技术领域Technical Field
本发明涉及布料防水剂领域，尤其是涉及一种耐候性聚氨酯防水剂及其制备方法。The invention relates to the field of fabric waterproofing agents, and in particular to a weather-resistant polyurethane waterproofing agent and a preparation method thereof.
背景技术Background technique
为了满足纺织品在雨天、暑天、高温等特殊环境中的使用，织物的防水处理尤为重要。防水处理是织物后整理的重要工序，是通过将防水剂涂覆在织物表面，从而赋予织物表面疏水性，使织物具有防水功能。In order to meet the use of textiles in special environments such as rainy days, hot days, and high temperatures, the waterproof treatment of fabrics is particularly important. Waterproofing is an important process in fabric finishing. It is to apply a waterproofing agent on the surface of the fabric to give the fabric surface hydrophobicity and make the fabric waterproof.
防水剂可以有效地阻止水分渗透到织物内部，保持织物的干燥和清洁。聚氨酯分子中含有亲水软段和疏水硬段，可以用于织物的防水透湿处理。聚氨酯防水剂是由异氰酸酯、多元醇等经过加成聚合反应形成的预聚体，再配以催化剂、助剂、溶剂等，经过混合等工序加工成的。聚氨酯防水剂强度高、延展率好、对面料表面变形的适应能力强。Waterproofing agents can effectively prevent moisture from penetrating into the fabric, keeping the fabric dry and clean. Polyurethane molecules contain hydrophilic soft segments and hydrophobic hard segments, which can be used for waterproof and breathable treatment of fabrics. Polyurethane waterproofing agents are prepolymers formed by addition polymerization of isocyanates, polyols, etc., and then mixed with catalysts, additives, solvents, etc. Polyurethane waterproofing agents have high strength, good elongation, and strong adaptability to fabric surface deformation.
聚氨酯防水剂通常使用油性溶剂溶解，油性聚氨酯具有耐磨、柔韧性好、防水透湿性能好的优点。但随着环保的原因，水性聚氨酯防水剂逐步取代了油性聚氨酯，但水性聚氨酯防水剂在防水性、耐候性和稳定性方面存在不足。Polyurethane waterproofing agents are usually dissolved in oily solvents. Oily polyurethane has the advantages of wear resistance, good flexibility, and good waterproof and breathable properties. However, due to environmental protection reasons, water-based polyurethane waterproofing agents have gradually replaced oily polyurethanes, but water-based polyurethane waterproofing agents have deficiencies in waterproofness, weather resistance and stability.
发明内容Summary of the invention
为了改善水性聚氨酯防水剂的防水性、耐候性和稳定性，本申请提供一种耐候性聚氨酯防水剂及其制备方法。In order to improve the waterproofness, weather resistance and stability of a water-based polyurethane waterproofing agent, the present application provides a weather-resistant polyurethane waterproofing agent and a preparation method thereof.
本申请提供的一种耐候性聚氨酯防水剂及其制备方法采用如下的技术方案：The present application provides a weather-resistant polyurethane waterproofing agent and a preparation method thereof using the following technical solutions:
第一方面，本申请提供一种耐候性聚氨酯防水剂，包括以下重量份的原料：In a first aspect, the present application provides a weather-resistant polyurethane waterproofing agent, comprising the following raw materials in parts by weight:
通过采用上述技术方案，在聚氨酯的制备中，通过丙烯酸酯和纳米纤维素晶须混合对聚氨酯进行接枝改性，丙烯酸酯单体与聚氨酯进行交联，可以提高聚氨酯防水剂的抗水性和力学性能，有利于强力和断裂伸长率的提升。纳米纤维素晶须作为纳米填料，分散在交联结构中，起到补强作用，提高了聚氨酯防水剂的强度、耐腐蚀性和耐候性。通过纳米纤维素晶须和丙烯酸酯协同分散，减少团聚现象，使得聚氨酯防水剂更加稳定，整理后的织物具有良好的防水透湿性能和良好的力学性能。By adopting the above technical scheme, in the preparation of polyurethane, polyurethane is grafted and modified by mixing acrylate and nanocellulose whiskers, and acrylate monomers are cross-linked with polyurethane, which can improve the water resistance and mechanical properties of polyurethane waterproofing agent, and is conducive to the improvement of strength and elongation at break. Nanocellulose whiskers are dispersed in the cross-linked structure as nanofillers, which play a reinforcing role and improve the strength, corrosion resistance and weather resistance of polyurethane waterproofing agent. Through the coordinated dispersion of nanocellulose whiskers and acrylates, the agglomeration phenomenon is reduced, making the polyurethane waterproofing agent more stable, and the finished fabric has good waterproof and breathable properties and good mechanical properties.
可选的，所述丙烯酸酯选用甲基丙烯酸羟乙酯和甲基丙烯酸月桂酯按照质量比为(0.7-0.9):(1.1-1.3)进行混合的混合物。Optionally, the acrylic ester is a mixture of hydroxyethyl methacrylate and lauryl methacrylate in a mass ratio of (0.7-0.9):(1.1-1.3).
