Bio-based polyurethane resin, preparation method thereof and bio-based high-moisture-permeability waterproof membrane

Abstract

The invention relates to the technical field of polyurethane material synthesis, in particular to bio-based polyurethane resin, a preparation method thereof and a bio-based high-moisture-permeability waterproof film. The bio-based polyurethane resin comprises main materials, and the main materials comprise the following raw materials in percentage by mass: 100% of bio-based polyether polyol, polyether glycol, diisocyanate and a chain extender; the molecular weight of the polyether glycol is 1000 to 6000 g / mol; the chain extender comprises a chain extender A and a chain extender B; the chain extender A comprises at least one of a sulfonate chain extender and a sulfonamide chain extender; and the chain extender B comprises at least one of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, bio-based 1, 3-propylene glycol and bio-based 1, 4-butanediol. The bio-based polyurethane resin provided by the invention has high bio-based content and excellent moisture permeability and hydrostatic pressure.

Description

Technical Field

[0001] The present invention relates to the technical field of polyurethane material synthesis, in particular to a bio-based polyurethane resin and a preparation method thereof, and a bio-based high-moisture-permeable waterproof membrane. Background Art

[0002] A moisture-permeable waterproof membrane is a functional film with selective permeability, allowing the passage of gaseous water molecules (water vapor) while effectively blocking the penetration of liquid water. This selective permeability makes this membrane valuable for applications in a variety of fields, including clothing, healthcare, and personal care products.

[0003] Currently, breathable waterproof membranes on the market are primarily categorized into three main categories: polytetrafluoroethylene (PTFE), thermoplastic polyurethane (TPU), and polyurethane (PU). PTFE membranes achieve their breathable and waterproof properties primarily through their microporous structure and surface hydrophobicity. They also possess excellent chemical stability and weather resistance. However, their poor processing stability, poor elasticity of the finished product, and resistance to natural degradation severely limit their application. TPU membranes, manufactured through casting, calendering, or blow molding, are widely favored in the market for their excellent elasticity and low price. However, TPU membranes rely on an "adsorption-diffusion" moisture permeability mechanism, resulting in limited moisture permeability, making them difficult to meet the stringent requirements of high-end outdoor equipment and medical protective equipment.

[0004] With the increasingly stringent environmental protection requirements, the development of bio-based breathable waterproof membranes has become a research hotspot. Compared with traditional petroleum-based materials, bio-based polymers made from renewable biomass (such as castor oil, corn starch, etc.) have the advantages of low carbon footprint and renewable nature. However, the inventors found that the moisture permeability of bio-based PU membranes is negatively correlated with the bio-based content. For example, the bio-based PU membrane prepared with bio-based polytrimethylene ether glycol has a national standard inverted cup method moisture permeability of only 7000 g / (m 2 24 hours), which is only about half the national standard inverted cup moisture permeability of existing ordinary PU membranes. Therefore, the development of a bio-based breathable waterproof membrane with high moisture permeability and simple processing is of great significance to promoting the green transformation of the industry.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The present invention aims to provide a bio-based polyurethane resin, a preparation method thereof, and a bio-based highly breathable waterproof membrane. The bio-based polyurethane resin of the present invention has both a high biobased content and high breathability, resolving the current issue of bio-based polyurethane membranes, which struggle to achieve both biobased content and breathability.

[0007] In order to achieve the above-mentioned object of the present invention, the first aspect of the present invention provides a bio-based polyurethane resin, including a main ingredient, wherein the main ingredient includes the following raw materials in percentage by weight: Bio-based polyether polyols 21%~53%; Polyether diol 9.5%~43%; Diisocyanate 20%~35%; Chain extender 5%~12%; The molecular weight of the polyether glycol is 1000-6000 g / mol; The chain extender includes chain extender A and chain extender B, and the molar ratio of chain extender A to chain extender B is (0.3-1.5):1; The chain extender A comprises at least one of a sulfonate chain extender and a sulfonamide chain extender; The chain extender B includes at least one of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, bio-based 1,3-propylene glycol, and bio-based 1,4-butanediol.

[0008] Furthermore, the bio-based polyurethane resin has a bio-based content of 25 wt% to 52 wt%.

[0009] Furthermore, the molecular weight of the polyether diol is 3000-5000 g / mol.

