CN102691207B - Preparation method for ultraviolet resistant and damp-heat aging resistant PBO (polybenzoxazole) fiber - Google Patents
Preparation method for ultraviolet resistant and damp-heat aging resistant PBO (polybenzoxazole) fiber Download PDFInfo
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Abstract
The invention relates to a preparation method for an ultraviolet resistant and damp-heat aging resistant PBO (polybenzoxazole) fiber. The preparation method comprises the specific steps as follows: (1) preparing organosilicon hydrophobic sol; (2) preparing an organosilicon hydrophobic sol composite finishing liquor; and (3) immersing a PBO fiber into the organosilicon hydrophobic sol composite finishing liquor obtained in the step 2 for 0.5 to 2 h, then taking out the fiber, naturally airing the fiber at room temperature for 12 to 48 h, and placing the fiber in a drying cabinet for curing for2 to 5 h at 80 to 100 DEG C, so as to obtain a PBO fiber with a uniform hydrophobic surface coating. The invention has the advantages that ethanol is adopted as dispersant to enable photostabilizer to be uniformly dispersed in an organosilicon coating precursor, so as to guarantee the dispersing uniformity and endow the PBO fiber with ultraviolet aging resistance; and in the curing process, the ethanol volatilizes, organosilicon is subjected to crosslinking curing on the surface of the fiber to form the hydrophobic organosilicon coating, so as to endow the fiber with damp-heat aging resistance.
Description
[technical field]
The present invention relates to the pbo fiber technical field, specifically, is a kind of preparation method who has the pbo fiber of ultraviolet resistance and wet and heat ageing resistant concurrently.
[background technology]
Polyhenylene Ben Bing Er oxazole (being called for short PBO) is a kind of rigid rod liquid crystal polymer of complete fragrant heterocycle, that the pbo fiber that is made by dry-jet wet spinning process has is high-strength, Gao Mo, numerous excellent properties such as high temperature resistant, be called as " super fiber of 21 century ", be one of high-performance fiber of present combination property the best, at high-technology fields such as Aero-Space, national defense and military very wide application prospect arranged.
Although pbo fiber excellent performance, but its goods ageing failure problem has in use perplexed the use of pbo fiber, especially obvious aging phenomenon has just appearred in the bulletproof jacket by the pbo fiber preparation within less than the time in 5 years, and has therefore caused serious casualties event.Because the aging conditions of pbo fiber under ultraviolet light and wet condition is fast more than original expectation, this has limited pbo fiber greatly at present in development and the application of high-technology field.For this reason, need the anti-aging technology of research pbo fiber, the good pbo fiber of preparation resistance to ag(e)ing.
Aging thermo-oxidative ageing, hydrothermal aging and ultraviolet light and aging three classes of mainly can being divided into of pbo fiber.Under normal environment for use, hydrothermal aging and ultraviolet light and aging are comparatively general and serious on the impact of pbo fiber performance.It is generally acknowledged, the hydrothermal aging of pbo fiber is because hydrone penetrates into pbo fiber inside by modes such as capillary effects, through a series of physics and chemistry process, causes fibrous mechanical property to descend; Ultraviolet light and aging then be in the situation that pbo fiber at UV-irradiation, molecular chain structure is destroyed, thereby causes the decline of fibrous mechanical property.
At present, many about the aging research and comparison of pbo fiber ultraviolet resistance both at home and abroad, for the technology of wet and heat ageing resistant, patent and the document reported are less, can accomplish simultaneously that preventing ultraviolet method aging and hydrothermal aging does not then have report.
At the aging technical elements of pbo fiber ultraviolet resistance, many patents and document have been arranged.Generally speaking, its technology is divided into two large classes, and the first kind is that antiaging agent is added in the polymerization system, carries out in-situ polymerization and spinning.Specifically, such as Chinese patent CN101397696A, it directly adds anti ultraviolet agent TM in reaction system, and reaction is extruded material after finishing with twin screw or single screw extruder, adopt dry-jet wet spinning process to be spun into pbo fiber, thereby improve the ultra-violet resistance energy of pbo fiber.And for example Chinese patent CN101215732A is to add polyphosphoric acids and nano-TiO in the PBO reaction system
2Mixture, make the pbo fiber of anti-ultraviolet by in-situ polymerization.These class methods tend to the polymerization process of PBO is exerted an influence owing to directly adding additive in reaction system, cause intensity and the molecular weight and molecular weight of pbo fiber; On the other hand, because the spinning solution of pbo fiber is dense, cause additive to be difficult to Uniform Dispersion in spinning solution, and TiO
2And so on inorganic nano-particle itself easily reunite, dispersion effect is poorer.
