CN112522802B - Anti-ultraviolet antibacterial polypropylene filament and preparation method thereof - Google Patents

Abstract

The invention discloses an anti-ultraviolet antibacterial polypropylene filament and a preparation method thereof. The anti-ultraviolet antibacterial polypropylene filament comprises the following raw materials in percentage by mass: 0.5 to 1 percent of modified graphene material and modified TiO₂ 0.5 to 1.5 percent; 2% of maleic anhydride grafted polypropylene; 0.1% of a dispersant; the balance is polypropylene (PP); the dispersant is a mixture of cellulose sulfonate and lignosulfonate with the mass ratio of 40-60. The preparation method comprises the steps of material preparation in the early stage, compound granulation, spinning and the like. The product obtained by the invention has excellent uvioresistant performance and antibacterial performance.

Description

Translated fromChinese

一种抗紫外抗菌丙纶长丝及其制备方法A kind of anti-ultraviolet and antibacterial polypropylene filament and preparation method thereof

技术领域technical field

本发明涉及丙纶长丝，具体涉及一种抗紫外抗菌丙纶长丝及其制备方法。The invention relates to polypropylene filaments, in particular to an anti-ultraviolet and antibacterial polypropylene filaments and a preparation method thereof.

背景技术Background technique

丙纶长丝学名聚丙烯纤维，具有质轻、耐磨耐腐蚀、强度高等优点，但其抗紫外抗菌性能差，耐热性差、低温易脆裂，在日光和紫外照射下，其分子链中大量的甲基侧链易发生氧化降解，因此极大限制了纤维的应用。纳米二氧化钛是一种重要的紫外线屏蔽剂和半导体光催化剂，具有较好的光催化活性、化学稳定性和热稳定性，以及无毒、无迁移性和食品可直接接触等优点，被广泛应用于高聚物抗紫外改性剂。在复合材料和纤维中，将石墨烯作为纳米填料添加到聚合物基体中，不仅能够提高复合材料的力学性能、导电导热性能，还能引入新的功能特性，如抗紫外、抗菌、吸波及抗静电性能等。本发明选取石墨烯和纳米TiO₂这两种典型无机纳米填料来改性聚丙烯纤维，提高其抗紫外抗菌等方面性能，通过改性可以改善上述纯聚丙烯以上缺点，得到具有功能性聚丙烯纤维，以拓展聚丙烯纤维在纺织领域上的应用范围。The scientific name of polypropylene filament is polypropylene fiber, which has the advantages of light weight, wear resistance and corrosion resistance, and high strength, but its anti-ultraviolet and antibacterial performance is poor, its heat resistance is poor, and it is easy to be brittle at low temperature. The methyl side chains of the fibers are prone to oxidative degradation, which greatly limits the application of fibers. Nano-titanium dioxide is an important ultraviolet shielding agent and semiconductor photocatalyst. It has good photocatalytic activity, chemical stability and thermal stability, as well as the advantages of non-toxicity, non-migration and direct contact with food. It is widely used in High polymer anti-ultraviolet modifier. In composite materials and fibers, adding graphene as a nano-filler to the polymer matrix can not only improve the mechanical properties, electrical and thermal conductivity of composite materials, but also introduce new functional properties, such as anti-ultraviolet, antibacterial, wave-absorbing and anti-corrosion. electrostatic properties, etc. In the present invention, graphene and nano-_TiO2 , two typical inorganic nanofillers, are selected to modify polypropylene fibers to improve their performance in terms of anti-ultraviolet and antibacterial properties. Through modification, the above-mentioned shortcomings of pure polypropylene can be improved, and functional polypropylene fibers can be obtained. Fiber, in order to expand the scope of application of polypropylene fiber in the textile field.

发明内容SUMMARY OF THE INVENTION

本发明的目的是提供一种抗紫外抗菌丙纶长丝及其制备方法。采用熔融纺丝工艺，将纳米石墨烯和二氧化钛经过改性处理后，加入聚丙烯中制备出具有综合性能优良并具有一定功能特性的复合纤维，The object of the present invention is to provide an anti-ultraviolet and antibacterial polypropylene filament and a preparation method thereof. Using the melt-spinning process, the nano-graphene and titanium dioxide are modified and added to polypropylene to prepare composite fibers with excellent comprehensive properties and certain functional properties.

本发明的技术方案为：The technical scheme of the present invention is:

一种抗紫外抗菌丙纶长丝，包括按质量百分比计的如下原料：改性石墨烯材料0.5％～1％，改性TiO₂ 0.5％～1.5％；马来酸酐接枝聚丙烯2％；分散剂0.1％；其余为聚丙烯即PP。An anti-ultraviolet and antibacterial polypropylene filament, including the following raw materials in terms of mass percentage: 0.5% to 1% of modified graphene material, 0.5% to 1.5% of modified TiO₂ ; 2% of maleic anhydride grafted polypropylene; Agent 0.1%; the rest is polypropylene or PP.

进一步地，所述分散剂为质量比为40～60:60～40的纤维素磺酸盐和木质素磺酸盐的混合物。Further, the dispersant is a mixture of cellulose sulfonate and lignosulfonate in a mass ratio of 40-60:60-40.

进一步地，所述改性石墨烯材料采用的改性剂为聚乙烯吡咯烷酮(PVP)、钛酸酯偶联剂(TMC-931)、硅烷偶联剂(KH560)中的一种，且经过研磨后得到直径为1.5～1.7μm。Further, the modifier used in the modified graphene material is one of polyvinylpyrrolidone (PVP), titanate coupling agent (TMC-931), silane coupling agent (KH560), and after grinding Finally, a diameter of 1.5 to 1.7 μm is obtained.

进一步地，所述改性TiO₂采用的改性剂为硅烷偶联剂(KM570)，且经过研磨后得到直径为0.26～0.30um。Further, the modifier used for the modified TiO₂ is a silane coupling agent (KM570), and after grinding, the diameter is 0.26-0.30um.

