Moisture-permeable waterproof film

Abstract

To provide a moisture-permeable waterproof film.SOLUTION: A moisture permeable waterproof film includes a polyurethane. The polyurethane includes a hard segment, a first soft segment and a second soft segment, the first soft segment includes an aromatic polyester-polyether group. A modulus of the moisture permeable waterproof film is more than about 50 kgf / cm2, and a moisture permeability of the moisture permeable waterproof film is more than about 30000 g / m2 24 hr. When an amount of the first soft segment is about 1 mole, an amount of the hard segment is about 4.5 moles or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a waterproof / breathable membrane. [Background technology]

[0002] Polyurethane is a common polymeric material in daily life and is widely used in foam products (e.g., sponges), shock-absorbing elastic materials (e.g., soles), paints (e.g., the coating layer of stainless steel cans), viscose, and waterproof / breathable membranes. Polyurethane can be widely used in various fields because polyurethanes with different properties can be prepared by combining different components. In general, polyurethane compositions mainly contain a number of different components such as isocyanates, polyols, and chain extenders, and the compositional components of the polyurethane composition used can be adjusted according to the properties required for different applications of polyurethane.

[0003] The polyurethane composition may contain a plurality of polyols, generally polyester polyol or polyether polyol, and recycled polyol may be used. For example, US4469823 discloses a method of reacting recycled polyethylene terephthalate (PET) with a C2-C4 dibasic acid and an aliphatic diol to obtain an aromatic polyester polyol, and then reacting the aromatic polyester polyol with a polyisocyanate to synthesize a polyurethane foam material. For example, US9458354 discloses a method of reacting recycled PET with a C2-C4 dibasic acid and a neopentyl glycol to obtain an aromatic polyester polyol, and then reacting the aromatic polyester polyol with a polyisocyanate to synthesize a polyurethane material. In addition, the type of chain extender in the polyurethane composition affects its properties. For example, US Pat. No. 4,540,768 discloses that a polyurethane material is prepared using a chain extender having an amine group, and the structure of the amine group has a high elastic modulus, so that the polyurethane material can be applied to an injection molding material.

[0004] The above techniques all use aromatic polyester polyol prepared from recycled polyester as one of the polyol formulations, the advantage of which is to make the product more environmentally friendly and reduce carbon dioxide, and if these formulations can be applied to other fields, such as waterproof and moisture-permeable membranes, they will be more environmentally friendly.However, the formulations obtained by the above techniques cannot be directly used in waterproof and moisture-permeable membranes, for example, the polyurethane with aliphatic dibasic acid group structure disclosed in US4469823 has high hardness, and when used in waterproof and moisture-permeable membranes, it is hard to the touch and reduces the comfort of wearing, and for example, the polyurethane with neopentyl glycol polyurethane structure disclosed in US9458354 has high hydrophobicity, and when used in polyurethane waterproof and moisture-permeable membranes, it reduces moisture permeability. In addition, TWI766384 discloses the use of derivatives of recycled PET bottles as a compound for preparing polyurethane, but the derivatives of recycled PET bottles have many different structures, and not all of them can prepare a waterproof and moisture-permeable film that is soft to the touch, has high moisture permeability, and has a high elastic modulus (high elasticity is usually accompanied by water pressure resistance). The polyurethane synthesized in the previous application TWI766384 has a different structure from that of the present application. The polyurethane in the previous application is mainly synthesized using derivatives of recycled PET bottles, and its structural formula is [ka] Although it is possible to improve the strength of polyurethane, it is not possible to simultaneously achieve sufficient moisture permeability.

[0005] As can be seen from the above explanation, in order to obtain a waterproof and moisture-permeable membrane that is environmentally friendly, reduces carbon dioxide, is soft to the touch, and has both moisture permeability and high elasticity, research and development of a chemical structure of polyurethane suitable for manufacturing the waterproof and moisture-permeable membrane is desired. Therefore, the present disclosure aims to provide a polyurethane composition that is highly comfortable to wear and can meet the physical property requirements (water pressure resistance and high moisture permeability) of the waterproof and moisture-permeable membrane. Summary of the Invention [Problem to be solved by the invention]

