WO2013056428A1 - 苯并噁嗪中间体及其制备方法 - Google Patents
苯并噁嗪中间体及其制备方法 Download PDFInfo
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- WO2013056428A1 WO2013056428A1 PCT/CN2011/080950 CN2011080950W WO2013056428A1 WO 2013056428 A1 WO2013056428 A1 WO 2013056428A1 CN 2011080950 W CN2011080950 W CN 2011080950W WO 2013056428 A1 WO2013056428 A1 WO 2013056428A1
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- carbon atoms
- derivative
- benzoxazine intermediate
- derivatives
- formula
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- 0 *N1COc2c(cc(cc3)Oc4cc(c(OCN(*)C5)c5cc5)c5cc4)c3ccc2C1 Chemical compound *N1COc2c(cc(cc3)Oc4cc(c(OCN(*)C5)c5cc5)c5cc4)c3ccc2C1 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
Definitions
- the present invention relates to a benzoxazine intermediate, and more particularly to a benzoxazine intermediate and a process for the preparation thereof. Background technique
- Benzooxazine is a benzoxazine intermediate obtained by a ring-forming reaction of a primary amine, a phenol or an aldehyde on the basis of a conventional method for preparing a phenolic resin. Under heating or a catalyst, the benzoxazine is opened and formed.
- a new type of thermosetting resin with a network structure, the cured product has good heat resistance, flame retardancy and electrical properties.
- the aldehydes used in the hydrazine include aqueous furfural and polyfurfural;
- the amines include aromatic, alkyl primary amines, alicyclic primary amines;
- phenols are mainly monophenolic compounds, bisphenols a compound, a trisphenol compound, a polyfunctional phenol, a phenol resin, a p-hydroxystyrene, a polymer or a copolymer thereof, but no phenol represented by the formula (2) is used as a phenol source to prepare a benzoxazine intermediate.
- 4 channels are mainly monophenolic compounds, bisphenols a compound, a trisphenol compound, a polyfunctional phenol, a phenol resin, a p-hydroxystyrene, a polymer or a copolymer thereof, but no phenol represented by the formula (2) is used as a phenol source to prepare a benzoxazine intermediate. 4 channels:
- An object of the present invention is to provide a benzoxazine intermediate which contains a naphthalene ring structure segment which has excellent high temperature resistance and flame retardancy and can be widely used in composite materials.
- Another object of the present invention is to provide a method for preparing a benzoxazine intermediate, which comprises using a compound represented by formula (2) as a phenol source, and preparing a benzene having a structure of formula (2) with a primary amine or an aldehyde. And an oxazine intermediate, simple and easy to operate.
- R 2 is an alicyclic hydrocarbon having 3 to 20 carbon atoms and a derivative thereof, an aliphatic hydrocarbon having 1 to 20 carbon atoms and a derivative thereof, or a carbon number of 2 to 20 Unsaturated aliphatic hydrocarbons and their derivatives.
- the present invention provides a preparation method using the above benzoxazine intermediate, which comprises the steps as follows:
- Step 1 The molar ratio of phenol, primary amine and aldehyde to phenolic hydroxyl group, amine group and acid group is 1: (0.8-1.2): (1.5-2.5), and the amount of catalyst added is 0.1-5% of the total amount. ;
- Step 2 Mixing phenol, primary amine and aldehyde, adding catalyst to adjust pH to 8-10, and heating to reflux reaction for 1-8 hours to complete the reaction;
- Step 3 Washing with deionized water, concentrating the obtained solution, purifying and drying to obtain a benzoxazine intermediate; the structural formula of the obtained benzoxazine intermediate is as follows:
- R 2 is an alicyclic hydrocarbon having 3 to 20 carbon atoms and a derivative thereof, an aliphatic hydrocarbon having 1 to 20 carbon atoms and a derivative thereof, or a carbon number of 2 to 20 Unsaturated aliphatic hydrocarbons and their derivatives.
- the catalyst is added in an amount of from 0.1 to 5% by total.
- C 0, S, S0 2 , an alicyclic hydrocarbon having 3 to 20 carbon atoms and a derivative thereof, an aliphatic hydrocarbon having 1 to 20 carbon atoms and a derivative thereof, or a carbon number of 2 ⁇ 20 unsaturated aliphatic hydrocarbons and derivatives thereof.
- the primary amine is: NH 2 R 2 , wherein R 2 is an alicyclic hydrocarbon having 3 to 20 carbon atoms and a derivative thereof, an aliphatic hydrocarbon having 1 to 20 carbon atoms and a derivative thereof or a carbon number of 2 to 20 Unsaturated aliphatic hydrocarbons and their derivatives.
- the primary amine is allylamine, aniline, cyclopropylamine, decylamine, or ethylamine.
- the aldehyde is an aqueous solution of furfural or polyfurfural.
