CN102775568B - Preparation method of modified phenolic resin - Google Patents
Preparation method of modified phenolic resin Download PDFInfo
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- CN102775568B CN102775568B CN201210264884.2A CN201210264884A CN102775568B CN 102775568 B CN102775568 B CN 102775568B CN 201210264884 A CN201210264884 A CN 201210264884A CN 102775568 B CN102775568 B CN 102775568B
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Abstract
The invention discloses a preparation method of modified phenolic resin, which comprises the following steps of: (a) mixing phenol, cardanol and a sulfonating agent, raising the temperature to 80-95 DEG C under the alkaline condition, reacting for 1-3 hours, then cooling to 50-60 DEG C, adding formaldehyde and reacting for 1-3 hours to obtain a mixture A; (b) mixing lignin with formaldehyde, raising the temperature to 50-100 DEG C under the alkaline condition, maintaining the constant temperature for 3-5 hours to obtain a mixture B, i.e. methylolated lignin; and (c) mixing the mixture A with the mixture B, controlling the temperature to be 70-90 DEG C and maintaining the constant temperature for above 1 hour to obtain the modified phenolic resin. The preparation method has the beneficial effects that as sulfonic acid groups are introduced in cardanol molecules through sulfonation reaction, the polarity of cardanol molecules is improved, so that the water solubility of the cardanol molecules is increased; and the obtained modified phenolic resin can be directly used for the spraying industry.
Description
Technical field
The present invention relates to resol field, be specifically related to a kind of preparation method of modified phenolic resins.
Background technology
Cardanol (Cardanol) is a kind ofly from natural cashew nut shell oil, through modern technique, to refine and to form, and can replace or part replaces phenol for the manufacture of epoxy hardener, liquid phenolic resin, liquid or pulverous heat-reactive phenolic resin.Because it belongs to renewable resources and raw material sources are wide, be widely used, one of them important application is by Cardanol Modified PF Resin production copper-clad plate, as Chinese patent literature CN102408672A discloses a kind of production method of Cardanol Modified PF Resin, by adding the steps such as reaction kettle for reaction to make modified phenolic resins phenol, cardanol, formaldehyde, triethylamine and ammoniacal liquor, the copper-clad plate finally making has good snappiness; Chinese patent literature CN101591418A discloses a kind of production method of modified phenolic resins, adopts cardanol, coordinates epoxidized vegetable oil modification resol, and the copper-clad plate making has the advantages such as snappiness is good, water-absorbent is low; Chinese patent literature CN102336879A discloses a kind of preparation method of phenolic resin used for paper copper cladded laminate, adopt dihydroxyphenyl propane, epoxy soybean oil, cardanol and phenol, formaldehyde and corresponding catalyzer to make resol, the copper-clad plate making has that snappiness is good, water-absorbent is low, make moist after the advantage such as high, the low cost of manufacture of electric insulating quality.The modification cardanol resin that aforesaid method is produced is extensive in copper-clad plate sector application, but the modification cardanol resin poorly water-soluble of producing due to aforesaid method cannot be applied in spraying industry.
Chinese patent literature CN101768326A discloses a kind of preparation and application thereof of modified phenolic resins, by phenol (being selected from phenol, cardanol and technical phenol), formaldehyde, urea at basic catalyst, 85-95 ℃, under pH=8-9, there is polycondensation, adjust after completion of the reaction pH to 6.5-7.0, then under vacuum condition, by the vacuum hydro-extraction of above-mentioned polycondensation thing, make its solid content at 80-85wt%, be down to normal temperature, adjusting viscosity is to 2.0-3.0Pa.s, finally add tensio-active agent and whipping agent, stir blowing, packing.When using this modified phenolic resins, also need to add composite curing agent to mix with it, with spray gun, be sprayed onto and be coated with on insulation object, foaming.Although modified phenolic resins prepared by the method can be used in spraying industry, poorly water-soluble, also needs during use to mix by a certain percentage with another kind of composite curing agent, is unfavorable for site operation, and complicated process of preparation, and cost is also higher.On the other hand, the resol of preparing by phenol sulfonation in prior art, while being used for spraying, there is the shortcoming that fragility is large, intensity is low, one of reason is in comparatively high temps sulfonation, also to add formaldehyde, because temperature is too high, polymerization can be large, in the incomplete situation of methylolation, will carry out next step condensation, easily causes reaction to be not exclusively terminated; Former two is therefore because the speed of reaction of phenols and aldehydes is faster than sulfonation reaction speed, adds at the same temperature sulphonating agent and formaldehyde, can cause sulfonation reaction incomplete, and then affect the performance of resol.