上述的抗紫外抗菌丙烯长丝的制备方法，包括如下步骤：The preparation method of above-mentioned anti-ultraviolet antibacterial propylene filament, comprises the steps:

(1)前期材料准备：分别对石墨烯和TiO₂进行改性和研磨，石墨烯改性采用的改性剂为聚乙烯吡咯烷酮(PVP)、钛酸酯偶联剂(TMC-931)、硅烷偶联剂(KH560)中的一种，TiO₂改性采用的改性剂为硅烷偶联剂(KM570)；(1) Preliminary material preparation: modify and grind graphene and TiO₂ respectively. The modifiers used for graphene modification are polyvinylpyrrolidone (PVP), titanate coupling agent (TMC-931), silane One of the coupling agents (KH560), the modifier used for_TiO2 modification is a silane coupling agent (KM570);

(2)复合造粒(2) Composite granulation

按上述质量百分比(即改性石墨烯材料0.5％～1％，改性TiO₂ 0.5％～1.5％；马来酸酐接枝聚丙烯2％；分散剂0.1％；其余为丙烯单体)配置改性石墨烯、改性TiO₂、PP母粒、马来酸酐接枝聚丙烯和分散剂，先进行人工预混合5～10min，使改性石墨烯、改性TiO₂与PP母料初步混合，然后再使用高速混合机将材料充分混合10～15min，使改性石墨烯、改性TiO₂均匀包覆在PP母料表面，将均匀混合的原料放入双螺杆挤出造粒,得到高聚物原料；According to the above mass percentage (that is, 0.5% to 1% of modified graphene material, 0.5% to 1.5% of modified TiO₂ ; 2% of maleic anhydride grafted polypropylene; 0.1% of dispersant; the rest is propylene monomer). Graphene, modified TiO₂ , PP masterbatch, maleic anhydride grafted polypropylene and dispersant, first artificially pre-mixed for 5-10 minutes to make the modified graphene, modified TiO₂ and PP masterbatch preliminarily mixed, Then use a high-speed mixer to fully mix the materials for 10 to 15 minutes, so that the modified graphene and modified TiO₂ are evenly coated on the surface of the PP masterbatch, and the uniformly mixed raw materials are put into twin-screw extrusion granulation to obtain high polymer material;

(3)纺丝(3) spinning

将步骤(2)得到的高聚物原料放入熔融纺丝机进行熔融纺丝，即得到抗紫外抗菌丙烯长丝。The high polymer raw material obtained in the step (2) is put into a melt spinning machine for melt spinning to obtain an anti-ultraviolet and antibacterial propylene filament.

进一步地，双螺杆挤出造粒工艺具体为：液体压力值1.5-2.0MPa，一区温度150-160℃，二区温度160-170℃，三区温度170-180℃，四区-九区温度170-190℃，机头温度170-190℃。主机转速250，螺杆转速80-120r/min，喂料转速频率20-30Hz。Further, the twin-screw extrusion granulation process is specifically: liquid pressure value 1.5-2.0MPa, temperature in zone 150-160°C, temperature in zone 2 160-170°C, temperature in zone 3 170-180°C, zone 4-9 The temperature is 170-190°C, and the head temperature is 170-190°C. The host speed is 250, the screw speed is 80-120r/min, and the feeding speed frequency is 20-30Hz.

进一步，熔融纺丝工艺具体为：纺丝温度180-200℃，一二区温度180-190℃,三四区温度为190-200℃，挤出头和箱体的温度为190-200℃；纺丝压力为7-9MPa；热辊温度为70-120℃；牵伸倍数为2.8-4倍；螺杆挤压机温度为160-170℃；卷绕速度为900-1100m/min；侧吹风温度为20-30℃，冷风送风量为0.2-0.3m/s。本发明的有益效果在于：Further, the melt spinning process is as follows: the spinning temperature is 180-200°C, the temperature in the first and second zones is 180-190°C, the temperature in the third and fourth zones is 190-200°C, and the temperature of the extrusion head and the box is 190-200°C; The spinning pressure is 7-9MPa; the temperature of the hot roller is 70-120°C; the draw ratio is 2.8-4 times; the temperature of the screw extruder is 160-170°C; the winding speed is 900-1100m/min; The temperature is 20-30℃, and the air volume of cold air is 0.2-0.3m/s. The beneficial effects of the present invention are:

(1)本发明将无机纳米填料石墨烯和TiO₂相结合，采用熔融纺丝工艺，利用石墨烯特殊的二维晶体结构和优异的力学、光学、及热学等性能，以及纳米TiO₂优异的抗紫外老化、抗菌等性能，从纺丝上来改性聚丙烯纤维使其具有较优异的抗紫外抗菌性能。(1) The present invention combines inorganic nano filler graphene and_TiO2 , adopts melt spinning process, utilizes graphene's special two-dimensional crystal structure and excellent mechanical, optical, and thermal properties, and nano-_TiO2 excellent Anti-ultraviolet aging, antibacterial and other properties, modified polypropylene fiber from spinning to make it have excellent anti-ultraviolet and antibacterial properties.

(2)本发明将石墨烯粉末和纳米二氧化钛粉末通过物理方法粉碎研磨后，又通过化学改性的方法，使其分散性更好，防止了纳米粒子的团聚。(2) In the present invention, after the graphene powder and the nano-titanium dioxide powder are pulverized and ground by a physical method, the chemical modification method is used to make the dispersibility better and prevent the agglomeration of the nanoparticles.

(3)本发明具有流程相对简单、低成本、易于大规模生产等特点。(3) The present invention has the characteristics of relatively simple process, low cost, and easy large-scale production.