[0006] In some embodiments, the present disclosure provides a waterproof / breathable membrane comprising a polyurethane, the polyurethane comprising a hard segment, a first soft segment, and a second soft segment, the first soft segment comprising an aromatic polyester-polyether group, the waterproof / breathable membrane having an elastic modulus of about 50 kgf / cm 2 and the moisture permeability is approximately 30,000 g / m 2 *24hr or more. When the first soft segment is about 1 mole, the hard segment is about 4.5 moles or more. The first soft segment comprises a structure represented by the following formula (I): -X1-Y1- Formula (I), In the formula, X1 comprises at least one aromatic isocyanate group, Y1 comprises an aromatic polyester-polyether group, and Y1 comprises a structure represented by the following formula (IA) or formula (IB): -[(CO)-R-(CO)-O-R'-O] n - of formula (IA), -[(CO)-R-(CO)-O-R'-O-(CO)-O-R'-O] n - Formula (IB), In the formula, R is an aromatic group, R' is a polyether group, R' in formula (IB) may be the same or different, CO groups bonded to R are at the ortho, meta or para positions, and n is an integer of 1 or more; The second soft segment comprises a structure represented by the following formula (II): -X2-Y2- Formula (II), In the formula, X2 comprises at least one aromatic isocyanate group, Y2 comprises an aliphatic polyether group having a number average molecular weight of about 3000 g / mol or more, and Y2 comprises a structure represented by the following formula (IIA): -[OR 1 ] m1 -O- Formula (IIA), In the formula, R 1 is a C2-C4 aliphatic hydrocarbon, m1 is an integer of 1 or more, and when m1 is an integer of 2 or more, R 1may be the same or different each time. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] The following disclosure provides many different embodiments or examples, each of which may be combined individually and to the extent possible with other aspects and embodiments disclosed in the present disclosure.

[0008] In this specification and claims, the singular forms "a," "an," and "the" all include the plural unless the context clearly dictates otherwise. Unless otherwise stated, any and all examples of this disclosure or exemplary language used (e.g., "etc.") are merely to better describe the disclosure and are not intended to limit the scope of the disclosure.

[0009] As used herein, the terms "about", "approximately", and "nearly" generally refer to within 20%, preferably within 10%, more preferably within 5%, or within 3%, or within 2%, or within 1%, or within 0.5% of a given value or range. Note that numbers referred to in this specification are approximate numbers, i.e., unless otherwise specified, the meanings of "about", "approximately", and "nearly" are implicitly included.

[0010] The embodiments of the present disclosure provide polyurethane, a waterproof and moisture-permeable film, and a method for producing polyurethane. The first soft segment of the polyurethane has an aromatic structure and a polyether structure at the same time, and the aromatic structure can improve the strength of the polyurethane, and the polyether structure can improve the hydrophilicity of the polyurethane, i.e., can compensate for the hydrophobicity of the aromatic structure, so that the polyurethane can have both high strength and hydrophilicity, which is advantageous for producing a waterproof and moisture-permeable film having a good elastic modulus and moisture permeability. In addition, when the molar ratio of the hard segment of the polyurethane to the first soft segment satisfies the conditions of the present disclosure (e.g., 4.5 or more), the polyurethane can have high structural strength, and thus the polyurethane product (e.g., waterproof and moisture-permeable film) can have a relatively high elastic modulus (e.g., at least about 50 kgf / cm 2 The elastic modulus may be 0.05 to 0.15.

[0011] In some embodiments, the present disclosure provides a polyurethane comprising at least one hard segment and at least one soft segment. The soft segment of the polyurethane may comprise at least one aromatic polyester-polyether group. The aromatic polyester-polyether group may also be referred to as an "aromatic polyetherester group". The soft segment of the polyurethane may also be referred to as an "aromatic polyester-polyether segment". According to some embodiments of the present disclosure, the soft segment of the polyurethane comprises a first soft segment of the polyurethane, the first soft segment having 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, so that the polyurethane can have both high strength and moisture permeability and hydrophilicity. According to some embodiments of the present disclosure, the synthesis of the polyurethane requires careful control of the ratio of the soft segment and the hard segment, as well as careful selection of the aromatic structure and the polyether structure. Accurate control is important to successfully synthesize a waterproof moisture permeable membrane, especially when using polyols obtained from recycled polyethylene terephthalate (rPET). Therefore, in the configuration of the present disclosure, the recovered and prepared polyol can be applied to the production of a polyurethane waterproof / moisture-permeable film having predetermined properties.

[0012] In some embodiments, when the first soft segment is about 1 mole, the hard segment is about 4.5 moles or more. In other words, the molar ratio of the polyurethane hard segment to the first soft segment (or aromatic polyester-polyether segment) may be about 4.5 or more. In some embodiments, the molar ratio of the polyurethane hard segment to the first soft segment may be about 4.8, 5, 5.3, 6, 7, 7.5, 8, 8.5, or 8.8 or more. In some embodiments, the molar ratio of the polyurethane hard segment to the first soft segment may be about 10 or less. In some embodiments, the molar ratio of the polyurethane hard segment to the first soft segment may be about 9.8, 9.5, 9.3, or 8.9 or less.

[0013] In some embodiments, the first soft segment may comprise a structure represented by formula (I): -X1-Y1- Formula (I), wherein X1 may comprise at least one aromatic isocyanate group. In some embodiments, X1 may comprise an aromatic diisocyanate group. For example, X1 may comprise the structure -[(CO)N-Rx-N(CO)]-, where Rx may be an aromatic group.