通过采用上述技术方案，甲基丙烯酸羟乙酯含有亲水性的羟基基团，有利于水蒸气的通过，从而有利于透湿性的提高，甲基丙烯酸月桂酯为疏水性分子，有利于抗水性的提升，通过混合比例使得聚氨酯防水剂的防水透湿性能和综合性能较佳。By adopting the above technical scheme, hydroxyethyl methacrylate contains a hydrophilic hydroxyl group, which is beneficial to the passage of water vapor, thereby improving the moisture permeability. Lauryl methacrylate is a hydrophobic molecule, which is beneficial to the improvement of water resistance. Through the mixing ratio, the waterproof and moisture permeability and comprehensive performance of the polyurethane waterproofing agent are better.
可选的，所述纳米纤维素晶须选用改性纳米纤维素晶须，所述改性纳米纤维素晶须包括以下重量份的原料：Optionally, the nanocellulose whiskers are modified nanocellulose whiskers, and the modified nanocellulose whiskers include the following raw materials in parts by weight:
纳米纤维素晶须5-8份；5-8 parts of nanocellulose whiskers;
硅烷偶联剂G-570 9-15份；Silane coupling agent G-570 9-15 parts;
乙酸2-5份。2-5 parts of acetic acid.
通过采用上述技术方案，选用硅烷偶联剂G-570对纳米纤维素晶须进行改性，促进纳米纤维素晶须在交联体系中的分散，减少纳米纤维素晶须的团聚现象，使得防水剂成膜更加致密，同时有机硅的表面能极低，防水剂整理织物后成膜，有机硅可以迁移到膜表面，使得织物的耐水性得到提升。By adopting the above technical scheme, the silane coupling agent G-570 is selected to modify the nanocellulose whiskers, so as to promote the dispersion of the nanocellulose whiskers in the cross-linking system and reduce the agglomeration of the nanocellulose whiskers, so that the film of the waterproofing agent is denser. At the same time, the surface energy of silicone is extremely low. After the waterproofing agent is used to finish the fabric, the silicone can migrate to the surface of the film, so that the water resistance of the fabric is improved.
可选的，所述二元醇选择聚乙二醇、聚四氢呋喃、聚碳酸酯二元醇和聚己内酯二元醇的一种或多种。Optionally, the diol is selected from one or more of polyethylene glycol, polytetrahydrofuran, polycarbonate diol and polycaprolactone diol.
可选的，所述二元醇选用含磷氮聚醚二元醇，所述含磷氮聚醚二元醇由以下原料制备而成：Optionally, the diol is a phosphorus-nitrogen-containing polyether diol, and the phosphorus-nitrogen-containing polyether diol is prepared from the following raw materials:
甲基膦酸二甲酯 20-26份；20-26 parts of dimethyl methylphosphonate;
二乙醇胺 24-30份；Diethanolamine 24-30 parts;
二月桂酸二丁基锡 0.2-0.3份。Dibutyltin dilaurate 0.2-0.3 parts.
通过采用上述技术方案，二元醇中含有磷氮，二元醇具有阻燃功能，从而使得聚氨酯防水剂可以充当阻燃整理剂。By adopting the above technical solution, phosphorus and nitrogen are contained in the diol, and the diol has a flame retardant function, so that the polyurethane waterproofing agent can serve as a flame retardant finishing agent.
可选的，所述二异氰酸酯选用甲苯二异氰酸酯、二环己基甲烷二异氰酸酯和异佛尔酮二异氰酸酯的一种或多种。Optionally, the diisocyanate is selected from one or more of toluene diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate.
可选的，所述扩链剂选用二羟甲基丙酸、三乙醇胺、乙二胺和二乙烯三胺的一种或多种；Optionally, the chain extender is selected from one or more of dimethylol propionic acid, triethanolamine, ethylenediamine and diethylenetriamine;
所述催化剂选用二月桂酸二丁基锡或辛酸亚锡中的一种；The catalyst is selected from dibutyltin dilaurate or stannous octoate;
所述中和剂选用三乙胺、氨水或醋酸中的一种；The neutralizing agent is selected from one of triethylamine, ammonia water or acetic acid;
所述封端剂选用内酰胺或亚硫酸氢钠中的一种。The end-capping agent is selected from one of lactam and sodium bisulfite.