附图说明Description of drawings

图1对金黄色葡萄球菌的定性抗菌测试平板菌落图，其中，(a)KH-MG/TiO₂/PP，(b)TMC-MG/TiO₂/PP，(c)PVP-MG/TiO₂/PP，(d)PP。Fig. 1 is to the qualitative antibacterial test plate colony figure of Staphylococcus aureus, wherein, (a) KH-MG/TiO₂ /PP, (b) TMC-MG/TiO₂ /PP, (c) PVP-MG/TiO₂ /PP, (d)PP.

图2对大肠杆菌的定性抗菌测试平板菌落图，其中，(a)KH-MG/TiO₂/PP，(b)TMC-MG/TiO₂/PP，(c)PVP-MG/TiO₂/PP，(d)PP。Fig. 2 is to the qualitative antibacterial test plate colony diagram of Escherichia coli, wherein, (a) KH-MG/TiO₂ /PP, (b) TMC-MG/TiO₂ /PP, (c) PVP-MG/TiO₂ /PP , (d) PP.

图3对金黄色葡萄球菌的定量抗菌测试平板菌落图，其中，(a)KH-MG/TiO₂/PP，(b)TMC-MG/TiO₂/PP，(c)PVP-MG/TiO₂/PP，(d)PP。Fig. 3 is to the quantitative antibacterial test plate colony diagram of Staphylococcus aureus, wherein, (a) KH-MG/TiO₂ /PP, (b) TMC-MG/TiO₂ /PP, (c) PVP-MG/TiO₂ /PP, (d)PP.

具体实施方式Detailed ways

下面结合具体实施例对本发明做进一步详细说明，但本发明并不限于此。The present invention will be described in further detail below in conjunction with specific examples, but the present invention is not limited thereto.

实施例1Example 1

(1)前期材料准备(1) Preliminary material preparation

石墨烯改性：将无水乙醇(质量分数为95％)与水配成含乙醇90％的含水乙醇溶液A；取40g上述A溶液和10gKH560配成含KH560 20wt％的水解液，搅拌水解30min；将10g石墨烯分散于一定量的水溶液中，超声分散30min；将上述50gKH560的无水乙醇水解液，滴加入石墨烯的分散液中，混合搅拌，并超声处理30min；用旋转蒸发仪将上述石墨烯/KH560的水分散液中的水蒸发掉，乙醇挥发掉；再进行干燥而后得到KH560改性处理的石墨烯，再经研磨后备用；Graphene modification: absolute ethanol (mass fraction is 95%) and water are made into aqueous ethanol solution A containing 90% ethanol; take 40g of the above-mentioned A solution and 10gKH560 and make it into a hydrolyzate containing 20wt% of KH560, stir and hydrolyze for 30min Disperse 10g of graphene in a certain amount of aqueous solution and ultrasonically disperse for 30min; add the above-mentioned 50gKH560 dehydrated alcohol hydrolyzate dropwise into the dispersion of graphene, mix and stir, and ultrasonically treat for 30min; The water in the water dispersion of graphene/KH560 evaporates, and the ethanol volatilizes; then dry and then obtain KH560 modified graphene, and then grind it for later use;

TiO₂改性：将硅烷偶联剂KH570滴加入到质量分数为95％的无水乙醇中进行水解，得到含硅烷偶联剂的乙醇溶液，再将含硅烷偶联剂的乙醇溶液质量5％的金红石纳米TiO₂加入含硅烷偶联剂的乙醇溶液中，将悬浮液置于室温下经30min高速搅拌后再用超声波分散15min，保持温度恒定在80℃的条件下高速搅拌4h，结束反应，冷却后过滤，用无水乙醇反复洗涤2-3次，再收集放入烘箱设定100℃干燥12小时，最后经粉碎、研磨、过筛，留待备用；TiO₂ modification: add the silane coupling agent KH570 dropwise into absolute ethanol with a mass fraction of 95% for hydrolysis to obtain an ethanol solution containing a silane coupling agent, and then add a 5% ethanol solution containing a silane coupling agent The rutile nano-_TiO2 was added to the ethanol solution containing silane coupling agent, the suspension was placed at room temperature, stirred at a high speed for 30 minutes, and then dispersed by ultrasonic waves for 15 minutes, and kept at a constant temperature of 80°C for 4 hours, and the reaction was terminated. After cooling, filter, wash repeatedly with absolute ethanol for 2-3 times, then collect and dry in an oven set at 100°C for 12 hours, and finally crush, grind, and sieve, and set aside for later use;

(2)造粒(2) Granulation

按重量份剂，包括以下重量百分比计的原料：Parts by weight include the raw materials in the following percentages by weight:

聚丙烯96.9％，Polypropylene 96.9%,

改性石墨烯0.5％，Modified Graphene 0.5%,

改性TiO₂0.5％，Modified TiO₂ 0.5%,

马来酸酐接枝聚丙烯2％，Maleic anhydride grafted polypropylene 2%,

分散剂(质量比为50:50的纤维素磺酸钠和木质素磺酸纳的混合物)0.1％。Dispersant (a mixture of sodium cellulose sulfonate and sodium lignosulfonate with a mass ratio of 50:50) 0.1%.

把称好的对应配比的改性石墨烯、改性TiO₂、PP母粒及马来酸酐接枝聚丙烯先进行人工预混合5min，使改性石墨烯、改性TiO₂与PP母料初步混合，然后再使用高速混合机将材料充分混合10min，使改性石墨烯、改性TiO₂均匀包覆在PP母料表面。将混合好的原料放入双螺杆挤出机造粒，双螺杆挤出机参数设置为:液体压力值1.6MPa，一区温度160℃，二区温度165℃，三区温度170℃，四区-九区温度175℃，机头温度175℃。主机转速250，螺杆转速100r/min，喂料转速频率25.2Hz。The modified graphene, modified TiO₂ , PP masterbatch and maleic anhydride grafted polypropylene were manually pre-mixed for 5 minutes to make the modified graphene, modified TiO₂ and PP masterbatch Preliminary mixing, and then use a high-speed mixer to fully mix the materials for 10 minutes, so that the modified graphene and modified TiO₂ are evenly coated on the surface of the PP masterbatch. Put the mixed raw materials into the twin-screw extruder for granulation. The parameters of the twin-screw extruder are set as follows: liquid pressure value 1.6MPa, temperature in zone 1 160°C, temperature in zone 2 165°C, temperature in zone 3 170°C, zone 4 -The temperature in the ninth zone is 175°C, and the temperature of the machine head is 175°C. The host speed is 250, the screw speed is 100r/min, and the feeding speed frequency is 25.2Hz.

