CN101906677B - Preparation method of anti-ultraviolet aging polyphenylene benzodioxazole fiber - Google Patents
Preparation method of anti-ultraviolet aging polyphenylene benzodioxazole fiber Download PDFInfo
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- CN101906677B CN101906677B CN2010102701807A CN201010270180A CN101906677B CN 101906677 B CN101906677 B CN 101906677B CN 2010102701807 A CN2010102701807 A CN 2010102701807A CN 201010270180 A CN201010270180 A CN 201010270180A CN 101906677 B CN101906677 B CN 101906677B
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Abstract
The invention relates to a preparation method of an anti-ultraviolet aging polyphenylene benzodioxazole fiber, which comprises the following steps: adding raw materials into a prepolymerizer according to the mixing ratio, removing chlorine hydride gas at certain temperature, gradually increasing the temperature to 160-180 DEG C, carrying out reaction for 12-48h, then transferring into a twin-screw reactor for carrying out postpolymerization, obtaining PBO/PPA spinning solution which is in line with requirements, and quantitatively conveying into a spinning component by a metering pump; and extruding the PBO/PPA spinning solution by a spinneret plate at 150-200 DEG C, passing through an air gap layer of 50-300cm for stretching, then entering into a coagulation bath, passing through a washing process of 50-300m with warm water at about 30-50 DEG C after passing through the coagulation bath, drying at 70-110 DEG C, then winding at the speed of 50-200m, obtaining a PBO protofilament, continuously carrying out heat treatment at 550-650 DEG C and obtaining the high-modulus PBO fiber, wherein an anti-aging agent is added in coagulation bath solution in advance. The anti-ultraviolet aging polyphenylene benzodioxazole fiber has the advantages that the anti-aging agent is closed and retained in the fiber, thereby giving the durable anti-aging property to the fiber; and the process is simple and applicable to the industrial operation.
Description
[technical field]
The present invention relates to polyphenylene Ben Bing Er oxazole (PBO) fiber production technical field, specifically, is a kind of preparation method of ageing resistance by ultraviolet light pbo fiber.
[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, the pbo fiber that is made by dry-jet wet spinning process has low-density, high-strength and high-modulus and high excellent properties such as heat-resisting and chemical stability, it is one of high-performance fiber of present combination property the best, be called as super organic fiber of 21st century, have broad application prospects in a lot of fields such as Aero-Space, high-tech equipment.
Though pbo fiber has good mechanical property and heat endurance, pbo fiber is for a long time in the following time of irradiation of ultraviolet light, and significantly descending can appear in fibre strength.In September, 2003, the U.S. second chance bulletproof jacket company just once circulated a notice of the decreased performance speed of pbo fiber under chance heat, light irradiation and wet environment than originally wanting fast many warning (Joannie Chin et al. in advance to the client, Polymer Degradation and Stability, 2007,92:1234).This has greatly influenced the application of pbo fiber in high-tech area.For this reason, need to improve the resistance to UV aging energy of pbo fiber.
As everyone knows, be exposed under the ultraviolet light irradiation for a long time and can cause macromolecule material aging and performance to reduce, this is the common shortcoming of macromolecule material product.In the industrial production field, by long term studies and practice, people have developed specific or general photo-oxidant stabilizer at the ultraviolet light and aging problem of various macromolecular materials, these photo-oxidant stabilizers usually can be by the method for in-situ polymerization or in the method for photo-oxidant stabilizer adding system being carried out blend by the process equipment such as screw extruder, photo-oxidant stabilizer is joined in the macromolecule material product, reach the purpose of anti-light aging.
