CN1446799A - Cyanate of addition product of dicyclopentadiene-phenol and its preparation method - Google Patents
Cyanate of addition product of dicyclopentadiene-phenol and its preparation method Download PDFInfo
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- CN1446799A CN1446799A CN 03114874 CN03114874A CN1446799A CN 1446799 A CN1446799 A CN 1446799A CN 03114874 CN03114874 CN 03114874 CN 03114874 A CN03114874 A CN 03114874A CN 1446799 A CN1446799 A CN 1446799A
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- dicyclopentadiene
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Abstract
A cyanate of bicyclopentadiene-phenol addition compound has 370-424 of average molecular weight and 2-4 min for gelatinizing time under catalysis of cobalt of isooctoate, and is prepared through dissolving said addition compound in solvent, adding cyanogen chloride and triethylamine, reaction, and collecting the target product from resultant. Its advantage is high purity of product.
Description
Technical field
The present invention relates to cyanate of a kind of dicyclopentadiene-phenol affixture and preparation method thereof.
Background technology
The cyanate of dicyclopentadiene-phenol affixture is widely used in high performance structures/field of functional materials with its excellent dielectric properties and good mechanical performance, thermotolerance and humidity resistance, (see: Yan Fusheng, Liang Guozheng as advanced composite material resin matrix, radome and high-speed figure printed circuit board (PCB) etc., macromolecular material, 1997,4 (2): 14-17; Qin Huayu, Liang Guozheng, New Chemical Materials, 1998,26 (10): 33-35; S.Y.Lipatov, A.M.Fainleib, T.A.Shantalii, L.M.Sergceva.Polym.Sci, 1992,34 (5): 407)
Cyanate of the present invention is meant the cyanate of dicyclopentadiene-phenol affixture, and its structural formula is as follows:
The cyanate of highly purified dicyclopentadiene-phenol affixture is very noticeable in aerospace and electronics industry as the monomer of performance resins, because the polymkeric substance that is obtained by its polymerization has as shown in Table 1 and Table 2 special mechanics and electric property.
The specific inductivity of table 1 cyanate ester resin
| The resin title | The specific inductivity of each wave band | |||
| X-band | The Ka wave band | The U wave band | The W wave band | |
| Resins, epoxy | ????3.75 | ????3.60 | ????3.55 | ????3.55 |
| Bimaleimide resin | ????3.55 | ????3.45 | ????3.45 | ????3.45 |
| Cyanate ester resin | ????3.25 | ????3.25 | ????3.27 | ????3.28 |
The dielectric loss of table 2 cyanate ester resin
| The resin title | The dielectric loss of each wave band | |||
| X-band | The Ka wave band | The U wave band | The W wave band | |
| Resins, epoxy | ??0.018 | ????0.017 | ????0.016 | ????0.011 |
| Bimaleimide resin | ??0.016 | ????0.015 | ????0.014 | ????0.010 |
| Cyanate ester resin | ??0.003 | ????0.003 | ????0.003 | ????0.003 |
By table 1 and table 2 as seen, the cyanate ester resin of dicyclopentadiene-phenol affixture is specially adapted to make printed-wiring board (PWB) and satellite, the antenna radar cover of high performance airplane, load bearing structure all being superior to the Resins, epoxy that is using at present aspect the over-all propertieies such as dielectric properties, hydrophobic nature, damage tolerance, second-order transition temperature and mechanical strength to some extent.The chemical constitution of above-mentioned cyanate ester polymer mainly is the repeating unit of symmetric triazine ring molecule, and the aromatic polymer that contains symmetric triazine ring molecular structure is compared with the bismaleimides thermosetting resin with Resins, epoxy also has following advantage:
1. lower crosslink density and high free volume content are given the resin system high tenacity, and it is higher to show as strain energy rate of release and tension set;
2. molecular polarity reaches balance behind the resin solidification, does not have hydrogen bond basically, therefore presents low rate of moisture absorption;
3. the high aromatic ring content that solidifies in the resin of back makes system have high glass transition temperature, low be fuming rate and flame-retarding characteristic.