[0014] In some embodiments, Y1 may include a structure represented by formula (IA) or (IB): -[(CO)-R-(CO)-O-R'-O] n - of formula (IA), -[(CO)-R-(CO)-O-R'-O-(CO)-O-R'-O] n - Formula (IB), In the formula, R may be an aromatic group, R' may be a polyether group, the R' in formula (IB) may be the same or different, the CO groups bonded to R are at the ortho, meta or para positions, and n may be an integer of 1 or more.

[0015] In some embodiments, Y1 may include a structure represented by formula (IA) above or formula (IA-1) below. In some embodiments, Y1 may include a structure represented by formula (IB) above or formula (IB-1) below.

[0016] -[(CO)-R-(CO)-O-R''-O] n - formula (IA-1), -[(CO)-R-(CO)-O-R''-O-(CO)-O-R''-O] n - Formula (IB-1).

[0017] Wherein R" can be a C2-C4 aliphatic hydrocarbon, in some embodiments, the number-average molecular weight (Mn) of the aromatic polyester-polyether group in the first soft segment is about 450 g / mol or more. In some embodiments, the number-average molecular weight of the aromatic polyester-polyether group is about 900 g / mol, 1200 g / mol, 1600 g / mol, or 1900 g / mol or more. In some embodiments, the number-average molecular weight of the aromatic polyester-polyether group is about 2000 g / mol or less.

[0018] In some embodiments, the aromatic polyester-polyether group may comprise repeat 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 comprise repeat units of polyethylene terephthalate-polyether, polytrimethylene terephthalate-polyether, polybutylene terephthalate-polyether, or the like. In some embodiments, the aromatic polyester-polyether group may comprise repeat units of polyethylene terephthalate-polyether, polytrimethylene terephthalate-polyether, polybutylene terephthalate-polyether, or the like.

[0019] In some embodiments, the aromatic polyester-polyether group may be or may include a depolymerization product derived from the reaction of a polyester with a polyether polyol. In some embodiments, the depolymerization product of the polyester is obtained by depolymerizing a polyester with a polyether polyol. The polyester may be or may include, for example, polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), or the like.

[0020] In some embodiments, the aromatic polyester-polyether group may be or may 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 may include a depolymerization product derived from the depolymerization reaction of, 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 polyether polyol is 130 g / mol or more. In some embodiments, the polyether polyol includes an aliphatic polyol. In some embodiments, the polyether polyol includes diethylene glycol (DEG), triethylene glycol (TEG), or a combination thereof. In some embodiments, the depolymerization product may include a structure represented by Formula (A), Formula (B), and / or Formula (C): [ka] [ka] [ka] In the formula, nA, nB, nC, mA, mB, and mC are each an integer of 1 or more.

[0021] In some embodiments, the aromatic polyester-polyether group may be or may include a depolymerization product of a polyester and a polyether polyol, a polymer obtained by reacting the depolymerization product of a polyester and a polyether polyol with a carbonate ester, or a combination thereof. In some embodiments, the aromatic polyester-polyether group may be or may include a depolymerization product obtained by depolymerizing a polyether polyol with, 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 may include a polymer obtained by further reacting the depolymerization product with a carbonate ester. In some embodiments, the number average molecular weight of the polyether polyol is about 130 g / mol or more. In some embodiments, the carbonate ester includes dimethyl carbonate (DMC), ethylene carbonate (EC), propylene carbonate (PC), and diphenyl carbonate (DPC).

[0022] Polyester (e.g., polyethylene terephthalate (PET)) has the characteristics of high strength and long life, and is therefore widely used in daily necessities such as PET bottles and textile fibers. However, the disposal of large amounts of generated polyester waste is also a major problem. In recent years, with the international emphasis on environmental protection measures, various technologies for recovering and reusing plastic waste (e.g., polyester waste) have been developed in the industry, and how to effectively recover polyester waste and reuse it in polyester products has already become one of the research and development issues in the industry. In some embodiments of the present disclosure, the aromatic polyester-polyether group may be derived from or may contain the depolymerization product of polyester, and can be used as one of the raw materials to directly carry out a polymerization reaction to prepare polyurethane, which has the advantages of being environmentally friendly and reducing energy consumption.

[0023] In addition, the depolymerization product of polyester contains an aromatic polyester polyol group, and the aromatic polyester polyol group has a relatively high hydrophobicity, but the polyurethane for producing a waterproof moisture-permeable membrane has a high hydrophilicity, so that the depolymerization product of polyester is generally not used as a raw material for producing polyurethane. In contrast, according to some embodiments of the present disclosure, the aromatic polyester-polyether group may be or may contain a depolymerization product derived from the reaction of a polyester with at least one polyether polyol, so that the depolymerization product has both a polyether structure and an aromatic structure, is a fluid liquid at room temperature, and is advantageous for supplying materials for the polymerization reaction, and can improve the processability and convenience of the process step in which the polymerization reaction is performed. In addition, the polyether structure can improve the hydrophilicity, which helps to improve the moisture permeability of polyurethane and its products (e.g., waterproof moisture-permeable membranes).

