CN102108115B - 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 PDFInfo
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- CN102108115B CN102108115B CN2011100063558A CN201110006355A CN102108115B CN 102108115 B CN102108115 B CN 102108115B CN 2011100063558 A CN2011100063558 A CN 2011100063558A CN 201110006355 A CN201110006355 A CN 201110006355A CN 102108115 B CN102108115 B CN 102108115B
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- 239000011819 refractory material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 14
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 14
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title abstract 3
- 239000005011 phenolic resin Substances 0.000 title abstract 3
- 229920001568 phenolic resin Polymers 0.000 title abstract 3
- 239000007787 solid Substances 0.000 claims abstract description 49
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- -1 phenolic aldehyde Chemical class 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229920006324 polyoxymethylene Polymers 0.000 claims description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 229920003987 resole Polymers 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 10
- 230000001143 conditioned effect Effects 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000018044 dehydration Effects 0.000 abstract description 3
- 238000006297 dehydration reaction Methods 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 abstract 5
- 229930040373 Paraformaldehyde Natural products 0.000 abstract 3
- 229920002866 paraformaldehyde Polymers 0.000 abstract 3
- 239000012670 alkaline solution Substances 0.000 abstract 2
- 239000003377 acid catalyst Substances 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The phenolic resin for the environment-friendly thermoplastic refractory material and the preparation method thereof comprise 100 parts of phenol, 20-25 parts of solid paraformaldehyde, 0.2-0.4 part of an acidic catalyst, 0.2-2.0 parts of an alkaline solution and 20-30 parts of a solvent. Adding phenol and an acid catalyst into a reactor, heating to 90 ℃, slowly adding all solid paraformaldehyde into the reactor within 2.5-3.5 hours, and controlling the temperature of a solution to be between 90-108 ℃; after the solid paraformaldehyde is added, controlling the temperature of the solution to be 95-110 ℃, and keeping the temperature for 3-4 hours to perform phenolic aldehyde polycondensation; after the reaction is finished, adding an alkaline solution into the solution, and adjusting the pH value of the solution to 6.5-7.5; and simultaneously adding a solvent into the solution to obtain the phenolic resin for the refractory material. The production process of the invention is safe and reliable, vacuum dehydration is not needed, sewage discharge is avoided, the ecological environment is protected, and the production efficiency is improved.
Description
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 treatment, 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 through the polycondensation of phenol and formalin; In building-up process; Phenol and formalin are joined in the reactor drum that whisking appliance, reflux exchanger, TM, steam heating interlayer and vacuum extractor are housed successively, and at the uniform velocity stirring adds 1/3rd of whole catalyzer after being warmed up to optimal temperature, and this moment, the polycondensation of phenol and aldehyde was very violent; Even boiling, and the steam that produced of boiling during through condensing surface cooling for reflux to reactor drum.After question response is steady, residual catalyst is all added, can occur the violent and boiling phenomenon of reaction once more in the reactor drum.If run into this moment cut off the water or operator handle untimely situation; There is hidden peril of explosion in reactor drum; Even if operator in time open the emptying valve, the violent boiling in the reactor drum also can be discharged into a large amount of phenol and aldehyde in the ambient air, is 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 compound 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 the problem that exists in 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 soln, 20～30 parts of solvents.
Said an acidic catalyst is that concentration is that 36% hydrochloric acid or concentration are 20% sulfuric acid.
Said basic soln is that concentration is that 28% ammoniacal liquor, concentration are that 40% sodium hydroxide or concentration are 99% triethanolamine solution.
Said solvent be terepthaloyl moietie and ethanol or methyl alcohol the two one of combination solvent.
The polymerization degree of said 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 drum that whisking appliance, reflux exchanger and TM 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 ℃; Begin in above-mentioned solution, slowly to add solid polyformaldehyde; 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 drum is 6～8%;
(4), after polycondensation finishes, add basic soln in the solution in reactor drum, stir the pH value to 6.5 of solution～7.5 in the conditioned reaction device; Add solvent in the solution in reactor drum simultaneously, make the viscosity of solution reach 4～18Pas/25 ℃, moisture 4～8%, promptly obtain qualified used for refractory material resol.
Said an acidic catalyst is that concentration is that 36% hydrochloric acid or concentration are 20% sulfuric acid.
Said basic soln is that concentration is that 28% ammoniacal liquor, concentration are that 40% sodium hydroxide or concentration are 99% triethanolamine solution.
Said solvent be terepthaloyl moietie and ethanol or methyl alcohol the two one of combination solvent.
The polymerization degree of said 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, and the needing no vacuum dehydration reaches without sewage discharge; Pollution-free, protected ecotope; In the preparation process, changed the adding order and the adding method of phenol, aldehyde and an acidic catalyst, after in reactor drum, adding phenol and an acidic catalyst; Slowly add solid polyformaldehyde within a certain period of time; Make the solution in the reactor drum 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, through embodiment, the present invention is set forth in detail below.
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 terepthaloyl moietie, 8 parts of ethanol.
Its preparation method comprises the steps:
(1), in the reactor drum that whisking appliance, reflux exchanger and TM 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 ℃; Begin in above-mentioned solution, slowly to add 24 parts of solid polyformaldehydes; 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 drum is 6～8%;
(4), after polycondensation finishes, add concentration in the solution in reactor drum 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 terepthaloyl moietie, 8 parts of ethanol simultaneously in the solution in reactor drum, 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 terepthaloyl moietie, 4 parts of methyl alcohol.
