CN1936129A - Trentment method for increasing residual carbon rate of phenolic fiber - Google Patents
Trentment method for increasing residual carbon rate of phenolic fiber Download PDFInfo
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- CN1936129A CN1936129A CN 200610048301 CN200610048301A CN1936129A CN 1936129 A CN1936129 A CN 1936129A CN 200610048301 CN200610048301 CN 200610048301 CN 200610048301 A CN200610048301 A CN 200610048301A CN 1936129 A CN1936129 A CN 1936129A
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Abstract
The invention relates to a manufacture method to improve phenol-formaldehyde resin radical peaty fiber charring char producing value that includes the following steps: taking vacuum dipping the phenol-formaldehyde resin radical peaty fiber, taking high temperature process in B, P, S inorganic acid and ethanol solution containing organic boric acid fat to gain the phenol-formaldehyde resin radical peaty fiber. The invention could sharply improve the thermal endurance of the fiber and the thermal decomposition separating out peel would be smooth-out.
Description
Technical field
The invention belongs to a kind of alkyd resin based fiber preparation method, relate in particular to a kind of preparation method who improves alkyd resin based fiber carbon residue rate.
Background technology
Both at home and abroad, the preparation of phenolic fiber mainly is to be raw material with formaldehyde and phenol novolac resin, the three-dimensional-structure fiber that make through carrying out crosslinked behind the melt spinning in hydrochloric acid and formaldehyde systems.At present, at high-tech military project, space flight and aviation field, phenolic fiber is a kind of extremely important anti-ablation, heat insulation material.Along with the raising of high-tech technical field to anti-ablation, heat insulation material performance requirement, to the performance of phenolic fibre, especially the carbon residue rate is had higher requirement.At present, the preparation of phenolic aldehyde based charcoal fiber generally all is that the fiber charing behind the above-mentioned sour aldehyde crosslinking curing of employing makes, its shortcoming is that the fiber heat resistance is poor, carbon residue rate under the high temperature is low, 800 ℃ carbon yield is generally 55%-60%, carbon yield under 1000 ℃ has only 50-55%, has limited its application, can not adapt to higher serviceability temperature and harsher environment for use.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who improves alkyd resin based fiber carbon residue rate.
The present invention is a raw material with formalin and the phenol novolac resin that polymerization gets under the oxalic acid catalytic action earlier, but makes spinning phenolic resins through a series of filtrations, steam after steaming slide, purification, vacuum drying treatment.Former raw silk through melt spinning makes in 80-110 ℃ of curing cross-linked in hydrochloric acid and formalin curing system, obtains alkyd resin based cured fiber.Phenolic aldehyde base fiber after will solidifying again soaks through vacuum in organic solvent earlier, after flood in the ethanol organic solution of B, P, S inorganic acid and organic boronic fat, dry except that after desolvating, handle through conventional charing again.Keeping under the constant condition of its key property, the carbon residue rate of the fiber after the processing improves greatly, and 800 ℃ and 1000 ℃ carbon yields down obtain the alkyd resin based fiber of a kind of high carbon residue rate all than the preceding raising 3-10% that is untreated.
Preparation method of the present invention comprises the steps:
(1) earlier the phenolic fiber that solidifies is put into organic solvent, under normal temperature, normal pressure, soak 3-6h, under the normal temperature, in the 40-50KPa vacuum, handle 1-2h then;
(2) boric acid, phosphoric acid, sulfuric acid, butyl borate, triethanolamine borate and absolute ethyl alcohol are prepared impregnation process liquid according to a certain percentage;
(3) under the normal pressure, earlier the fiber after the application of vacuum is put into the impregnation process liquid for preparing, impregnation process 1-2h in normal temperature is then at 110-140 ℃ of high temperature impregnation process 3-6h;
(4) uses deionized water rinsing earlier through the fiber after the impregnation process, put into vacuum drying oven again, dried under 100-110 ℃, vacuum 30-50KPa;
(5) fiber after the dried is handled through charing, obtains the alkyd resin based fiber of high carbon residue rate;
The mass ratio of each component is in the described impregnation process liquid:
Boric acid: phosphoric acid: sulfuric acid: butyl borate: triethanolamine borate: absolute ethyl alcohol
＝1-1.5∶1-1.5∶0.3-0.5∶0.01-0.02∶0.01-0.02∶80-95。
Aforesaid organic solvent is ethanol, methyl alcohol or acetone.