For pbo fiber, the report that some similar approach are also arranged, in Chinese patent CN101215732A, nano titanium oxide is pre-mixed in PPA, join then in the polymer raw system, obtain PBO/ nanometer titanium dioxide blending solution after the polymerization, and obtain the PBO/ nanometer titanium dioxide fiber by dry-jet wet spinning process, nano titanium oxide provides the uvioresistant effect.And for example among the Chinese patent CN101397696A, the inventor directly adds anti ultraviolet agent TM in the polymer material, carries out the PBO/PPA solution that in-situ polymerization obtains being mixed with TM, is used for direct fabrics to obtain containing the pbo fiber of anti ultraviolet agent.
For pbo fiber, a large amount of studies show that, the age resister that improves most of macromolecule material product resistance to UV aging that those are general, to resistance to UV aging effect and bad (the Walsh PJ et al that improves pbo fiber, Journal of Applied Polymer Science, 2006,102:3525).The another one problem is process: additive is present in the polymerization system as a kind of impurity during in-situ polymerization, inevitably can disturb polymerization process; The PBO/PPA spinning solution has than general macromolecular fibre spinning solution or the much higher viscosity of spinning melt in addition, and inorganic nano-particle is very easily reunited, and therefore is difficult to make nano particle to realize nano level dispersion in the spinning solution of hyperviscosity; In addition, the spinning process of liquid crystal polymer is very responsive for the rheological property of spinning solution, add additive in the spinning solution as antiaging agent and so on, can have influence on the rheological property of liquid crystal polymer, disturb the orientation of macromolecular chain segment and the formation of ordered structure, increase the spinning difficulty,, also can influence the intensity and the modulus of fiber greatly even because structural tiny flaw.
[summary of the invention]
The objective of the invention is to overcome the deficiencies in the prior art, a kind of ageing resistance by ultraviolet light polyphenylene Ben Bing Er oxazole (PBO) fiber preparation method is provided.
The objective of the invention is to be achieved through the following technical solutions:
A kind of ageing resistance by ultraviolet light polyphenylene Ben Bing Er oxazole (PBO) fiber preparation method, its concrete steps are:
In prepolymerization reactor, press mass ratio and add 1 part 4, the 6-diamino resorcin hydrochlorate, 0.75～0.85 part of terephthalic acid (TPA), 3.8～4.8 parts of polyphosphoric acids, 2.2～3.2 parts of phosphorus pentoxides, after removing hydrogen chloride gas under 70～110 ℃, progressively be warming up to 160～180 ℃, react after 12～48 hours, the pre-polymerization material is transferred to double-screw reactor carries out the back polymerization, obtain satisfactory PBO/PPA spinning solution, quantitatively be transported to filament spinning component by measuring pump; The PBO/PPA spinning solution extrudes through spinnerets in 150～200 ℃ that (orifice diameter is 0.15～0.40mm), by entering coagulating bath after the stretching of 50～300cm air gap layer, added in advance specific age resister in the coagulation bath, after the process coagulating bath, 30～50 ℃ of warm water washes journey through about 50～300 meters, dry down at 70～110 ℃, reel with 50～200 meters speed then, obtain PBO precursor (AS fiber), continuation is heat-treated at 550～650 ℃ and is then obtained ageing resistance by ultraviolet light polyphenylene Ben Bing Er oxazole fiber;
Described age resister is meant the compound that contains metal ion, as the bases compound of metal ion salt compounds and metal ion; These metal ion compounds, the ionic compound of preferred transition metal and rare earth element, the most preferably iron in the transition metal, copper, cobalt ions, and the europium in the rare earth element, iridium ion compound;
Described metal ion salt compounds, be meant the inorganic salts or the organic salt of metal ion, choice criteria is that this kind salt can be dissolved in solidification liquid and gets final product, and the chloride of preferable alloy ion wherein is as iron chloride, copper chloride, cobalt chloride, Europium chloride, iridium chloride;
The bases compound of described metal ion refers to the hydroxide of metal ion, wherein preferred iron hydroxide and Kocide SD;
Described age resister is a kind of compound of above-mentioned metal ion compound or the mixture of several compounds;
Described age resister, the mass percent in solidification liquid are 0.1%～10%, and preferable range is 2%～4%;
Described solidification liquid refers to be used for the conventional media of PBO spinning coagulation bath, and the most frequently used is water/phosphoric acid solution, has disclosed in a large number kind and prescriptions about PBO spinning solidification liquid in the document;
Described coagulating bath, can adopt the form of single-stage coagulating tank or multistage coagulating tank, if adopt multistage coagulating tank, then must add age resister in first coagulating tank, all the other coagulating tanks at different levels can add also can not add age resister, and ageing-resistant concentration can identically with first coagulating tank also can be successively decreased; But preferred scheme is the age resister that coagulating tanks at different levels all add same concentrations.
