CN86106758A - A kind of synthetic method of resol - Google Patents
A kind of synthetic method of resol Download PDFInfo
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- CN86106758A CN86106758A CN 86106758 CN86106758A CN86106758A CN 86106758 A CN86106758 A CN 86106758A CN 86106758 CN86106758 CN 86106758 CN 86106758 A CN86106758 A CN 86106758A CN 86106758 A CN86106758 A CN 86106758A
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- methylal
- resol
- phenol
- formaldehyde
- methyl alcohol
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Abstract
The invention provides a kind of novel method of not having the novolak resin of phenolic wastewater generation.
This technology is the semiclosed cyclic process that is made of condensation reaction and polycondensation two portions.At first by methyl alcohol and formaldehyde carry out continuous condensating react the intermediate methylal, mix with phenol by methylal again, in acidic medium, carry out polycondensation and get resol.No phenolic wastewater generates in the reaction.The methyl alcohol of by-product can be used for making methylal again, and another kind of by-product phenol can be used as the raw material of synthetic resins, and the purity of intermediate methylal is greater than 92%, and the productive rate of resol is more than 98%.
Description
The invention belongs to the synthetic method of organic high molecular compound, be applicable to and produce resol.
Resol has good acidproof, alkaline-resisting, heat-resisting and electrical insulating property, is widely used in many aspects such as telecommunication, electrical equipment, instrument, daily necessities, light building material.Synthetic adopt usually " formaldehyde method " of past resol, promptly polycondensation in acidic medium forms thermoplastic lacquer resins by phenols and formalin, or polycondensation becomes heat-reactive phenolic resin in alkaline medium, and its reaction formula is:
The main drawback of this method is to react a large amount of phenolic wastewater of generation, one ton of resin of common every production will produce 0.6～0.8 ton of waste water that contains the phenol amount up to 30,000 mg/litre, need the cost huge investment to carry out sewage disposal, because phenolic wastewater treatment technology level is limited at present, therefore still environment is caused certain pollution.
Provided by the present inventionly produce the technology of resol by methylal and phenols, WPI and WPIL database retrieval through U.S. ORBIT system prove that forefathers did not study as yet.
The novel process of producing resol that the object of the present invention is to provide simple, the no phenolic wastewater of a kind of technology to generate.
The present invention divides two steps to implement: i.e. the preparation of the continuous condensating of methylal and resin.Existing division is as follows:
1, the continuous condensating of methylal
With methyl alcohol and two kinds of solution of formaldehyde in molar ratio 2.0～2.5 ratio be mixed with mixed solution.After being preheating to 40～60 ℃, be passed into the built-up type conversion zone, in temperature is under 65～90 ℃, catalysis and centrifugation by means of Zeo-karb, carry out the continuous condensating reaction, resultant of reaction is separated the stable ternary azeotrope of composition through built-up type conversion zone and stripping section under the effect of hot-fluid, wherein the concentration of methylal is generally 93.5% more than or equal to 92%.In addition, feed methyl alcohol again from conversion zone bottom and continue to react, make in the still liquid formaldehyde residual volume smaller or equal to 100PPm with unreacted a small amount of formaldehyde.
Principal reaction is:
2, resin is synthetic
With methylal and phenol in molar ratio 0.7～0.95 proportioning mix, add an acidic catalyst (hydrochloric acid, sulfuric acid) down at 40～60 ℃, temperature of reaction is controlled at 65～75 ℃, polycondensation is 3～7 hours under normal pressure, reactant is after concentrating, air distillation removes methyl alcohol, and underpressure distillation removes phenol again, promptly obtains water white transparency or milky resin.The cut that contains methyl alcohol, minor amount of water and a small amount of methylal more than 85% that air distillation goes out, as the raw material of system methylal, the cut based on phenol of underpressure distillation gained, the raw material as synthetic resins recycles.Owing to contain less water (because of bringing in hydrochloric acid or the sulfuric acid) in the reduced pressure distillate, in recycling, will cause water small amount of accumulation during the course, can burn by distillation discharge system.The productive rate of gained resol is more than 98%.
Principal reaction is:
The technological process of invention sees Fig. 1 for details.
Fig. 1 is an acetal method novolak resin process flow diagram.
The invention provides a kind of new method of producing resol, technological process is simple, in reaction process, in raw material, bring anhydrous generation the less water into, by product recycles in system, entire reaction is semiclosed working cycle, avoided " formaldehyde method " a large amount of phenolic wastewater that technology produced to handle, phenolic waste liquor has been eliminated in technological process, not the output three wastes.The method of serialization synthesizing dimethoxym ethane not only provides the ideal intermediate for resol, has also promoted C
1The methyl alcohol CHEMICAL DEVELOPMENT.Technical indicator advanced person, methylal concentration is greater than 92%, and the resol productive rate is more than 98%, softening temperature＞95 ℃, poly-speed 40～60 seconds, viscosity 30～40 seconds (No. four cups) contains phenol amount＜6%.The resol that resol provided by the present invention and formaldehyde method are produced is different on the end-group structure of macromolecular chain, and the former is ehter bond-methoxyl group (OCH
3), the latter is alcoholic extract hydroxyl group (CH
2OH), therefore, the resin that the present invention obtained also has the characteristics of good fluidity.