The advantage of these molecular structures self makes above-mentioned cyanate polymkeric substance be suitable as the matrix of high-performance poly condensation material.
United States Patent (USP) 5340912 and Organic Syntheses mention the synthetic of above-mentioned cyanate among the CV 7,435, but to adopt cyanogen bromide be cyanating reagent for they, and this reagent costs an arm and a leg, and therefore is unfavorable for suitability for industrialized production.
United States Patent (USP) 4748270 discloses a kind of synthetic method of cyanate, in the product that uses this method to obtain a lot of impurity is arranged.Mainly be because the cyanating reagent purity of using is not high, so that gel time reaches a few hours, thereby can not satisfy follow-up processing request.
Summary of the invention
One of technical issues that need to address of the present invention are the cyanates that discloses a kind of dicyclopentadiene-phenol affixture;
Two of the technical issues that need to address of the present invention provide a kind of method for preparing the cyanate of dicyclopentadiene-phenol affixture, to overcome the above-mentioned defective that prior art exists, satisfy need of industrial production.
The cyanate of dicyclopentadiene of the present invention-phenol affixture is the polymkeric substance with following structure fragment:
Molecular-weight average is 370～424, and Infrared spectroscopy is at 2250cm
-1Strong absorption peak is arranged, and gel time is 2～4 minutes under 1.5% cobalt iso-octoate catalysis in the time of 160 ℃.
Method of the present invention comprises the steps:
Dicyclopentadiene-phenol affixture is dissolved in the solvent, adds mauguinite and triethylamine successively, wherein the mol ratio of dicyclopentadiene-phenol affixture and mauguinite is 1: 2.0～1: 5, preferably 1: 2.5～1: 3.0; Temperature of reaction is-20～10 ℃, preferably-10～5 ℃; Reaction times is 0.5～5 hour, is preferably 1～2 hour, after reaction finishes, collects target product with conventional method from reaction product.
Said dicyclopentadiene-phenol affixture can be the commercial goods, also can adopt United States Patent (USP) 4927905 disclosed methods to be prepared.
Said solvent comprises one or more in toluene, dimethylbenzene, acetone, methylene dichloride or the trichloromethane etc., and preferably toluene is or/and acetone.The chemical reaction general formula is:
What the present invention used is pure mauguinite (boiling point 12-13.8 ℃), contains other impurity hardly, and this has just improved the purity of final product greatly, and gel time is very short, can satisfy the requirement of synthetic polymer.
Specific implementation method
Below will the present invention is further illustrated by embodiment.
Embodiment 1
Dicyclopentadiene phenol affixture (200g, molecular-weight average M=250-360) is dissolved in the 1L acetone, stirs and cool to-10 ℃, add aqueous mauguinite (86g, 1.38mol) and triethylamine (126g, 1.38mol), finish insulated and stirred 60min, subsequently, feed nitrogen and drive excessive mauguinite gas out of reactor, filter and remove the chloro triethylamine that generates, obtain the acetone soln of dicyclopentadiene phenol addition compound cyanate.
Above-mentioned solution is poured in the 1L frozen water, treat to extract (300ml * 3) with toluene behind the ice-out, obtain the toluene solution of dicyclopentadiene-phenol addition compound cyanate, this solution is used saturated sodium carbonate solution, water, dilute hydrochloric acid, water washing more successively, and distillation is removed toluene and obtained dicyclopentadiene-phenol addition compound cyanate 210g under 2-5mmHg again.Product through Infrared spectroscopy at 2250cm
-1Strong absorption peak is arranged, and this is the characteristic peak of cyano group infrared absorption.The GPC method records repeating unit n=1～10, molecular-weight average M=400, and gel time is 2～4 minutes under 1.5% cobalt iso-octoate catalysis in the time of 160 ℃.
Embodiment 2
Dicyclopentadiene phenol affixture (200g, molecular-weight average M=250-360) is dissolved in the 1L toluene, stirs and cool to-10 ℃, add aqueous mauguinite (77g, 1.24mol) and triethylamine (113g, 1.24mol), finish insulated and stirred 90min, subsequently, feed nitrogen and drive excessive mauguinite gas out of reactor, filter and remove the chloro triethylamine that generates, obtain the toluene solution of the cyanate of dicyclopentadiene phenol affixture.
