CN101525783A - Polyimide fiber and preparation method thereof - Google Patents
Polyimide fiber and preparation method thereof Download PDFInfo
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- CN101525783A CN101525783A CN200910029601A CN200910029601A CN101525783A CN 101525783 A CN101525783 A CN 101525783A CN 200910029601 A CN200910029601 A CN 200910029601A CN 200910029601 A CN200910029601 A CN 200910029601A CN 101525783 A CN101525783 A CN 101525783A
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Abstract
The invention discloses a polyimide fiber and a preparation method thereof. Synthesizing polyamide acid with a ternary polymerization method destroys the regularity and the symmetry property of molecular chains, so that the crystallization tendency of the molecular chains is reduced and the spinning property of PAA solution is improved; and partial cyclization treatment limits the degradation of polyamide acid, and spinning serum is easy to solidify and form when entering into coagulation bath. The microwave method is adopted to treat polyamide acid fiber, the cyclization rate is accelerated, and the reaction time is shortened; and simultaneously, no any side reaction is aroused under the microwave radiation. The prepared polyimide nascent fiber has high strength and good thermal resistance.
Description
Technical field
The present invention relates to a kind of synthetic fiber and preparation method thereof, particularly a kind of polyimide fiber and preparation method thereof belongs to technical field of polymer materials.
Background technology
Polyimides (PI) fiber is as a kind of high-performance fiber, the time of existing decades, it is the macromolecular material that contains imide ring on the molecule main chain, has performances such as remarkable machinery, dielectric, insulation, radiation hardness, corrosion-resistant, high-low temperature resistant, belongs to high-performance fiber.Because its outstanding feature aspect performance and preparation is no matter be that great application prospect is familiar with by people as structural material or functional material.Particularly radiation resistance, electrical insulation capability are more more excellent than other high-performance fiber, therefore can be widely used in fire-fighting, electronics, high-temperature medium and fields such as the filtration of radiativity material, space flight and aviation and war industry.
The seventies, the D.S.G of U.S. A Yuehan company in laboratory development success polyimides 2080 fibers, be called for short PIM2080, this fiber fabrication process is simple, have high temperature resistant, electric insulation and radiation resistance.Austria Lenzing AG (being present Inspec Fibers) company has released the P84 fiber, it is a business-like polyimide fiber the earliest, this fiber is made by BDTA and diphenylmethane diisocyanate ester and toluene-2,4-diisocyanate, main application fields is high temperature filtration and protective clothing, in addition as encapsulant and heat-insulating material.France Phone-Poulence company has also released a kind of special polyimide fiber Kernel, model is 235AGF, the performance of this fiber mainly be do not fire, molten, do not form particulate, be heated and do not shrink, very strong powerful, acidproof, the organic solvent-resistant of machinery is arranged, can be widely used as materials such as security blanket, seat protective cover, protective clothing, high temperature filtration.
The preparation method of polyimide fiber generally is divided into two kinds.A kind of is first synthesis of polyimides solution, and Direct Spinning is made polyimide fiber then, and its shortcoming is: need to adopt phenol solvent, solvent toxicity is big, and residual quantity is big in the fiber.Second kind is two-step method, and first synthesizing polyamides acid solution is spun to the polyamic acid fiber then, handles through imidizate again, obtains polyimide fiber.Because polyamic acid solidifies difficulty in coagulating bath, occur the roll banding phenomenon easily, therefore, adopt the fiber of this method preparation, its intensity has much room for improvement.
At present, the preparation of polyimide fiber is based on two-step method.At publication number is in the Chinese invention patent " a kind of polyimide fiber and preparation method thereof " of CN 1821457A, adopt two-step method to prepare polyimide fiber, with binary copolymerization method synthesizing polyamides acid and be spun to the polyamic acid as-spun fibre, handle through acid imide, obtain as-spun polyimide fibers.In the above-mentioned technology, owing to polyamic acid easily decomposes, and when solidifying spinning, solidify difficulty, solvent residual amount is big, the easy roll banding of strand; In the acid imide process, easily produce some side reactions and hydrolysis phenomenon or the like simultaneously, therefore, fibre strength is restricted to a certain extent.
Summary of the invention
In order to overcome the deficiency that prior art exists, the invention provides that a kind of spinnability is strong, imidizate efficient height, polyimide fiber that fibre strength is good and preparation method thereof.
