CN101724133B

CN101724133B - Method for producing phenolic resin by utilizing paraformaldehyde

Info

Publication number: CN101724133B
Application number: CN2009102266719A
Authority: CN
Inventors: 黎超; 喻泽
Original assignee: HUNAN ZHONGYE HIGH-TECH SPECIAL MATERIAL Co Ltd
Current assignee: HUNAN ZHONGYE HIGH-TECH SPECIAL MATERIAL Co Ltd
Priority date: 2009-12-18
Filing date: 2009-12-18
Publication date: 2011-07-13
Anticipated expiration: 2029-12-18
Also published as: CN101724133A

Abstract

The invention relates to a method for producing phenolic resin by utilizing paraformaldehyde, which comprises the following steps of: 1. preparing raw materials in the following parts by weight: 350-400 phenol, 176-224 paraformaldehyde, 1.5-2 sodium hydroxide, 10-15 barium hydroxide, 14-20 urea and 80-150 water; 2. adding the phenol, the sodium hydroxide and the barium hydroxide into a reaction kettle for heating; adding 1/8 of paraformaldehyde and controlling the temperature in the kettle; and adding again every 15-25 minutes and adding totally seven time; 3. preserving heat for 60-80 minutes and then heating to the temperature of 95-110 DEG C for high temperature reaction for 30-50 minutes; and 4. when an opacifying point reaches 52-57 DEG C, adding the urea and the water and discharging when the temperature in the kettle is decreased to 50 DEG C to obtain a finished product. The method overcomes the problems of inconvenient liquid formaldehyde transportation, large energy consumption, environmental pollution and the like troubling enterprise development for a long time, and is beneficial to the development of the industry.

Description

A kind of method of utilizing Paraformaldehyde 96 to produce resol

Technical field

The present invention relates to a kind of production method of resol, belong to the macromolecular organic compound technical field.

Background technology

Phenol formaldehyde foam is a kind of light energy conservation product of excellent performance, has multinomial functions such as fire prevention, heat insulation, sound insulation, is widely used at aspects such as airduct, wall thermal insulating, aviation, chemical industry.And be used to produce the raw material resol of phenol formaldehyde foam, current, it is that 37% liquid formaldehyde solution reacts generation under the katalysis of basic catalyst that the overwhelming majority still adopts phenol and concentration.Use traditional this technology, be used for the problems such as dehydration of resin, also have a large amount of contaminated wastewater problem of environment of discharging except existing liquid formaldehyde transportation inconvenience, needs to consume a large amount of energy.These problems are the difficult problem of puzzlement enterprise development for a long time always.

Summary of the invention

The technical problem to be solved in the present invention is at the defective that prior art exists, to propose a kind of method of utilizing Paraformaldehyde 96 to produce resol.This method is produced all environmental issues that resol should avoid above-mentioned traditional technology to bring by utilizing solid polyformaldehyde to substitute liquid formaldehyde.

Technical solution of the present invention is that described a kind of method of utilizing Paraformaldehyde 96 to produce resol is for adopting following raw material and step to produce resol:

(1), by following weight ratio backup raw material:

Phenol 350～400,

Paraformaldehyde 96 176～224,

Sodium hydroxide 1.5～2,

Hydrated barta 10～15,

Urea 14～20,

Water 80～150;

(2), step (1) be equipped with phenol, sodium hydroxide, hydrated barta drop in the reactor, stop heating after temperature in the kettle is risen to 60 ℃.In reactor, drop into 1/8 step (1) and be equipped with Paraformaldehyde 96, the control temperature in the kettle, temperature controlling range is 75～95 ℃.After for the first time in reactor, dropping into Paraformaldehyde 96, in reactor, drop into again and the Paraformaldehyde 96 of Paraformaldehyde 96 input amount equivalent for the first time every 15～25min, thrown for 7 times;

(3), temperature in the kettle is controlled at 75～85 ℃ of scope insulation 60～80min.Be warmed up to 95～110 ℃ of pyroreaction 30～50min then.Re-use resol milkiness point in the ordinary method test still, 52～57 ℃ of milkiness points are reaction end;

(4), when the milkiness point reaches 52～57 ℃ when promptly reaching reaction end, step (1) is equipped with urea and water drops in the reactor, reduce temperature in the kettle, when temperature in the kettle was reduced to 50 ℃, discharging promptly got the resol finished product.

Above-mentioned steps (4) gained resol finished product can be taken out from still, detect errorless just can inserting in the dedicated storage jar through sampling and store.

