CN102108115A - Phenolic resin for environment-friendly thermoplastic refractory material and preparation method thereof - Google Patents

Phenolic resin for environment-friendly thermoplastic refractory material and preparation method thereof Download PDF

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CN102108115A
CN102108115A CN 201110006355 CN201110006355A CN102108115A CN 102108115 A CN102108115 A CN 102108115A CN 201110006355 CN201110006355 CN 201110006355 CN 201110006355 A CN201110006355 A CN 201110006355A CN 102108115 A CN102108115 A CN 102108115A
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solution
reactor
concentration
parts
refractory material
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CN102108115B (en
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吕仁祥
刘在春
孙晓丽
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SHANDONG LUDONG REFRACTORY CO Ltd
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SHANDONG LUDONG REFRACTORY CO Ltd
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Abstract

The invention relates to phenolic resin for an environment-friendly thermoplastic refractory material and a preparation method thereof, and the material comprises the following components: 100 parts of phenol, 20-25 parts of solid paraformaldehyde, 0.2-0.4 part of acid catalyst, 0.2-2.0 part of alkaline solution and 20-30 parts of solvent. The phenol and the acid catalyst are added into a reactor, the temperature is raised to 90 DEG C, then all the solid paraformaldehyde is slowly and completely added into the reactor within 2.5-3.5 hours, and the solution temperature is controlled to be 90-108 DEG C; after the solid paraformaldehyde is added completely, the solution temperature is controlled to be 95-110 DEG C, and then the constant temperature is kept for 3-4 hours for performing phenolic aldehyde polycondensation reaction; after the reaction is finished, the alkaline solution is further added into the solution, and the pH value of the solution is regulated to 6.5-7.5; and a solvent is simultaneously added into the solution, and the phenolic resin for the refractory material is finally obtained. The production process is safe and reliable, vacuum dehydration is unnecessary, sewage discharge can be avoided, an ecological environment can be protected, and the production efficiency can be improved.

