stirring speed of 100rpm. Add 20.691g of MDI under continuous stirring, and make the temperature of the reaction system reach 70°C, then start the reaction. When the viscosity of the reactants increases to the point where the rod climbing phenomenon occurs, add 104g of solvent DMAc to completely dissolve the product in the solvent. At this time, the product batch is 200g, and the solid content is 30wt%. The preparation process is described above using Example 1 as an example. The polymerization steps of Examples 1 to 7 and Comparative Examples 1 to 7 are the same, and the only difference is the type and content of the reactant raw materials. The experimental conditions of the polymerization steps of Examples 1 to 7 and Comparative Examples 1 to 7 and the physical properties of the prepared polyurethanes are shown in the following Tables 3, 4A and 4B. Table 3 shows the amount of raw materials used (ie, the amount of each reactant added) in Examples 1 to 7 and Comparative Examples 1 to 7, and is expressed by weight in grams (g). Table 3 In Table 4A and Table 4B, "H1:S2:S1" represents the molar ratio of the hard segment: the second soft segment: the first soft segment in the polyurethane, "S2 / S1" represents the molar ratio of the second soft segment to the first soft segment in the polyurethane, "H1 / S1" represents the molar ratio of the hard segment to the first soft segment in the polyurethane, "X1", "X2", "X3", "Y1", "Y2" and "Y3" represent different groups, "M1" represents the molar ratio of the first soft segment to the sum of the hard segment, the first soft segment and the second soft segment (M1 = (S1 / (H1+S1+S2))*100), and the unit of "100% modulus" is "Kgf / cm 2 ", the unit of "moisture permeability" is "g / m 2*24hr". "100% modulus" is the secant modulus at 100% elongation, and its test method is based on ASTMD638 specification (LoadCell: 50N, Crosshead Speed: 200mm / min). "Moisture permeability" is the moisture permeability of the sample at a temperature of 30°C and a humidity of 65%RH, and is measured in accordance with the JIS L1099 B1 standard test method. Both "100% modulus" and "moisture permeability" in Table 4B are measured on samples with a film thickness of 20μm. Table 4A Table 4B It can be seen from the results of Table 3, Table 4A and Table 4B above that in some embodiments, when the molar ratio of the hard segment of the polyurethane to the first soft segment (or the aromatic polyester-polyether segment) meets the conditions of the present disclosure (e.g., equal to or greater than 4.5), the polyurethane can have a hardness of at least about 50 kgf / cm 2 Furthermore, from the results of Table 3, Table 4 and Table 4B above, it can be seen that in some embodiments, when the number average molecular weight of the aliphatic polyol (Y2) is greater than 3000 g / mol, the polyurethane can have a modulus greater than about 30000 g / m 2 *24hr moisture permeability. In some comparative examples, the derivative "rPHB05" series produced by recycling PET bottles has a reaction formula as shown by the following formula (VI): Wherein, Rn and Rm are derived from diol compounds, amino alcohol compounds or a combination thereof, the diol compounds include aliphatic diols, aromatic diols or polyether diols, and the amino alcohol compounds include aliphatic monoalcohol monoamines or aromatic monoalcohol monoamines. The polyurethane waterproof films of Comparative Examples 6 to 7 are made using derivatives of recycled PET bottles as starting materials, wherein the derivatives "rPHB05_600" and "rPHB05_1000" have a reaction formula as shown in Formula (VII), wherein n4+m4 is 8 to 22, and "rPHB05_600" and "rPHB05_1000" each have properties as shown in Table 5. Table 5 rPHB05_600 rPHB05_1000 Number average molecular weight (g / mol) 600 1000 Alcohol value (mg KOH / g) 18.7 11.2 <![CDATA[n4+m4]]> 10.6 19.7 The first soft segment (aromatic polyester-polyether group) in the polyurethane waterproof membrane of Comparative Example 6 has a chemical structure as shown in the following formula (VIII), and its number average molecular weight is 600 g / mol. Under normal circumstances, the chemical structures of the above formula (VII) and formula (VIII) are the chemical structures produced by degrading PET using polyether diol. From the results of Comparative Example 6, it can be seen that when the above structure is used to synthesize polyurethane, although the obtained polyurethane has a relatively large modulus, its water vapor permeability is insufficient. From the results of Comparative Example 7, it can be seen that if the molecular weight of polyether diol is increased in order to increase its water vapor permeability, the increase in water vapor permeability is not large, but the modulus is seriously reduced, thereby losing the water pressure resistance property. In contrast, the first soft segment (aromatic polyester-polyether group) used in Example 4 has a chemical structure as shown in the following formula (IX): Therefore, the polyurethane waterproof membrane of Example 4 can have sufficient moisture permeability and modulus at the same time, and the above structure has a relatively high proportion of recycled materials, which can also have the effect of environmental protection and carbon reduction. Furthermore, it can be seen from the results of Comparative Example 5 and Example 7 that when the molecular weight of the second soft segment (aliphatic polyether segment) is relatively low, the resulting polyurethane also has a lower moisture permeability. Although the present disclosure is disclosed as above with the aforementioned embodiments, it is not intended to limit the present disclosure. Those with ordinary knowledge in the technical field to which the present disclosure belongs may make some changes and modifications without departing from the spirit and scope of the present disclosure. Therefore, the protection scope of the present disclosure shall be determined by the scope of the attached patent application. In addition, each patent application constitutes an independent embodiment, and the combination of various patent application scopes and embodiments is within the scope of the present disclosure.

