CN102634976B - Method of Surface Deposited (POSS/TiO2)n Thin Film to Enhance PBO Fiber's UV Stability - Google Patents
Method of Surface Deposited (POSS/TiO2)n Thin Film to Enhance PBO Fiber's UV Stability Download PDFInfo
- Publication number
- CN102634976B CN102634976B CN201210118341XA CN201210118341A CN102634976B CN 102634976 B CN102634976 B CN 102634976B CN 201210118341X A CN201210118341X A CN 201210118341XA CN 201210118341 A CN201210118341 A CN 201210118341A CN 102634976 B CN102634976 B CN 102634976B
- Authority
- CN
- China
- Prior art keywords
- poss
- pbo fiber
- pbo
- tio
- resistance stability
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract description 38
- 239000010409 thin film Substances 0.000 title description 2
- 239000000835 fiber Substances 0.000 claims abstract description 93
- -1 aminophenyl Chemical group 0.000 claims abstract description 21
- 230000008021 deposition Effects 0.000 claims abstract description 18
- 230000006750 UV protection Effects 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 13
- 238000012986 modification Methods 0.000 claims abstract description 7
- 230000004048 modification Effects 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 32
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 22
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims 5
- 238000001035 drying Methods 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 13
- 238000000151 deposition Methods 0.000 abstract description 8
- 230000032683 aging Effects 0.000 abstract description 5
- HSAOVLDFJCYOPX-UHFFFAOYSA-N 2-[4-(1,3-benzothiazol-2-yl)phenyl]-1,3-benzothiazole Chemical compound C1=CC=C2SC(C3=CC=C(C=C3)C=3SC4=CC=CC=C4N=3)=NC2=C1 HSAOVLDFJCYOPX-UHFFFAOYSA-N 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 description 15
- 238000002474 experimental method Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- 229960000935 dehydrated alcohol Drugs 0.000 description 9
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000002535 lyotropic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
技术领域 technical field
本发明涉及一种增强PBO纤维耐紫外光稳定性的方法。 The invention relates to a method for enhancing the stability of PBO fibers against ultraviolet light. the
背景技术 Background technique
聚对苯撑苯并二噁唑(PBO，Poly-p-phenylenebenzobisthiazole)属于一种芳香族杂环刚性棒状液晶聚合物，具有良好的化学性能，阻燃性，高温稳定性，抗蠕变性，耐化学腐蚀性和耐物理磨损性。PBO是根据分子结构与性能原理开发出的新型聚合物，其分子结构式如下： Poly-p-phenylenebenzobisthiazole (PBO, Poly-p-phenylenebenzobisthiazole) belongs to an aromatic heterocyclic rigid rod-shaped liquid crystal polymer with good chemical properties, flame retardancy, high temperature stability, creep resistance, Chemical and physical abrasion resistance. PBO is a new type of polymer developed according to the principle of molecular structure and performance. Its molecular structure is as follows:
其链接角(即刚性主链单元上的环外键之间的夹角)均为180°，且重复单元结构中只存在苯环两侧的两个单键，不能内旋转，所以为刚性棒状分子，能够形成溶致液晶。PBO分子结构中无弱键，加之液晶纺丝工艺使得纤维中不仅保持了液晶分子良好的取向，而且赋予了纤维一定程度的二维和三维有序性，其优异的性能首先表现为拉伸强度达5.8GPa，拉伸模量为280～380GPa，其密度仅为1.56×103kg/m3，热分解温度高达650℃。PBO纤维优异的性能，决定了其在航空航天，军工产品，体育用品等许多领域中应用前景十分广阔。PBO纤维作为增强材料在弹道导弹壳体，火箭发动机和行星探索气球领域的应用，对武器装备的轻量化，小型化和高性能化起着至关重要的作用。用PBO纤维制造的高温过滤袋和过滤毡，高温下长期使用仍可保持高强度高耐磨性；用其制造的高性能消防服和焊接工作服等耐热工作服在火焰中不燃烧，不收缩，非常柔软；利用PBO纤维高模量的特性，可用于光导纤维的增强。在橡胶增强方面，用其代替钢丝作为轮胎的增强材料，使轮胎轻量化，有助于节能。PBO纤维也可在密封垫片，胶管等橡胶制品，各种树脂，塑料，钢筋混凝土抗震水泥构件和高性能同步传动带中作为增强材料；同时，PBO纤维还是制作各种高性能绳索，光缆保护层材料，运动服，航空服，体育器材，防弹材料的理想材料。与其他聚合物一样，PBO聚合物对光，特别是紫外光存在着敏感性。