[0024] In some embodiments, the first soft segment does not include an aliphatic dibasic acid group and a neopentyl glycol group. In some embodiments, the first soft segment does not include a reaction product of a polyester depolymerization product with an aliphatic dibasic acid (e.g., a C2-C4 dibasic acid). In some embodiments, the first soft segment does not include a reaction product of a polyester with neopentyl glycol.

[0025] According to some embodiments of the present disclosure, the first soft segment of the polyurethane does not include aliphatic dibasic acid groups and / or those derived from a reaction product of polyester and aliphatic dibasic acid, and since the structure of the aliphatic dibasic acid group induces partial crystallization and has high hardness, when used in polyurethane and products thereof (e.g., waterproof and moisture-permeable membranes), the touch is hard and the comfort of wearing is reduced. Therefore, the polyurethane and products thereof (e.g., waterproof and moisture-permeable membranes) of the present disclosure are soft to the touch, and the manufactured clothes have good wearing comfort. Also, according to some embodiments of the present disclosure, the first soft segment of the polyurethane does not include neopentyl glycol groups and / or those derived from a reaction product of polyester and neopentyl glycol, and since the structure of neopentyl glycol has high hydrophobicity, when used in polyurethane and products thereof (e.g., waterproof and moisture-permeable membranes), the moisture permeability is reduced. Therefore, the polyurethane and products thereof (e.g., waterproof and moisture-permeable membranes) of the present disclosure have high hydrophilicity and therefore good moisture permeability.

[0026] In some embodiments, the polyurethane may further include another soft segment (also referred to as a "second soft segment") different from the first soft segment. In some embodiments, the second soft segment may include an aliphatic polyether group. The second soft segment of the polyurethane may be referred to as an "aliphatic polyether segment."

[0027] In some embodiments, 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) may be about 3 or more. In some embodiments, the molar ratio of the first soft segment of the polyurethane to the second soft segment may be about 31.45 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 mol, the second soft segment is about 0.1 to 1 mol. In some embodiments, when the first soft segment is about 1 mol, the second soft segment is about 0.11 mol, about 0.3 mol, about 0.4 mol, about 0.5 mol, about 0.6 mol, about 0.7 mol, or about 0.8 mol.

[0028] In some embodiments, the second soft segment may include a structure represented by formula (II): -X2-Y2- Formula (II), wherein X2 may comprise at least one aromatic isocyanate group and Y2 may comprise an aliphatic polyether group. In some embodiments, X2 may comprise an aromatic diisocyanate group. For example, X2 may comprise the structure -[(CO)N-Rx-N(CO)]-, where Rx may be an aromatic group.

[0029] In some embodiments, Y2 may include a structure represented by formula (IIA): -[OR 1 ] m1 -O- Formula (IIA), In the formula, R 1 is a C2-C4 aliphatic hydrocarbon, m1 is an integer of 1 or more, and when m1 is an integer of 2 or more, R 1 may be the same or different each time.

[0030] In some embodiments, the number average molecular weight of the aliphatic polyether group in the second soft segment is 3000 g / mol or more. In some embodiments, the number average molecular weight of the aliphatic polyether group is 3000 g / mol to 9000 g / mol. In some embodiments, the number average molecular weight of the aliphatic polyether group is about 3000 g / mol, 3400 g / mol, 6000 g / mol, or 9000 g / mol or more. In some embodiments, the number average molecular weight of the aliphatic polyether group is about 10000 g / mol or less.

[0031] In some embodiments, the aliphatic polyether group may include a polyglycol group repeat unit. In some embodiments, the aliphatic polyether group may include a polyethylene glycol (PEG) group repeat unit, a polypropylene glycol (PPG) group repeat unit, a polytetramethylene ether glycol (PTMEG) group repeat 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.

[0032] In some embodiments, the aliphatic polyether group may be a repeat unit prepared from a polyether polyol. In some embodiments, the aliphatic polyether group may be or include a group or repeat unit prepared from polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether glycol (PTMEG), or any combination thereof.

[0033] In some embodiments, the hard segment may comprise a structure represented by formula (III): -X3-Y3- Formula (III), wherein X3 may comprise at least one aromatic isocyanate group. In some embodiments, X3 may comprise an aromatic diisocyanate group. For example, X3 may comprise the structure -[(CO)N-Rx-N(CO)]-, where Rx may be an aromatic group.

[0034] In some embodiments, Y3 may include a structure represented by formula (IIIA): -OR a -O- Formula (IIIA), In the formula, R a is an aliphatic hydrocarbon. In some embodiments, R a is a C2-C4 aliphatic hydrocarbon.

