CN1470541A

CN1470541A - Method for manufacturing phenol resin using ion exchange resin as catalyst

Info

Publication number: CN1470541A
Application number: CNA021253455A
Authority: CN
Inventors: 夏红元
Original assignee: Individual
Current assignee: Individual
Priority date: 2002-07-26
Filing date: 2002-07-26
Publication date: 2004-01-28

Abstract

The present invention discloses a method for synthesizing phenol resin ion exchange resin as catalyst. Said method includes: using 5% hydrochloric acid to treat macroporous cation exchange resin, when the exchange equivalent determined is 3.0-5.0 mg equivalent/g, using lots of distilled water to wash exchanged resin to neutrality, filtering and removing free water, pouring the resin into disk, drying at 90-120 deg.C in drying over for stand-by; mixing phenols of phenol, bisphenol A and p-tert-butylphenol, etc. and aldehydes of formaldehyde and acetaldehyde, etc. according to the mole ratio of 1:0.5-1:2, and under the catalysis of the hydrogen-type macroporous cation exchange resin according to weight percentage of 15-50%, in the presence of solvent toluene or xylene or in non-solvent system.

Description

Spent ion exchange resin is that the phenols of catalyzer is the manufacture method of resin

Technical field

The present invention relates to resene, the phenols that the present invention relates to a kind of spent ion exchange resin in particular and be catalyzer is the manufacture method of resin.

Background technology

Resol is still main synthetic resins at present, and employed catalyzer majority is sulfuric acid, hydrochloric acid, Phenylsulfonic acid, oxalic acid etc. in the production process of linear phenolic resin.These catalyzer also must neutralize except that equipment is had the heavy corrosion in the production process, a series of auxiliary process process complexity such as washing, and the serious problems of phenol environmental pollution by water.

Summary of the invention

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 in producing again, simplify production technique, prevent the novel process of phenol environmental pollution by water as catalyzer.

The present invention is achieved by following technical proposals

The used strong acid cation exchange resin catalyst of the present invention is that commercially available large-scale property Zeo-karb 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 3.0～5.0 milligramequivalents/gram, extremely neutral with a large amount of distilled water flushings, the elimination free-water, resin is poured in the dish, in 90-120 ℃ of drying baker, dried, store for future use.

Synthetic lacquer resin be by phenols such as phenol, dihydroxyphenyl propane, cresols, right-this phenol of the tertiary butyl, 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 linear 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 reactant behind the catalyzer under 120-180 ℃, improve vacuum degree of reading 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.

The invention has the beneficial effects as follows:

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.

Embodiment

The present invention is further illustrated below in conjunction with embodiment:

The preparation of example one, resin catalyst

Macroporous type D72 ion exchange resin is carried out ion-exchange with 4 times of 5% aqueous hydrochloric acids to the resin volume become h type resin, when measuring resins exchange equivalent 〉=4 milligramequivalents/gram, extremely neutral with a large amount of distilled water, the elimination free-water, wet resin is poured in the dish, in 120 ℃ of baking ovens, dry, store for future use.

The preparation of right-this fluosite of the tertiary butyl:

Get right-this phenol of tertiary butyl 25g, 35% formaldehyde 17ml, toluene solution 100ml, the Hydrogen D72 resin catalyst 25g of above-mentioned preparation, be added to 250ml successively and take 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, there is peak heat release to occur when being reflected at before the reflux temperature about 80 ℃, should notes control, with reaction solution and catalyst separating, the catalyzer after the separation can use continuously then.Reaction solution is placed on to heat up gradually in the 250cm^3 flask water and solvent is steamed, and shut-down operation when the question response liquidus temperature reaches 150 ℃ takes advantage of a favourable situation to pour out, and obtains right-about 30g of this fluosite of the tertiary butyl, about 100 ℃ of softening temperature.

Example two,

The dried D72 resin catalyst of Hydrogen 100g with example one method system, right-this phenol of tertiary butyl 300g, 37% formaldehyde 180cm^3 is added to 1000cm^3 and takes back in the four-hole bottle of stream, stirring, must notice that to the resin catalyst that uses for the first time temperature control slowly heats, and reacts 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 heats, vacuumizes dehydration in the 1000cm^3 flask, 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, vacuumizes dehydration under 0.07Mpa, and during to 150 ℃ of liquidus temperatures, product is poured out in shut-down operation while hot, obtains the about 110g of resol, about 100 ℃ of softening temperature.

Claims

1. the manufacture method that spent ion exchange resin is the phenol resin of catalyzer is characterized in that, takes the following step:

(1) with large pores cation exchange resin with 5% salt acid treatment, when to measure exchanging equivalent be 3.0-5.0 milligramequivalent/gram, the resin after exchanging is washed till neutrality with distilled water, the elimination free-water is poured resin in the dish into, dry for standby in 90-120 ℃ of baking oven;

(2) with phenol, dihydroxyphenyl propane, p-tert-butylphenol class and formaldehyde, acetaldehyde, its aldehydes in molar ratio 1: 0.5-1: 2 mixed 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 resin.