CN100445310C - Preparation method of boron modified phenolic resin - Google Patents
Preparation method of boron modified phenolic resin Download PDFInfo
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- CN100445310C CN100445310C CNB2006100483021A CN200610048302A CN100445310C CN 100445310 C CN100445310 C CN 100445310C CN B2006100483021 A CNB2006100483021 A CN B2006100483021A CN 200610048302 A CN200610048302 A CN 200610048302A CN 100445310 C CN100445310 C CN 100445310C
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Abstract
This invention relates to a preparation method of boron modified phenol-formaldehyde resin used for imitation silk. The steps: mix formaldehyde and carbolic acid, whip uniformity, add oxalic acid for regurgitation, stand ing, heating-up underlayer solution to 110 - 120 deg under 8 to 12.6 kpa pressure, take reaction for 1 to 1.5 hours, then use absolute ethyl alcohol of 3 to 4 times quality for dissolution, wet distillation, then add borate, carry out wet distillation, take out lower resin and use absolute ethyl alcohol to dissolve, then use ultrasonic to disperse uniformity, finally at 20 to 25.3 KPa vacuum degree and 100 to 200 deg.C for 23 to 25 hours, gin waterproof boron modified phenol-formaldehyde resin used for imitation silk. This invention introduce a given mass of boron in bakelite, at the same time solve the problem of boron modified phenol-formaldehyde resin easily dissolve in water.
Description
Technical field
The invention belongs to a kind of preparation method of modified phenolic resins, is a kind of melt-spinning hydrolysis preparation method of boron modified phenolic resin specifically.
Background technology
Compare with common resol, boron modified phenolic resin is a kind of better heat-resisting, ablation resistance resin that has, and have characteristics such as good cementability, dielectricity, crushing resistance and intercept neutrons, thereby be widely used in fields such as space flight, aviation, rocket, guided missile, space vehicle, Nuclear power plants, nuclear-propelled submarine and automobile brake sheet.Select boron to be based on phenolic resin modified: the bond energy of (1) B-O is higher, and behind the introducing boron, the thermotolerance of resin, instantaneous resistance to elevated temperatures greatly improve; (2) owing to the introducing of B-O key, the mechanical property of resin, anti-ablation are enhanced.
Phenolic resin fibre is a kind of material with high thermal resistance, anti-ablation excellent properties, has characteristics such as light weight, instantaneous high temperature resistant, high non-flame properties energy, low thermal conductivity, low signature.The preparation overwhelming majority that is used as the phenolic fibre of anti-ablation, lagging material both at home and abroad adopts melt-spinnings, promptly adopt formaldehyde and the phenol novolac resin that polymerization gets under an acidic catalyst effect through melt-spinning, in hydrochloric acid and formaldehyde mixing solutions, be cured crosslinking reaction again, form insoluble fusion-free fiber.Material requirements now and harsher working conditions wish that the high thermal resistance of phenolic resin fibre, anti-ablation property have further raising on the original basis.Adopt the boron modified phenolic resin melt-spinning to make phenolic resin fibre, can in fiber, introduce B, make mechanical property, high thermal resistance, anti-ablative being further improved of fiber, have more high performance anti-ablation, lagging material thereby make.
Adopt existing thermoplasticity boron modified phenolic resin melt-spinning, solidify the preparation fiber, a fatal problem is arranged in preparation process.The preparation of existing thermoplasticity boron modified phenolic resin mainly is to adopt following two kinds of technologies: (1) with a certain proportion of phenol, formalin under HCL or the effect of oxalic acid an acidic catalyst, stir and heat up, 60 ℃ of-80 ℃ of insulation reaction, decompression dehydration gets saligenol.Slowly a certain amount of boric acid is added the people in the saligenol of heat then, be warming up to 100-120 ℃ of reaction, decompression dehydration, get the thermoplasticity boron bakelite resin at last.(2) a certain amount of boric acid and phenol react the generation boric acid ester at a certain temperature, and then the pyroreaction certain hour final vacuum dehydration under an acidic catalyst effect with formalin or Paraformaldehyde 96, generate boron bakelite resin.
The shortcoming of the boron modified phenolic resin maximum that so prepares is very easily hydrolysis, and in melt-spinning, the precursor after the spinning is very easily hydrolysis and also molten in air.Adopt general formaldehyde/aqueous hydrochloric acid curing system at present, one puts into solid solution in solidification process, and horse back will take place also molten, and fiber can not solidifying formation.
Summary of the invention
The objective of the invention is to overcome above-mentioned shortcoming, prepare the boron modified phenolic resin that is suitable for melt-spinning usefulness hydrolysis.