[0010] Furthermore, the polyether glycol includes at least one of polyethylene glycol, polypropylene glycol and polyethylene oxide-propylene oxide glycol.

[0011] Furthermore, the sulfonate chain extender includes at least one of sodium 1,4-dihydroxy-2-butanesulfonate and sodium 2,3-dihydroxypropane-1-sulfonate; and the sulfonamide chain extender includes at least one of sulfonamide and p-aminobenzenesulfonamide.

[0012] Furthermore, the molar ratio of the chain extender A to the polyether diol is (2.1-13.5):1, and further is (2.8-12):1.

[0013] Furthermore, the bio-based polyether polyol includes at least one of bio-based polytrimethylene ether glycol (PO3G) and bio-based polytetramethylene ether glycol (PTMEG).

[0014] Furthermore, the molecular weight of the bio-based polyether polyol is 500-2800 g / mol.

[0015] Furthermore, the diisocyanate includes at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dimethyl diphenyl diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate and dicyclohexylmethane diisocyanate.

[0016] Furthermore, the method further comprises a solvent, wherein the solvent comprises an aprotic polar solvent.

[0017] Furthermore, the solvent includes at least one of N,N-dimethylformamide, acetone, cyclohexanone, tetrahydrofuran and dioxane.

[0018] Furthermore, the solid content of the bio-based polyurethane resin is 30% to 35%.

[0019] Furthermore, the bio-based polyurethane resin also includes auxiliary materials, and the auxiliary materials account for 1% to 10% of the mass of the main material.

[0020] Furthermore, the auxiliary material includes a hydrophilic additive, which includes at least one of disodium cocoyl monoethanolamide sulfosuccinate, sodium succinate monooctadecylamide sulfonate, and organosilicon.

[0021] Furthermore, in the bio-based polyurethane resin, the hydrophilic additive accounts for 1.6% to 10% of the mass of the main material.

[0022] Furthermore, the auxiliary material includes a capping agent, which includes at least one of methanol, ethanol, isopropanol and sodium bisulfite.

[0023] Furthermore, in the bio-based polyurethane resin, the end-capping agent is 0.1% to 1% by mass of the main material.

[0024] The second aspect of the present invention provides a method for preparing the bio-based polyurethane resin provided in the first aspect of the present invention, comprising the following steps: Bio-based polyether polyol, polyether diol, chain extender, diisocyanate, solvent, optional catalyst and optional antioxidant are mixed and reacted. When the viscosity of the reaction system reaches 40-60 Pa·s / 25°C, a blocking agent is optionally added for end blocking. After the viscosity of the resin stabilizes, a hydrophilic additive is added and mixed to obtain the bio-based polyurethane resin.

[0025] The third aspect of the present invention provides a bio-based high moisture permeability waterproof membrane, comprising the bio-based polyurethane resin provided by the first aspect of the present invention.

[0026] Furthermore, the thickness of the bio-based high moisture permeability waterproof membrane is 0.015~0.020mm.

[0027] The fourth aspect of the present invention provides a method for preparing the bio-based highly moisture-permeable waterproof membrane provided in the third aspect of the present invention, comprising the steps of coating and drying a slurry containing a bio-based polyurethane resin to form the bio-based highly moisture-permeable waterproof membrane.

[0028] Furthermore, the slurry containing bio-based polyurethane resin includes bio-based polyurethane resin, solvent and matting powder.

[0029] Furthermore, in the slurry containing the bio-based polyurethane resin, the amount of the solvent is 45 wt% to 55 wt% of the bio-based polyurethane resin.

[0030] Furthermore, the amount of the matting powder is 2 wt% to 5 wt% of the bio-based polyurethane resin.

[0031] Furthermore, in the slurry containing the bio-based polyurethane resin, the solvent includes at least one of N,N-dimethylformamide, ethyl acetate and methyl ethyl ketone.

[0032] Furthermore, the drying temperature is 120-150°C.

[0033] Compared with the prior art, the present invention has the following beneficial effects: (1) In the bio-based polyurethane resin of the present invention, a specific chain extender is compounded with a polyether diol having a certain molecular weight, and the polyether diol aggregates in the polyurethane molecular chain to form a molecular scaffold channel. After the chain extender quickly absorbs moisture, it is introduced into the molecular scaffold channel formed by the polyether diol, so that the bio-based polyurethane resin of the present invention has excellent moisture permeability and hydrostatic pressure while having a high bio-based content.

