CN1309141A - Modified phenolic resin and its preparing process - Google Patents
Modified phenolic resin and its preparing process Download PDFInfo
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- CN1309141A CN1309141A CN 01107177 CN01107177A CN1309141A CN 1309141 A CN1309141 A CN 1309141A CN 01107177 CN01107177 CN 01107177 CN 01107177 A CN01107177 A CN 01107177A CN 1309141 A CN1309141 A CN 1309141A
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- benzyl chloride
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Abstract
A modified phenolic resin is prpared from phenol and formaldehyde through quickly raising temp in the presence of alkali solution to obtain low-polymerized phenolic resin, etherifying with benzyl chloride as alkylating agent in boiling state, water washing, separation, and vacuum dewatering. The resultant phenolic resin features low viscosity (less than 90 seconds at 25 deg.C), high solid content (80% or more), high acid and alkali resistance (99% or more), and long storage period. It is a thermosetting resin.
Description
The present invention relates to a kind of modified phenolic resins and production method thereof, particularly a kind of low viscosity, highly filled not only acidproof but also alkali proof resol and production method thereof; Be particularly useful for the carbon materials production and make binding agent or soaker.
Resol has the good characteristics of unique heat-resisting, anti-combustion, electrical insulating property, mechanical property and dimensional stabilizing as the synthetic resins of realizing suitability for industrialized production in the world the earliest, mass production still so far, and range of application is more extensive.At its shortcoming, various study on the modification work are still being carried out widely.Wherein studying more is to inquire into by some processing method or adopt different starting material further to change or improve the characteristic that common resol had originally, perhaps increase some characteristic, so that further broadened application field, or expand the application performance of its application product, for example, improve its product resistance toheat, reduce its viscosity etc.
No. 90208812 documents of Chinese science and technology achievement have been put down in writing with the legal system that is rapidly heated and have been equipped with low viscosity resol, are used for the method for formed glass steel.This resol viscosity has reduced, but does not have an alkali resistance.English Patent GB927914A has put down in writing the method for reacting the polyphenylene oxide phenolic resin (DP resin) that makes the linear phenolic resin type with phenol and trimethylammonium oxygen ylmethyl biphenyl ether under acidic catalyst, has higher thermotolerance behind this resin solidification.And on old just all monograph " anti-corrosion non-metallic material " books of south China polytechnical university, then introduced with α, γ-dichloro-propane etherified hydroxy groups and made the method for resol.The product that English Patent GB927914A method makes is used in carbon materials and makes the field, and its purpose is intended to improve the thermotolerance of solidifying the back product.α, γ-dichloro-propane etherification of phenolic resin phenolic hydroxyl group method, to use in α, γ-dichloro-propane adding resol in the time of can only using at the scene, adding back viscosity raises rapidly, quality guaranteed period is short, though can improve the resol alkali resistance, but viscosity is too big, can't be impregnated in the small pore of carbon materials, therefore is not suitable for carbon materials and uses.
The objective of the invention is research, produce a kind of modified phenolic resins and production method thereof.This resin to reach alkali resistance and the mechanical property that improves carbon materials, reduces the purposes such as temperature, pressure and production cost of dip treating as binding agent or soaker.
