CN104727133B - The preparation method of the pbo fiber of the finishing agent of resistance to UVB and resistance to UVB - Google Patents

Abstract

The invention discloses a UVB-resistant finishing agent, which is composed of the following components according to mass percentage: 1-10% of nano-TiO ₂ , 1-20% of absolute ethanol, 1-5% of organic benzophenone finishing agent, and 0.1-1% of emulsifier %, 0.1-1% dispersant, the balance of deionized water, the sum of the mass percentages of the above-mentioned components is 100%; the above-mentioned components are mixed and emulsified and stirred to obtain nano-TiO ₂ / organic benzophenone UVB-resistant finishing agent , using the finishing agent to finish the PBO fiber after low-temperature plasma surface treatment to obtain UVB-resistant PBO fiber. The UVB-resistant finishing agent of the present invention has good synergy and good light stability, and the prepared UVB-resistant PBO fiber has enhanced anti-UVB irradiation ability, and the strength repair reaches more than 95%, which improves the mechanical properties of the fiber. The environment is pollution-free and has good economic and social benefits.

Description

Preparation method of UVB-resistant finishing agent and UVB-resistant PBO fiber

technical field

The invention belongs to the technical field of material modification, and in particular relates to a UVB-resistant finishing agent, and also relates to a preparation method of UVB-resistant PBO fibers.

Background technique

Poly(p-phenylenebenzobisoxazole) (PBO) fibers have high strength and heat resistance, and are widely used, especially in defense applications. However, it has a fatal flaw. The mechanical properties of poly-p-phenylenebenzobisoxazole (PBO) fibers decrease greatly after being irradiated by ultraviolet light, especially in the UVB band for a certain period of time. At present, the research on the aging of PBO fibers is mainly focused on photoaging, especially ultraviolet light. The UV resistance stability of fibers is mainly improved by the method of organic or inorganic anti-ultraviolet finishing agents, but due to the regular and orderly structure of PBO molecules The orientation structure makes the surface of the fiber very smooth, and most of the polar heteroatoms on the molecular chain are wrapped inside the fiber, and the polarity of the fiber surface is also very small, which makes the fiber show a strong chemical inertness, and the connection between the fiber and the matrix It is very weak. The methods currently used to improve the fiber's UV resistance include chemical modification, plasma treatment, surface bonding, etc., but the surface of the fiber is damaged to a certain extent, which reduces the strength of the fiber and greatly hinders the PBO fiber in Application and development in the field of high-performance composite materials. Therefore, improving the light damage of PBO fibers is still the focus of current research.

Contents of the invention

The purpose of the present invention is to provide a UVB-resistant finishing agent.

Another object of the present invention is to provide a preparation method of UVB-resistant PBO fiber, the prepared PBO fiber has enhanced ability to resist UVB irradiation, and improves the mechanical properties of the fiber.

The technical scheme adopted in the present invention is: UVB-resistant finishing agent, which is composed of the following components according to mass percentage: 1%-10% of nano-TiO ₂ , 1%-20% of absolute ethanol, 1%-20% of organic benzophenone finishing agent 5%, emulsifier 0.1%-1%, dispersant 0.1%-1%, deionized water balance, the sum of the mass percentages of the above components is 100%.

The present invention is also characterized in that,

The organic benzophenone finishing agent is any one of dihydroxybenzophenone, hydroxymethoxybenzophenone and oxybenzophenone.

Emulsifiers are nonionic surfactants.

The dispersant is an organic amine compound.

Another technical scheme adopted in the present invention is: the preparation method of the PBO fiber of resistance to UVB, specifically comprises the following steps:

Step 1: Weigh the following components according to the mass percentage: nano-TiO ₂ 1%-10%, absolute ethanol 1%-20%, organic benzophenone finishing agent 1%-5%, emulsifier 0.1%-1 %, 0.1% to 1% dispersant, the balance of deionized water, the sum of the mass percentages of the above components is 100%; mix the components, ultrasonic emulsification, and then high-speed stirring to obtain nano-TiO ₂ /organic benzophenones UVB-resistant finishing agent;

Step 2: Treat PBO fibers with low-temperature plasma generated by glow discharge for 190-210s to obtain surface-treated PBO fibers;

Step 3: Take 1% to 3.5% of the nano- _TiO2 /organic phenone finishing agent obtained in step 1, mix it with 0.1% to 0.4% NaOH, 0.1% to 0.5% NaCl and deionized water to obtain a finishing solution , the sum of the mass percentages of the above-mentioned components is 100%; the PBO fibers treated with low-temperature plasma in step 2 are immersed in the finishing liquid at room temperature and then dried and cured to obtain reinforced composite UVB-resistant PBO fibers.