[0035] According to some embodiments of the present disclosure, the polyurethane further comprises a first soft segment (or an "aromatic polyester-polyether segment"), which can improve the hydrophilicity of the polyurethane due to the polyether structure, and can also improve the strength of the polyurethane due to the aromatic structure, thereby imparting high structural strength to the polyurethane, so that the polyurethane product (e.g., waterproof and moisture-permeable membrane) can have a water resistance of at least about 50 kgf / cm. 2 The elastic modulus may be

[0036] According to some embodiments of the present disclosure, the polyurethane further includes a second soft segment (or an aliphatic polyether segment) having a relatively high number average molecular weight, and the aliphatic polyether segment having a relatively high number average molecular weight can further improve the moisture permeability of a polyurethane product (e.g., a waterproof moisture permeable membrane). According to some embodiments of the present disclosure, the molar ratio of the first soft segment (or the aromatic polyester-polyether segment) to the second soft segment (or the aliphatic polyether segment) of the polyurethane satisfies the above-mentioned conditions, and thus the polyurethane can further have both high strength and hydrophilicity.

[0037] In some embodiments, "S1" represents the number of moles of the first soft segment (or aromatic polyester-polyether segment), "S2" represents the number of moles of the second soft segment, "H1" represents the number of moles of the hard segment, and "M1" represents the molar ratio of the first soft segment (or aromatic polyester-polyether segment) to the total of the hard segment, the first soft segment, and the second soft segment (M1 = (S1 / (H1 + S1 + S2)) * 100), where M1 is about 20 or less. In some embodiments, M1 is about 18, 17.5, or 17 or less. In some embodiments, M1 is about 9 or more. In some embodiments, M1 is about 9.2 or 9.5 or more.

[0038] In some embodiments, the present disclosure provides a waterproof / breathable membrane comprising the polyurethane described above. In some embodiments, the waterproof / breathable membrane has an elastic modulus of about 50 kgf / cm 2 In some embodiments, the waterproof / breathable membrane has a modulus of elasticity of about 52 kgf / cm 2 , 53kgf / cm 2 or 54kgf / cm 2 In some embodiments, the waterproof / breathable membrane has an elastic modulus of about 80 kgf / cm 2 In some embodiments, the waterproof / breathable membrane has an elastic modulus of about 75 kgf / cm 2 , 70kgf / cm 2 , 65kgf / cm 2 or 60kgf / cm 2 In some embodiments, the water vapor permeability of the waterproof and moisture permeable membrane is about 30,000 g / m 2 *Greater than 24hr. The "elastic modulus (or "100% elastic modulus")" described in this disclosure is the secant elastic modulus at 100% elongation, and the test method is in accordance with the ASTM D638 standard (Load Cell: 50N, Crosshead Speed: 200mm / min). The "moisture permeability" described in this disclosure is the moisture permeability of a sample at a temperature of 30°C and a humidity of 65% RH, and its unit is g / m 2*24 hours, measured according to the JIS L1099 B1 standard test method.

[0039] In some embodiments, the present disclosure provides a method for producing a polyurethane, which may include at least the steps of providing an isocyanate, a linear glycol, an aliphatic polyol (e.g., a polyether polyol having a long carbon chain) and an aromatic polyester-polyether polyol, mixing the isocyanate, the linear glycol, the aliphatic polyol and the aromatic polyester-polyether polyol to obtain a mixture, and subsequently heating the mixture to carry out a polymerization reaction to obtain a polyurethane.

[0040] 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 comprises 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, isocyan ...tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate and / or octamethylene diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate, tetramethylene diisocyanate, tetra 1,4-bis(isocyanatomethyl)cyclohexane (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, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and / or 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), 2,4-tolylene diisocyanate and / or 2,6-tolylene diisocyanate (TDI), o-tolidine diisocyanate (TODI), paraphenylene diisocyanate (PPDI), 1,2-diphenyl The isocyanate may include phenylethane 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 xylylene diisocyanate (TMXDI), or any combination thereof.

[0041] 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 about 3000 g / mol or more. In some embodiments, the number average molecular weight of the aliphatic polyether polyol is about 3000 g / mol, 3400 g / mol, 6000 g / mol, or 9000 g / mol or more. In some embodiments, the aliphatic polyether group may comprise a polyglycol group repeat unit. In some embodiments, the aliphatic polyether polyol may comprise a copolymer of polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene ether glycol (PTMEG), or any combination thereof. In some embodiments, the aliphatic polyether polyol may comprise PEG, co-PEG-PPG, co-PEG-PTMEG, or the like.

[0042] In some embodiments, the method for producing an aromatic polyester-polyether polyol may include at least the steps of providing a polyester, followed by adding a polyether polyol to the polyester, and depolymerizing the polyester, thereby obtaining an aromatic polyester-polyether polyol. In some embodiments, the alcohol number of the prepared aromatic polyester-polyether polyol is about 37.4 mg KOH / g or less. In some embodiments, the alcohol number of the prepared aromatic polyester-polyether polyol is about 37 mg KOH / g, 30 mg KOH / g, 20 mg KOH / g, 13 mg KOH / g, or 12.5 mg KOH / g or less. The "alcohol number" described in this disclosure refers to the number of milligrams (mg) of KOH required to neutralize the OH functional groups in 1 gram (g) of sample, and its unit is "mg KOH / g", and is measured according to the standard method of ASTM E1899-16.