[0034] (2) The bio-based high moisture permeability waterproof membrane prepared by using the bio-based polyurethane resin of the present invention not only has excellent moisture permeability and hydrostatic pressure, but also can alleviate the precipitation of auxiliary materials and additives in the waterproof membrane and improve the performance stability of the waterproof membrane. DETAILED DESCRIPTION

[0035] The technical scheme of the present invention will be clearly and completely described below in conjunction with specific embodiments, but it will be understood by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work premise belong to the scope of protection of the present invention. Those who do not specify specific conditions in the embodiments are carried out according to normal conditions or the conditions recommended by the manufacturer. Those whose reagents or instruments are not specified by the manufacturer are conventional products that can be purchased commercially.

[0036] The first aspect of the present invention provides a bio-based polyurethane resin, including a main ingredient, wherein the main ingredient comprises the following raw materials in percentage by weight: Bio-based polyether polyols 21%~53%; Polyether diol 9.5%~43%; Diisocyanate 20%~35%; Chain extender 5%~12%; The molecular weight of polyether diol is 1000~6000g / mol; The chain extender includes chain extender A and chain extender B, and the molar ratio of chain extender A to chain extender B is (0.3~1.5) : 1; The chain extender A comprises at least one of a sulfonate chain extender and a sulfonamide chain extender; The chain extender B includes at least one of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, bio-based 1,3-propylene glycol, and bio-based 1,4-butanediol.

[0037] In the bio-based polyurethane resin of the present invention, a specific chain extender is compounded with a polyether diol having a certain molecular weight. The polyether diol aggregates in the polyurethane molecular chain to form a molecular scaffold channel. The chain extender A quickly absorbs moisture and then introduces it into the molecular scaffold channel formed by the polyether diol. As a result, the bio-based polyurethane resin of the present invention has excellent moisture permeability, moisture permeability rate, and hydrostatic pressure while having a high bio-based content.

[0038] For example, in different embodiments, the mass percentage of each component in the main material of the bio-based polyurethane resin can be as follows: The content of the bio-based polyether polyol can be 21%, 25%, 30%, 35%, 40%, 45%, 50%, 53%, or any two thereof. The bio-based polyether polyol content within the above range not only has good environmental advantages, but also can cooperate with other components to impart excellent moisture permeability to the bio-based polyurethane resin. The content of the polyether diol can be 9.5%, 10%, 11%, 15%, 20%, 25%, 30%, 35%, 40%, 43%, or any two thereof. When the content of the polyether diol is within the above range, the hydrophilic chain segments of the polyether diol increase the hydrophilic groups in the polyurethane resin molecular chain. Furthermore, the polyether diol, combined with its own molecular weight, increases its aggregation in the polyurethane resin molecular chain, forming molecular scaffold channels, thereby synergistically enhancing moisture permeability. The content of diisocyanate can be 20%, 22%, 25%, 28%, 30%, 32%, 35%, or any two thereof; the content of diisocyanate is regulated within the above range to take into account the mechanical properties, moisture permeability and hydrostatic pressure of the polyurethane resin; The content of the chain extender can be 5%, 6%, 8%, 10%, 12% or a range consisting of any two thereof; wherein the molar ratio of chain extender A to chain extender B can be 0.3:1, 0.35:1, 0.4:1, 0.45:1, 0.5:1, 0.55:1, 0.6:1, 0.65:1, 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.15:1, 1.2:1, 1 .25:1, 1.3:1, 1.35:1, 1.4:1, 1.45:1 or 1.5:1 or a range consisting of any two of them; a certain amount of sulfonate chain extender and / or sulfonamide chain extender is introduced into the chain extender of the present invention, which can quickly absorb moisture and introduce the molecular scaffold channel formed by polyether diol to improve its moisture permeability; the ratio of chain extender A and chain extender B is regulated to meet the above conditions, so as to take into account the improvement of moisture permeability, hydrostatic pressure and long-term stability.

[0039] In a specific embodiment of the present invention, the bio-based polyurethane resin has a biobased content of 25 wt% to 52 wt%, for example, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 46 wt%, 47 wt%, 48 wt%, 49 wt%, 50 wt%, 51 wt%, 52 wt%, or any combination thereof. The biobased content is calculated as follows: biobased content = (mass of bio-based polyether polyol + mass of bio-based chain extender) / mass of the main ingredient.

