CN103467682B - Process for circularly producing thermoplastic barium sulfate phenolic resin by precipitation method - Google Patents
Process for circularly producing thermoplastic barium sulfate phenolic resin by precipitation method Download PDFInfo
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- CN103467682B CN103467682B CN201310365666.2A CN201310365666A CN103467682B CN 103467682 B CN103467682 B CN 103467682B CN 201310365666 A CN201310365666 A CN 201310365666A CN 103467682 B CN103467682 B CN 103467682B
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Abstract
The invention provides a process for circularly producing thermoplastic barium sulfate phenolic resin by a precipitation method. The process comprises the following steps: according to a formula of synthetic resin, adding phenol, solid aldehyde and water into a reaction kettle with a cooler and a stirrer, heating to a temperature of 50 to 80 DEG C, depolymerizing and adding sulfuric acid to perform the catalytic reaction until a sampled sample is not sticky and is slightly hard in water with a temperature of 20 DEG C; cooling a reaction material to a temperature of 95 to 96 DEG C and adding barium hydroxide with stirring to stop the catalytic reaction; neutralizing the sulfuric acid by the barium hydroxide to generate water and barium sulfate precipitates, enabling the pH value of the reaction material to be 7, firstly carrying out normal pressure processing and then carrying out vacuum dehydration to obtain the semitransparent solid thermoplastic barium sulfate phenolic resin product and a polycondensation dehydration fraction; reusing the polycondensation dehydration fraction into the reaction kettle to carry out circular production. The process has zero discharge of wastewater, is beneficial to the environment protection, is suitable for industrial production and has good economic benefits.
Description
Technical field
The invention belongs to resol synthesis field, be specifically related to a kind of technique of precipitator method cyclic production thermoplastic barium sulfate phenolic resin, wastewater zero discharge can be accomplished, raw material phenol utilization ratio almost reaches 100%.
Background technology
Novolac resin product is mainly used in the industries such as bonding wood materials processing, moulding compound, insulating material, heat-insulating and sound-proof material, friction material section, coating, ink, oil field, paint, rubber, and the resol wherein through modification is being widely used in military affairs, Aeronautics and Astronautics and other sophisticated technology field as high-temperature-resistant adhesive and body material.
Novolac resin traditional mode of production adopts phenol and formalin to form through polycondensation under an acidic catalyst.Novolac resin production method is commonly used for existing friction materials, production method is as follows: with water cooler, phenol is added in the reactor of agitator, formaldehyde (37%) aqueous solution, 1/3rd of hydrochloric acid, be heated to 70 ~ 80 DEG C utilize reaction heat to be warmed up to material to have backflow, residue hydrochloric acid is slowly added after material reaction is mild, react after 60 minutes and sample, sample is tack-free in 20 DEG C of water is reaction end, the water adding 50 ~ 60 DEG C of 1/2nd of amount of resin is washed, stop stirring after a moment, vacuum sucked upper water liquid and carry out second time washing, the water adding 50 ~ 60 DEG C of 1/2nd of amount of resin is again washed, stop stirring after a moment, vacuum sucked upper water liquid and dewater, first normal pressure final vacuum is dewatered to pressure when be 80KPa material temperature being 125 DEG C is dehydration reaction terminal, blowing cools to charging tray, obtain transparent solid novolac resin and polycondensation dehydrated fraction.
There is following drawback in aforesaid method: can produce a large amount of waste water in (1) washing process production process, often produces one ton of resol and produce two tons of waste water, the derivative containing hydrochloric acid, free phenol, loss resin and phenol in waste water, and administer containing Cl
--, high, the expense of phenolic wastewater difficulty is large, need drop into a large amount of manpowers, equipment and fund, regulation effect is also difficult to reach people's will, will cause great pollution to environment.(2) washing process can not stop catalyzed reaction completely, a slowed down reaction speed.During washing, resin easily runs off, and the resin run off can only make the lower small-molecular-weight resin of price when wastewater treatment.(3) a small amount of Cl of containing of resin
--ion can affect product and preserve, and easily makes resin variable color.
Because novolac resin tradition washing process raw material availability is low, unit output production cost is high, yield is low, waste is large, preservation period is short, large, the waste water treatment occupation of land of power consumption, water consumption greatly, defect that cost is high, seriously hinder the development of phenolic aldehyde industry.
