CN101205635A - Method for preparing hollow phenolic fiber by shaped spinneret melt spinning - Google Patents
Method for preparing hollow phenolic fiber by shaped spinneret melt spinning Download PDFInfo
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- CN101205635A CN101205635A CNA2007101395535A CN200710139553A CN101205635A CN 101205635 A CN101205635 A CN 101205635A CN A2007101395535 A CNA2007101395535 A CN A2007101395535A CN 200710139553 A CN200710139553 A CN 200710139553A CN 101205635 A CN101205635 A CN 101205635A
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Abstract
The invention relates to a method for preparing hollow phenolic fibers by means of melt spinning through a special spinneret, wherein, firstly, thermoplastic phenolic resins are purified by means of solvent dissolution and vapor distillation; secondly, melt spinning of high purity phenolic resins after purification is performed by using an arc slit spinneret; thirdly, spun hollow phenolic resin protofilaments are solidified in a solidification system which is formed by aldehydes and acids and then taken out for rinsing and airing, and then the hollow phenolic fibers with a certain hollowness degree are obtained after heat treatment. The invention has the advantages of low cost and easily obtained raw materials, simple operating technology and time saving.
Description
Technical field
This method belongs to a kind of preparation method of doughnut, relates to specifically using profile spinneret to carry out melt spinning to prepare hollow phenolic fiber method.
Background technology
Phenolic fiber is that phenolic fibre is to adopt low-molecular-weight linear phenolic resin melt spinning, or by means of being the spinning of fibre polymer solution, is cross-linked into insoluble not molten fiber then.Nineteen sixty-eight is succeeded in developing by U.S. Carborundum Co., and is cited as one of world's synthetic fiber ten big inventions in 1969.Set up triumphant Knoll Inc. (Kynol Co) in the U.S. in 1979, the nineties in last century, Kynol company has released the phenolic fibre series of products: Kynol paper, Kynol fibrofelt, Kynol fabric etc.Phenolic fibre is a kind of three-dimensional cross-linked organic fiber.Have performances such as highly fire-retardant, resistance to chemical attack, adiabatic sound insulation, after succeeding in developing, at first adopted as senior aerospace heat-barrier material by the U.S., only phenolic fibre and fabric thereof are widely used in the lining material etc. of sleeping bag, mattress etc. in Work Clothes before various protective clothings such as heat-resisting clothes, racing car clothes, the high temperature furnace, fire-entry suit, apron, gloves, safe cover, acidproof clothes, insulated cold wear and submarine, the naval vessel heat insulating material formed and chemicals storage tank and container to its thermal conductivity subsequently for 0.026W/m.k..U.S. Carborundum Co. adopts phenolic fibre to strengthen phenolic resins and makes the insulation resin of anti-ablation based composites (diameter 19.1mm, the sheet material of thickness 12.7mm), after 2500 ℃ of oxyacetylene torches contact 50s, its back temperature still is lower than 100 ℃, and the anti-ablation and the heat-proof quality of excellence arranged than the charcoal fiber/phenolic resin-base composite of same size.
Doughnut is that core is hollow tubular fiber.What research was more now is the doughnut that is applied to separation field and warming heat insulation field, also has some as the acrylonitrile group of structural material and the hollow charcoal fiber of asphaltic base.Particularly aspect warming fabric development rapidly, doughnut is because of being enclosed with a large amount of still airs in its inner hollow cavity, and still air thermal conductivity in all material is minimum, so doughnut can improve the heat-proof quality of original fiber greatly.Present warming fabric is in order further to improve its heat-proof quality, manyly all adopts doughnut, and obtains good effect.But phenolic fibre seldom has the report with its cavitation as very outstanding heat-barrier material itself.Patent CN1737225 has prepared the hollow phenolic fibre by semi-solid preparation-leaching, but this method technology is relatively complicated.
Summary of the invention
The purpose of this invention is to provide a kind of technology simply uses profile spinneret to carry out melt spinning to prepare hollow phenolic fiber method.
Shaped spinneret melt spinning of the present invention prepares the method for hollow phenolic fibre, use the method for dissolution with solvents and steam distillation that novolac resin is purified, high pure novolac resin after purifying is carried out melt spinning with circular arc slit spinnerets, in the curing system of aldehyde and acid, spun hollow phenolic resins precursor is cured at last, take out flushing and dry, can obtain having the hollow phenolic fibre of certain degree of hollowness after heat-treating.