[0040] The present invention regulates the molecular weight of the polyether diol to be between 1000 and 6000 g / mol, for example, 1000 g / mol, 2000 g / mol, 3000 g / mol, 4000 g / mol, 5000 g / mol, 6000 g / mol, or any combination thereof, to achieve a better balance between hydrostatic pressure and moisture permeability. When the molecular weight of the polyether diol is less than 1000 g / mol, although the polyether diol is evenly distributed in the polyurethane resin molecular chain, the effect on improving moisture permeability is not significant. When the molecular weight of the polyether diol is greater than 6000 g / mol, the hydrostatic pressure decreases significantly. In some specific embodiments of the present invention, the molecular weight of the polyether diol is between 3000 and 5000 g / mol. The degree of aggregation of the polyether diol in the polyurethane resin molecular chain increases, forming molecular scaffold channels. When combined with a chain extender, the moisture permeability is significantly improved while maintaining the hydrostatic pressure.

[0041] In a specific embodiment of the present invention, the polyether glycol includes at least one of polyethylene glycol (PEG), polypropylene glycol (PPG) and polyethylene oxide-propylene oxide glycol (PEG-PPG).

[0042] In a specific embodiment of the present invention, the sulfonate chain extender includes at least one of sodium 1,4-dihydroxy-2-butanesulfonate and sodium 2,3-dihydroxypropane-1-sulfonate; the sulfonamide chain extender includes at least one of sulfonamide and p-aminobenzenesulfonamide.

[0043] In a specific embodiment of the present invention, the molar ratio of chain extender A to polyether diol is (2.1-13.5):1, such as 2.1:1, 2.5:1, 2.8:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 13.5:1, or a range consisting of any two thereof, preferably (2.8-12):1. Chain extender A introduces hydrophilic sulfonic acid and / or sulfonamide groups into the molecular chains of the polyurethane resin, allowing rapid moisture absorption and introduction into the molecular scaffolding channels formed by the polyether diol. Further controlling the molar ratio of chain extender A to polyether diol within the above range helps to fully utilize the synergistic effect of the sulfonic acid and / or sulfonamide groups with the polyether diol.

[0044] In a specific embodiment of the present invention, the bio-based polyether polyol includes at least one of bio-based polytrimethylene ether glycol (PO3G) and bio-based polytetramethylene ether glycol (PTMEG).

[0045] In a specific embodiment of the present invention, the molecular weight of the bio-based polyether polyol is 500-2800 g / mol, such as 500 g / mol, 1000 g / mol, 2000 g / mol, 2800 g / mol or any two thereof.

[0046] In a specific embodiment of the present invention, the diisocyanate includes at least one of toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dimethyl diphenyl diisocyanate (TODI), naphthalene diisocyanate (NDI), p-phenylene diisocyanate (PPDI) and dicyclohexylmethane diisocyanate (HMDI).

[0047] In a specific embodiment of the present invention, the bio-based polyurethane resin further includes a solvent. The solvent includes an aprotic polar solvent. Further, the solvent includes at least one of N,N-dimethylformamide (DMF), acetone (ACE), cyclohexanone (CYC), tetrahydrofuran (THF), and dioxane.

[0048] In a specific embodiment of the present invention, the solid content of the bio-based polyurethane resin is 30% to 35%.

[0049] In a specific embodiment of the present invention, the bio-based polyurethane resin further includes auxiliary materials, and the auxiliary materials account for 1% to 10% of the mass of the main material.

[0050] In a specific embodiment of the present invention, the auxiliary material includes a hydrophilic additive. The hydrophilic additive includes at least one of cocoyl monoethanolamide sulfosuccinate disodium salt, sodium succinate monooctadecylamide sulfonate, and organosilicon. The hydrophilic additive of the present invention contains amide and sulfonic groups, which can form hydrogen bonds with the polyurethane resin molecular chains, enhancing moisture permeability. It also contributes to synergistic effects with the molecular scaffold channel formed by the polyether diol, increasing long-term stability. Furthermore, the hydrophilic additive structure is similar to that of chain extender A, which can reduce precipitation of the auxiliary additive.

[0051] In a specific embodiment of the present invention, the hydrophilic additive in the bio-based polyurethane resin comprises 1.6% to 10% by weight of the main material, for example, 1.6%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, or any combination thereof. The hydrophilic additive can be added directly or dispersed in a solvent (e.g., DMF).

