CN101948408A - Novel preparation method of paraxylene-base binary cyanate resin - Google Patents
Novel preparation method of paraxylene-base binary cyanate resin Download PDFInfo
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- CN101948408A CN101948408A CN2010102766784A CN201010276678A CN101948408A CN 101948408 A CN101948408 A CN 101948408A CN 2010102766784 A CN2010102766784 A CN 2010102766784A CN 201010276678 A CN201010276678 A CN 201010276678A CN 101948408 A CN101948408 A CN 101948408A
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Abstract
The invention discloses a novel preparation method of a paraxylene-base binary cyanate resin disclosed as formula (1), namely 4,4'-(1,4-dimethylene phenyl)-diphenyl cyanate. The resin is cream crystals, and the melting point is 130 DEG C. The cured paraxylene-base binary cyanate resin prepared by the method has the advantages of favorable fire retardancy and high thermal stability. The formula (1) is disclosed in the specification.
Description
Technical field
The present invention relates to a kind of preparation method of novel p-Xylol base bicyanate resin.This resin is a yellow crystals, does not have small molecules during curing and emits.Have good flame retardancy, heat and thermal stability behind the resin solidification, suitable fire retardant material or the high temperature material done.
Background technology
Cyanate ester resin is to contain two or more cyanate functional group (novel high-performance resin OCN).Be solidified into the paracyanogen acid esters reticulated structure that obtains of ring by cyanate functional group and have high glass-transition temperature, excellent dielectric properties, low rate of moisture absorption, high heat stability performance and favorable mechanical performance.These excellent performances make it can satisfy the strict demand of aerospace field.
The raw material terephthaldehyde ether of utilization of the present invention is simple and easy to, and is introduced in the backbone structure of resin, has increased the space length of cyanate group, has improved flame retardant properties, resistance toheat and the thermal stability of resin.
Summary of the invention
Main purpose of the present invention is to provide a kind of preparation method of novel p-Xylol base bicyanate resin; Secondly the curing process of this new type resin and the performance of curing back resin are done to describe.Resin structure novelty involved in the present invention, filled up the blank of existing cyanate ester resin kind, the preparing product raw material is easy to get, with low cost, resin has good flame retardancy and thermal characteristics, can be widely used in fields such as aerospace flight vehicle, satellite, high-performance printed-wiring board (PWB).
Prepare a kind of p-Xylol base bicyanate resin of the present invention, its structure is shown below:
The preparation method comprises the steps:
A: after the mixing solutions of phenol and tosic acid is heated to 120～140 ℃, in system, drip terephthaldehyde's ether, dropwise the back in 130～150 ℃ of insulations 2～4 hours down; After reaction finishes, add alkali lye in reaction system and be neutralized to neutrality, excessive phenol is removed in underpressure distillation, and the solid matter that obtains carries out promptly getting 4,4 '-(1,4-dimethylene phenyl)-biphenol after recrystallization is purified with organic solvent;
The mol ratio of reactant is a phenol: tosic acid: terephthaldehyde's ether is 2～10:0.02～0.19:1;
Reaction formula is as follows:
B: in another reactor, add organic solvent, add ClCN after system being cooled to-20～0 ℃; The mixing solutions of 4,4 '-(1,4-dimethylene phenyl)-biphenol compound, triethylamine and the organic solvent that will be made by step (1) is added drop-wise in the reactor, simultaneously temperature of reaction is remained on-20～0 ℃; Dropwise back insulation 2～6 hours; After reaction finishes, with products therefrom respectively through washing, separate, dry and steam and obtain crude product after desolventizing;
Wherein, the mol ratio of 4,4 '-(1,4-dimethylene phenyl)-biphenol compound, ClCN, triethylamine and organic solvent is 1:2.02～3.2:2.01～3.00:5～20;
Reaction formula is as follows:
Described organic solvent is one or more the mixed solvent in toluene, butanone, acetonitrile, ethanol, Virahol or the methylene dichloride.
Described organic solvent is the mixed solvent with arbitrary proportion blended butanone and methylene dichloride.
The present invention has following advantage:
1, the used raw material of the present invention: terephthaldehyde's ether and phenol are with low cost to be easy to get;
2, method of the present invention, preparation technology is simple, and product at room temperature resin is a yellow solid, helps subsequent disposal;
3, prepared 4,4 '-(1,4-dimethylene phenyl)-the phenylbenzene cyanate ester resin is promptly curable under the effect of heat or catalyzer, has excellent flame-retardant, heat and thermal stability behind the resin solidification, can be used for fields such as aerospace flight vehicle, radome.