Preparation method of the present invention is characterized in that comprising the steps:
(1) novolac resin is dissolved by putting into organic solvent less than the mass ratio of its solubility, distill purification with steam;
(2) 3-8 the distillation back 80-150 ℃ of baking under vacuum condition of purifying obtained free phenol content in 15-50 hour and is lower than 0.2% high pure novolac resin repeatedly;
(3) the high pure novolac resin after will purifying carries out melt spinning with circular arc slit spinnerets;
(4) acid, aldehyde are added to the water, stirring is made into consolidation liquid, the spun hollow phenolic resins of fusion method precursor is put into consolidation liquid heat up gradually curing and constant temperature a period of time;
(5) fiber is taken out water and wash, dry, put into stove after heat-treating the raising curing degree under the protection of inert gas, just can obtain the hollow phenolic fibre.
Described novolac resin is 2123 to wait the novolac resin of all models;
Described organic solvent is the organic liquid that methyl alcohol, ethanol, acetone, chloroform etc. can dissolve phenolic resins;
Described melt-spun is company's processings such as spinneretss such as C shape, 2C shape, 3C shape, Changzhou spinnerets factory with circular arc slit spinnerets;
Described melt spinning is the method for general melt-spinning fiber, as: US Patent3650102, US Patent3808289, described in the patents such as US Patent 3996327;
The mass concentration of acid and aldehyde is in the described consolidation liquid:
Aldehyde: 10-30%, acid: 5-25%
Acid in the described consolidation liquid is one or more in hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, formic acid, oxalic acid, P-TOLUENE SULFO ACID 99, the p-methyl benzenesulfonic acid; Aldehyde in the consolidation liquid is formaldehyde, paraformaldehyde or its mixture;
Heating rate when described consolidation liquid solidifies is 5-40 ℃/hr, and solidification temperature is 70-110 ℃, and constant temperature time is 1-10 hour; Heat treated temperature is 140-300 ℃, and constant temperature time is 1-10 hour.
The present invention compared with prior art has following advantage:
(1) though use the technology of profile spinneret spinning doughnut to be widely used in the preparation of many doughnuts, also it is not applied in the report of preparation hollow phenolic fibre at present.
(2) the hollow phenolic fibre of the present invention's preparation can do than traditional solid fibers better heat-proof quality is arranged; Also can be used as simultaneously the presoma of hollow carbon fiber and hollow activated carbon fiber, and the latter there is purposes widely at aspects such as structural material, adsorption filtration, catalyst carrier, energy storage materials;
(3) cheap and easy to get, the operating procedure of raw material of the present invention simply saves time.
The specific embodiment
Embodiment 1:
Take by weighing 200g thermoplasticity 2123 phenolic resins, the absolute ethyl alcohol of putting into 1000ml heats stirring and dissolving, steam is fed resin solution with distilling purification, after distillation finishes, outwell the water after the layering, lower-layer resin is fed steam distillation after with anhydrous alcohol solution once more.So distill repeatedly is purified after three times, with the resin anhydrous alcohol solution, puts into vacuum drying oven and dries by the fire 50 hours for 80 ℃, obtains free phenol content and be 0.19% high pure novolac resin.Resin slicer after purifying is put into the spinning still that circular arc slit 3C shape spinnerets is housed, be warmed up to 150 ℃ with nitrogen protection, add and overwhelm 1.0MPa and carry out melt spinning, receiving silk speed is 400m/min.With spun hollow resin precursor put into concentration of formaldehyde be 18% and concentration of hydrochloric acid be the curing that heats up of 18% the aqueous solution; heating rate is 15 ℃/hr; to 100 ℃ of constant temperature 2 hours; after the flushing airing is taken out in cooling; put into stove 300 ℃ of constant temperature 1 hour under protection of nitrogen gas, can obtain diameter 30 μ, degree of hollowness 25%, draw the hollow phenolic fibre of strong 150MPa, extension at break 12%.