Summary of the invention
First technical problem to be solved by this invention is the modified phenolic resins poorly water-soluble that utilizes cardanol to produce in prior art, is unfavorable for site operation, and complicated process of preparation, cost are high.
Second technical problem to be solved by this invention is the resol of preparing by phenol sulfonation in prior art in prior art, has the shortcoming that fragility is large, intensity is low when spraying.
For solving the problems of the technologies described above, the invention provides a kind of preparation method of modified phenolic resins, comprise the following steps:
(a) phenol, cardanol and sulphonating agent are mixed, under alkaline condition, be warmed up to 80-95 ℃ of reaction 1-3h, then cool to 50-60 ℃, add formaldehyde reaction 1-3h, obtain mixture A;
(b) xylogen and formaldehyde are mixed, under alkaline condition, be warmed up to 50-100 ℃, constant temperature 3-5h obtains mixture B, i.e. hydroxymethylated lignin;
(c) mixture A and B are mixed, control temperature at 70-90 ℃, more than constant temperature 1h, obtain modified phenolic resins.
Described sulphonating agent is sulphur trioxide, the vitriol oil, chlorsulfonic acid, S-WAT, one or more in sodium bisulfite.
Phenol in described step (a), cardanol, the mass ratio of sulphonating agent and formaldehyde is 100:5-30:4-20:38-137.
In described step (b), the mass ratio of xylogen and formaldehyde is 100:150-350.
In described step (c), mixture A and mixture B mix with the mass ratio of 1:7-9.
In described mixture A, phenol content is not more than 3%.
In described step (a), regulate pH to 8-9, be slowly warming up to 80-95 ℃.
In described step (b), regulate pH to 8-9, be slowly warming up to 70-75 ℃.
Described sulphonating agent is chlorsulfonic acid and the vitriol oil.
Modified phenolic resins is added to water adjusting viscosity to 4-100Mpa.s.
Compared with prior art, technical solutions according to the invention tool has the following advantages:
1. the preparation method of modified phenolic resins of the present invention, in step (a), by sulfonation reaction, in cardanol molecule, introduce sulfonic group, improve the water-soluble of modified phenolic resins, can add water regulates modified phenolic resins to arrive compared with low viscosity, be used for spraying industry, widen the Application Areas of cardanol, solved Cardanol Modified PF Resin poorly water-soluble in prior art, be unfavorable for the problem of site operation.
2. the preparation method of modified phenolic resins of the present invention, in step (a) between 80-95 ℃ sulfonation cardanol and phenol, rear cooling adds formaldehyde to obtain methylolation phenol at 50-60 ℃, then in step (c), is warmed up to 70-90 ℃ of polycondensation and obtains final Cardanol Modified PF Resin.One of reason is if also add formaldehyde between 80-95 ℃ simultaneously, and because temperature is too high, polymerization can be large, in the incomplete situation of methylolation, will carry out next step condensation, easily causes reaction to be not exclusively terminated; Former two is therefore because the speed of reaction of phenols and aldehydes is faster than sulfonation reaction speed, therefore first carry out sulfonation reaction, after sulfonation fully, carrying out the synthetic of resol, the resol good water solubility obtaining like this, snappiness is good, there is again higher intensity, improved the shortcoming that current spraying is large by resin fragility, intensity is low simultaneously.