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
Constant pressure funnel, prolong, agitator and thermometer are housed, to wherein adding 240g phenol and 16g tosic acid on the 500ml four-hole boiling flask.After system is heated to 130 ℃,, dropwise after 1 hour to wherein dripping 83g terephthaldehyde ether.System has methyl alcohol to separate out in 130 ℃ of insulations 4 hours in the reaction process.Reaction finishes the back and add sodium hydroxide lye in system, in and system to neutral, excessive phenol is removed in underpressure distillation then.Product after the distillation is dissolved with toluene, and, be cooled to crystallization below 0 ℃, obtain yellow crystals, be 4,4 '-(1,4-dimethylene phenyl)-biphenol compound through after the washing for several times.160 ℃ of fusing points.Utilize the KBr pressed disc method to measure the infrared spectra of product, at 3427cm
-1Strong hydroxyl absorption peak appears in the place.
In the four-hole bottle of the 250ml for preparing in addition, equip thermometer, whipping appts, constant pressure funnel and nitrogen protection device.After system being cooled to about-5～0 ℃, to wherein adding 7.82g ClCN and 80g methylene dichloride.Keep system temperature-5～0 ℃ left and right sides constant, continuation drips 4 through constant pressure funnel in system, the mixing solutions of 4 '-(1,4-dimethylene phenyl)-biphenol compound 20g, triethylamine 12.77g and methylene dichloride 40g dropwised the back in one hour and was incubated two hours.Reaction is carried out alkali cleaning, washing, pickling respectively with product after finishing, at last through repeatedly separating organic phase after the washing, add anhydrous slufuric acid hydrogen sodium drying then, filter, unnecessary solvent is removed in last underpressure distillation, obtains yellow crude product, this crude product is carried out recrystallization with Virahol, obtain yellow crystals, be 4,4 '-(1,4-dimethylene phenyl)-and the phenylbenzene cyanate ester resin, fusing point (130～132) ℃.With the infrared spectra of KBr pressed disc method mensuration product, the result shows that product is at 2262cm
-1C ≡ N base absorption peak appears in the place.Results of elemental analyses is as follows: C
22H
16N
2O
2: calculated value: C, 77.63%; H, 4.74%; N, 8.23%; O, 9.40%; Actual test value: C, 77.40%; H, 4.60%; N, 8.13%; O, 9.87%.
Above-mentioned organic solvent can also be toluene, butanone, acetonitrile, ethanol, Virahol and their mixed solvent except being methylene dichloride, also can be the mixed solvent with arbitrary proportion blended butanone and methylene dichloride.
Embodiment 2
Constant pressure funnel, prolong, agitator and thermometer are housed, to wherein adding 450g phenol and 16g tosic acid on the 1000ml four-hole boiling flask.After system is heated to 135 ℃,, dropwise after 1 hour to wherein dripping 83g water white transparency shape terephthaldehyde ether.System has methyl alcohol to separate out in 135 ℃ of insulations 4 hours in the reaction process.Reaction finishes the back and add sodium hydroxide lye in system, in and system to neutral, excessive phenol is removed in underpressure distillation then.Product after the distillation is dissolved with toluene, and, be cooled to crystallization below 0 ℃, obtain yellow crystals, be 4,4 '-(1,4-dimethylene phenyl)-biphenol compound through after the washing for several times.160 ℃ of fusing points.Utilize the KBr pressed disc method to measure the infrared spectra of product, at 3427cm
-1Strong hydroxyl absorption peak appears in the place.
In the four-hole bottle of the 500ml for preparing in addition, equip thermometer, whipping appts, constant pressure funnel and nitrogen protection device.After system being cooled to about-5～0 ℃, to wherein adding 19g ClCN and 300g methylene dichloride.Keep system temperature-5～0 ℃ left and right sides constant, continuation drips 4 through constant pressure funnel in system, the mixing solutions of 4 '-(1,4-dimethylene phenyl)-biphenol compound 30g, triethylamine 30g and methylene dichloride 80g dropwised the back in two hours and was incubated two hours.Reaction is carried out alkali cleaning, washing, pickling respectively with product after finishing, at last through repeatedly separating organic phase after the washing, add anhydrous slufuric acid hydrogen sodium drying then, filter, unnecessary solvent is removed in last underpressure distillation, obtains yellow crude product, this crude product is carried out recrystallization with Virahol, obtain yellow crystals, be 4,4 '-(1,4-dimethylene phenyl)-and the phenylbenzene cyanate ester resin, fusing point (130～132) ℃.With the infrared spectra of KBr pressed disc method mensuration product, the result shows that product is at 2262cm
-1C ≡ N base absorption peak appears in the place.Results of elemental analyses is as follows: C
22H
16N
2O
2: calculated value: C, 77.63%; H, 4.74%; N, 8.23%; O, 9.40%; Actual test value: C, 77.40%; H, 4.60%; N, 8.13%; O, 9.87%.