紫外光照射引发PBO纤维分子链断裂，纤维的分子量和取向度降低，导致纤维的力学性能降低。因此，紫外光防护是PBO纤维应用的一个重要研究课题。到目前为止，关于PBO纤维涂层提高纤维耐紫外光老化的报道很少。 Its link angle (that is, the angle between the external bonds of the ring on the rigid main chain unit) is 180°, and there are only two single bonds on both sides of the benzene ring in the repeating unit structure, which cannot be rotated internally, so it is a rigid rod molecules capable of forming lyotropic liquid crystals. There are no weak bonds in the molecular structure of PBO, and the liquid crystal spinning process not only maintains the good orientation of liquid crystal molecules in the fiber, but also endows the fiber with a certain degree of two-dimensional and three-dimensional order. Its excellent performance is firstly manifested in tensile strength. It reaches 5.8GPa, the tensile modulus is 280-380GPa, its density is only 1.56×10 3 kg/m 3 , and its thermal decomposition temperature is as high as 650°C. The excellent performance of PBO fiber determines its broad application prospects in aerospace, military products, sporting goods and many other fields. The application of PBO fiber as a reinforcing material in the fields of ballistic missile shells, rocket engines and planetary exploration balloons plays a vital role in the lightweight, miniaturization and high performance of weapons and equipment. High-temperature filter bags and filter felts made of PBO fibers can still maintain high strength and high wear resistance after long-term use at high temperatures; heat-resistant work clothes such as high-performance firefighting clothes and welding work clothes made of them do not burn or shrink in flames, Very soft; Utilizing the high modulus of PBO fiber, it can be used to strengthen the optical fiber. In terms of rubber reinforcement, it is used instead of steel wire as a reinforcing material for tires, which reduces the weight of tires and contributes to energy saving. PBO fibers can also be used as reinforcing materials in sealing gaskets, rubber hoses and other rubber products, various resins, plastics, reinforced concrete anti-seismic cement components and high-performance synchronous transmission belts; at the same time, PBO fibers can also be used to make various high-performance ropes and optical cable protective layers Ideal material for sportswear, aviation suits, sports equipment, bulletproof materials. Like other polymers, PBO polymers are sensitive to light, especially ultraviolet light. The molecular chains of PBO fibers were broken due to ultraviolet light irradiation, and the molecular weight and orientation degree of the fibers were reduced, resulting in a decrease in the mechanical properties of the fibers. Therefore, UV protection is an important research topic for the application of PBO fibers. So far, there are few reports on the improvement of fiber aging resistance by PBO fiber coating.
发明内容 Contents of the invention
本发明为了解决紫外光照射引发PBO纤维分子链断裂，纤维的分子量和取向度降低，导致PBO纤维的特征黏度降低、力学性能降低的技术问题，提供了一种表面沉积(POSS/TiO2)n薄膜增强PBO纤维耐紫外光稳定性的方法。 In order to solve the technical problems that the molecular chains of PBO fibers are broken due to ultraviolet light irradiation, the molecular weight and orientation degree of the fibers are reduced, resulting in a decrease in the intrinsic viscosity and mechanical properties of the PBO fibers, a surface deposition (POSS/TiO 2 ) n A method for film-enhanced UV stability of PBO fibers.