[0052] In a specific embodiment of the present invention, the auxiliary material includes a capping agent, which includes at least one of methanol, ethanol, isopropanol and sodium bisulfite.

[0053] In a specific embodiment of the present invention, in the bio-based polyurethane resin, the end-capping agent accounts for 0.1% to 1% of the mass of the main material, for example, it can be 0.1%, 0.3%, 0.5%, 0.6%, 0.8%, 1% or any two thereof.

[0054] In a specific embodiment of the present invention, the bio-based polyurethane resin further comprises at least one of a catalyst and an antioxidant.

[0055] Catalysts include conventional catalysts used in the polyurethane resin production field, including but not limited to tertiary amine catalysts and organometallic catalysts, such as zinc and bismuth composite catalysts. Antioxidants include but are not limited to phosphite antioxidants, such as ALKANOX™ 240 (tris(2,4-di-tert-butylphenyl) phosphite), Antioxidant 168, and Antioxidant 626.

[0056] In specific embodiments of the present invention, other conventional additives used in the polyurethane resin field may also be included, such as any one or more of UV absorbers, light stabilizers, leveling agents, and lubricants. The addition of additives is sufficient as long as they do not degrade the bio-based polyurethane resin of the present invention. The method for adding additives is not particularly limited and can be accomplished by known methods such as direct addition and mixing during the reaction, or melt blending or direct blending during subsequent processing.

[0057] The second aspect of the present invention provides a method for preparing the bio-based polyurethane resin provided in the first aspect of the present invention, comprising the following steps: Bio-based polyether polyol, polyether diol, chain extender, diisocyanate, solvent, optional catalyst and optional antioxidant are mixed and reacted. When the viscosity of the reaction system reaches 40-60 Pa·s / 25°C, a blocking agent is optionally added for end-blocking. After the viscosity of the resin stabilizes, a hydrophilic additive is added and mixed to obtain a bio-based polyurethane resin.

[0058] In a specific embodiment of the present invention, during the mixing reaction, the reaction temperature is 60-90°C.

[0059] The third aspect of the present invention provides a bio-based high moisture permeability waterproof membrane, comprising the bio-based polyurethane resin provided by the first aspect of the present invention.

[0060] In a specific embodiment of the present invention, the thickness of the bio-based high moisture permeability waterproof membrane is 0.015-0.020 mm, such as 0.015 mm, 0.018 mm, 0.020 mm, etc.

[0061] The fourth aspect of the present invention provides a method for preparing the bio-based highly moisture-permeable waterproof membrane provided by the third aspect of the present invention, comprising the following steps: coating and drying a slurry containing a bio-based polyurethane resin to form a bio-based highly moisture-permeable waterproof membrane.

[0062] In a specific embodiment of the present invention, the slurry containing the bio-based polyurethane resin includes the bio-based polyurethane resin, a solvent, and a matting agent.

[0063] In a specific embodiment of the present invention, in the slurry containing the bio-based polyurethane resin, the amount of the solvent used is 45 wt% to 55 wt% of the bio-based polyurethane resin, such as 45 wt%, 48 wt%, 50 wt%, 52 wt%, 55 wt% or any two thereof.

[0064] In a specific embodiment of the present invention, the amount of matting agent used is 2 wt% to 5 wt% of the bio-based polyurethane resin, such as 2 wt%, 3 wt%, 4 wt%, 5 wt% or any two thereof.

[0065] In a specific embodiment of the present invention, in the slurry containing the bio-based polyurethane resin, the solvent includes at least one of N,N-dimethylformamide (DMF), ethyl acetate (EAC) and methyl ethyl ketone (MEK).

[0066] In a specific embodiment of the present invention, the drying temperature is 120-150°C.

[0067] The present invention provides an optional method for preparing a bio-based highly moisture-permeable waterproof membrane, comprising: coating a slurry containing a bio-based polyurethane resin on a release paper, drying at 120-150°C, and removing the release paper to obtain a bio-based highly moisture-permeable waterproof membrane.

