CN101628856A - Dicyclopentadiene phenol-containing compound preparation method - Google Patents
Dicyclopentadiene phenol-containing compound preparation method Download PDFInfo
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- CN101628856A CN101628856A CN200910056647A CN200910056647A CN101628856A CN 101628856 A CN101628856 A CN 101628856A CN 200910056647 A CN200910056647 A CN 200910056647A CN 200910056647 A CN200910056647 A CN 200910056647A CN 101628856 A CN101628856 A CN 101628856A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a method for preparing a phenol-containing compound containing dicyclopentadiene unit by using toluenesulfonic acid or phosphoric acid as catalyst. Toluenesulfonic acid or phosphoric acid is used as catalyst instead of boron trifluoride ethyl ether complex used in conventional synthesis method, thus avoiding the problem that boron trifluoride has strong corrosivity to devices. The phenolic monomer prepared by the invention can be used as the intermediate of epoxy resin and cyanate resin.
Description
Technical field
The invention belongs to the synthetic field of organic polymer, relating to tosic acid and phosphoric acid is the method that contains phenolic compound that contains dicyclopentadiene unit in catalyzer, the preparation structure.
Background technology
Dicyclopentadiene is mainly derived from C
5Cut separates, because its polarity is little, water absorption resistance is good and cost is low, is the raw material of the low dielectric polymer of preparation.Dicyclopentadiene and phenol reactant generate contains the cyanate that the phenol monomer is made after cyaniding, it has excellent dielectric properties after solidifying, and can be used for aspects such as printed circuit board (PCB).Conventional preparation dicyclopentadiene phenol-containing compound is to be catalyzer with boron trifluoride ethyl ether complex, but boron trifluoride moisture-sensitive generation fluoroboric acid and boric acid are harmful to stainless steel and glass equipment seriously corroded and boron trifluoride.
In order to overcome above drawback, the present invention adopts tosic acid, phosphoric acid or heteropolyacid to prepare dicyclopentadiene phenol-containing compound as catalyzer, with the expectation be after the preparation cyanate supply raw materials.
Summary of the invention
The objective of the invention is to adopt tosic acid, phosphoric acid or heteropolyacid as catalyzer, is raw material with phenol and dicyclopentadiene, prepares dicyclopentadiene phenol-containing compound by addition reaction.
The dicyclopentadiene phenol-containing compound structural formula of the present invention's preparation is as follows
Implementation method of the present invention is as follows:
Mechanical stirring is being housed, in the four-hole bottle of thermometer and reflux condensing tube, phenol and the dicyclopentadiene mass ratio with 4: 1～20: 1 is dropped in the reaction flask, catalyzer is tosic acid (phosphoric acid or a heteropolyacid), catalyst consumption is 0.5～10% (by weight) of used phenol and dicyclopentadiene total amount, drip dicyclopentadiene at 60～90 ℃, after dropwising temperature is risen to 120～160 ℃ and be incubated 1～6 hour, be cooled to 80 ℃ then and add the sodium hydroxide neutralization, the intact phenol of unreacted is removed in underpressure distillation, obtain crude product, add the toluene after washing 5～6 times, remove the phenol monomer that obtains containing dicyclopentadiene structure behind toluene and the water at last, productive rate is 60～90%.
Catalyzer can be selected tosic acid, phosphoric acid, heteropolyacid such as phospho-molybdic acid, phospho-wolframic acid etc., and the difference of catalyzer is all influential to molecular weight, softening temperature and the productive rate of product, is excellent with tosic acid wherein.
The synthetic route of dicyclopentadiene phenol-containing compound is as follows:
The used catalyzer of the application is nowadays all not report in industrial circle and the existing periodical literature, and the exploration of its reactivity worth is not seen that the people set foot in yet.It is existing with the corrosion effect of catalyzer to reactor that the use of this type of catalyzer has been avoided greatly, and very big practicality is arranged.
Embodiment
The invention will be further described below by embodiment, and its purpose is to understand content of the present invention better, rather than limitation of the present invention.
Embodiment 1
In the four-hole boiling flask that mechanical stirring, thermometer, reflux condensate device and constant pressure funnel are housed, add 94g phenol and 4g tosic acid.Begin to drip dicyclopentadiene 23g when temperature is raised to 80 ℃, dropwise after 20 minutes, then temperature is raised to 150 ℃ after the insulation 4 hours.Reaction finishes to add excessive sodium hydroxide neutralization behind the postcooling to 80 ℃, and unreacted phenol is completely removed in underpressure distillation.Add toluene crude product is dissolved, wash then six times, toluene and water are removed in underpressure distillation, obtain dicyclopentadiene phenol-containing compound 58g.Its softening temperature is 78.5 ℃, and free phenol is less than 5 ‰, and the weight-average molecular weight that GPC records is 1023.
Embodiment 2
In the four-hole boiling flask that mechanical stirring, thermometer, reflux condensate device and constant pressure funnel are housed, add 376g phenol and 4g tosic acid.Begin to drip dicyclopentadiene 19g when temperature is raised to 80 ℃, half hour, dropwise, then temperature is raised to 150 ℃ after the insulation 4 hours.Reaction finishes to add excessive sodium hydroxide neutralization behind the postcooling to 60 ℃, and unreacted phenol is completely removed in underpressure distillation.Add toluene crude product is dissolved, wash then six times, toluene and water are removed in underpressure distillation, obtain dicyclopentadiene phenol-containing compound 58g.Its softening temperature is 78.5 ℃, and free phenol is less than 5 ‰, and the weight-average molecular weight that GPC records is 462.