Adopt existing thermoplasticity boron modified phenolic resin very easily the reason of hydrolysis be the boron atom that has electron deficiency in the resin molecule, be easy to accept water etc. and have the attack of nucleophilic reagent of last share electron pair and hydrolysis.Studies show that its hydrolysis rate is subjected to the influence of steric requirements on the one hand, then relevant on the other hand with the intramolecule structure.That the present invention adopts is nitrogenous, the boric acid ester of coordinate bond in the boron, as modification boron source, reduces the electron deficiency of boron atom, and it is water-disintegrable thereby reduce.This is because N → B coordinate bond makes molecule stable on the one hand; Be that the combination of boron atom becomes three-dimensional arrangement by two dimensional structure after forming coordinate bond on the other hand, make the water molecules attack become difficult.Present method is nitrogenous by adding in the resol polymerization later stage, the boric acid ester of coordinate bond in the boron, introduces boron and carries out modification.The synthetic boron modified phenolic resin is owing to have coordination structure in nitrogen, the boron, and sterically hindered and electronic structure makes it have good stability to hydrolysis.
Preparation method of the present invention, after comprising the steps: that (1) stirs a certain amount of formaldehyde solution, phenol, add the oxalic acid of oxalic acid total amount 50-62.5% earlier, behind the reflux 5-10min, add remaining oxalic acid again, continue backflow 1-1.5h, cool off, leave standstill, remove the solution on upper strata, with lower floor's solution under 8-12.6KPa pressure, be warmed up to 110-120 ℃, reaction 1-1.5h obtains green resin just;
(2) with behind the anhydrous alcohol solution of first green resin with 3-4 times of quality, filter, wet distillation, repetitive operation twice, each 6-8h obtains blank resin;
(3 add the boric acid fat of boric acid ester total amount 15-35% by a certain percentage earlier in blank resin, carry out wet distillation 6-8h for the third time, after taking out the anhydrous alcohol solution of resin with 3-4 times of quality of lower floor, add remaining boric acid fat again, even with ultrasonic dispersing;
(4) at last in vacuum tightness is the vacuum drying oven of 20-25.3KPa, be warmed up to 100-120 ℃ and handle 23-25h, make spinning hydrolysis boron modified phenolic resin;
Wherein the mol ratio of each component is:
Phenol: formaldehyde: oxalic acid=1.1-1.5: 1: 0.015-0.019.
The mass percent of boric acid ester in modified resin is 9-19%.
Aforesaid boric acid ester is trolamine boric acid fat or tri-isopropanolamine boric acid ester.
B content 0.5-1.1% in the modified phenolic resins that employing present method makes, spinning property is estimated wire drawing continuously, evenly, available formaldehyde after the spinning/aqueous hydrochloric acid system solidifying formation, fiber is swelling, also insoluble not, has good curing fiberizability.Simultaneously, the carbon residue rate of the phenolic fibre that makes behind the unmodified blank resol melt-spinning has only 55-60%, the carbon residue rate of phenolic fibre after 800 ℃ of conventional charings that makes behind the modified phenolic resins melt-spinning that adopts present method to make can reach 60-63%, improves 2-5% than unmodified blank fiber.Gained solidifies in the fiber of back owing to introduce boron, at high temperature can generate norbide, boron nitride with carbon, fiber is had than unmodified phenolic resin fibre have better anti-oxidant, high thermal resistance and anti-ablation characteristics.
Advantage of the present invention:
1) after employing present method is handled, both in resol, introduced a certain amount of boron, solved simultaneously the very easily problem of hydrolysis of boron modified phenolic resin again, spun fiber can be in the conventional curing system of formaldehyde/aqueous hydrochloric acid curing cross-linked, make the boron modified phenolic resin cured fiber.
2) this treatment process, cost is low, and is easy to operate, reliable.
3) after employing present method was handled, in the modified phenolic resins, boron content can reach 0.5-1.1%.Adopt in the phenolic fibre that makes behind the modified phenolic resins melt-spinning boron content 0.17-0.48%.
4) gained boron modified phenolic resin base cured fiber has good anti-oxidant, high thermal resistance and anti-ablation characteristics.
