CN1440989A - Synthesis of high-purity phenolic resin preparing superfine fiber - Google Patents
Synthesis of high-purity phenolic resin preparing superfine fiber Download PDFInfo
- Publication number
- CN1440989A CN1440989A CN 03108145 CN03108145A CN1440989A CN 1440989 A CN1440989 A CN 1440989A CN 03108145 CN03108145 CN 03108145 CN 03108145 A CN03108145 A CN 03108145A CN 1440989 A CN1440989 A CN 1440989A
- Authority
- CN
- China
- Prior art keywords
- phenol
- aldehyde
- novolac resin
- ultra
- prepare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The high-purity phenolic resin for preparing superfine fiber is synthesized with phenol and aldehyde as raw material and special organic solvent and through condensation in the presence of acid catalyst, filtering the produced mixture, decompressed water vapor distillation of the filtrate, and final vacuum drying. The said process can prepare high-purity phenolic resin for preparing superfine fiber.
Description
Affiliated field:
The invention belongs to the synthetic method of resin, relate in particular to a kind of synthetic method that is used to prepare the high pure novolac resin of ultra-fine fibre.
Background technology:
Phenolic fibre is owing to have flame proof, anti-combustion, thermal insulation and characteristic such as anti-corrosion, can be used for adiabatic in space travel, national defence and the aircraft industry, insulation and corrosion resistant material, also can be used as fire prevention, protection against corrosion is obeyed and acidproof, corrosion-resistant filtering material.Be again the primary raw materials of special fibres such as charcoal fiber, graphite fibre, active carbon fibre peacekeeping ion-exchange simultaneously.Modern industry and science and technology development, the appearance of ultra-fine phenolic fibre has proposed harsh more requirement to the composition structure of raw material resol and performance.
Phenolic fibre can be made through the scorification spinning by novolac resin, also can be made through wet-spinning by heat-reactive phenolic resin.Because latter's trivial operations, operation is long, generally is not used.The method of traditional synthetic thermoplastic resol, select for use formaldehyde and excessive phenol under the strong acid katalysis, the ortho position of formaldehyde and phenol or contraposition generation addition reaction obtain a methylolphenol, this intermediate product is reset rapidly, with the unreacted hydrogen atom generation in ortho position dehydration condensation on another phenol molecule, connect with the methyne bridging, form the linear pattern novolac resin.Resol with this method preparation contains 5～20% free phenol, brings many disadvantageous effects for the fusion mode.Free phenol and resin are immiscible two-phase, and the existence of free phenol can cause melt-spun not carry out continuously, spin fiber and break end many; Owing to can not obtain good drawing-off, it is inhomogeneous to spin fiber, and Fibre diameter is thicker, has a strong impact on the quality and the performance of subsequent product.
U.S.Pat.No.3,714,111 (Economy et al.1973), U.S.Pat.No.4,115,364 (Kimura et al.1978), and A.OYA, in the work that Carbon 31:1 (71～73) (1993) is done, remove that free phenol and other micromolecular method are in the resol: resin was kept several days under the normal temperature vacuum state.The time-consuming power consumption of this method, and free phenol removes not exclusively, has a strong impact on and spins fiber quality.
The purpose of this invention is to provide a kind of simple, save time, free phenol content is less than 0.2% the synthetic method of high pure novolac resin that is used to prepare ultra-fine fibre.
It is raw material that the present invention adopts excessive phenol and formaldehyde, in organic medium, uses the organic acid catalysis polycondensation; With the mixture heat filtering that generates, gained filtrate feeds the water vapour underpressure distillation then, and settling vacuum-drying can make high-purity spinning property novolac resin.
