CN103122054A - Method for modifying phenolic resin by using cardanol - Google Patents
Method for modifying phenolic resin by using cardanol Download PDFInfo
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- CN103122054A CN103122054A CN2013100528075A CN201310052807A CN103122054A CN 103122054 A CN103122054 A CN 103122054A CN 2013100528075 A CN2013100528075 A CN 2013100528075A CN 201310052807 A CN201310052807 A CN 201310052807A CN 103122054 A CN103122054 A CN 103122054A
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Abstract
The invention discloses a method for modifying phenolic resin by using cardanol. According to the method, phenolic resin is modified by using cardanol, the advantages of the phenolic resin are reserved, and the modified resin has certain toughness; and the material cost is lowered. Compared with the traditional process, the invention mainly uses cardanol and a common catalyst, the production process flow is not changed a lot, and no new additional equipment is needed. Besides, the used catalyst is low in price and can be easily bought, so that the cost of the product can not be increased.
Description
Technical field
The invention belongs to material science, relate to the manufacturing process that a kind of insulating material is used resol, especially a kind of method with Cardanol Modified PF Resin.
Background technology
With pure phenolic resin when making the phenolic aldehyde paper-based copper-coated board, owing to showing crisp hard, the shortcoming such as water-absorbent is large, electrical insulation properties is on the low side of goods, so generally will carry out modification to resin with dry vegetable oil.Consider from over-all properties, mostly adopt at present tung oil to carry out modification to resin, tung oil have the title of " little epoxy ", and the electrical insulation properties after having that snappiness is good, water-intake rate is low, soak or make moist with its paper substrate copper coated foil plate of making is high, the advantages such as low cost of manufacture.
Cardanol is a kind of active single-component phenol that extracts in cashew shell liquid, is mainly mono-hydroxy phenol, and general position betwixt is upper with a C who contains 1-3 two keys
15Long-chain alkene, therefore, the characteristic of the existing phenolic compound of cardanol has again the snappiness of fats compound and the polymerizability of unsaturated compound.Cardanol can with formaldehyde, the phenol one generation modified phenolic resins that reacts, can carry out addition polymerization, oxypolymerization, thermopolymerization etc. again simultaneously.So the resol with its modification has toughness, hydrophobic nature and electrical property preferably.
Summary of the invention
The object of the invention is to overcome the shortcoming of above-mentioned prior art, a kind of method with Cardanol Modified PF Resin is provided, the method adopts cardanol Pyrogentisinic Acid formaldehyde resin to carry out modification, has kept the advantage of resol, and has made the resin after modification have certain toughness.
The objective of the invention is to solve by the following technical programs:
This method with Cardanol Modified PF Resin comprises the following steps:
1) at first, according to weight part, add successively the phenol of 10～15 parts, the cardanol of 20～25 parts, the formaldehyde of 24～28 parts and the catalyzer of 0.9～1.3 part in reactor, opening vapour heats up, make temperature of charge be raised to 90 ℃～95 ℃, the beginning timing, gel time is surveyed in sampling after being incubated 50～100 minutes at this temperature, it is 150s～270s that gel time requires under the condition of 160 ± 2 ℃ and the little skill in using a kitchen knife in cookery, if the gel time that records is defective, continue to be incubated at this temperature, until gel time is qualified;
2) begin to vacuumize after gel time that step 1) records is qualified, when vacuumizing, vacuum tightness is more than 0.07MPa, when temperature of charge gos up 85 ℃ the time, get resin and survey gel time, if gel time at 120s～150s, thinks that gel time is qualified, remove vacuum, adding weight part is the solvent methanol of 28～32 parts and the solvent toluene of 39～43 parts, if defective continuation of gel time vacuumizes until qualified.
Above-mentioned catalyzer is sodium hydroxide, hexamethylenetetramine, ammoniacal liquor or triethylamine.
Above-mentioned methyl alcohol and toluene are industrial goods.
Above-mentioned formaldehyde mass concentration is 37%.
The present invention has following beneficial effect:
The present invention carries out modification with cardanol to resol, and Pyrogentisinic Acid's formaldehyde phenolic resin synthesis technique has carried out suitable adjustment, has selected suitable catalyzer.Resin after modification has certain toughness, use with itself and other mixed with resin, both be conducive to reduce product cost, be conducive to again improve the toughness of sheet material, sheet material color with this production of resins is incarnadine, is faint yellow with the sheet material color of unmodified production of resins.