Advantage of the present invention:
1) after employing this method was handled, the carbon residue rate of fiber improved 5-10% than untreated fibers, and a large amount of heat decomposition temperatures are slow to prolong 30-50 ℃.
2) this processing method does not influence other key property of fiber, product charcoal yield height, and cost is low, and is easy to operate, reliable.
3) after employing this method was handled, the element percentage content of boron and phosphorus can reach respectively on the fiber: boron %=0.20-3.0, phosphorus %=0.20-3.0
The specific embodiment
Embodiment:
Embodiment 1: adopting 800 ℃ of following carbon residue rates is that 58.2%, 1000 ℃ of following carbon residue rate is 54.3% alkyd resin based cured fiber.Phenolic fibre after earlier 5g being solidified soaks 3h in the small-sized dipping still of 1500ml absolute ethyl alcohol, discharge solution then, is evacuated to normal temperature processing 1h in the 40-50KPa vacuum again.Take by weighing 10g boric acid, 10g phosphoric acid, 3g sulfuric acid, 0.2g butyl borate, 0.2g triethanolamine borate and be dissolved in the ethanol of 1000ml, with the ultrasonic dispersing dissolving evenly, suck small-sized dipping still then.Under the normal pressure, the fiber impregnation after soaking in the boron phosphorus impregnation process liquid for preparing, is handled 6h at 110 ℃.Take out fiber at 100 ℃, handle 1h in the vacuum drying oven of vacuum 40KPa, use deionized water rinsing at last.Fiber is at (N
2Under the atmosphere) the carbon residue rate of 800 ℃ of charings can reach 63.7%, 1000 ℃ of carbon residue rate 60.3%.
Embodiment 2: adopt same alkyd resin based cured fiber with example 1.Phenolic fibre immersion treatment after with example 1 10g being solidified.Take by weighing 10g boric acid, 15g phosphoric acid, 3g sulfuric acid, 0.1g butyl borate, 0.2g triethanolamine borate and be dissolved in the ethanol of 1200ml, with the ultrasonic dispersing dissolving evenly, suck small-sized dipping still then.Under the normal pressure, the fiber impregnation after soaking in the boron phosphorus impregnation process liquid for preparing, is handled 4h at 130 ℃.Take out fiber at 110 ℃, handle 1h in the vacuum drying oven of vacuum 30KPa, use deionized water rinsing at last.Fiber is at (N
2Under the atmosphere) the carbon residue rate of 800 ℃ of charings can reach 67.2%, 1000 ℃ of carbon residue rate 63.1%.
Embodiment 3: adopt same alkyd resin based cured fiber with example 1.Phenolic fibre after earlier 10g being solidified soaks 5h in the small-sized dipping still of 1500ml methyl alcohol organic solvent, discharge solution then, and fiber normal temperature in vacuum 40-50KPa vacuum is handled 1h.Equally prepare impregnation process liquid with example 1.Under the normal pressure, the fiber impregnation after soaking in the boron phosphorus impregnation process liquid for preparing, is handled 5h at 120 ℃.Take out fiber at 110 ℃, handle 1h in the vacuum drying oven of vacuum 30KPa, use deionized water rinsing at last.Fiber is at (N
2Under the atmosphere) the carbon residue rate of 800 ℃ of charings can reach 64.7%, 1000 ℃ of carbon residue rate 61.5%.
Embodiment 4: adopt same alkyd resin based cured fiber with example 1.Phenolic fibre after earlier 10g being solidified soaks 6h in the small-sized dipping still of 1500ml acetone organic solvent, take out fiber normal temperature in vacuum 40-50KPa vacuum then and handle 2h.Take by weighing 15g boric acid, 10g phosphoric acid, 5g sulfuric acid, 0.2g butyl borate, 0.1g triethanolamine borate and be dissolved in the ethanol of 1500ml, with the ultrasonic dispersing dissolving evenly, suck small-sized dipping still then.Under the normal pressure, the fiber impregnation after soaking in the boron phosphorus impregnation process liquid for preparing, is handled 3h at 140 ℃.Take out fiber at 110 ℃, handle 1h in the vacuum drying oven of vacuum 50KPa, use deionized water rinsing at last.Fiber is at (N
2Under the atmosphere) the carbon residue rate of 800 ℃ of charings can reach 66.2%, 1000 ℃ of carbon residue rate 62.3%.