Embodiment 2:
Press the process for purifying distillation of phenolic resins among the embodiment 1, resin distillation is purified after four times, put into 100 ℃ of bakings of baking oven 38 hours, obtain free phenol content and be 0.18% high pure novolac resin.This resin slicer is put into the spinning still that circular arc slit 2C shape spinnerets is housed, be warmed up to 152 ℃ with nitrogen protection, add and overwhelm 1.2MPa and carry out melt spinning, receiving silk speed is 500m/min.With spun hollow resin precursor put into paraformaldehyde concentration be 30% and concentration of nitric acid be the curing that heats up of 10% the aqueous solution; heating rate is 5 ℃/hr; to 70 ℃ of constant temperature 10 hours; after the flushing airing is taken out in cooling; put into stove 150 ℃ of constant temperature 6 hours under protection of nitrogen gas, can obtain diameter 27 μ, degree of hollowness 20%, draw the hollow phenolic fibre of strong 1650MPa, extension at break 14%.
Embodiment 3:
Press the process for purifying distillation of phenolic resins among the embodiment 1, resin distillation is purified after five times, put into 120 ℃ of bakings of baking oven 30 hours, obtain free phenol content and be 0.16% high pure novolac resin.This resin slicer is put into the spinning still that circular arc slit C shape spinnerets is housed, be warmed up to 155 ℃ with nitrogen protection, add and overwhelm 1.4MPa and carry out melt spinning, receiving silk speed is 700m/min.With spun hollow resin precursor put into the formaldehyde aldehyde concentration be 10% and acetate concentration be the curing that heats up of 15% the aqueous solution; heating rate is 40 ℃/hr; to 110 ℃ of constant temperature 1 hour; after the flushing airing is taken out in cooling; put into stove 180 ℃ of constant temperature 4 hours under the protection of argon gas, can obtain diameter 20 μ, degree of hollowness 22%, draw the hollow phenolic fibre of strong 180MPa, extension at break 18%.
Embodiment 4:
Press the process for purifying distillation of phenolic resins among the embodiment 1, resin distillation is purified after eight times, put into 135 ℃ of bakings of baking oven 20 hours, obtain free phenol content and be 0.11% high pure novolac resin.This resin slicer is put into the spinning still that circular arc slit 2C shape spinnerets is housed, be warmed up to 151 ℃ with nitrogen protection, add and overwhelm 1.1MPa and carry out melt spinning, receiving silk speed is 400m/min.To put into the paraformaldehyde aldehyde concentration be 20% and be the curing that heats up of 25% the aqueous solution to toluene semi-annular jade pendant acid acid concentration with spun hollow resin precursor; heating rate is 25 ℃/hr; to 100 ℃ of constant temperature 4 hours; after the flushing airing is taken out in cooling; put into stove 250 ℃ of constant temperature 2 hours under protection of nitrogen gas, can obtain diameter 33 μ, degree of hollowness 23%, draw the hollow phenolic fibre of strong 130MPa, extension at break 10%.
Embodiment 5:
Press the process for purifying distillation of phenolic resins among the embodiment 1, resin distillation is purified after six times, put into 150 ℃ of bakings of baking oven 15 hours, obtain free phenol content and be 0.15% high pure novolac resin.This resin slicer is put into the spinning still that circular arc slit C shape spinnerets is housed, be warmed up to 158 ℃ with nitrogen protection, add and overwhelm 1.1MPa and carry out melt spinning, receiving silk speed is 750m/min.With spun hollow resin precursor put into the formaldehyde aldehyde concentration be 15% and phosphoric acid concentration be the curing that heats up of 5% the aqueous solution; heating rate is 30 ℃/hr; to 85 ℃ of constant temperature 7 hours; after the flushing airing is taken out in cooling; put into stove 140 ℃ of constant temperature 10 hours under protection of nitrogen gas, can obtain diameter 17 μ, degree of hollowness 16%, draw strong 200MPa, the hollow phenolic fibre of fracture body elongation 20%.
Claims (9)
1. a shaped spinneret melt spinning prepares the method for hollow phenolic fibre, it is characterized in that comprising the steps:
(1) novolac resin is dissolved by putting into organic solvent less than the mass ratio of its solubility, distill purification with steam;
(2) 3-8 the distillation back 80-150 ℃ of baking under vacuum condition of purifying obtained free phenol content in 15-50 hour and is lower than 0.2% high pure novolac resin repeatedly;
(3) the high pure novolac resin after will purifying carries out melt spinning with circular arc slit spinnerets;
(4) acid, aldehyde are added to the water, stirring is made into consolidation liquid, the spun hollow phenolic resins of fusion method precursor is put into consolidation liquid heat up gradually curing and constant temperature a period of time;
(5) fiber is taken out water and wash, dry, put into stove after heat-treating the raising curing degree under the protection of inert gas, just can obtain the hollow phenolic fibre.
