CN1737225A - A kind of method for preparing the hollow phenolic fiber - Google Patents
A kind of method for preparing the hollow phenolic fiber Download PDFInfo
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- CN1737225A CN1737225A CN 200510012803 CN200510012803A CN1737225A CN 1737225 A CN1737225 A CN 1737225A CN 200510012803 CN200510012803 CN 200510012803 CN 200510012803 A CN200510012803 A CN 200510012803A CN 1737225 A CN1737225 A CN 1737225A
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Abstract
A kind of method for preparing the hollow phenolic fiber is that acid, aldehyde are added to the water successively, and stirring is made into consolidation liquid; The uncured silk of fusion or the spun phenolic resins of solwution method is put into consolidation liquid be cured, the phenolic fiber after the curing takes out the water flushing; The phenolic fiber of wash clean is placed on and soaks dissolving 0.1-100 minute in the organic solution, and fiber is taken out the water flushing, dries, and obtains the hollow phenolic fiber.The present invention has raw material timesaving cheap and easy to get, simple to operate advantage.
Description
Technical field
This method belongs to the preparation method of doughnut, relates to preparation hollow phenolic fiber method specifically.
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.Doughnut research beginning early, nineteen sixty, Du Pont is the raw material doughnut that begins one's study with the polyamide fibre, after 5 years, they have delivered doughnut " B-5 ".The seventies, doughnut begins to produce in enormous quantities, the 80s and 90s, doughnut research is increasingly mature, about different method for makings of doughnut and application achievements emerge in multitude, study more be the polyvinyl alcohol, the polysulfones that are applied to separation field, gather doughnut and hollow composite fibre such as cellulose ester.The doughnut of different performance is made into different assemblies, is used for the separation and the enrichment of medium as ultrafilter, dialyzer, contactor etc., is used widely aspect the separating of industry and field of medicaments.The insulation packing material that doughnut also has is ventilative, insulation, characteristic such as fluffy are widely used in clothes, bed clothes.In addition, also have polyacrylonitrile and asphaltic base hollow charcoal fiber and hollow activated carbon fiber.The method for preparing doughnut mainly uses profile spinneret directly to spin.Phenolic fiber is owing to have performances such as good heat insulation, anti-ablation, resistance to chemical attack, if be made into doughnut, because hollow-core construction, its excellent heat-proof quality can further improve the particularly heat insulation protection of Application Areas such as Work Clothes, fire-entry suit, insulated cold wear before heat-resisting clothes, high temperature furnace on original basis.But by literature search, the relevant report that does not also prepare the hollow phenolic fiber, Japan Patent JP2001073230 is by sneaking into the phenolic fibre that hole is contained in polyethene preparation inside in the phenolic resins of spinning, can not calculating the hollow phenolic fibre of real meaning.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the hollow phenolic fiber.
The object of the present invention is achieved like this, the phenolic resins of handling well is carried out fusion or solvent spinning, carrying out special part epidermis in the curing system of aldehyde and acid solidifies, in organic liquid, soak and dissolve its core, after flushing is dried, can obtain smooth surface, inside and outside aperture is even, diameter and the adjustable high-quality hollow of degree of hollowness phenolic fiber.
Preparation method of the present invention comprises the steps:
(1) acid, aldehyde are added to the water successively, stirring is made into consolidation liquid;
(2) consolidation liquid is put in fusion or the uncured silk of the spun phenolic resins of solwution method;
(3) temperature programming of consolidation liquid being pressed 5---100 ℃/h is to 10---100 ℃, constant temperature 0.1-5 hour;
(4) phenolic fiber after will solidifying takes out the water flushing;
(5) phenolic fiber of wash clean is placed on soaks dissolving 0.1---100 minute in the organic solution;
(6) fiber is taken out water and wash, dry, obtain the hollow phenolic fiber.
The mass percent that above-mentioned consolidation liquid is formed is:
Acid 2-26% aldehyde 2-26% water: 48----90%
Acid in the described consolidation liquid can provide H in a large number for hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, formic acid, oxalic acid, P-TOLUENE SULFO ACID 99 or p-methyl benzenesulfonic acid etc.