Embodiment
embodiment 1
Get 100g phenol, 5g cardanol, 4g concentration is 50% vitriol oil and chlorsulfonic acid, is placed in reactor, is uniformly mixed, and with sodium hydroxide, regulates pH to 7.5, is warmed up to 80 ℃, and reaction 3h, then cools to 50 ℃, adds 38g formaldehyde, and reaction 1h, obtains mixture A;
Get 100g xylogen and 150g formaldehyde, be placed in reactor, stir, mix, with sodium hydroxide, regulate pH to 7.5, be warmed up to 50 ℃, constant temperature 5h obtains mixture B, i.e. hydroxymethylated lignin;
Mixture A and mixture B are mixed with the mass ratio of 1:7, be warmed up to 70 ℃, constant temperature 2h obtains modified phenolic resins.
embodiment 2
Get 100g phenol, 30g cardanol, 20g concentration is 50% vitriol oil and S-WAT, is placed in reactor, is uniformly mixed, and with sodium hydroxide, regulates pH to 10, is warmed up to 95 ℃, and reaction 1h, then cools to 60 ℃, adds 137g formaldehyde, and reaction 3h, obtains mixture A;
Get 100g xylogen and 350g formaldehyde, be placed in reactor, stir, mix, with sodium hydroxide, regulate pH to 10, be warmed up to 100 ℃, constant temperature 3h obtains mixture B, i.e. hydroxymethylated lignin;
Mixture A and mixture B are mixed with the mass ratio of 1:9, be warmed up to 90 ℃, constant temperature 1h obtains modified phenolic resins.
embodiment 3
Get 100g phenol, 17.5g cardanol, 12g S-WAT, is placed in reactor, is uniformly mixed, and with sodium hydroxide, regulates pH to 8, is warmed up to 90 ℃, and reaction 2h, then cools to 55 ℃, adds 87.5g formaldehyde, and reaction 2h, obtains mixture A;
Get 100g xylogen and 250g formaldehyde, be placed in reactor, stir, mix, with sodium hydroxide, regulate pH to 8.5, be warmed up to 75 ℃, constant temperature 2h obtains mixture B, i.e. hydroxymethylated lignin;
Mixture A and mixture B are mixed with the mass ratio of 1:8, be warmed up to 80 ℃, constant temperature 2h obtains modified phenolic resins.
embodiment 4
Get 100g phenol, 20g cardanol, 8g chlorsulfonic acid, is placed in reactor, is uniformly mixed, and with sodium hydroxide, regulates pH to 10, is warmed up to 85 ℃, and reaction 3h, then cools to 55 ℃, adds 160g formaldehyde, and reaction 3h, obtains mixture A;
Get 100g xylogen and 200g formaldehyde, be placed in reactor, stir, mix, with sodium hydroxide, regulate pH to 9.5, be warmed up to 85 ℃, constant temperature 2h obtains mixture B, i.e. hydroxymethylated lignin;
Mixture A and mixture B are mixed with the mass ratio of 1:9, be warmed up to 75 ℃, constant temperature 2h obtains modified phenolic resins.
embodiment 5
Get 200g phenol, 40g cardanol, 20g S-WAT, is placed in reactor, is uniformly mixed, and with sodium hydroxide, regulates pH to 9, is warmed up to 88 ℃, and reaction 2h, then cools to 60 ℃, adds 207g formaldehyde, and reaction 2h, obtains mixture A;
Get 100g xylogen and 330g formaldehyde, be placed in reactor, stir, mix, with sodium hydroxide, regulate pH to 9, be warmed up to 85 ℃, constant temperature 2h obtains mixture B, i.e. hydroxymethylated lignin;
Mixture A and mixture B are mixed with the mass ratio of 1:9, be warmed up to 80 ℃, constant temperature 1.5h obtains modified phenolic resins.
embodiment 6
Get 200g phenol, 60g cardanol, 20g sodium bisulfite, is placed in reactor, is uniformly mixed, and with sodium hydroxide, regulates pH to 10, is warmed up to 90 ℃, and reaction 2h, then cools to 60 ℃, adds 230g formaldehyde, and reaction 2h, obtains mixture A;
Get 100g xylogen and 230g formaldehyde, be placed in reactor, stir, mix, with sodium hydroxide, regulate pH to 10, be warmed up to 95 ℃, constant temperature 2h obtains mixture B, i.e. hydroxymethylated lignin;
Mixture A and mixture B are mixed with the mass ratio of 1:8, be warmed up to 90 ℃, constant temperature 3h obtains modified phenolic resins.