Summary of the invention
The object of the invention is to overcome the above-mentioned defect existed in prior art, a kind of technique of precipitator method cyclic production thermoplastic barium sulfate phenolic resin is provided, wastewater zero discharge can be done, raw material phenol utilization ratio almost reaches 100%.
The technique of precipitator method cyclic production thermoplastic barium sulfate phenolic resin, is characterized in that, comprise the following steps:
A (), according to synthetic resins formula, adds phenol, solid aldehyde and water in the reactor with water cooler, agitator, be heated to 50 ~ 80 DEG C of depolymerization after vulcanization acid catalyzed reactions tack-free firmly micro-in 20 DEG C of water to sampling sample;
B () cooling reaction mass to 95 ~ 96 DEG C, under agitation add hydrated barta and stop catalyzed reaction, hydrated barta neutralisation of sulphuric acid, generate water and barium sulfate precipitate, make reaction mass pH value be 7;
C () first normal pressure again vacuum hydro-extraction obtains translucent solid thermoplastic barium sulfate phenolic resin product and polycondensation dehydrated fraction; Wherein, the weight percent 1 ~ 3% of barium sulfate in resol product; Free phenol containing 2000 ~ 5000mg/l in polycondensation dehydrated fraction, the free formaldehyde of 1000 ~ 3000mg/l, loss resin and organic low molecular compounds and micro-barium sulfate;
In reactor described in the reuse to step (a) of (d) polycondensation dehydrated fraction, cyclic production.
Further, the phenol described in step (a) is phenol or phenol and polyphenol, or phenol and cardanol; Described aldehyde is formaldehyde, acetaldehyde or furfural, can also be other aldehydes.The add-ons of water etc. overweight the weight of phenol, the add-on of sulfuric acid is 0.2 ~ 2% of the gross weight that feeds intake.
In step (b), the add-on of hydrated barta is equivalent sulfuric acid.
In step (d), the concrete steps of polycondensation dehydrated fraction reuse are: add phenol, solid formaldehyde, polycondensation dehydrated fraction according to synthetic resins formula, the add-on of polycondensation dehydrated fraction is with gross weight 1:1 ~ 1.2 of phenol; Then repeating step (b)-(d).
The reaction formula of phenol-formaldehyde reaction is as follows:
The reaction formula that hydrated barta neutralisation of sulphuric acid generates water and barium sulfate precipitate is:
H
2SO
4+Ba(OH)
2=BaSO
4↓+H
2O。
With sulfuric acid (H
2sO
4) as phenol-formaldehyde reaction catalyzer, with hydrated barta (Ba (OH)
2* 8H
2o) be the method for reaction terminating agent, reaction end can be controlled well, guarantee thermoplastic barium sulfate phenolic resin steady quality, and resin is easily preserved.Thermoplastic barium sulfate phenolic resin output capacity is high, and in resin, free phenol content is low, and free phenol in polycondensation dehydrated fraction, free formaldehyde content are low, component substantially constant, and cut adds corresponding formula recycle does not affect resin formula component structure.And avoid the hydrochloric acid adding and affect subsequent product quality index, for the recycle of polycondensation dehydrated fraction creates condition in the material of reaction; Barium sulfate (BaSO4) precipitation generated can improve high-temperature behavior, the raising cohesive strength of resin; Barium sulfate can reduce the hardness of friction materials, improves shock strength, reduces wear rate, can control the fluctuation of rubbing factor with temperature preferably high temperature 350 DEG C.
Utilize the thermoplastic barium sulfate phenolic resin product moisture 1 ~ 4% that the inventive method is obtained, building-up process produces the water of reducible resin finished product 9%, have little time to cool during underpressure distillation dehydration under 100 ~ 150 DEG C of high temperature, 0 ~ 80KPa vacuum cause part steam, low molecule enters vacuum system and the water of 3 ~ 10% of the resin finished product that runs off and low molecule, therefore may need during recycle cut to add part water.
Beneficial effect of the present invention:
(1) thermoplastic barium sulfate phenolic resin does not wash with water, reduces energy consumption, labour cost, eliminates water rate, avoids the generation of waste water.