+Inorganic and organic acid one or more;
Aldehyde in the described consolidation liquid is formaldehyde, paraformaldehyde or its mixture;
Described fusion or solwution method spinning are the general fusion or the method for solution spinning phenolic fibre, as: US Patent 3639953, US Patent 3650102, US Patent3808289, described in the patents such as US Patent 3996327;
The organic liquid of described immersion dissolving usefulness be methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, acetone, chloroform etc. all can dissolve organic liquid or its mixed solution of phenolic resins.
Numerous areas such as that the prepared hollow phenolic fibre of the present invention can be used for is extremely heat insulation, high temperature ablation, chemical attack protection and top-grade building material.
The present invention compared with prior art has following advantage:
(1) it is even also not prepare this inner and outer diameter now, the relevant report of ganoid hollow phenolic fiber, there is one piece of inner hollow phenolic fibre patent that contains hole of preparation in Japan, and the hollow phenolic fibre for preparing with this patent belongs to diverse two conceptions of species of structure;
(2) the prepared hollow phenolic fiber of the present invention is compared with the phenolic fibre that contains hole of Japan Patent preparation, and the structure of this fiber has more excellent performance and purposes widely, particularly can be greatly improved in the performance aspect the heat insulation protection;
(3) the hollow phenolic fibre of the present invention's preparation can be used as the presoma of hollow carbon fiber and hollow activated carbon fiber, and the latter has purposes widely at aspects such as structural material, adsorption filtration, catalyst carrier, energy storage materials;
(4) raw material of the present invention is cheap and easy to get, simple to operate saves time.
The specific embodiment
Embodiment 1:
Measure paraformaldehyde 200g, 37% hydrochloric acid 400ml, p-methyl benzenesulfonic acid 100ml and water 400ml place in the curing still that stirring arm, thermocouple and reflux condenser are housed, and stir.Is softening point after 140 ℃ phenolic resins is purified, at 160 ℃, spinning under the condition of 1MPa, receiving silk speed is 1000 rev/mins, get the silk 10g that is spun and add in the consolidation liquid, with the program of 30 ℃/h to be warming up to 90 ℃, constant temperature 1 hour.Be cooled to room temperature, take out fiber, water is rinsed well, puts in the 1000ml ethanolic solution and soaks 90 minutes, takes out the flushing of fiber water and dries, and can obtain degree of hollowness and be 3% hollow phenolic fiber.
Embodiment 2:
Measure 37% formaldehyde 150ml, phosphatase 11 50ml and distilled water 500ml place in the curing still that stirring arm, thermocouple and reflux condenser are housed, and stir.Is softening point after 145 ℃ phenolic resins is purified, at 166 ℃, spinning under the condition of 1MPa, receiving silk speed is 900 rev/mins, get the silk 10g that is spun and add in the consolidation liquid, with the program of 40 ℃/h to be warming up to 85 ℃, constant temperature 5 hours.Be cooled to room temperature, take out fiber, water is rinsed well, puts in the 1000ml butanol solution and soaks 80 minutes, takes out the flushing of fiber water and dries, and can obtain degree of hollowness and be 5% hollow phenolic fiber.
Embodiment 3:
Measure 37% formaldehyde 150ml, paraformaldehyde 50g, formic acid 450ml and distilled water 400ml place in the curing still that stirring arm, thermocouple and reflux condenser are housed, and stir.Is softening point after 135 ℃ phenolic resins is purified, at 158 ℃, spinning under the condition of 0.9MPa, receiving silk speed is 1000 rev/mins, get the silk 10g that is spun and add in the consolidation liquid, with the program of 25 ℃/h to be warming up to 75 ℃, constant temperature 3 hours.Be cooled to room temperature, take out fiber, water is rinsed well, puts in 500ml ethanol and the 500ml propanol solution and soaks 55 minutes, takes out the flushing of fiber water and dries, and can obtain degree of hollowness and be 10% hollow phenolic fiber.
