CN101024679A - Method for preparing methbond resin using gas formol - Google Patents
Method for preparing methbond resin using gas formol Download PDFInfo
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- CN101024679A CN101024679A CN 200710021142 CN200710021142A CN101024679A CN 101024679 A CN101024679 A CN 101024679A CN 200710021142 CN200710021142 CN 200710021142 CN 200710021142 A CN200710021142 A CN 200710021142A CN 101024679 A CN101024679 A CN 101024679A
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Abstract
The invention relates to a method to make phenolic resin by using formaldehyde that includes the following steps: adding 100 weight portions phenol or alkyl phenol to 5-100 weight portions water, adding 0.1-10 weight portions catalyst, whisking and heating to 40-99 degree centigrade, passing through formaldehyde under the liquid surface of reacting material, recycling the water phase that would be used as the reacting medium water for the next time, and the down layer reacting material could heating to take polycondensation reaction at 90-190 degree centigrade, reacting to 60-180 degree centigrade to gain the phenolic resin product. The invention could use recycled water and have high reacting degree that the free phenol content is below 0.1%.
Description
One, technical field
The invention belongs to a kind of preparation method of resol, relate in particular to a kind of method of using gas prepared formaldehyde resol
Two, background technology
Resol be by phenol or alkylphenol and formaldehyde under alkalescence or acidic conditions, obtain methylolphenol or alkylphenol by addition reaction, obtain having the resol of various uses again by polycondensation.Wherein, what the use basic catalyst obtained is heat-reactive phenolic resin, and what the use an acidic catalyst obtained is novolac resin.Resol is used for industries such as tackiness agent, coating, plastics.Its phenoplast have very big market as type material.At present, a lot of world-famous chemical enterprises are founded the factory at home.The processing of the phenolic wastewater that produces in wherein producing is a difficult point, needs to drop into a large amount of funds.
Wang Jiefan uses liquid formaldehyde (37%) to be raw material in CN1850875A (2006.10.25), when after finishing the phenolic aldehyde addition reaction, carrying out polycondensation, need carry out layering to the water that is contained in the raw material liq formaldehyde (37%) that is added into 63% and separate or all steam.Need a large amount of heat energy in this course.In addition, responseless phenol is formed volatilization phenol together with water vapour and brings out, and causes the phenolic wastewater of intractable.
In view of above two kinds of defective workmanships, how people answers the zero-discharge technology of water to produce resol in resol production if beginning one's study.Shenyang Institute of Chemical Technology CN86106758B (1988.1.13) uses the condensation intermediate methylal of methyl alcohol and formaldehyde to obtain resol with phenol reactant.The CN1290887C of Northwestern Polytechnical University (2006.12.20) uses solid polyformaldehyde to produce resol.Above technology tool claims to reach non-wastewater discharge, and still, these methods have increased raw materials cost and production cost, are difficult to industrializing implementation.
Three, summary of the invention
The present invention is directed to the problems referred to above, provide a kind of environment is not produced the method for the using gas prepared formaldehyde resol of pollution, realized the zero release of phenol resin production waste water.
The technology of the present invention solution, that is: the method for using gas prepared formaldehyde resol is:
A. 100 mass parts phenol or alkylphenol are joined in the water of 5～100 mass parts as reaction medium, add the basic catalyst or an acidic catalyst of 0.1～10 mass parts again, stirring and evenly mixing also is heated to 40～99 ℃,
B. feed formaldehyde gas below the liquid level of above reaction mass, to making phenol or alkylphenol total overall reaction, its phenol or alkylphenol content are reduced to below 0.1%,
C. place and be cooled to room temperature, reaction mass is divided into two layers, and the reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 90～190 ℃, reacts to 60～180 ℃ of softening temperatures, obtains having the resol product of various uses.
Wherein: the described alkylphenol of step a is cresols, xylenol, Resorcinol, tert.-butyl phenol, nonylphenol, benzylphenol, dihydroxyphenyl propane.