(2) recycle of cut makes the utilization rate of raw materials such as phenol almost reach 100%, eliminates expensive waste water treatment expense simultaneously, really reaches cyclic production, wastewater zero discharge, be conducive to environment protection.
(3) add barium sulfate in novolac resin and can improve high-temperature behavior, cohesive strength; Barium sulfate can reduce the hardness of friction materials, improves shock strength, reduces wear rate.Each index controlled range of thermoplastic barium sulfate phenolic resin product is as following table.
Barium sulfate phenolic resin product quality controlled range
| Sequence number | Project | Index |
| 1 | Gelation time | 20—100S/150℃ |
| 2 | Softening temperature | 75—120℃ |
| 3 | Degree of mobilization | 10—70MM |
| 4 | Free phenol | ≤4% |
| 5 | Moisture content | 1—4% |
The inventive method is applicable to suitability for industrialized production, has good economic benefit.
Embodiment
Embodiment 1: preparation thermoplastic barium sulfate phenolic resin
Preparation thermoplastic barium sulfate phenolic resin formula can be following scope:
Start 1000 liters of band condensers, agitator, fast opening, the stirring of jacket steam heating and water-cooled reactor, add phenol 250Kg, solid formaldehyde 65Kg, polycondensation dehydrated fraction or deionized water 250Kg, open and be steam heated to 50 ~ 80 DEG C by after formaldehyde depolymerization, slowly add sulfuric acid (50%) 1Kg, be warmed up to backflow carefully, after question response divides secondary slowly to add residual sulfuric acid (50%) 2Kg gently afterwards, backflow samples for 1 hour, sample in 20 DEG C of water tack-free harder time chuck be cooled to material temperature to be 96 DEG C, slowly add hydrated barta (Ba (OH)
2* 8H
2o) 4.8Kg neutralisation of sulphuric acid, termination catalyzed reaction, generate barium sulfate precipitate and water, then vacuum hydro-extraction is carried out when intensification normal pressure is dewatered to material temperature 110 DEG C, be reaction end when pressure be 80KPa material temperature is 126 DEG C, blowing, to charging tray cooling, obtains translucent solid thermoplastic barium sulfate phenolic resin and polycondensation dehydrated fraction, polycondensation dehydrated fraction vacuum is extracted in cut storage tank for subsequent use, feeds intake by this technical recipe and carry out the production of next still, with this cyclic production, wastewater zero discharge.
Embodiment 2: the preparation of low cardanol thermoplastic barium sulfate phenolic resin
Formula can be following scope:
Start 1000 liters of band condensers, agitator, fast opening, the stirring of jacket steam heating and water-cooled reactor, add phenol 345Kg, solid formaldehyde 91Kg, cardanol 59Kg, polycondensation dehydrated fraction 345Kg, open and be steam heated to 50 ~ 80 DEG C by after formaldehyde depolymerization, slowly add sulfuric acid (50%) 2.3Kg, be warmed up to backflow carefully, after question response divides secondary slowly to add residual sulfuric acid (50%) 5.4.Kg gently afterwards, backflow samples for 1 hour, sample in 20 DEG C of water tack-free harder time chuck be cooled to material temperature to be 95-96 DEG C, slowly add hydrated barta (Ba (OH)
2* 8H
2o) 12.4Kg neutralisation of sulphuric acid, termination catalyzed reaction, generate barium sulfate precipitate and water, then vacuum hydro-extraction is carried out when intensification normal pressure is dewatered to material temperature 110 DEG C, be reaction end when pressure be 80KPa material temperature is 138 DEG C, blowing, to charging tray cooling, obtains low cardanol solid thermoplastic barium sulfate phenolic resin and polycondensation dehydrated fraction, polycondensation dehydrated fraction vacuum is extracted in cut storage tank for subsequent use, feeds intake by this technical recipe and carry out the production of next still, with this cyclic production, wastewater zero discharge.
The preparation of the high cardanol thermoplastic barium sulfate phenolic resin of embodiment 3.
