CN102220652A - Method for effectively preparing polyimide fiber - Google Patents
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- CN102220652A CN102220652A CN 201010146335 CN201010146335A CN102220652A CN 102220652 A CN102220652 A CN 102220652A CN 201010146335 CN201010146335 CN 201010146335 CN 201010146335 A CN201010146335 A CN 201010146335A CN 102220652 A CN102220652 A CN 102220652A
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- ALTVSEFNOLOASZ-UHFFFAOYSA-N CC(C)(c(cc1)cc(C(O2)=O)c1C2=O)c(cc1)cc(C(O2)=O)c1C2=O Chemical compound CC(C)(c(cc1)cc(C(O2)=O)c1C2=O)c(cc1)cc(C(O2)=O)c1C2=O ALTVSEFNOLOASZ-UHFFFAOYSA-N 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N O=C(c(c1c2)cc(C(O3)=O)c2C3=O)OC1=O Chemical compound O=C(c(c1c2)cc(C(O3)=O)c2C3=O)OC1=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N O=C(c(cc1)c2cc1-c(cc1)cc(C(O3)=O)c1C3=O)OC2=O Chemical compound O=C(c(cc1)c2cc1-c(cc1)cc(C(O3)=O)c1C3=O)OC2=O WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N O=C(c(cc1)cc(C(O2)=O)c1C2=O)c(cc1C(O2)=O)ccc1C2=O Chemical compound O=C(c(cc1)cc(C(O2)=O)c1C2=O)c(cc1C(O2)=O)ccc1C2=O VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 2
- IKPDWXPKZUEPFR-UHFFFAOYSA-N O=C(c1ccc(Cc(cc2)cc(C(O3)=O)c2C3=O)cc11)OC1=O Chemical compound O=C(c1ccc(Cc(cc2)cc(C(O3)=O)c2C3=O)cc11)OC1=O IKPDWXPKZUEPFR-UHFFFAOYSA-N 0.000 description 2
- OKYQMTWDNPXGPE-UHFFFAOYSA-N CCCCNNNC Chemical compound CCCCNNNC OKYQMTWDNPXGPE-UHFFFAOYSA-N 0.000 description 1
- YAXFUNZOGOFHCM-UHFFFAOYSA-N N=C(c1c2cc(C(C(F)(F)F)(C(F)(F)F)c(cc3)cc(C(O4)=O)c3C4=N)cc1)OC2=O Chemical compound N=C(c1c2cc(C(C(F)(F)F)(C(F)(F)F)c(cc3)cc(C(O4)=O)c3C4=N)cc1)OC2=O YAXFUNZOGOFHCM-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N O=C(c(cc1)c2cc1Oc(cc1)cc(C(O3)=O)c1C3=O)OC2=O Chemical compound O=C(c(cc1)c2cc1Oc(cc1)cc(C(O3)=O)c1C3=O)OC2=O QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N O=C(c1c2cc(C(C(F)(F)F)(C(F)(F)F)c(cc3)cc(C(O4)=O)c3C4=O)cc1)OC2=O Chemical compound O=C(c1c2cc(C(C(F)(F)F)(C(F)(F)F)c(cc3)cc(C(O4)=O)c3C4=O)cc1)OC2=O QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract
The invention discloses a method for effectively preparing polyimide fiber, wherein a dry-process spinning device is used for directly preparing polyimide fiber; the method comprises the following steps of: (1) condensing dianhydride and diamine monomers to form precursor spinning solution used for spinning, adding chemical cyclizing agent or not; (2) spinning the fiber at a high temperature in a drying manner; (3) and hot-stretching the polyimide fiber. The polyimide fiber prepared in the invention has good high-temperature resistance, corrosion resistance, mechanical performance, and the like, and the production efficiency is greatly improved and the manufacturing procedure of cyclization reaction is omitted; and the polyimide fiber prepared in the invention can be widely applied to composite material reinforcing fiber, cable reinforcing core, car and ship mooring rope, filter material of high-temperature or radioactive substance, etc.