Described catalyzer is alkalescence or an acidic catalyst.When the preparation heat-reactive phenolic resin, use basic catalyst, comprising: sodium hydroxide, potassium hydroxide, ammoniacal liquor, hydrated barta, magnesium oxide, yellow soda ash, zinc acetate.When the preparation novolac resin, use an acidic catalyst, comprising: hydrochloric acid, oxalic acid, acetate, formic acid, phosphoric acid, sulfuric acid, tosic acid.
The present invention obtains following technique effect: 1. used gas formaldehyde to prepare resol, the water that reaches as reaction medium does not increase, and can recycle non-wastewater discharge.2. level of response height, free phenol content is below 0.1%.3. solved in the present production technique,, when after finishing the phenolic aldehyde addition reaction, carrying out polycondensation, used a large amount of heats to steam to be contained in the raw material liq formaldehyde (37%) that is added into 63% water because use liquid formaldehyde (37%) to be raw material.Saved the energy.4. avoided using liquid formaldehyde (37%) or solid polyformaldehyde to cause the local vigorous reaction of crossing, produced the bumping that a large amount of addition reaction heat causes, caused the operational safety accident as raw material.5. recycled repeatedly at the alkalescence or an acidic catalyst of aqueous phase.
Four, description of drawings
Fig. 1 is the gel chromatography figure of the resol product that made by the present invention.
Fig. 2 is the infrared spectrogram of the resol product that made by the present invention.
Five, embodiment
Embodiment 2. joins 10 mass parts cresols the water of the reaction generation that obtains among the embodiment 1 and the water merging on upper strata and reclaims in the 90 mass parts water (reaction medium) that obtain, and adds the catalyzer oxalic acid of 0.2 mass parts again, and stirring and evenly mixing also is heated to 90 ℃.Below the liquid level of above reaction mass, feed formaldehyde gas, sampling in per 20 minutes 1 time, analytical test, cresols content is reduced to below 0.1%.Placement is cooled to room temperature, and reaction mass is divided into two layers.The water on upper strata is reclaimed, as the reaction medium of next one reaction.The reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 120 ℃, sampling in per 10 minutes 1 time, analytical test reacts to 120 ℃ of softening temperatures (ring and ball method), stopped reaction.Obtain softening temperature (ring and ball method) at 120 ℃ novolac resin product.The water on the water of reaction generation and upper strata is merged recovery, as reaction medium next time.
Embodiment 3. joins 20 mass parts xylenols the water of the reaction generation that obtains among the embodiment 2 and the water merging on upper strata and reclaims in the 80 mass parts water (reaction medium) that obtain, and adds the catalyzer acetate of 0.3 mass parts again, and stirring and evenly mixing also is heated to 80 ℃.Below the liquid level of above reaction mass, feed formaldehyde gas, sampling in per 20 minutes 1 time, analytical test, xylenol content is reduced to below 0.1%.Placement is cooled to room temperature, and reaction mass is divided into two layers.The water on upper strata is reclaimed, as the reaction medium of next one reaction.The reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 140 ℃, sampling in per 10 minutes 1 time, analytical test reacts to 130 ℃ of softening temperatures (ring and ball method), stopped reaction.The water that obtains water that softening temperature (ring and ball method) produces reaction at 130 ℃ novolac resin product and upper strata merges and reclaims, as reaction medium next time.
Embodiment 4. joins 30 mass parts tert.-butyl phenols the water of the reaction generation that obtains among the embodiment 3 and the water merging on upper strata and reclaims in the 70 mass parts water (reaction medium) that obtain, and adds the catalyzer formic acid of 0.3 mass parts again.Stirring and evenly mixing also is heated to 80 ℃.Below the liquid level of above reaction mass, feed formaldehyde gas, sampling in per 20 minutes 1 time, analytical test, tert.-butyl phenol content is reduced to below 0.1%.Placement is cooled to room temperature, and reaction mass is divided into two layers.The water on upper strata is reclaimed, as the reaction medium of next one reaction.The reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 140 ℃, sampling in per 10 minutes 1 time, analytical test reacts to 110 ℃ of softening temperatures (ring and ball method), stopped reaction.Obtain softening temperature (ring and ball method) at 110 ℃ novolac resin product.The water on the water of reaction generation and upper strata is merged recovery, as reaction medium next time.
Embodiment 6. is 80 mass parts benzylphenols, joining the water of the reaction generation that obtains among the embodiment 5 and the water merging on upper strata reclaims in the 20 mass parts water (reaction medium) that obtain, the catalyst sulfuric acid that adds 0.5 mass parts again, stirring and evenly mixing also is heated to 30 ℃.Below the liquid level of above reaction mass, feed formaldehyde gas, sampling in per 20 minutes 1 time, analytical test, benzylphenol content is reduced to below 0.1%.Placement is cooled to room temperature, and reaction mass is divided into two layers.The water on upper strata is reclaimed, as the reaction medium of next one reaction.The reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 170 ℃, sampling in per 10 minutes 1 time, analytical test reacts to 150 ℃ of softening temperatures (ring and ball method), stopped reaction.Obtain softening temperature (ring and ball method) at 150 ℃ novolac resin product.The water on the water of reaction generation and upper strata is merged recovery, as reaction medium next time.
Embodiment 7. is 90 mass parts dihydroxyphenyl propanes, joining the water of the reaction generation that obtains among the embodiment 6 and the water merging on upper strata reclaims in the 20 mass parts water (reaction medium) that obtain, the catalyzer tosic acid that adds 10 mass parts again, stirring and evenly mixing also is heated to 90 ℃.Below the liquid level of above reaction mass, feed formaldehyde gas, sampling in per 20 minutes 1 time, analytical test, content of bisphenol A is reduced to below 0.1%.Placement is cooled to room temperature, and reaction mass is divided into two layers.The water on upper strata is reclaimed, as the reaction medium of next one reaction.The reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 180 ℃, sampling in per 10 minutes 1 time, analytical test reacts to 160 ℃ of softening temperatures (ring and ball method), stopped reaction.Obtain softening temperature (ring and ball method) at 160 ℃ novolac resin product.The water on the water of reaction generation and upper strata is merged recovery, as reaction medium next time.
Embodiment 8. joins 100 mass parts tert.-butyl phenols in the 30 mass parts water (reaction medium), adds the catalyzer potassium hydroxide of 0.8 mass parts again.Stirring and evenly mixing also is heated to 99 ℃.Below the liquid level of above reaction mass, feed formaldehyde gas, sampling in per 20 minutes 1 time, analytical test, tert.-butyl phenol content is reduced to below 0.1%.Placement is cooled to room temperature, and reaction mass is divided into two layers.The water on upper strata is reclaimed, as the reaction medium of next one reaction.The reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 190 ℃, sampling in per 10 minutes 1 time, analytical test reacts to 180 ℃ of softening temperatures (ring and ball method), stopped reaction.Obtain softening temperature (ring and ball method) at 180 ℃ heat-reactive phenolic resin product.The water on the water of reaction generation and upper strata is merged recovery, as reaction medium next time.
Embodiment 9. is 10 mass parts phenol, joining the water of the reaction generation that obtains among the embodiment 8 and the water merging on upper strata reclaims in the 90 mass parts water (reaction medium) that obtain, the catalyzer sodium hydroxide that adds 0.1 mass parts again, stirring and evenly mixing also is heated to 99 ℃.Below the liquid level of above reaction mass, feed formaldehyde gas, sampling in per 20 minutes 1 time, analytical test, phenol content is reduced to below 0.1%.Placement is cooled to room temperature, and reaction mass is divided into two layers.The water on upper strata is reclaimed, as the reaction medium of next one reaction.The reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 120 ℃, sampling in per 10 minutes 1 time, analytical test reacts to 100 ℃ of softening temperatures (ring and ball method), stopped reaction.Obtain softening temperature (ring and ball method) at 100 ℃ heat-reactive phenolic resin product.The water on the water of reaction generation and upper strata is merged recovery, as reaction medium next time.
Embodiment 11. is 70 mass parts phenol, joining the water of the reaction generation that obtains among the embodiment 10 and the water merging on upper strata reclaims in the 20 mass parts water (reaction medium) that obtain, the catalyzer hydrated barta that adds 5 mass parts again, stirring and evenly mixing also is heated to 40 ℃.Below the liquid level of above reaction mass, feed formaldehyde gas, sampling in per 20 minutes 1 time, analytical test, phenol content is reduced to below 0.1%.Placement is cooled to room temperature, and reaction mass is divided into two layers.The water on upper strata is reclaimed, as the reaction medium of next one reaction.The reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 140 ℃, sampling in per 10 minutes 1 time, analytical test reacts to 100 ℃ of softening temperatures (ring and ball method), stopped reaction.Obtain softening temperature (ring and ball method) at 100 ℃ heat-reactive phenolic resin product.The water on the water of reaction generation and upper strata is merged recovery, as reaction medium next time.
Embodiment 12. is 100 mass parts phenol, joining the water of the reaction generation that obtains among the embodiment 11 and the water merging on upper strata reclaims in the 50 mass parts water (reaction medium) that obtain, the catalyst oxidation magnesium salts acid that adds 1 mass parts again, stirring and evenly mixing also is heated to 80 ℃.Below the liquid level of above reaction mass, feed formaldehyde gas, sampling in per 20 minutes 1 time, analytical test, phenol content is reduced to below 0.1%.Placement is cooled to room temperature, and reaction mass is divided into two layers.The water on upper strata is reclaimed, as the reaction medium of next one reaction.The reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 130 ℃, sampling in per 10 minutes 1 time, analytical test reacts to 110 ℃ of softening temperatures (ring and ball method), stopped reaction.Obtain softening temperature (ring and ball method) at 110 ℃ heat-reactive phenolic resin product.The water on the water of reaction generation and upper strata is merged recovery, as reaction medium next time.
Embodiment 13. joins 90 mass parts phenol the water of the reaction generation that obtains among the embodiment 9 and the water merging on upper strata and reclaims in the 50 mass parts water (reaction medium) that obtain, and adds the catalyzer carbonic acid sodium of 10 mass parts again, and stirring and evenly mixing also is heated to 80 ℃.Below the liquid level of above reaction mass, feed formaldehyde gas, sampling in per 20 minutes 1 time, analytical test, phenol content is reduced to below 0.1%.Placement is cooled to room temperature, and reaction mass is divided into two layers.The water on upper strata is reclaimed, as the reaction medium of next one reaction.The reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 160 ℃, sampling in per 10 minutes 1 time, analytical test reacts to 150 ℃ of softening temperatures (ring and ball method), stopped reaction.Obtain softening temperature (ring and ball method) at 150 ℃ heat-reactive phenolic resin product.The water on the water of reaction generation and upper strata is merged recovery, as reaction medium next time.
Embodiment 14. joins 90 mass parts phenol the water of the reaction generation that obtains among the embodiment 9 and the water merging on upper strata and reclaims in the 50 mass parts water (reaction medium) that obtain, and adds the catalyzer zinc acetate of 10 mass parts again, and stirring and evenly mixing also is heated to 80 ℃.Below the liquid level of above reaction mass, feed formaldehyde gas, sampling in per 20 minutes 1 time, analytical test, phenol content is reduced to below 0.1%.Placement is cooled to room temperature, and reaction mass is divided into two layers.The water on upper strata is reclaimed, as the reaction medium of next one reaction.The reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 130 ℃, sampling in per 10 minutes 1 time, analytical test reacts to 120 ℃ of softening temperatures (ring and ball method), stopped reaction.Obtain softening temperature (ring and ball method) at 120 ℃ heat-reactive phenolic resin product.The water on the water of reaction generation and upper strata is merged recovery, as reaction medium next time.
100 mass parts phenol are joined in the 50 mass parts water (reaction medium), add the catalyzer hydrochloric acid of 0.1 mass parts again, stirring and evenly mixing also is heated to 70 ℃.Below the liquid level of above reaction mass, feed formaldehyde gas, sampling in per 20 minutes 1 time, analytical test reacts to phenol content and reduces to below 0.1%.Placement is cooled to room temperature, and reaction mass is divided into two layers.The water on upper strata is reclaimed, as the reaction medium of next one reaction.The reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 120 ℃, sampling in per 10 minutes 1 time, analytical test reacts to 110 ℃ of softening temperatures (ring and ball method), stopped reaction.Obtain softening temperature (ring and ball method) at 110 ℃ novolac resin product.The water on the water of reaction generation and upper strata is merged recovery, as reaction medium next time.
90 mass parts phenol, join a preparation process and reclaim in the 50 mass parts water (reaction medium) that obtain, add the catalyzer tosic acid of 10 mass parts again, stirring and evenly mixing also is heated to 80 ℃.Below the liquid level of above reaction mass, feed formaldehyde gas, sampling in per 20 minutes 1 time, analytical test, phenol content is reduced to below 0.1%.Placement is cooled to room temperature, and reaction mass is divided into two layers.The water on upper strata is reclaimed, as the reaction medium of next one reaction.The reactant of lower floor (resin prepolymer) is continued the heating polycondensation at 130 ℃, sampling in per 10 minutes 1 time, analytical test reacts to 120 ℃ of softening temperatures (ring and ball method), stopped reaction.Obtain softening temperature (ring and ball method) at 120 ℃ novolac resin product.The water on the water of reaction generation and upper strata is merged recovery, as reaction medium next time.
The novolac resin product of the softening temperature that obtains above (ring and ball method), do infrared spectra, gel chromatography analysis respectively at 120 ℃.
Analytical results: Infrared spectroscopy, with reference to Fig. 1, instrument model: MAGNA-IR550 type; U.S. Buddhist nun's high-tensile strength company makes; Infrared spectrogram is seen accompanying drawing 1.Among Fig. 1: γ 1361.29-1613.33cm
-1Phenyl ring hydrogen; γ 2837.5.3-2914.68cm
-1(CH
2OCH
2-); γ 3017.56cm
-1(CH
2-A
r-); γ 3351.90cm
-1(CH
2-OH).Gel chromatography is analyzed, with reference to Fig. 2, and instrument model: Waters1515 type; U.S. Waters company makes; Gel chromatography figure sees among accompanying drawing 2. Fig. 2: molecular weight 2485.
Claims (9)
1. the method for a using gas prepared formaldehyde resol is characterized in that the preparation method is:
D. 100 mass parts phenol or alkylphenol are joined in 5～100 mass parts water, water is as reaction medium,, add the basic catalyst or an acidic catalyst of 0.1～10 mass parts again, stirring and evenly mixing also is heated to 40～99 ℃,
E. feed formaldehyde gas below the liquid level of above reaction mass, to making phenol or alkylphenol total overall reaction, its phenol or alkylphenol content are reduced to below 0.1%,
F. place and be cooled to room temperature, reaction mass is divided into two layers, and the reactant of lower floor, the resin prepolymer continues the heating polycondensation at 90～190 ℃, reacts to softening temperature ring and ball method, 60～180 ℃, the resol product that obtains having various uses.
2. the method for using gas prepared formaldehyde resol according to claim 1 is characterized in that described phenol or alkylphenol, and alkylphenol is cresols, xylenol, Resorcinol, tert.-butyl phenol, nonylphenol, benzylphenol, dihydroxyphenyl propane.
3. the method for using gas prepared formaldehyde resol according to claim 1, it is characterized in that described basic catalyst, be used to prepare heat-reactive phenolic resin, this basic catalyst be highly basic, weak base or be alkalescence salt they be sodium hydroxide, potassium hydroxide, ammoniacal liquor, hydrated barta, magnesium oxide, yellow soda ash or zinc acetate.
4. the method for using gas prepared formaldehyde resol according to claim 1, it is characterized in that described an acidic catalyst, be used to prepare novolac resin, this an acidic catalyst be strong acid, weak acid or acid-salt they be hydrochloric acid, oxalic acid, acetate, formic acid, phosphoric acid, sulfuric acid or tosic acid.
5. the method for using gas prepared formaldehyde resol according to claim 1 is characterized in that 100 mass parts phenol or alkylphenol are joined in 20～70 mass parts water, and water is as reaction medium.
6. the method for using gas prepared formaldehyde resol according to claim 1 is characterized in that feeding formaldehyde gas below the liquid level of above reaction mass.
7. the method for using gas prepared formaldehyde resol according to claim 1, it is characterized in that above reaction mass placement is cooled to room temperature, reaction mass is divided into two layers, the reactant of lower floor, the resin prepolymer continues the heating polycondensation at 90～190 ℃, react to softening temperature, ring and ball method, 60～180 ℃, the resol product that obtains having various uses.
8. the method for using gas prepared formaldehyde resol according to claim 1, it is characterized in that the reaction mass layering after, with the water on upper strata as next time reaction medium water.
9. the method for using gas prepared formaldehyde resol according to claim 1 is characterized in that the water of heating polycondensation gained as next time reaction medium water.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014040300A1 (en) * | 2012-09-17 | 2014-03-20 | 华奇（张家港）化工有限公司 | Alkyl phenolic resin and process for producing same |
| CN104403067A (en) * | 2014-12-26 | 2015-03-11 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing thermoplastic phenol formaldehyde resin from gas formaldehyde |
| CN107429038A (en) * | 2015-03-31 | 2017-12-01 | 住友电木株式会社 | First rank modifying phenolic resin composition, its manufacture method and adhesive |
| US9932436B2 (en) | 2013-10-17 | 2018-04-03 | Si Group, Inc. | Modified alkylphenol-aldehyde resins stabilized by a salicylic acid |
| US9944744B2 (en) | 2013-10-17 | 2018-04-17 | Si Group, Inc. | In-situ alkylphenol-aldehyde resins |
| CN109796653A (en) * | 2018-12-24 | 2019-05-24 | 浙江金华万里橡塑实业有限公司 | A kind of weatherability high intensity drainpipe and preparation method thereof |
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Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4146739A (en) * | 1976-12-08 | 1979-03-27 | Akutin Modest S | Process for producing phenol-formaldehyde oligomers of ortho-specific structure |
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- 2007-03-30 CN CNB2007100211426A patent/CN100567354C/en not_active Expired - Fee Related
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| WO2014040300A1 (en) * | 2012-09-17 | 2014-03-20 | 华奇（张家港）化工有限公司 | Alkyl phenolic resin and process for producing same |
| US9932436B2 (en) | 2013-10-17 | 2018-04-03 | Si Group, Inc. | Modified alkylphenol-aldehyde resins stabilized by a salicylic acid |
| US9944744B2 (en) | 2013-10-17 | 2018-04-17 | Si Group, Inc. | In-situ alkylphenol-aldehyde resins |
| US10647806B2 (en) | 2013-10-17 | 2020-05-12 | Si Group, Inc. | In-situ alkylphenol-aldehyde resins |
| US11155667B2 (en) | 2013-10-17 | 2021-10-26 | Si Group, Inc. | In-situ alkylphenol-aldehyde resins |
| CN104403067A (en) * | 2014-12-26 | 2015-03-11 | 中国林业科学研究院林产化学工业研究所 | Method for synthesizing thermoplastic phenol formaldehyde resin from gas formaldehyde |
| CN107429038A (en) * | 2015-03-31 | 2017-12-01 | 住友电木株式会社 | First rank modifying phenolic resin composition, its manufacture method and adhesive |
| CN109796653A (en) * | 2018-12-24 | 2019-05-24 | 浙江金华万里橡塑实业有限公司 | A kind of weatherability high intensity drainpipe and preparation method thereof |
| CN109796655A (en) * | 2018-12-24 | 2019-05-24 | 浙江万里新材料科技有限公司 | A kind of Radiation Crosslinked Polyethylene foam material and preparation method thereof |
| CN109796655B (en) * | 2018-12-24 | 2021-11-30 | 浙江万里新材料科技有限公司 | Irradiation crosslinking polyethylene foam material and preparation method thereof |
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