Claims

1. A waterproof and breathable membrane comprising polyurethane, wherein the polyurethane comprises a hard segment, a first soft segment and a second soft segment, the first soft segment comprises an aromatic polyester-polyether group, and the modulus of the waterproof and breathable membrane is greater than 50 kgf / cm 2 , and the moisture permeability of the waterproof and breathable membrane is greater than 30000g / m 2 *24hr, wherein when the first soft segment is 1 mol, the hard segment is equal to or greater than 4.5 mol, The first soft segment comprises a structure shown in the following formula (I): -X1-Y1-formula (I); Wherein X1 comprises at least one aromatic isocyanate group, and Y1 comprises the aromatic polyester-polyether group, wherein Y1 comprises a structure as shown in the following formula (IA) or formula (IB): -[(CO)-R-(CO)-O-R'-O] n -Formula (IA); and -[(CO)-R-(CO)-O-R'-O-(CO)-O-R”-O] n - formula (IB); wherein R is an aromatic group, R' is a polyether group, R" is a C2-C4 aliphatic hydrocarbon, which may be the same or different, the CO groups attached to R are ortho, meta or para to each other, and n is an integer equal to or greater than 1; The second soft segment comprises a structure shown in the following formula (II): -X2-Y2-formula (II); Wherein X2 comprises at least one aromatic isocyanate group, Y2 comprises an aliphatic polyether group, the number average molecular weight of the aliphatic polyether group is equal to or greater than 3000 g / mol, and Y2 comprises a structure as shown in the following formula (IIA): -[O-R 1 m1 -O-formula (IIA);​ Where R 1 is a C2-C4 aliphatic hydrocarbon, m1 is an integer equal to or greater than 1, and when m1 is an integer equal to or greater than 2, R 1 Each occurrence may be the same or different. 2 . The waterproof and moisture-permeable membrane according to claim 1 , wherein when the first soft segment is 1 mol, the hard segment is equal to or less than 10 mol. 3 . The waterproof and moisture-permeable membrane according to claim 1 , wherein the number average molecular weight of the aromatic polyester-polyether group is equal to or greater than 450 g / mol.

4. The waterproof and breathable membrane according to claim 1, wherein the aromatic polyester-polyether group is derived from a depolymerization product of a polyester and a polyether polyol, a polymer of the depolymerization product of the polyester and the polyether polyol reacting with a carbonate, or a combination thereof.

5. The waterproof and breathable membrane according to claim 1, wherein the hard segment comprises a structure represented by the following formula (III): -X3-Y3-formula (III); Wherein X3 comprises at least one aromatic isocyanate group, and Y3 comprises a structure as shown in the following formula (IIIA): -O-R a -O-formula (IIIA); Where R a It is a C2-C4 aliphatic hydrocarbon.

6. The waterproof and breathable membrane according to claim 1, wherein the modulus is equal to or less than 80 kgf / cm 2 . 7 . The waterproof and moisture-permeable membrane according to claim 1 , wherein the number average molecular weight of the aliphatic polyether group is 3000 g / mol to 9000 g / mol.

8. The waterproof and breathable membrane according to claim 1, wherein the molar number of the first soft segment is S1, the molar number of the second soft segment is S2, the molar number of the hard segment is H1, and the molar ratio of the first soft segment to the polyurethane is M1 and is expressed as: M1=(S1 / (H1+S1+S2))*100, wherein M1 is equal to or less than 20. 9 . The waterproof and moisture-permeable membrane according to claim 1 , wherein when the first soft segment is 1 mol, the second soft segment is 0.1 to 1 mol.

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