The embodiment of the invention is as follows:
Producing of methylal
At first add methanol solution on mixing tank top, the device bottom feeds formaldehyde, the ratio of components that makes methyl alcohol and formaldehyde is 2.2 moles, after the mixing, be preheating to 45～60 ℃, add the built-up type conversion zone, under 75～90 ℃,, carry out condensation reaction by means of catalysis, the centrifugation of Zeo-karb (732 types, 1000 milliliters).In the resultant of reaction, methylal is separated into the stable ternary azeotrope of composition well through knockdown distilling period under the hot-fluid effect, unreacted formaldehyde completely further reacts through the small amount of methanol of adding bottom conversion zone again, last discharge at the bottom of the still of water sepn section, this liquid effluent is for absorbing the formaldehyde water, and methylal concentration is＞92% in the cat head production fluid.
Synthesizing of resin
In the reactor that agitator, condenser and thermometer are housed, adding purity restrains greater than 99% phenol 144, methylal 103.8 grams of purity 93.7%.When under agitation being heated to 50～60 ℃, stop heating, slowly splashing into 7.7 milliliters of hydrochloric acid (proportion 1.16) must begin to descend by temperature of charge, under agitation reflux is after 4 hours, add solid sodium hydroxide 1.5 grams, after treating the solid caustic soda dissolving, under normal pressure, boil off methyl alcohol earlier, carry out underpressure distillation then.When temperature rose to 160 ℃, blowing got the water white lacquer resins of softening temperature more than 90 ℃, and productive rate is 98%.
Resin properties sees Table 1
Claims (4)
1, a kind of synthetic method of resol, it is characterized in that with the methylal being that raw material and phenol polycondensation form, methylal is by formaldehyde and methanol mixed, be preheated to 40～60 ℃, in temperature of reaction is under 65～90 ℃, catalysis by Zeo-karb, centrifugation, carry out the serialization condensation reaction, obtain forming the stable ternary azeotrope based on methylal through fractionation by distillation again, water is discharged at the bottom of the tower still, for absorbing the formaldehyde water, methylal is mixed by a certain percentage with phenol, under 40～60 ℃ of temperature, add the concentrated hydrochloric acid or the vitriol oil while stirring, 65～75 ℃ of following polyreactions 3～7 hours, through distillation, refining water white transparency or the milky resin of obtaining, reclaim the raw material of solvent methanol solution as the system methylal, phenol recycles as the raw material of synthetic resins.
2, resol synthetic method according to claim 1 is characterized in that the mol ratio of methyl alcohol and formaldehyde is 2.0～2.5 in the condensation reaction.
3, resol synthetic method according to claim 1 is characterized in that the mol ratio of methylal and phenol is 0.7～0.95 in the polycondensation.
4, according to claim 1 and 2 described resol synthetic methods, it is characterized in that in the condensation reaction, replenish methyl alcohol from the conversion zone bottom.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86106758A CN86106758B (en) | 1986-10-20 | 1986-10-20 | Synthetic method of phenolic resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86106758A CN86106758B (en) | 1986-10-20 | 1986-10-20 | Synthetic method of phenolic resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86106758A true CN86106758A (en) | 1987-04-22 |
| CN86106758B CN86106758B (en) | 1988-01-13 |
Family
ID=4803354
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86106758A Expired CN86106758B (en) | 1986-10-20 | 1986-10-20 | Synthetic method of phenolic resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN86106758B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182368B (en) * | 2007-12-11 | 2010-11-03 | 武汉理工大学 | Method for synthesizing high-molecular-weight thermoplastic phenol resin |
| CN103214641A (en) * | 2013-05-09 | 2013-07-24 | 沙县宏盛塑料有限公司 | Production method of melamine-formaldehyde resin |
| CN104230676A (en) * | 2014-08-13 | 2014-12-24 | 山东滨州新天阳化工有限责任公司 | Process for preparing methylal |
| CN105154035A (en) * | 2015-09-10 | 2015-12-16 | 西南石油大学 | Amphoteric phenolic resin high-temperature drilling fluid filtrate reducer and preparation method thereof |
-
1986
- 1986-10-20 CN CN86106758A patent/CN86106758B/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182368B (en) * | 2007-12-11 | 2010-11-03 | 武汉理工大学 | Method for synthesizing high-molecular-weight thermoplastic phenol resin |
| CN103214641A (en) * | 2013-05-09 | 2013-07-24 | 沙县宏盛塑料有限公司 | Production method of melamine-formaldehyde resin |
| CN103214641B (en) * | 2013-05-09 | 2015-02-18 | 沙县宏盛塑料有限公司 | Production method of melamine-formaldehyde resin |
| CN104230676A (en) * | 2014-08-13 | 2014-12-24 | 山东滨州新天阳化工有限责任公司 | Process for preparing methylal |
| CN105154035A (en) * | 2015-09-10 | 2015-12-16 | 西南石油大学 | Amphoteric phenolic resin high-temperature drilling fluid filtrate reducer and preparation method thereof |
| CN105154035B (en) * | 2015-09-10 | 2018-06-15 | 西南石油大学 | A kind of amphoteric acrylamide copolymer high temperature mud fluid loss additive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN86106758B (en) | 1988-01-13 |
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