(3)纺丝(3) spinning

将得到的高聚物原料放入熔融纺丝机进行熔融纺丝，即得到抗紫外抗菌丙烯长丝，记为MG/TiO₂/PP。熔融纺丝工艺为：纺丝温度180-200℃，纺丝一区温度180℃；纺丝二区温度185℃；纺丝三区温度190℃；挤出头和箱体的温度为200℃；纺丝压力为8MPa；二热辊温度70℃；三热辊温度105℃；四热辊温度120℃；牵伸倍数为3；螺杆挤压机温度为165℃；卷绕速度为1050m/min；侧吹风温度为25℃；冷风送风量为0.2m/s。The obtained high polymer raw material is put into a melt spinning machine for melt spinning to obtain an anti-ultraviolet and antibacterial propylene filament, which is denoted as MG/TiO₂ /PP. The melt spinning process is as follows: spinning temperature 180-200°C, temperature of spinning zone 1 is 180°C; temperature of spinning zone 2 is 185°C; temperature of spinning zone 3 is 190°C; temperature of extrusion head and box is 200°C; The spinning pressure is 8MPa; the temperature of the second hot roll is 70°C; the temperature of the third hot roll is 105°C; the temperature of the fourth hot roll is 120°C; the draw ratio is 3; the temperature of the screw extruder is 165°C; The side blowing temperature is 25°C; the cold air supply volume is 0.2m/s.

实施例2Example 2

本实施例与实施例1相比仅在于原料配比不同：Compared with Example 1, this embodiment is only different in raw material proportioning:

聚丙烯96.4％Polypropylene 96.4%

改性石墨烯0.5％Modified graphene 0.5%

改性TiO₂1％Modified TiO₂ 1%

马来酸酐接枝聚丙烯2％Maleic anhydride grafted polypropylene 2%

分散剂(质量比为50:50的纤维素磺酸钠和木质素磺酸钠的混合物)0.1％Dispersant (a mixture of sodium cellulose sulfonate and sodium lignosulfonate with a mass ratio of 50:50) 0.1%

实施例3Example 3

本实例与实例1相比仅在于原料配比不同：Compared with example 1, this example is only different in the ratio of raw materials:

聚丙烯95.9％Polypropylene 95.9%

改性石墨烯0.5Modified graphene 0.5

改性TiO₂1.5Modified TiO₂ 1.5

马来酸酐接枝聚丙烯2％Maleic anhydride grafted polypropylene 2%

分散剂(质量比为50:50的纤维素磺酸钠和木质素磺酸钠的混合物)0.1％Dispersant (a mixture of sodium cellulose sulfonate and sodium lignosulfonate with a mass ratio of 50:50) 0.1%

实施例4Example 4

本实施例与实施例1相比仅在于原料配比不同：Compared with Example 1, this embodiment is only different in raw material proportioning:

聚丙烯96.4％Polypropylene 96.4%

改性石墨烯1％Modified Graphene 1%

改性TiO₂0.5％Modified TiO₂ 0.5%

马来酸酐接枝聚丙烯2％Maleic anhydride grafted polypropylene 2%

分散剂(质量比为50:50的纤维素磺酸钠盐和木质素磺酸盐的混合物)0.1％Dispersant (a mixture of sodium cellulose sulfonate and lignosulfonate with a mass ratio of 50:50) 0.1%

实施例5Example 5

(1)前期材料准备(1) Preliminary material preparation

石墨烯改性：先用异丙醇将TMC931进行稀释，然后采用干混合法将稀释后的钛酸酯喷洒于放入高速搅拌机中的石墨烯粉末中，再搅拌数分钟，冷却，使少量钛酸酯均匀地包覆在填料表面,再将改性后的石墨烯烘干、磨后备用。Graphene modification: first dilute TMC931 with isopropanol, and then spray the diluted titanate on the graphene powder in the high-speed mixer by dry mixing method, then stir for several minutes, cool down, and make a small amount of titanium The acid ester is evenly coated on the surface of the filler, and then the modified graphene is dried and ground for later use.

TiO₂改性：将硅烷偶联剂KH570滴加入到质量分数为95％的无水乙醇中进行水解，得到含硅烷偶联剂的乙醇溶液，再将含硅烷偶联剂的乙醇溶液质量5％的金红石纳米TiO₂加入含硅烷偶联剂的乙醇溶液中，将悬浮液置于室温下经30min高速搅拌后再用超声波分散15min，保持温度恒定在80℃的条件下高速搅拌4h，结束反应，冷却后过滤，用无水乙醇反复洗涤2-3次，再收集放入烘箱设定100℃干燥12小时，最后经粉碎、研磨、过筛，留待备用。TiO₂ modification: add the silane coupling agent KH570 dropwise into absolute ethanol with a mass fraction of 95% for hydrolysis to obtain an ethanol solution containing a silane coupling agent, and then add a 5% ethanol solution containing a silane coupling agent The rutile nano-_TiO2 was added to the ethanol solution containing silane coupling agent, the suspension was placed at room temperature, stirred at a high speed for 30 minutes, and then dispersed by ultrasonic waves for 15 minutes, and kept at a constant temperature of 80°C for 4 hours, and the reaction was terminated. After cooling, filter, wash repeatedly with absolute ethanol 2-3 times, then collect and dry in an oven set at 100°C for 12 hours, and finally crush, grind, and sieve, and set aside for later use.