Description
Technical field
The present invention relates to the preparation method that a kind of polyimide fiber is made, its characteristics are, the polyamic acid spinning slurry is directly made polyimide fiber by the high temperature spinning shaft, make polyimide fiber after hot-stretch.
Background technology
Polyimide fiber is a kind of high-performance fiber, has many superior performances such as high strength, high-modulus, high temperature resistant, anti-combustion, radiation hardness, resistance to chemical attack.The preparation method of polyimide fiber has multiple: the one, and one step technique route: synthesis of polyimides solution at first, as the raw material direct fabrics, after hot-stretch, obtain polyimide fiber, this method spinning technique is comparatively simple, but choice of Solvent is difficulty comparatively, often has higher toxicity, therefore the kind restriction to polyimides is very big, national inventing patent ZL 02112048.X, U.S. Pat 4370290 and US 5378420 disclose the employing one-step method and have prepared the polyimide fiber method.Another kind is the two-step mode technique route: at first be the synthesizing polyamides acid solution, prepare the polyamic acid fiber as spinning slurry, make the polyamic acid fiber change polyimide fiber into by cyclization afterwards, obtain the polyimide fiber of certain intensity again through hot-stretch.Prepare in the technology path of polyimide fiber in two-step method, can adopt wet method or dry-wet spinning method, all adopt this method wet spinning or dry-jet wet-spinning technology path to prepare polyimide fiber as national inventing patent CN 1821457A, day disclosure special permission communique JP 3287815, a JP 4018115.But the polyamic acid fiber instability that this preparation method obtains is difficult to make high-intensity fiber.For making things convenient for cyclization, Chinese patent Chinese patent 200910029601.4 and document Polymer, 2001, vol42, pg10087 disclose chemical cyclizing agent have been joined in the spinning solution, adopt wet spinning or dried wet method to prepare polyimide fiber.But in wet spinning and the dry-jet wet-spinning route spinning process solvent and coagulating agent to separate cost recovery higher relatively.
The dry spinning technology path is a preparation polyimide fiber other method, as national inventing patent 200610116652.7, U.S. Pat P 3415782, USP 4640972 all discloses this method, at first polyamic acid solution enters the high temperature path by spinneret orifice, solvent at high temperature volatilizees, form polyamic acid fiber (precursor fibre), winding shaping; Afterwards, precursor fibre obtains polyimide fiber through heating or chemical cyclisation, and last drawn operation obtains high-performance fiber.Required time of the thermal cyclization of disclosed polyimide fiber dry spinning route relative complex, especially precursor fibre or chemical cyclisation is long, and energy consumption is big, and production efficiency is low, causes the production cost of fiber to increase; And polyamic acid is comparatively responsive to water and temperature, in technical process such as the storage of centre and deaeration, is prone to degradation behavior, influences the performance of fiber.
Characteristics of the present invention are to have overcome this problem, in polymer solution, add suitable cyclizing agent, when the polyamic acid solution thread passes through in the high temperature spinning shaft, when polymer solution became solid fiber, under the acting in conjunction of high temperature and cyclizing agent, the precursor fibre fast transition was a polyimides, thereby directly obtain constitutionally stable polyimide fiber, reduce cyclization process, helped the after-drawing of fiber like this, can access the superior fiber of mechanical property.Simultaneously, owing to carried out the chemical cyclization of part in advance, the stability of spinning solution improves, and by improving the dry spinning temperature, the cyclization step is finished in the spinning technique process, has reduced follow-up independent cyclisation operation and equipment, has improved production efficiency greatly.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of efficient production polyimide fiber, to remedy the deficiencies in the prior art or defective, meets the demands of production and living.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of method of efficient production polyimides high-performance fiber comprises following (1), (2) and (4), perhaps (1)～(4) step 2 kind method:
(1) preparation of the employed presoma polyamic acid solution of spinning: by mol ratio is that 0.95～1.05 dianhydride and diamine monomer made the presoma polyamic acid solution in 5～10 hours as spinning slurry 0-30 ℃ of polymerization, the solvent that uses is dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone, the concentration of polyamic acid solution is 15-30wt%, and preferably concentration is 20-25wt%;
(2) adding of cyclisation chemical agent: cyclizing agent is joined in the polyamic acid solution of step (1) preparation, and under 0-30 ℃ temperature, stir.Cyclizing agent comprises acetic anhydride, pyridine or triethylamine, and the cyclizing agent addition is 0-1.1 with respect to the mol ratio of diamines.Preferably the mol ratio of cyclizing agent and diamines is 0.3-0.9.