The object of the present invention is achieved like this: in the phenol (also can be other phenols raw materials such as dihydroxy-benzene) of 1 part of weight, add some parts of weight formaldehyde, acetaldehyde, one of them aldehydes raw material such as phenyl aldehyde or phenylacetic aldehyde, as add the formaldehyde (concentration 37%) of 1.075～1.250 parts of weight (preferably 1.140～1.180 parts of weight) and the yellow soda ash of 0.085 part of weight, mixture system is heated, make it in 1～5 minute, to rise to 102 ℃ of boilings rapidly by room temperature, under this temperature, kept 12～15 minutes, temporarily stop heating, and add a kind of alkylating agent rapidly, Benzyl Chloride as 1.345 parts of weight (claims benzyl chloride again, or toluene(mono)chloride, molecular formula is C
6H
5CH
2Cl) and the sodium hydroxide solution of 2.128 parts of weight (concentration 20%), when treating that system temperature is reduced to 80 ℃ of left and right sides, reheat to boiling makes it to take place etherification reaction, keeps (reaction) 6～17 minutes, preferably 9～11 minutes.At last, add an amount of cold water and make the cooling of material system, and constantly stirring body is a material.At this moment, system will be divided into two-layer up and down.After discarding the supernatant liquid material, with the hot wash of leftover materials with about 60 ℃, and under the 70 ℃ of left and right sides conditions decompression dehydration, promptly get resol of the present invention.
Resol of the present invention is compared with common commercial phenolic resin, and its molecular structural formula is
Form, each phenolic hydroxyl group include an ether-OCH all by etherificate
2C
6H
5Therefore, this resin has highly filled more than 80%, and viscosity is 30～90 seconds (25 ℃ are coated with 4 glasss) simultaneously, particularly has to be higher than 99% alkali resistance, the comprehensive characteristics of the shelf stable for periods more than a year.This has just greatly widened the Application Areas of resin, also improves and expanded the use properties of its application product, for example has fabulous alkali resistance.This resin is a kind of thermosetting resin, is specially adapted to do in the carbon materials production binding agent or soaker.The soaker use is not directly done in the solubilizing agent dilution, can permeate the carbon materials matrix at lesser temps and pressure working condition condition, and can reduce dipping, and the cure cycle number of times shortens the production cycle, reduces cost.Shelf stable for periods is a long quality-guarantee period, helps remote sale, and the user also is convenient to buying.Because special tool alkali resistance, the carbon materials behind the dipping both can be used in the acidic medium, also can be used in the alkaline medium, have the performance of dipping furane resin, and resin price is lower.Since the solids content height, the dipping rate of body weight gain in the time of can improving the carbonization yield when making binding agent and make soaker.These characteristics have profound significance in lithium-ion secondary cell manufacturing and high conductive paper of carbon fiber manufacturing.
With embodiment the present invention is described below, but the present invention is not limited only to the content that these embodiment explain.
Embodiment 1
Take by weighing phenol 94 grams, add formaldehyde (concentration 37%) 107.2～110.9 grams and yellow soda ash 0.8 gram, and place the there-necked flask of belt stirrer, with mixture heating up, make it in 1～5 minute, to rise to 102 ℃ (boilings) rapidly by room temperature, kept this temperature 12～15 minutes, temporarily stop heating then, and the rapid 126.5 gram Benzyl Chlorides and 200 that add restrain sodium hydroxide solutions (concentration 20%) in system, when the system temperature of charge for the treatment of is reduced to 80 ℃ of left and right sides, reheat to boiling again, and kept 9～11 minutes, add an amount of cold water cooling at last, and ceaselessly stir, treat the system material layering after, discard supernatant liquid, to the hot wash of residuum, remove remaining alkali lye and sodium-chlor with about 60 ℃.At last, with the following decompression dehydration about 70 ℃ of the material after the washing, in prolong till the no water droplet.Promptly get resol of the present invention.With the gained resin, press HG5-1340-80 standard testing viscosity, with reference to HG5-1342-80 standard testing free phenol content, with reference to HG5-1343-80 standard testing content of free aldehyde, press GB1725-79 test solids content, with reference to GB4738-84 standard testing fastness to alkali, press GB6753-86 standard testing package stability.Test result is listed in the table 1.
Embodiment 2
Take by weighing phenol 94 grams, the operation steps of pressing embodiment 1 adds 101.4 gram formaldehyde (concentration 37%) and 0.8 gram yellow soda ash.The boiling hold-time behind adding Benzyl Chloride and the sodium hydroxide solution is 9～11 minutes.All the other are with embodiment 1.Gained resin property test result is also listed in the table 1.