The technical solution adopted in the present invention is: a kind of polyimide fiber is provided, and its structure is shown below:
The preparation method of above-mentioned polyimide fiber comprises the steps:
A. pyromellitic dianhydride and diamines are joined N, in N '-dimethylacetamide solvent, the synthetic ternary polymerization polyamic acid solution of copolymerization under-5～40 ℃ temperature conditions, wherein, the mol ratio of pyromellitic dianhydride and diamines is 1: 1～1: 1.05; Described diamines is p-phenylenediamine (PPD) and 4,4 '-diaminodiphenyl ether, and its mol ratio is 1: 9～9: 1;
B. acetic anhydride, catalyst and N are prepared into acid imide cyclisation agent after N '-dimethylacetamide solvent mixing, join in the above-mentioned polyamic acid solution, and wherein, the mol ratio of acetic anhydride and diamines is 0.1: 1～0.9: 1;
C. with the solution of step b preparation after filtration, after deaeration handles, adopt dry-wet spinning technology, obtain part cyclisation polyamic acid fiber;
D. above-mentioned part cyclisation polyamic acid fiber is carried out imidizate and handle under microwave condition, the preparation polyimide fiber.
In the technique scheme, described microwave condition is: microwave frequency 300～3500MHz, and microwave treatment time 1～15 minute, environment is nitrogen, vacuum or air.
Studies show that, to make it rigidity stronger because of containing a large amount of phenyl ring etc. for general polyamic acid strand, compliance is relatively poor, and the existence of the amide group in the strand causes its easy decomposition, and the polyamic acid fiber of spinning continues to degrade because of the moisture of emitting when the later stage acid imide is handled.All there are the more factor that makes the polyamic acid fiber degradation in chemistry and heat treatment, and especially when hot acid imide was handled more than 150 ℃, the polyamic acid fiber decomposed more rapid.The present invention is according to molecular chain structure design theory and polyamic acid decomposition mechanism, introduces this 3rd monomer of p-phenylenediamine (PPD), adopts the acid of ternary polymerization method synthesizing polyamides; Continue to add the part cyclizing agent on this basis, generate better part cyclisation polyamic acid of stability.Cause the decomposition of polyamic acid fiber when acid imide is handled when chemical and hot acid imide is handled, the present invention adopts microwave method to make polyamic acid fiber imidizate, prepares polyimide fiber.
The spinnability that the present invention is directed to present polyamic acid is easily decomposed poor, the easy decomposition when solidifying difficulty and acid imide, problems such as efficient is low, adopt the ternary polymerization polyamic acid fiber of microwave method processing section cyclisation, make it imidizate, thereby obtain intensity as-spun polyimide fibers preferably, its advantage is:
(1) purpose of introducing the third monomer has been to destroy the regularity and the symmetry of strand, and its crystallization tendency is reduced, and the compliance of strand increases, and improves the spinnability of PAA solution; The part cyclisation is handled and has been reduced labile polyamide group in the strand, has increased metastable imide group, thereby has limited the decomposition of polyamic acid, and PAA solution spinnability is improved, and is easy to moulding when spinning slurry enters coagulating bath.
(2) adopt microwave method to handle the polyamic acid fiber, accelerated cyclisation speed, shorten the reaction time, can not cause any side reaction under the microwave radiation simultaneously, product all is a polyimides.Microwave method is compared with chemical acid imide method and hot acid imide method, has finely avoided the side reaction generation, has suppressed the decomposition of fiber simultaneously, improves imidizate efficient.
Description of drawings
Accompanying drawing 1 is the infrared spectrogram by the polyimide fiber of the embodiment of the invention 2 technical schemes preparation.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is further described:
Embodiment 1:
Prepare a kind of part cyclisation polyamic acid fiber, step is as follows:
(1) the ternary polymerization polyamic acid solution is synthetic
Under the nitrogen protection; (mol ratio is 2: 8 a p-phenylenediamine (PPD) and 4 with diamines in there-necked flask; the mixing of 4 '-diaminodiphenyl ether) joins N; in N '-dimethylacetylamide (total solid content the is 10%) solvent; stir fast and make its dissolving; control reaction temperature is at 0 ℃; after treating that diamines dissolves fully; in flask, add one time pyromellitic dianhydride every half an hour; divide and add for four times; the mol ratio of pyromellitic dianhydride and diamines is 1: 1.02, and with an amount of acetamide drip washing bottle wall for several times, the copolymerization synthetic reaction obtains ternary polymerization polyamic acid (PAA) solution of faint yellow thickness after 3～4 hours.
(2) preparation of part cyclisation polyamic acid
By acetic anhydride: the diamines mol ratio is to add the part cyclizing agent (mixed solution of acetic anhydride, triethylamine and acetamide at 0.3: 1, wherein the mol ratio of triethylamine and acetic anhydride is 1: 1, acetamide 3ml), continues reaction 2～4 hours, obtain the performed polymer of golden yellow part cyclisation polyamic acid.