The Equations of The Second Kind method then is to process after the fibre spinning moulding.The characteristics of this class methods maximum are fiber to be processed after the pbo fiber spinning moulding again, can reach desired effects, do not disturb again the spinning process of pbo fiber and affect fibre property.What this class methods report was more is to prepare TiO with sol-gel process
2Coating is utilized TiO
2Preventing ultraviolet be used for improving the light fastness aging of fiber.Concrete has, and the hydrolysis of the employing butyl titanates such as Liu Xiaoyan prepares TiO
2The hydrosol, and cure drying at 150 ℃, form TiO at fiber
2Coating, the light resistance of fiber has certain improvement after the coating.(Liu Xiaoyan. sol-gel process is improved the light resistance of kevlar fabric. textile journal, 2009,30 (2): 85～88, Liu Xiao-yan.Improving the photo-stability of high performance aramid fibers by sol-gel treatment.Fibers and Polymers, 2008,9 (4): 455～460).Qiu Jun etc. utilize the TiO of specific proportioning
2Colloidal sol forms TiO on the pbo fiber surface
2Coating has improved the ultraviolet-resistant performance of pbo fiber.(Qiu Jun. nano-TiO2 hydrosol preparation and on the impact of pbo fiber ageing resistance by ultraviolet light. journal of YCIT (natural science edition), 2009,22 (1): 35～39)
But, above method is used TiO
2The hydrosol is directly as ageing-proof coating, and treatment temperature is high, and exists nano-TiO
2Particle is easily reunited at fiber surface, difficulty is disperseed and do not reach the problem that fiber surface is effectively covered.For this reason, some researcher has used the method for dispersant, can greatly improve dispersing uniformity.Such as patent CN102277726A, at first prepare TiO
2-ZnO Compound Water colloidal sol dressing liquid uses polyethylene glycol as dispersant, and pbo fiber is immersed in the vibration of overfulfiling a production target in the dressing liquid, and is dry afterwards in pbo fiber surface formation uvioresistant coating, thereby reaches the aging effect of preventing ultraviolet.But, this patent is in order to disperse uniformly the nano particle in the colloidal sol, and the dispersant polyethylene glycol of use is hydrophilic, and this causes fiber surface to become hydrophilic, when improving the light fastness aging of pbo fiber, can aggravate on the contrary the hydrothermal aging of pbo fiber.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, a kind of pbo fiber preparation method who has ultraviolet resistance and wet and heat ageing resistant concurrently is provided, the preventing ultraviolet of taking into account pbo fiber wears out and anti-hydrothermal aging.
The objective of the invention is to be achieved through the following technical solutions:
A kind of preparation method who has the pbo fiber of ultraviolet resistance and wet and heat ageing resistant concurrently, its concrete steps are:
(1) gets respectively Ludox predecessor, ethanol (EtOH) and hydrochloric acid (HCl) and under 25～30 ℃ of conditions, heat mixing, mix rear adding hydrophobicity siloxanes, continuation is reacted 3～5h under 25～30 ℃ of conditions, obtain uniform and stable organic silicon hydrophobic colloidal sol;
Described Ludox predecessor is a kind of in ethyl orthosilicate, the methyl silicate;
Described hydrophobicity siloxanes is the siloxanes with hydrophobic grouping, for example a kind of in trimethoxy-benzene base silane, triethoxyphenylsilan, perfluor triethoxysilane, MTES, MTMS, dodecyltrimethoxysilane, cetyl trimethoxy silane, vinyltriethoxysilane, the octyltri-ethoxysilane;
The volume ratio of described Ludox predecessor, ethanol, hydrochloric acid, hydrophobicity siloxanes is 1: 5～10: 0.05～1: 1.5～5.0;
(2) the organic silicon hydrophobic colloidal sol that step (1) is obtained is warmed up to 40～80 ℃, add UV absorbers, and under supersonic oscillations are auxiliary, UV absorbers and organic silicon hydrophobic colloidal sol are mixed, duration of oscillation is 0.5～2h, then be cooled to room temperature, and the adding curing catalysts, obtain uniform and stable organic silicon hydrophobic colloidal sol composite finishing liquid;
Described UV absorbers is the UV absorbers that dissolves in ethanol, for example the mixture of one or more among UV-9, UV-328, UV-531, UV-O, phenyl salicytate, the ultra-violet absorber RMB;
The mass fraction of described UV absorbers is with respect to 0.1%～2% of organic silicon hydrophobic colloidal sol gross mass;
Described curing catalysts is conventional organosilicon crosslinked curing catalysts, such as acetylcholine, aluminium acetylacetonate, dibutyl tin laurate, diethylenetriamine, triethylene tetramine, triethanolamine, silicon nitrogen oligomer, p-methyl benzenesulfonic acid, dimethyl benzylamine, cobalt naphthenate etc. disclosed a large amount of about the prescription of this class catalyst and the report of optimum addition in the document.