Embodiment 3
Take by weighing phenol 94 grams, the operation steps of pressing embodiment 1 adds 117.6 gram formaldehyde (concentration 37%) and 0.8 gram yellow soda ash.The boiling hold-time behind adding Benzyl Chloride and the sodium hydroxide solution is 9～11 minutes.All the other are with embodiment 1.Gained resin property test result is also listed in the table 1.
Embodiment 4
Take by weighing phenol 94 grams, the operation steps of pressing embodiment 1 adds 107.2～110.9 gram formaldehyde (concentration 37%) and 0.8 gram yellow soda ash.The boiling hold-time after adding Benzyl Chloride and sodium hydroxide solution changed into 6 minutes, and all the other are with embodiment 1.Gained resin property test result is also listed in the table 1.
Embodiment 5
Take by weighing phenol 94 grams, the operation steps of pressing embodiment 1 adds 107.2～110.9 gram formaldehyde (concentration 37%) and 0.8 gram yellow soda ash.The boiling hold-time after adding Benzyl Chloride and sodium hydroxide solution changed into 17 minutes, and all the other are with embodiment 1.Gained resin property test result is also listed in the table 1.
Embodiment 6
With the trade mark is that M120 carbon lump (3～4 gram) was dried 24 hours in 110 ℃ of baking ovens, takes out to place the moisture eliminator internal cooling to room temperature.Place the container of vacuum-pumping then, vacuumized 30 minutes.The resol of the present invention that has added solidifying agent is slowly injected from separating funnel, and the submergence carbon lump, keep vacuumizing 10 minutes.After shedding vacuum, take out carbon lump and remove the unnecessary resin that goes surface adhesion, place 110 ℃ of baking ovens to solidify then 24 hours.After the cooling, the sample carbon lump is pressed GB2997-82 standard testing water-intake rate, void content and dipping rate of body weight gain.The results are shown in Table 2.
Comparative Examples 1～2
Pressing the operation steps of embodiment 6, adopt the carbon lump of material of the same race and same size size, is that used soaker changes (1) commercially available general resol or (2) furane resin into.Carbon lump The performance test results behind its dipping is also listed in the table 2 in the lump.
5 90 2.71 0.42 87.2 one years 99.6 table 2 apparent porosity % water absorption rate % dippings of table 1 viscosity (the free aldehyde % solids content % shelf stable for periods fastness to alkali % of 25 ℃, free phenol % is coated with 4 glasss) second embodiment 2 30 3.06 0.94 84.6 one years 99.3 embodiment, 4 58 3.08 0.97 85.2 one years 99.2 embodiment of 3 82 2.47 0.29 90.6 one years 99.5 embodiment of 1 37 2.97 0.78 84.9 one years 99.6 embodiment rate of body weight gain % embodiment, 6 2.07 1.06 7.2 Comparative Examples, 1 2.69 1.47 5.9 Comparative Examples 2 3.12 1.73 3.8
Claims (10)
1. modified phenolic resins, the condensation reaction under base catalysis by phenols and aldehydes organic raw material, and handle through etherificate, dehydration makes, and it is characterized in that carrying out etherificate with alkylating agent handles, and the structural formula of resin is
Form, the equal etherificate of each phenolic hydroxyl group includes the resol of ether-O-R.
2. resin according to claim 1 is characterized in that carrying out etherificate with Benzyl Chloride handles, and the resinous molecular structure formula is
Form, the equal etherificate of each phenolic hydroxyl group includes an ether-OCH
2C
6H
5Resol.
3. resol according to claim 1 and 2 is characterized in that viscosity is 30～90 seconds, and solids content is greater than 80%, and free phenol is less than 5%, and free aldehyde is less than 1%, and fastness to alkali is greater than 99%, the resol of shelf stable for periods more than 1 year.