- the catalyst is: aqueous KOH solution, aqueous NaOH solution, aqueous ammonia, triethanolamine, or triethylamine.
- the benzoxazine intermediate is prepared by a solution synthesis method or a melt synthesis method.
- the solvent is: ⁇ Benzene, diphenylbenzene, ethanol, acetone, butanone, decyl isobutyl ketone, ethylene glycol monoterpene ether, ethylene glycol ether, ethylene glycol monoterpene ether, ethylene glycol oxime ether acetate, mercapto amide
- One or more intercomplexes in tetrahydrofuran is prepared by a solution synthesis method or a melt synthesis method.
- the benzoxazine intermediate of the present invention is prepared by using a phenol represented by the formula (2) as a phenol source, and preparing a benzoxazine intermediate with a primary amine or an aldehyde, and containing a naphthalene ring structure fragment. Therefore, it has excellent high temperature resistance and flame retardant properties, and can be widely used in composite materials; the preparation method is simple and easy to operate. detailed description
- the invention provides a benzoxazine intermediate, which has the following structural formula:
- R 2 is an alicyclic hydrocarbon having 3 to 20 carbon atoms and a derivative thereof, an aliphatic hydrocarbon having 1 to 20 carbon atoms and a derivative thereof, or a carbon number of 2 to 20 Unsaturated aliphatic hydrocarbons and their derivatives.
- Step 1 the phenol, primary amine, aldehyde according to the phenolic hydroxyl group, the amine group, the acid group functional group molar ratio of 1: (0.8-1.2): (1.5-2.5) quantitative; the structural formula of the phenol is as follows:
- the primary amine is: NH 2 R 2 , wherein R 2 is an alicyclic hydrocarbon having 3 to 20 carbon atoms and a derivative thereof, an aliphatic hydrocarbon having 1 to 20 carbon atoms and a derivative thereof or a carbon number of 2 to 20
- the unsaturated aliphatic hydrocarbons and derivatives thereof are, for example, allylamine, aniline, cyclopropylamine, decylamine, or ethylamine.
- the aldehyde is an aqueous solution of furfural (formalin) or polyfurfural.
- Step 2 adding phenol, primary amine and aldehyde to the solvent, adding a catalyst to adjust the pH to 8-10, adding the catalyst to the total amount of 0.1-5%, and heating the reflux reaction for 1-8 hours to complete the reaction;
- the catalyst is : KOH aqueous solution, aqueous NaOH solution, ammonia water, triethanolamine, or triethylamine; solvent: toluene, diphenylbenzene, ethanol, acetone, butanone, mercaptoisobutylketone, ethylene glycol monoterpene ether, ethylene glycol
- solvent toluene, diphenylbenzene, ethanol, acetone, butanone, mercaptoisobutylketone, ethylene glycol monoterpene ether, ethylene glycol
- Step 3 Washing with deionized water, concentrating the resulting solution, removing the residual solvent, purifying and drying to obtain a benzoxazine intermediate.
- Another method for preparing the benzoxazine intermediate is a solventless melt synthesis method comprising the following steps:
- Step ⁇ the phenol, primary amine, aldehyde according to the phenolic hydroxyl group, the amine group, the aldehyde group functional group molar ratio of 1: (0.8-1.2): (1.5-2.5) quantitative; the structural formula of the phenol is as follows:
- the primary amine is: NH 2 R 2 , wherein R 2 is an alicyclic hydrocarbon having 3 to 20 carbon atoms and a derivative thereof, an aliphatic hydrocarbon having 1 to 20 carbon atoms and a derivative thereof or a carbon number of 2 to 20
- the unsaturated aliphatic hydrocarbons and derivatives thereof are, for example, allylamine, aniline, cyclopropylamine, decylamine, or ethylamine.
- the aldehyde is an aqueous solution of furfural (formalin) or polyfurfural.
- Step 2 mixing phenol, primary amine and aldehyde, adding a catalyst to adjust the pH to 8-10, adding the catalyst to the total amount of 0.1-5%, and heating the reflux reaction for l-8 hr to terminate the reaction.
- the catalyst is: aqueous KOH solution, aqueous NaOH solution, aqueous ammonia, triethanolamine, or triethylamine.
- Step 3 washing with deionized water, concentrating the resulting solution, purifying and drying to obtain a benzoxazine intermediate.
- Example 1 The embodiments of the present invention are described in detail below, but the present invention is not limited to the scope of the embodiments.