Description

A kind of environment-protecting thermoplastic used for refractory material resol and preparation method thereof
Technical field:
The present invention relates to a kind of resol and preparation method thereof, especially a kind of environment-protecting thermoplastic used for refractory material resol and preparation method thereof.
Background technology:
Used for refractory material resol, owing to have higher carbon residue rate, refractory aggregate and graphite had good wetting property, can carry out mixing, the moulding of pug at normal temperatures, after drying is handled, resol generation carbonization forms successive combined carbon skeleton, can improve the intensity and the erosion-resisting characteristics of carbon composite refractory.
Resol in the past obtains by the polycondensation of phenol and formalin, in building-up process, phenol and formalin are joined in the reactor that agitator, reflux exchanger, thermometer, steam heating interlayer and vacuum extractor are housed successively, at the uniform velocity stirring adds 1/3rd of whole catalyzer after being warmed up to optimal temperature, this moment, the polycondensation of phenol and aldehyde was very violent, even boiling, and the steam that produced of boiling during by condenser cooling for reflux to reactor.After question response is steady, residual catalyst is all added, can occur the violent and boiling phenomenon of reaction once more in the reactor.If run into this moment cut off the water or operator handle untimely situation, there is hidden peril of explosion in reactor, even if operator in time open the emptying valve, violent boiling in the reactor also can be discharged into a large amount of phenol and aldehyde in the ambient air, be detrimental to health, etching apparatus, contaminate environment.In addition, necessary vacuum hydro-extraction after the phenolic aldehyde polycondensation finishes, and contain a large amount of free phenols and free aldehyde in the trade effluent of discharging, and pollute rivers and lakes, destroy ecotope.And, traditional synthetic method power consumption, consumption power, the production cycle is long, and efficient is low.
Summary of the invention:
The invention provides a kind of environment-protecting thermoplastic used for refractory material resol and preparation method thereof; its advantages of simple; whole process of production is safe and reliable; and the no excess water needing no vacuum dehydration of reaction, without sewage discharge has been protected ecotope; greatly reduce energy consumption and cost of labor simultaneously; shorten the production cycle, improved production efficiency, solved problems of the prior art.
The present invention solves the problems of the technologies described above the technical scheme that is adopted to be: a kind of environment-protecting thermoplastic used for refractory material resol, material component are 100 parts of phenol, 20~25 parts of solid polyformaldehydes, 0.2~0.4 part of an acidic catalyst, 0.2~2.0 part of basic solution, 20~30 parts of solvents.
Described an acidic catalyst is that concentration is that 36% hydrochloric acid or concentration are 20% sulfuric acid.
Described basic solution is that concentration is that 28% ammoniacal liquor, concentration are that 40% sodium hydroxide or concentration are 99% triethanolamine solution.
Described solvent be ethylene glycol and ethanol or methyl alcohol the two one of combination solvent.
The polymerization degree of described solid polyformaldehyde is 8~12.
A kind of preparation method of environment-protecting thermoplastic used for refractory material resol comprises the steps:
(1), in the reactor that agitator, reflux exchanger and thermometer are housed, add fused phenol, add an acidic catalyst simultaneously, while stirring heating;
(2), when the solution temperature of phenol and an acidic catalyst rises to 90 ℃, beginning slowly adds solid polyformaldehyde in above-mentioned solution, solid polyformaldehyde should be controlled in 2.5~3.5 hours and all add, in the adition process of solid polyformaldehyde, the temperature of solution is between 90~108 ℃ in the controlling reactor;
(3), solid polyformaldehyde add finish after, the temperature of solution is between 95~110 ℃ in the controlling reactor, constant temperature carried out the phenolic aldehyde polycondensation in 3~4 hours, the free phenol content that makes solution in the reactor is 6~8%;
(4), after polycondensation finishes, add basic solution in the solution in reactor, stir the pH value to 6.5 of solution~7.5 in the conditioned reaction device; Add solvent in the solution in reactor simultaneously, make the viscosity of solution reach 4~18Pas/25 ℃, moisture 4~8%, promptly obtain qualified used for refractory material resol.
Described an acidic catalyst is that concentration is that 36% hydrochloric acid or concentration are 20% sulfuric acid.
Described basic solution is that concentration is that 28% ammoniacal liquor, concentration are that 40% sodium hydroxide or concentration are 99% triethanolamine solution.
Described solvent be ethylene glycol and ethanol or methyl alcohol the two one of combination solvent.
The polymerization degree of described solid polyformaldehyde is 8~12.