第二方面，本申请提供一种耐候性聚氨酯防水剂的制备方法，包括如下步骤：In a second aspect, the present application provides a method for preparing a weather-resistant polyurethane waterproofing agent, comprising the following steps:
步骤1、对二元醇进行脱水处理，将脱水后的二元醇、纳米纤维素晶须、催化剂进行混合，并加入二异氰酸酯反应得到聚氨酯预聚体；Step 1, dehydrating the diol, mixing the dehydrated diol, nanocellulose whiskers, and a catalyst, and adding diisocyanate to react to obtain a polyurethane prepolymer;
步骤2、向聚氨酯预聚体中加入扩链剂反应，加入封端剂反应后再加入丙烯酸酯进行反应，得到改性聚氨酯；Step 2, adding a chain extender to the polyurethane prepolymer for reaction, adding a capping agent for reaction, and then adding acrylate for reaction to obtain a modified polyurethane;
步骤3、向改性聚氨酯中加入中和剂中和至pH值为7-8，最后再加入去离子水在高剪切力下进行乳化，得到聚氨酯防水剂。Step 3: Add a neutralizing agent to the modified polyurethane to neutralize it to a pH value of 7-8, and finally add deionized water to emulsify it under high shear force to obtain a polyurethane waterproofing agent.
通过采用上述技术方案，聚氨酯防水剂的合成方法，环保安全，并且步骤简单。By adopting the above technical scheme, the synthesis method of the polyurethane waterproofing agent is environmentally friendly and safe, and the steps are simple.
可选的，当所述纳米纤维素晶须选用改性纳米纤维素晶须时，所述改性纳米纤维素晶须的制备步骤如下：Optionally, when the nanocellulose whiskers are modified nanocellulose whiskers, the preparation steps of the modified nanocellulose whiskers are as follows:
称取硅烷偶联剂G-570，加入一定体积的乙醇水溶液，其中乙醇和水的质量比为8：2，用乙酸调节pH在3.5-4.5，搅拌进行水解；将纳米纤维素晶须加入溶液中，搅拌2-3h，将混合物进行洗涤，离心干燥得到改性纳米纤维素晶须。Weigh the silane coupling agent G-570, add a certain volume of ethanol aqueous solution, wherein the mass ratio of ethanol to water is 8:2, adjust the pH to 3.5-4.5 with acetic acid, and stir for hydrolysis; add nanocellulose whiskers to the solution, stir for 2-3 hours, wash the mixture, and centrifuge and dry to obtain modified nanocellulose whiskers.
通过采用上述技术方案，通过选用乙醇水溶液，并且加入乙酸将溶液呈现为酸性，使得硅烷偶联剂与纳米纤维素晶须充分接触，提高纳米纤维素晶须的接枝率。By adopting the above technical solution, by selecting an ethanol aqueous solution and adding acetic acid to make the solution acidic, the silane coupling agent is fully in contact with the nanocellulose whiskers, thereby improving the grafting rate of the nanocellulose whiskers.
可选的，当所述二元醇选用含磷氮聚醚二元醇时，所述含磷氮聚醚二元醇的制备步骤如下：Optionally, when the diol is a phosphorus-nitrogen-containing polyether diol, the preparation steps of the phosphorus-nitrogen-containing polyether diol are as follows:
称取甲基膦酸二甲酯和二月桂酸二丁基锡混合，加热至110-120℃，滴入二乙醇胺反应2-3h，使用真空泵抽除甲醇，冷却至室温，得到含磷氮聚醚二元醇。Weigh dimethyl methylphosphonate and dibutyltin dilaurate, mix them, heat to 110-120° C., drop diethanolamine into them and react for 2-3 hours, remove methanol with a vacuum pump, and cool to room temperature to obtain phosphorus-nitrogen-containing polyether diol.
通过采用上述技术方案，通过甲基膦酸二甲酯和二乙醇胺进行酯交换反应，制得含磷氮聚醚二元醇。By adopting the technical scheme, dimethyl methylphosphonate and diethanolamine are subjected to ester exchange reaction to prepare phosphorus-nitrogen-containing polyether diol.
综上所述，本申请具有以下有益效果：In summary, this application has the following beneficial effects:
1.通过丙烯酸酯和纳米纤维素晶须混合对聚氨酯进行接枝改性，丙烯酸酯单体与聚氨酯进行交联，可以提高聚氨酯防水剂的抗水性和力学性能，有利于强力和断裂伸长率的提升。纳米纤维素晶须作为纳米填料，分散在交联结构中，起到补强作用，提高了聚氨酯防水剂的强度、耐腐蚀性和耐候性。通过纳米纤维素晶须和丙烯酸酯协同分散，减少团聚现象，使得聚氨酯防水剂更加稳定，整理后的织物具有良好的防水透湿性能和良好的力学性能。1. The polyurethane is grafted and modified by mixing acrylate and nanocellulose whiskers. The acrylate monomer is cross-linked with the polyurethane, which can improve the water resistance and mechanical properties of the polyurethane waterproofing agent, and is conducive to the improvement of strength and elongation at break. Nanocellulose whiskers, as nanofillers, are dispersed in the cross-linked structure, playing a reinforcing role, improving the strength, corrosion resistance and weather resistance of the polyurethane waterproofing agent. The synergistic dispersion of nanocellulose whiskers and acrylates reduces the agglomeration phenomenon, making the polyurethane waterproofing agent more stable, and the finished fabric has good waterproof and moisture permeability and good mechanical properties.