Preparation method of the present invention comprises the steps:
(1) phenol, aldehyde and an acidic catalyst are joined in the organic solvent successively, stir:
(2) solution is heated to boiling, backflow 1-6 hour, stirs; The mixed solution heat filtering;
(3) feed the water vapour underpressure distillation in the filtrate, pressure range :-0.02～-0.08MPa; The control overhead product speed of distillating is 1～5%/min. of filtrate;
(4) the gained distillment obtains high-purity spinning property novolac resin 40～140 ℃ of following vacuum-dryings 10～20 hours;
Each constitutive molar ratio is in the above-mentioned steps:
Phenol: aldehyde=1.0～1.5: l
Organic solvent: aldehyde and phenol=3.0～10.0: 1
Catalyzer: organic solvent, aldehyde and phenol=2 * 10
-3～8 * 10
-3: 1.
Best proportioning is:
Phenol: aldehyde=1.1～1.3: 1
Organic solvent: aldehyde and phenol=5.0～8.0: 1
Organic acid: organic solvent, aldehyde and phenol=5 * 10
-3～7 * 10
-3: 1
Described phenol is phenol or p-cresol.
Described aldehyde is formaldehyde or acetaldehyde.
Described catalyzer is hydrochloric acid, sulfuric acid, acetic acid, formic acid, P-TOLUENE SULFO ACID 99 or tosic acid.
Described organic solvent is methyl alcohol, ethanol, butanols or acetone.
Described vacuum-drying temperature is controlled at 40～120 ℃.
The present invention compared with prior art has following advantage:
(1) raw material is cheap and easy to get, and step is simple, saves time.
(2) the resin purity height of present method preparation can be used for preparing high-quality ultra-fine phenolic fibre.
Embodiment:
Embodiment 1
Take by weighing phenol 100g, 37% formaldehyde 70g, acetic acid 1.0g places the there-necked flask that stirring rake, thermopair and reflux exchanger are housed, and adds 400ml ethanol and reacts under reflux temperature.After 4 hours, stop to stir and heating heat filtering.Gained filtrate is fed the water vapour underpressure distillation, and the control pressure scope is at-0.06Mpa, and the control overhead product speed of distillating is the 3%/min of filtrate, deposits fully until resin; Settling 60 ℃ of following vacuum-dryings 17 hours, is made the high pure novolac resin, free phenol content: 0.16%, the calcination resistates: 0.01%, 110 ℃ of softening temperatures.
Embodiment 2
Take by weighing phenol 100g, 37% formaldehyde 50g to oxalic acid 0.3g, places the there-necked flask that stirring rake, thermopair and reflux exchanger are housed, and adds 300ml acetone and reacts under reflux temperature.After 3 hours, stop to stir and heating heat filtering.Gained filtrate is fed the water vapour underpressure distillation, and the control pressure scope is at-0.05Mpa, and the control overhead product speed of distillating is the 4%/min of filtrate, deposits fully until resin; Settling 90 ℃ of following vacuum-dryings 15 hours, is made the high pure novolac resin, free phenol content: 0.10%, the calcination resistates: 0.01%, softening temperature: 120 ℃.
Embodiment 3
Take by weighing phenol 100g, formaldehyde 80g, tosic acid 2.0g places the there-necked flask that stirring rake, thermopair and reflux exchanger are housed, and adds 300ml methyl alcohol and reacts under reflux temperature.After 3 hours, stop to stir and heating heat filtering.Gained filtrate is fed the water vapour underpressure distillation, and the control pressure scope is at-0.07Mpa, and the control overhead product speed of distillating is the 2%/min of filtrate, deposits fully until resin; Settling 120 ℃ of following vacuum-dryings 12 hours, is made the high pure novolac resin, free phenol content: 0.13%, the calcination resistates: 0.02%, softening temperature: 125 ℃.
Embodiment 4
Take by weighing phenol 120g, acetaldehyde 100g, formic acid 1.0g places the there-necked flask that stirring rake, thermopair and reflux exchanger are housed, and adds 400ml methyl alcohol and reacts under reflux temperature.After 4 hours, stop to stir and heating heat filtering.Gained filtrate is fed the water vapour underpressure distillation, and the control pressure scope is at-0.4Mpa, and the control overhead product speed of distillating is the 5%/min of filtrate, deposits fully until resin; Settling 80 ℃ of following vacuum-dryings 26 hours, is made the high pure novolac resin, free phenol content: 0.14%, the calcination resistates: 0.01%, softening temperature: 110 ℃.