Preparation method of the present invention comprises two committed steps, the one, and fiber is through containing ageing-resistant coagulating bath, so that solidification liquid is brought fibrous inside into to the diffusion of fibrous inside and with age resister; The 2nd, fiber is through drying process, so that the sealing of fiber surface micropore, it is smooth that fiber surface becomes, with the age resister permanent closure in fiber.
The present invention does not change the polymer raw prescription of PBO, do not disturb polymerization process, spinning, drying and aftertreatment technology and equipment are not changed yet, and only be in coagulating bath, to utilize solidification liquid to bring age resister into fibrous inside to the diffusion of fibrous inside.This moment, fiber sprayed a moulding, therefore can not disturb spinning process, also can not influence the mechanical property of fiber.
Compared with prior art, good effect of the present invention is:
(1) anti-light aging agent of the present invention is to add in the operation after the spray silk, so can not cause extra influence to polymerization and spinning process, need not go specially to adjust existing technology for this reason; After the spray silk, processes such as macromolecular orientation are finished substantially in addition, add the mechanical property that the anti-light aging agent does not influence fiber this moment;
(2) age resister of the present invention is dissolved in coagulation bath, does not exist to assemble and disperse uneven problem, age resister freely to diffuse into and absorption is retained in the fiber micropore;
(3) to diffuse into the process of fibrous inside be to utilize the directional diffusion of PPA and coagulation bath to finish in coagulating bath to age resister of the present invention, accomplished the integrated continuously of spinning-anti-aging processing, not additional additional process does not need existing equipment is changed yet.
[specific embodiment]
The specific embodiment of a kind of ageing resistance by ultraviolet light polyphenylene of the present invention Ben Bing Er oxazole (PBO) fiber preparation method below is provided.
Comparative Examples 1
In prepolymerization reactor, add 1000 grams 4 by proportioning, the 6-diamino resorcin hydrochlorate, 785 gram terephthalic acid (TPA)s, 4360 gram polyphosphoric acids, 2710 gram phosphorus pentoxides, after removing hydrogen chloride gas under 90 ℃, progressively be warming up to 170 ℃, react after 36 hours, the pre-polymerization material is transferred to double-screw reactor carries out the back polymerization, be transported to filament spinning component by measuring pump, extrude through spinnerets under 170 ℃, orifice diameter is 0.15mm, enter length after stretching by the 80cm air gap layer and be 2 meters single-stage coagulating bath, coagulation bath is water/phosphoric acid solution, and phosphoric acid quality percentage is 20%, then through 150 meters long washings, 50 ℃ of water temperatures, dry under 90 ℃, reel with the speed of 80 meters/min, obtain flavous pbo fiber.
The TENSILE STRENGTH of the pbo fiber that present embodiment obtains is 4.7GPa, through 1100w/m
2Behind the UV-irradiation 100 hours, strength retention is 54%.
Embodiment 1
What present embodiment and Comparative Examples 1 were different is, adds iron chloride in coagulating bath, and mass percent is 4%, and other is identical with Comparative Examples 1.
The TENSILE STRENGTH of the pbo fiber that present embodiment obtains is 4.6GPa, through 1100w/m
2Behind the UV-irradiation 100 hours, strength retention is 66%.