Formula can be following scope:
Start 1000 liters of band condensers, agitator, fast opening, the stirring of jacket steam heating and water-cooled reactor, add phenol 220Kg, solid formaldehyde 65Kg, cardanol 72Kg, polycondensation dehydrated fraction and deionized water 220Kg, open and be steam heated to 50 ~ 80 DEG C by after formaldehyde depolymerization, slowly add sulfuric acid (50%) 2Kg, be warmed up to backflow carefully, after question response divides secondary slowly to add residual sulfuric acid (50%) 6Kg gently afterwards, backflow samples for 1 hour, sample in 20 DEG C of water tack-free harder time chuck be cooled to material temperature to be 96 DEG C, slowly add hydrated barta (Ba (OH)
2* 8H
2o) 4.8Kg neutralisation of sulphuric acid, termination catalyzed reaction, generate barium sulfate precipitate and water, then vacuum hydro-extraction is carried out when intensification normal pressure is dewatered to material temperature 110 DEG C, be reaction end when pressure be 80KPa material temperature is 138 DEG C, blowing, to charging tray cooling, obtains solid height cardanol thermoplastic barium sulfate phenolic resin and polycondensation dehydrated fraction, polycondensation dehydrated fraction vacuum is extracted in cut storage tank for subsequent use, feeds intake by this technical recipe and carry out the production of next still, with this cyclic production, wastewater zero discharge.
Claims (4)
1. the technique of precipitator method cyclic production thermoplastic barium sulfate phenolic resin, is characterized in that, comprises the following steps:
A (), according to synthetic resins formula, adds phenol, solid aldehyde and water in the reactor with water cooler, agitator, be heated to 50 ~ 80 DEG C of depolymerization after vulcanization acid catalyzed reactions tack-free firmly micro-in 20 DEG C of water to sampling sample; Described phenol is phenol or phenol and cardanol;
(b) cooling reaction mass to 95 ~ 96 DEG C, under agitation add hydrated barta and stop catalyzed reaction, the add-on of hydrated barta is equivalent sulfuric acid; Hydrated barta neutralisation of sulphuric acid, generates water and barium sulfate precipitate, makes reaction mass pH value be 7;
C () first normal pressure again vacuum hydro-extraction obtains translucent solid thermoplastic barium sulfate phenolic resin product and polycondensation dehydrated fraction; Wherein, the weight percent 1 ~ 3% of barium sulfate in resol product; Free phenol containing 2000 ~ 5000 mg/L in polycondensation dehydrated fraction, the free formaldehyde of 1000 ~ 3000 mg/L, loss resin and organic low molecular compounds and micro-barium sulfate;
In reactor described in the reuse to step (a) of (d) polycondensation dehydrated fraction, cyclic production.
2. technique according to claim 1, is characterized in that, in step (a), described aldehyde is formaldehyde, acetaldehyde or furfural.
3. technique according to claim 1, is characterized in that, in step (a), the add-on of water etc. overweight the weight of phenol, the add-on of sulfuric acid is 0.2 ~ 2% of the gross weight that feeds intake.
4. technique according to claim 1, it is characterized in that, in step (d), the concrete steps of polycondensation dehydrated fraction reuse are: add phenol, solid formaldehyde, polycondensation dehydrated fraction according to synthetic resins formula, the add-on of polycondensation dehydrated fraction is with gross weight 1:1 ~ 1.2 of phenol; Then repeating step (b)-(d).
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| CN105315418B (en) * | 2015-11-14 | 2019-02-05 | 浙江越拓新材料科技有限公司 | Tungsten disulfide phenol-formaldehyde resin modified and preparation method thereof |
| CN107987237B (en) * | 2017-12-12 | 2021-03-02 | 济南鲁东耐火材料有限公司 | Preparation method of phenolic resin for refractory material |
| CN113234202B (en) * | 2021-06-15 | 2022-07-29 | 河北泽田化工有限公司 | High-moisture-retention phenolic resin and preparation method thereof |
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| CN102002139B (en) * | 2010-10-22 | 2012-06-20 | 兰州石化职业技术学院 | Method for preparing modified phenolic resin for coating with cresol residue |
| CN103059237B (en) * | 2012-12-12 | 2015-09-30 | 江苏锋芒复合材料科技集团有限公司 | A kind of novolac resin preparation method of wastewater zero discharge |
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