Embodiment 5
Take by weighing p-cresol 120g, 37% formaldehyde 55g, acetic acid 1.2g places the there-necked flask that stirring rake, thermopair and reflux exchanger are housed, and adds 400ml ethanol and reacts under reflux temperature.After 5 hours, stop to stir and heating heat filtering.Gained filtrate is fed the water vapour underpressure distillation, and the control pressure scope is at-0.05Mpa, and the control overhead product speed of distillating is the 5%/min of filtrate, deposits fully until resin; Settling 130 ℃ of following vacuum-dryings 10 hours, is made the high pure novolac resin, free phenol content: 0.10%, the calcination resistates: 0.01%, softening temperature: 145 ℃.
Embodiment 6
Take by weighing p-cresol 120g, 37% formaldehyde 55g, P-TOLUENE SULFO ACID 99 3.5g places the there-necked flask that stirring rake, thermopair and reflux exchanger are housed, and adds 400ml acetone and reacts under reflux temperature.After 1 hour, stop to stir and heating heat filtering.Gained filtrate is fed the water vapour underpressure distillation, and the control pressure scope is at-0.4Mpa, and the control overhead product speed of distillating is the 2%/min of filtrate, deposits fully until resin; Settling 80 ℃ of following vacuum-dryings 26 hours, is made the high pure novolac resin, free phenol content: 0.14%, the calcination resistates: 0.02%, softening temperature: 110 ℃.
Claims (7)
1. a synthetic method that is used to prepare the high pure novolac resin of ultra-fine fibre is characterized in that comprising the steps:
(1) phenol, aldehyde and an acidic catalyst are joined in the organic solvent successively, stir;
(2) solution is heated to boiling, backflow 1-6 hour, stirs; The mixed solution heat filtering;
(3) feed the water vapour underpressure distillation in the filtrate, pressure range :-0.02～-0.08MPa; The control overhead product speed of distillating is 1～5%/min. of filtrate;
(4) the gained distillment obtains high-purity spinning property novolac resin 40～140 ℃ of following vacuum-dryings 10～20 hours;
Each constitutive molar ratio is in the above-mentioned steps:
Phenol: aldehyde=1.0～1.5: 1
Organic solvent: aldehyde and phenol=3.0～10.0: 1
Catalyzer: organic solvent, aldehyde and phenol=2 * 10
-3～8 * 10
-3: 1.
2. a kind of synthetic method that is used to prepare the high pure novolac resin of ultra-fine fibre according to claim 1 is characterized in that each constitutive molar ratio is:
Phenol: aldehyde=1.1～1.3: 1
Organic solvent: aldehyde and phenol=5.0～8.0: 1
Organic acid: organic solvent, aldehyde and phenol=5 * 10
-3～7 * 10
-3: 1
3. a kind of synthetic method that is used to prepare the high pure novolac resin of ultra-fine fibre according to claim 1 and 2 is characterized in that described catalyzer is hydrochloric acid, sulfuric acid, acetic acid, formic acid, P-TOLUENE SULFO ACID 99 or tosic acid.
4. a kind of synthetic method that is used to prepare the high pure novolac resin of ultra-fine fibre according to claim 1 and 2 is characterized in that described solvent is methyl alcohol, ethanol, butanols or acetone.
5. a kind of synthetic method that is used to prepare the high pure novolac resin of ultra-fine fibre according to claim 1 and 2 is characterized in that described phenol is phenol or p-cresol.
6. a kind of synthetic method that is used to prepare the high pure novolac resin of ultra-fine fibre according to claim 1 and 2 is characterized in that described aldehyde is formaldehyde or acetaldehyde.