Embodiment 3
In the four-hole boiling flask that mechanical stirring, thermometer, reflux condensate device and constant pressure funnel are housed, add 178g phenol and 4g tosic acid.Begin to drip dicyclopentadiene 19g when temperature is raised to 60 ℃, half hour, dropwise, then temperature is raised to 150 ℃ after the insulation 4 hours.Reaction finishes to add excessive sodium hydroxide neutralization behind the postcooling to 100 ℃, and unreacted phenol is completely removed in underpressure distillation.Add toluene crude product is dissolved, wash then six times, toluene and water are removed in underpressure distillation, obtain dicyclopentadiene phenol-containing compound 30g.Its softening temperature is 78.5 ℃, and free phenol is less than 5 ‰, and the weight-average molecular weight that GPC records is 800.
Embodiment 4
In the four-hole boiling flask that mechanical stirring, thermometer, reflux condensate device and constant pressure funnel are housed, add 376g phenol and 9.4g phosphoric acid.Begin to drip dicyclopentadiene 25g when temperature is raised to 80 ℃, dropwise behind the 45min, then temperature is raised to 140 ℃ after the insulation 5 hours.Reaction finishes to add excessive sodium hydroxide neutralization behind the postcooling to 70 ℃, and unreacted phenol is completely removed in underpressure distillation.Add toluene crude product is dissolved, wash then six times, toluene and water are removed in underpressure distillation, obtain dicyclopentadiene phenol-containing compound 46g.Its softening temperature is 32 ℃, and free phenol is less than 5 ‰, and the weight-average molecular weight that GPC records is 389.
Embodiment 5
In the four-hole boiling flask that mechanical stirring, thermometer, reflux condensate device and constant pressure funnel are housed, add 376g phenol and 23.5g phosphoric acid.Begin to drip dicyclopentadiene 30g when temperature is raised to 80 ℃, dropwised in one hour, then temperature is raised to 150 ℃ after the insulation 6 hours.Reaction finishes to add excessive sodium hydroxide neutralization behind the postcooling to 60 ℃, and unreacted phenol is completely removed in underpressure distillation.Add toluene crude product is dissolved, wash then six times, toluene and water are removed in underpressure distillation, obtain dicyclopentadiene phenol-containing compound 43g.Its softening temperature is 50 ℃, and free phenol is less than 5 ‰, and the weight-average molecular weight that GPC records is 380.
Embodiment 6
In the four-hole boiling flask that mechanical stirring, thermometer, reflux condensate device and constant pressure funnel are housed, add 376g phenol and 2g phospho-molybdic acid.Begin to drip dicyclopentadiene 20g when temperature is raised to 90 ℃, half hour, dropwise, then temperature is raised to 160 ℃ after the insulation 4 hours.Reaction finishes to add excessive sodium hydroxide neutralization behind the postcooling to 80 ℃, and unreacted phenol is completely removed in underpressure distillation.Add toluene crude product is dissolved, wash then six times, toluene and water are removed in underpressure distillation, obtain dicyclopentadiene phenol-containing compound 44g.Its softening temperature is 37 ℃, and free phenol is less than 5 ‰, and the weight-average molecular weight that GPC records is 392.
Claims (3)
1, a kind of preparation method of dicyclopentadiene phenol-containing compound is characterized in that, this structural formula that contains phenolic compound is shown below:
Wherein, n=0.2～0.3;
Adopting mass ratio is that 4: 1～20: 1 phenol and dicyclopentadiene is raw material, is catalyzer with phosphoric acid or tosic acid or heteropolyacid; 60～90 ℃ interpolations drip dicyclopentadiene in the phenol of described catalyzer, after dropwising temperature is risen to 120～160 ℃ and be incubated 1～6 hour, add the alkali lye neutralization then when system temperature is 60～100 ℃, the intact phenol of unreacted is removed in underpressure distillation, obtains product.
2, preparation method according to claim 1 is characterized in that, described catalyst consumption is 0.5～10% of used phenol and dicyclopentadiene total amount by weight.
3, preparation method according to claim 1 is characterized in that, described heteropolyacid is phospho-molybdic acid or phospho-wolframic acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200910056647A CN101628856A (en) | 2009-08-19 | 2009-08-19 | Dicyclopentadiene phenol-containing compound preparation method |
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| CN200910056647A CN101628856A (en) | 2009-08-19 | 2009-08-19 | Dicyclopentadiene phenol-containing compound preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542970A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | The method that a kind of synthesis of dicyclopentadiene phenol resin and feedstock circulation are utilized |
| CN114656376A (en) * | 2022-04-13 | 2022-06-24 | 常州大学 | Method for synthesizing cardanol modified dicyclopentadiene phenol resin by adopting bisphenol method |
-
2009
- 2009-08-19 CN CN200910056647A patent/CN101628856A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106542970A (en) * | 2015-09-23 | 2017-03-29 | 中国石油化工股份有限公司 | The method that a kind of synthesis of dicyclopentadiene phenol resin and feedstock circulation are utilized |
| CN114656376A (en) * | 2022-04-13 | 2022-06-24 | 常州大学 | Method for synthesizing cardanol modified dicyclopentadiene phenol resin by adopting bisphenol method |
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Application publication date: 20100120 |