(2)造粒(2) Granulation

按重量份剂，包括以下重量百分比计的原料：Parts by weight include the raw materials in the following percentages by weight:

聚丙烯96.9％Polypropylene 96.9%

改性石墨烯0.5％Modified graphene 0.5%

改性TiO₂0.5％Modified TiO₂ 0.5%

马来酸酐接枝聚丙烯2％Maleic anhydride grafted polypropylene 2%

分散剂(质量比为40:60的纤维素磺酸钠和木质素磺酸纳的混合物)0.1％Dispersant (a mixture of sodium cellulose sulfonate and sodium lignosulfonate with a mass ratio of 40:60) 0.1%

把称好的对应配比的改性石墨烯、改性TiO₂、PP母粒及马来酸酐接枝聚丙烯先进行人工预混合5min，使改性石墨烯、改性TiO₂与PP母料初步混合，然后再使用高速混合机将材料充分混合10min，使改性石墨烯、改性TiO₂均匀包覆在PP母料表面。将混合好的原料放入双螺杆挤出机造粒，双螺杆挤出机参数设置为:液体压力值1.6MPa，一区温度160℃，二区温度165℃，三区温度170℃，四区-九区温度175℃，机头温度175℃。主机转速250，螺杆转速100r/min，喂料转速频率25.2Hz。The modified graphene, modified TiO₂ , PP masterbatch and maleic anhydride grafted polypropylene were manually pre-mixed for 5 minutes to make the modified graphene, modified TiO₂ and PP masterbatch Preliminary mixing, and then use a high-speed mixer to fully mix the materials for 10 minutes, so that the modified graphene and modified TiO₂ are evenly coated on the surface of the PP masterbatch. Put the mixed raw materials into the twin-screw extruder for granulation. The parameters of the twin-screw extruder are set as follows: liquid pressure value 1.6MPa, temperature in zone 1 160°C, temperature in zone 2 165°C, temperature in zone 3 170°C, zone 4 -The temperature in the ninth zone is 175°C, and the temperature of the machine head is 175°C. The host speed is 250, the screw speed is 100r/min, and the feeding speed frequency is 25.2Hz.

(3)纺丝(3) spinning

将得到的高聚物原料放入熔融纺丝机进行熔融纺丝，即得到抗紫外抗菌丙烯长丝。熔融纺丝工艺为：纺丝温度180-200℃，纺丝一区温度180℃；纺丝二区温度185℃；纺丝三区温度190℃；挤出头和箱体的温度为200℃；纺丝压力为8MPa；二热辊温度70℃；三热辊温度105℃；四热辊温度120℃；牵伸倍数为3；螺杆挤压机温度为165℃；卷绕速度为1050m/min；侧吹风温度为25℃；冷风送风量为0.2m/s。The obtained high polymer raw material is put into a melt spinning machine for melt spinning to obtain an anti-ultraviolet and antibacterial propylene filament. The melt spinning process is as follows: spinning temperature 180-200°C, temperature of spinning zone 1 is 180°C; temperature of spinning zone 2 is 185°C; temperature of spinning zone 3 is 190°C; temperature of extrusion head and box is 200°C; The spinning pressure is 8MPa; the temperature of the second hot roll is 70°C; the temperature of the third hot roll is 105°C; the temperature of the fourth hot roll is 120°C; the draw ratio is 3; the temperature of the screw extruder is 165°C; The side blowing temperature is 25°C; the cold air supply volume is 0.2m/s.

实施例6Example 6

本实施例与实施例5相比仅在于原料配比不同：Compared with Example 5, this embodiment is only different in raw material proportioning:

聚丙烯96.4％Polypropylene 96.4%

改性石墨烯0.5％Modified graphene 0.5%

改性TiO₂1％Modified TiO₂ 1%

马来酸酐接枝聚丙烯2％Maleic anhydride grafted polypropylene 2%

分散剂(质量比为40:60的纤维素磺酸钠和木质素磺酸纳的混合物)0.1％Dispersant (a mixture of sodium cellulose sulfonate and sodium lignosulfonate with a mass ratio of 40:60) 0.1%

实施例7Example 7

本实施例与实施例5相比仅在于原料配比不同：Compared with Example 5, this embodiment is only different in raw material proportioning:

聚丙烯95.9％Polypropylene 95.9%

改性石墨烯0.5％Modified graphene 0.5%

改性TiO₂ 1.5％Modified TiO₂ 1.5%

马来酸酐接枝聚丙烯2％Maleic anhydride grafted polypropylene 2%

分散剂(质量比为40:60的纤维素磺酸钠和木质素磺酸纳的混合物)0.1％Dispersant (a mixture of sodium cellulose sulfonate and sodium lignosulfonate with a mass ratio of 40:60) 0.1%

实施例8Example 8

本实施例与实施例5相比仅在于原料配比不同：Compared with Example 5, this embodiment is only different in raw material proportioning:

聚丙烯96.4％Polypropylene 96.4%

改性石墨烯1％Modified Graphene 1%

改性TiO₂ 0.5％Modified TiO₂ 0.5%

马来酸酐接枝聚丙烯2％Maleic anhydride grafted polypropylene 2%

分散剂(质量比为40:60的纤维素磺酸钠和木质素磺酸纳的混合物)0.1％Dispersant (a mixture of sodium cellulose sulfonate and sodium lignosulfonate with a mass ratio of 40:60) 0.1%

