CN102936322B - Thermosetting phenolic resin preparation method without wastewater discharge - Google Patents
Thermosetting phenolic resin preparation method without wastewater discharge Download PDFInfo
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- CN102936322B CN102936322B CN201210533780.7A CN201210533780A CN102936322B CN 102936322 B CN102936322 B CN 102936322B CN 201210533780 A CN201210533780 A CN 201210533780A CN 102936322 B CN102936322 B CN 102936322B
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Abstract
The invention discloses a thermosetting phenolic resin preparation method without wastewater discharge. The preparation method comprises the steps of respectively weighing phenol and solid aldehyde according to the mole ratio of 1:(1.0-2.0), weighing alkali according to the mass ratio of alkali to phenol being (0.5-4):100; mixing the phenol, the alkali and the solid aldehyde, and then adding proper amount of water, raising the temperature to be 80-90 DEG C, wherein the proper amount of water is 0.5-2.5 times of the total aldehyde addition amount; maintaining a mixture at 80-90 DEG C and reacting until the water-turbidity ratio reaches the standard, reducing the pressure and discharging water; and in the pressure reduction and water discharging process, stopping discharging water when the viscosity of a reactant conforms to the standard to obtain the thermosetting phenolic resin. According to the preparation method, zero-wastewater discharge in the phenolic resin production is realized, and the performance of the phenolic resin can not be reduced.
Description
Technical field
The present invention relates to a kind of preparation method of resol, specifically a kind of heat-reactive phenolic resin preparation method of no effuent discharge.
Background technology
Resol phenolic resin is called for short PF, is industrialized synthetic resins the earliest.Resol is as one of three large thermosetting resins, and greatly, developing history is long for wide application, amount.The most important feature of resol has two: one, and high thermal resistance, even at very high temperature, also can keep the globality of its structure and the stability of size.Just because of this reason, resol is just applied to some high-temperature fields, for example refractory materials, friction materials and casting industry.The 2nd, there is certain cohesive strength, its another important Application Areas is exactly as tackiness agent, at each key areas of national economy such as aerospace, military project apparatus, automotive electronics, communications and transportation, building materials chemical industry, mining, has irreplaceable vital role.
Resol is a base polymer of preparing by condensation polymerization with phenols and aldehydes, by adopting different phenol and aldehyde and the two different proportioning, different catalysts and differential responses technique, can make the resol product of different properties and purposes.
In traditional resol production process, all adopting phenol and massfraction is that the formalin of 37% left and right is as reaction monomers.Owing to containing a large amount of moisture in this formaldehyde solution, and in the polycondensation of phenolic aldehyde, also can produce a certain amount of water, for promoting the carrying out of polycondensation must remove these water.In the production of resol, just inevitably generate so a large amount of trade effluents.According to statistics, the heat-reactive phenolic resin of producing 1 ton will produce the waste water of 500-600 kilogram, and in this waste water, objectionable constituent and content thereof are very surprising.Wherein, two indexs of phenol content and COD all can surpass national tens thousand of and thousands of times of allowing emission standard conventionally.Due to too high containing phenol amount, very serious to environmental influence, intractability is also very high.
Make a general survey of the various treatment processs of resol, no matter be chemical extraction method, chemical transformation, biological oxidation process, biological degradation method, or absorption process, electrolytic process etc., although each has something to recommend him, but be all just useless control useless, to lower concentration phenolic wastewater or resultful, but for resol, produce the high-concentration phenolic wastewater of discharging, very undesirable.The today day by day strengthening in environmental requirement, whether the processing of waste water, and the effect of processing and cost have become the key that determines Business survival, become the bottleneck of controlling resol enterprise development.
Summary of the invention
Technical problem to be solved by this invention is, the shortcoming existing for above prior art, propose the heat-reactive phenolic resin preparation method of no effuent discharge, can realize the no effuent discharge that resol is produced, and can guarantee that the performance of resol itself does not reduce.