Embodiment 3
Constant pressure funnel, prolong, agitator and thermometer are housed, to wherein adding 1128g phenol and 34g tosic acid on the 2000ml four-hole boiling flask.After system is heated to 130 ℃,, dropwise after 3 hours to wherein dripping 232g terephthaldehyde ether.System has methyl alcohol to separate out in 130 ℃ of insulations 4 hours in the reaction process.Reaction finishes the back and add sodium hydroxide lye in system, in and system to neutral, excessive phenol is removed in underpressure distillation then.Product after the distillation is dissolved with toluene, and, be cooled to crystallization below 0 ℃, obtain yellow crystals, be 4,4 '-(1,4-dimethylene phenyl)-biphenol compound through after the washing for several times.160 ℃ of fusing points.Utilize the KBr pressed disc method to measure the infrared spectra of product, at 3427cm
-1Strong hydroxyl absorption peak appears in the place.
In the four-hole bottle of the 2000ml for preparing in addition, equip thermometer, whipping appts, constant pressure funnel and nitrogen protection device.After system being cooled to about-5～0 ℃, to wherein adding 61g ClCN and 500g methylene dichloride.Keep system temperature-5～0 ℃ left and right sides constant, continuation drips 4 through constant pressure funnel in system, the mixing solutions of 4 '-(1,4-dimethylene phenyl)-biphenol compound 90g, triethylamine 94g and methylene dichloride 1000g dropwised the back in one hour and was incubated two hours.Reaction is carried out alkali cleaning, washing, pickling respectively with product after finishing, at last through repeatedly separating organic phase after the washing, add anhydrous slufuric acid hydrogen sodium drying then, filter, unnecessary solvent is removed in last underpressure distillation, obtains yellow crude product, this crude product is carried out recrystallization with Virahol, obtain yellow crystals, be 4,4 '-(1,4-dimethylene phenyl)-and the phenylbenzene cyanate ester resin, fusing point (130～132) ℃.With the infrared spectra of KBr pressed disc method mensuration product, the result shows that product is at 2262cm
-1C ≡ N base absorption peak appears in the place.
Embodiment 4
With 4,4 '-(1,4-dimethylene phenyl)-phenylbenzene cyanate ester resin is cured, and curing process is as follows: 160 ℃/2h+180 ℃/4h+200 ℃/2h, afterwards again through 230 ℃ of aftertreatment 2h, solidification process finishes.It is as shown in table 1 below that test obtains resin property:
Table 14,4 '-(1,4-dimethylene phenyl)-phenylbenzene cyanate ester resin performance
* Td5: the temperature during thermal weight loss 5%.
* wet-hot aging performance: the test casting resin under boiling water boils condition, 100 hours weightening finish percentage.
Claims (3)
1. the preparation method of a novel p-Xylol base bicyanate resin is characterized in that, comprises the steps:
(1) mixing solutions of phenol and tosic acid is heated to 120～140 ℃ after, in system, drip terephthaldehyde's ether, dropwise the back in 130～150 ℃ of insulations 2～4 hours down; After reaction finishes, add alkali lye in reaction system and be neutralized to neutrality, excessive phenol is removed in underpressure distillation, and the solid matter that obtains carries out promptly getting 4,4 '-(1,4-dimethylene phenyl)-biphenol after recrystallization is purified with organic solvent;
The mol ratio of reactant is a phenol: tosic acid: terephthaldehyde's ether is 2～10:0.02～0.19:1;
(2) in another reactor, add organic solvent, add ClCN after system being cooled to-20～0 ℃; The mixing solutions of 4,4 '-(1,4-dimethylene phenyl)-biphenol compound, triethylamine and the organic solvent that will be made by step (1) is added drop-wise in the reactor, simultaneously temperature of reaction is remained on-20～0 ℃; Dropwise back insulation 2～6 hours; After reaction finishes, with products therefrom respectively through washing, separate, dry and steam and obtain crude product after desolventizing;
Wherein, the mol ratio of 4,4 '-(1,4-dimethylene phenyl)-biphenol compound, ClCN, triethylamine and organic solvent is 1:2.02～3.2:2.01～3.00:5～20;
(3) described crude product is carried out recrystallization with organic solvent, promptly get target product;
Described target product is 4, and 4 '-(1,4-dimethylene phenyl)-phenylbenzene cyanate has structure shown in the following formula:
2. preparation method according to claim 1 is characterized in that, described organic solvent is one or more the mixed solvent in toluene, butanone, acetonitrile, ethanol, Virahol or the methylene dichloride.