embodiment 7
Get 200g phenol, 60g cardanol is placed in reactor, passes into sulphur trioxide 40g, is uniformly mixed, and with sodium hydroxide, regulates pH to 11, is warmed up to 85 ℃, and reaction 2h, then cools to 60 ℃, adds 210g formaldehyde, and reaction 2h, obtains mixture A;
Get 100g xylogen and 260g formaldehyde, be placed in reactor, stir, mix, with sodium hydroxide, regulate pH to 11, be warmed up to 95 ℃, constant temperature 2h obtains mixture B, i.e. hydroxymethylated lignin;
Mixture A and mixture B are mixed with the mass ratio of 1:7, be warmed up to 100 ℃, constant temperature 2h obtains modified phenolic resins.
embodiment 8
Get 100g phenol, 17.5g cardanol, 12g sodium bisulfite, is placed in reactor, is uniformly mixed, and with sodium hydroxide, regulates pH to 8.5, is warmed up to 85 ℃, and reaction 2h, then cools to 55 ℃, adds 87.5g formaldehyde, and reaction 3h, obtains mixture A;
Get 100g xylogen and 250g formaldehyde, be placed in reactor, stir, mix, with sodium hydroxide, regulate pH to 8.5, be warmed up to 95 ℃, constant temperature 2h obtains mixture B, i.e. hydroxymethylated lignin;
Mixture A and mixture B are mixed with the mass ratio of 1:8, be warmed up to 90 ℃, constant temperature 2h obtains modified phenolic resins.
comparative example 1
Get 200g phenol, 60g cardanol, 200g formaldehyde, is placed in reactor, is uniformly mixed, and with sodium hydroxide, regulates pH to 10, controls temperature at 65 ℃, and reaction 2h, obtains mixture A, surveys phenol content 1.3%;
Get 100g xylogen and 405g formaldehyde, be placed in reactor, stir, mix, sodium hydroxide regulates pH to 10, controls temperature at 100 ℃, and constant temperature 3h obtains mixture B, i.e. hydroxymethylated lignin;
Mixture A and mixture B are mixed to the resol of 90 ℃ of constant temperature 1.5h with the mass ratio of 1:7.5.
comparative example 2
Get 115g phenol, 12g sodium bisulfite, is placed in reactor, is uniformly mixed, and with sodium hydroxide, regulates pH to 10, is warmed up to 80 ℃ of reaction 2h, then cools to 60 ℃, adds 110 parts of formaldehyde, and reaction 2h, obtains mixture A;
Get 100g xylogen and 210g formaldehyde, be placed in reactor, stir, mix, with sodium hydroxide, regulate pH to 10, be warmed up to 85 ℃, reaction 4h obtains mixture B, i.e. hydroxymethylated lignin;
Mixture A and mixture B are mixed with the mass ratio of 1:8, be warmed up to 80 ℃, constant temperature 3h obtains resol.
performance comparison experiment 1
Performance to the resol of above-described embodiment 1-8 and comparative example 1 preparation is measured, according to GB/T 1843-2008, select NDJ-79 type rotational viscosimeter viscosimetric, with deionized water, carry out water-soluble mensuration (measuring the ratio make the muddy deionized water used of resin and resin quality), result is as table 1:
Table 1
From above-mentioned performance comparison experiment, can find out, the modified phenolic resins that utilizes preparation method of the present invention to make, the resol of preparing with prior art is compared, and water-soluble raising can add water and be adjusted to compared with low viscosity, for spraying.
performance comparison experiment 2
Performance to the resol of above-described embodiment 1-8 and comparative example 2 preparations is measured, according to GB/T 1843-2008, select NDJ-79 type rotational viscosimeter viscosimetric, with deionized water, carry out water-soluble mensuration (measuring the ratio that makes the muddy deionized water used of resin and resin quality), by the method for standard No. GB/T1449-2005, measure flexural strength, by the method for standard No. GB/T1451-2005, measure shock strength, result is as table 2:
Table 2
From the experiment of above-mentioned performance comparison, can find out, the modified phenolic resins that utilizes preparation method of the present invention to make, the resol of preparing with phenol with prior art is compared, water-soluble, viscosity is suitable, but snappiness is better, and intensity is higher, is more suitable for for spraying.
Although the present invention elaborates it by above-mentioned specific embodiment; but; those skilled in the art should be understood that any form that does not exceed claim protection domain made on this basis and the variation of details, all belong to invention which is intended to be protected.