实施例9Example 9

(1)前期材料准备(1) Preliminary material preparation

石墨烯改性：首先称取适量的研磨后石墨粉末，分散于一定量的去离子水中，使其浓度为0.5mg/ml，将溶液放置在数控超声波清洗机中超声剥离2h后，取上述金黄色溶液与PVP在烧瓶中混合，使PVP溶解，配成浓度1mg/ml的混合液，再150W超声30min，然后向上述溶液中加入一定量的水合肼和氨水，95℃反应1h，反应结束时获得黑色溶液，该溶液即为PVP-GR悬浊液，经过滤、洗涤、干燥即得到PVP功能化的石墨烯，再经研磨后备用。Graphene modification: First, weigh an appropriate amount of ground graphite powder, disperse it in a certain amount of deionized water to make the concentration 0.5 mg/ml, place the solution in a numerically controlled ultrasonic cleaner for ultrasonic peeling for 2 hours, and take the above gold Mix the yellow solution and PVP in a flask to dissolve the PVP and make a mixed solution with a concentration of 1mg/ml, then ultrasonicate at 150W for 30min, then add a certain amount of hydrazine hydrate and ammonia water to the above solution, and react at 95°C for 1h. Obtain a black solution, which is the PVP-GR suspension, which is filtered, washed, and dried to obtain PVP-functionalized graphene, which is then ground for later use.

TiO₂改性：将硅烷偶联剂KH570滴加入到质量分数为95％的无水乙醇中进行水解，得到含硅烷偶联剂的乙醇溶液，再将含硅烷偶联剂的乙醇溶液质量5％的金红石纳米TiO₂加入含硅烷偶联剂的乙醇溶液中，将悬浮液置于室温下经30min高速搅拌后再用超声波分散15mim，保持温度恒定在80℃的条件下高速搅拌4h，结束反应，冷却后过滤，用无水乙醇反复洗涤2-3次，再收集放入烘箱设定100℃干燥12小时，最后经粉碎、研磨、过筛，留待备用。TiO₂ modification: add the silane coupling agent KH570 dropwise into absolute ethanol with a mass fraction of 95% for hydrolysis to obtain an ethanol solution containing a silane coupling agent, and then add a 5% ethanol solution containing a silane coupling agent Add the rutile nano-_TiO2 into the ethanol solution containing silane coupling agent, place the suspension at room temperature, stir at high speed for 30min, and then disperse it with ultrasonic waves for 15mim, keep the temperature constant at 80°C and stir at high speed for 4h to end the reaction. After cooling, filter, wash repeatedly with absolute ethanol 2-3 times, then collect and dry in an oven set at 100°C for 12 hours, and finally crush, grind, and sieve, and set aside for later use.

(2)造粒(2) Granulation

按重量份剂，包括以下重量百分比计的原料：Parts by weight include the raw materials in the following percentages by weight:

聚丙烯96.4％Polypropylene 96.4%

改性石墨烯1％Modified Graphene 1%

改性TiO₂ 0.5％Modified TiO₂ 0.5%

马来酸酐接枝聚丙烯2％Maleic anhydride grafted polypropylene 2%

分散剂(质量比为60:40的纤维素磺酸钠和木质素磺酸纳的混合物)0.1％Dispersant (a mixture of sodium cellulose sulfonate and sodium lignosulfonate with a mass ratio of 60:40) 0.1%

把称好的对应配比的改性石墨烯、改性TiO₂、PP母粒及马来酸酐接枝聚丙烯先进行人工预混合5min，使改性石墨烯、改性TiO₂与PP母料初步混合，然后再使用高速混合机将材料充分混合10min，使改性石墨烯、改性TiO₂均匀包覆在PP母料表面。将混合好的原料放入双螺杆挤出机造粒，双螺杆挤出机参数设置为:液体压力值1.6MPa，一区温度160℃，二区温度165℃，三区温度170℃，四区-九区温度175℃，机头温度175℃。主机转速250，螺杆转速100r/min，喂料转速频率25.2Hz。The modified graphene, modified TiO₂ , PP masterbatch and maleic anhydride grafted polypropylene were manually pre-mixed for 5 minutes to make the modified graphene, modified TiO₂ and PP masterbatch Preliminary mixing, and then use a high-speed mixer to fully mix the materials for 10 minutes, so that the modified graphene and modified TiO₂ are evenly coated on the surface of the PP masterbatch. Put the mixed raw materials into the twin-screw extruder for granulation. The parameters of the twin-screw extruder are set as follows: liquid pressure value 1.6MPa, temperature in zone 1 160°C, temperature in zone 2 165°C, temperature in zone 3 170°C, zone 4 -The temperature in the ninth zone is 175°C, and the temperature of the machine head is 175°C. The host speed is 250, the screw speed is 100r/min, and the feeding speed frequency is 25.2Hz.

(3)纺丝(3) spinning

得到的高聚物原料放入熔融纺丝机进行熔融纺丝，即得到抗紫外抗菌丙烯长丝。熔融纺丝工艺为：纺丝温度180-200℃，纺丝一区温度180℃；纺丝二区温度185℃；纺丝三区温度190℃；挤出头和箱体的温度为200℃；纺丝压力为8MPa；二热辊温度70℃；三热辊温度105℃；四热辊温度120℃；牵伸倍数为3；螺杆挤压机温度为165℃；卷绕速度为1050m/min；侧吹风温度为25℃；冷风送风量为0.2m/s。The obtained high polymer raw material is put into a melt spinning machine for melt spinning to obtain an anti-ultraviolet and antibacterial propylene filament. The melt spinning process is as follows: spinning temperature 180-200°C, temperature of spinning zone 1 is 180°C; temperature of spinning zone 2 is 185°C; temperature of spinning zone 3 is 190°C; temperature of extrusion head and box is 200°C; The spinning pressure is 8MPa; the temperature of the second hot roll is 70°C; the temperature of the third hot roll is 105°C; the temperature of the fourth hot roll is 120°C; the draw ratio is 3; the temperature of the screw extruder is 165°C; The side blowing temperature is 25°C; the cold air supply volume is 0.2m/s.