[0068] Sources of raw materials in the examples: Bio-based polytrimethylene ether glycol (PO3G), SK Chemicals Co., Ltd., South Korea; Bio-based polytetramethylene ether glycol (PTMEG), Huafeng Chemical Co., Ltd.; PEG-PPG copolymer, with 60% PEG and 40% PPG; Matting agent, Evonik AEROSIL R208; Cocoyl monoethanolamide sulfosuccinate disodium salt: CAS 61791-66-0; Sodium succinate monooctadecylamide sulfonate: CAS 14481-60-8; Silicone hydrophilic additive: Guangzhou Silok New Materials Co., Ltd., Silok®8008.

[0069] Examples 1 to 12 The method for preparing the bio-based polyurethane resin of the embodiment comprises the following steps: A bio-based polyether polyol, polyether diol, and antioxidant (a phosphite antioxidant such as Antioxidant 168, 0.2% by weight of the main material) were added to a reaction vessel. The mixture was heated to 90°C, vacuum-dried, and stirred until uniformly dissolved. An appropriate amount of solvent (enough to ensure dissolution of all components), a chain extender, a diisocyanate, and a catalyst (a zinc-bismuth composite catalyst, 0.1% by weight of the main material) were then added. The reaction was continued at 60-90°C (e.g., 70-75°C). During this reaction, solvent was added to control the solids content of the reaction system to 30%-35% and the viscosity to 40-60 Pa·s / 25°C. An end-capping agent was optionally added. After the viscosity stabilized, a hydrophilic additive was added and mixed until uniformly dissolved to produce a bio-based polyurethane resin. The raw material components for Examples 1-12 are shown in Tables 1-2.

[0070] Table 1 Information on the components of Examples 1 to 6 (amount in g)

[0071] Note: In Table 1, the main ingredients refer to bio-based polyether polyol, polyether diol, diisocyanate, and chain extender; the system solid content refers to the solid content of the system before the addition of the end-capping agent. The same applies to the following tables.

[0072] Table 2 Information on the components of Examples 7 to 12 (amount in g)

[0073] Comparative Example 1 Comparative Example 1 is prepared in the same manner as Example 1, except that the type and amount of the chain extender are different. The chain extender in Comparative Example 1 is bio-based 1,3-propylene glycol, and the amount used is 33.5 g.

[0074] Comparative Example 2 Comparative Example 2 was prepared by referring to Example 2, except that the type and amount of the chain extender were different. In Comparative Example 2, the chain extender was ethylene glycol, and the amount used was 24.4 g.

[0075] Comparative Example 3 Comparative Example 3 is prepared in the same manner as Example 1, except that the type and amount of the chain extender are different. The chain extender in Comparative Example 3 is sodium 2,3-dihydroxypropane-1-sulfonate, and the amount used is 78.5 g.

[0076] Comparative Example 4 Comparative Example 4 follows the same preparation method as Example 2, differing only in the amounts of bio-based polyether polyol PO3G, polyether diol, and diisocyanate MDI. In Comparative Example 4, 280 g of bio-based polyether polyol PO3G, 20 g of polyether diol, and 125 g of diisocyanate MDI were used, resulting in a biobased content of 59%.

[0077] Experimental example The bio-based polyurethane resins of different embodiments and comparative examples were made into waterproof membrane samples. The preparation of the waterproof membrane samples included: taking 100 g of bio-based polyurethane resin, 50 g of DMF, and 3 g of Evonik AEROSIL R208 matting powder, stirring them evenly and degassing them to obtain a slurry; using a 0.15 mm scraping rod to scrape the slurry onto the surface of a plain matte release paper, and then placing it in a 135°C oven for 3 minutes, and removing the release paper to obtain a waterproof membrane sample with a thickness of 0.018 mm.

[0078] The following tests were performed on different samples, and the test results are shown in Table 3.

[0079] (1) Water vapor transmission rate: refer to GB / T 12704.2 Method B inverted cup method to test the water vapor transmission rate of the sample; (2) Hydrostatic pressure: Test the hydrostatic pressure of the sample with reference to GB / T 4744-2013; (3) 100% modulus: The 100% modulus of the sample was tested with reference to ASTM D412; (4) Long-term moisture permeability stability: The samples were washed in a drum washing machine under the same conditions in the quick wash mode for 30 minutes, and then the water vapor permeability of the samples was tested with reference to the inverted cup method in GB / T 12704.2 Method B.

[0080] Table 3 Performance test results

[0081] From the above test results, it can be seen that the bio-based high moisture permeability waterproof membrane prepared by using the bio-based polyurethane resin of the present invention has excellent moisture permeability, waterproofness and long-term moisture permeability stability.