Than traditional technology, the present invention has used cardanol and suitable catalyzer, and not larger change of the technological process of production needn't increase new installation.Selected catalyzer in addition, low price is easy to buying, can not improve the cost of related products.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail:
Embodiment 1
1) at first, according to weight part, add successively the phenol of 10 parts, the cardanol of 20 parts, the formaldehyde of 24 parts and the catalyzer of 0.9 part in reactor, open vapour and heat up, make temperature of charge be raised to 90 ℃, the beginning timing, insulation at this temperature after 50 minutes sampling survey gel time, it is 150s～270s that gel time requires under the condition of 160 ± 2 ℃ and the little skill in using a kitchen knife in cookery, if the gel time that records is defective, continue to be incubated at this temperature, until gel time is qualified;
2) begin to vacuumize after gel time that step 1) records is qualified, when vacuumizing, vacuum tightness is more than 0.07MPa, when temperature of charge gos up 85 ℃ the time, get resin and survey gel time, if gel time at 120s～150s, thinks that gel time is qualified, remove vacuum, adding weight part is the solvent methanol of 28 parts and the solvent toluene of 39 parts, if defective continuation of gel time vacuumizes until qualified.
Embodiment 2
1) at first, according to weight part, add successively the phenol of 15 parts, the cardanol of 25 parts, the formaldehyde of 28 parts and the catalyzer of 0.9～1.3 part in reactor, open vapour and heat up, make temperature of charge be raised to 95 ℃, the beginning timing, insulation at this temperature after 100 minutes sampling survey gel time, it is 150s～270s that gel time requires under the condition of 160 ± 2 ℃ and the little skill in using a kitchen knife in cookery, if the gel time that records is defective, continue to be incubated at this temperature, until gel time is qualified;
2) begin to vacuumize after gel time that step 1) records is qualified, when vacuumizing, vacuum tightness is more than 0.07MPa, when temperature of charge gos up 85 ℃ the time, get resin and survey gel time, if gel time at 120s～150s, thinks that gel time is qualified, remove vacuum, adding weight part is the solvent methanol of 32 parts and the solvent toluene of 43 parts, if defective continuation of gel time vacuumizes until qualified.
Embodiment 3
1) at first, according to weight part, add successively the phenol of 11 parts, the cardanol of 22 parts, the formaldehyde of 25 parts and the catalyzer of 1 part in reactor, open vapour and heat up, make temperature of charge be raised to 92 ℃, the beginning timing, insulation at this temperature after 70 minutes sampling survey gel time, it is 150s～270s that gel time requires under the condition of 160 ± 2 ℃ and the little skill in using a kitchen knife in cookery, if the gel time that records is defective, continue to be incubated at this temperature, until gel time is qualified;
2) begin to vacuumize after gel time that step 1) records is qualified, when vacuumizing, vacuum tightness is more than 0.07MPa, when temperature of charge gos up 85 ℃ the time, get resin and survey gel time, if gel time at 120s～150s, thinks that gel time is qualified, remove vacuum, adding weight part is the solvent methanol of 30 parts and the solvent toluene of 40 parts, if defective continuation of gel time vacuumizes until qualified.
Embodiment 4
1) at first, according to weight part, add successively the phenol of 13 parts, the cardanol of 23 parts, the formaldehyde of 27 parts and the catalyzer of 1.1 parts in reactor, open vapour and heat up, make temperature of charge be raised to 94 ℃, the beginning timing, insulation at this temperature after 90 minutes sampling survey gel time, it is 150s～270s that gel time requires under the condition of 160 ± 2 ℃ and the little skill in using a kitchen knife in cookery, if the gel time that records is defective, continue to be incubated at this temperature, until gel time is qualified;
2) begin to vacuumize after gel time that step 1) records is qualified, when vacuumizing, vacuum tightness is more than 0.07MPa, when temperature of charge gos up 85 ℃ the time, get resin and survey gel time, if gel time at 120s～150s, thinks that gel time is qualified, remove vacuum, adding weight part is the solvent methanol of 31 parts and the solvent toluene of 41 parts, if defective continuation of gel time vacuumizes until qualified.
Embodiment 5
start stirring, the industrial phenol that adds successively 300kg in reactor, the cardanol of 500kg, 37% the formaldehyde of 590kg and catalyzer-aqueous sodium hydroxide solution of 20kg, opening vapour heats up, make temperature of charge be raised to 90-95 ℃, the beginning timing, gel time is surveyed in sampling after being incubated 50～100min at this temperature, it is 150s～270s that gel time requires under the condition of 160 ± 2 ℃ and the little skill in using a kitchen knife in cookery, if the gel time that records is defective, continue to be incubated at this temperature, until gel time is qualified, begin to vacuumize (if defective after gel time is qualified, continuation is incubated at this temperature, until gel time is qualified), more than when vacuumizing, vacuum will reach 0.07MPa, when temperature of charge gos up 85 ℃ the time, get resin and survey gel time, if gel time is at 120s～150s, think that gel time is qualified, removing vacuum, to add mass percent be that 28%～32% solvent methanol and mass percent are 39%～43% solvent toluene, if defective the continuation vacuumizes until qualified gel time.
