技术领域Technical Field
本发明涉及复合纤维技术领域，具体是一种基于石墨烯的复合纤维及其制备工艺。The present invention relates to the technical field of composite fibers, and in particular to a graphene-based composite fiber and a preparation process thereof.
背景技术Background Art
基于石墨烯的复合纤维作为一种新型材料，在当今科技和工程领域具有巨大的潜力和应用前景。这种材料融合了石墨烯的特殊性能和纤维的结构优势，为各个行业带来了新的可能性。As a new type of material, graphene-based composite fiber has great potential and application prospects in today's science and engineering fields. This material combines the special properties of graphene and the structural advantages of fiber, bringing new possibilities to various industries.
石墨烯复合纤维在材料领域具有突出的优势。石墨烯本身具有极高的强度，使得其复合纤维可以制成轻量化且高强度的材料，因此这种材料可以被广泛应用于航空航天、汽车、船舶等领域，大幅降低结构重量，提升运载效率和安全性。另外，石墨烯复合纤维具有优异的导电性。由于石墨烯的高导电性，所以石墨烯复合纤维可用于制造高效导电性能的电子产品，如柔性电子设备、智能穿戴设备等。而且，石墨烯复合纤维还具有优异的导热性和耐磨性，这使得它在热管理领域有着广泛的应用前景。例如，它可以被用来制造高效的散热材料，用于电子设备和汽车引擎等高温环境下，以帮助有效地散发热量，保持设备稳定运行。同时，由于其耐磨性，石墨烯复合纤维还在纺织领域展现出巨大潜力，可以用于制造耐久耐磨的纺织品，提升产品的品质和使用寿命。Graphene composite fiber has outstanding advantages in the field of materials. Graphene itself has extremely high strength, so that its composite fiber can be made into lightweight and high-strength materials. Therefore, this material can be widely used in aerospace, automobile, shipbuilding and other fields, greatly reducing the weight of the structure and improving transportation efficiency and safety. In addition, graphene composite fiber has excellent conductivity. Due to the high conductivity of graphene, graphene composite fiber can be used to manufacture electronic products with high-efficiency conductive properties, such as flexible electronic devices, smart wearable devices, etc. Moreover, graphene composite fiber also has excellent thermal conductivity and wear resistance, which makes it have a wide range of application prospects in the field of thermal management. For example, it can be used to make efficient heat dissipation materials for high-temperature environments such as electronic equipment and car engines to help effectively dissipate heat and keep the equipment running stably. At the same time, due to its wear resistance, graphene composite fiber also shows great potential in the textile field. It can be used to manufacture durable and wear-resistant textiles to improve the quality and service life of products.
然而，在实际应用中，纤维材料表面的污染物会降低材料的性能和使用寿命，而具有良好疏水性能的石墨烯复合纤维可以减少污染物的附着，保持表面清洁，延长材料的使用寿命，降低维护成本。此外，随着科技的不断发展，石墨烯复合纤维被广泛应用于航空航天、汽车、建筑等领域，这些领域对材料的拉伸性能要求较高。通过提升拉伸性能，可以使石墨烯复合纤维具备更好的承载能力和抗压性能，保障其在复杂工程环境中的安全可靠性。However, in practical applications, pollutants on the surface of fiber materials will reduce the performance and service life of the materials, while graphene composite fibers with good hydrophobic properties can reduce the adhesion of pollutants, keep the surface clean, extend the service life of the materials, and reduce maintenance costs. In addition, with the continuous development of science and technology, graphene composite fibers are widely used in aerospace, automobiles, construction and other fields, which have high requirements for the tensile properties of materials. By improving the tensile properties, graphene composite fibers can have better load-bearing capacity and compressive resistance, ensuring their safety and reliability in complex engineering environments.
综上所述，提升石墨烯复合纤维的疏水性能和拉伸性能具有重要意义，不仅可以改善纤维材料的性能和耐久性，还可以拓展其应用领域和市场空间，推动相关产业的发展和进步。In summary, improving the hydrophobicity and tensile properties of graphene composite fibers is of great significance, which can not only improve the performance and durability of fiber materials, but also expand their application areas and market space, and promote the development and progress of related industries.
为了克服现有技术的缺陷，本发明提供了一种基于石墨烯的复合纤维及其制备工艺。In order to overcome the defects of the prior art, the present invention provides a graphene-based composite fiber and a preparation process thereof.
发明内容Summary of the invention
本发明的目的在于提供一种基于石墨烯的复合纤维及其制备工艺，以解决现有技术中的问题。The purpose of the present invention is to provide a graphene-based composite fiber and a preparation process thereof to solve the problems in the prior art.