(3) pbo fiber is immersed in the organic silicon hydrophobic colloidal sol composite finishing liquid that step (2) obtains, time is 0.5～2h, then take out fiber, at room temperature naturally dry 12～48h, place 80～100 ℃ of lower 2～5h of curing of drying box, obtain the pbo fiber that there is the uniform hydrophobic coating on the surface.
Compared with prior art, good effect of the present invention is:
(1) core thinking of the present invention is, uses ethanol as dispersant, and light stabilizer is dispersed in the organic silicon coating presoma, has guaranteed the uniformity of disperseing, and gives its ultraviolet resistance aging ability; And in the crosslinking curing process, the ethanol volatilization, organosiloxane is cross-linked to form hydrophobic organic silicon coating at fiber surface, gives fiber wet and heat ageing resistant ability.
(2) the present invention carries out anti-aging to the surface of finished product pbo fiber to process, and can not cause interference to polymerization and the spinning process of PBO, can not affect the original excellent properties of pbo fiber.
(3) the present invention adopts organic silicon coating, in colloidal sol, add the method for UV absorbers, because coating itself is hydrophobic, hydrone is difficult to absorption and penetrates into fibrous inside, so that this method can improve resistance to UV aging and the wet and heat ageing resistant performance of fiber simultaneously.
(4) preparation process of colloidal sol system of the present invention is simple, do not need at high temperature to process, and UV absorbers is uniformly dispersed in Ludox, does not have agglomeration traits, and UV absorbers is better at the distributing homogeneity of fiber surface behind the curing of coatings.
[specific embodiment]
The preparation method's of a kind of pbo fiber that has ultraviolet resistance and wet and heat ageing resistant concurrently of the present invention the specific embodiment below is provided.
Comparative Examples 1
Pbo fiber is without any processing, at 1100w/m
2Behind lower 110 hours of the UV-irradiation, the fibre strength conservation rate is 52%.Be 80% and do not have under the UV-irradiation condition with relative humidity at 80 ℃, only investigate the wet and heat ageing resistant performance of fiber, the fibre strength conservation rate is 79% after 360 hours.
Comparative Examples 2
(1) takes by weighing respectively 5mL ethyl orthosilicate, 25mL ethanol (EtOH) and 4mL hydrochloric acid (HCl) and after heating under 25 ℃ of conditions mixes, add 7.5mL trimethoxy-benzene base silane, continuation is at 25 ℃ of lower 5h that stir, add the curing catalysts aluminium acetylacetonate, stir 0.5h, obtain uniform and stable organic silicon hydrophobic colloidal sol dressing liquid.
(2) pbo fiber is immersed in the resulting organic silicon hydrophobic colloidal sol of step (1) dressing liquid, 0.5h after take out fiber, at room temperature naturally dry 12h, place again drying box at 90 ℃ of lower crosslinking curing 2h, obtain the pbo fiber that there is the uniform hydrophobic coating on the surface.
In this example, only adopt organic silicon coating and do not add UV absorbers, the contact angle of the pbo fiber that obtains has been brought up to 105.8 ° from original 60.2 °.At 1100w/m
2Behind lower 110 hours of the UV-irradiation, the fibre strength conservation rate is 61%.Being under 80% condition without UV-irradiation, 80 ℃ and relative humidity, only investigate the wet and heat ageing resistant performance of fiber, the fibre strength conservation rate is 96% after 360 hours.Compare with Comparative Examples 1, in the situation that there is organic silicon coating, the wet and heat ageing resistant ability of fiber improves highly significant, and the light aging resisting ability of fiber also improves.
Embodiment 1
(1) takes by weighing respectively 5mL ethyl orthosilicate, 25mL ethanol (EtOH) and 4mL hydrochloric acid (HCl) and after heating under 25 ℃ of conditions mixes, add 7.5mL trimethoxy-benzene base silane, continuation obtains uniform and stable organic silicon hydrophobic colloidal sol dressing liquid at 25 ℃ of lower 5h that stir.