Embodiment 4:
Measure 37% formaldehyde 150ml, formic acid 350ml, acetate 100ml and distilled water 400ml place in the curing still that stirring arm, thermocouple and reflux condenser are housed, and stir.Is softening point after 130 ℃ phenolic resins is purified, at 152 ℃, spinning under the condition of 0.7MPa, receiving silk speed is 800 rev/mins, get the silk 10g that is spun and add in the consolidation liquid, with the program of 35 ℃/h to be warming up to 80 ℃, constant temperature 3 hours.Be cooled to room temperature, take out fiber, water is rinsed well, puts in the 1000ml ethylene glycol solution and soaks 55 minutes, takes out the flushing of fiber water and dries, and can obtain degree of hollowness and be 15% hollow phenolic fiber.
Embodiment 5:
Measure 37% formaldehyde 400ml, 98% sulfuric acid 100ml and distilled water 500ml place in the curing still that stirring arm, thermocouple and reflux condenser are housed, and stir.Is softening point after 145 ℃ phenolic resins is purified, at 170 ℃, and spinning under the condition of 0.3MPa, receiving silk speed is 500 rev/mins, get the silk 10g that is spun and add in the consolidation liquid, with the program of 20 ℃/h to be warming up to 70 ℃, constant temperature 1 hour is cooled to room temperature, takes out fiber, water is rinsed well, put in the 1000ml acetone soln and to soak 30 minutes, take out the flushing of fiber water and dry, can obtain degree of hollowness and be 35% hollow phenolic fiber.
Embodiment 6:
Measure paraformaldehyde 150g, p-methyl benzenesulfonic acid 550ml and distilled water 350ml place in the curing still that stirring arm, thermocouple and reflux condenser are housed, and stir.Is softening point after 150 ℃ phenolic resins is purified, at 175 ℃, and spinning under the condition of 0.9MPa, receiving silk speed is 800 rev/mins, get the silk 10g that is spun and add in the consolidation liquid, with the program of 15 ℃/h to be warming up to 55 ℃, constant temperature 2 hours, be cooled to room temperature, take out fiber, water is rinsed well, puts in 500ml propyl alcohol and the 500ml alcohol mixed solution and soaks 25 minutes, take out the flushing of fiber water and dry, can obtain degree of hollowness and be 50% hollow phenolic fiber.
Embodiment 7:
Measure 37% formaldehyde 250ml, red fuming nitric acid (RFNA) 150ml and distilled water 600ml place in the curing still that stirring arm, thermocouple and reflux condenser are housed, and stir.Is softening point after 125 ℃ phenolic resins is purified, spinning under the condition of 150 ℃ of 0.5MPa, and receiving silk speed is 600 rev/mins, gets the silk 10g that is spun and adds in the consolidation liquid, to be warming up to 45 ℃, constant temperature 1 hour is cooled to room temperature with the program of 30 ℃/h.Take out fiber, water is rinsed well, puts in the 1000ml propanol solution and soaks 40 minutes, takes out the flushing of fiber water and dries, and can obtain degree of hollowness and be 60% hollow phenolic fiber.
Embodiment 8:
Measure 37% formaldehyde 250ml, acetic acid 350ml and distilled water 400ml place in the curing still that stirring arm, thermocouple and reflux condenser are housed, and stir.Is softening point after 135 ℃ phenolic resins is purified, at 158 ℃, spinning under the condition of 0.9MPa, receiving silk speed is 1000 rev/mins, get the silk 10g that is spun and add in the consolidation liquid, with the program of 35 ℃/h to be warming up to 45 ℃, constant temperature 0.8 hour.Be cooled to room temperature, take out fiber, water is rinsed well, puts in the 1000ml chloroformic solution and soaks 20 minutes, takes out the flushing of fiber water and dries, and can obtain degree of hollowness and be 85% hollow phenolic fiber.
Embodiment 9:
Measure 37% formaldehyde 200ml, 37% hydrochloric acid 300ml and distilled water 500ml place in the curing still that stirring arm, thermocouple and reflux condenser are housed, and stir.Is softening point after 135 ℃ phenolic resins is purified, at 158 ℃, and spinning under the condition of 0.9MPa, receiving silk speed is 1000 rev/mins, gets the silk 10g that is spun and adds in the consolidation liquid, to be warming up to 40 ℃, constant temperature 0.6 hour is cooled to room temperature with the program of 10 ℃/h.Take out fiber, water is rinsed well, puts in the 1000ml methanol solution and soaks 0.5 minute, takes out the flushing of fiber water and dries, and can obtain degree of hollowness and be 96% hollow phenolic fiber.