为了解决上述技术问题，本发明提供如下技术方案：In order to solve the above technical problems, the present invention provides the following technical solutions:
一种基于石墨烯的复合纤维的制备工艺，包括以下步骤：A preparation process of a graphene-based composite fiber comprises the following steps:
步骤一：在氮气环境下，将乙氧化季戊四醇和3-氨基丙基三乙氧基硅烷混合，再添加催化剂，于85-95℃反应4-5h，制备得到端氨基超支化聚硅氧烷；Step 1: In a nitrogen environment, ethoxylated pentaerythritol and 3-aminopropyltriethoxysilane are mixed, a catalyst is added, and the mixture is reacted at 85-95° C. for 4-5 hours to prepare an amino-terminated hyperbranched polysiloxane;
步骤二：将N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷溶解于异丙醇中，得到溶液1；将四甲基氢氧化铵溶解于异丙醇中，得到溶液2；将溶液1滴加至溶液2中，于25-30℃搅拌反应6-7h，减压蒸馏除去异丙醇，再添加二甲苯进行溶解，于135-140℃回流反应6-8h，反应结束后经冷却、减压蒸馏，制备得到NH2-POSS；Step 2: dissolving N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane in isopropanol to obtain solution 1; dissolving tetramethylammonium hydroxide in isopropanol to obtain solution 2; adding solution 1 dropwise to solution 2, stirring and reacting at 25-30° C. for 6-7 hours, removing isopropanol by vacuum distillation, adding xylene to dissolve, reflux at 135-140° C. for 6-8 hours, cooling and vacuum distilling after the reaction to prepare NH2 -POSS;
步骤三：将端氨基超支化聚硅氧烷、1-十二烷氧基-2,4-苯二胺、NH2-POSS和氧化石墨烯溶解于四氢呋喃中，再添加催化剂并搅拌均匀，于60-65℃回流反应50-55h，反应结束后除去溶剂四氢呋喃，将剩余固体产物于120-130℃加热处理8.5-9.5h，再将产物溶解于四氢呋喃中，再倒入甲醇沉淀出复合石墨烯材料；Step 3: dissolving the amino-terminated hyperbranched polysiloxane, 1-dodecyloxy-2,4-phenylenediamine, NH2 -POSS and graphene oxide in tetrahydrofuran, adding a catalyst and stirring evenly, reflux reacting at 60-65° C. for 50-55 hours, removing the solvent tetrahydrofuran after the reaction, heating the remaining solid product at 120-130° C. for 8.5-9.5 hours, dissolving the product in tetrahydrofuran, and then pouring methanol to precipitate the composite graphene material;
步骤四：将复合石墨烯材料和聚酰胺混合，经熔融造粒得到母粒；将母粒、相容剂和聚丙烯混合，经熔融纺丝得到成品。Step 4: Mix the composite graphene material and polyamide, and obtain a masterbatch by melt granulation; mix the masterbatch, compatibilizer and polypropylene, and obtain a finished product by melt spinning.
较为优化地，步骤一中，乙氧化季戊四醇、3-氨丙基三乙氧基硅烷和催化剂的质量比为（8-10）：11：0.11。More optimally, in step 1, the mass ratio of ethoxylated pentaerythritol, 3-aminopropyltriethoxysilane and catalyst is (8-10):11:0.11.
较为优化地，所述催化剂为氢氧化钡。Preferably, the catalyst is barium hydroxide.
较为优化地，步骤二中，N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷和四甲基氢氧化铵的反应质量比为（35-40）：7。More optimally, in step 2, the reaction mass ratio of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and tetramethylammonium hydroxide is (35-40):7.
较为优化地，步骤三中，端氨基超支化聚硅氧烷、1-十二烷氧基-2,4-苯二胺、NH2-POSS和氧化石墨烯的反应质量比为0.02：（0.05-0.07）：0.03：5。More optimally, in step three, the reaction mass ratio of amino-terminated hyperbranched polysiloxane, 1-dodecyloxy-2,4-phenylenediamine, NH2 -POSS and graphene oxide is 0.02:(0.05-0.07):0.03:5.
较为优化地，步骤三中，所述催化剂为二环己基碳二亚胺。More optimally, in step three, the catalyst is dicyclohexylcarbodiimide.
较为优化地，步骤四中，熔融造粒参数：温度为200-250℃，转速为120-140rpm。More optimally, in step 4, the melt granulation parameters are: temperature is 200-250°C, and rotation speed is 120-140rpm.
较为优化地，步骤四中，熔融纺丝参数：温度为200-300℃，卷绕速度为1000-1200m/min。More optimally, in step 4, the melt spinning parameters are: temperature of 200-300°C, winding speed of 1000-1200m/min.
较为优化地，步骤四中，成品各组分含量为：以质量分数计，4-6%复合石墨烯材料、30-36%聚酰胺、50-55%聚丙烯，余量为相容剂。More optimally, in step four, the contents of the components of the finished product are: by mass fraction, 4-6% composite graphene material, 30-36% polyamide, 50-55% polypropylene, and the remainder is compatibilizer.
本发明的有益效果：Beneficial effects of the present invention:
本发明通过添加乙氧化季戊四醇、3-氨基丙基三乙氧基硅烷和催化剂氢氧化钡，制备得到端氨基超支化聚硅氧烷。再将N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷和四甲基氢氧化铵进行混合反应，制备得到NH2-POSS。通过添加端氨基超支化聚硅氧烷、1-十二烷氧基-2,4-苯二胺和NH2-POSS对氧化石墨烯进行改性，经过回流反应制备得到复合石墨烯材料。最后以复合石墨烯材料、聚酰胺、相容剂和聚丙烯为原料，经熔融纺丝得到成品。The invention prepares amino-terminated hyperbranched polysiloxane by adding ethoxylated pentaerythritol, 3-aminopropyltriethoxysilane and catalyst barium hydroxide. Then, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and tetramethylammonium hydroxide are mixed and reacted to prepare NH2- POSS. Graphene oxide is modified by adding amino-terminated hyperbranched polysiloxane, 1-dodecyloxy-2,4-phenylenediamine and NH2- POSS, and a composite graphene material is prepared through a reflux reaction. Finally, the composite graphene material, polyamide, a compatibilizer and polypropylene are used as raw materials, and a finished product is obtained through melt spinning.