(3) dry-wet spinning becomes part cyclisation polyamic acid fiber
With the part cyclisation polyamic acid solution that obtained after filtration, after deaeration handles, adopt conventional doing/wet spinning, spinning temperature is controlled at 30～40 ℃, the employing diameter is 0.5mm, draw ratio is 6 single hole shower nozzle, and used coagulating bath is the mixture of methyl alcohol and water, and its volume ratio is 40: 60, the draw ratio of spinning stage fiber is 2, obtains part cyclisation polyamic acid fiber sample 1.
In step (2), the mol ratio of acetic anhydride and diamines is as shown in table 1 respectively, and the part cyclisation polyamic acid fiber by the technique scheme preparation obtains sample 2, sample 3, sample 4 and sample 5.
To carry out mechanics performance determining by the part cyclisation polyamic acid fiber sample 1～5 of present embodiment technical scheme preparation, its method is: adopt the electronic fiber tensometer that different fibers are carried out extension test, fixed length 10mm, draw speed is 10mm/min, surely extend 20mm, observe its fracture strength, the results are shown in Table 1.Table 1 is the result's contrast by the part cyclisation polyamic acid fiber sample mechanical property of different acetic anhydrides, the preparation of diamines mol ratio.
Table 1
| Sample | Acetic anhydride/diamines (mol ratio) | Solution properties viscosity/dLg -1 | Intensity/cN/dtex |
| 1 | 0.3/1 | 6.013 | 1.166 |
| 2 | 0.5/1 | 6.291 | 1.210 |
| 3 | 0.7/1 | 7.280 | 1.530 |
| 4 | 0.9/1 | 7.446 | 1.434 |
| 5 | 0/1 | 5.690 | 0.789 |
By table 1 as seen, within the specific limits, increase cyclisation dosage, the inherent viscosity of PAA solution and the fracture strength of fiber all improve.Part cyclisation PAA fibrous mechanical property all is better than the PAA fiber.
(4) microwave treatment
Part cyclisation polyamic acid (PAA) fiber sample 1 is carried out microwave treatment under nitrogen atmosphere, 1 kilogram of tension force condition, the processing time was respectively 3,6,10 and 15 minutes, prepared polyimide fiber behind the cyclodehydration.
To carry out mechanics performance determining by the polyimide fiber of above-mentioned steps preparation, its method is: adopt the electronic fiber tensometer to carry out extension test, fixed length 10mm, draw speed are 10mm/min, extend 20mm surely, observe its fracture strength.
Table 2 is part cyclisation polyamic acid fibers (microwave treatment time 0 minute) and the intensity contrast of polyimides (PI) fiber (different microwave treatment times) of microwave acid imide method preparation.
Table 2
By table 2 as seen, after the microwave imidizate was handled, the polyimide fiber fracture strength obviously improved, and within a short period of time, intensity reached maximum, and microwave treatment time is long will to cause the fiber coking, and intensity reduces.
Embodiment 2:
Press embodiment 1 technical scheme steps (1) synthesis of ternary copolyamide acid solution.
The solution of acetic anhydride, triethylamine and acetamide is mixed, wherein, the mol ratio of triethylamine and acetic anhydride is 1: 1, acetamide 3ml, be prepared into the part cyclizing agent, by acetic anhydride: the diamines mol ratio is 0.7: 1, adds part cyclizing agent and diamines in polyamic acid solution, reacted 2～4 hours, and obtained the performed polymer of golden yellow part cyclisation polyamic acid.
Make part cyclisation polyamic acid fiber by embodiment 1 technical scheme steps (3) dry-wet spinning.
Part cyclisation polyamic acid (PAA) fiber that is obtained behind the loose coiling, carries out microwave treatment under vacuum condition, the processing time was respectively 3,6,10 and 15 minutes, through cyclodehydration Processing of Preparation polyimide fiber.
To carry out mechanics performance determining by the polyimide fiber of present embodiment technical scheme preparation, its method is with embodiment 1, and the result is referring to table 3.
Table 3 is part cyclisation polyamic acid fibers (microwave treatment time 0 minute) and the intensity contrast of polyimides (PI) fiber (different microwave treatment times) of microwave acid imide method preparation.
Table 3
Can be seen equally that by table 3 after the microwave imidizate was handled, the polyimide fiber fracture strength obviously improved, and within a short period of time, intensity reached maximum, microwave treatment time is long will to cause the fiber coking, and intensity reduces.
Claims (3)
1. polyimide fiber, its characteristics are that the structure of described polyimides is shown below:
2. the preparation method of a polyimide fiber is characterized in that comprising the steps:
A. pyromellitic dianhydride and diamines are joined N, in N '-dimethylacetamide solvent, the synthetic ternary polymerization polyamic acid solution of copolymerization under-5～40 ℃ temperature conditions, wherein, the mol ratio of pyromellitic dianhydride and diamines is 1: 1～1: 1.05; Described diamines is p-phenylenediamine (PPD) and 4,4 '-diaminodiphenyl ether, and its mol ratio is 1: 9～9: 1;
B. acetic anhydride, catalyst and N are prepared into acid imide cyclisation agent after N '-dimethylacetamide solvent mixing, join in the above-mentioned polyamic acid solution, and wherein, the mol ratio of acetic anhydride and diamines is 0.1: 1～0.9: 1;
C. with the solution of step b preparation after filtration, after deaeration handles, adopt dry-wet spinning technology, obtain part cyclisation polyamic acid fiber;
D. above-mentioned part cyclisation polyamic acid fiber is carried out imidizate and handle under microwave condition, the preparation polyimide fiber.