The technical scheme that the present invention solves above technical problem is:
A heat-reactive phenolic resin preparation method for no effuent discharge, carries out according to the following steps:
(i) 1:1.0-2.0 takes respectively phenol and solid aldehyde in molar ratio, by the mass ratio of alkali and phenol, is that 0.5-4:100 takes alkali;
(ii) phenol, alkali and solid aldehyde are mixed, then add appropriate water, be warming up to 80-90 ℃, wherein said appropriate water is 0.5-2.5 times that aldehyde always adds weight;
(iii) step mixture is (ii) maintained to 80-90 ℃ of reaction, turbid than up to standard to water, decompression dehydration;
(iv) in step, (iii) in decompression dehydration process, when the viscosity of detecting reactant reaches requirement, stop dehydration, obtain heat-reactive phenolic resin.
The technical scheme that the present invention further limits is:
The heat-reactive phenolic resin preparation method of aforesaid no effuent discharge, step (iii) in, temperature of reaction is 83-88 ℃.
The heat-reactive phenolic resin preparation method of aforesaid no effuent discharge, the mol ratio of phenol and solid aldehyde is 1:1.3-1.8.
The heat-reactive phenolic resin preparation method of aforesaid no effuent discharge, the turbid ratio of water is 2.0-2.4.
The heat-reactive phenolic resin preparation method of aforesaid no effuent discharge, viscosity is 800-2000mPa.s.
The heat-reactive phenolic resin preparation method of aforesaid no effuent discharge, phenol is selected from one or more the mixing in phenol, cresols, xylenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol or cardanol.
The heat-reactive phenolic resin preparation method of aforesaid no effuent discharge, solid aldehyde is selected from one or more the mixture in the solid polymer of formaldehyde, acetaldehyde or butyraldehyde, and the suspension liquid of above-mentioned one or more aldehyde.
The heat-reactive phenolic resin preparation method of aforesaid no effuent discharge, alkali is selected from one or more the mixing in sodium hydroxide, potassium hydroxide, hydrated barta, calcium hydroxide, sodium carbonate, salt of wormwood, ammoniacal liquor.
The invention has the beneficial effects as follows: the present invention be take solid aldehydes as raw material production resol, adopt solid aldehydes to substitute conventional aldehydes solution, for example use solid formaldehyde to substitute 37% conventional formaldehyde solution, thereby realized " no effuent discharge " that resol is produced, broken through the environmental protection bottleneck of puzzlement industry development, when realizing energy-saving, emission-reducing, environment friendly requirement, still kept the performance of resol itself not reduce.China's resol output has reached 700,000 tons, and all adopts the production technique of formaldehyde solution, if adopt technique of the present invention, the quantity discharged of being often only high phenolic wastewater just can reduce 350,000 tons, and its environment protection significance is huge.Specific performance of the present invention is as shown in table 1 below:
Table 1 performance of the present invention
Embodiment
embodiment 1
The present embodiment is a kind of heat-reactive phenolic resin preparation method of no effuent discharge, and concrete technology is:
By 500g phenol, 300g paraformaldehyde, 4g sodium hydroxide, 500g water joins in the 2000mL four-hole bottle that stirring and prolong are housed and mixes, be warming up to 88 ℃, react and to the turbid ratio of water, reach at 2.4 o'clock and start decompression dehydration, until tested viscosity reaches 25 ℃ of 1000mPa.s@, can obtain heat-reactive phenolic resin.The number-average molecular weight Mn that this resin records is 459, and weight-average molecular weight Mw is 574, content of free aldehyde 0.22%, free phenol content 6.95%, gel time 96s.
embodiment 2
The present embodiment is a kind of heat-reactive phenolic resin preparation method of no effuent discharge, and concrete technology is:
By 400g phenol, 240g trioxymethylene, 4g hydrated barta, 400g water joins in the 2000mL four-hole bottle that stirring and prolong are housed and mixes, be warming up to 85 ℃, react and to the turbid ratio of water, reach at 2.0 o'clock and start decompression dehydration, until tested viscosity reaches 25 ℃ of 1250mPa.s@, can obtain heat-reactive phenolic resin.The number-average molecular weight Mn that this resin records is 563, and weight-average molecular weight Mw is 852, content of free aldehyde 0.35%, free phenol content 6.55%, gel time 90s.