The present invention is also characterized in that,

In step 1, the organic benzophenone finishing agent is any one of dihydroxybenzophenone, hydroxymethoxybenzophenone, and oxybenzophenone; the emulsifier is a nonionic surfactant; the dispersant is an organic Amine compounds.

The nonionic surfactant is preferably Tween, OP-10, polyester, fatty alcohol polyoxyethylene ether, or polyoxyethylene ester; the organic amine compound is preferably polyacrylamide, vinylbisstearamide, or ethanolamine.

In step 1, the temperature of ultrasonic emulsification is 85° C., and the time is 30 min; the speed of high-speed stirring is 3500 r/min, and the time is 60 min.

In step 2, in the low-temperature plasma treatment, the intake air volume is controlled to be 25 sccm, the stabilization time is 55-65 s, the discharge pressure is 28-32 Pa, and the discharge power is 190-210 w.

In step 3, the immersion time is 15s, the drying temperature is 100°C and the time is 30s, and the curing temperature is 130°C and the time is 90s.

The beneficial effects of the present invention are: the preparation method of the UVB-resistant PBO fiber of the present invention uses nano-TiO ₂ /organic benzophenone finishing agent for PBO fiber, and through processes such as impregnation, adsorption, drying, and curing, the nano-TiO2 ₂ / The organic benzophenone finishing agent is coated on the surface of PBO fiber, forming a spatial network structure on the surface of the fiber, tightly covering the fiber, forming a protective layer for the fiber, and the prepared PBO fiber has enhanced anti-UVB radiation ability and improved the fiber The mechanical properties have successfully solved the problem of PBO fiber strength reduction under UVB irradiation, and the strength repair has reached more than 95%. The process is simple, has no pollution to the environment, and has good economic and social benefits.

Description of drawings

Fig. 1 is the particle size diagram of the nano _TiO2 /organobenzophenone finishing agent prepared by the present invention;

Fig. 2 is the electron micrograph of the PBO fiber surface before low-temperature plasma treatment of the present invention;

Fig. 3 is the electron micrograph of the PBO fiber surface after the low-temperature plasma treatment of the present invention;

Fig. 4 is the infrared spectrogram of the PBO fiber before and after low-temperature plasma treatment of the present invention;

Fig. 5 is an effect diagram of the mechanical properties of the reinforced composite PBO fiber prepared by the present invention under ultraviolet UVB irradiation.

detailed description

The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments.

The UVB-resistant finishing agent of the present invention is composed of the following components according to mass percentage: 1%-10% of nano-TiO ₂ , 1%-20% of absolute ethanol, 1%-5% of organic benzophenone finishing agent, and 0.1% of emulsifier ~1%, dispersant 0.1%~1%, deionized water balance, the sum of the mass percentages of the above components is 100%;

The organic benzophenone finishing agent is any one of dihydroxybenzophenone, hydroxymethoxybenzophenone and oxybenzophenone;

The emulsifier is a nonionic surfactant, preferably Tween, OP-10, polyester, fatty alcohol polyoxyethylene ether, or polyoxyethylene ester;

The dispersant is an organic amine compound, preferably polyacrylamide, vinylbisstearamide, or ethanolamine.

The preparation method of the PBO fiber of resistance to UVB, specifically comprises the following steps:

Step 1: Weigh the following components according to the mass percentage: nano-TiO ₂ 1%-10%, absolute ethanol 1%-20%, organic benzophenone finishing agent 1%-5%, emulsifier 0.1%-1 %, 0.1% to 1% dispersant, the balance of deionized water, the sum of the mass percentages of the above components is 100%; mix the weighed components, ultrasonic emulsify at 85°C for 30min, and then use 3500r/min Stir at a high speed for 60 minutes to obtain a nano-TiO ₂ /organobenzophenone UVB-resistant finishing agent;

Among them, the organic benzophenone finishing agent is any one of dihydroxybenzophenone, hydroxymethoxybenzophenone, and oxybenzophenone; the emulsifier is a nonionic surfactant, preferably Tween, OP -10. Polyester, fatty alcohol polyoxyethylene ether, or polyoxyethylene ester; the dispersant is an organic amine compound, preferably polyacrylamide, vinylbisstearamide, or ethanolamine;

Step 2: Treat the PBO fiber with low-temperature plasma generated by glow discharge for 190-210s, then take out the PBO fiber to obtain the surface-treated PBO fiber. ～32Pa, the discharge power is 190～210w;

Step 3: Take 1% to 3.5% of the nano- _TiO2 /organic phenone finishing agent obtained in step 1, mix it with 0.1% to 0.4% NaOH, 0.1% to 0.5% NaCl and deionized water to obtain a finishing solution , the sum of the mass percentages of the above-mentioned components is 100%; the PBO fibers treated by low-temperature plasma in step 2 are immersed in the finishing solution at room temperature for 15s, dried at 100°C for 30s, and then cured at 130°C for 90s , to obtain reinforced composite UVB-resistant PBO fibers.

The beneficial effects of the present invention are: _TiO2 is an inorganic anti-ultraviolet finishing agent, but its photocatalyzed product will further react with water and oxygen while shielding ultraviolet rays, and damage fibers, and organic benzophenone finishing agents can make up for this Defects, it can absorb ultraviolet rays in the UVB band, has good compatibility, has good compatibility with TiO ₂ , can produce good synergy, and has good light stability. Therefore, using them together with PBO fibers can well shield the damage to PBO fibers caused by ultraviolet and UVB bands, thereby significantly improving the mechanical properties of the fibers. The surface of PBO fiber is treated with low-temperature plasma, so as to increase the surface wettability and adsorption performance of PBO fiber. The nano-TiO ₂ /organic benzophenone finishing agent works together on the PBO fiber. After impregnation, adsorption, drying, curing and other processes, the nano-TiO ₂ /organic benzophenone finishing agent can be coated on the surface of the PBO fiber. It forms a spatial network structure, tightly covers the fibers, and forms a protective layer for the fibers to improve the damage of the fiber strength after ultraviolet radiation. The reinforced composite PBO fiber made has enhanced UVB radiation resistance and improved mechanical properties of the material.

Example 1

Step 1: Weigh the following components according to the mass percentage: nano-TiO ₂ 5g, absolute ethanol 10g, dihydroxybenzophenone 3g, OP-101g, ethanolamine 0.5g, deionized water 80.5g, weigh the The components were mixed, ultrasonically emulsified at 85°C for 30 minutes, and then stirred at a high speed of 3500r/min for 60 minutes to obtain nano-TiO ₂ /organobenzophenone UVB-resistant finishing agent;

The particle size analysis of the nano-TiO ₂ /organic benzophenone finishing agent emulsion is shown in Figure 1. Figure 1 shows that the particle size of the finishing agent emulsion is concentrated around 100nm, and the stabilization effect is good.

Step 2: Treat the PBO fiber with low-temperature plasma generated by glow discharge for 200s, then take out the PBO fiber to obtain the surface-treated PBO fiber, control the air intake to 25sccm, the stabilization time to 55s, the discharge pressure to 30Pa, and the discharge power to 210w;

The surface morphology of PBO fiber before and after low-temperature plasma treatment is shown in Figure 2 and Figure 3. It can be seen from Figure 2 and Figure 3 that the surface of the PBO fiber without plasma treatment is very smooth, and the surface of the treated PBO fiber has fine cracks and grooves. The infrared spectrum of PBO fiber after glow discharge low-temperature plasma treatment is shown in Figure 4. Figure 4 shows that after glow discharge treatment, new absorption peaks appeared in the PBO fiber between 2000cm ^-1 and 4000cm ^-1 , indicating that active groups such as -OH and -CH ₃ were introduced on the surface of the fiber, and the surface properties of the fiber were improved. improved, while the skeleton structure of the fiber itself remains intact;

Step 3: Get the nano- _TiO2 / organic benzophenone finishing agent 2g that step 1 obtains, mix with the NaOH of 0.1g, the NaCl of 0.1g and the deionized water of 97.8g, obtain the finishing solution, the low temperature The PBO fibers after plasma treatment were immersed in the finishing solution at room temperature for 15s, dried at 100°C for 30s, and then cured at 130°C for 90s to obtain reinforced composite UVB-resistant PBO fibers.

Example 2

Step 1: Weigh the following components according to the mass percentage: nano-TiO ₂ 1g, absolute ethanol 1g, hydroxymethoxybenzophenone 1g, Tween 0.1g, polyacrylamide 1g, deionized water 95.9g, The weighed components were mixed, ultrasonically emulsified at 85°C for 30 minutes, and then stirred at a high speed of 3500r/min for 60 minutes to obtain nano-TiO ₂ /organobenzophenone UVB-resistant finishing agent;

Step 2: Treat the PBO fiber with the low-temperature plasma generated by glow discharge for 190s and then take out the PBO fiber to obtain the surface-treated PBO fiber. 200w;

Step 3: Get the nano- _TiO2 /organic phenone finishing agent 1g that step 1 obtains, mix with the NaOH of 0.2g, the NaCl of 0.3g and the deionized water of 98.5g, obtain the finishing solution, the low temperature The PBO fibers after plasma treatment were immersed in the finishing solution at room temperature for 15s, dried at 100°C for 30s, and then cured at 130°C for 90s to obtain reinforced composite UVB-resistant PBO fibers.

Example 3

Step 1: Weigh the following components according to the mass percentage: nano-TiO ₂ 10g, absolute ethanol 20g, oxybenzophenone 5g, fatty alcohol polyoxyethylene ether 0.8g, ethanolamine 0.1g, deionized water 64.1g , mixed the weighed components, ultrasonically emulsified at 85°C for 30min, and then stirred at a high speed of 3500r/min for 60min to obtain nano-TiO ₂ /organobenzophenone UVB-resistant finishing agent;

Step 2: Treat the PBO fiber with low-temperature plasma generated by glow discharge for 210s, then take out the PBO fiber to obtain the surface-treated PBO fiber, control the air intake to 25sccm, the stabilization time to 65s, the discharge pressure to 32Pa, and the discharge power to 190w;

Step 3: Get the nano- _TiO2 /organic phenones finishing agent 3.5g that step 1 obtains, mix with the NaOH of 0.4g, the NaCl of 0.5g and the deionized water of 95.5g, obtain the finishing solution, the process of step 2 The PBO fibers treated with low-temperature plasma were immersed in the finishing solution at room temperature for 15s, dried at 100°C for 30s, and then cured at 130°C for 90s to obtain reinforced composite UVB-resistant PBO fibers.

Example 4

Step 1: Weigh the following components according to mass percentage: 8g of nano-TiO ₂ , 15g of absolute ethanol, 4g of hydroxymethoxybenzophenone, 0.7g of polyoxyethylene ester, 0.6g of vinylbisstearamide, 71.7g of deionized water, mixed the weighed components, ultrasonic emulsified at 85°C for 30min, and then stirred at a high speed of 3500r/min for 60min to obtain nano- _TiO2 /organobenzophenone UVB-resistant finishing agent;

Step 2: Treat the PBO fiber with low-temperature plasma generated by glow discharge for 200s, then take out the PBO fiber to obtain the surface-treated PBO fiber, control the air intake to 25 sccm, the stabilization time to 60s, the discharge pressure to 30Pa, and the discharge power to 200w;

Step 3: Get the nano- _TiO2 / organic benzophenone finishing agent 3g that step 1 obtains, mix with the NaOH of 0.3g, the NaCl of 0.2g and the deionized water of 96.5g, obtain the finishing solution, the low temperature The PBO fibers after plasma treatment were immersed in the finishing solution at room temperature for 15s, dried at 100°C for 30s, and then cured at 130°C for 90s to obtain reinforced composite UVB-resistant PBO fibers.

The UVB-resistant PBO fiber prepared by the present invention was irradiated by changing the irradiation time under UVB irradiation, and the influence of UVB irradiation (illumination intensity: 292 μw/cm ² ) time on the fiber strength was studied, and the results are shown in Fig. 5 . It can be seen from Figure 5 that after UVB irradiation, the UVB resistance of the reinforced composite PBO fiber is increased compared with that of the PBO fibril, and the fiber strength damage is significantly reduced. When the UVB wavelength is 308nm, the light intensity is 292μw/cm ² , and the irradiation time is 6 days, the strength retention rate of the reinforced composite PBO fiber is 94.6%, the irradiation time is 9 days, the strength retention rate of the reinforced composite PBO fiber is 91.4%, and the irradiation time is 11 days , the strength retention rate of the reinforced composite PBO fiber is 85.9%, and the strength retention rate of the reinforced composite PBO fiber can reach 82% when the irradiation time is 13 days.

Claims (8)

1. UVB-resistant finishing agent, characterized in that it consists of the following components according to mass percentage: nano-TiO ₂ 1%-10%, absolute ethanol 1%-20%, organic benzophenone finishing agent 1%-5%, 0.1% to 1% of emulsifier, 0.1% to 1% of dispersant, the balance of deionized water, the sum of the mass percentages of the above components is 100%, and the organic benzophenone finishing agent is dihydroxybenzophenone, One of hydroxymethoxybenzophenone and oxybenzophenone. 2. UVB-resistant finishing agent as claimed in claim 1, is characterized in that, described emulsifying agent is nonionic surfactant. 3. The anti-UVB finishing agent according to claim 1, characterized in that, the dispersant is an organic amine compound. 4. the preparation method of the PBO fiber of resistance to UVB is characterized in that, specifically comprises the following steps: Step 1: Weigh the following components according to the mass percentage: nano-TiO ₂ 1%-10%, absolute ethanol 1%-20%, organic benzophenone finishing agent 1%-5%, emulsifier 0.1%-1 %, 0.1% to 1% dispersant, the balance of deionized water, the sum of the mass percentages of the above components is 100%; mix the components, ultrasonic emulsification, and then stir at a high speed to obtain nano-TiO ₂ / organic benzophenone UVB-resistant finishing agent, the temperature of the ultrasonic emulsification is 85°C, and the time is 30 minutes; the speed of high-speed stirring is 3500r/min, and the time is 60 minutes; Step 2: Treat PBO fibers with low-temperature plasma generated by glow discharge for 190-210s to obtain surface-treated PBO fibers; Step 3: Take 1% to 3.5% of the nano- _TiO2 /organic phenone finishing agent obtained in step 1, mix it with 0.1% to 0.4% NaOH, 0.1% to 0.5% NaCl and deionized water to obtain a finishing solution , the sum of the mass percentages of the above-mentioned components is 100%; the PBO fibers treated with low-temperature plasma in step 2 are immersed in the finishing liquid at room temperature and then dried and cured to obtain reinforced composite UVB-resistant PBO fibers. 5. the preparation method of the PBO fiber of anti-UVB as claimed in claim 4 is characterized in that, in described step 1, organic benzophenone finishing agent is dihydroxybenzophenone, hydroxymethoxybenzophenone, Any one of oxybenzophenones; the emulsifier is a nonionic surfactant; the dispersant is an organic amine compound. 6. the preparation method of the PBO fiber of anti-UVB as claimed in claim 5 is characterized in that, the preferred polysorbate of described nonionic surfactant, OP-10, polyester, fatty alcohol polyoxyethylene ether or polyoxyethylene Vinyl ester; the organic amine compound is preferably polyacrylamide, vinylbisstearamide, or ethanolamine. 7. the preparation method of the PBO fiber of anti-UVB as claimed in claim 4 is characterized in that, in described step 2, low-temperature plasma treatment control air intake is 25sccm, and stabilization time is 55～65s, and discharge pressure is 28～ 32Pa, the discharge power is 190~210w. 8. The preparation method of UVB-resistant PBO fiber as claimed in claim 4, characterized in that, in the step 3, the dipping time is 15s, the drying temperature is 100°C and the time is 30s, and the curing temperature is 130°C and the time is 90s.