本发明的特点在于，步骤一中，通过添加乙氧化季戊四醇、3-氨基丙基三乙氧基硅烷和催化剂，制备得到端氨基超支化聚硅氧烷；该步骤中乙氧化季戊四醇中的羟基和3-氨基丙基三乙氧基硅烷中的乙氧基发生取代反应，最终制备得到端氨基超支化聚硅氧烷，该有机产物中含有一定量的氨基；此外由于端氨基超支化聚硅氧烷的主要结构为聚硅氧烷，因此该产物具有良好的拉伸性能和疏水性能。The invention is characterized in that, in step 1, ethoxylated pentaerythritol, 3-aminopropyltriethoxysilane and a catalyst are added to prepare amino-terminated hyperbranched polysiloxane; in the step, a hydroxyl group in the ethoxylated pentaerythritol and an ethoxy group in the 3-aminopropyltriethoxysilane undergo a substitution reaction to finally prepare amino-terminated hyperbranched polysiloxane, wherein the organic product contains a certain amount of amino groups; in addition, since the main structure of the amino-terminated hyperbranched polysiloxane is polysiloxane, the product has good tensile properties and hydrophobic properties.
步骤二中，通过添加N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷和四甲基氢氧化铵进行混合反应，制备得到NH2-POSS；该步骤制备得到具有笼型结构的多面体聚硅氧烷NH2-POSS，该结构以Si-O纳米结构框架为核心，外围由-NH2构成，组成了一种无机-有机复合材料，该有机材料具有良好的拉伸性能和疏水性能。In step 2, NH2- POSS is prepared by adding N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and tetramethylammonium hydroxide for mixed reaction. This step prepares polyhedral polysiloxane NH2- POSS with a cage structure, which has a Si-O nanostructure framework as the core and is composed of-NH2 on the periphery, forming an inorganic-organic composite material, and the organic material has good tensile properties and hydrophobic properties.
步骤三中，通过添加端氨基超支化聚硅氧烷、1-十二烷氧基-2,4-苯二胺和NH2-POSS对氧化石墨烯进行改性，经过回流反应制备得到复合石墨烯材料。该步骤反应原理为端氨基超支化聚硅氧烷、1-十二烷氧基-2,4-苯二胺和NH2-POSS中的氨基和氧化石墨烯表面的环氧基和羧基发生反应，最终制备得到复合石墨烯材料。该步骤中将端氨基超支化聚硅氧烷、1-十二烷氧基-2,4-苯二胺、NH2-POSS和氧化石墨烯按照一定比例范围进行复配和调整，确定在质量配比为0.02：（0.05-0.07）：0.03：5的范围内使得反应效率达到最优，在该范围内可以最大程度的提升复合石墨烯材料的拉伸性能和疏水性能。In step three, the graphene oxide is modified by adding amino-terminated hyperbranched polysiloxane, 1-dodecyloxy-2,4-phenylenediamine and NH2 -POSS, and a composite graphene material is prepared by reflux reaction. The reaction principle of this step is that the amino groups in amino-terminated hyperbranched polysiloxane, 1-dodecyloxy-2,4-phenylenediamine and NH2 -POSS react with the epoxy groups and carboxyl groups on the surface of graphene oxide to finally prepare a composite graphene material. In this step, amino-terminated hyperbranched polysiloxane, 1-dodecyloxy-2,4-phenylenediamine, NH2 -POSS and graphene oxide are compounded and adjusted in a certain proportion range, and it is determined that the reaction efficiency is optimized within the mass ratio of 0.02: (0.05-0.07): 0.03: 5, and the tensile properties and hydrophobic properties of the composite graphene material can be maximized within this range.
最后，步骤四中以复合石墨烯材料、聚酰胺、相容剂和聚丙烯为原料，经熔融纺丝得到成品。通过添加具备卓越拉伸性能和疏水性的复合石墨烯材料，制备得到的成品纤维在断裂伸长率和疏水性方面也表现了出色的性能，因此其在复合纤维领域具有无尽的潜力和广阔的应用前景。Finally, in step 4, the composite graphene material, polyamide, compatibilizer and polypropylene are used as raw materials to obtain the finished product through melt spinning. By adding the composite graphene material with excellent tensile properties and hydrophobicity, the prepared finished fiber also shows excellent performance in terms of elongation at break and hydrophobicity, so it has endless potential and broad application prospects in the field of composite fibers.
具体实施方式DETAILED DESCRIPTION
下面将结合本发明的实施例，对本发明中的技术方案进行清楚、完整的描述，显然，所描述的实施例仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.
原料来源：Source of raw materials:
相容剂，由广东川亨新材料科技有限公司提供，型号为CH-906；氧化石墨烯，由常州市耀邦摩擦材料厂提供，粒径为2nm；聚酰胺，由东莞市创仕塑胶原料有限公司提供，型号为A3K；聚丙烯，由东莞市锦泰新材料科技有限公司提供，型号为GH41。以质量份数计，一份为1g。Compatibilizer, model CH-906, provided by Guangdong Chuanheng New Material Technology Co., Ltd.; graphene oxide, provided by Changzhou Yaobang Friction Material Factory, with a particle size of 2nm; polyamide, provided by Dongguan Chuangshi Plastic Raw Materials Co., Ltd., model A3K; polypropylene, provided by Dongguan Jintai New Material Technology Co., Ltd., model GH41. In terms of mass parts, one part is 1g.