The present invention adopts solid polyformaldehyde to replace formalin, reduced the introducing of water in the building-up process, the moisture that phenolic aldehyde polycondensation in the building-up process is produced can satisfy the moisture content requirement of used for refractory material resol, the needing no vacuum dehydration, reach without sewage discharge, pollution-free, protected ecotope; In preparation process, the adding order and the adding method of phenol, aldehyde and an acidic catalyst have been changed, after in reactor, adding phenol and an acidic catalyst, slowly add solid polyformaldehyde within a certain period of time, make the solution in the reactor vigorous reaction can not occur, as meet by chance and cut off the water, solid polyformaldehyde will stop to add automatically, response intensity will reduce gradually, and entire synthesis process is safe and reliable.The present invention is needing no vacuum distillation and vacuum hydro-extraction in entire synthesis process, therefore, greatly reduces energy consumption and cost of labor, has shortened the production cycle, has improved production efficiency.
Embodiment:
For clearly demonstrating the technical characterstic of this programme, below by embodiment, the present invention will be described in detail.
Embodiment 1: a kind of environment-protecting thermoplastic used for refractory material resol, material component are 100 parts of phenol, 25 parts of solid polyformaldehydes, 0.4 part of hydrochloric acid, 0.25 part of ammoniacal liquor, 17 parts of ethylene glycol, 8 parts of ethanol.
Its preparation method comprises the steps:
(1), in the reactor that agitator, reflux exchanger and thermometer are housed, add 100 parts of fused phenol, add concentration simultaneously and be 0.3 part of 36% hydrochloric acid, heating while stirring;
(2), when the solution temperature of phenol and hydrochloric acid rises to 90 ℃, beginning slowly adds 24 parts of solid polyformaldehydes in above-mentioned solution, solid polyformaldehyde should be controlled in 3.5 hours and all add, in the adition process of solid polyformaldehyde, the temperature of solution is between 90~108 ℃ in the controlling reactor;
(3), solid polyformaldehyde add finish after, the temperature of solution is between 102~110 ℃ in the controlling reactor, constant temperature carried out the phenolic aldehyde polycondensation in 4 hours, the free phenol content that makes the solution in the reactor is 6~8%;
(4), after polycondensation finishes, add concentration in the solution in reactor and be 0.25 part of 28% ammoniacal liquor, stir the pH value to 6.5 of solution~7.5 in the conditioned reaction device; Add 17 parts of ethylene glycol, 8 parts of ethanol in the solution in reactor simultaneously, make the viscosity of solution reach 6~11Pas/25 ℃, moisture 5~8%, promptly obtain qualified used for refractory material resol.
Embodiment 2: a kind of environment-protecting thermoplastic used for refractory material resol, material component are 100 parts of phenol, 23.5 parts of solid polyformaldehydes, 0.37 part in sulfuric acid, 2 parts of trolamines, 20 parts of ethylene glycol, 4 parts of methyl alcohol.
Its preparation method comprises the steps:
(1), in the reactor that agitator, reflux exchanger and thermometer are housed, add 100 parts of fused phenol, add concentration simultaneously and be 0.37 part in 20% sulfuric acid, heating while stirring;
(2), when phenol and vitriolic solution temperature rise to 90 ℃, beginning slowly adds 23.5 parts of solid polyformaldehydes in above-mentioned solution, solid polyformaldehyde should be controlled in 3 hours and all add, in the adition process of solid polyformaldehyde, the temperature of solution is between 90~105 ℃ in the controlling reactor;
(3), solid polyformaldehyde add finish after, the temperature of solution is between 100~105 ℃ in the controlling reactor, constant temperature carried out the phenolic aldehyde polycondensation in 3.5 hours, the free phenol content that makes solution in the reactor is 6~8%;
(4), after polycondensation finishes, add concentration in the solution in reactor and be 2 parts of 99% trolamines, stir the pH value to 6.8 of solution~7.3 in the conditioned reaction device; Add 20 parts of ethylene glycol, 4 parts of methyl alcohol in the solution in reactor simultaneously, make the viscosity of solution reach 7~12Pas/25 ℃, moisture 5~8%, promptly obtain qualified used for refractory material resol.
Embodiment 3: a kind of environment-protecting thermoplastic used for refractory material resol, material component are 100 parts of phenol, 24 parts of solid polyformaldehydes, 0.3 part of hydrochloric acid, 0.3 part in sodium hydroxide, 17 parts of ethylene glycol, 3 parts of ethanol.
Its preparation method comprises the steps:
(1), in the reactor that agitator, reflux exchanger and thermometer are housed, add 100 parts of fused phenol, add concentration simultaneously and be 0.3 part of 36% hydrochloric acid, heating while stirring;
(2), when the solution temperature of phenol and hydrochloric acid rises to 90 ℃, beginning slowly adds 24 parts of solid polyformaldehydes in above-mentioned solution, solid polyformaldehyde should be controlled in 2.8 hours and all add, in the adition process of solid polyformaldehyde, the temperature of solution is between 90~108 ℃ in the controlling reactor;
(3), solid polyformaldehyde add finish after, the temperature of solution is between 100~110 ℃ in the controlling reactor, constant temperature carried out the phenolic aldehyde polycondensation in 3.6 hours, the free phenol content that makes solution in the reactor is 6~8%;