Claims (6)
1, a kind of method for preparing the hollow phenolic fiber is characterized in that comprising the steps: that (1) is added to the water acid, aldehyde successively, stirs to be made into consolidation liquid;
(2) consolidation liquid is put in fusion or the uncured silk of the spun phenolic resins of solwution method;
(3) temperature programming of consolidation liquid being pressed 5---100 ℃/h is to 10---100 ℃, constant temperature 0.1-5 hour;
(4) phenolic fiber after will solidifying takes out the water flushing;
(5) phenolic fiber of wash clean is placed on soaks dissolving 0.1---100 minute in the organic solution;
(6) fiber is taken out water and wash, dry, obtain the hollow phenolic fiber;
The mass percent that above-mentioned consolidation liquid is formed is:
Acid 2-26% aldehyde 2---26% water: 48----90%.
2, a kind of method for preparing the hollow phenolic fiber as claimed in claim 1, the acid of its feature in described consolidation liquid for inorganic acid that H+ can be provided and organic acid one or more.
3, a kind of method for preparing the hollow phenolic fiber as claimed in claim 2, its feature is hydrochloric acid, nitric acid, phosphoric acid or sulfuric acid at described inorganic acid.
4, a kind of method for preparing the hollow phenolic fiber as claimed in claim 2, its feature is acetic acid, formic acid, oxalic acid, P-TOLUENE SULFO ACID 99 or p-methyl benzenesulfonic acid at described organic acid.
5, a kind of method for preparing the hollow phenolic fiber as claimed in claim 1, the aldehyde of its feature in described consolidation liquid is formaldehyde, paraformaldehyde or its mixture.
6, a kind of method for preparing the hollow phenolic fiber as claimed in claim 1, its feature is organic liquid or its mixed solution that methyl alcohol, ethanol, propyl alcohol, butanols, ethylene glycol, acetone or chloroform can dissolve phenolic resins at described organic liquid.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200510012803XA CN100354462C (en) | 2005-09-08 | 2005-09-08 | Method for preparing hollow phenolic resin fiber |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB200510012803XA CN100354462C (en) | 2005-09-08 | 2005-09-08 | Method for preparing hollow phenolic resin fiber |
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| CN1737225A true CN1737225A (en) | 2006-02-22 |
| CN100354462C CN100354462C (en) | 2007-12-12 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205635B (en) * | 2007-09-29 | 2010-12-08 | 中国科学院山西煤炭化学研究所 | Method for preparing hollow phenolic fiber in shaped spinneret melt spinning preparaiton |
| CN101205636B (en) * | 2007-09-29 | 2011-06-22 | 中国科学院山西煤炭化学研究所 | Method for preparing skin-core structural hollow phenolic fiber |
| CN102505191A (en) * | 2011-12-02 | 2012-06-20 | 中国科学院山西煤炭化学研究所 | Fully sealed curing method for preparing phenolic fiber |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1204313C (en) * | 2003-05-29 | 2005-06-01 | 中国科学院山西煤炭化学研究所 | Solidified method for preparing high crosslinking phenolic fibre |
-
2005
- 2005-09-08 CN CNB200510012803XA patent/CN100354462C/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205635B (en) * | 2007-09-29 | 2010-12-08 | 中国科学院山西煤炭化学研究所 | Method for preparing hollow phenolic fiber in shaped spinneret melt spinning preparaiton |
| CN101205636B (en) * | 2007-09-29 | 2011-06-22 | 中国科学院山西煤炭化学研究所 | Method for preparing skin-core structural hollow phenolic fiber |
| CN102505191A (en) * | 2011-12-02 | 2012-06-20 | 中国科学院山西煤炭化学研究所 | Fully sealed curing method for preparing phenolic fiber |
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| CN100354462C (en) | 2007-12-12 |
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