Embodiment 6
start stirring, the industrial phenol that adds successively 400kg in reactor, 37% the formaldehyde of the cardanol of 700kg and 590kg and catalyzer-ammoniacal liquor of 20kg, opening vapour heats up, make temperature of charge be raised to 90-95 ℃, the beginning timing, gel time is surveyed in sampling after being incubated 50～100min at this temperature, it is 150s～270s that gel time requires under the condition of 160 ± 2 ℃ and the little skill in using a kitchen knife in cookery, if the gel time that records is defective, continue to be incubated at this temperature, until gel time is qualified, begin to vacuumize (if defective after gel time is qualified, continuation is incubated at this temperature, until gel time is qualified), more than when vacuumizing, vacuum will reach 0.07MPa, when temperature of charge gos up 85 ℃ the time, get resin and survey gel time, if gel time is at 120s～150s, think that gel time is qualified, removing vacuum, to add mass percent be that 28%～32% solvent methanol and mass percent are 39%～43% solvent toluene, if defective the continuation vacuumizes until qualified gel time.
Embodiment 7
start stirring, the industrial phenol that adds successively 500kg in reactor, the cardanol of 920kg, 37% the formaldehyde of 980kg and catalyzer-triethylamine of 20kg, opening vapour heats up, make temperature of charge be raised to 90-95 ℃, the beginning timing, gel time is surveyed in sampling after being incubated 50～100min at this temperature, it is 50s～270s that gel time requires under the condition of 160 ± 2 ℃ and the little skill in using a kitchen knife in cookery, if the gel time that records is defective, continue to be incubated at this temperature, until gel time is qualified, begin to find time after gel time is qualified (if defective, continuation is incubated at this temperature, until gel time is qualified), more than when vacuumizing, vacuum tightness will reach 0.07MPa, when temperature of charge gos up 85 ℃ the time, get resin and survey gel time, if gel time is at 120s～150s, think that gel time is qualified, removing vacuum, to add mass percent be that 28%～32% solvent methanol and mass percent are 39%～43% solvent toluene, if defective the continuation vacuumizes until qualified gel time.
Be described in detail doing with the performance of the prepared resin of method of the present invention below in conjunction with application example:
Application Example 5,6,7 resin leading indicator detect as following table:
| Sequence number | The resin forming time (160 ± 2 ℃, the little skill in using a kitchen knife in cookery, S) | Resin solid amount % |
| Embodiment 5 | 120 | 55 |
| Embodiment 6 | 125 | 55 |
| Embodiment 7 | 132 | 55 |
Claims (4)
1. the method with Cardanol Modified PF Resin, is characterized in that, comprises the following steps:
1) at first, according to weight part, add successively the phenol of 10～15 parts, the cardanol of 20～25 parts, the formaldehyde of 24～28 parts and the catalyzer of 0.9～1.3 part in reactor, opening vapour heats up, make temperature of charge be raised to 90 ℃～95 ℃, the beginning timing, gel time is surveyed in sampling after being incubated 50～100 minutes at this temperature, it is 150s～270s that gel time requires under the condition of 160 ± 2 ℃ and the little skill in using a kitchen knife in cookery, if the gel time that records is defective, continue to be incubated at this temperature, until gel time is qualified;
2) begin to vacuumize after gel time that step 1) records is qualified, when vacuumizing, vacuum tightness is more than 0.07MPa, when temperature of charge gos up 85 ℃ the time, get resin and survey gel time, if gel time at 120s～150s, thinks that gel time is qualified, remove vacuum, adding weight part is the solvent methanol of 28～32 parts and the solvent toluene of 39～43 parts, if defective continuation of gel time vacuumizes until qualified.
2. the method with Cardanol Modified PF Resin according to claim 1, is characterized in that, described catalyzer is sodium hydroxide, hexamethylenetetramine, ammoniacal liquor or triethylamine.
3. the method with Cardanol Modified PF Resin according to claim 1, is characterized in that, described methyl alcohol and toluene are industrial goods.
4. the method with Cardanol Modified PF Resin according to claim 1, is characterized in that, described formaldehyde mass concentration is 37%.