实施例1：步骤一：在氮气环境下，将8g乙氧化季戊四醇和11g3-氨基丙基三乙氧基硅烷混合，再添加0.11g氢氧化钡，于95℃反应5h，制备得到端氨基超支化聚硅氧烷；Example 1: Step 1: Under a nitrogen environment, 8 g of ethoxylated pentaerythritol and 11 g of 3-aminopropyltriethoxysilane were mixed, and then 0.11 g of barium hydroxide was added, and the mixture was reacted at 95° C. for 5 h to prepare an amino-terminated hyperbranched polysiloxane;
步骤二：将35gN-(β-氨乙基)-γ-氨丙基三甲氧基硅烷溶解于异丙醇中，得到溶液1；将7g四甲基氢氧化铵溶解于异丙醇中，得到溶液2；将溶液1滴加至溶液2中，于30℃搅拌反应7h，减压蒸馏除去异丙醇，再添加二甲苯进行溶解，于140℃回流反应8h，反应结束后经冷却、减压蒸馏，制备得到NH2-POSS；Step 2: dissolving 35g of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane in isopropanol to obtain solution 1; dissolving 7g of tetramethylammonium hydroxide in isopropanol to obtain solution 2; adding solution 1 dropwise to solution 2, stirring and reacting at 30°C for 7h, removing isopropanol by vacuum distillation, adding xylene to dissolve, reflux at 140°C for 8h, cooling and vacuum distilling after the reaction to prepareNH2 -POSS;
步骤三：将0.02g端氨基超支化聚硅氧烷、0.05g1-十二烷氧基-2,4-苯二胺、0.03gNH2-POSS和5g氧化石墨烯溶解于四氢呋喃中，再添加二环己基碳二亚胺并搅拌均匀，于65℃回流反应55h，反应结束后除去溶剂四氢呋喃，将剩余固体产物于130℃加热处理9.5h，再将产物溶解于四氢呋喃中，再倒入甲醇沉淀出复合石墨烯材料；Step 3: dissolving 0.02g of amino-terminated hyperbranched polysiloxane, 0.05g of 1-dodecyloxy-2,4-phenylenediamine, 0.03g ofNH2 -POSS and 5g of graphene oxide in tetrahydrofuran, adding dicyclohexylcarbodiimide and stirring evenly, reflux at 65°C for 55h, removing the solvent tetrahydrofuran after the reaction, heating the remaining solid product at 130°C for 9.5h, dissolving the product in tetrahydrofuran, and then pouring methanol to precipitate the composite graphene material;
步骤四：以质量分数计，将5%复合石墨烯材料和30%聚酰胺混合，在温度为250℃、转速为140rpm的条件下进行熔融造粒得到母粒；将母粒、15%相容剂和50%聚丙烯混合，在温度为300℃、卷绕速度为1200m/min的条件下进行熔融纺丝得到成品。Step 4: Mix 5% of the composite graphene material and 30% of the polyamide by mass fraction, and perform melt granulation at a temperature of 250°C and a rotation speed of 140 rpm to obtain a masterbatch; mix the masterbatch, 15% of the compatibilizer and 50% of the polypropylene, and perform melt spinning at a temperature of 300°C and a winding speed of 1200 m/min to obtain the finished product.
实施例2：步骤一：在氮气环境下，将8g乙氧化季戊四醇和11g3-氨基丙基三乙氧基硅烷混合，再添加0.11g氢氧化钡，于93℃反应4.7h，制备得到端氨基超支化聚硅氧烷；Example 2: Step 1: Under a nitrogen environment, 8 g of ethoxylated pentaerythritol and 11 g of 3-aminopropyltriethoxysilane were mixed, and 0.11 g of barium hydroxide was added, and the mixture was reacted at 93° C. for 4.7 h to prepare an amino-terminated hyperbranched polysiloxane;
步骤二：将35gN-(β-氨乙基)-γ-氨丙基三甲氧基硅烷溶解于异丙醇中，得到溶液1；将7g四甲基氢氧化铵溶解于异丙醇中，得到溶液2；将溶液1滴加至溶液2中，于28℃搅拌反应6.7h，减压蒸馏除去异丙醇，再添加二甲苯进行溶解，于139℃回流反应7.5h，反应结束后经冷却、减压蒸馏，制备得到NH2-POSS；Step 2: dissolving 35g of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane in isopropanol to obtain solution 1; dissolving 7g of tetramethylammonium hydroxide in isopropanol to obtain solution 2; adding solution 1 dropwise to solution 2, stirring and reacting at 28°C for 6.7h, removing isopropanol by vacuum distillation, adding xylene to dissolve, and reacting under reflux at 139°C for 7.5h. After the reaction is completed, cooling and vacuum distillation are performed to prepareNH2 -POSS;
步骤三：将0.02g端氨基超支化聚硅氧烷、0.05g1-十二烷氧基-2,4-苯二胺、0.03gNH2-POSS和5g氧化石墨烯溶解于四氢呋喃中，再添加二环己基碳二亚胺并搅拌均匀，于64℃回流反应53h，反应结束后除去溶剂四氢呋喃，将剩余固体产物于127℃加热处理9.3h，再将产物溶解于四氢呋喃中，再倒入甲醇沉淀出复合石墨烯材料；Step 3: dissolving 0.02g of amino-terminated hyperbranched polysiloxane, 0.05g of 1-dodecyloxy-2,4-phenylenediamine, 0.03g ofNH2 -POSS and 5g of graphene oxide in tetrahydrofuran, adding dicyclohexylcarbodiimide and stirring evenly, reflux reacting at 64°C for 53h, removing the solvent tetrahydrofuran after the reaction, heating the remaining solid product at 127°C for 9.3h, dissolving the product in tetrahydrofuran, and then pouring methanol to precipitate the composite graphene material;
步骤四：以质量分数计，将5%复合石墨烯材料和30%聚酰胺混合，在温度为235℃、转速为135rpm的条件下进行熔融造粒得到母粒；将母粒、15%相容剂和50%聚丙烯混合，在温度为270℃、卷绕速度为1150m/min的条件下进行熔融纺丝得到成品。Step 4: Mix 5% of the composite graphene material and 30% of the polyamide by mass fraction, and perform melt granulation at a temperature of 235°C and a rotation speed of 135 rpm to obtain a masterbatch; mix the masterbatch, 15% of the compatibilizer and 50% of the polypropylene, and perform melt spinning at a temperature of 270°C and a winding speed of 1150 m/min to obtain the finished product.
实施例3：步骤一：在氮气环境下，将8g乙氧化季戊四醇和11g3-氨基丙基三乙氧基硅烷混合，再添加0.11g氢氧化钡，于90℃反应4.5h，制备得到端氨基超支化聚硅氧烷；Example 3: Step 1: Under a nitrogen environment, 8 g of ethoxylated pentaerythritol and 11 g of 3-aminopropyltriethoxysilane were mixed, and then 0.11 g of barium hydroxide was added, and the mixture was reacted at 90° C. for 4.5 h to prepare an amino-terminated hyperbranched polysiloxane;
步骤二：将35gN-(β-氨乙基)-γ-氨丙基三甲氧基硅烷溶解于异丙醇中，得到溶液1；将7g四甲基氢氧化铵溶解于异丙醇中，得到溶液2；将溶液1滴加至溶液2中，于27℃搅拌反应6.5h，减压蒸馏除去异丙醇，再添加二甲苯进行溶解，于137℃回流反应7h，反应结束后经冷却、减压蒸馏，制备得到NH2-POSS；Step 2: dissolving 35g of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane in isopropanol to obtain solution 1; dissolving 7g of tetramethylammonium hydroxide in isopropanol to obtain solution 2; adding solution 1 dropwise to solution 2, stirring and reacting at 27°C for 6.5h, removing isopropanol by vacuum distillation, adding xylene to dissolve, reflux at 137°C for 7h, cooling and vacuum distilling after the reaction to prepareNH2 -POSS;
步骤三：将0.02g端氨基超支化聚硅氧烷、0.05g1-十二烷氧基-2,4-苯二胺、0.03gNH2-POSS和5g氧化石墨烯溶解于四氢呋喃中，再添加二环己基碳二亚胺并搅拌均匀，于63℃回流反应52h，反应结束后除去溶剂四氢呋喃，将剩余固体产物于125℃加热处理9h，再将产物溶解于四氢呋喃中，再倒入甲醇沉淀出复合石墨烯材料；Step 3: dissolving 0.02g of amino-terminated hyperbranched polysiloxane, 0.05g of 1-dodecyloxy-2,4-phenylenediamine, 0.03g ofNH2 -POSS and 5g of graphene oxide in tetrahydrofuran, adding dicyclohexylcarbodiimide and stirring evenly, reflux reacting at 63°C for 52h, removing the solvent tetrahydrofuran after the reaction, heating the remaining solid product at 125°C for 9h, dissolving the product in tetrahydrofuran, and then pouring methanol to precipitate the composite graphene material;
步骤四：以质量分数计，将5%复合石墨烯材料和30%聚酰胺混合，在温度为225℃、转速为130rpm的条件下进行熔融造粒得到母粒；将母粒、15%相容剂和50%聚丙烯混合，在温度为250℃、卷绕速度为1100m/min的条件下进行熔融纺丝得到成品。Step 4: Mix 5% of the composite graphene material and 30% of the polyamide by mass fraction, and perform melt granulation at a temperature of 225°C and a rotation speed of 130 rpm to obtain a masterbatch; mix the masterbatch, 15% of the compatibilizer and 50% of the polypropylene, and perform melt spinning at a temperature of 250°C and a winding speed of 1100 m/min to obtain the finished product.
实施例4：步骤一：在氮气环境下，将8g乙氧化季戊四醇和11g 3-氨基丙基三乙氧基硅烷混合，再添加0.11g氢氧化钡，于87℃反应4.3h，制备得到端氨基超支化聚硅氧烷；Example 4: Step 1: Under a nitrogen environment, 8 g of ethoxylated pentaerythritol and 11 g of 3-aminopropyltriethoxysilane were mixed, and then 0.11 g of barium hydroxide was added, and the mixture was reacted at 87° C. for 4.3 h to prepare an amino-terminated hyperbranched polysiloxane;
步骤二：将35gN-(β-氨乙基)-γ-氨丙基三甲氧基硅烷溶解于异丙醇中，得到溶液1；将7g四甲基氢氧化铵溶解于异丙醇中，得到溶液2；将溶液1滴加至溶液2中，于26℃搅拌反应6.3h，减压蒸馏除去异丙醇，再添加二甲苯进行溶解，于136℃回流反应6.5h，反应结束后经冷却、减压蒸馏，制备得到NH2-POSS；Step 2: dissolving 35g of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane in isopropanol to obtain solution 1; dissolving 7g of tetramethylammonium hydroxide in isopropanol to obtain solution 2; adding solution 1 dropwise to solution 2, stirring and reacting at 26°C for 6.3h, removing isopropanol by vacuum distillation, adding xylene to dissolve, and reacting under reflux at 136°C for 6.5h. After the reaction is completed, cooling and vacuum distillation are performed to prepareNH2 -POSS;
步骤三：将0.02g端氨基超支化聚硅氧烷、0.05g 1-十二烷氧基-2,4-苯二胺、0.03gNH2-POSS和5g氧化石墨烯溶解于四氢呋喃中，再添加二环己基碳二亚胺并搅拌均匀，于61℃回流反应51h，反应结束后除去溶剂四氢呋喃，将剩余固体产物于123℃加热处理8.7h，再将产物溶解于四氢呋喃中，再倒入甲醇沉淀出复合石墨烯材料；Step 3: dissolving 0.02g of amino-terminated hyperbranched polysiloxane, 0.05g of 1-dodecyloxy-2,4-phenylenediamine, 0.03g ofNH2 -POSS and 5g of graphene oxide in tetrahydrofuran, adding dicyclohexylcarbodiimide and stirring evenly, reflux at 61°C for 51h, removing the solvent tetrahydrofuran after the reaction, heating the remaining solid product at 123°C for 8.7h, dissolving the product in tetrahydrofuran, and then pouring methanol to precipitate the composite graphene material;
步骤四：以质量分数计，将5%复合石墨烯材料和30%聚酰胺混合，在温度为210℃、转速为125rpm的条件下进行熔融造粒得到母粒；将母粒、15%相容剂和50%聚丙烯混合，在温度为225℃、卷绕速度为1050m/min的条件下进行熔融纺丝得到成品。Step 4: Mix 5% of the composite graphene material and 30% of the polyamide by mass fraction, and perform melt granulation at a temperature of 210°C and a rotation speed of 125 rpm to obtain a masterbatch; mix the masterbatch, 15% of the compatibilizer and 50% of the polypropylene, and perform melt spinning at a temperature of 225°C and a winding speed of 1050 m/min to obtain the finished product.
实施例5：步骤一：在氮气环境下，将8g乙氧化季戊四醇和11g 3-氨基丙基三乙氧基硅烷混合，再添加0.11g氢氧化钡，于85℃反应4h，制备得到端氨基超支化聚硅氧烷；Example 5: Step 1: Under a nitrogen environment, 8 g of ethoxylated pentaerythritol and 11 g of 3-aminopropyltriethoxysilane were mixed, and 0.11 g of barium hydroxide was added, and the mixture was reacted at 85° C. for 4 h to prepare an amino-terminated hyperbranched polysiloxane;
步骤二：将35g N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷溶解于异丙醇中，得到溶液1；将7g四甲基氢氧化铵溶解于异丙醇中，得到溶液2；将溶液1滴加至溶液2中，于25℃搅拌反应6h，减压蒸馏除去异丙醇，再添加二甲苯进行溶解，于135℃回流反应6h，反应结束后经冷却、减压蒸馏，制备得到NH2-POSS；Step 2: dissolving 35 g of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane in isopropanol to obtain solution 1; dissolving 7 g of tetramethylammonium hydroxide in isopropanol to obtain solution 2; adding solution 1 dropwise to solution 2, stirring and reacting at 25° C. for 6 h, removing isopropanol by vacuum distillation, adding xylene to dissolve, reflux at 135° C. for 6 h, cooling and vacuum distilling after the reaction to prepare NH2 -POSS;
步骤三：将0.02g端氨基超支化聚硅氧烷、0.05g 1-十二烷氧基-2,4-苯二胺、0.03g NH2-POSS和5g氧化石墨烯溶解于四氢呋喃中，再添加二环己基碳二亚胺并搅拌均匀，于60℃回流反应50h，反应结束后除去溶剂四氢呋喃，将剩余固体产物于120℃加热处理8.5h，再将产物溶解于四氢呋喃中，再倒入甲醇沉淀出复合石墨烯材料；Step 3: dissolving 0.02g of amino-terminated hyperbranched polysiloxane, 0.05g of 1-dodecyloxy-2,4-phenylenediamine, 0.03g of NH2- POSS and 5g of graphene oxide in tetrahydrofuran, adding dicyclohexylcarbodiimide and stirring evenly, reflux at 60°C for 50h, removing the solvent tetrahydrofuran after the reaction, heating the remaining solid product at 120°C for 8.5h, dissolving the product in tetrahydrofuran, and then pouring methanol to precipitate the composite graphene material;
步骤四：以质量分数计，将5%复合石墨烯材料和30%聚酰胺混合，在温度为200℃、转速为120rpm的条件下进行熔融造粒得到母粒；将母粒、15%相容剂和50%聚丙烯混合，在温度为200℃、卷绕速度为1000m/min的条件下进行熔融纺丝得到成品。Step 4: Mix 5% of the composite graphene material and 30% of the polyamide by mass fraction, and perform melt granulation at a temperature of 200°C and a rotation speed of 120 rpm to obtain a masterbatch; mix the masterbatch, 15% of the compatibilizer and 50% of the polypropylene, and perform melt spinning at a temperature of 200°C and a winding speed of 1000 m/min to obtain the finished product.
对比例1：将复合石墨烯材料替换为由常州市耀邦摩擦材料厂提供的氧化石墨烯，其余与实施例1相同，具体步骤如下：步骤一：以质量分数计，将5%石墨烯材料和30%聚酰胺混合，在温度为250℃、转速为140rpm的条件下进行熔融造粒得到母粒；将母粒、15%相容剂和50%聚丙烯混合，在温度为300℃、卷绕速度为1200m/min的条件下进行熔融纺丝得到成品。Comparative Example 1: The composite graphene material is replaced with graphene oxide provided by Changzhou Yaobang Friction Material Factory. The rest is the same as Example 1, and the specific steps are as follows: Step 1: Mix 5% graphene material and 30% polyamide by mass fraction, and melt granulate at a temperature of 250°C and a rotation speed of 140 rpm to obtain a masterbatch; mix the masterbatch, 15% compatibilizer and 50% polypropylene, and melt spin at a temperature of 300°C and a winding speed of 1200 m/min to obtain a finished product.
对比例2：将端氨基超支化聚硅氧烷、1-十二烷氧基-2,4-苯二胺、NH2-POSS和氧化石墨烯的反应质量比调整为0.02：0.01：0.03：5，其余与实施例1相同，具体步骤如下：步骤一：在氮气环境下，将8g乙氧化季戊四醇和11g 3-氨基丙基三乙氧基硅烷混合，再添加0.11g氢氧化钡，于95℃反应5h，制备得到端氨基超支化聚硅氧烷；Comparative Example 2: The reaction mass ratio of amino-terminated hyperbranched polysiloxane, 1-dodecyloxy-2,4-phenylenediamine, NH2 -POSS and graphene oxide was adjusted to 0.02:0.01:0.03:5, and the rest was the same as Example 1, and the specific steps were as follows: Step 1: Under a nitrogen environment, 8 g of ethoxylated pentaerythritol and 11 g of 3-aminopropyltriethoxysilane were mixed, and 0.11 g of barium hydroxide was added, and the mixture was reacted at 95° C. for 5 h to prepare amino-terminated hyperbranched polysiloxane;
步骤二：将35g N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷溶解于异丙醇中，得到溶液1；将7g四甲基氢氧化铵溶解于异丙醇中，得到溶液2；将溶液1滴加至溶液2中，于30℃搅拌反应7h，减压蒸馏除去异丙醇，再添加二甲苯进行溶解，于140℃回流反应8h，反应结束后经冷却、减压蒸馏，制备得到NH2-POSS；Step 2: dissolving 35 g of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane in isopropanol to obtain solution 1; dissolving 7 g of tetramethylammonium hydroxide in isopropanol to obtain solution 2; adding solution 1 dropwise to solution 2, stirring and reacting at 30° C. for 7 h, removing isopropanol by vacuum distillation, adding xylene to dissolve, reflux at 140° C. for 8 h, cooling and vacuum distilling after the reaction to prepare NH2 -POSS;
步骤三：将0.02g端氨基超支化聚硅氧烷、0.01g 1-十二烷氧基-2,4-苯二胺、0.03g NH2-POSS和5g氧化石墨烯溶解于四氢呋喃中，再添加二环己基碳二亚胺并搅拌均匀，于65℃回流反应55h，反应结束后除去溶剂四氢呋喃，将剩余固体产物于130℃加热处理9.5h，再将产物溶解于四氢呋喃中，再倒入甲醇沉淀出复合石墨烯材料；Step 3: dissolving 0.02g of amino-terminated hyperbranched polysiloxane, 0.01g of 1-dodecyloxy-2,4-phenylenediamine, 0.03g of NH2- POSS and 5g of graphene oxide in tetrahydrofuran, adding dicyclohexylcarbodiimide and stirring evenly, reflux at 65°C for 55h, removing the solvent tetrahydrofuran after the reaction, heating the remaining solid product at 130°C for 9.5h, dissolving the product in tetrahydrofuran, and then pouring methanol to precipitate the composite graphene material;
步骤四：以质量分数计，将5%复合石墨烯材料和30%聚酰胺混合，在温度为250℃、转速为140rpm的条件下进行熔融造粒得到母粒；将母粒、15%相容剂和50%聚丙烯混合，在温度为300℃、卷绕速度为1200m/min的条件下进行熔融纺丝得到成品。Step 4: Mix 5% of the composite graphene material and 30% of the polyamide by mass fraction, and perform melt granulation at a temperature of 250°C and a rotation speed of 140 rpm to obtain a masterbatch; mix the masterbatch, 15% of the compatibilizer and 50% of the polypropylene, and perform melt spinning at a temperature of 300°C and a winding speed of 1200 m/min to obtain the finished product.
检测试验：Detection test:
疏水性测试：将本发明制备得到的成品作为试样，按照标准GB/T 24368-2009对试样进行测试，随机抽取一根待测试样纤维，对准待测试样纤维喷射小水滴，当电脑捕捉到水与纤维的接触图像时立即固定图像，用五点法测量纤维与水的接触角，每根纤维重复测三次，取算术平均值作为测试结果。Hydrophobicity test: The finished product prepared by the present invention is used as a sample, and the sample is tested according to the standard GB/T 24368-2009. A sample fiber to be tested is randomly selected, and a small water droplet is sprayed on the sample fiber to be tested. When the computer captures the contact image of water and fiber, the image is immediately fixed, and the contact angle between the fiber and water is measured by the five-point method. Each fiber is measured three times, and the arithmetic mean is taken as the test result.