实施例10Example 10

将纯聚丙烯长丝放入熔融纺丝机进行熔融纺丝。熔融纺丝工艺为：纺丝温度210-230℃，纺丝一区温度200℃；纺丝二区温度210℃；纺丝三区温度220℃；挤出头和箱体温度230℃；纺丝压力值10MPa；二热辊温度80℃；三热辊温度115℃；四热辊温度135℃；牵伸倍数4；螺杆挤压造粒温度175℃；卷绕速度1930m/min；侧吹风温度35℃；冷风送风量0.3m/s。Pure polypropylene filaments are put into a melt spinning machine for melt spinning. The melt spinning process is: spinning temperature 210-230°C, spinning temperature 200°C in the first spinning zone; spinning temperature in the second zone 210°C; spinning third zone temperature 220°C; The pressure value is 10MPa; the temperature of the second hot roller is 80°C; the temperature of the third hot roller is 115°C; the temperature of the fourth hot roller is 135°C; ℃; cold air supply volume 0.3m/s.

对上述实施例进行标号：将实施例1-10依次标号为A、B、C、D、E、F、G、H、I、J。The above-mentioned embodiments are marked: the embodiments 1-10 are marked as A, B, C, D, E, F, G, H, I, J in turn.

将上述实施例所得产品(简称复合纤维)和纯丙纶长丝(纯PP)作为对比例进行性能测试，结果如下：The above-mentioned embodiment gained product (being called for short composite fiber) and pure polypropylene filament (pure PP) carry out performance test as comparative example, and the results are as follows:

(1)复合纤维的紫外防护性能(1) UV protection performance of composite fiber

表1复合纤维的紫外防护性能Table 1 UV protective properties of composite fibers

从表1可以说明，KH560-MG、TMC-MG和纳米TiO₂粉体的少量加入，可极大地提高聚丙烯纤维的抗紫外性能。It can be shown from Table 1 that the addition of a small amount of KH560-MG, TMC-MG and nano TiO₂ powder can greatly improve the UV resistance of polypropylene fibers.

(2)复合纤维的抗菌性能(2) Antibacterial properties of composite fibers

选取方案4、8、9、10纤维样品为代表，把布样均先进性灭菌处理，再培养细菌，把浓度稀释到3×105CFU/mL～5×108CFU/mL，取100μl均匀涂到琼脂平板上，然后把经过灭菌处理的布样贴在上面，然后将其放置于恒温箱，35℃震荡18小时后看测试结果，所有工作均在超净工作台上完成。测试结果如图1至图3所示。经过测试发现，本发明所得复合纤维对金黄色葡萄球菌有较好的抑菌作用，而对大肠杆菌没有明显的抗菌性，其中对金黄色葡萄球菌抗菌性D＞H＞I＞J。Select the fiber samples of plans 4, 8, 9, and 10 as representatives, and sterilize the cloth samples first, then culture bacteria, dilute the concentration to 3×105CFU/mL～5×108CFU/mL, take 100μl and evenly spread it on the agar Then paste the sterilized cloth sample on it, then place it in the incubator, shake it at 35°C for 18 hours, and check the test results. All the work is done on the ultra-clean workbench. The test results are shown in Figures 1 to 3. After testing, it is found that the composite fiber obtained by the present invention has good antibacterial effect on Staphylococcus aureus, but has no obvious antibacterial effect on Escherichia coli, wherein the antibacterial effect on Staphylococcus aureus is D>H>I>J.

Claims (4)