[0082] The test results of Example 1 and Examples 5 to 8 show that by further controlling the molecular weight of the polyether diol, a better balance can be achieved between hydrostatic pressure and moisture permeability. Specifically, when an equimolar or equal-mass polyether diol with a molecular weight of 1000 g / mol is used in Examples 5 to 6 to replace the polyether diol with a molecular weight of 3000 g / mol in Example 1, the molecular weight of the polyether diol is lower, which helps to improve the uniformity of the distribution of the polyether diol and thus increase the hydrostatic pressure, but the effect of improving the moisture permeability is relatively insignificant. Among them, the significant deterioration of moisture permeability in Example 5 is not only due to the low molecular weight of the polyether diol, but also due to the reduced content of the polyether diol. When an equimolar or equal-mass polyether diol with a molecular weight of 6000 g / mol is used in Examples 7 to 8 to replace the polyether diol with a molecular weight of 3000 g / mol in Example 1, the molecular weight of the polyether diol is higher, which leads to a decrease in hydrostatic pressure.

[0083] The test results of Examples 2-3 and Examples 9-10 show that further regulating the molar ratio of chain extender A to polyether diol can help to fully exert the synergistic effect of sulfonic acid and / or sulfonamide groups and polyether diol; specifically, compared with Example 3, Example 9 reduces the amount of chain extender A 2,3-dihydroxypropane-1-sodium sulfonate, and its molar ratio to polyether diol is 2.1:1, resulting in deterioration of the moisture permeability, hydrostatic pressure and long-term moisture permeability stability of the sample; compared with Example 2, Example 10 increases the amount of chain extender A p-aminobenzenesulfonamide, and its molar ratio to polyether diol is approximately 13.1:1, resulting in deterioration of the moisture permeability, hydrostatic pressure and long-term moisture permeability stability of the sample.

[0084] Example 11 uses an equimolar amount of methanol to replace the sodium bisulfite in Example 1. The test results of the two show that using sodium bisulfite for end-capping can improve moisture permeability and long-term moisture permeability stability compared to methanol.

[0085] Example 12 uses an equal mass of silicone hydrophilic additive to replace the sodium monooctadecanamide sulfonate in Example 1. The test results of the two show that compared with the silicone hydrophilic additive, the amide group and sulfonic group contained in the sodium monooctadecanamide sulfonate can form hydrogen bonds with the polyurethane resin molecular chain, which is more helpful to enhance the moisture permeability, and can synergistically enhance the molecular scaffold channel formed by polyether diol to increase long-term stability.

[0086] It can be seen from the test results of Examples 1 to 2 and Comparative Examples 1 to 3 that the present invention helps to improve moisture permeability, hydrostatic pressure and long-term stability by compounding chain extender A and chain extender B; specifically, compared with Example 1, Comparative Example 1 uses only chain extender B bio-based 1,3-propylene glycol, when its molar amount is the same as the sum of the molar amounts of chain extender A and chain extender B in Example 1, which will cause the moisture permeability and long-term moisture permeability stability in the sample to deteriorate significantly; compared with Example 2, Comparative Example 2 uses only chain extender B ethylene glycol, when its molar amount is the same as the sum of the molar amounts of chain extender A and chain extender B in Example 1, which will also cause the moisture permeability and long-term moisture permeability stability in the sample to deteriorate significantly; compared with Example 1, Comparative Example 3 uses only chain extender A 2,3-dihydroxypropane-1-sulfonate sodium, when its molar amount is the same as the sum of the molar amounts of chain extender A and chain extender B in Example 1, which will cause the hydrostatic pressure and long-term moisture permeability stability in the sample to deteriorate significantly.

[0087] It can be seen from the test results of Example 2 and Comparative Example 4 that when the amount of bio-based polyether polyol used is too much, the moisture permeability of the sample will be significantly deteriorated.

[0088] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the above embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the above embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. Bio-based polyurethane resin, characterized in that Including the main ingredients, based on 100% by mass, the main ingredients include the following raw materials in percentage by mass: Bio-based polyether polyols 21%~53%; Polyether diol 9.5%~43%; Diisocyanate 20%~35%; Chain extender 5%~12%; The molecular weight of the polyether glycol is 1000-6000 g / mol; The chain extender includes chain extender A and chain extender B, and the molar ratio of chain extender A to chain extender B is (0.3-1.5):1; The chain extender A comprises at least one of a sulfonate chain extender and a sulfonamide chain extender; The chain extender B includes at least one of ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, bio-based 1,3-propylene glycol, and bio-based 1,4-butanediol.