7. a kind of synthetic method that is used to prepare the high pure novolac resin of ultra-fine fibre according to claim 1 and 2 is characterized in that described vacuum-drying temperature is controlled at 40～120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03108145 CN1440989A (en) | 2003-03-21 | 2003-03-21 | Synthesis of high-purity phenolic resin preparing superfine fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03108145 CN1440989A (en) | 2003-03-21 | 2003-03-21 | Synthesis of high-purity phenolic resin preparing superfine fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1440989A true CN1440989A (en) | 2003-09-10 |
Family
ID=27770202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03108145 Pending CN1440989A (en) | 2003-03-21 | 2003-03-21 | Synthesis of high-purity phenolic resin preparing superfine fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1440989A (en) |
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 |
| CN101709516B (en) * | 2009-11-26 | 2011-08-17 | 陕西师范大学 | Method for preparing toughening agent modified phenolic fiber |
| CN102383216A (en) * | 2011-10-17 | 2012-03-21 | 中国科学院山西煤炭化学研究所 | Preparation method of ultrafine phenolic fiber |
-
2003
- 2003-03-21 CN CN 03108145 patent/CN1440989A/en active Pending
Cited By (4)
| 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 |
| CN101709516B (en) * | 2009-11-26 | 2011-08-17 | 陕西师范大学 | Method for preparing toughening agent modified phenolic fiber |
| CN102383216A (en) * | 2011-10-17 | 2012-03-21 | 中国科学院山西煤炭化学研究所 | Preparation method of ultrafine phenolic fiber |
| CN102383216B (en) * | 2011-10-17 | 2013-05-01 | 中国科学院山西煤炭化学研究所 | Preparation method of ultrafine phenolic fiber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111718515B (en) | Method for degrading epoxy resin cured by catalytic anhydride | |
| CN106750062A (en) | A kind of phenolic resin of modified by cardanol and the preparation method of phenolaldehyde moulding compound | |
| CN103319672A (en) | Tear resistant phenolic resin and preparation method thereof | |
| CN102219883B (en) | Production method of solid-thermosetting phenolic resin | |
| CN1440989A (en) | Synthesis of high-purity phenolic resin preparing superfine fiber | |
| CN109289870B (en) | Sulfonated carbon and preparation method and application thereof | |
| CN100448907C (en) | Phenolic resin and its production process | |
| CN111484587A (en) | Method for preparing lignin-based phenolic resin | |
| CN106811823B (en) | Modified phenolic resin fiber and preparation method and application thereof | |
| CN101045778A (en) | Preparation method of boron modified phenolic resin | |
| CN112300384A (en) | Bio-based nylon, modified material thereof, preparation method and application of 3D printing | |
| CA1193387A (en) | Process for curing thermoset resins using phenyl esters of carboxylic acids as latent catalysts | |
| CN1440990A (en) | Prepn of high-moleculr weight phenolic resin for spinning | |
| CN101368298A (en) | Preparation method for high ductility phenolic fibre with cashew case oil as modifier | |
| CN1204313C (en) | Solidified method for preparing high crosslinking phenolic fibre | |
| CN1351003A (en) | Catalytic oxidizing process for preparing solid formaldehyde from methylal and air | |
| CN117229461B (en) | Preparation method and application of furfuryl ketone resin | |
| KR101423689B1 (en) | THE METHOD FOR THE PRODUCTION OF AROMATIC COMPOUNDS USING SOLID BASE CATALYST FOR HYDROLYSIS OF β-O-4 LINKAGE OF LIGNIN IN NEAR-CRITICAL WATER | |
| CN1219842C (en) | Prepn of arylkyl phenolic resin adhesive solution specially for electrician | |
| CN1259355C (en) | Shell-core polymer containing phenolic resin and use thereof | |
| CN1302037C (en) | Modified phenol aldehyde resin and its producing process | |
| CN110790876A (en) | Thermoplastic phenolic resin with low content of bisphenol compounds, and preparation method and application thereof | |
| CA2072738C (en) | Novolak resin from fractionated fast-pyrolysis oils | |
| CN115467050A (en) | Preparation method of boron-modified wood liquefied carbon fiber spinning solution | |
| CN112604622B (en) | Method for degrading unsaturated polyester resin by microwave |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |