CN1045402A - Synthesizing of ion-exchange resin catalyzed phenol resin down - Google Patents
Synthesizing of ion-exchange resin catalyzed phenol resin down Download PDFInfo
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- CN1045402A CN1045402A CN89109679A CN89109679A CN1045402A CN 1045402 A CN1045402 A CN 1045402A CN 89109679 A CN89109679 A CN 89109679A CN 89109679 A CN89109679 A CN 89109679A CN 1045402 A CN1045402 A CN 1045402A
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- Prior art keywords
- resin
- catalyzer
- phenol
- synthetic
- phenol resin
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
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- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention belongs to catalyzer and polymer.The present invention adopts large pores cation exchange resin to make the catalyzer that synthesizes phenol resin through acidification, and carries out the synthetic of phenol resin with this catalyzer.This catalyzer has overcome the problem of the serious phenol environmental pollution by water that technologies such as the heavy corrosion of equipment and neutralization, washing is brought with catalyzer such as traditional sulfuric acid, hydrochloric acid, oxalic acid, Phenylsulfonic acids.Utilize the novel process process of the synthetic phenol resin of catalyzer of the present invention simple, not neutralization, washing, and phenol water pollution problems, reusable, tangible economic benefit is arranged.
Description
The invention belongs to catalyzer and polymer.
Resol is still main synthetic resins at present, employed catalyzer majority is sulfuric acid, hydrochloric acid, Phenylsulfonic acid, oxalic acid etc. in the production of line style phenolic resin, these catalyzer are except that equipment is had the heavy corrosion in the production process, also must neutralize, a series of auxiliary process processes such as washing, the serious problems of phenol environmental pollution by water in addition.
The objective of the invention is storng-acid cation exchange resin to be used for the polycondensation of phenol and aldehyde, overcome the shortcoming that existing inorganic acid catalyst exists aborning, simplify production technique, prevent the novel process of phenol environmental pollution by water as catalyzer.
The used strong acid cation exchange resin catalyst of the present invention is that commercially available macroporous type storng-acid cation exchange resin is exchanged into h type resin with 5% aqueous hydrochloric acid, the consumption of this acid solution is 4 times of resin volume, when to measure the resins exchange equivalent be 4.8 milligramequivalents/gram, extremely neutral with a large amount of distilled water flushings, the elimination free-water, wet resin is poured in the dish, in 90-120 ℃ of baking oven, dried, store standby.
Synthetic lacquer resins is by phenols such as phenol, dihydroxyphenyl propane, cresols, p-tert-butylphenol, to octyl phenol etc. and aldehydes such as formaldehyde, poly aldehyde, acetaldehyde, etc. under the Hydrogen large hole cation exchanger resin catalysis of system of the present invention, under solvent toluene or dimethylbenzene existence or non-solvent system, obtain the line style phenolic resinoid.The mol ratio of phenol and aldehyde is 1: 0.5-1: 2, catalyst consumption is 15-50%(weight %), reaction mixture is reusable through separating rear catalyst, remove reaction product behind the catalyzer under 120-180 ℃, do condition of high vacuum degree 100-700mmHq gradually and remove water or solvent in the system, dehydration inclines product to go out after finishing, and measures product output and softening temperature.Adopt hydrogen type cation exchange resin catalyzer of the present invention that equipment is not had corrosion, the neutralization of prior art has been avoided in separable repeated use, and there be not the pollution problem of a large amount of phenol water to environment in processes such as washing.
Example one. the preparation of resin catalyst.
Macroporous type D72 ion exchange resin is carried out ion-exchange with 5% aqueous hydrochloric acid of 4 times of dried resin volumes become h type resin, when measuring resins exchange equivalent 〉=4 milligramequivalents/gram, extremely neutral with a large amount of distilled water flushings, the elimination free-water, wet resin is poured in the dish, in 120 ° of baking ovens, dry, store standby.
The preparation of p-tert-butylphenol formaldehyde resin:
Get p-tert-butylphenol 25g, 35% formaldehyde 17ml, toluene solution 100ml, the Hydrogen D72 resin catalyst 25g of above-mentioned preparation, being added to 250ml successively takes back in the four-hole bottle of flow condenser and agitator, slowly heat up, stir simultaneously, reaction is 2 hours under reflux temperature, when noting using the new system resin catalyst for the first time, has peak heat release to occur when being reflected at before the reflux temperature about 80 ℃, should note control, with reaction solution and catalyst separating, the catalyzer after the separation can use continuously then, and reaction solution is placed on 250cm
3Heating up gradually in the flask steams water and solvent, and shut-down operation when the question response liquidus temperature reaches 150 ℃ takes advantage of a favourable situation to pour out, and obtains the about 30g of p-tert-butylphenol formaldehyde resin, about 100 ℃ of softening temperature.
Example two.
With the dried D72 resin catalyst of the Hydrogen 100g of example one method system, p-tert-butylphenol 300g, 37% formaldehyde 180cm
3Be added to 1000cm
3In the four-hole boiling flask that take back stream, stirs, must notice that to the resin catalyst that uses for the first time temperature control slowly heats, reaction is 2 hours under reflux temperature.With reaction solution and catalyst separating, attention is more sticking because of solvent-free system then, needs to separate rapidly under comparatively high temps.Catalyzer is reusable, and reusable catalyzer does not have peak heat release.Reaction liquid is at 1000cm
3Heating in the flask, vacuumize dehydration, when liquidus temperature was 150 ℃, product was poured out in shut-down operation while hot, obtains the about 330g of resin, about 100 ℃ of softening temperature.
Example three,
With the dried D72 resin catalyst of Hydrogen 25g, phenol 100g, the 37% formaldehyde 80ml of example one method system, be added in the four-hole boiling flask of taking back stream, stirring of 500ml, must note temperature control to the resin catalyst that uses for the first time, slowly heating, or formaldehyde adds in batches, reaction is 3 hours under reflux temperature, with reaction solution and catalyst separating, catalyzer is reusable then.Reactant heats in the 500ml flask, 0.07
MPVacuumize dehydration under a, during to 150 ℃ of liquidus temperatures, product is poured out in shut-down operation while hot, obtains the about 110g of resol.
Claims (3)
1, the invention belongs to and use sulfuric acid, hydrochloric acid, oxalic acid, Phenylsulfonic acid etc. to carry out the synthetic of phenol resin as catalyzer in catalyzer and polymer, the prior art, feature of the present invention is to adopt large pores cation exchange resin to make catalyzer to carry out the synthetic of phenol resin.
2, large pores cation exchange resin catalyzer according to claim 1, it is characterized in that large pores cation exchange resin with 5% salt acid treatment, when to measure exchanging equivalent be 3.0-5.0 milligramequivalent/gram, resin after the exchange is extremely neutral with a large amount of distilled water flushings, the elimination free-water, resin is poured in the dish into dry for standby in 90-120 ℃ of baking oven.
3, phenol resin according to claim 1 is synthetic, it is characterized in that phenol, dihydroxyphenyl propane, phenols such as p-tert-butylphenol and formaldehyde, acetaldehyde, etc. aldehydes in molar ratio 1: 0.5-1: 2 mix after, be under the catalysis of 15-50% Hydrogen large hole cation exchanger resin by weight percentage, under solvent toluene or dimethylbenzene existence or non-solvent system, make the line style phenolic resinoid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89109679A CN1017053B (en) | 1989-12-29 | 1989-12-29 | Phenol resin synthesis catalyzed by ion-exchange resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN89109679A CN1017053B (en) | 1989-12-29 | 1989-12-29 | Phenol resin synthesis catalyzed by ion-exchange resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1045402A true CN1045402A (en) | 1990-09-19 |
| CN1017053B CN1017053B (en) | 1992-06-17 |
Family
ID=4858122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89109679A Expired CN1017053B (en) | 1989-12-29 | 1989-12-29 | Phenol resin synthesis catalyzed by ion-exchange resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1017053B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347212C (en) * | 2006-04-25 | 2007-11-07 | 徐州工业职业技术学院 | Method for catalyzing and producing phenyl phenol formaldehyde resin using macropore strong acid cation exchange resin |
| CN100347211C (en) * | 2006-04-25 | 2007-11-07 | 徐州工业职业技术学院 | Method for catalyzing and producing phenyl phenol formaldehyde resin using macropore alkali anion exchange resin |
| CN112574006A (en) * | 2020-12-31 | 2021-03-30 | 江西赣锋循环科技有限公司 | Preparation method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol |
-
1989
- 1989-12-29 CN CN89109679A patent/CN1017053B/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347212C (en) * | 2006-04-25 | 2007-11-07 | 徐州工业职业技术学院 | Method for catalyzing and producing phenyl phenol formaldehyde resin using macropore strong acid cation exchange resin |
| CN100347211C (en) * | 2006-04-25 | 2007-11-07 | 徐州工业职业技术学院 | Method for catalyzing and producing phenyl phenol formaldehyde resin using macropore alkali anion exchange resin |
| CN112574006A (en) * | 2020-12-31 | 2021-03-30 | 江西赣锋循环科技有限公司 | Preparation method of 4-tert-butyl-2 (alpha-methylbenzyl) phenol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1017053B (en) | 1992-06-17 |
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