Embodiment 2
What present embodiment and Comparative Examples 1 were different is, adds iridium chloride in coagulating bath, and mass percent is 4%, and other is identical with Comparative Examples 1.
The TENSILE STRENGTH of the pbo fiber that present embodiment obtains is 4.7GPa, through 1100w/m
2Behind the UV-irradiation 100 hours, strength retention is 71%.
Embodiment 3
What present embodiment and Comparative Examples 1 were different is, adds iron chloride/copper chloride in coagulating bath, and gross mass percentage is 4%, and wherein iron chloride is 3%, and copper chloride is 1%, and other is identical with Comparative Examples 1.
The TENSILE STRENGTH of the pbo fiber that present embodiment obtains is 4.5GPa, through 1100w/m
2Behind the UV-irradiation 100 hours, strength retention is 67%.
Embodiment 4
What present embodiment and Comparative Examples 1 were different is, adds Kocide SD in coagulating bath, and mass percent is 4%, and other is identical with Comparative Examples 1.
The TENSILE STRENGTH of the pbo fiber that present embodiment obtains is 4.6GPa, through 1100w/m
2Behind the UV-irradiation 100 hours, strength retention is 75%.
Embodiment 5
Present embodiment adopts 3 coagulating tanks as different from Example 4, and the length of each groove is 2 meters, and the mass percent of Kocide SD is 4% in the coagulating tank, and concentration of phosphoric acid is identical with embodiment 4 in each coagulating tank.
The TENSILE STRENGTH of the pbo fiber that present embodiment obtains is 4.8GPa, through 1100w/m
2Behind the UV-irradiation 100 hours, strength retention is 82%.
Embodiment 6
Present embodiment as different from Example 5, the mass percent of Kocide SD is followed successively by 4%, 3% and 1% in 3 coagulating tanks, other is identical with embodiment 5.
The TENSILE STRENGTH of the pbo fiber that present embodiment obtains is 4.6GPa, through 1100w/m
2Behind the UV-irradiation 100 hours, strength retention is 78%.
The present invention can make pbo fiber obtain good ageing resistance by ultraviolet light performance by existing PBO dry-jet wet spinning process is improved.The main feature of this method is that specific age resister is joined in the coagulating bath in proportion, and dissolving obtains containing ageing-resistant uniform coagulation bath.Replace solidification liquid in original technology with this solidification liquid, when the PBO spinning solution forms as-spun fibre through the solidification liquid groove, polyphosphoric acids in the spinning solution from as-spun fibre inside to external diffusion, in as-spun fibre, form micropore, and age resister can diffuse into and be retained in these micropores owing to the PBO molecule suction-operated is arranged with solidification liquid.When as-spun fibre process subsequent drying step, the micropore sealing of fiber surface, thus the age resister sealing is retained in the fiber, give fiber lasting ageing resistance.The present invention carries out later in the moulding of fiber spray silk, does not influence polymerization technique, does not also need existing spinning equipment is changed on a large scale, does not need to adjust especially spinning technique, therefore can not influence the mechanical property of fiber, and technology simply is fit to the industrialization operation.
The above only is a preferred implementation 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. ageing resistance by ultraviolet light polyphenylene benzene and two oxazole fiber preparation method, it is characterized in that, concrete steps are: press mass ratio and add 1 part 4 in prepolymerization reactor, the 6-diamino resorcin hydrochlorate, 0.75～0.85 part of terephthalic acid (TPA), 3.8～4.8 parts of polyphosphoric acids, 2.2～3.2 parts of phosphorus pentoxides, after removing hydrogen chloride gas under 70～110 ℃, progressively be warming up to 160～180 ℃, react after 12～48 hours, the pre-polymerization material is transferred to double-screw reactor carries out the back polymerization, obtain satisfactory PBO/PPA spinning solution, quantitatively be transported to filament spinning component by measuring pump; The PBO/PPA spinning solution is extruded through spinnerets in 150～200 ℃, orifice diameter is 0.15～0.40mm, by entering coagulating bath after the stretching of 50～300cm air gap layer, added age resister in the coagulation bath, after the process coagulating bath, the journey of washing through 50～300 meters 30～50 ℃ of warm water, dry under 70～110 ℃, reel with 50～200 meters speed then, obtain the PBO precursor, continuation is heat-treated at 550～650 ℃, then obtains ageing resistance by ultraviolet light polyphenylene Ben Bing Er oxazole fiber.