表面沉积(POSS/TiO2)n薄膜增强PBO纤维耐紫外光稳定性的方法如下： The method of surface deposition (POSS/TiO 2 ) n film to enhance the stability of PBO fiber against ultraviolet light is as follows:
一、PBO纤维表面的氧等离子体改性：将PBO纤维放置在等离子体表面处理仪中，于真空度为0.1mbar的氧气氛围中，在电压为100～200V的条件下处理5～20min； 1. Oxygen plasma modification on the surface of PBO fiber: place the PBO fiber in a plasma surface treatment instrument, treat it in an oxygen atmosphere with a vacuum of 0.1mbar, and treat it at a voltage of 100-200V for 5-20min;
二、表面接枝氨基苯基POSS：将经过步骤一处理的PBO纤维浸入质量浓度为0.1～1％的氨基苯基POSS的四氢呋喃溶液中，然后在60～100℃条件下反应1～4h； 2. Grafting aminophenyl POSS on the surface: immerse the PBO fiber treated in step 1 in a tetrahydrofuran solution with a mass concentration of 0.1-1% aminophenyl POSS, and then react at 60-100°C for 1-4 hours;
三、二氧化钛溶胶溶液的制备：将四氯化钛溶解于无水乙醇中，制成质量浓度为0.1～1％的四氯化钛的无水乙醇溶液，将四氯化钛的无水乙醇溶液滴入质量浓度为0.1～1％的四丁基氢氧化铵的无水乙醇溶液中，四氯化钛与四丁基氢氧化铵的摩尔比为1∶1，水解12～48h，调节pH值为10，得到二氧化钛溶胶溶液； 3. Preparation of titanium dioxide sol solution: dissolve titanium tetrachloride in dehydrated alcohol to make a dehydrated ethanol solution of titanium tetrachloride with a mass concentration of 0.1 to 1%, and dissolve the dehydrated ethanol solution of titanium tetrachloride Drop into the dehydrated ethanol solution of tetrabutylammonium hydroxide whose mass concentration is 0.1～1%, the molar ratio of titanium tetrachloride and tetrabutylammonium hydroxide is 1: 1, hydrolyze for 12～48h, adjust the pH value to be 10, obtain Titanium dioxide sol solution;
四、将经过步骤二处理的PBO纤维在二氧化钛溶胶溶液中沉积10min，再在质量浓度为1％的氨基苯基POSS的四氢呋喃溶液中沉积10min，然后进行水洗和干燥； Four, deposit 10min in the titanium dioxide sol solution through the PBO fiber treated in step 2, then deposit 10min in the tetrahydrofuran solution of aminophenyl POSS with a mass concentration of 1%, then wash and dry;
五、重复步骤四的操作n次，在PBO纤维表面得到(POSS/TiO2)n薄膜，其中n为正整数。 5. Repeat the operation of step 4 n times to obtain a (POSS/TiO 2 ) n film on the surface of the PBO fiber, wherein n is a positive integer.
采用本发明方法处理后的PBO纤维经受紫外光加速老化后PBO纤维的分子量和取向度是降低不明显，拉伸强度保有率和特性粘度保有率高于未处理的PBO纤维。 The molecular weight and orientation degree of the PBO fiber processed by the method of the present invention are not significantly reduced after being subjected to accelerated aging by ultraviolet light, and the retention rate of tensile strength and intrinsic viscosity is higher than that of the untreated PBO fiber. the
附图说明 Description of drawings
图1是经过实验三处理的PBO纤维与未经过处理的PBO纤维经受紫外光加速老化后拉伸强度保有率曲线，图中 
具体实施方式 Detailed ways
本发明技术方案不局限于以下所列举具体实施方式，还包括各具体实施方式间的任意组合。 The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments. the
具体实施方式一：本实施方式中表面沉积(POSS/TiO2)n薄膜增强PBO纤维耐紫外光稳定性的方法如下： Specific implementation mode 1: In this implementation mode, the method of surface deposition (POSS/TiO 2 ) n thin film to enhance the stability of PBO fiber against ultraviolet light is as follows:
一、PBO纤维表面的氧等离子体改性：将PBO纤维放置在等离子体表面处理仪中，于真空度为0.1mbar的氧气氛围中，在电压为100～200V的条件下处理5～20min； 1. Oxygen plasma modification on the surface of PBO fiber: place the PBO fiber in a plasma surface treatment instrument, treat it in an oxygen atmosphere with a vacuum of 0.1mbar, and treat it at a voltage of 100-200V for 5-20min;