(3) dry spinning of fiber in the high temperature path is shaped: the polyamic acid solution deaeration in a vacuum of step (2) preparation, polyamic acid solution enters spinning shaft by filament spinning component, polyamic acid solution volatilization by solvent in the high temperature path forms the polyamic acid fiber, cyclisation simultaneously is a polyimide fiber, winding shaping under the path; The temperature of spinning shaft is 200～320 ℃, 8～12 meters of length;
(4) hot-stretch of polyimide fiber: temperature is at 370～550 ℃, and draw ratio is 2～8 times.
As optimized technical scheme, the structural formula of employed dianhydride is:
The structural formula of employed diamines is:
The invention has the beneficial effects as follows: in the high temperature path of dry spinning, directly obtain polyimide fiber, reduced independent thermal cyclization or chemical cyclisation operation and equipment, improved production efficiency greatly.The polyimide fiber of the present invention's preparation can be widely used in the composite fortifying fibre, the enhancing core of cable, the hawser of car and boat, the filtering material of high temperature or radioactive substance etc.
The specific embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.
Embodiment 1
With 0.226kg 3,4 '-diamines yl diphenyl ether joins in the 2L dimethylacetylamide, is stirred to dissolving fully.Afterwards, the 0.245kg pyromellitic acid dianhydride is joined in this solution in batches, stirred 6 hours under the room temperature, obtain the polyamic acid solution of faint yellow thickness.58g acetic anhydride and equimolar pyridine are added in the polyamic acid solution, stirring reaction 2-4 hour, promptly get spinning solution.
To on air spinning machine, carry out dry spinning after the spinning solution deaeration of above preparation, 10 meters of path length, the epimere of path temperature is 255 ℃, 285 ℃ of hypomeres, winding shaping obtains fiber afterwards.Fiber stretches 2 times down at 430 ℃, promptly obtains the high-performance polyimide fiber, and fracture strength is 5.5cN/dtex, fracture elongation 32%.
Embodiment 2
With 2.246kg 4,4 '-two amido diphenyl-methanes join in the 20L dimethylacetylamide, are stirred to dissolving fully.Afterwards, the 2.471kg pyromellitic acid dianhydride is joined in this solution in batches, stirred 8 hours under the room temperature, obtain the polyamic acid solution of faint yellow thickness.578g acetic anhydride and equimolar triethylamine are added in the polyamic acid solution, stirring reaction 2-4 hour, can obtain spinning solution.
To on air spinning machine, carry out dry spinning after the spinning solution deaeration of above preparation, 12 meters of path length, the epimere of path temperature is 280 ℃, 320 ℃ of hypomeres, winding shaping obtains fiber afterwards.Fiber stretches 7 times down at 500 ℃, promptly obtains the high-performance polyimide fiber, and fracture strength is 17cN/dtex, fracture elongation 5%.
Embodiment 3
The 0.689kg phenylenediamine is joined in the 10L N-Methyl pyrrolidone, be stirred to dissolving fully.Afterwards, the 1.876kg biphenyl dianhydride is joined in this solution in batches, stirred 10 hours under the room temperature, obtain the polyamic acid spinning solution of faint yellow thickness.
To on air spinning machine, carry out dry spinning after the spinning solution deaeration of above preparation, 9 meters of path length, the epimere of path temperature is 290 ℃, 320 ℃ of hypomeres, winding shaping obtains fiber afterwards.Fiber stretches 5 times down at 510 ℃, promptly obtains the high-performance polyimide fiber, and fracture strength is 10.3cN/dtex, fracture elongation 8%.