Embodiment
Embodiment 1:
1) the first step, formaldehyde solution, 320g phenol and the 2g oxalic acid of adding 185g 37% in the 2500ml there-necked flask.After stirring, heated mixt.Behind the backflow 5min, add 2g oxalic acid again, continue backflow 1h, add the 1000ml deionized water.After the thing cooling to be mixed, leave standstill 40min, behind the sucking-off upper water, remove excessive phenol, oxalic acid.Under 8-12.6KPa pressure, be warmed up to 110-120 ℃ then, reaction 1-1.5h obtains 280g green resin just.2) second step, after just green resin is used the 1000ml anhydrous alcohol solution with this 280g, filter wet distillation, repetitive operation twice, each 8h.Add 10g trolamine boric acid fat again, carry out wet distillation 8h for the third time.3) the 3rd step after the resin of taking-up lower floor is used the 1000ml anhydrous alcohol solution, adds 18g trolamine boric acid fat, and is even with ultrasonic dispersing.At last in vacuum tightness is the vacuum drying oven of 20KPa, be warmed up to 100 ℃ and handle 25h, make spinning hydrolysis boron modified phenolic resin.In the gained modified phenolic resins, boron content 0.56%.Softening point temperature 120-130 ℃, spinning property is estimated wire drawing continuously, evenly.The phenolic fibre that makes behind the melt-spinning can be used formaldehyde/aqueous hydrochloric acid system solidifying formation, and fiber is swelling, also insoluble not, and the B content in the gained fiber is 0.17%.
Embodiment 2:
1) the first step, formaldehyde solution, 235g phenol and the 2g oxalic acid of adding 185g 37% in the 2500ml there-necked flask.After stirring, heated mixt.Behind the backflow 5min, add 1.5g oxalic acid again, continue backflow 1h, add the 1000ml deionized water.After the thing cooling to be mixed, leave standstill 40min, behind the sucking-off upper water, remove excessive phenol, oxalic acid.Under 8-12.6KPa pressure, be warmed up to 110-120 ℃ then, reaction 1-1.5h obtains 270g green resin just.2) second step, after just green resin is used the 1000ml anhydrous alcohol solution with this 270g, filter wet distillation, repetitive operation twice, each 6h.Add 10g trolamine boric acid fat again, carry out wet distillation 6h for the third time.The trolamine boric acid fat that the preparation of boron modified phenolic resin added except that the 3rd step becomes the 36g, and all the other are all with example 1.In the gained modified phenolic resins, boron content 0.87%, softening point temperature 125-135 ℃, spinning property is estimated wire drawing continuously, evenly.The phenolic fibre that makes behind the melt-spinning can be used formaldehyde/aqueous hydrochloric acid system solidifying formation, and fiber is swelling, also insoluble not, and the B content in the gained fiber is 0.31%.
Embodiment 3:
1) the first step, second step are with example 1.2) the 3rd step behind the resin usefulness 1000ml anhydrous alcohol solution with lower floor, adds 55g trolamine boric acid fat, and is even with ultrasonic dispersing.At last in vacuum tightness is the vacuum drying oven of 22.5KPa, be warmed up to 110 ℃ and handle 24h, make spinning hydrolysis boron modified phenolic resin.In the gained modified phenolic resins, boron content 1.08%, softening point temperature 120-130 ℃, spinning property is estimated wire drawing continuously, evenly.The phenolic fibre that makes behind the melt-spinning can be used formaldehyde/aqueous hydrochloric acid system solidifying formation, and fiber is swelling, also insoluble not, and the B content in the gained fiber is 0.48%.
Embodiment 4.
1) the first step prepares 280g green resin just with example 1.2) second step, after just green resin is used the 1000ml anhydrous alcohol solution with this 280g, filter wet distillation, repetitive operation twice, each 8h.Add 10g tri-isopropanolamine boric acid fat again, carry out wet distillation 8h for the third time.3) the 3rd step, after the resin of taking-up lower floor was used the 1000ml anhydrous alcohol solution, adding 18g tri-isopropanolamine boric acid fat was even with ultrasonic dispersing.At last in vacuum tightness is the vacuum drying oven of 25.33KPa, be warmed up to 100 ℃ and handle 25h, make spinning hydrolysis boron modified phenolic resin.In the gained modified phenolic resins, boron content 0.52%, softening point temperature 125-135 ℃, spinning property is estimated wire drawing continuously, evenly.The phenolic fibre that makes behind the melt-spinning can be used formaldehyde/aqueous hydrochloric acid system solidifying formation, and fiber is swelling, also insoluble not, and the B content in the gained fiber is 0.18%.Embodiment 5.
1) the first step, second step are with example 4.2) the 3rd step, behind the resin usefulness 1000ml anhydrous alcohol solution with lower floor, adding 50g tri-isopropanolamine boric acid fat is even with ultrasonic dispersing.At last in vacuum tightness is the vacuum drying oven of 25.33KPa, be warmed up to 120 ℃ and handle 23h, make spinning hydrolysis boron modified phenolic resin.In the gained modified phenolic resins, boron content 0.75%, softening point temperature 120-130 ℃, spinning property is estimated wire drawing continuously, evenly.The phenolic fibre that makes behind the melt-spinning can be used formaldehyde/aqueous hydrochloric acid system solidifying formation, and fiber is swelling, also insoluble not, and the B content in the gained fiber is 0.30%.