拉伸性能测试：将本发明制备得到的成品作为试样，按照标准GB/T 14337-2008对试样进行测试，随机抽取一根待测试样纤维，将待测试样纤维一端夹持在夹持器中，一端使用0.13cN/dtex的张力夹在纸框中，保证纤维轴向伸长进行拉伸试验，拉伸速度为每分钟100%名义隔距长度，测试得到试样的断裂伸长值，再使用公式计算得到断裂伸长率。结果如下表：Tensile performance test: The finished product prepared by the present invention is used as a sample, and the sample is tested according to the standard GB/T 14337-2008. A sample fiber to be tested is randomly selected, and one end of the sample fiber to be tested is clamped in a clamp, and the other end is clamped in a paper frame with a tension of 0.13 cN/dtex to ensure that the fiber is axially elongated for tensile testing. The stretching speed is 100% of the nominal gauge length per minute. The elongation at break value of the sample is tested, and then the elongation at break is calculated using the formula. The results are shown in the following table:
结论：实施例1~实施例5用量不变，只修改部分反应参数。由实验数据可知，试样的各项性能并无明显波动变化。Conclusion: The dosage of Examples 1 to 5 remains unchanged, and only some reaction parameters are modified. From the experimental data, it can be seen that the various properties of the samples have no obvious fluctuations.
对比例1：将复合石墨烯材料替换为由常州市耀邦摩擦材料厂提供的氧化石墨烯，其余与实施例1相同，由实验数据可知，与实施例1相比，水接触角降低为138°，断裂伸长率降低为28%，分析原因为：本发明通过制备添加端氨基超支化聚硅氧烷、1-十二烷氧基-2,4-苯二胺和NH2-POSS对氧化石墨烯进行改性，制备得到复合石墨烯材料；通过添加该复合石墨烯材料，有效提升了试样的疏水性能和拉伸性能，因此将复合石墨烯材料替换为由常州市耀邦摩擦材料厂提供的氧化石墨烯材料，试样的水接触角和断裂伸长率均降低。Comparative Example 1: The composite graphene material is replaced with graphene oxide provided by Changzhou Yaobang Friction Material Factory, and the rest is the same as Example 1. It can be seen from the experimental data that, compared with Example 1, the water contact angle is reduced to 138°, and the elongation at break is reduced to 28%. The reason is analyzed as follows: the present invention prepares the composite graphene material by modifying graphene oxide by adding terminal amino hyperbranched polysiloxane, 1-dodecyloxy-2,4-phenylenediamine and NH2- POSS; by adding the composite graphene material, the hydrophobicity and tensile properties of the sample are effectively improved, so the composite graphene material is replaced with the graphene oxide material provided by Changzhou Yaobang Friction Material Factory, and the water contact angle and elongation at break of the sample are reduced.
对比例2：将端氨基超支化聚硅氧烷、1-十二烷氧基-2,4-苯二胺、NH2-POSS和氧化石墨烯的反应质量比调整为0.02：0.01：0.03：5，其余与实施例1相同，由实验数据可知，与实施例1相比，水接触角降低为152°，断裂伸长率降低为37%，分析原因为：对比例2将本发明的设置的最优反应配比进行变动，将1-十二烷氧基-2,4-苯二胺的用量减少，将反应物之间的反应比例打破，导致副产物增多，降低反应效率，因此制备得到的试样的水接触角和断裂伸长率均降低。Comparative Example 2: The reaction mass ratio of terminal amino hyperbranched polysiloxane, 1-dodecyloxy-2,4-phenylenediamine, NH2- POSS and graphene oxide is adjusted to 0.02:0.01:0.03:5, and the rest is the same as Example 1. It can be seen from the experimental data that, compared with Example 1, the water contact angle is reduced to 152°, and the elongation at break is reduced to 37%. The reasons are analyzed as follows: Comparative Example 2 changes the optimal reaction ratio of the present invention, reduces the amount of 1-dodecyloxy-2,4-phenylenediamine, breaks the reaction ratio between the reactants, increases by-products, and reduces the reaction efficiency. Therefore, the water contact angle and elongation at break of the prepared sample are reduced.
需要说明的是，在本文中，诸如第一和第二等之类的关系术语仅仅用来将一个实体或者操作与另一个实体或操作区分开来，而不一定要求或者暗示这些实体或操作之间存在任何这种实际的关系或者顺序。而且，术语“包括”“包含”或者其任何其他变体意在涵盖非排他性的包含，从而使得包括一系列要素的过程方法物品或者设备不仅包括那些要素，而且还包括没有明确列出的其他要素，或者是还包括为这种过程方法物品或者设备所固有的要素。It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variations thereof are intended to cover non-exclusive inclusion, so that a process method article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process method article or device.
最后应说明的是：以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.
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| CN202410709928.0ACN118668319A (en) | 2024-06-03 | 2024-06-03 | Composite fiber based on graphene and preparation process thereof |
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| CN202410709928.0ACN118668319A (en) | 2024-06-03 | 2024-06-03 | Composite fiber based on graphene and preparation process thereof |
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| CN109056104A (en)* | 2018-09-21 | 2018-12-21 | 佛山皖和新能源科技有限公司 | A kind of preparation method of conducting polypropylene fiber |
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