The present embodiment 1-2 has also carried out the contrast of key index with domestic and international product, and its comparing result is as shown in table 1:
From the above results, it seems, the resol product that solid formaldehyde method of the present invention is produced has has met or exceeded the performance of external imported product on key index.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (4)
1. a heat-reactive phenolic resin preparation method for no effuent discharge, is characterized in that: carry out according to the following steps:
(i) 1:1.3-1.8 takes respectively phenol and solid aldehyde in molar ratio, by the mass ratio of alkali and phenol, is that 0.5-4:100 takes alkali;
(ii) phenol, alkali and solid aldehyde are mixed, then add appropriate water, be warming up to 80-90 ℃, wherein said appropriate water is 0.5-2.5 times that aldehyde always adds weight;
(iii) step mixture is (ii) maintained to 83-88 ℃ of reaction, turbid than up to standard to water, decompression dehydration, the turbid ratio of described water is 2.0-2.4;
(iv) in step, (iii) in described decompression dehydration process, when the viscosity of detecting reactant reaches requirement, stop dehydration, obtain heat-reactive phenolic resin, described viscosity is 800-2000mPas.
2. the heat-reactive phenolic resin preparation method of no effuent discharge as claimed in claim 1, is characterized in that: described phenol is selected from one or more the mixing in phenol, cresols, xylenol, nonylphenol, dihydroxyphenyl propane, Bisphenol F, Resorcinol or cardanol.
3. the heat-reactive phenolic resin preparation method of no effuent discharge as claimed in claim 1, is characterized in that: described solid aldehyde is selected from one or more the mixture in the solid polymer of formaldehyde, acetaldehyde or butyraldehyde, or the suspension liquid of above-mentioned one or more aldehyde.
4. the heat-reactive phenolic resin preparation method of no effuent discharge as claimed in claim 1, is characterized in that: described alkali is selected from one or more the mixing in sodium hydroxide, potassium hydroxide, hydrated barta, calcium hydroxide, sodium carbonate, salt of wormwood, ammoniacal liquor.
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| CN201210533780.7A CN102936322B (en) | 2012-12-12 | 2012-12-12 | Thermosetting phenolic resin preparation method without wastewater discharge |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20180079938A1 (en) * | 2015-03-31 | 2018-03-22 | Sumitomo Bakelite Co., Ltd. | Resol type modified phenol resin composition, method for producing the same, and adhesive |
| CN107118720A (en) * | 2017-05-27 | 2017-09-01 | 江苏省江南新型复合研磨材料及制品工程技术研究中心有限公司 | A kind of preparation method of emery cloth phenolic resin |
| CN110860441A (en) * | 2019-12-03 | 2020-03-06 | 南通旭日船用机械有限公司 | Outboard cooler external thermal phenolic resin protective coating and preparation method thereof |
| CN111978497B (en) * | 2020-08-12 | 2021-12-07 | 浙江自立高分子化工材料有限公司 | Preparation method, product and application of semi-solid thermosetting phenolic resin |
| CN112321780B (en) * | 2021-01-04 | 2021-04-09 | 山东友泉新材料有限公司 | Continuous production method of thermosetting phenolic resin |
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| CN101597364B (en) * | 2009-06-30 | 2011-01-19 | 陕西师范大学 | Synthesis method of thermosetting phenol-formaldehyde resin in solid at normal temperature |
| CN102086256B (en) * | 2010-12-28 | 2012-05-30 | 何洪清 | Method for synthesizing high-performance non-dehydration foamed phenolic resin |
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