3. the preparation method of a kind of polyimide fiber according to claim 2, its characteristics are: described microwave condition is: microwave frequency 300～3500MHz, microwave treatment time 1～15 minute, environment is nitrogen, vacuum or air.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102168317A (en) * | 2011-03-11 | 2011-08-31 | 北京化工大学 | Method for preparing polyimide fibers |
| CN102191581A (en) * | 2011-03-28 | 2011-09-21 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
| CN103774268A (en) * | 2014-01-20 | 2014-05-07 | 江苏巨贤合成材料有限公司 | Preparation method of polyamide imide fibrid |
| CN104357944A (en) * | 2014-11-06 | 2015-02-18 | 东华大学 | Method for preparing polyimide fiber through dry spinning |
| CN105239188A (en) * | 2015-11-10 | 2016-01-13 | 东华大学 | Method for preparing polyamide-imide copolymer fibers |
| CN106832279A (en) * | 2017-02-21 | 2017-06-13 | 北京化工大学 | A kind of method that utilization microwave radiation technology imidization prepares Kapton or fiber |
| CN109734909A (en) * | 2019-01-16 | 2019-05-10 | 江苏先诺新材料科技有限公司 | A kind of polyimides powder and preparation method thereof |
| CN112865239A (en) * | 2021-01-22 | 2021-05-28 | 苏州大学 | Preparation method of wireless charging device capable of being sewn on fabric and device |
| CN113416346A (en) * | 2021-06-17 | 2021-09-21 | 中国科学院山西煤炭化学研究所 | Method for preparing polyamic acid by microwave controllable breaking of carbon-nitrogen bond |
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2009
- 2009-03-27 CN CN200910029601A patent/CN101525783A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102168317B (en) * | 2011-03-11 | 2012-07-25 | 北京化工大学 | Method for preparing polyimide fibers |
| US20120228797A1 (en) * | 2011-03-11 | 2012-09-13 | Beijing University Of Chemical Technology | Methods of Continuously Manufacturing Polymide Fibers |
| US9011739B2 (en) * | 2011-03-11 | 2015-04-21 | Beijing University Of Technology | Methods of continuously manufacturing polymide fibers |
| CN102168317A (en) * | 2011-03-11 | 2011-08-31 | 北京化工大学 | Method for preparing polyimide fibers |
| CN102191581A (en) * | 2011-03-28 | 2011-09-21 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
| CN102191581B (en) * | 2011-03-28 | 2012-10-24 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
| CN103774268B (en) * | 2014-01-20 | 2016-05-11 | 江苏巨贤合成材料有限公司 | A kind of preparation method of polyamidoimide fibrid |
| CN103774268A (en) * | 2014-01-20 | 2014-05-07 | 江苏巨贤合成材料有限公司 | Preparation method of polyamide imide fibrid |
| CN104357944A (en) * | 2014-11-06 | 2015-02-18 | 东华大学 | Method for preparing polyimide fiber through dry spinning |
| CN105239188A (en) * | 2015-11-10 | 2016-01-13 | 东华大学 | Method for preparing polyamide-imide copolymer fibers |
| CN105239188B (en) * | 2015-11-10 | 2017-09-26 | 东华大学 | A kind of preparation method of polyamide-imide copolymer fiber |
| CN106832279A (en) * | 2017-02-21 | 2017-06-13 | 北京化工大学 | A kind of method that utilization microwave radiation technology imidization prepares Kapton or fiber |
| CN109734909A (en) * | 2019-01-16 | 2019-05-10 | 江苏先诺新材料科技有限公司 | A kind of polyimides powder and preparation method thereof |
| CN112865239A (en) * | 2021-01-22 | 2021-05-28 | 苏州大学 | Preparation method of wireless charging device capable of being sewn on fabric and device |
| CN113416346A (en) * | 2021-06-17 | 2021-09-21 | 中国科学院山西煤炭化学研究所 | Method for preparing polyamic acid by microwave controllable breaking of carbon-nitrogen bond |
| CN113416346B (en) * | 2021-06-17 | 2022-05-31 | 中国科学院山西煤炭化学研究所 | Method for preparing polyamic acid by microwave controllable breaking of carbon-nitrogen bond |
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