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| CN2013100528075A CN103122054A (en) | 2013-02-19 | 2013-02-19 | Method for modifying phenolic resin by using cardanol |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772632A (en) * | 2014-01-23 | 2014-05-07 | 抚顺唯特化工有限公司 | Synthesis method of thermosetting cardanol resin |
| CN103923285A (en) * | 2014-04-30 | 2014-07-16 | 山东圣泉化工股份有限公司 | Cardanol-modified nitrogen-containing phenolic resin and preparation method thereof |
| CN104497244A (en) * | 2014-12-11 | 2015-04-08 | 贵阳学院 | Preparation method of anacardol modified phenolic resin |
| CN104965389A (en) * | 2015-01-08 | 2015-10-07 | 苏州瑞红电子化学品有限公司 | FPD/TP positive photoresist used for flexible substrate |
| CN105461871A (en) * | 2015-12-17 | 2016-04-06 | 福建利豪电子科技股份有限公司 | Preparation method and application of cashew nut phenolic resin and manufacturing method of paper-based copper-clad plate |
| CN107033537A (en) * | 2017-05-18 | 2017-08-11 | 山东四达工贸股份有限公司 | One kind makes tea tray insulation board and preparation method thereof |
| CN107474205A (en) * | 2017-09-04 | 2017-12-15 | 夏青 | A kind of preparation method of timber oxidation Cardanol Modified PF Resin adhesive |
| CN108752546A (en) * | 2018-05-17 | 2018-11-06 | 苏州保力瑞生物材料科技开发有限公司 | A kind of plant polyenoid phenol phenol-formaldehyde resin modified and preparation method thereof |
| CN109251288A (en) * | 2018-08-20 | 2019-01-22 | 贵阳学院 | A kind of preparation method of lamination type friction braking material biology base phenolic resin |
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| CN101353405A (en) * | 2008-08-12 | 2009-01-28 | 西安电力机械制造公司 | Method for modifying tung oil modified phenolic resin with melamine |
| CN102408672A (en) * | 2011-08-05 | 2012-04-11 | 江苏星源航天材料股份有限公司 | Production method for cardanol modified phenolic resin |
| CN102775570A (en) * | 2012-08-07 | 2012-11-14 | 衡阳恒缘电工材料有限公司 | Cardanol-modified phenol resin |
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Patent Citations (3)
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| CN101353405A (en) * | 2008-08-12 | 2009-01-28 | 西安电力机械制造公司 | Method for modifying tung oil modified phenolic resin with melamine |
| CN102408672A (en) * | 2011-08-05 | 2012-04-11 | 江苏星源航天材料股份有限公司 | Production method for cardanol modified phenolic resin |
| CN102775570A (en) * | 2012-08-07 | 2012-11-14 | 衡阳恒缘电工材料有限公司 | Cardanol-modified phenol resin |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103772632A (en) * | 2014-01-23 | 2014-05-07 | 抚顺唯特化工有限公司 | Synthesis method of thermosetting cardanol resin |
| CN103772632B (en) * | 2014-01-23 | 2016-05-04 | 抚顺唯特化工有限公司 | The synthetic method of thermosetting cashew pnenolic aldehyde resin |
| CN103923285A (en) * | 2014-04-30 | 2014-07-16 | 山东圣泉化工股份有限公司 | Cardanol-modified nitrogen-containing phenolic resin and preparation method thereof |
| CN104497244A (en) * | 2014-12-11 | 2015-04-08 | 贵阳学院 | Preparation method of anacardol modified phenolic resin |
| CN104965389A (en) * | 2015-01-08 | 2015-10-07 | 苏州瑞红电子化学品有限公司 | FPD/TP positive photoresist used for flexible substrate |
| CN105461871A (en) * | 2015-12-17 | 2016-04-06 | 福建利豪电子科技股份有限公司 | Preparation method and application of cashew nut phenolic resin and manufacturing method of paper-based copper-clad plate |
| CN107033537A (en) * | 2017-05-18 | 2017-08-11 | 山东四达工贸股份有限公司 | One kind makes tea tray insulation board and preparation method thereof |
| CN107474205A (en) * | 2017-09-04 | 2017-12-15 | 夏青 | A kind of preparation method of timber oxidation Cardanol Modified PF Resin adhesive |
| CN108752546A (en) * | 2018-05-17 | 2018-11-06 | 苏州保力瑞生物材料科技开发有限公司 | A kind of plant polyenoid phenol phenol-formaldehyde resin modified and preparation method thereof |
| CN109251288A (en) * | 2018-08-20 | 2019-01-22 | 贵阳学院 | A kind of preparation method of lamination type friction braking material biology base phenolic resin |
| CN109251288B (en) * | 2018-08-20 | 2021-03-19 | 贵阳学院 | Preparation method of bio-based phenolic resin for laminated friction brake material |
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Application publication date: 20130529 |