Embodiment 4
With 2.108kg 4,4 '-diamines yl diphenyl ether joins in the 20L dimethyl sulfoxide (DMSO), is stirred to dissolving fully.Afterwards, with 3.392kg 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (ketone acid anhydride) joins in this solution in batches, stirs 8 hours under the room temperature, obtains the polyamic acid solution of faint yellow thickness.537g acetic anhydride and equimolar pyridine are added in the polyamic acid solution, stirring reaction 2-4 hour, can obtain spinning solution.
To on air spinning machine, carry out dry spinning after the spinning solution deaeration of above preparation, 10 meters of path length, the epimere of path temperature is 275 ℃, 295 ℃ of hypomeres, winding shaping obtains fiber afterwards.Fiber stretches 3 times down at 470 ℃, promptly obtains the high-performance polyimide fiber, and fracture strength is 8.5cN/dtex, fracture elongation 17%.
Embodiment 5
With 2.257kg 4,4 '-diamines yl diphenyl ether joins in the mixed solvent of 20L dimethyl formamide and dimethylacetylamide (1: 1), is stirred to dissolving fully.Afterwards, the 3.317kg biphenyl dianhydride is joined in this solution in batches, stirred 6 hours under the room temperature, obtain the polyamic acid solution of faint yellow thickness.The 575g acetic anhydride is added in the polyamic acid solution, stirring reaction 2-4 hour, can obtains spinning solution.
To on air spinning machine, carry out dry spinning after the spinning solution deaeration of above preparation, 11 meters of path length, the epimere of path temperature is 280 ℃, 300 ℃ of hypomeres, winding shaping obtains fiber afterwards.Fiber stretches 7.5 times down at 500 ℃, promptly obtains the high-performance polyimide fiber, and fracture strength is 23cN/dtex, fracture elongation 3.5%.
Embodiment 6
1.692kg 2,2 '-dimethyl diphenyl diamines is joined in the 15L dimethylacetylamide, be stirred to dissolving fully.Afterwards, 2.224kg 4,4 '-hexafluoro isopropyl phthalic anhydride (hexafluorodianhydride (6FDA)) is joined in this solution in batches, stirred 6 hours under the room temperature, obtain the polyamic acid solution of faint yellow thickness.430g acetic anhydride and equimolar pyridine are added in the polyamic acid solution, stirring reaction 2-4 hour, promptly get spinning solution.
To on air spinning machine, carry out dry spinning after the spinning solution deaeration of above preparation, 10 meters of path length, the epimere of path temperature is 270 ℃, 290 ℃ of hypomeres, winding shaping obtains fiber afterwards.Fiber stretches 8 times down at 520 ℃, promptly obtains the high-performance polyimide fiber, and fracture strength is 25.5cN/dtex, fracture elongation 2%.
Claims (4)
1. method for preparing polyimide fiber is characterized in that by (1), (2) and (4) perhaps (1)～(4) step:
(1) preparation of the employed presoma polyamic acid solution of spinning: being 1: 0.95～1.05 dianhydride and diamine monomer in 0-30 ℃ and polar organic solvent by mol ratio, polymerization made the presoma polyamic acid solution in 5～10 hours as spinning slurry, and the concentration of polyamic acid solution is 15-30wt%;
(2) cyclizing agent is joined in the polyamic acid solution of step (1) preparation, and under 0-30 ℃ temperature, stir; Described cyclizing agent is acetic anhydride, pyridine or triethylamine, and the addition of cyclizing agent is 0-1.1 with respect to the mol ratio of diamines;
(3) dry spinning of fiber in the high temperature path is shaped: the polyamic acid solution deaeration in a vacuum of step (2) preparation, polyamic acid solution enters spinning shaft by filament spinning component, polyamic acid solution volatilization by solvent in the high temperature path forms the polyamic acid fiber, cyclisation simultaneously is a polyimide fiber, winding shaping under the path; The temperature of spinning shaft is 200～320 ℃, 8～12 meters of length;
(4) hot-stretch of polyimide fiber: temperature is at 370～550 ℃, and draw ratio is 2～8 times;
Wherein, described dianhydride has following structural formula:
Described diamines has following structural formula:
2. preparation method according to claim 1 is characterized in that the polar organic solvent described in the described step (1) is that solvent is dimethyl formamide, dimethylacetylamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone.
3. preparation method according to claim 1, the concentration that it is characterized in that the polyamic acid solution described in the described step (1) is for being 20-25wt%.
4. preparation method according to claim 1, the mol ratio that it is characterized in that cyclizing agent described in the described step (2) and diamines is 0.3-0.9.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978734A (en) * | 2012-11-19 | 2013-03-20 | 东华大学 | Preparation method of fine denier/superfine denier polyimide fibers |
| CN103628215A (en) * | 2013-12-05 | 2014-03-12 | 江苏奥神新材料有限责任公司 | Efficient polyamide acid fiber cyclizing method |
| CN104294391A (en) * | 2014-09-12 | 2015-01-21 | 东华大学 | Method for spinning polyimide fiber by utilizing dry-process spinning technology |
| CN104357944A (en) * | 2014-11-06 | 2015-02-18 | 东华大学 | Method for preparing polyimide fiber through dry spinning |
| CN105040120A (en) * | 2015-06-17 | 2015-11-11 | 天津工业大学 | Method for preparing two-step synthesized polyimide-based micro/nano fibers |
| CN105239188A (en) * | 2015-11-10 | 2016-01-13 | 东华大学 | Method for preparing polyamide-imide copolymer fibers |
| CN105239196A (en) * | 2015-11-10 | 2016-01-13 | 东华大学 | Method for preparing polyamideimide precipitation fibers |
| RU2687417C1 (en) * | 2017-12-25 | 2019-05-13 | Общество с ограниченной ответственностью "ЛИРСОТ" | High-strength high-modulus thermal-, fire-resistant polyimide thread and method for production thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1932091A (en) * | 2006-09-28 | 2007-03-21 | 东华大学 | Prepn process of polyimide fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1932091A (en) * | 2006-09-28 | 2007-03-21 | 东华大学 | Prepn process of polyimide fiber |
Non-Patent Citations (1)
| Title |
|---|
| 《苏州大学硕士论文》 20090930 陈亮 三元共聚/部分环化法制备聚酰亚胺纤维的研究 第7-32页 1-4 , * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102978734A (en) * | 2012-11-19 | 2013-03-20 | 东华大学 | Preparation method of fine denier/superfine denier polyimide fibers |
| CN103628215A (en) * | 2013-12-05 | 2014-03-12 | 江苏奥神新材料有限责任公司 | Efficient polyamide acid fiber cyclizing method |
| CN103628215B (en) * | 2013-12-05 | 2016-02-10 | 江苏奥神新材料股份有限公司 | A kind of polyamic acid fiber cyclization method |
| CN104294391A (en) * | 2014-09-12 | 2015-01-21 | 东华大学 | Method for spinning polyimide fiber by utilizing dry-process spinning technology |
| CN104294391B (en) * | 2014-09-12 | 2017-01-11 | 东华大学 | Method for spinning polyimide fiber by utilizing dry-process spinning technology |
| CN104357944A (en) * | 2014-11-06 | 2015-02-18 | 东华大学 | Method for preparing polyimide fiber through dry spinning |
| CN105040120A (en) * | 2015-06-17 | 2015-11-11 | 天津工业大学 | Method for preparing two-step synthesized polyimide-based micro/nano fibers |
| CN105239188A (en) * | 2015-11-10 | 2016-01-13 | 东华大学 | Method for preparing polyamide-imide copolymer fibers |
| CN105239196A (en) * | 2015-11-10 | 2016-01-13 | 东华大学 | Method for preparing polyamideimide precipitation fibers |
| CN105239188B (en) * | 2015-11-10 | 2017-09-26 | 东华大学 | A kind of preparation method of polyamide-imide copolymer fiber |
| CN105239196B (en) * | 2015-11-10 | 2017-10-24 | 东华大学 | A kind of preparation method of polyamidoimide fibrid |
| RU2687417C1 (en) * | 2017-12-25 | 2019-05-13 | Общество с ограниченной ответственностью "ЛИРСОТ" | High-strength high-modulus thermal-, fire-resistant polyimide thread and method for production thereof |
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