(4), after polycondensation finishes, add concentration in the solution in reactor and be 0.3 part in 40% sodium hydroxide, stir the pH value to 6.5 of solution~7.5 in the conditioned reaction device; Add 17 parts of ethylene glycol, 3 parts of ethanol in the solution in reactor simultaneously, make the viscosity of solution reach 14~18Pas/25 ℃, moisture 4~8%, promptly obtain qualified used for refractory material resol.
Embodiment 4: a kind of environment-protecting thermoplastic used for refractory material resol, material component are 100 parts of phenol, 22 parts of solid polyformaldehydes, 0.37 part of hydrochloric acid, 0.23 part of ammoniacal liquor, 18 parts of ethylene glycol, 5 parts of ethanol.
Its preparation method comprises the steps:
(1), in the reactor that agitator, reflux exchanger and thermometer are housed, add 100 parts of fused phenol, add concentration simultaneously and be 0.37 part of 36% hydrochloric acid, heating while stirring;
(2), when the solution temperature of phenol and hydrochloric acid rises to 90 ℃, beginning slowly adds 22 parts of solid polyformaldehydes in above-mentioned solution, solid polyformaldehyde should be controlled in 3.2 hours and all add, in the adition process of solid polyformaldehyde, the temperature of solution is between 90~108 ℃ in the controlling reactor;
(3), solid polyformaldehyde add finish after, the temperature of solution is between 100~110 ℃ in the controlling reactor, constant temperature carried out the phenolic aldehyde polycondensation in 3.2 hours, the free phenol content that makes solution in the reactor is 6~8%;
(4), after polycondensation finishes, add concentration in the solution in reactor and be 0.23 part of 28% ammoniacal liquor, stir the pH value to 6.5 of solution~7.5 in the conditioned reaction device; Add 18 parts of ethylene glycol, 5 parts of ethanol in the solution in reactor simultaneously, make the viscosity of solution reach 8~15Pas/25 ℃, moisture 5~8%, promptly obtain qualified used for refractory material resol.
Embodiment 5: a kind of environment-protecting thermoplastic used for refractory material resol, material component are 100 parts of phenol, 20 parts of solid polyformaldehydes, 0.2 part in sulfuric acid, 1.1 parts of trolamines, 25 parts of ethylene glycol, 5 parts of methyl alcohol.
Its preparation method comprises the steps:
(1), in the reactor that agitator, reflux exchanger and thermometer are housed, add 100 parts of fused phenol, add concentration simultaneously and be 0.2 part in 20% sulfuric acid, heating while stirring;
(2), when phenol and vitriolic solution temperature rise to 90 ℃, beginning slowly adds 20 parts of solid polyformaldehydes in above-mentioned solution, solid polyformaldehyde should be controlled in 2.5 hours and all add, in the adition process of solid polyformaldehyde, the temperature of solution is between 90~105 ℃ in the controlling reactor;
(3), solid polyformaldehyde add finish after, the temperature of solution is between 100~105 ℃ in the controlling reactor, constant temperature carried out the phenolic aldehyde polycondensation in 3 hours, the free phenol content that makes solution in the reactor is 6~8%;
(4), after polycondensation finishes, add concentration in the solution in reactor and be 1.1 parts of 99% trolamines, stir the pH value to 6.8 of solution~7.3 in the conditioned reaction device; Add 25 parts of ethylene glycol, 5 parts of methyl alcohol in the solution in reactor simultaneously, make the viscosity of solution reach 4~6Pas/25 ℃, moisture 4~7%, promptly obtain qualified used for refractory material resol.
Embodiment 6: a kind of environment-protecting thermoplastic used for refractory material resol, material component are 100 parts of phenol, 21 parts of solid polyformaldehydes, 0.2 part of hydrochloric acid, 0.2 part in sodium hydroxide, 15 parts of ethylene glycol, 7 parts of ethanol.
Its preparation method comprises the steps:
(1), in the reactor that agitator, reflux exchanger and thermometer are housed, add 100 parts of fused phenol, add concentration simultaneously and be 0.2 part of 36% hydrochloric acid, heating while stirring;
(2), when the solution temperature of phenol and hydrochloric acid rises to 90 ℃, beginning slowly adds 21 parts of solid polyformaldehydes in above-mentioned solution, solid polyformaldehyde should be controlled in 2.5 hours and all add, in the adition process of solid polyformaldehyde, the temperature of solution is between 90~108 ℃ in the controlling reactor;
(3), solid polyformaldehyde add finish after, the temperature of solution is between 100~110 ℃ in the controlling reactor, constant temperature carried out the phenolic aldehyde polycondensation in 3 hours, the free phenol content that makes solution in the reactor is 6~8%;
(4), after polycondensation finishes, add concentration in the solution in reactor and be 0.2 part in 40% sodium hydroxide, stir the pH value to 6.5 of solution~7.5 in the conditioned reaction device; Add 15 parts of ethylene glycol, 7 parts of ethanol in the solution in reactor simultaneously, make the viscosity of solution reach 5~12Pas/25 ℃, moisture 5~8%, promptly obtain qualified used for refractory material resol.
The present invention does not describe part in detail, is those skilled in the art of the present technique's known technology.