(2) the organic silicon hydrophobic colloidal sol that step (1) is obtained is warmed up to 60 ℃, add 0.08g UV absorbers UV-9, and under supersonic oscillations are auxiliary, UV absorbers and organic silicon hydrophobic colloidal sol are mixed, duration of oscillation is 1h, then be cooled to room temperature, and add the curing catalysts aluminium acetylacetonate, obtain uniform and stable organic silicon hydrophobic colloidal sol composite finishing liquid.
(3) pbo fiber is immersed in the organic silicon hydrophobic colloidal sol composite finishing liquid that step (2) obtains, time is 0.5h, then takes out fiber, at room temperature naturally dries 12h, place again 90 ℃ of lower crosslinking curing 2h of drying box, obtain the pbo fiber that there is the uniform hydrophobic coating on the surface.
The pbo fiber that this example obtains is at process 1100w/m
2Behind the UV-irradiation 110 hours, strength retention is 75%.Be under the 80% hydrothermal aging condition without UV-irradiation, 80 ℃ and relative humidity, the fibre strength conservation rate is 97% after 360 hours.
Embodiment 2
What the present embodiment added as different from Example 1 is the perfluor triethoxysilane, rather than the trimethoxy-benzene base silane, and other are identical with Comparative Examples 1.
The pbo fiber that this example obtains is at process 1100w/m
2Behind the UV-irradiation 110 hours, strength retention is 84%.Be under the 80% hydrothermal aging condition without UV-irradiation, 80 ℃ and relative humidity, the fibre strength conservation rate is 98% after 360 hours.
Embodiment 3
The UV absorbers that the present embodiment adds as different from Example 1 is UV-531, and other are identical with Comparative Examples 1.
The pbo fiber that this example obtains is at process 1100w/m
2Behind the UV-irradiation 110 hours, strength retention is 78%.Be under the 80% hydrothermal aging condition without UV-irradiation, 80 ℃ and relative humidity, the fibre strength conservation rate is 96% after 360 hours.
Embodiment 4
The amount of the UV absorbers UV-9 that the present embodiment adds as different from Example 1 is 0.12g, and other are identical with Comparative Examples 1.
The pbo fiber that this example obtains is at process 1100w/m
2Behind the UV-irradiation 110 hours, strength retention is 79%.Be under the 80% hydrothermal aging condition without UV-irradiation, 80 ℃ and relative humidity, the fibre strength conservation rate is 97% after 360 hours.
Embodiment 5
The UV absorbers that the present embodiment adds as different from Example 1 is UV-531 and UV-O 1: 1 composite in mass ratio, total addition of UV absorbers is 0.20g, other are identical with Comparative Examples 1.
The pbo fiber that this example obtains is at process 1100w/m
2Behind the UV-irradiation 110 hours, strength retention is 81%.Be under the 80% hydrothermal aging condition without UV-irradiation, 80 ℃ and relative humidity, the fibre strength conservation rate is 97% after 360 hours.
The above only is preferred embodiment of the present invention; should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (9)
1. a preparation method who has the pbo fiber of ultraviolet resistance and wet and heat ageing resistant concurrently is characterized in that, concrete steps are:
(1) gets respectively Ludox predecessor, ethanol and hydrochloric acid and under 25～30 ℃ of conditions, heat mixing, mix rear adding hydrophobicity siloxanes, continue under 25～30 ℃ of conditions, to react 3～5h, obtain uniform and stable organic silicon hydrophobic colloidal sol;
(2) the organic silicon hydrophobic colloidal sol that step (1) is obtained is warmed up to 40～80 ℃, add UV absorbers, and under supersonic oscillations are auxiliary, UV absorbers and organic silicon hydrophobic colloidal sol are mixed, duration of oscillation is 0.5～2h, then be cooled to room temperature, and the adding curing catalysts, obtain uniform and stable organic silicon hydrophobic colloidal sol composite finishing liquid;
(3) pbo fiber is immersed in the organic silicon hydrophobic colloidal sol composite finishing liquid that step (2) obtains, time is 0.5～2h, then take out fiber, at room temperature naturally dry 12～48h, place 80～100 ℃ of lower crosslinking curing 2～5h of drying box, obtain the pbo fiber that there is the uniform hydrophobic coating on the surface.
2. a kind of preparation method who has the pbo fiber of ultraviolet resistance and wet and heat ageing resistant concurrently as claimed in claim 1 is characterized in that, in described step (1), described Ludox predecessor is a kind of in ethyl orthosilicate, the methyl silicate.