二、表面接枝氨基苯基POSS：将经过步骤一处理的PBO纤维浸入质量浓度为0.1～1％的氨基苯基POSS的四氢呋喃溶液中，然后在60～100℃条件下反应1～4h； 2. Grafting aminophenyl POSS on the surface: immerse the PBO fiber treated in step 1 in a tetrahydrofuran solution with a mass concentration of 0.1-1% aminophenyl POSS, and then react at 60-100°C for 1-4 hours;
三、二氧化钛溶胶溶液的制备：将四氯化钛溶解于无水乙醇中，制成质量浓度为0.1～1％的四氯化钛的无水乙醇溶液，将四氯化钛的无水乙醇溶液滴入质量浓度为0.1～1％的四丁基氢氧化铵的无水乙醇溶液中，四氯化钛与四丁基氢氧化铵的摩尔比为1∶1，水解12～48h，调节pH值为10，得到二氧化钛溶胶溶液； 3. Preparation of titanium dioxide sol solution: dissolve titanium tetrachloride in dehydrated alcohol to make a dehydrated ethanol solution of titanium tetrachloride with a mass concentration of 0.1 to 1%, and dissolve the dehydrated ethanol solution of titanium tetrachloride Drop into the dehydrated ethanol solution of tetrabutylammonium hydroxide whose mass concentration is 0.1～1%, the molar ratio of titanium tetrachloride and tetrabutylammonium hydroxide is 1: 1, hydrolyze for 12～48h, adjust the pH value to be 10, obtain Titanium dioxide sol solution;
四、将经过步骤二处理的PBO纤维在二氧化钛溶胶溶液中沉积10min，再在质量浓度为1％的氨基苯基POSS的四氢呋喃溶液中沉积10min，然后进行水洗和干燥； Four, deposit 10min in the titanium dioxide sol solution through the PBO fiber treated in step 2, then deposit 10min in the tetrahydrofuran solution of aminophenyl POSS with a mass concentration of 1%, then wash and dry;
五、重复步骤四的操作n次，在PBO纤维表面得到(POSS/TiO2)n薄膜，其中n为正整数。 5. Repeat the operation of step 4 n times to obtain a (POSS/TiO 2 ) n film on the surface of the PBO fiber, wherein n is a positive integer.
具体实施方式二：本实施方式与具体实施方式一不同的是步骤一中在电压为110～190V的条件下处理。其它与具体实施方式一相同。 Embodiment 2: The difference between this embodiment and Embodiment 1 is that in step 1, the voltage is 110-190V. Others are the same as in the first embodiment. the
具体实施方式三：本实施方式与具体实施方式一不同的是步骤一中在电压为120～180V的条件下处理。其它与具体实施方式一相同。 Embodiment 3: The difference between this embodiment and Embodiment 1 is that in step 1, the voltage is 120-180V. Others are the same as in the first embodiment. the
具体实施方式四：本实施方式与具体实施方式一不同的是步骤一中在电压为150V的条件下处理。其它与具体实施方式一相同。 Embodiment 4: This embodiment is different from Embodiment 1 in that step 1 is processed under the condition of a voltage of 150V. Others are the same as in the first embodiment. the
具体实施方式五：本实施方式与具体实施方式一不同的是步骤二中将经过步骤一处理的PBO纤维浸入质量浓度为1％的氨基苯基POSS的四氢呋喃溶液中。其它与具体实施方式一相同。 Embodiment 5: The difference between this embodiment and Embodiment 1 is that in Step 2, the PBO fibers treated in Step 1 are immersed in a tetrahydrofuran solution with a mass concentration of 1% aminophenyl POSS. Others are the same as in the first embodiment. the
具体实施方式六：本实施方式与具体实施方式一不同的是步骤二中在70～90℃条件下反应2h。其它与具体实施方式一相同。 Embodiment 6: This embodiment is different from Embodiment 1 in that in Step 2, the reaction is carried out at 70-90° C. for 2 hours. Others are the same as in the first embodiment.
具体实施方式七：本实施方式与具体实施方式一不同的是步骤二中在80℃条件下反应3h。其它与具体实施方式一相同。 Embodiment 7: The difference between this embodiment and Embodiment 1 is that in step 2, the reaction is carried out at 80° C. for 3 hours. Others are the same as in the first embodiment.
具体实施方式八：本实施方式与具体实施方式一不同的是步骤三中将四氯化钛溶解于无水乙醇中，制成质量浓度为0.2～0.9％的四氯化钛的无水乙醇溶液。其它与具体实施方式一相同。 Embodiment 8: The difference between this embodiment and Embodiment 1 is that in step 3, titanium tetrachloride is dissolved in absolute ethanol to make a dehydrated alcohol solution of titanium tetrachloride with a mass concentration of 0.2 to 0.9%. . Others are the same as in the first embodiment.