[0043] In some embodiments, the number average molecular weight of the polyether polyol for polyester depolymerization is about 130 g / mol or more. In some embodiments, the polyether polyol includes an aliphatic polyol. In some embodiments, the polyether polyol includes diethylene glycol (DEG).

[0044] Providing the aromatic polyester-polyether polyol further includes, during the period in which the depolymerization step is performed, adding a carbonate compound to the intermediate product of the depolymerization step when the alcohol value of the intermediate product of the depolymerization step reaches 245 to 255 mgKOH / g to carry out a polymerization reaction, and terminating the reaction when the alcohol value reaches about 56 mgKOH / g to obtain the product.

[0045] In some other embodiments, the aromatic polyester-polyether polyol may be prepared by a polymerization reaction. In some embodiments, the aromatic polyester-polyether polyol may be prepared by a polymerization reaction using terephthalic acid (TPA), ethylene glycol (EG), and polyethylene glycol (PEG).

[0046] In some embodiments, the method for preparing the polyurethane may include a chain extender, which may include an aliphatic compound and / or an aromatic compound. In some embodiments, the chain extender may include a diamine and / or an alkanediol, for example, a C2-C8 alkanediol, or may only have primary hydroxyl groups. In some embodiments, a linear glycol is used as a chain extender in the polymerization reaction. In some embodiments, the chain extender may include 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 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(2-hydroxyethyl)ether (HQEE), or any combination thereof. In some embodiments, the chain extender includes an amine compound, so that the prepared polyurethane has a high elastic modulus. In some embodiments, the chain extender may not include an amine compound because the first soft segment (or aromatic polyester-polyether segment) of the polyurethane already contains an aromatic structure, which helps to improve the elastic modulus of the polyurethane.

[0047] In some embodiments, the mixture is heated to cause a polymerization reaction to proceed, resulting in a polyurethane. In some embodiments, the hard segments of the polyurethane are formed by polymerization reaction of the chain extender group with an isocyanate (e.g., an aromatic diisocyanate). In some embodiments, the first soft segment (or aromatic polyester-polyether segment) of the polyurethane is formed by polymerization reaction of the aromatic polyester-polyether polyol with an isocyanate (e.g., an aromatic diisocyanate). In some embodiments, the second soft segment (or aliphatic polyether segment) of the polyurethane is formed by polymerization reaction of the aliphatic polyol with an isocyanate (e.g., an aromatic diisocyanate). This forms the polyurethane of the present disclosure.

[0048] The present disclosure is further described by the following examples and comparative examples, which are merely illustrative and should not be construed as limiting the practice of the present disclosure.

[0049] [Raw materials] <Isocyanate>: 4,4'-diphenylmethane diisocyanate (MDI), a product of Tosoh Millionate MT, Japan.

[0050] The <Aliphatic polyol> is shown in Table 1 below.

[0051] [Table 1]

[0052] The <aromatic polyester-polyether polyol> is shown in Table 2 below.

[0053] [Table 2]

[0054] The manufacturing process of "rPET041" is as follows: PET (100g, 0.52mol), DEG (138g, 1.30mol) and zinc acetate (0.1g, 0.1wt% based on PET) are placed in a 500mL round-bottom flask, the reactants are heated to 200°C under nitrogen atmosphere to start the depolymerization reaction, the alcohol value of the reactants is tracked, and when the alcohol value reaches 250±5mgKOH / g, the reaction is terminated, and aromatic polyester-polyether polyol "rPET041" is obtained.

[0055] The manufacturing process of "rPET201" is as follows: PET (100g, 0.52mol), DEG (138g, 1.30mol) and zinc acetate (0.1g, 0.1wt% of PET) are put into a 500mL round-bottom flask, the reactants are heated to 200°C under nitrogen atmosphere to start the depolymerization reaction, the alcohol value of the reactants is kept tracked, when the alcohol value is 250±5mgKOH / g, the pressure of the reaction atmosphere in the round-bottom flask is adjusted to 2torr, and the reaction is continued, when the alcohol value of the reactants is 56.1±3mgKOH / g, the reaction is terminated, and the aromatic polyester-polyether polyol "rPET201" is obtained at this time.

[0056] In some embodiments, the reaction process for depolymerizing PET to obtain "rPET201" and "rPET041" is represented by the reaction formula (IV) below. [ka] In the formula, n 1 and n 2 are integers equal to or greater than 1, and n 1 >n 2 "rPET201" and "rPET041" have the same structure, n 2 Only the value and number average molecular weight are different.