3. preparation method according to claim 2 is characterized in that, described organic solvent is the mixed solvent with arbitrary proportion blended butanone and methylene dichloride.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532801A (en) * | 2010-12-24 | 2012-07-04 | 广东生益科技股份有限公司 | Cyanate resin composition as well as prepreg and laminated material manufactured using same |
| CN102702741A (en) * | 2012-06-12 | 2012-10-03 | 华东理工大学 | Cyanate ester based thermosetting resin and application thereof |
| WO2013021869A1 (en) * | 2011-08-09 | 2013-02-14 | 三菱瓦斯化学株式会社 | Novel cyanic acid ester compound, method for producing same, curable resin composition containing novel cyanic acid ester compound, and cured product of curable resin composition |
| CN103987753A (en) * | 2011-12-07 | 2014-08-13 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, and laminate |
| CN110330445A (en) * | 2019-07-18 | 2019-10-15 | 扬州天启新材料股份有限公司 | A kind of triphenol A type cyanate and preparation method thereof |
| CN114805801A (en) * | 2022-06-08 | 2022-07-29 | 黑龙江省科学院石油化学研究院 | Cyanate ester resin with low hygroscopicity and preparation method thereof |
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| CN101735108A (en) * | 2009-12-02 | 2010-06-16 | 华东理工大学 | Novel o-methyl binary cyanate resin and preparation method thereof |
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| CN101735108A (en) * | 2009-12-02 | 2010-06-16 | 华东理工大学 | Novel o-methyl binary cyanate resin and preparation method thereof |
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Cited By (15)
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| CN102532801B (en) * | 2010-12-24 | 2014-04-09 | 广东生益科技股份有限公司 | Cyanate resin composition as well as prepreg and laminated material manufactured using same |
| CN102532801A (en) * | 2010-12-24 | 2012-07-04 | 广东生益科技股份有限公司 | Cyanate resin composition as well as prepreg and laminated material manufactured using same |
| KR101892784B1 (en) | 2011-08-09 | 2018-08-28 | 미츠비시 가스 가가쿠 가부시키가이샤 | Novel cyanic acid ester compound, method for producing same, curable resin composition containing novel cyanic acid ester compound, and cured product of curable resin composition |
| US10155835B2 (en) | 2011-08-09 | 2018-12-18 | Mitsubishi Gas Chemical Company, Inc. | Cyanate ester compound and method for producing the same, and curable resin composition comprising the compound, and cured product thereof composition |
| WO2013021869A1 (en) * | 2011-08-09 | 2013-02-14 | 三菱瓦斯化学株式会社 | Novel cyanic acid ester compound, method for producing same, curable resin composition containing novel cyanic acid ester compound, and cured product of curable resin composition |
| CN103732642A (en) * | 2011-08-09 | 2014-04-16 | 三菱瓦斯化学株式会社 | Novel cyanic acid ester compound, method for producing same, curable resin composition containing novel cyanic acid ester compound, and cured product of curable resin composition |
| KR20140046007A (en) * | 2011-08-09 | 2014-04-17 | 미츠비시 가스 가가쿠 가부시키가이샤 | Novel cyanic acid ester compound, method for producing same, curable resin composition containing novel cyanic acid ester compound, and cured product of curable resin composition |
| JPWO2013021869A1 (en) * | 2011-08-09 | 2015-03-05 | 三菱瓦斯化学株式会社 | Novel cyanate ester compound and method for producing the same, curable resin composition containing the compound, and cured product thereof |
| CN103732642B (en) * | 2011-08-09 | 2015-05-27 | 三菱瓦斯化学株式会社 | Novel cyanic acid ester compound, method for producing same, curable resin composition containing novel cyanic acid ester compound, and cured product of curable resin composition |
| CN103987753A (en) * | 2011-12-07 | 2014-08-13 | 三菱瓦斯化学株式会社 | Resin composition, prepreg, and laminate |
| US9706651B2 (en) | 2011-12-07 | 2017-07-11 | Mitsubishi Gas Chemical Company, Inc. | Resin composition, prepreg, and laminate |
| CN102702741A (en) * | 2012-06-12 | 2012-10-03 | 华东理工大学 | Cyanate ester based thermosetting resin and application thereof |
| CN110330445A (en) * | 2019-07-18 | 2019-10-15 | 扬州天启新材料股份有限公司 | A kind of triphenol A type cyanate and preparation method thereof |
| CN114805801A (en) * | 2022-06-08 | 2022-07-29 | 黑龙江省科学院石油化学研究院 | Cyanate ester resin with low hygroscopicity and preparation method thereof |
| CN114805801B (en) * | 2022-06-08 | 2023-07-25 | 黑龙江省科学院石油化学研究院 | Cyanate resin with low hygroscopicity and preparation method thereof |
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Application publication date: 20110119 |