具体实施方式九：本实施方式与具体实施方式一不同的是步骤三中将四氯化钛溶解于无水乙醇中，制成质量浓度为0.5％的四氯化钛的无水乙醇溶液。其它与具体实施方式一 相同。 Embodiment 9: The difference between this embodiment and Embodiment 1 is that in step 3, titanium tetrachloride is dissolved in absolute ethanol to prepare a solution of titanium tetrachloride in absolute ethanol with a mass concentration of 0.5%. Others are the same as in Embodiment 1. the
具体实施方式十：本实施方式与具体实施方式一不同的是步骤三中水解时间为24h。其它与具体实施方式一相同。 Embodiment 10: This embodiment is different from Embodiment 1 in that the hydrolysis time in step 3 is 24 hours. Others are the same as in the first embodiment.
采用下述实验验证本发明的效果： Adopt following experiment to verify effect of the present invention:
实验一： experiment one:
表面沉积(POSS/TiO2)n薄膜增强PBO纤维耐紫外光稳定性的方法如下： The method of surface deposition (POSS/TiO 2 ) n film to enhance the stability of PBO fiber against ultraviolet light is as follows:
一、PBO纤维表面的氧等离子体改性：将PBO纤维放置在等离子体表面处理仪中，于真空度为0.1mbar的氧气氛围中，在电压为100V的条件下处理5min； 1. Oxygen plasma modification on the surface of PBO fiber: place the PBO fiber in a plasma surface treatment instrument, and treat it for 5 minutes under the condition of a voltage of 100V in an oxygen atmosphere with a vacuum degree of 0.1mbar;
二、表面接枝氨基苯基POSS：将经过步骤一处理的PBO纤维浸入质量浓度为0.1％的氨基苯基POSS的四氢呋喃溶液中，然后在60℃条件下反应1h； 2. Grafting aminophenyl POSS on the surface: immerse the PBO fiber treated in step 1 in a tetrahydrofuran solution with a mass concentration of 0.1% aminophenyl POSS, and then react at 60°C for 1 hour;
三、二氧化钛溶胶溶液的制备：将四氯化钛溶解于无水乙醇中，制成质量浓度为0.1％的四氯化钛的无水乙醇溶液，将四氯化钛的无水乙醇溶液滴入质量浓度为0.1％的四丁基氢氧化铵的无水乙醇溶液中，四氯化钛与四丁基氢氧化铵的摩尔比为1∶1，水解12h，调节pH值为10，得到二氧化钛溶胶溶液； 3. Preparation of titanium dioxide sol solution: dissolve titanium tetrachloride in absolute ethanol to make a dehydrated ethanol solution of titanium tetrachloride with a mass concentration of 0.1%, drop the dehydrated ethanol solution of titanium tetrachloride into Mass concentration is 0.1% in the dehydrated ethanol solution of tetrabutylammonium hydroxide, the molar ratio of titanium tetrachloride and tetrabutylammonium hydroxide is 1: 1, hydrolysis 12h, adjust pH value to be 10, obtain titanium dioxide sol solution;
四、将经过步骤二处理的PBO纤维在二氧化钛溶胶溶液中沉积10min，再在质量浓度为1％的氨基苯基POSS的四氢呋喃溶液中沉积10min，然后进行水洗和干燥； Four, deposit 10min in the titanium dioxide sol solution through the PBO fiber treated in step 2, then deposit 10min in the tetrahydrofuran solution of aminophenyl POSS with a mass concentration of 1%, then wash and dry;
五、重复步骤四的操作1次，在PBO纤维表面得到(POSS/TiO2)1薄膜。 5. Repeat step 4 once to obtain a (POSS/TiO 2 ) 1 film on the surface of the PBO fiber.
实验二： Experiment 2:
表面沉积(POSS/TiO2)n薄膜增强PBO纤维耐紫外光稳定性的方法如下： The method of surface deposition (POSS/TiO 2 ) n film to enhance the stability of PBO fiber against ultraviolet light is as follows:
一、PBO纤维表面的氧等离子体改性：将PBO纤维放置在等离子体表面处理仪中，于真空度为0.1mbar的氧气氛围中，在电压为200V的条件下处理20min； 1. Oxygen plasma modification on the surface of PBO fiber: place the PBO fiber in a plasma surface treatment instrument, and treat it for 20 minutes under the condition of a voltage of 200V in an oxygen atmosphere with a vacuum degree of 0.1mbar;
二、表面接枝氨基苯基POSS：将经过步骤一处理的PBO纤维浸入质量浓度为1％的氨基苯基POSS的四氢呋喃溶液中，然后在100℃条件下反应4h； 2. Grafting aminophenyl POSS on the surface: immerse the PBO fiber treated in step 1 in a tetrahydrofuran solution with a mass concentration of 1% aminophenyl POSS, and then react at 100°C for 4 hours;
三、二氧化钛溶胶溶液的制备：将四氯化钛溶解于无水乙醇中，制成质量浓度为1％的四氯化钛的无水乙醇溶液，将四氯化钛的无水乙醇溶液滴入质量浓度为1％的四丁基氢氧化铵的无水乙醇溶液中，四氯化钛与四丁基氢氧化铵的摩尔比为1∶1，水解48h，调节pH值为10，得到二氧化钛溶胶溶液； Three, the preparation of titanium dioxide sol solution: dissolve titanium tetrachloride in dehydrated alcohol, make the dehydrated alcohol solution that mass concentration is 1% titanium tetrachloride, drop the dehydrated alcohol solution of titanium tetrachloride into Mass concentration is 1% in the dehydrated ethanol solution of tetrabutylammonium hydroxide, the molar ratio of titanium tetrachloride and tetrabutylammonium hydroxide is 1: 1, hydrolysis 48h, adjust pH value to be 10, obtain titanium dioxide sol solution;
四、将经过步骤二处理的PBO纤维在二氧化钛溶胶溶液中沉积10min，再在质量浓度为1％的氨基苯基POSS的四氢呋喃溶液中沉积10min，然后进行水洗和干燥； Four, deposit 10min in the titanium dioxide sol solution through the PBO fiber treated in step 2, then deposit 10min in the tetrahydrofuran solution of aminophenyl POSS with a mass concentration of 1%, then wash and dry;
五、重复步骤四的操作3次，在PBO纤维表面得到(POSS/TiO2)3薄膜。 5. Repeat step 4 three times to obtain a (POSS/TiO 2 ) 3 film on the surface of the PBO fiber.
实验三： Experiment three:
表面沉积(POSS/TiO2)n薄膜增强PBO纤维耐紫外光稳定性的方法如下： The method of surface deposition (POSS/TiO 2 ) n film to enhance the stability of PBO fiber against ultraviolet light is as follows:
一、PBO纤维表面的氧等离子体改性：将PBO纤维放置在等离子体表面处理仪中，于真空度为0.1mbar的氧气氛围中，在电压为150V的条件下处理10min； 1. Oxygen plasma modification on the surface of PBO fiber: place the PBO fiber in a plasma surface treatment instrument, and treat it for 10 minutes at a voltage of 150V in an oxygen atmosphere with a vacuum of 0.1mbar;
二、表面接枝氨基苯基POSS：将经过步骤一处理的PBO纤维浸入质量浓度为1％的氨基苯基POSS的四氢呋喃溶液中，然后在80℃条件下反应4h； 2. Grafting aminophenyl POSS on the surface: immerse the PBO fiber treated in step 1 in a tetrahydrofuran solution with a mass concentration of 1% aminophenyl POSS, and then react at 80°C for 4h;
三、二氧化钛溶胶溶液的制备：将四氯化钛溶解于无水乙醇中，制成质量浓度为1％的四氯化钛的无水乙醇溶液，将四氯化钛的无水乙醇溶液滴入质量浓度为1％的四丁基氢氧化铵的无水乙醇溶液中，四氯化钛与四丁基氢氧化铵的摩尔比为1∶1，水解48h，调节pH值为10，得到二氧化钛溶胶溶液； Three, the preparation of titanium dioxide sol solution: dissolve titanium tetrachloride in dehydrated alcohol, make the dehydrated alcohol solution that mass concentration is 1% titanium tetrachloride, drop the dehydrated alcohol solution of titanium tetrachloride into Mass concentration is 1% in the dehydrated ethanol solution of tetrabutylammonium hydroxide, the molar ratio of titanium tetrachloride and tetrabutylammonium hydroxide is 1: 1, hydrolysis 48h, adjust pH value to be 10, obtain titanium dioxide sol solution;
四、将经过步骤二处理的PBO纤维在二氧化钛溶胶溶液中沉积10min，再在质量浓度为1％的氨基苯基POSS的四氢呋喃溶液中沉积10min，然后进行水洗和干燥； Four, deposit 10min in the titanium dioxide sol solution through the PBO fiber treated in step 2, then deposit 10min in the tetrahydrofuran solution of aminophenyl POSS with a mass concentration of 1%, then wash and dry;
五、重复步骤四的操作8次，在PBO纤维表面得到(POSS/TiO2)8薄膜。 5. Repeat the operation of step 4 8 times to obtain a (POSS/TiO 2 ) 8 film on the surface of the PBO fiber.
将经过实验三处理的PBO纤维与未处理的PBO纤维放置在紫外光源下进行照射，然后测定PBO纤维的拉伸强度保有率和特性粘度保有率，由图1和图2可以看出经过实验三处理的PBO纤维的拉伸强度保有率和特性粘度保有率明显高于未处理的PBO纤维。 The PBO fiber treated by Experiment 3 and the untreated PBO fiber were placed under the ultraviolet light source for irradiation, and then the tensile strength retention rate and intrinsic viscosity retention rate of the PBO fiber were measured. It can be seen from Figure 1 and Figure 2 that after Experiment 3 The tensile strength retention rate and intrinsic viscosity retention rate of treated PBO fibers were significantly higher than those of untreated PBO fibers. the
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210118341XA CN102634976B (en) | 2012-04-20 | 2012-04-20 | Method of Surface Deposited (POSS/TiO2)n Thin Film to Enhance PBO Fiber's UV Stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210118341XA CN102634976B (en) | 2012-04-20 | 2012-04-20 | Method of Surface Deposited (POSS/TiO2)n Thin Film to Enhance PBO Fiber's UV Stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102634976A CN102634976A (en) | 2012-08-15 |
| CN102634976B true CN102634976B (en) | 2013-12-11 |
Family
ID=46619543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210118341XA Active CN102634976B (en) | 2012-04-20 | 2012-04-20 | Method of Surface Deposited (POSS/TiO2)n Thin Film to Enhance PBO Fiber's UV Stability |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102634976B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031272A (en) * | 2014-07-02 | 2014-09-10 | 哈尔滨工业大学 | Amination nano-silica modified PBO polymer and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104292461B (en) * | 2014-09-16 | 2016-06-29 | 哈尔滨工业大学 | The preparation method of the PBO polymer that a kind of POSS is modified |
| CN106521967B (en) * | 2016-11-10 | 2018-10-26 | 成都纺织高等专科学校 | One kind is based on POSS grafting uvioresistant AROMATIC HIGH PERFORMANCE FIBERSs and its method of modifying |
| CN108486861B (en) * | 2018-04-25 | 2020-06-02 | 浙江梵彼斯特轻纺发展有限公司 | Preparation process of anti-ultraviolet aging PBO fiber |
| CN109295690A (en) * | 2018-10-09 | 2019-02-01 | 哈尔滨工业大学 | A kind of construction method of UV-resistant/antigenic oxygen nano-silicon-containing coating on the surface of PBO fiber |
| CN115897219B (en) * | 2023-02-24 | 2024-11-22 | 润华(江苏)新材料有限公司 | Light-resistant para-aramid fiber and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101050595B (en) * | 2007-05-22 | 2010-12-29 | 北京科技大学 | Nano inorganic powder coated high molecular fiber and its preparing method |
| CN101397696A (en) * | 2008-11-12 | 2009-04-01 | 东华大学 | Method for preparing anti-ultraviolet ageing poly-p-phenylene-benzobisoxazole (PBO) fiber |
| CN101613892B (en) * | 2009-07-14 | 2011-04-06 | 华东理工大学 | Preparation method of poly(p-phenylene benzobisoxazole) composite fiber containing nano-TiO2 |
| CN101906676B (en) * | 2010-08-17 | 2012-06-13 | 东华大学 | Ultraviolet aging-resistance poly(p-phenylene benzobisoxazole) (PBO) fibers and preparation method thereof |
| CN102277726A (en) * | 2011-09-02 | 2011-12-14 | 北京理工大学 | Anti-ultraviolet aging method for p-phenylene benzobisoxazole (PBO) fiber |
-
2012
- 2012-04-20 CN CN201210118341XA patent/CN102634976B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031272A (en) * | 2014-07-02 | 2014-09-10 | 哈尔滨工业大学 | Amination nano-silica modified PBO polymer and preparation method thereof |
| CN104031272B (en) * | 2014-07-02 | 2017-02-15 | 哈尔滨工业大学 | Amination nano-silica modified PBO polymer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102634976A (en) | 2012-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102634976B (en) | Method of Surface Deposited (POSS/TiO2)n Thin Film to Enhance PBO Fiber's UV Stability | |