[0057] The manufacturing process of "PCrP201" is 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 flask, and the reactants are heated to 200°C under nitrogen atmosphere to start the depolymerization reaction, and the alcohol value of the reactants is tracked. When the alcohol value is 250±5mgKOH / g, dimethyl carbonate (37.47g, 0.42mol) is added to the reactants, and the reaction temperature is adjusted to 150°C, and the pressure of the reaction atmosphere in the round-bottom flask is adjusted to 30torr, and the reaction is continued. When the alcohol value of the reactants is 56.1±3mgKOH / g, the reaction is terminated, and aromatic polyester-polyether polyol "PCrP201" is obtained at this time.

[0058] In some embodiments, the reaction process of further reacting the depolymerization product of PET with dimethyl carbonate (DMC) to form "PCrP201" is represented by the reaction formula represented by the following formula (V).

Chemical formula

[0059] <Chain extender>: Ethylene glycol (EG), manufactured by Donglian Chemical Co., Ltd.

[0060] <S solvent>: Dimethylacetamide (DMAc), manufactured by Acros

[0061] [Polymerization reaction]

[0062] [Examples 1 to 7 and Comparative Examples 1 to 7] Weigh 16.283 g of PEG9000, 16.397 g of aromatic polyester-polyether polyol "rPET201", 2.477 g of aromatic polyester-polyether polyol "rPET041", 4.151 g of EG and 56 g of solvent DMAc. Put the above compounds into a glass reaction tank and react under nitrogen. Set the stirring rotation speed to 100 rpm. While continuing to stir, add 20.691 g of MDI. Set the temperature of the reaction system to 70°C and start the reaction at this time. After the viscosity of the reactant increases and the Weissenberg effect occurs, add 104 g of solvent DMAc to completely dissolve the product in the solvent. At this time, the total amount of the product is 200 g and the solid content is 30 wt%.

[0063] The preparation process is described above using Example 1 as an example, and the polymerization steps are the same in Examples 1 to 7 and Comparative Examples 1 to 7, with only the types and amounts of reactant raw materials being different. The experimental conditions for the polymerization steps in Examples 1 to 7 and Comparative Examples 1 to 7 and the physical properties of the prepared polyurethanes are shown in Tables 3, 4A, and 4B below.

[0064] Table 3 shows the amounts of raw materials used (ie, the amounts of each reactant added) in Examples 1 to 7 and Comparative Examples 1 to 7, expressed by weight in grams (g).

[0065] [Table 3]

[0066] In Tables 4A and 4B, "H1:S2:S1" indicates the molar ratio of the hard segment:second soft segment:first soft segment in the polyurethane, "S2 / S1" indicates the molar ratio of the second soft segment to the first soft segment in the polyurethane, "H1 / S1" indicates the molar ratio of the hard segment to the first soft segment in the polyurethane, "X1", "X2", "X3", "Y1", "Y2" and "Y3" indicate different groups, "M1" indicates the molar ratio of the first soft segment to the total of the hard segment, the first soft segment and the second soft segment (M1=(S1 / (H1+S1+S2))*100), the unit of "100% elastic modulus" is "kgf / cm2", and the unit of "moisture permeability" is "g / m 2 *24hr". "100% elastic modulus" is the secant elastic modulus at 100% elongation, and the test method is in accordance with the ASTM D638 standard (Load Cell: 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 was measured in accordance with JIS L1099 B1. "100% elastic modulus" and "moisture permeability" in Table 4B were both measured for samples with a film thickness of 20μm.

[0067] [Table 4A]

[0068] [Table 4B]

[0069] As can be seen from the results in Tables 3, 4A and 4B above, in some embodiments, when the molar ratio of the hard segment to the first soft segment (or aromatic polyester-polyether segment) of the polyurethane satisfies the aforementioned conditions of the present disclosure (e.g., is 4.5 or more), the polyurethane has a viscosity of at least about 50 kgf / cm 2 As can be seen from the results of Tables 3, 4A and 4B above, in some examples, when the number average molecular weight of the aliphatic polyol (Y2) is greater than 3000 g / mol, the polyurethane can have an elastic modulus of about 30000 g / m 2 *It can have a moisture permeability of 24 hours.

[0070] In some comparative examples, the derivative "rPHB05" series of aliphatic polyol (Y1) produced from recycled plastic bottles (PET) has the reaction formula represented by the following formula (VI). [ka] In the formula, Rn and Rm are derived from a diol compound, an amino alcohol compound, or a combination thereof, the diol compound includes an aliphatic diol, an aromatic diol, or a polyether diol, and the amino alcohol compound includes an aliphatic mono-ol mono-amine or an aromatic mono-ol mono-amine.