Claims (2)
1, a kind of processing method that improves phenolic fibre carbon residue rate is characterized in that comprising the steps:
(1) earlier the phenolic fiber that solidifies is put into organic solvent, under normal temperature, normal pressure, soak 3-6h, under the normal temperature, in the 40-50KPa vacuum, handle 1-2h then;
(2) boric acid, phosphoric acid, sulfuric acid, butyl borate, triethanolamine borate and absolute ethyl alcohol are prepared impregnation process liquid according to a certain percentage;
(3) under the normal pressure, earlier the fiber after the application of vacuum is put into the impregnation process liquid for preparing, impregnation process 1-2h in normal temperature is then at 110-140 ℃ of high temperature impregnation process 3-6h;
(4) uses deionized water rinsing earlier through the fiber after the impregnation process, put into vacuum drying oven again, dried under 100-110 ℃, vacuum 30-50KPa;
(5) fiber after the dried is handled through charing, obtains the alkyd resin based fiber of high carbon residue rate;
The mass ratio of each component is in the described impregnation process liquid:
Boric acid: phosphoric acid: sulfuric acid: butyl borate: triethanolamine borate: absolute ethyl alcohol=1-1.5: 1-1.5: 0.3-0.5: 0.01-0.02: 0.01-0.02: 80-95.
2, a kind of processing method that improves phenolic fibre carbon residue rate as claimed in claim 1 is characterized in that described organic solvent is ethanol, methyl alcohol or acetone.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100483017A CN100417756C (en) | 2006-09-15 | 2006-09-15 | Trentment method for increasing residual carbon rate of phenolic fiber |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100483017A CN100417756C (en) | 2006-09-15 | 2006-09-15 | Trentment method for increasing residual carbon rate of phenolic fiber |
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| CN1936129A true CN1936129A (en) | 2007-03-28 |
| CN100417756C CN100417756C (en) | 2008-09-10 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106007761A (en) * | 2016-05-16 | 2016-10-12 | 中国科学院宁波材料技术与工程研究所 | Preparation method of boron-containing pyrolytic carbon layer on fiber surface |
| CN113789592A (en) * | 2021-11-15 | 2021-12-14 | 因达孚先进材料(苏州)有限公司 | Method for improving carbonization yield of viscose-based carbon felt |
| CN114481369A (en) * | 2022-02-16 | 2022-05-13 | 浙江大学 | Preparation method of graphene fiber with high graphite crystallinity |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61152717A (en) * | 1984-12-27 | 1986-07-11 | Sumitomo Deyurezu Kk | Phenolic resin composition modified with boric acid |
| CN1027898C (en) * | 1993-09-08 | 1995-03-15 | 肖宏遥 | Boron modified phenolic resin composite material with glass scale and its production method |
| JPH09286679A (en) * | 1996-04-24 | 1997-11-04 | Hitachi Chem Co Ltd | Boron carbide coated carbon material, its production and material confronting plasma |
| JP3754166B2 (en) * | 1997-02-25 | 2006-03-08 | 昭和高分子株式会社 | Method for producing fiber-reinforced phenolic resin molded product |
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2006
- 2006-09-15 CN CNB2006100483017A patent/CN100417756C/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106007761A (en) * | 2016-05-16 | 2016-10-12 | 中国科学院宁波材料技术与工程研究所 | Preparation method of boron-containing pyrolytic carbon layer on fiber surface |
| CN113789592A (en) * | 2021-11-15 | 2021-12-14 | 因达孚先进材料(苏州)有限公司 | Method for improving carbonization yield of viscose-based carbon felt |
| CN113789592B (en) * | 2021-11-15 | 2022-02-08 | 因达孚先进材料(苏州)有限公司 | Method for improving carbonization yield of viscose-based carbon felt |
| CN114481369A (en) * | 2022-02-16 | 2022-05-13 | 浙江大学 | Preparation method of graphene fiber with high graphite crystallinity |
| CN114481369B (en) * | 2022-02-16 | 2022-12-06 | 浙江大学 | Preparation method of graphene fiber with high graphite crystallinity |
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