| Wang et al. | Titanium dioxide nanoparticles-coated aramid fiber showing enhanced interfacial strength and UV resistance properties | |
| Zhang et al. | Facile preparation of hyperbranched polysiloxane-grafted aramid fibers with simultaneously improved UV resistance, surface activity, and thermal and mechanical properties | |
| CN102797152A (en) | Aramid fiber surface modification method | |
| Cao et al. | Strong, conductive aramid fiber functionalized by graphene | |
| US20200048763A1 (en) | Multilayer encapsulation thin-film | |
| CN108867025B (en) | A kind of color carbon fiber material based on one-dimensional photonic crystal and preparation method thereof | |
| CN101791608B (en) | Preparation method of self-repairing super hydrophobic coating | |
| Song et al. | Preparation and characterization of (POSS/TiO 2) n multi-coatings based on PBO fiber surface for improvement of UV resistance | |
| Chen et al. | Acrylic acid polymer coatings on silk fibers by room‐temperature APGD plasma jets | |
| CN101050595A (en) | Nano inorganic powder coated high molecular fiber and its preparing method | |
| Zhao et al. | Enhanced mechanical property of continuous carbon fiber/polyamide thermoplastic composites by combinational treatments of carbon fiber fabric | |
| Fan et al. | Wear‐resistant cotton fabrics modified by PU coatings prepared via mist polymerization | |
| Dong et al. | Fabrication of highly efficient ultraviolet absorbing PVDF membranes via surface polydopamine deposition | |
| Zhang et al. | Application of polybenzimidazole as a panchromatic ultraviolet absorber in poly (vinyl chloride) film | |
| CN114086273A (en) | Graphene anti-ultraviolet anti-cutting high-stretch-resistance composite fiber and preparation method thereof | |
| Zhao et al. | Pinene‐functionalized polysiloxane as an excellent self‐healing superhydrophobic polymer | |
| Xu et al. | Nano‐silica/fluorinated polyacrylate composites as surface protective coatings for simulated stone cultural relic protection | |
| Zhou et al. | Enhancement of antimicrobial and UV resistant properties of aramid III fiber through surface coating | |
| Mao et al. | Ultraviolet resistance modification of poly (p‐phenylene‐1, 3, 4‐oxadiazole) and poly (p‐phenylene terephthalamide) fibers with polyhedral oligomeric silsesquioxane | |
| He et al. | Facile fabrication of multifunctional aramid fibers for excellent UV resistance in extreme environments | |
| Amesimeku et al. | Fabrication of electrically conductive and improved UV-resistant aramid fabric via bio-inspired polydopamine and graphene oxide coating | |
| Zhang et al. | Biomimetic nanoporous transparent universal fire-resistant coatings | |
| CN102634970A (en) | Method of Surface Depositing (PAA/PEI)m/(PAA/TiO2)n Thin Film to Enhance PBO Fiber's UV Stability | |
| CN101892582B (en) | Light aging resistant finishing liquor for aramid fiber and method for finishing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20120815 Assignee: Harbin Topfrp Composite Co., Ltd. Assignor: Harbin Institute of Technology Contract record no.: 2014230000386 Denomination of invention: Method for enhancing ultraviolet resistance stability of PBO (poly-p-phenylenebenzobisthiazole) fibers by depositing (PAA (polyacrylic acid)/PEI (polyethyleneimine))m/(PAA/TiO2)n films on surfaces Granted publication date: 20131211 License type: Exclusive License Record date: 20140723 |
|
| LICC | Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model |