[0071] The polyurethane waterproofing films of Comparative Examples 6 to 7 were produced using derivatives of recycled PET bottles as starting materials. The derivatives "rPHB05_600" and "rPHB05_1000" have the reaction formula represented by the following formula (VII), in which n 4 +m 4The properties of "rPHB05_600" and "rPHB05_1000" are shown in Table 5. [ka]

[0072] [Table 5]

[0073] The first soft segment (aromatic polyester-polyether group) of the polyurethane waterproof membrane of Comparative Example 6 has a chemical structure represented by the following formula (VIII) and has a number average molecular weight of 600 g / mol. [ka]

[0074] In general, the chemical structures of formula (VII) and formula (VIII) above are chemical structures formed after decomposing PET using polyether diol. As can be seen from the results of Comparative Example 6, when polyurethane is synthesized using the above structures, the polyurethane obtained has a relatively high elastic modulus, but its moisture permeability is insufficient. As can be seen from the results of Comparative Example 7, when the molecular weight of polyether diol is increased to improve the moisture permeability, the improvement in moisture permeability is small and the elastic modulus is greatly reduced, so that the water pressure resistance property is impaired.

[0075] In contrast, the first soft segment (aromatic polyester-polyether group) used in Example 4 has a chemical structure represented by the following formula (IX). [ka]

[0076] Therefore, the polyurethane waterproof membranes of Examples 1 to 5 can simultaneously have sufficient moisture permeability and elastic modulus, and the above structure has a relatively high proportion of recycled materials, making it environmentally friendly and more effective in reducing carbon dioxide emissions.

[0077] Furthermore, as can be seen from the results of Comparative Example 5 and Example 7, when the molecular weight of the second soft segment (aliphatic polyether segment) is relatively low, the polyurethane prepared therefrom also has low moisture permeability.

[0078] Although the present disclosure has been disclosed as the above-mentioned embodiment, the above-mentioned embodiment does not limit the present disclosure. Those skilled in the art may make some changes and modifications without departing from the spirit and scope of the present disclosure. Therefore, the scope of protection of the present disclosure is based on the content specified in the claims. In addition, each claim constitutes an independent embodiment, and the combination of each claim and the embodiment is included in the scope of the present disclosure.

Claims

1. A waterproof and moisture-permeable membrane comprising polyurethane, the polyurethane comprising a hard segment, a first soft segment and a second soft segment, the first soft segment comprising an aromatic polyester-polyether group, the waterproof and moisture-permeable membrane having an elastic modulus of about 50 kgf / cm ２ and the moisture permeability is about 30,000 g / m ２ * When the first soft segment is about 1 mole and the first soft segment is greater than 24 hours, the hard segment is about 4.5 moles or more; The first soft segment comprises a structure represented by the following formula (I): -X1-Y1- Formula (I), In the formula, X1 contains at least one aromatic isocyanate group, Y1 contains the aromatic polyester-polyether group, and Y1 contains a structure represented by the following formula (IA) or formula (IB): -[(CO)-R-(CO)-O-R'-O] ｎ - formula (IA), -[(CO)-R-(CO)-O-R'-O-(CO)-O-R'-O] ｎ - Formula (IB), In the formula, R is an aromatic group, R' is a polyether group, R' in formula (IB) may be the same or different, CO groups bonded to R are at the ortho, meta or para positions, and n is an integer of 1 or more. The second soft segment includes a structure represented by the following formula (II): -X2-Y2- Formula (II), In the formula, X2 includes at least one aromatic isocyanate group, Y2 includes an aliphatic polyether group, and the number average molecular weight of the aliphatic polyether group is about 3000 g / mol or more, and Y2 includes a structure represented by the following formula (IIA): - [O-R １ ｍ１ -O- formula (IIA),​ In the formula, R １ is a C2-C4 aliphatic hydrocarbon, m1 is an integer of 1 or more, and when m1 is an integer of 2 or more, R １ The waterproof and breathable membrane may be the same or different each time.

2. 2. The waterproof / breathable membrane of claim 1, wherein when the first soft segment is about 1 mole, the hard segment is about 10 moles or less.

3. The waterproof and moisture permeable membrane according to claim 1, wherein the number average molecular weight of the aromatic polyester-polyether group is about 450 g / mol or more.

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

5. The hard segment includes a structure represented by the following formula (III): -X3-Y3- Formula (III), In the formula, X3 includes at least one aromatic isocyanate group, and Y3 includes a structure represented by the following formula (IIIA): -O-R ａ -O- of formula (IIIA), In the formula, R ａ The waterproof and moisture permeable membrane according to claim 1, wherein the aryl group is a C2-C4 aliphatic hydrocarbon.

6. The elastic modulus is about 80 kgf / cm ２ The waterproof and moisture permeable membrane according to claim 1, wherein:

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 molar ratio of the number of moles of the first soft segment to the number of moles of the hard segment, the number of moles of the first soft segment, and the number of moles of the second soft segment is M1, which is expressed as M1 = (S1 / (H1 + S1 + S2)) * 100, where S1 is the number of moles of the first soft segment, S2 is the number of moles of the second soft segment, and H1 is the number of moles of the hard segment, and in the formula, M1 is about 20 or less. The waterproof and moisture permeable membrane of claim 1.

9. 2. The waterproof and moisture permeable membrane according to claim 1, wherein the first soft segment is about 1 mole, and the second soft segment is about 0.1 to 1 mole.

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