Claims (10)
1. a preparation method for modified phenolic resins, is characterized in that, comprises the following steps:
(a) phenol, cardanol and sulphonating agent are mixed, under alkaline condition, be warmed up to 80-95 ℃ of reaction 1-3h, then cool to 50-60 ℃, add formaldehyde reaction 1-3h, obtain mixture A;
(b) xylogen and formaldehyde are mixed, under alkaline condition, be warmed up to 50-100 ℃, constant temperature 3-5h obtains mixture B, i.e. hydroxymethylated lignin;
(c) mixture A and B are mixed, control temperature at 70-90 ℃, more than constant temperature 1h, obtain modified phenolic resins.
2. the preparation method of modified phenolic resins according to claim 1, is characterized in that, described sulphonating agent is sulphur trioxide, the vitriol oil, chlorsulfonic acid, S-WAT, one or more in sodium bisulfite.
3. the preparation method of modified phenolic resins according to claim 1 and 2, is characterized in that, phenol in described step (a), and cardanol, the mass ratio of sulphonating agent and formaldehyde is 100:5-30:4-20:38-137.
4. the preparation method of modified phenolic resins according to claim 3, is characterized in that, in described step (b), the mass ratio of xylogen and formaldehyde is 100:150-350.
5. the preparation method of modified phenolic resins according to claim 4, is characterized in that, in institute's step (c), mixture A and mixture B mix with the mass ratio of 1:7-9.
6. the preparation method of modified phenolic resins according to claim 5, is characterized in that, in described mixture A, phenol content is not more than 3%.
7. the preparation method of modified phenolic resins according to claim 6, is characterized in that, in described step (a), regulates pH to 8-9, is slowly warming up to 80-95 ℃.
8. the preparation method of modified phenolic resins according to claim 7, is characterized in that, in described step (b), regulates pH to 8-9, is slowly warming up to 70-75 ℃.
9. the preparation method of modified phenolic resins according to claim 8, is characterized in that, described sulphonating agent is chlorsulfonic acid and the vitriol oil.
10. the application of the modified phenolic resins that prepared by claim 1 to 9 either method in spraying, is characterized in that, modified phenolic resins is added to water adjusting viscosity to 4-100mPas.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104140508B (en) * | 2013-05-09 | 2016-08-03 | 东北林业大学 | A kind of preparation method of enzymolysis xylogen base phenolic resin |
| CN103522209B (en) * | 2013-10-31 | 2016-07-27 | 山东圣泉新材料股份有限公司 | A kind of resin wheel |
| CN104974320B (en) * | 2015-06-25 | 2017-03-01 | 中国林业科学研究院林产化学工业研究所 | Oxidation Cardanol Modified PF Resin and its preparation method and application |
| CN106750067A (en) * | 2016-12-16 | 2017-05-31 | 沙县宏盛塑料有限公司 | A kind of preparation method of lignin Cardanol Modified PF Resin |
| CN106750068A (en) * | 2016-12-16 | 2017-05-31 | 沙县宏盛塑料有限公司 | A kind of preparation method of lignin modification phenolic resin |
| CN106800631B (en) * | 2017-02-18 | 2019-03-19 | 滨州盛华建材有限公司 | A kind of phenolic resin and preparation method thereof for interlayer type composite thermal-insulating wall |
| CN108409941B (en) * | 2018-03-22 | 2020-03-24 | 黄山五环科技有限公司 | Clean production process of solid epoxy resin |
| CN110483795B (en) * | 2019-08-23 | 2020-12-01 | 广东方中高新材料有限公司 | Supermolecule sulfonated phenolic polycondensate and preparation method and application thereof |
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| CN101062971A (en) * | 2006-04-28 | 2007-10-31 | 中国科学院化学研究所 | Modified alkyd resin for laminated board and preparation method and usage thereof |
| CN101284899A (en) * | 2008-06-03 | 2008-10-15 | 吉林大学 | Lignose and process for modifying phenolic resin with derivates thereof |
| CN101492522A (en) * | 2009-02-27 | 2009-07-29 | 中国林业科学研究院林产化学工业研究所 | Method of preparing alkali lignin modified phenolic resin |
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