2.甲基丙烯酸羟乙酯含有亲水性的羟基基团，有利于水蒸气的通过，从而有利于透湿性的提高，甲基丙烯酸月桂酯为疏水性分子，有利于抗水性的提升，通过混合比例使得聚氨酯防水剂的防水透湿性能和综合性能较佳。2. Hydroxyethyl methacrylate contains a hydrophilic hydroxyl group, which is beneficial to the passage of water vapor, thereby improving moisture permeability. Lauryl methacrylate is a hydrophobic molecule, which is beneficial to improving water resistance. Through the mixing ratio, the waterproof and moisture permeability and comprehensive performance of the polyurethane waterproofing agent are better.
具体实施方式Detailed ways
以下结合实施例1-11和对比例1-2对本申请作进一步详细说明。The present application is further described in detail below in conjunction with Examples 1-11 and Comparative Examples 1-2.
制备例Preparation Example
制备例1Preparation Example 1
一种改性纳米纤维素晶须的制备Preparation of modified nanocellulose whiskers
分别称取9g硅烷偶联剂G-570，然后加入30g乙醇水溶液(乙醇/水：8/2)，用2g乙酸调节pH为3.5，在室温下磁力搅拌，水解30min。称取5g纳米纤维素晶须，加入到水解完成的硅烷偶联剂溶液中，继续磁力搅拌2h。最后将混合物洗涤3—5次，离心收集沉淀，干燥3h，得到改性纳米纤维素晶须。Weigh 9g of silane coupling agent G-570, then add 30g of ethanol aqueous solution (ethanol/water: 8/2), adjust the pH to 3.5 with 2g of acetic acid, stir magnetically at room temperature, and hydrolyze for 30min. Weigh 5g of nanocellulose whiskers, add them to the hydrolyzed silane coupling agent solution, and continue to stir magnetically for 2h. Finally, wash the mixture 3-5 times, collect the precipitate by centrifugation, and dry for 3h to obtain modified nanocellulose whiskers.
制备例2Preparation Example 2
一种改性纳米纤维素晶须的制备Preparation of modified nanocellulose whiskers
分别称取15g硅烷偶联剂G-570，然后加入50g乙醇水溶液(乙醇/水：8/2)，用5g乙酸调节pH为4.5，在室温下磁力搅拌，水解30min。称取8g纳米纤维素晶须，加入到水解完成的硅烷偶联剂溶液中，继续磁力搅拌3h。最后将混合物洗涤3—5次，离心收集沉淀，干燥3h，得到改性纳米纤维素晶须。Weigh 15g of silane coupling agent G-570, then add 50g of ethanol aqueous solution (ethanol/water: 8/2), adjust the pH to 4.5 with 5g of acetic acid, stir magnetically at room temperature, and hydrolyze for 30min. Weigh 8g of nanocellulose whiskers, add them to the hydrolyzed silane coupling agent solution, and continue to stir magnetically for 3h. Finally, wash the mixture 3-5 times, collect the precipitate by centrifugation, and dry for 3h to obtain modified nanocellulose whiskers.
制备例3Preparation Example 3
一种含磷氮聚醚二元醇的制备Preparation of a phosphorus-nitrogen-containing polyether diol
称取20g甲基膦酸二甲酯和0.2g催化剂二月桂酸二丁基锡装入四口烧瓶中，并通入氮气排出烧瓶中的空气，将烧瓶搅拌加热至110℃。随后用恒压滴液漏斗将24g二乙醇胺缓缓加入烧瓶中，保温反应2h，然后使用真空泵将残余的甲醇抽去，并冷却至室温，即得到含磷氮聚醚二元醇。20 g of dimethyl methylphosphonate and 0.2 g of catalyst dibutyltin dilaurate were weighed and placed in a four-necked flask, and nitrogen was introduced to expel the air in the flask, and the flask was stirred and heated to 110° C. Subsequently, 24 g of diethanolamine was slowly added to the flask using a constant pressure dropping funnel, and the reaction was kept warm for 2 h, and then the residual methanol was removed using a vacuum pump, and the mixture was cooled to room temperature to obtain a phosphorus-nitrogen-containing polyether diol.
制备例4Preparation Example 4
一种含磷氮聚醚二元醇的制备Preparation of a phosphorus-nitrogen-containing polyether diol
称取26g甲基膦酸二甲酯和0.3g催化剂二月桂酸二丁基锡装入四口烧瓶中，并通入氮气排出烧瓶中的空气，将烧瓶搅拌加热至120℃。随后用恒压滴液漏斗将30g二乙醇胺缓缓加入烧瓶中，保温反应3h，然后使用真空泵将残余的甲醇抽去，并冷却至室温，即得到含磷氮聚醚二元醇。26 g of dimethyl methylphosphonate and 0.3 g of catalyst dibutyltin dilaurate were weighed and placed in a four-necked flask, and nitrogen was introduced to expel the air in the flask, and the flask was stirred and heated to 120° C. Subsequently, 30 g of diethanolamine was slowly added to the flask using a constant pressure dropping funnel, and the reaction was kept warm for 3 h, and then the residual methanol was removed using a vacuum pump, and the mixture was cooled to room temperature to obtain a phosphorus-nitrogen-containing polyether diol.
