CN113293614B - PBO fiber sizing agent with ultraviolet aging resistance, PBO fiber and preparation method thereof - Google Patents
PBO fiber sizing agent with ultraviolet aging resistance, PBO fiber and preparation method thereof Download PDFInfo
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- D06M2200/40—Reduced friction resistance, lubricant properties; Sizing compositions
Abstract
The invention discloses a PBO fiber sizing agent with ultraviolet aging resistance, a PBO fiber and a preparation method thereof, wherein the PBO fiber sizing agent with ultraviolet aging resistance can be prepared by mixing 0.1-5% by mass of a silane coupling agent, 0.1-5% by mass of an epoxy resin, 1-10% by mass of a light absorbing agent and 1-10% by mass of a light stabilizer, and coating the sizing agent on the PBO fiber in a sizing process. The invention solves the defects that the PBO fiber with the ultraviolet light resistance function prepared by the prior method has mechanical property defects, the production process is not easy to control, the industrial production is not facilitated and the like, improves the problem of poor interface bonding property of the PBO fiber sizing agent under the condition of not losing the fiber, and simultaneously, the PBO fiber produced by the method has good mechanical property and excellent ultraviolet light resistance and aging resistance.
Description
Technical Field
The invention belongs to the technical field of high-performance fibers, and particularly relates to a PBO fiber sizing agent with ultraviolet aging resistance, a PBO fiber and a preparation method thereof.
Background
PBO (poly-p-phenylene benzobisoxazole) fiber is a high-performance aromatic heterocyclic organic fiber prepared from PBO by a liquid crystal spinning technique, has tensile strength and elastic modulus about twice those of kevlar (aramid fiber), and is considered to have an ultimate elastic modulus as a straight-chain polymer. Due to the rigid molecular chain structure, the PBO fiber has excellent heat resistance, the heat resistance of the PBO fiber is 100 ℃ higher than that of aramid fiber, and the PBO fiber is an organic fiber with the most excellent comprehensive performance at present. And is thus also reputed as "21 st century microfiber". Therefore, the PBO fiber is widely used for reinforcement of advanced composite materials for aerospace and civil use. The PBO fiber has the main characteristics of high strength, high modulus, light weight, low moisture regain, high temperature resistance, and excellent impact resistance, friction resistance and dimensional stability. Since the development of PBO fibers by DOW chemical company in the united states in the 50's of the 20 th century, PBO fibers have received much attention for their excellent properties, their high strength, high modulus and dielectric constant of only 2.1, and thus are destined to have a wide range of applications in the scientific and technological fields of aviation and aerospace.
Although the PBO fiber is excellent in mechanical property and heat resistance, the mechanical property of the PBO fiber is greatly reduced under the irradiation of ultraviolet-visible light, so that the application of the PBO fiber in personal protection, armor protection, bridge ropes and the like is greatly limited. Therefore, how to improve the violet light resistance of the PBO fiber is a real problem to be solved urgently. Therefore, several methods for preparing PBO fibers with uv resistant additives have been proposed in succession.
For example, the invention patent with publication number CN103160950A discloses a preparation method of ultraviolet-proof PBO fiber. The method is characterized in that an ultraviolet-resistant agent is added in a polymerization stage and then liquid crystal spinning is carried out to prepare the ultraviolet-resistant PBO fiber, but the stability of the polymer stage is poor and the process stability is not easy to control.