Claims (1)
1, a kind of preparation method of boron modified phenolic resin is characterized in that comprising the steps:
(1) a certain amount of formaldehyde solution, phenol are stirred after, the oxalic acid that adds oxalic acid total amount 50-62.5% earlier, behind the reflux 5-10min, add remaining oxalic acid again, continue backflow 1-1.5h, cool off, leave standstill, remove the solution on upper strata, lower floor's solution under 8-12.6KPa pressure, is warmed up to 110-120 ℃, reaction 1-1.5h obtains green resin just;
(2) with behind the anhydrous alcohol solution of first green resin with 3-4 times of quality, filter, wet distillation, repetitive operation twice, each 6-8h obtains blank resin;
(3 add the boric acid fat of boric acid ester total amount 15-35% by a certain percentage earlier in blank resin, carry out wet distillation 6-8h for the third time, after taking out the anhydrous alcohol solution of resin with 3-4 times of quality of lower floor, add remaining boric acid fat again, even with ultrasonic dispersing;
(4) at last in vacuum tightness is the vacuum drying oven of 20-25.3KPa, be warmed up to 100-120 ℃ and handle 23-25h, make spinning hydrolysis boron modified phenolic resin;
Wherein the mol ratio of each component is:
Phenol: aldehyde: oxalic acid=1.1-1.5: 1: 0.015-0.019.
The mass percent of boric acid ester in modified resin is 9-19%;
Described boric acid ester is trolamine boric acid fat or tri-isopropanolamine boric acid ester.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101565491B (en) * | 2008-04-25 | 2011-06-08 | 辽阳前进耐火材料有限公司 | Thermoplastic liquid phenolic resin and preparation method thereof |
| JP5581046B2 (en) * | 2009-01-09 | 2014-08-27 | 昭和電工株式会社 | Method for producing novolac resin and novolac resin |
| CN101805435B (en) * | 2010-04-19 | 2013-01-16 | 山东圣泉化工股份有限公司 | Preparation method of boron modified phenolic resin |
| CN103881044B (en) * | 2014-03-25 | 2015-11-18 | 宁夏共享集团有限责任公司 | The production method of the boric acid modified resol of a kind of amines catalysis |
| CN105001593B (en) * | 2015-07-06 | 2017-04-05 | 西北工业大学 | Suitable for the boron modified phenolic resin and preparation method of dry method prepreg moulding process |
| CN114031840A (en) * | 2021-12-01 | 2022-02-11 | 江苏弘奇金属科技有限公司 | High-temperature-resistant anti-puncture winding film and production process thereof |
Citations (5)
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| US4182697A (en) * | 1978-02-08 | 1980-01-08 | Bayer Aktiengesellschaft | Process for the preparation of boron-containing phenol-formaldehyde resins |
| US5004789A (en) * | 1986-06-05 | 1991-04-02 | Societe Chimiques Des Charbonnages S.A. | Resin compositions based on phenolic resins |
| CN1085916A (en) * | 1992-08-17 | 1994-04-27 | Dsm有限公司 | The method for preparing resol |
| CN1760229A (en) * | 2004-10-12 | 2006-04-19 | 李青山 | Preparing heat-resistant phenolic resins |
| CN1817928A (en) * | 2006-03-09 | 2006-08-16 | 同济大学 | Production of modified phenolic resin with high boron content |
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2006
- 2006-09-15 CN CNB2006100483021A patent/CN100445310C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4182697A (en) * | 1978-02-08 | 1980-01-08 | Bayer Aktiengesellschaft | Process for the preparation of boron-containing phenol-formaldehyde resins |
| US5004789A (en) * | 1986-06-05 | 1991-04-02 | Societe Chimiques Des Charbonnages S.A. | Resin compositions based on phenolic resins |
| CN1085916A (en) * | 1992-08-17 | 1994-04-27 | Dsm有限公司 | The method for preparing resol |
| CN1760229A (en) * | 2004-10-12 | 2006-04-19 | 李青山 | Preparing heat-resistant phenolic resins |
| CN1817928A (en) * | 2006-03-09 | 2006-08-16 | 同济大学 | Production of modified phenolic resin with high boron content |
Non-Patent Citations (2)
| Title |
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| 硼酸三乙醇胺酯的合成及表征. 胡晓兰，梁国正.高分子材料科学与工程，第20卷第2期. 2004 |
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