In the step of the invention described above, control wherein active to resin and viscosity is very important.When the activity control of Paraformaldehyde 96 resin is bad, when producing phenol formaldehyde foam high fragility or phenomenons such as multiple hole or red lump will appear, even have both at the same time.Catalyzer sodium hydroxide among the present invention has stronger catalytic effect to the addition reaction of phenolic aldehyde, and makes the primary polycondensate thing that solubility property preferably be arranged in reaction medium, uses hydrated barta then can obtain high adjacent position phenolic resin.The composite catalyst of the two formation can be controlled the quantity of the active group methylol of whole resin, thereby make the resin activity controlled by the side cardinal sum speed of response of control molecular chain.The control of above-mentioned viscosity is mainly regulated by the control water yield and reaction times.

The invention has the beneficial effects as follows because overcome traditional technology liquid formaldehyde transportation inconvenience, energy consumption is big and the problem of long-term puzzlement such as the big contaminate environment of wastewater discharge enterprise development.Under the megatrend that obtains day by day paying attention in environment protection now, the novel process that use Paraformaldehyde 96 of the present invention is produced resol can constitute the technical object that the industry is promoted, thus the development of the very favourable industry.

Embodiment:

Embodiment 1:

(1), by following weight ratio backup raw material:

Phenol 350kg,

Paraformaldehyde 96 176kg,

Sodium hydroxide 1.5kg,

Hydrated barta 10kg,

Urea 14kg,

Water 80kg;

(2), step (1) be equipped with phenol, sodium hydroxide, hydrated barta drop in the reactor, stop heating after temperature in the kettle is risen to 60 ℃.In reactor, drop into the 22kg Paraformaldehyde 96, the control temperature in the kettle, temperature controlling range is 75～95 ℃.After for the first time in reactor, dropping into Paraformaldehyde 96, in reactor, drop into the 22kg Paraformaldehyde 96 again every 15～25min, thrown for 7 times;

(3), temperature in the kettle is controlled at 75～85 ℃ of scope insulation 60min.Be warmed up to 95～110 ℃ of pyroreaction 30min then.Re-use resol milkiness point in the ordinary method test still, 52～57 ℃ of milkiness points are reaction end;

(4), when the milkiness point reaches 52～57 ℃, step (1) is equipped with urea and water drops in the reactor, reduce temperature in the kettle, when temperature in the kettle was reduced to 50 ℃, discharging promptly got the resol finished product.

Embodiment 2:

(1), by following weight ratio backup raw material:

Phenol 400g,

Paraformaldehyde 96 224g,

Sodium hydroxide 2g,

Hydrated barta 15g,

Urea 20g,

Water 150g;

(2), step (1) be equipped with phenol, sodium hydroxide, hydrated barta drop in the reactor, stop heating after temperature in the kettle is risen to 60 ℃.In reactor, drop into the 28g Paraformaldehyde 96, the control temperature in the kettle, temperature controlling range is 75～95 ℃.After for the first time in reactor, dropping into Paraformaldehyde 96, in reactor, drop into the 28g Paraformaldehyde 96 again every 15～25min, thrown for 7 times;

(3), temperature in the kettle is controlled at 75～85 ℃ of scope insulation 80min.Be warmed up to 95～110 ℃ of pyroreaction 50min then.Re-use resol milkiness point in the ordinary method test still, 52～57 ℃ of milkiness points are reaction end;

Step (4) is with embodiment 1.

Claims

1. method of utilizing Paraformaldehyde 96 to produce resol, this method is the following step:

(1), by following weight ratio backup raw material:

Phenol 350～400,

Paraformaldehyde 96 176～224,

Sodium hydroxide 1.5～2,

Hydrated barta 10～15,

Urea 14～20,

Water 80～150;

(2), step (1) is equipped with in phenol, sodium hydroxide, the hydrated barta input reactor, stop heating after temperature in the kettle risen to 60 ℃, in reactor, drop into 1/8 step (1) and be equipped with Paraformaldehyde 96, the control temperature in the kettle, temperature controlling range is 75～95 ℃, after for the first time in reactor, dropping into Paraformaldehyde 96, in reactor, drop into again and the Paraformaldehyde 96 of Paraformaldehyde 96 input amount equivalent for the first time every 15～25min, thrown for 7 times;

(3), temperature in the kettle is controlled at 75～85 ℃ of scopes insulation, 60～80min, be warmed up to 95～110 ℃ of pyroreaction 30～50min then, re-use resol milkiness point in the ordinary method test still, 52～57 ℃ of milkiness points are reaction end;