实施例Example
实施例1Example 1
一种聚氨酯防水剂的制备Preparation of a polyurethane waterproofing agent
步骤1、将12g聚乙二醇加入到连接有搅拌装置的反应容器中，将反应容器内的聚乙二醇升温至100℃后进行抽真空脱水处理，处理20min，完成后降温至30℃，得到脱水后的聚乙二醇。Step 1: Add 12 g of polyethylene glycol to a reaction vessel connected to a stirring device, heat the polyethylene glycol in the reaction vessel to 100° C. and perform vacuum dehydration for 20 minutes. After completion, cool the temperature to 30° C. to obtain dehydrated polyethylene glycol.
在氮气的保护下，将脱水后的聚乙二醇、1g纳米纤维素晶须、0.02g辛酸亚锡加入到装有温度计、搅拌器的四颈瓶中，升温至75℃，向四颈瓶中滴加4g甲苯二异氰酸酯反应2h，得到聚氨酯预聚体。Under the protection of nitrogen, dehydrated polyethylene glycol, 1 g of nanocellulose whiskers and 0.02 g of stannous octoate were added to a four-necked flask equipped with a thermometer and a stirrer, the temperature was raised to 75°C, 4 g of toluene diisocyanate was added dropwise to the four-necked flask and reacted for 2 h to obtain a polyurethane prepolymer.
步骤2、向聚氨酯预聚体中加入1.2g二羟甲基丙酸反应0.5h，加入一定量丁酮降低粘度，加入2g亚硫酸氢钠反应0.5h后再加入3g甲基丙烯酸羟乙酯进行反应1h，加入一定量丁酮降粘，得到改性聚氨酯。Step 2: add 1.2 g of dimethylolpropionic acid to the polyurethane prepolymer and react for 0.5 h, add a certain amount of butanone to reduce the viscosity, add 2 g of sodium bisulfite and react for 0.5 h, then add 3 g of hydroxyethyl methacrylate and react for 1 h, add a certain amount of butanone to reduce the viscosity, and obtain a modified polyurethane.
步骤3、向改性聚氨酯中加入0.5g乙二胺中和至pH值为7，最后再加入60g去离子水在高剪切力下进行乳化，得到聚氨酯防水剂。Step 3: add 0.5 g of ethylenediamine to the modified polyurethane to neutralize to a pH value of 7, and finally add 60 g of deionized water to emulsify under high shear force to obtain a polyurethane waterproofing agent.
实施例2Example 2
一种聚氨酯防水剂的制备Preparation of a polyurethane waterproofing agent
步骤1、将15g聚四氢呋喃加入到连接有搅拌装置的反应容器中，将反应容器内的聚四氢呋喃升温至110℃后进行抽真空脱水处理，处理30min，完成后降温至45℃，得到脱水后的聚四氢呋喃。Step 1, add 15g of polytetrahydrofuran into a reaction container connected with a stirring device, heat the polytetrahydrofuran in the reaction container to 110°C and then perform vacuum dehydration treatment for 30 minutes, and then cool to 45°C to obtain dehydrated polytetrahydrofuran.
在氮气的保护下，将脱水后的聚四氢呋喃、3g纳米纤维素晶须、0.05g二月桂酸二丁基锡加入到装有温度计、搅拌器的四颈瓶中，升温至85℃，向四颈瓶中滴加10g异佛尔酮二异氰酸酯反应2.5h，得到聚氨酯预聚体。Under the protection of nitrogen, dehydrated polytetrahydrofuran, 3 g of nanocellulose whiskers, and 0.05 g of dibutyltin dilaurate were added to a four-necked flask equipped with a thermometer and a stirrer, the temperature was raised to 85°C, and 10 g of isophorone diisocyanate was added dropwise to the four-necked flask for reaction for 2.5 h to obtain a polyurethane prepolymer.
步骤2、向聚氨酯预聚体中加入2.5g二乙烯三胺反应1h，加入一定量丁酮降低粘度，加入4g内酰胺反应0.5h后再加入8g甲基丙烯酸甲酯进行反应1.5h，加入一定量丁酮降粘，得到改性聚氨酯。Step 2: Add 2.5 g of diethylenetriamine to the polyurethane prepolymer and react for 1 h, add a certain amount of butanone to reduce the viscosity, add 4 g of lactam and react for 0.5 h, then add 8 g of methyl methacrylate and react for 1.5 h, add a certain amount of butanone to reduce the viscosity, and obtain a modified polyurethane.
步骤3、向改性聚氨酯中加入1g氨水中和至pH值为8，最后再加入70g去离子水在高剪切力下进行乳化，得到聚氨酯防水剂。Step 3: add 1 g of ammonia water to the modified polyurethane to neutralize it to a pH value of 8, and finally add 70 g of deionized water to emulsify it under high shear force to obtain a polyurethane waterproofing agent.
实施例3Example 3
一种聚氨酯防水剂的制备Preparation of a polyurethane waterproofing agent
步骤1、将13g聚碳酸酯二元醇加入到连接有搅拌装置的反应容器中，将反应容器内的聚碳酸酯二元醇升温至110℃后进行抽真空脱水处理，处理30min，完成后降温至30℃，得到脱水后的聚碳酸酯二元醇。Step 1: Add 13 g of polycarbonate diol into a reaction vessel connected to a stirring device, heat the polycarbonate diol in the reaction vessel to 110° C. and perform vacuum dehydration for 30 minutes. After completion, cool the temperature to 30° C. to obtain dehydrated polycarbonate diol.
在氮气的保护下，将脱水后的聚碳酸酯二元醇、2g纳米纤维素晶须、0.04g二月桂酸二丁基锡加入到装有温度计、搅拌器的四颈瓶中，升温至80℃，向四颈瓶中滴加7g异佛尔酮二异氰酸酯反应2.5h，得到聚氨酯预聚体。Under the protection of nitrogen, the dehydrated polycarbonate diol, 2 g of nanocellulose whiskers, and 0.04 g of dibutyltin dilaurate were added to a four-necked flask equipped with a thermometer and a stirrer, the temperature was raised to 80°C, and 7 g of isophorone diisocyanate was added dropwise to the four-necked flask for reaction for 2.5 h to obtain a polyurethane prepolymer.
步骤2、向聚氨酯预聚体中加入2g二乙烯三胺反应1h，加入一定量丁酮降低粘度，加入3g内酰胺反应0.5h后再加入6g甲基丙烯酸月桂酯进行反应1.5h，加入一定量丁酮降粘，得到改性聚氨酯。Step 2: Add 2 g of diethylenetriamine to the polyurethane prepolymer and react for 1 h, add a certain amount of butanone to reduce the viscosity, add 3 g of lactam and react for 0.5 h, then add 6 g of lauryl methacrylate and react for 1.5 h, add a certain amount of butanone to reduce the viscosity, and obtain a modified polyurethane.
步骤3、向改性聚氨酯中加入0.8g乙二胺中和至pH值为8，最后再加入65g去离子水在高剪切力下进行乳化，得到聚氨酯防水剂。Step 3: add 0.8 g of ethylenediamine to the modified polyurethane to neutralize to a pH of 8, and finally add 65 g of deionized water to emulsify under high shear force to obtain a polyurethane waterproofing agent.
实施例4Example 4
本申请与实施例1的不同之处在于：用1.05g甲基丙烯酸羟乙酯和1.95g甲基丙烯酸月桂酯代替3g甲基丙烯酸羟乙酯。The present application is different from Example 1 in that 3 g of hydroxyethyl methacrylate is replaced by 1.05 g of hydroxyethyl methacrylate and 1.95 g of lauryl methacrylate.
其中聚氨酯防水剂的制备方法与实施例1相同。The preparation method of the polyurethane waterproofing agent is the same as that in Example 1.
实施例5Example 5
本申请与实施例1的不同之处在于：用1.35g甲基丙烯酸羟乙酯和1.65g甲基丙烯酸月桂酯代替3g甲基丙烯酸羟乙酯。The present application is different from Example 1 in that 3 g of hydroxyethyl methacrylate is replaced by 1.35 g of hydroxyethyl methacrylate and 1.65 g of lauryl methacrylate.
其中聚氨酯防水剂的制备方法与实施例1相同。The preparation method of the polyurethane waterproofing agent is the same as that in Example 1.
实施例6Example 6
本申请与实施例1的不同之处在于：用制备例1制得的1g改性纳米纤维素晶须代替纳米纤维素晶须。The present application is different from Example 1 in that 1 g of modified nanocellulose whiskers prepared in Preparation Example 1 is used instead of nanocellulose whiskers.
其中聚氨酯防水剂的制备方法与实施例1相同。The preparation method of the polyurethane waterproofing agent is the same as that in Example 1.
实施例7Example 7
本申请与实施例1的不同之处在于：用制备例2制得的1g改性纳米纤维素晶须代替纳米纤维素晶须。The present application is different from Example 1 in that 1 g of modified nanocellulose whiskers prepared in Preparation Example 2 is used instead of nanocellulose whiskers.
其中聚氨酯防水剂的制备方法与实施例1相同。The preparation method of the polyurethane waterproofing agent is the same as that in Example 1.
实施例8Example 8
本申请与实施例1的不同之处在于：用制备例3制得的12g含磷氮聚醚二元醇代替聚乙二醇。The present application is different from Example 1 in that 12 g of phosphorus-nitrogen-containing polyether diol prepared in Preparation Example 3 is used instead of polyethylene glycol.
其中聚氨酯防水剂的制备方法与实施例1相同。The preparation method of the polyurethane waterproofing agent is the same as that in Example 1.
实施例9Example 9
本申请与实施例1的不同之处在于：用制备例4制得的12g含磷氮聚醚二元醇代替聚乙二醇。The difference between the present application and Example 1 is that 12 g of phosphorus-nitrogen-containing polyether diol prepared in Preparation Example 4 is used instead of polyethylene glycol.
其中聚氨酯防水剂的制备方法与实施例1相同。The preparation method of the polyurethane waterproofing agent is the same as that in Example 1.
实施例10Example 10
本申请与实施例1的不同之处在于：用制备例1制得的1g改性纳米纤维素晶须代替纳米纤维素晶须；用制备例3制得的12g含磷氮聚醚二元醇代替聚乙二醇；用1.35g甲基丙烯酸羟乙酯和1.65g甲基丙烯酸月桂酯代替3g甲基丙烯酸羟乙酯。The present application is different from Example 1 in that: 1 g of modified nanocellulose whiskers prepared in Preparation Example 1 is used instead of nanocellulose whiskers; 12 g of phosphorus-nitrogen-containing polyether diol prepared in Preparation Example 3 is used instead of polyethylene glycol; 1.35 g of hydroxyethyl methacrylate and 1.65 g of lauryl methacrylate are used instead of 3 g of hydroxyethyl methacrylate.
其中聚氨酯防水剂的制备方法与实施例1相同。The preparation method of the polyurethane waterproofing agent is the same as that in Example 1.
实施例11Embodiment 11
本申请与实施例1的不同之处在于：用制备例2制得的1g改性纳米纤维素晶须代替纳米纤维素晶须；用制备例4制得的12g含磷氮聚醚二元醇代替聚乙二醇；用1.05g甲基丙烯酸羟乙酯和1.95g甲基丙烯酸月桂酯代替3g甲基丙烯酸羟乙酯。The difference between the present application and Example 1 is that: 1 g of modified nanocellulose whiskers prepared in Preparation Example 2 is used instead of nanocellulose whiskers; 12 g of phosphorus-nitrogen-containing polyether diol prepared in Preparation Example 4 is used instead of polyethylene glycol; 1.05 g of hydroxyethyl methacrylate and 1.95 g of lauryl methacrylate are used instead of 3 g of hydroxyethyl methacrylate.
其中聚氨酯防水剂的制备方法与实施例1相同。The preparation method of the polyurethane waterproofing agent is the same as that in Example 1.
对比例Comparative Example
对比例1Comparative Example 1
本对比例与实施例1的不同之处在于：在聚氨酯防水剂的原料中，未添加纳米纤维素晶须。The difference between this comparative example and Example 1 is that no nanocellulose whiskers are added to the raw materials of the polyurethane waterproofing agent.
其中聚氨酯防水剂的制备方法与实施例1相同。The preparation method of the polyurethane waterproofing agent is the same as that in Example 1.
对比例2Comparative Example 2
本对比例与实施例1的不同之处在于：在聚氨酯防水剂的原料中，未添加丙烯酸酯。The difference between this comparative example and Example 1 is that no acrylate is added to the raw materials of the polyurethane waterproofing agent.
其中聚氨酯防水剂的制备方法与实施例1相同。The preparation method of the polyurethane waterproofing agent is the same as that in Example 1.
性能检测Performance Testing
分别采用实施例1-11及对比例1-2制备得到的聚氨酯防水剂，采用一浸一轧法对棉织物面料进行疏水整理，在150℃下烘干3min，得到待测面料。The polyurethane waterproofing agents prepared in Examples 1-11 and Comparative Examples 1-2 were respectively used to perform hydrophobic finishing on cotton fabrics by a dipping and padding method, and then dried at 150° C. for 3 minutes to obtain fabrics to be tested.
1.耐水压测试：按照GB/T 4744-1997《纺织织物抗渗水性测定静水压试验》用抗渗水性测试仪进行测试，并将测试结果记录在表1。1. Water pressure resistance test: Test with a water resistance tester in accordance with GB/T 4744-1997 "Hydrostatic pressure test for determination of water resistance of textile fabrics", and record the test results in Table 1.
2.透湿性测试：按照GB/T 12704-1991《织物透湿量测定方法透视杯法》中的吸湿法进行测试，并将测试结果记录在表1。2. Moisture permeability test: Test according to the moisture absorption method in GB/T 12704-1991 "Determination of moisture permeability of fabrics - Transparent cup method" and record the test results in Table 1.
3.断裂强力测试：按照GB/T 3923.1-2013《纺织品织物拉伸性能第1部分：断裂强力和断裂伸长率的测定(条样法)》进行测试，并将测试结果记录在表1。3. Breaking strength test: Test according to GB/T 3923.1-2013 “Tensile properties of textile fabrics Part 1: Determination of breaking strength and elongation at break (strip method)” and record the test results in Table 1.
表1Table 1
结果分析：Result analysis:
实施例1-3按照本申请的配方制作的聚氨酯防水剂，对纯棉织物做防水整理后，织物的防水性、透湿性和力学强度优异。根据不同的丙烯酸酯种类可以看出，当选用甲基丙烯酸羟乙酯对聚氨酯进行改性后，有利于聚氨酯防水剂的透湿量的提升，这是因为亲水集团提供了化学集团用于吸附-扩散-解析水蒸汽，作为水蒸气分子的阶石。而选用甲基丙烯酸月桂酯对聚氨酯进行改性时，疏水基团多，交联成的网状结构使得棉织物纤维之间的抱合力增强，有利于聚氨酯防水剂的耐水性和强度的提升。The polyurethane waterproofing agent prepared according to the formula of the present application in Examples 1-3 is used to waterproof pure cotton fabric, and the fabric has excellent waterproofness, moisture permeability and mechanical strength. According to different types of acrylates, it can be seen that when hydroxyethyl methacrylate is used to modify polyurethane, it is beneficial to improve the moisture permeability of the polyurethane waterproofing agent, because the hydrophilic group provides a chemical group for adsorption-diffusion-analysis of water vapor, as a stepping stone for water vapor molecules. When lauryl methacrylate is used to modify polyurethane, there are many hydrophobic groups, and the cross-linked mesh structure enhances the cohesion between cotton fabric fibers, which is beneficial to improve the water resistance and strength of the polyurethane waterproofing agent.
实施例4-5选用质量比在(0.7-0.9):(1.1-1.3)的甲基丙烯酸羟乙酯和甲基丙烯酸月桂酯的混合物作为改性单体丙烯酸酯，从而使得聚氨酯防水剂的耐水性和透湿性的综合性能得到提升，织物涂层的力学强度得到增强。In Example 4-5, a mixture of hydroxyethyl methacrylate and lauryl methacrylate in a mass ratio of (0.7-0.9):(1.1-1.3) is selected as the modified monomer acrylate, thereby improving the comprehensive performance of water resistance and moisture permeability of the polyurethane waterproofing agent and enhancing the mechanical strength of the fabric coating.
实施例6-7选用改性纳米纤维素晶须代替纳米纤维素晶须，通过选用硅烷偶联剂G-670对纳米纤维素晶须进行改性，提高改性纳米纤维素晶须与聚氨酯体系的分散性和相容性，使得整理后的织物涂层更加致密，断裂强力得到增强。同时在体系中引入了有机硅，通过有机硅的迁移提高织物的耐水性。In Example 6-7, modified nanocellulose whiskers are used instead of nanocellulose whiskers. The nanocellulose whiskers are modified by using silane coupling agent G-670 to improve the dispersibility and compatibility of the modified nanocellulose whiskers with the polyurethane system, so that the finished fabric coating is more dense and the breaking strength is enhanced. At the same time, organic silicon is introduced into the system to improve the water resistance of the fabric through the migration of organic silicon.
实施例8-9选用含磷氮聚醚二元醇作为聚氨酯防水剂的原料，使得聚氨酯防水剂进一步具有了阻燃性能。In Examples 8-9, phosphorus-nitrogen-containing polyether diols are selected as the raw materials of the polyurethane waterproofing agent, so that the polyurethane waterproofing agent further has flame retardant properties.
对比例1和对比例2相比于实施例1，对比例1在聚氨酯防水剂的制备原料中未添加纳米纤维素晶须，对比例2在原料中未添加丙烯酸酯，制备的聚氨酯防水剂，相比于实施例1在耐水性、透湿性和断裂强力上大幅下降。说明了纳米纤维素晶须和丙烯酸酯混合对聚氨酯防水剂改性的协同作用。Compared with Example 1, Comparative Example 1 did not add nanocellulose whiskers to the raw materials for preparing the polyurethane waterproofing agent, and Comparative Example 2 did not add acrylate to the raw materials. The prepared polyurethane waterproofing agents had significantly lower water resistance, moisture permeability and breaking strength than those of Example 1. This illustrates the synergistic effect of the mixture of nanocellulose whiskers and acrylate on the modification of the polyurethane waterproofing agent.
本具体实施方式仅仅是对本申请的解释，其并不是对本申请的限制，本领域技术人员在阅读完本说明书后可以根据需要对本具体实施方式做出没有创造性贡献的修改，但只要在本申请的权利要求范围内都受到专利法的保护。This specific implementation manner is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the specific implementation manner as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.
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| CN111004361A (en)* | 2019-01-28 | 2020-04-14 | 江南大学 | A kind of polyurethane-acrylate water repellent prepared by using side chain double bond |
| US20200354498A1 (en)* | 2019-01-28 | 2020-11-12 | Jiangnan University | Polyurethane-acrylate Water Repellant Prepared by Double Bonds in Side Chain |
| CN109880046A (en)* | 2019-02-26 | 2019-06-14 | 昆山嘉力普制版胶粘剂油墨有限公司 | A kind of preparation method of the whisker modified aqueous polyurethane of amination nano-cellulose |
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| CN119570096A (en)* | 2024-12-07 | 2025-03-07 | 广东彩龙新材料股份有限公司 | A kind of polylactic acid aluminum-plated film and preparation method thereof |
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