2. a kind of shaped spinneret melt spinning as claimed in claim 1 prepares the method for hollow phenolic fibre, it is characterized in that described novolac resin is the novolac resin of 2123 models.
3. a kind of shaped spinneret melt spinning as claimed in claim 1 prepares the method for hollow phenolic fibre, it is characterized in that described organic solvent is methyl alcohol, ethanol, acetone or chloroform.
4. a kind of shaped spinneret melt spinning as claimed in claim 1 prepares the method for hollow phenolic fibre, it is characterized in that described melt-spun is spinneretss such as C shape, 2C shape, 3C shape with circular arc slit spinnerets.
5. a kind of shaped spinneret melt spinning as claimed in claim 1 prepares the method for hollow phenolic fibre, it is characterized in that mass concentration sour and aldehyde is in the described consolidation liquid:
Aldehyde: 10-30%, acid: 5-25%.
6. a kind of shaped spinneret melt spinning as claimed in claim 5 prepares the method for hollow phenolic fibre, it is characterized in that acid in the described consolidation liquid is one or more in hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, formic acid, oxalic acid, P-TOLUENE SULFO ACID 99, the p-methyl benzenesulfonic acid.
7. a kind of shaped spinneret melt spinning as claimed in claim 5 prepares the method for hollow phenolic fibre, it is characterized in that the aldehyde in the described consolidation liquid is formaldehyde, paraformaldehyde or its mixture.
8. a kind of shaped spinneret melt spinning as claimed in claim 1 prepares the method for hollow phenolic fibre, it is characterized in that the heating rate when described consolidation liquid solidifies is 5-40 ℃/hr, and solidification temperature is 70-110 ℃, and constant temperature time is 1-10 hour.
9. a kind of shaped spinneret melt spinning as claimed in claim 1 prepares the method for hollow phenolic fibre, it is characterized in that described heat treated temperature is 140-300 ℃, and constant temperature time is 1-10 hour.
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| CN2007101395535A CN101205635B (en) | 2007-09-29 | 2007-09-29 | Method for preparing hollow phenolic fiber in shaped spinneret melt spinning preparaiton |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011201A (en) * | 2010-12-15 | 2011-04-13 | 四川省纺织科学研究院 | Melt-spinning method for polyformaldehyde fibers |
| CN107338491A (en) * | 2017-07-06 | 2017-11-10 | 辽宁胜达化纤有限公司 | Down-like fiber |
| CN111501114A (en) * | 2020-05-15 | 2020-08-07 | 唐山开滦化工科技有限公司 | Preparation method of phenolic fiber |
| CN116641150A (en) * | 2023-06-07 | 2023-08-25 | 中原工学院 | Method for rapidly preparing high-toughness phenolic epoxy resin fiber through microwave curing |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3996327A (en) * | 1972-12-20 | 1976-12-07 | Nippon Kynol Inc. | Process for spinning composite fiber of phenolic resin |
| CN1440989A (en) * | 2003-03-21 | 2003-09-10 | 中国科学院山西煤炭化学研究所 | Synthesis of high-purity phenolic resin preparing superfine fiber |
| CN100354462C (en) * | 2005-09-08 | 2007-12-12 | 中国科学院山西煤炭化学研究所 | Method for preparing hollow phenolic resin fiber |
-
2007
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011201A (en) * | 2010-12-15 | 2011-04-13 | 四川省纺织科学研究院 | Melt-spinning method for polyformaldehyde fibers |
| CN102011201B (en) * | 2010-12-15 | 2012-10-10 | 四川省纺织科学研究院 | Melt-spinning method for polyformaldehyde fibers |
| CN107338491A (en) * | 2017-07-06 | 2017-11-10 | 辽宁胜达化纤有限公司 | Down-like fiber |
| CN111501114A (en) * | 2020-05-15 | 2020-08-07 | 唐山开滦化工科技有限公司 | Preparation method of phenolic fiber |
| CN116641150A (en) * | 2023-06-07 | 2023-08-25 | 中原工学院 | Method for rapidly preparing high-toughness phenolic epoxy resin fiber through microwave curing |
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| CN101205635B (en) | 2010-12-08 |
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