For another example, the invention patent with publication number CN109295690A discloses a method for constructing a PBO fiber surface ultraviolet/atomic oxygen resistant nano silicon-containing coating. Firstly, acid etching modification is adopted to increase the roughness of the fiber surface, and then the acidified PBO fiber is irradiated by gamma rays with 60Co as an irradiation source or treated by oxygen plasma to excite substances in the irradiation liquid and synthesize the silicon-containing nano coating on the PBO fiber surface in situ. The invention patent with publication number CN108486861A discloses a preparation process of an anti-ultraviolet aging PBO fiber with excellent mechanical properties such as ultrahigh elasticity, high modulus ratio and the like. The process adopts acid etching to form grooves and fine lines on the surface of the PBO fiber, then the grooves and the fine lines react with carbon-based turbid liquid, graphite oxide and fine aluminum powder generated by the reaction are used for filling cracks on the surface of the PBO fiber, and finally the ultraviolet aging resistant coating is carried out. The invention patent with the publication number of CN107620204A discloses a PBO fiber with ultraviolet light resistance and a preparation method thereof. And sequentially carrying out surface chemical treatment, surface free radical reaction, sizing treatment by an anti-ultraviolet agent and drying on the PBO fiber to obtain the ultraviolet-resistant PBO fiber. The methods related to the above patents all adopt an acid etching method to increase the roughness of the fiber surface to improve the bonding property of the fiber and the sizing agent, but the etching degree is not easy to control, grooves and cracks are formed on the fiber surface, the fiber strength is easy to reduce, and the industrial production is not facilitated.
The invention patent with publication number CN102277726A discloses a method for resisting ultraviolet light aging of poly-p-phenylene benzobisoxazole fibers. The composite hydrosol of nano titanium dioxide and nano zinc oxide is dissolved in the dispersing agent, and the PBO finished product can be directly subjected to ultraviolet light aging resistant finishing, so that the surface of the PBO fiber is coated with a layer of sol, the internal structure of the PBO fiber is not changed, and the mechanical property of the PBO is not influenced. The PBO mechanical property is improved mainly because the nano titanium dioxide and the nano zinc oxide form a coating layer on the surface of the fiber, and ultraviolet light is blocked from directly acting on the PBO fiber. The research finds that: after the nano particles are coated, the light stability of the PBO is improved to a certain extent, but the effect is not obvious, and the improvement amplitude is less than 10%.
The invention patent with publication number CN107385919A discloses a coating material for PBO fiber surface modification, a surface modified PBO fiber, preparation and application thereof. The coating material comprises an ultraviolet absorbent, heptadecafluorodecyltrimethoxysilane, alicyclic epoxy resin, a curing agent and an organic solvent, when the modified PBO fiber is prepared, the PBO fiber to be treated is treated by a coupling agent, then surface activation is carried out, and the activated PBO fiber is soaked in the coating material and cured to form the coating. However, the method disclosed by the patent firstly uses the silane coupling agent for treatment and then uses the ultraviolet-resistant coating for coating, two working procedures are required, the curing time is long, and the method is not beneficial to industrial production.
Disclosure of Invention
Because the PBO fiber with the ultraviolet light resistance function prepared by the existing method has the defects of mechanical property, difficulty in controlling the production process, inconvenience for industrial production and the like, the invention provides the PBO fiber sizing agent with the ultraviolet aging resistance, the PBO fiber and the preparation method thereof, the problem of poor interface bonding property of the PBO fiber sizing agent is solved under the condition of no fiber loss, and meanwhile, the PBO fiber produced by the PBO fiber has good mechanical property and excellent ultraviolet aging resistance.
The invention is realized by the following technical scheme: the PBO fiber sizing agent with the ultraviolet aging resistance is prepared by mixing 0.1-5 mass percent of silane coupling agent, 0.1-5 mass percent of epoxy resin, 0.1-5 mass percent of light absorbing agent and 0.1-5 mass percent of light stabilizer.
The silane coupling agent is selected from one of gamma-aminopropyltriethoxysilane (KH 550), gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane (KH 560) and gamma- (methacryloyloxy) propyltrimethoxysilane (KH 570).
The epoxy resin is bisphenol A type waterborne epoxy resin, the epoxy value is 0.48-0.54, and the viscosity is 1100-1400 mps.
The light absorber is one or two selected from benzotriazole ultraviolet resistant agents (such as UV328, UV 326) and benzophenone ultraviolet absorbers (UV 531).
The light stabilizer is selected from one of hindered amine light stabilizers (such as UV770 and UV 622).
A preparation method of a PBO fiber sizing agent with ultraviolet aging resistance comprises the following steps:
A. respectively preparing 0.1-5% aqueous solution of silane coupling agent and 0.1-5% aqueous solution of epoxy resin, and mixing them to obtain modified epoxy resin, in which the silane coupling agent content is 0.1-5%;
B. preparing acetone solutions of the light absorbent and the light stabilizer, wherein the light stabilizer and the ratio of the light absorbent to acetone are 1;
C. and adding acetone solution of a light absorbent and a light stabilizer into the modified epoxy resin, and controlling the mass fractions of the light absorbent and the light stabilizer to be 0.1-5% respectively to obtain the PBO fiber sizing agent.
The PBO fiber with ultraviolet aging resistance is prepared by coating the PBO fiber sizing agent of claim 1 on the PBO fiber in a sizing process.
The PBO fiber sizing agent is 0.5-10% by mass.
In the sizing process, the sizing time is controlled to be 5-30 s, the grouting force is 0.1-0.5 MPa, and the drying temperature is 100-200 ℃.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) According to the invention, the silane coupling agent is added into the water-based epoxy resin, the modified epoxy resin sizing agent is prepared according to a specific formula and proportion, and then sizing treatment is carried out, so that the production process flow is simplified, the complex procedures of two times of drying treatment are avoided, the shrinkage condensation effect of the silane coupling agent is kept, and meanwhile, the interface binding property of the sizing agent and the fiber surface can be effectively improved, and the ultraviolet aging resistance of the fiber is further improved.
(2) According to the sizing agent, the ultraviolet absorbent and the light stabilizer are matched in proportion, the ultraviolet absorbent can absorb ultraviolet bands with different wavelengths, the light stabilizer can improve the light stability and the oxidation resistance of the material, and the ultraviolet absorbent and the light stabilizer can be coordinated when used at the same time, so that the ultraviolet resistance of the fiber can be effectively improved.
(3) The strength retention rate of PBO fibers treated by the sizing agent reaches 95% after being irradiated by ultraviolet light at 254nm for 100 hours, and the strength retention rate of untreated PBO fibers after being irradiated by ultraviolet light is only about 50%.
Drawings
FIG. 1 is a schematic flow diagram of a sizing process of the present invention.
The spinning device comprises a spinning frame, a yarn guide 2, a gum dipping tank 3, a squeezing roller 4, a drying box 5 and a yarn winder 6.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1:
the embodiment is a PBO fiber sizing agent with ultraviolet aging resistance, which is prepared by the following steps:
a. adding 2g of silane coupling agent KH560 into 98g of deionized water to prepare a silane coupling agent solution with the mass fraction of 2%, and stirring for 60min by adopting ultrasonic waves to obtain a transparent silane coupling agent hydrolysis solution;
b. adding 3g of bisphenol A type waterborne epoxy resin into 47g of deionized water to prepare a solution with the mass fraction of 6%, adding 50g of a silane coupling agent hydrolysis solution with the mass fraction of 2% into the solution, and stirring uniformly again to obtain a silane coupling agent modified epoxy resin solution with the mass percentage concentration of 3%;
c. dissolving 0.2g of benzotriazole ultraviolet resistant agent UV328 and 0.2g of hindered amine light stabilizer UV770 in 1.6g of acetone to prepare 2g of solution with the mass fraction of 20%;
d. and d, adding 2g of acetone solution dissolved with the ultraviolet light agent and the light stabilizer in the step c into the silane coupling agent modified epoxy resin solution prepared in the step b, and stirring for 30min at the temperature of 25 ℃ to obtain the PBO fiber sizing agent with the ultraviolet aging resistance, wherein the PBO fiber sizing agent has the ultraviolet aging resistance and the mass percentage of 4.4%.
Example 2:
the embodiment is a PBO fiber sizing agent with ultraviolet aging resistance, and the PBO fiber sizing agent is prepared according to the following steps:
a. adding 1g of silane coupling agent KH560 into 99g of deionized water to prepare a silane coupling agent solution with the mass fraction of 1%, and stirring for 60min by adopting ultrasonic waves to obtain a transparent silane coupling agent hydrolysis solution;
b. adding 4g of bisphenol A type waterborne epoxy resin into 46g of deionized water to prepare a solution with the mass fraction of 8%, adding 50g of silane coupling agent hydrolysis solution with the mass fraction of 1% into the solution, and stirring uniformly again to obtain a silane coupling agent modified epoxy resin solution with the mass percentage concentration of 4%;
c. dissolving 0.2g of benzotriazole ultraviolet resistant agent UV328 and 0.2g of hindered amine light stabilizer UV770 in 1.6g of acetone to prepare 2g of solution with the mass fraction of 20%;
d. and (c) adding 2g of acetone solution dissolved with the ultraviolet light agent and the light stabilizer in the step (c) into the silane coupling agent modified epoxy resin solution prepared in the step (b), and stirring for 30min at the temperature of 25 ℃ to obtain the PBO fiber sizing agent with the ultraviolet aging resistance, wherein the PBO fiber sizing agent has the mass percentage of 4.9%.
Example 3:
the embodiment is a PBO fiber sizing agent with ultraviolet aging resistance, and the PBO fiber sizing agent is prepared according to the following steps:
a. adding 5g of silane coupling agent KH550 into 95g of deionized water to prepare a silane coupling agent solution with the mass fraction of 5%, and stirring for 50min by adopting ultrasonic waves to obtain a transparent silane coupling agent hydrolysis solution;
b. adding 2.5g of bisphenol A type waterborne epoxy resin into 47.5g of deionized water to prepare a solution with the mass fraction of 5%, adding 50g of a silane coupling agent hydrolysis solution with the mass fraction of 5% into the solution, and stirring uniformly again to obtain a silane coupling agent modified epoxy resin solution with the mass percentage concentration of 2.5%;
c. dissolving 0.1g of benzotriazole ultraviolet resistant agent UV328 and 0.1g of hindered amine light stabilizer UV770 in 1.8g of acetone to prepare 2g of solution with the mass fraction of 10%;
d. adding 2g of acetone solution dissolved with the ultraviolet light agent and the light stabilizer in the step c into the silane coupling agent modified epoxy resin solution prepared in the step b, and stirring for 30min at the temperature of 25 ℃ to obtain the epoxy resin with the mass percentage of5.1% of PBO fiber sizing agent with ultraviolet aging resistance.
Example 4:
the embodiment is a PBO fiber sizing agent with ultraviolet aging resistance, and the PBO fiber sizing agent is prepared according to the following steps:
a. adding 3g of silane coupling agent KH570 into 97g of deionized water to prepare a silane coupling agent solution with the mass fraction of 3%, and stirring for 60min by adopting ultrasonic waves to obtain a transparent silane coupling agent hydrolysis solution;
b. adding 2g of bisphenol A type waterborne epoxy resin into 48g of deionized water to prepare a solution with the mass fraction of 4%, adding 50g of silane coupling agent hydrolysis solution with the mass fraction of 3% into the solution, and stirring uniformly again to obtain a silane coupling agent modified epoxy resin solution with the mass percentage concentration of 2%;
c. dissolving 0.05g of benzotriazole ultraviolet resistant agent UV531 and 0.05g of hindered amine light stabilizer UV770 in 1.9g of acetone to prepare 2g of solution with the mass fraction of 5%;
d. adding 2g of acetone solution dissolved with the ultraviolet light agent and the light stabilizer in the step c into the silane coupling agent modified epoxy resin solution prepared in the step b, and stirring for 30min at the temperature of 25 ℃ to obtain the epoxy resin with the mass percentage of3.5% of PBO fiber sizing agent with ultraviolet aging resistance.
Example 5:
the embodiment is a PBO fiber sizing agent with ultraviolet aging resistance, and the PBO fiber sizing agent is prepared according to the following steps:
a. adding 4g of silane coupling agent KH560 into 96g of deionized water to prepare a silane coupling agent solution with the mass fraction of 4%, and stirring for 30min by adopting ultrasonic waves to obtain a transparent silane coupling agent hydrolysis solution;
b. adding 0.5g of bisphenol A type waterborne epoxy resin into 49.5g of deionized water to prepare a solution with the mass fraction of 1%, adding 50g of a silane coupling agent hydrolysis solution with the mass fraction of 1% into the solution, and stirring uniformly again to obtain a silane coupling agent modified epoxy resin solution with the mass percentage concentration of 3%;
c. dissolving 0.3g of benzotriazole ultraviolet resistant agent UV326 and 0.3g of hindered amine light stabilizer UV622 in 1.4g of acetone to prepare 2g of solution with the mass fraction of 30%;
d. adding 2g of acetone solution dissolved with the ultraviolet light agent and the light stabilizer in the step c into the silane coupling agent modified epoxy resin solution prepared in the step b, and stirring for 30min at the temperature of 25 ℃ to obtain the product with the mass percentage3% of PBO fiber sizing agent having uv aging resistance.
Example 6:
this example is a PBO fiber with uv aging resistance.
The PBO fiber sizing agent with the ultraviolet aging resistance described in the embodiment 1 is used for sizing the existing PBO fiber, and the sizing treatment is carried out according to the following steps:
a. PBO fiber is placed on a spinning frame 1, sequentially passes through a yarn guide 2, a glue dipping tank 3, a squeezing roller 4, a drying box 5 and a yarn winding device 6, and is fixed on the yarn winding frame;
b. pouring the prepared sizing agent with the mass fraction of 4.4% into a glue dipping tank 3, and enabling the sizing agent to immerse a squeezing roller 4;
c. and (3) adjusting the grouting force to be 0.2MPa, starching when the temperature of the oven is 120 ℃, and controlling the starching time to be 5s to obtain the ultraviolet-resistant PBO fiber with the starching rate of 3%.
The sizing schematic in this example is shown in FIG. 1. The tensile strength of the untreated PBO fiber precursor is 34cN/dtex, and the strength retention rate is 56% after the untreated PBO fiber precursor is irradiated by 254nm ultraviolet light for 100 hours. The strength of the protofilament coated by the sizing agent is 36cN/dtex, and the strength retention rate is 92% after the protofilament is irradiated by 254nm ultraviolet light for 100 hours.
Example 7:
this example is a PBO fiber with uv aging resistance.
The existing PBO fiber is subjected to sizing treatment by using the PBO fiber sizing agent with the ultraviolet aging resistance described in the example 1, the treatment process is the same as that of the example 6, and the schematic sizing diagram is shown in figure 1. The only difference is that: the grouting force is 0.1MPa, and the ultraviolet-resistant PBO fiber with the grouting rate of 4 percent is obtained.
In the present example, the tensile strength of the untreated PBO fiber precursor was 34cN/dtex, and the strength retention ratio after irradiation with 254nm ultraviolet light for 100 hours was 56%. The strength of the protofilament coated by the sizing agent is 35cN/dtex, and the strength retention rate is 93% after the protofilament is irradiated by 254nm ultraviolet light for 100 hours.
Example 8:
this example is a PBO fiber with uv aging resistance.
The PBO fiber sizing agent with the ultraviolet aging resistance described in the example 1 is used for sizing the existing PBO fiber, the processing technology is the same as that of the example 6, and the schematic diagram of sizing is shown in figure 1. The only difference is that: and controlling the sizing time to be 6s to obtain the ultraviolet-resistant PBO fiber with the sizing rate of 5%.
In the present example, the tensile strength of the untreated PBO fiber precursor was 34cN/dtex, and the strength retention ratio after irradiation with 254nm ultraviolet light for 100 hours was 56%. The strength of the precursor coated by the sizing agent is 35.5cN/dtex, and the strength retention rate is 91% after the precursor is irradiated by 254nm ultraviolet light for 100 hours.
Example 9:
this example is a PBO fiber with uv aging resistance.
The PBO fiber sizing agent with the ultraviolet aging resistance described in the embodiment 4 is used for sizing the existing PBO fiber, the processing technology is the same as that of the embodiment 6, and the schematic diagram of sizing is shown in figure 1. The only difference is that: and starching when the temperature of the oven is 150 ℃ to obtain the ultraviolet-resistant PBO fiber with the starching rate of 3%.
In the present example, the tensile strength of the untreated PBO fiber precursor was 34cN/dtex, and the strength retention ratio after irradiation with 254nm ultraviolet light for 100 hours was 56%. The strength of the precursor coated with the sizing agent is 35cN/dtex, and the strength retention rate is 93% after the precursor is irradiated by 254nm ultraviolet light for 100 hours.
Example 10:
this example is a PBO fiber with uv aging resistance.
The PBO fiber sizing agent with the ultraviolet aging resistance described in the example 5 is used for sizing the existing PBO fiber, the processing technology is the same as that of the example 6, and the schematic diagram of sizing is shown in figure 1. The only difference is that: and (3) starching at the grouting force of 0.1MPa when the temperature of the oven is 180 ℃, and controlling the starching time to be 5s to obtain the ultraviolet-resistant PBO fiber with the starching rate of 4%.
In the present example, the tensile strength of the untreated PBO fiber precursor was 34cN/dtex, and the strength retention ratio after irradiation with 254nm ultraviolet light for 100 hours was 56%. The strength of the protofilament coated by the sizing agent is 35.5cN/dtex, and the strength retention rate is 95% after the protofilament is irradiated by 254nm ultraviolet light for 100 hours.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modifications and equivalent variations of the above embodiment according to the technical spirit of the present invention are within the scope of the present invention.
Claims (3)
1. The PBO fiber sizing agent with ultraviolet aging resistance is characterized in that: mixing 0.1-5% of silane coupling agent, 0.1-5% of epoxy resin, 0.1-5% of light absorbing agent and 0.1-5% of light stabilizer to obtain the PBO fiber sizing agent,
the silane coupling agent is selected from one of gamma-aminopropyltriethoxysilane, gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane, the epoxy resin is bisphenol A type waterborne epoxy resin, the epoxy value of the epoxy resin is 0.48-0.54, the viscosity of the epoxy resin is 1100-1400 mPa & s, the light absorber is selected from one or two of benzotriazole type ultraviolet resistant agents and benzophenone type ultraviolet absorbers, and the light stabilizer is selected from hindered amine type light stabilizers.
2. A method for preparing the PBO fiber sizing agent with ultraviolet aging resistance of claim 1, which is characterized in that: the method comprises the following steps:
A. respectively preparing 0.1-5% aqueous solution of silane coupling agent and 0.1-5% aqueous solution of epoxy resin, and mixing them to obtain modified epoxy resin, in which the silane coupling agent content is 0.1-5%;
B. preparing acetone solutions of the light absorbent and the light stabilizer, wherein the light stabilizer and the ratio of the light absorbent to acetone are 1;
C. and adding acetone solution of the light absorber and the light stabilizer into the modified epoxy resin, and controlling the mass fractions of the light absorber and the light stabilizer to be 0.1-5% to obtain the PBO fiber sizing agent.
3. The PBO fiber with ultraviolet aging resistance is characterized in that: in the sizing process, the PBO fiber sizing agent with the mass percent of 0.5-10% in the claim 1 is coated on the PBO fiber, the sizing time is controlled to be 5-30 s, the grouting force is 0.1-0.5 MPa, and the drying temperature is 100-200 ℃, so that the PBO fiber with the ultraviolet aging resistance is prepared.
Priority Applications (1)
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| JP2015151650A (en) * | 2014-02-18 | 2015-08-24 | 第一工業製薬株式会社 | fiber sizing agent |
| CN111825696B (en) * | 2019-04-18 | 2021-10-29 | 中国科学院化学研究所 | Benzoxazole ion compound, PBO fiber emulsion sizing agent containing benzoxazole ion compound and preparation method of PBO fiber emulsion sizing agent |
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