2. The bio-based polyurethane resin according to claim 1, characterized in that The bio-based polyurethane resin has a bio-based content of 25 wt% to 52 wt%; Preferably, the molecular weight of the polyether diol is 3000-5000 g / mol; Preferably, the polyether glycol includes at least one of polyethylene glycol, polypropylene glycol and polyethylene oxide-propylene oxide glycol.

3. The bio-based polyurethane resin according to claim 1, characterized in that The sulfonate chain extender includes at least one of 1,4-dihydroxy-2-butane sodium sulfonate and 2,3-dihydroxypropane-1-sodium sulfonate; The sulfonamide chain extender includes at least one of sulfonamide and p-aminobenzenesulfonamide; Preferably, the molar ratio of the chain extender A to the polyether diol is (2.1-13.5):1, preferably (2.8-12):

1.

4. The bio-based polyurethane resin according to claim 1, characterized in that The bio-based polyether polyol includes at least one of bio-based polytrimethylene ether glycol and bio-based polytetramethylene ether glycol; Preferably, the molecular weight of the bio-based polyether polyol is 500-2800 g / mol; Preferably, the diisocyanate includes at least one of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dimethyl diphenyl diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate and dicyclohexylmethane diisocyanate.

5. The bio-based polyurethane resin according to claim 1, characterized in that Also includes solvents; Preferably, the solvent comprises an aprotic polar solvent; Preferably, the solvent comprises at least one of N,N-dimethylformamide, acetone, cyclohexanone, tetrahydrofuran and dioxane; Preferably, the solid content of the bio-based polyurethane resin is 30% to 35%.

6. The bio-based polyurethane resin according to claim 1, characterized in that It also includes auxiliary materials, which account for 1% to 10% of the mass of the main material; Preferably, the auxiliary material includes a hydrophilic auxiliary agent; Preferably, the hydrophilic adjuvant includes at least one of disodium coconut oil monoethanolamide sulfosuccinate, sodium succinate monooctadecylamide sulfonate and silicone; Preferably, in the bio-based polyurethane resin, the hydrophilic additive accounts for 1.6% to 10% of the mass of the main material; Preferably, the excipient includes a capping agent; Preferably, the capping agent includes at least one of methanol, ethanol, isopropanol and sodium bisulfite; Preferably, in the bio-based polyurethane resin, the end-capping agent accounts for 0.1% to 1% of the mass of the main material.

7. The method for preparing a bio-based polyurethane resin according to any one of claims 1 to 6, wherein: The method comprises the following steps: mixing and reacting a bio-based polyether polyol, a polyether diol, a chain extender, a diisocyanate, a solvent, an optional catalyst and an optional antioxidant; when the viscosity of the reaction system reaches 40-60 Pa·s / 25°C, optionally adding a blocking agent for blocking; and then adding a hydrophilic additive and mixing to obtain the bio-based polyurethane resin.

8. A bio-based highly moisture-permeable waterproof membrane, characterized in that: The bio-based polyurethane resin comprises the bio-based polyurethane resin according to any one of claims 1 to 6.

9. The bio-based highly moisture-permeable waterproof membrane according to claim 8, characterized in that: The thickness of the bio-based high moisture permeability waterproof membrane is 0.015-0.020 mm.

10. The method for preparing a bio-based highly moisture-permeable waterproof membrane according to claim 8 or 9, wherein: The method comprises the following steps: coating and drying a slurry containing a bio-based polyurethane resin to form the bio-based highly moisture-permeable waterproof membrane; Preferably, the slurry containing bio-based polyurethane resin comprises bio-based polyurethane resin, solvent and matting powder; Preferably, the amount of the solvent is 45 wt% to 55 wt% of the bio-based polyurethane resin; Preferably, the amount of the matting agent is 2 wt% to 5 wt% of the bio-based polyurethane resin; Preferably, the solvent comprises at least one of N,N-dimethylformamide, ethyl acetate and methyl ethyl ketone; Preferably, the drying temperature is 120-150°C.

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