CN101348548A - Environment-protective process for synthesizing phenolic resin - Google Patents

Environment-protective process for synthesizing phenolic resin Download PDF

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Publication number
CN101348548A
CN101348548A CNA2007102021159A CN200710202115A CN101348548A CN 101348548 A CN101348548 A CN 101348548A CN A2007102021159 A CNA2007102021159 A CN A2007102021159A CN 200710202115 A CN200710202115 A CN 200710202115A CN 101348548 A CN101348548 A CN 101348548A
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China
Prior art keywords
formaldehyde
phenol
solid
environment
reactor
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Pending
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CNA2007102021159A
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Chinese (zh)
Inventor
李绍通
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Individual
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Individual
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Priority to CNA2007102021159A priority Critical patent/CN101348548A/en
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Abstract

The invention provides an environment-friendly process for synthesizing a varnish type solid and a thermosetting type liquefied phenolic resin through the reaction of formaldehyde and phenol or cresol. The process adopts solid formaldehyde and liquefied formaldehyde as raw materials, and the process also recycles waste water which is produced by the reaction and contains the phenol and the aldehyde without discharging the waste water.

Description

The environment-protective process of novolak resin
Technical field
The present invention relates to the environment-protective process that formaldehyde and phenol or cresols are the main raw material(s) novolak resin, belong to the macromolecular organic compound technical field.
Background technology
Resol has good acidproof, alkaline-resisting, heat-resisting and electrical insulating property, is widely used in fields such as paint, refractory materials, telecommunication, electrical equipment, instrument, daily necessities and light building material.
Traditional resol synthesis technique adopts liquid formaldehyde and phenol or cresols, catalyzer etc. to drop into conversion unit according to certain ratio, again according to the certain process conditions novolak resin.The advantage of traditional synthesis is to adopt liquid formaldehyde polymeric reaction condition gentleness, operation control easily; Shortcoming is to produce a large amount of phenol aldehyde-containing sewages that contain, and processing costs is big, and contaminate environment.
CN1223620 discloses and adopted Paraformaldehyde 96, weak base is the method for preparing mixed alkyl resol condenses under the catalyzer condition.This method has just reduced the phenol aldehyde-containing sewage amount that contains that reaction produces, and does not thoroughly solve wastewater problem; And all adopt polyreaction fierceness, the operation of Paraformaldehyde 96 to control difficulty, easily implode.
Summary of the invention
The present invention is directed to the defective that prior art exists, propose to adopt the environment-protective process of formaldehyde and phenol or cresols reaction synthetic varnish type solid and heat curing-type liquid phenolic resin, it is raw material that this technology alternately adopts solid formaldehyde and liquid formaldehyde, what make that reaction produces contains the recycle of phenol aldehyde-containing sewage, does not discharge to contain the phenol aldehyde-containing sewage.
Technical solution of the present invention is:
(1) with acid is Catalyst Production varnish type solid phenolic resin scheme
Adopt phenol, formaldehyde and acid catalyst synthetic varnish type solid phenolic resin, wherein the mol ratio of raw material phenol and formaldehyde is 1: (0.6-0.9), catalytic amount is the 0.5%-10% of raw material phenol weight; Catalyzer is hydrochloric acid or phosphoric acid; Liquid formaldehyde concentration is 36-37%, and solid formaldehyde concentration is 80%-96%.
In the glassed steel reaction vessels that agitator, condenser, vacuum system, temperature control survey device are housed, drop into liquid phenol, 37% formaldehyde of preheating, 30% hydrochloric acid or 85% phosphoric acid divide the secondary input.
After raw material has been thrown, start agitator and stir the reacting kettle jacketing internal heating, after reactor temperature rises to 50-70 ℃, add the part catalyzer, close heating when the temperature in the reactor rises to 90 ℃, the chuck to reactor when the temperature in the reactor rises to 95-98 ℃ cools off.When the temperature in the reactor reaches 100 ℃, pick up counting, add remaining catalyzer, reacted 90-180 minute.Between the reaction period, the temperature in the reactor is controlled between 92-105 ℃, and leads to the temperature of regulating in the reacting kettle jacketing in the control reactor.Vacuumize decompression dehydration when milkiness occurring, dehydration finishes the qualified back of viscosity blowing.
Put into the solid formaldehyde dissolution kettle with vacuumizing the phenol aldehyde-containing sewage of deviating from that contains that reduces pressure, add the 80%-96% solid formaldehyde that measures, make the proportioning of formaldehyde the same with the front.Heating makes the solid formaldehyde dissolving, and solid formaldehyde fully dissolves the back and adds glassed steel reaction vessels continuation reaction.
(2) with alkali be Catalyst Production heat curing-type liquid phenolic resin scheme
Adopt phenol, formaldehyde and alkaline catalysts synthetic, wherein the mol ratio of raw material phenol and formaldehyde is 1: 1.1-2.0, catalyzer account for the 3%-15% of raw material phenol weight; Catalyzer is a sodium hydroxide, divides the secondary input; Liquid formaldehyde concentration is 36-37%, and solid formaldehyde concentration is 80-96%.
In the glassed steel reaction vessels that agitator, condenser, vacuum system, temperature control survey device are housed, drop into liquid phenol, 37% formaldehyde of preheating; Sodium hydroxide is made into 30% solution, throws half earlier.
After raw material has been thrown, start agitator and stir, heat in the reacting kettle jacketing, after reactor temperature rises to 50-65 ℃, stop heating, throw second half sodium hydroxide.Between the reaction period, the temperature in the reactor is controlled between 90-110 ℃, and leads to and heat in the reacting kettle jacketing or cool off, regulates the interior temperature of control reactor.Reacted 90-180 minute, and vacuumized decompression dehydration when milkiness occurring, dehydration finishes the qualified back of viscosity blowing.
Put into the solid formaldehyde dissolution kettle with vacuumizing the phenol aldehyde-containing sewage of deviating from that contains that reduces pressure, add the 80%-96% solid formaldehyde that measures, make the proportioning of formaldehyde the same with the front.Heating makes the solid formaldehyde dissolving, and solid formaldehyde fully dissolves the back and adds glassed steel reaction vessels continuation reaction.
Embodiment:
Embodiment is just in order to further specify the present invention, rather than as limiting the scope of the invention, protection scope of the present invention is determined by claim.
Embodiment 1:
In 3000 liters of glassed steel reaction vessels that agitator, condenser, vacuum system, temperature control survey device are housed, drop into 10 kilograms of the liquid phenol of 1200 kilograms of preheatings, 1320 kilogram of 37% formaldehyde, 30% sodium hydroxide.
After raw material has been thrown, start agitator and stir, heat in the reacting kettle jacketing, after reactor temperature rises to 50-65 ℃, stop heating, throw 10 kilograms in 30% sodium hydroxide.
Between the reaction period, the temperature in the reactor is controlled between 95-105 ℃, and leads to advance steam or water in the reacting kettle jacketing and regulate temperature in the control reactor.
Reacted 180 minutes, and vacuumized decompression dehydration when milkiness occurring.Viscosity is qualified, and dehydration finishes, and dehydrating amount is about 840 kilograms, contains phenol 4%, contains formaldehyde 2.5%.
840 kilograms of vacuumizing that decompression deviates from are contained the phenol aldehyde-containing sewage put into the solid formaldehyde dissolution kettle, add 520 kilograms of 93% solid formaldehydes that measure, the proportioning of formaldehyde is with the front is the same substantially.Heating makes the solid formaldehyde dissolving, and solid formaldehyde fully dissolves the back and adds glassed steel reaction vessels, continues to participate in reaction.
Embodiment 2:
In 2000 liters of glassed steel reaction vessels that agitator, condenser, vacuum system, temperature control survey device are housed, drop into 3 kilograms of the liquid phenol of 1000 kilograms of preheatings, 660 kilogram of 37% formaldehyde, 85% phosphoric acid.
After raw material has been thrown, start agitator and stir, heat in the reacting kettle jacketing, after reactor temperature rises to 55-65 ℃, stop heating, throw 3 kilograms of 85% phosphoric acid.
Water inlet cooling in the chuck of reactor picked up counting when the temperature in the reactor reaches 100 ℃ when the temperature in the steam off when temperature in the reactor rises to 90 ℃, reactor rose to 95 ℃, reacted 150-180 minute.Between the reaction period, the temperature in the reactor is controlled between 90-105 ℃, and leads to the temperature of regulating in the reacting kettle jacketing in the control reactor.
Vacuumize decompression dehydration when milkiness occurring.Viscosity is qualified, and dehydration finishes, and dehydrating amount is about 430 kilograms, contains phenol 3.5%, contains formaldehyde 2.5%.
430 kilograms of vacuumizing that decompression deviates from are contained the phenol aldehyde-containing sewage put into the solid formaldehyde dissolution kettle, add 250 kilograms of 96% solid formaldehydes that measure, the proportioning of formaldehyde is with the front is the same substantially.Heating makes the solid formaldehyde dissolving, and solid formaldehyde fully dissolves the back and adds glassed steel reaction vessels, continues to participate in reaction.