Claims (10)

1. environment-protecting thermoplastic used for refractory material resol, it is characterized in that: material component is 100 parts of phenol, 20~25 parts of solid polyformaldehydes, 0.2~0.4 part of an acidic catalyst, 0.2~2.0 part of basic solution, 20~30 parts of solvents.
2. a kind of environment-protecting thermoplastic used for refractory material resol according to claim 1 is characterized in that: described an acidic catalyst is that concentration is that 36% hydrochloric acid or concentration are 20% sulfuric acid.
3. a kind of environment-protecting thermoplastic used for refractory material resol according to claim 1 is characterized in that: described basic solution is that concentration is that 28% ammoniacal liquor, concentration are that 40% sodium hydroxide or concentration are 99% triethanolamine solution.
4. a kind of environment-protecting thermoplastic used for refractory material resol according to claim 1 is characterized in that: described solvent be ethylene glycol and ethanol or methyl alcohol the two one of combination solvent.
5. a kind of environment-protecting thermoplastic used for refractory material resol according to claim 1, it is characterized in that: the polymerization degree of described solid polyformaldehyde is 8~12.
6. the preparation method of an environment-protecting thermoplastic used for refractory material resol as claimed in claim 1 is characterized in that: comprise the steps:
(1), in the reactor that agitator, reflux exchanger and thermometer are housed, add fused phenol, add an acidic catalyst simultaneously, while stirring heating;
(2), when the solution temperature of phenol and an acidic catalyst rises to 90 ℃, beginning slowly adds solid polyformaldehyde in above-mentioned solution, solid polyformaldehyde should be controlled in 2.5~3.5 hours and all add, in the adition process of solid polyformaldehyde, the temperature of solution is between 90~108 ℃ in the controlling reactor;
(3), solid polyformaldehyde add finish after, the temperature of solution is between 95~110 ℃ in the controlling reactor, constant temperature carried out the phenolic aldehyde polycondensation in 3~4 hours, the free phenol content that makes solution in the reactor is 6~8%;
(4), after polycondensation finishes, add basic solution in the solution in reactor, stir the pH value to 6.5 of solution~7.5 in the conditioned reaction device; Add solvent in the solution in reactor simultaneously, make the viscosity of solution reach 4~18Pas/25 ℃, moisture 4~8%, promptly obtain qualified used for refractory material resol.
7. preparation method according to claim 6 is characterized in that: described an acidic catalyst is that concentration is that 36% hydrochloric acid or concentration are 20% sulfuric acid.
8. preparation method according to claim 6 is characterized in that: described basic solution is that concentration is that 28% ammoniacal liquor, concentration are that 40% sodium hydroxide or concentration are 99% triethanolamine solution.
9. preparation method according to claim 6 is characterized in that: described solvent be ethylene glycol and ethanol or methyl alcohol the two one of combination solvent.
10. preparation method according to claim 6 is characterized in that: the polymerization degree of described solid polyformaldehyde is 8~12.
CN2011100063558A 2011-01-13 2011-01-13 Phenolic resin for environment-friendly thermoplastic refractory material and preparation method thereof Expired - Fee Related CN102108115B (en)

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Cited By (4)

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CN102633966A (en) * 2012-03-23 2012-08-15 本溪市瑞事达化工有限公司 Catalyst and method for synthesizing phenolic resin
CN103059237A (en) * 2012-12-12 2013-04-24 江苏锋芒复合材料科技集团有限公司 Wastewater zero discharge preparing method of thermoplastic phenolic resin
CN107141432A (en) * 2017-07-05 2017-09-08 郑州振东科技有限公司 A kind of production method of phenolic resin
CN107987237A (en) * 2017-12-12 2018-05-04 济南鲁东耐火材料有限公司 A kind of preparation method of phenolic resin for refractory material

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CN101338013A (en) * 2008-08-11 2009-01-07 华奇(张家港)化工有限公司 Improved process for producing alkylphenols thermoplastic resin
CN101619125A (en) * 2009-07-28 2010-01-06 陕西师范大学 Dual catalyst system thermoplastic phenolic resin preparation method and application for preparing coated sand thereof
CN101831042A (en) * 2010-05-27 2010-09-15 西北工业大学 Preparation method of thermoplastic phenolic resin with high solid content

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US5043412A (en) * 1988-06-23 1991-08-27 Borden, Inc. Ambient temperature curing, high carbon contributing compositions
CN101020735A (en) * 2006-12-28 2007-08-22 李超 Synthesis process of phosphoric phenolic resin
CN101289528A (en) * 2008-06-13 2008-10-22 陕西师范大学 Method for preparing high-ortho novolac resin
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102633966A (en) * 2012-03-23 2012-08-15 本溪市瑞事达化工有限公司 Catalyst and method for synthesizing phenolic resin
CN103059237A (en) * 2012-12-12 2013-04-24 江苏锋芒复合材料科技集团有限公司 Wastewater zero discharge preparing method of thermoplastic phenolic resin
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CN107141432A (en) * 2017-07-05 2017-09-08 郑州振东科技有限公司 A kind of production method of phenolic resin
CN107987237A (en) * 2017-12-12 2018-05-04 济南鲁东耐火材料有限公司 A kind of preparation method of phenolic resin for refractory material

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