3. a kind of preparation method who has the pbo fiber of ultraviolet resistance and wet and heat ageing resistant concurrently as claimed in claim 1 is characterized in that, in described step (1), described hydrophobicity siloxanes is the siloxanes with hydrophobic grouping.
4. a kind of preparation method who has the pbo fiber of ultraviolet resistance and wet and heat ageing resistant concurrently as claimed in claim 3, it is characterized in that, described siloxanes with hydrophobic grouping is a kind of in trimethoxy-benzene base silane, triethoxyphenylsilan, MTES, MTMS, dodecyltrimethoxysilane, cetyl trimethoxy silane, vinyltriethoxysilane, the octyltri-ethoxysilane.
5. a kind of preparation method who has the pbo fiber of ultraviolet resistance and wet and heat ageing resistant concurrently as claimed in claim 1, it is characterized in that, in described step (1), the volume ratio of described Ludox predecessor, ethanol, hydrochloric acid, hydrophobicity siloxanes is 1: 5～10: 0.05～1: 1.5～5.0.
6. a kind of preparation method who has the pbo fiber of ultraviolet resistance and wet and heat ageing resistant concurrently as claimed in claim 1 is characterized in that, in described step (2), described UV absorbers is the UV absorbers that dissolves in ethanol.
7. a kind of preparation method who has the pbo fiber of ultraviolet resistance and wet and heat ageing resistant concurrently as claimed in claim 6, it is characterized in that, described UV absorbers is one or more the mixture among UV-9, UV-328, UV-531, UV-O, phenyl salicytate, the ultra-violet absorber RMB.
8. a kind of preparation method who has the pbo fiber of ultraviolet resistance and wet and heat ageing resistant concurrently as claimed in claim 1, it is characterized in that, in described step (2), the mass fraction of described UV absorbers is with respect to 0.1%～2% of organic silicon hydrophobic colloidal sol gross mass.
9. a kind of preparation method who has the pbo fiber of ultraviolet resistance and wet and heat ageing resistant concurrently as claimed in claim 1 is characterized in that, in described step (2), described curing catalysts is conventional organic silicon coating crosslinking curing catalyst.
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| CN103243411B (en) * | 2013-05-24 | 2015-02-18 | 黑龙江大学 | Preparation method of high-performance organic fibers on basis of 4,4'-diaminodiphenyl ether |
| CN103243410B (en) * | 2013-05-24 | 2015-04-15 | 黑龙江大学 | Preparation method of high-performance organic fibers on basis of 2,3,5,6-tetraaminopyridine hydrochloride |
| CN105199102A (en) * | 2015-07-09 | 2015-12-30 | 华东理工大学 | Novel thermosetting ultraviolet stabilizer and preparation method thereof |
| CN107217474A (en) * | 2016-03-22 | 2017-09-29 | 孙彦飞 | A kind of cloth with waterproof oleophobic function and preparation method thereof |
| CN106012492B (en) * | 2016-05-30 | 2018-01-19 | 哈尔滨工业大学 | A kind of method that difunctionality hyperbranched siloxane improves pbo fiber uvioresistant performance |
| CN107237136B (en) * | 2017-07-06 | 2019-08-20 | 国网湖南省电力公司带电作业中心 | A kind of coating material and coating production applied to pbo fiber surface |
| CN107385919B (en) * | 2017-07-06 | 2020-03-10 | 国网湖南省电力公司带电作业中心 | A coating material for surface modification of PBO fibers; surface modified PBO fiber, preparation and application thereof |
| CN107201660B (en) * | 2017-07-06 | 2019-07-30 | 国网湖南省电力公司带电作业中心 | A kind of hydrophobic coating material and coating production applied to pbo fiber surface |
| CN107880599A (en) * | 2017-11-27 | 2018-04-06 | 安徽中能众诚新能源科技有限公司 | A kind of solar paint for improving efficiency of light absorption and preparation method thereof |
| CN108624228A (en) * | 2018-04-08 | 2018-10-09 | 湖北大学 | A kind of preparation method of the super-hydrophobic micro nano structure of material surface |
| 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 |
| CN112921656A (en) * | 2021-02-05 | 2021-06-08 | 西安工程大学 | Shell-core nano-coated PBO fiber and preparation method thereof |
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| CN101397754B (en) * | 2008-11-03 | 2011-04-27 | 东华大学 | Method for preparing floride-free super-hydrophobic cotton fabric |
| CN102021819B (en) * | 2010-10-22 | 2012-08-29 | 东华大学 | Fluorine-free superhydrophobic finishing agent containing modified nano silicon dioxide hydrosol and application thereof |
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