Above-mentioned solution is poured in the 1L frozen water, is treated to use saturated sodium carbonate solution, water, dilute hydrochloric acid, water washing successively behind the ice-out, again pressure for 2-5mmHg time distillation remove toluene and obtain dicyclopentadiene-phenol addition compound cyanate 210g.
Product through Infrared spectroscopy at 2250cm
-1Strong absorption peak is arranged, and this is the characteristic peak of cyano group infrared absorption.The GPC method records repeating unit n=1～10, molecular-weight average M=370, and gel time is 2～4 minutes under 1.5% cobalt iso-octoate catalysis in the time of 160 ℃.
Embodiment 3
Dicyclopentadiene phenol affixture (400g, molecular-weight average M=250-360) is dissolved in the 2L acetone, stirs and cool to-10 ℃, add aqueous mauguinite (175g, 2.8mol) and triethylamine (255g, 2.8mol), finish insulated and stirred 120min, subsequently, feed nitrogen, filter and remove the chloro triethylamine that generates, obtain the acetone soln of dicyclopentadiene phenol addition compound cyanate.
Above-mentioned solution is poured in the 2L frozen water, treat to extract (600ml * 3) with toluene behind the ice-out, obtain the toluene solution of dicyclopentadiene-phenol addition compound cyanate, this solution is used saturated sodium carbonate solution, water, dilute hydrochloric acid, water washing more successively, again pressure for 2-5mmHg time distillation remove toluene and obtain dicyclopentadiene-phenol addition compound cyanate 420g.
Product through Infrared spectroscopy at 2250cm
-1Strong absorption peak is arranged, and this is the characteristic peak of cyano group infrared absorption.The GPC method records repeating unit n=1～10, molecular-weight average M=424, and gel time is 2～4 minutes under 1.5% cobalt iso-octoate catalysis in the time of 160 ℃.
Claims (8)
1. the cyanate of dicyclopentadiene-phenol affixture is characterized in that, has the polymkeric substance of following structure fragment:
Molecular-weight average is 370～424.
2. the cyanate of dicyclopentadiene according to claim 1-phenol affixture is characterized in that, in the time of 160 ℃ under 1.5% cobalt iso-octoate catalysis gel time be 2～4 minutes.
3. the preparation method of the cyanate of dicyclopentadiene according to claim 1 and 2-phenol affixture is characterized in that comprising the steps:
Dicyclopentadiene-phenol affixture is dissolved in the solvent, adds pure mauguinite (boiling point 12-13.8 ℃) and triethylamine, wherein the mol ratio of dicyclopentadiene-phenol affixture and mauguinite is 1: 2.0～1: 5; Temperature of reaction is-20～10 ℃; Reaction times is 0.5～5 hour, after reaction finishes, collects target product with conventional method from reaction product.
4. method according to claim 3 is characterized in that, the mol ratio of dicyclopentadiene-phenol affixture and mauguinite is 1: 2.5～1: 3.0.
5. method according to claim 3 is characterized in that, temperature of reaction is-10～5 ℃.
6. method according to claim 3 is characterized in that, the reaction times is 1～2 hour.
7. method according to claim 3 is characterized in that said solvent comprises one or more in toluene, dimethylbenzene, acetone, methylene dichloride or the trichloromethane.
8. method according to claim 7 is characterized in that, said solvent is that toluene is or/and acetone.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942684A (en) * | 2012-11-08 | 2013-02-27 | 广东生益科技股份有限公司 | Thermosetting cyanate resin composition and application of thermosetting cyanate resin composition |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102942684A (en) * | 2012-11-08 | 2013-02-27 | 广东生益科技股份有限公司 | Thermosetting cyanate resin composition and application of thermosetting cyanate resin composition |
| CN102942684B (en) * | 2012-11-08 | 2015-06-17 | 广东生益科技股份有限公司 | Thermosetting cyanate resin composition and application of thermosetting cyanate resin composition |
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