Its preparation method comprises the steps:
(1), in the reactor drum that whisking appliance, reflux exchanger and TM 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 ℃; Begin in above-mentioned solution, slowly to add 23.5 parts of solid polyformaldehydes; 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 drum is 6～8%;
(4), after polycondensation finishes, add concentration in the solution in reactor drum 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 terepthaloyl moietie, 4 parts of methyl alcohol simultaneously in the solution in reactor drum, 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 terepthaloyl moietie, 3 parts of ethanol.
Its preparation method comprises the steps:
(1), in the reactor drum that whisking appliance, reflux exchanger and TM 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 ℃; Begin in above-mentioned solution, slowly to add 24 parts of solid polyformaldehydes; 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 drum is 6～8%;
(4), after polycondensation finishes, add concentration in the solution in reactor drum 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 terepthaloyl moietie, 3 parts of ethanol simultaneously in the solution in reactor drum, 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 terepthaloyl moietie, 5 parts of ethanol.
Its preparation method comprises the steps:
(1), in the reactor drum that whisking appliance, reflux exchanger and TM 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 ℃; Begin in above-mentioned solution, slowly to add 22 parts of solid polyformaldehydes; 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 drum is 6～8%;
(4), after polycondensation finishes, add concentration in the solution in reactor drum 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 terepthaloyl moietie, 5 parts of ethanol simultaneously in the solution in reactor drum, 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 terepthaloyl moietie, 5 parts of methyl alcohol.
Its preparation method comprises the steps:
(1), in the reactor drum that whisking appliance, reflux exchanger and TM 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 ℃; Begin in above-mentioned solution, slowly to add 20 parts of solid polyformaldehydes; 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 drum is 6～8%;
(4), after polycondensation finishes, add concentration in the solution in reactor drum 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 terepthaloyl moietie, 5 parts of methyl alcohol simultaneously in the solution in reactor drum, 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 terepthaloyl moietie, 7 parts of ethanol.
Its preparation method comprises the steps:
(1), in the reactor drum that whisking appliance, reflux exchanger and TM 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 ℃; Begin in above-mentioned solution, slowly to add 21 parts of solid polyformaldehydes; 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 drum is 6～8%;
(4), after polycondensation finishes, add concentration in the solution in reactor drum 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 terepthaloyl moietie, 7 parts of ethanol simultaneously in the solution in reactor drum, 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 detail part, is those skilled in the art of the present technique's known technology.
Claims (5)
1. the preparation method of an environment-protecting thermoplastic used for refractory material resol is characterized in that: comprise the steps:
(1), in the reactor drum that whisking appliance, reflux exchanger and TM 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 ℃; Begin in above-mentioned solution, slowly to add solid polyformaldehyde; 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 drum is 6～8%;
(4), after polycondensation finishes, add basic soln in the solution in reactor drum, stir the pH value to 6.5 of solution～7.5 in the conditioned reaction device; Add solvent in the solution in reactor drum simultaneously, make the viscosity of solution reach 4～18 Pas/25 ℃, moisture 4～8%, promptly obtain qualified used for refractory material resol;
The material component for preparing above-mentioned resol 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 soln, 20～30 parts of solvents.
2. preparation method according to claim 1 is characterized in that: said an acidic catalyst is that concentration is that 36% hydrochloric acid or concentration are 20% sulfuric acid.
3. preparation method according to claim 1 is characterized in that: said basic soln is that concentration is that 28% ammoniacal liquor, concentration are that 40% sodium hydroxide or concentration are 99% triethanolamine solution.
4. preparation method according to claim 1 is characterized in that: said solvent be terepthaloyl moietie and ethanol or methyl alcohol the two one of combination solvent.
5. preparation method according to claim 1 is characterized in that: the polymerization degree of said solid polyformaldehyde is 8～12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN2011100063558A CN102108115B (en) | 2011-01-13 | 2011-01-13 | Phenolic resin for environment-friendly thermoplastic refractory material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011100063558A CN102108115B (en) | 2011-01-13 | 2011-01-13 | Phenolic resin for environment-friendly thermoplastic refractory material and preparation method thereof |
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| CN102108115B true CN102108115B (en) | 2012-05-23 |
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| CN102633966B (en) * | 2012-03-23 | 2014-02-19 | 本溪市瑞事达化工有限公司 | Catalyst and method for synthesizing phenolic resin |
| CN103059237B (en) * | 2012-12-12 | 2015-09-30 | 江苏锋芒复合材料科技集团有限公司 | A kind of novolac resin preparation method of wastewater zero discharge |
| 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 |
| CN107987237B (en) * | 2017-12-12 | 2021-03-02 | 济南鲁东耐火材料有限公司 | Preparation method of phenolic resin for refractory material |
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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 |
| CN101289527A (en) * | 2008-06-13 | 2008-10-22 | 陕西师范大学 | Method for preparing high-ortho novolac resin under single catalytic system |
| CN101289528A (en) * | 2008-06-13 | 2008-10-22 | 陕西师范大学 | Method for preparing high-ortho novolac resin |
| CN101307124A (en) * | 2008-07-14 | 2008-11-19 | 江苏九鼎新材料股份有限公司 | Thermoplastic phenolic resin and production process thereof |
| CN101307125A (en) * | 2008-07-14 | 2008-11-19 | 江苏九鼎新材料股份有限公司 | Thermosetting phenolic resin and production process thereof |
| CN101338013B (en) * | 2008-08-11 | 2013-08-07 | 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 |
| CN101831042B (en) * | 2010-05-27 | 2012-07-04 | 西北工业大学 | Preparation method of thermoplastic phenolic resin with high solid content |
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