2. a kind of ageing resistance by ultraviolet light polyphenylene Ben Bing Er oxazole fiber preparation method as claimed in claim 1, it is characterized in that, described age resister, be meant the compound that contains metal ion, be one or several mixtures in the bases compound of metal ion salt compounds and metal ion.
3. a kind of ageing resistance by ultraviolet light polyphenylene Ben Bing Er oxazole fiber preparation method as claimed in claim 2 is characterized in that the compound of described metal ion is the ionic compound of transition metal and rare earth element.
4. a kind of ageing resistance by ultraviolet light polyphenylene benzene as claimed in claim 2 and two oxazole fiber preparation method, described metal ion salt compounds is meant the inorganic salts or the organic salt of metal ion.
5. a kind of ageing resistance by ultraviolet light polyphenylene Ben Bing Er oxazole fiber preparation method as claimed in claim 2, the bases compound of described metal ion refers to the hydroxide of metal ion.
6. a kind of ageing resistance by ultraviolet light polyphenylene Ben Bing Er oxazole fiber preparation method as claimed in claim 5, the bases compound of described metal ion is iron hydroxide and Kocide SD.
7. a kind of ageing resistance by ultraviolet light polyphenylene Ben Bing Er oxazole fiber preparation method as claimed in claim 1, described age resister, the mass percent in solidification liquid are 0.1%～10%.
8. a kind of ageing resistance by ultraviolet light polyphenylene Ben Bing Er oxazole fiber preparation method as claimed in claim 7, described age resister, the mass percent in solidification liquid are 2%～4%.
9. a kind of ageing resistance by ultraviolet light polyphenylene Ben Bing Er oxazole fiber preparation method as claimed in claim 1, described coagulating bath, the form of employing single-stage coagulating tank or multistage coagulating tank.
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| CN2010102701807A CN101906677B (en) | 2010-08-31 | 2010-08-31 | Preparation method of anti-ultraviolet aging polyphenylene benzodioxazole fiber |
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| CN2010102701807A CN101906677B (en) | 2010-08-31 | 2010-08-31 | Preparation method of anti-ultraviolet aging polyphenylene benzodioxazole fiber |
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| CN101906677B true CN101906677B (en) | 2011-12-21 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104727133B (en) * | 2015-03-10 | 2016-07-06 | 西安工程大学 | The preparation method of the pbo fiber of the finishing agent of resistance to UVB and resistance to UVB |
| CN105566628B (en) * | 2016-01-08 | 2017-10-20 | 哈尔滨工业大学 | A kind of preparation method of the penylene naphtho- Sulfadiazine Compound polymer of 2,5 dihydroxy 1,4 and its fiber |
| CN111926438A (en) * | 2020-08-18 | 2020-11-13 | 中国科学院宁波材料技术与工程研究所 | Ultraviolet-resistant high-strength high-modulus PBO fiber and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE202007007357U1 (en) * | 2007-03-12 | 2007-08-02 | I.G. Bauerhin Gmbh | Fabric in the form of a knitted, woven or fleece-like clothing part or for a seat or for a textile surface or for a textile element |
| CN101451275A (en) * | 2007-12-07 | 2009-06-10 | 东丽纤维研究所（中国）有限公司 | Ultraviolet resistant functional fabric |
| CN101215732B (en) * | 2008-01-02 | 2010-12-01 | 东华大学 | Ultraviolet resisting PBO fibre and preparing method thereof |
| 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 |
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