4. production method of making the described resol of claim 1, comprise by phenols and aldehydes organic raw material, condensation reaction under base catalysis, and handle through etherificate, dehydration, it is characterized in that in the phenol of 1 part of weight, the concentration that adds 1.075～1.250 parts of weight is 37% the formaldehyde and the yellow soda ash of 0.085 part of weight, the heated mixt system is to boiling rapidly, and kept 12～15 minutes, stop heating then, add the Benzyl Chloride of 1.345 parts of weight and 2.128 parts of weight concentrations rapidly and be 20% sodium hydroxide solution, reheat was to boiling when objects system temperature to be mixed was reduced to 80 ℃ of left and right sides, and kept 6～17 minutes, add an amount of cold water cooling and constantly stirring then, treat decompression dehydration under the concrete conditions in the establishment of a specific crime, thereby obtain the production method of modified phenolic resins.
5. production method according to claim 4, it is characterized in that adding 1.140～1.180 parts of weight concentrations and be 37% the formaldehyde and the yellow soda ash of 0.085 part of weight in the phenol of 1 part of weight, is 9～11 minutes production method and add boiling hold-time behind Benzyl Chloride and the sodium hydroxide solution.
6. production method according to claim 4, it is characterized in that in the phenol of 1 part of weight adding 1.075 parts of weight concentrations and be 37% the formaldehyde and the yellow soda ash of 0.085 part of weight, is 9～11 minutes production method and add boiling hold-time behind Benzyl Chloride and the sodium hydroxide solution.
7. production method according to claim 4, it is characterized in that in the phenol of 1 part of weight adding 1.250 parts of weight concentrations and be 37% the formaldehyde and the yellow soda ash of 0.085 part of weight, is 9～11 minutes production method and add boiling hold-time behind Benzyl Chloride and the sodium hydroxide solution.
8. according to claim 4 or 5 described production methods, it is characterized in that boiling hold-time behind described adding Benzyl Chloride and the sodium hydroxide solution is 6 minutes a production method.
9. according to claim 4 or 5 described production methods, it is characterized in that boiling hold-time behind described adding Benzyl Chloride and the sodium hydroxide solution is 17 minutes a production method.
10. according to the application method of claim 1 or 2 described modified phenolic resinss, it is characterized in that this resol can be exclusively used in to make binding agent or soaker in the carbon materials manufacturing.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01107177 CN1309141A (en) | 2001-02-22 | 2001-02-22 | Modified phenolic resin and its preparing process |
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|---|---|---|---|
| CN 01107177 CN1309141A (en) | 2001-02-22 | 2001-02-22 | Modified phenolic resin and its preparing process |
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| CN1309141A true CN1309141A (en) | 2001-08-22 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009286944A (en) * | 2008-05-30 | 2009-12-10 | Dic Corp | Thermosetting resin composition, its cured product, new phenol resin, and its production method |
| CN101696255B (en) * | 2009-10-29 | 2011-10-05 | 中国林业科学研究院木材工业研究所 | Preparation method, application and using method for phenolic aldehyde storing liquid |
| CN110357632A (en) * | 2019-07-05 | 2019-10-22 | 中国科学院化学研究所 | A kind of ZrC/SiC complex phase ceramic presoma and preparation method thereof |
-
2001
- 2001-02-22 CN CN 01107177 patent/CN1309141A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009286944A (en) * | 2008-05-30 | 2009-12-10 | Dic Corp | Thermosetting resin composition, its cured product, new phenol resin, and its production method |
| CN101696255B (en) * | 2009-10-29 | 2011-10-05 | 中国林业科学研究院木材工业研究所 | Preparation method, application and using method for phenolic aldehyde storing liquid |
| CN110357632A (en) * | 2019-07-05 | 2019-10-22 | 中国科学院化学研究所 | A kind of ZrC/SiC complex phase ceramic presoma and preparation method thereof |
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