Claims (1)

1. the environment-protective process of novolak resin, it is characterized in that: adopting liquid formaldehyde earlier is raw material, with phenol or cresols reaction synthetic varnish type solid or heat curing-type liquid phenolic resin, contain phenol aldehyde-containing sewage Hybrid Heating, be made into formaldehyde solution after dissolving and recycle with what solid formaldehyde and reaction produced again.
CNA2007102021159A 2007-10-18 2007-10-18 Environment-protective process for synthesizing phenolic resin Pending CN101348548A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNA2007102021159A CN101348548A (en) 2007-10-18 2007-10-18 Environment-protective process for synthesizing phenolic resin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNA2007102021159A CN101348548A (en) 2007-10-18 2007-10-18 Environment-protective process for synthesizing phenolic resin

Publications (1)

Publication Number Publication Date
CN101348548A true CN101348548A (en) 2009-01-21

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CNA2007102021159A Pending CN101348548A (en) 2007-10-18 2007-10-18 Environment-protective process for synthesizing phenolic resin

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CN (1) CN101348548A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101899137A (en) * 2010-04-15 2010-12-01 河南许绝电工绝缘材料有限公司 Method for producing phenolic insulating resin
CN102241802A (en) * 2011-04-28 2011-11-16 北京化工大学 Comprehensive utilization of phenol-containing wastewater
CN102336878A (en) * 2011-07-18 2012-02-01 山东圣泉化工股份有限公司 Low free phenol phenolic resin and preparation method thereof
CN109232841A (en) * 2018-09-18 2019-01-18 新乡市炬能耐材有限公司 A kind of preparation method of precoated sand composite phenolic resin

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101899137A (en) * 2010-04-15 2010-12-01 河南许绝电工绝缘材料有限公司 Method for producing phenolic insulating resin
CN102241802A (en) * 2011-04-28 2011-11-16 北京化工大学 Comprehensive utilization of phenol-containing wastewater
CN102336878A (en) * 2011-07-18 2012-02-01 山东圣泉化工股份有限公司 Low free phenol phenolic resin and preparation method thereof
CN109232841A (en) * 2018-09-18 2019-01-18 新乡市炬能耐材有限公司 A kind of preparation method of precoated sand composite phenolic resin

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Open date: 20090121