Translated fromChinese

1.一种抗紫外抗菌丙纶长丝，其特征在于，包括按质量百分比计的如下原料：改性石墨烯材料0.5％～1％，改性TiO₂0.5％～1.5％；马来酸酐接枝聚丙烯2%；分散剂0.1%；其余为聚丙烯即PP；所述分散剂为质量比为40~60:60~40的纤维素磺酸盐和木质素磺酸盐的混合物；所述改性石墨烯材料采用的改性剂为聚乙烯吡咯烷酮、钛酸酯偶联剂、硅烷偶联剂中的一种；所述改性TiO₂采用的改性剂为硅烷偶联剂KM570；1. an anti-ultraviolet and antibacterial polypropylene fiber filament, is characterized in that, comprises following raw material by mass percent: modified graphene material 0.5%～1%, modified TiO₂ 0.5%～1.5%; Maleic anhydride grafting 2% polypropylene; 0.1% dispersant; the rest is polypropylene or PP; the dispersant is a mixture of cellulose sulfonate and lignosulfonate with a mass ratio of 40~60:60~40; the modified The modifying agent that the permanent graphene material adopts is a kind of in polyvinylpyrrolidone, titanate coupling agent, silane coupling agent; Described modified_TiO The modifying agent that adopts is silane coupling agent KM570;所述抗紫外抗菌丙纶长丝的制备方法，包括如下步骤：The preparation method of described anti-ultraviolet antibacterial polypropylene filament, comprises the steps:（1）前期材料准备：分别对石墨烯和TiO₂进行改性和研磨，石墨烯改性采用的改性剂为聚乙烯吡咯烷酮、钛酸酯偶联剂、硅烷偶联剂中的一种，TiO₂改性采用的改性剂为KM570；(1) Preliminary material preparation: modify and grind graphene and TiO₂ respectively. The modifier used for graphene modification is one of polyvinylpyrrolidone, titanate coupling agent, and silane coupling agent. The modifier used for_TiO2 modification is KM570;（2）复合造粒(2) Composite granulation按改性石墨烯材料0.5％～1％，改性TiO₂0.5％～1.5％；马来酸酐接枝聚丙烯2%；分散剂0.1%；其余为丙烯单体的质量百分比配置改性石墨烯、改性TiO₂、PP母粒、马来酸酐接枝聚丙烯和分散剂，先进行人工预混合5~10min，使改性石墨烯、改性TiO₂与PP母料初步混合，然后再使用高速混合机将材料充分混合10~15min，使改性石墨烯、改性TiO₂均匀包覆在PP母料表面，将均匀混合的原料放入双螺杆挤出造粒；According to the modified graphene material 0.5% ~ 1%, modified TiO₂ 0.5% ~ 1.5%; maleic anhydride grafted polypropylene 2%; dispersant 0.1%; the rest is the mass percentage of propylene monomer to configure modified graphene , modified TiO₂ , PP masterbatch, maleic anhydride grafted polypropylene, and dispersant, first pre-mixed manually for 5-10 minutes, so that the modified graphene, modified TiO₂ and PP masterbatch are initially mixed, and then used The high-speed mixer fully mixes the materials for 10-15 minutes, so that the modified graphene and modified TiO₂ are evenly coated on the surface of the PP masterbatch, and the uniformly mixed raw materials are put into twin-screw extrusion for granulation;（3）纺丝(3) spinning将步骤（2）得到的高聚物原料放入熔融纺丝机进行熔融纺丝，即得到抗紫外抗菌丙烯长丝。The high polymer raw material obtained in step (2) is put into a melt spinning machine for melt spinning to obtain UV-resistant and antibacterial propylene filaments.2.权利要求1所述的抗紫外抗菌丙纶长丝的制备方法，其特征在于，包括如下步骤：2. the preparation method of the anti-ultraviolet antibacterial polypropylene filament described in claim 1, is characterized in that, comprises the steps:（1）前期材料准备：分别对石墨烯和TiO₂进行改性和研磨，石墨烯改性采用的改性剂为聚乙烯吡咯烷酮、钛酸酯偶联剂、硅烷偶联剂中的一种，TiO₂改性采用的改性剂为KM570；(1) Preliminary material preparation: modify and grind graphene and TiO₂ respectively. The modifier used for graphene modification is one of polyvinylpyrrolidone, titanate coupling agent, and silane coupling agent. The modifier used for_TiO2 modification is KM570;（2）复合造粒(2) Composite granulation按改性石墨烯材料0.5％～1％，改性TiO₂0.5％～1.5％；马来酸酐接枝聚丙烯2%；分散剂0.1%；其余为丙烯单体的质量百分比配置改性石墨烯、改性TiO₂、PP母粒、马来酸酐接枝聚丙烯和分散剂，先进行人工预混合5~10min，使改性石墨烯、改性TiO₂与PP母料初步混合，然后再使用高速混合机将材料充分混合10~15min，使改性石墨烯、改性TiO₂均匀包覆在PP母料表面，将均匀混合的原料放入双螺杆挤出造粒；According to the modified graphene material 0.5% ~ 1%, modified TiO₂ 0.5% ~ 1.5%; maleic anhydride grafted polypropylene 2%; dispersant 0.1%; the rest is the mass percentage of propylene monomer to configure modified graphene , modified TiO₂ , PP masterbatch, maleic anhydride grafted polypropylene, and dispersant, first pre-mixed manually for 5-10 minutes, so that the modified graphene, modified TiO₂ and PP masterbatch are initially mixed, and then used The high-speed mixer fully mixes the materials for 10-15 minutes, so that the modified graphene and modified TiO₂ are evenly coated on the surface of the PP masterbatch, and the uniformly mixed raw materials are put into twin-screw extrusion for granulation;（3）纺丝(3) Spinning将步骤（2）得到的高聚物原料放入熔融纺丝机进行熔融纺丝，即得到抗紫外抗菌丙烯长丝。The high polymer raw material obtained in step (2) is put into a melt spinning machine for melt spinning to obtain UV-resistant and antibacterial propylene filaments.3.根据权利要求2所述的抗紫外抗菌丙纶长丝的制备方法，其特征在于，双螺杆挤出造粒工艺具体为：液体压力值1.5-2.0MPa，一区温度150-160℃，二区温度160-170℃，三区温度170-180℃，四区-九区温度170-190℃，机头温度170-190℃；主机转速250，螺杆转速80-120r/min，喂料转速频率20-30Hz。3. The preparation method of anti-ultraviolet and antibacterial polypropylene filament according to claim 2, characterized in that, the twin-screw extrusion granulation process is specifically: the liquid pressure value is 1.5-2.0MPa, the first zone temperature is 150-160°C, the second Zone temperature 160-170°C, zone 3 temperature 170-180°C, zone 4-9 zone temperature 170-190°C, head temperature 170-190°C; host speed 250, screw speed 80-120r/min, feeding speed frequency 20-30Hz.4.根据权利要求2所述的抗紫外抗菌丙纶长丝的制备方法，其特征在于，熔融纺丝工艺具体为：纺丝温度180-200℃，一二区温度180-190℃,三四区温度为190-200℃，挤出头和箱体的温度为190-200℃；纺丝压力为7-9MPa；热辊温度为70-120℃；牵伸倍数为2.8-4倍；螺杆挤压机温度为160-170℃；卷绕速度为900-1100m/min；侧吹风温度为20-30℃，冷风送风量为0.2-0.3m/s。4. The preparation method of anti-ultraviolet and antibacterial polypropylene filament according to claim 2, characterized in that the melt spinning process is specifically: spinning temperature 180-200°C, temperature in the first and second zones 180-190°C, temperature in the third and fourth zones The temperature is 190-200°C, the temperature of the extrusion head and the box is 190-200°C; the spinning pressure is 7-9MPa; the temperature of the hot roll is 70-120°C; the draft ratio is 2.8-4 times; screw extrusion The machine temperature is 160-170°C; the winding speed is 900-1100m/min; the side blowing temperature is 20-30°C, and the cold air supply volume is 0.2-0.3m/s.

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