- Example 1
- the phenol is dissolved in absolute ethanol at room temperature to adjust the pH to 8-10, and the molar ratio of phenolic hydroxyl group, amine group and aldehyde functional group is 1: 1.2: 2.5, and toluene, aniline and polyfurfural are added. After stirring uniformly, the mixture was heated to reflux. After reacting for 4 hours, ethanol, water and toluene were distilled off under reduced pressure, and the apparatus was cooled to obtain a pale yellow translucent viscous body. After washing, purification and drying, a benzoxazine intermediate was obtained. ,
- Phenol, allylamine and polyfurfural were added at a molar ratio of phenolic hydroxyl group, amine group, acid group functional group of 1: 1 : 2 at room temperature. After stirring uniformly, the temperature is raised to a molten state. After reacting for 4 hours, the apparatus is cooled to obtain a pale yellow translucent viscous body. After washing, purification, and drying, benzene is obtained.
- Phenol, cyclohexylamine and polyfurfural were added at a molar ratio of phenolic hydroxyl group, amine group, acid group functional group of 1: 1: 2 at room temperature. After stirring, the mixture was heated to reflux. After reacting for 4 hours, the apparatus was cooled to obtain a pale yellow translucent viscous body. After washing, purification and drying, a benzoxazine intermediate was obtained in a yield of 80.6%.
- the structural formula of the obtained benzoxazine intermediate is as follows:
- Phenol, aniline and polyfurfural were added at room temperature with a molar ratio of phenolic hydroxyl group, amine group and acid group functional group of 1: 1:2. After stirring, the mixture was heated to reflux. After 4 hours of reaction, the apparatus was cooled to obtain a pale yellow translucent viscous body. After washing, purification, and drying, the benzoxazine was obtained as follows:
- the benzoxazine intermediate of the present invention is prepared by using a phenol as shown in formula (2) as a phenol source, a benzoxazine intermediate prepared from a primary amine or an aldehyde, and a naphthalene ring structure fragment. Therefore, it has excellent high temperature resistance and flame retardant properties, and can be widely used in composite materials; the preparation method is simple and easy to operate. .
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11874158.6A EP2769975B1 (en) | 2011-10-18 | 2011-10-18 | Benzoxazine intermediate and preparation method thereof |
US14/235,374 US9062011B2 (en) | 2011-10-18 | 2011-10-18 | Benzoxazine intermediate and preparation method thereof |
PCT/CN2011/080950 WO2013056428A1 (zh) | 2011-10-18 | 2011-10-18 | 苯并噁嗪中间体及其制备方法 |
KR1020147004405A KR101579387B1 (ko) | 2011-10-18 | 2011-10-18 | 벤족사진 중간체 및 이를 제조하는 방법 |
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PCT/CN2011/080950 WO2013056428A1 (zh) | 2011-10-18 | 2011-10-18 | 苯并噁嗪中间体及其制备方法 |
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WO2013056428A1 true WO2013056428A1 (zh) | 2013-04-25 |
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US (1) | US9062011B2 (zh) |
EP (1) | EP2769975B1 (zh) |
KR (1) | KR101579387B1 (zh) |
WO (1) | WO2013056428A1 (zh) |
Families Citing this family (4)
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US10266504B2 (en) | 2014-06-30 | 2019-04-23 | Kolon Industries, Inc. | Polybenzoxazine precursor and method for preparing same |
WO2016003167A1 (ko) * | 2014-06-30 | 2016-01-07 | 코오롱인더스트리 주식회사 | 폴리벤족사진 전구체 및 그 제조방법 |
CN108997574A (zh) * | 2018-08-22 | 2018-12-14 | 西南石油大学 | 一种通过苯并噁嗪与异腈共聚制备聚酰胺类衍生物的方法 |
CN109265633B (zh) * | 2018-08-28 | 2021-02-02 | 广西师范学院 | 木质素型苯并噁嗪及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1900068A (zh) * | 2006-07-04 | 2007-01-24 | 电子科技大学 | 苯并噁嗪树脂中间体、树脂、固化物及其制备方法和用途 |
CN101235131A (zh) * | 2008-02-27 | 2008-08-06 | 山东大学 | 含炔丙基醚的新型苯并噁嗪中间体及其树脂的制备方法 |
US20090240006A1 (en) * | 2008-03-24 | 2009-09-24 | Case Western Reserve University | Novel naphthoxazine composition |
CN102516194A (zh) * | 2011-10-18 | 2012-06-27 | 广东生益科技股份有限公司 | 苯并噁嗪中间体及其制备方法 |
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TWI295288B (en) | 2006-08-17 | 2008-04-01 | Univ Nat Chunghsing | New route for the synthesis of benzoxazine |
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- 2011-10-18 EP EP11874158.6A patent/EP2769975B1/en active Active
- 2011-10-18 WO PCT/CN2011/080950 patent/WO2013056428A1/zh active Application Filing
- 2011-10-18 KR KR1020147004405A patent/KR101579387B1/ko active IP Right Grant
- 2011-10-18 US US14/235,374 patent/US9062011B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1900068A (zh) * | 2006-07-04 | 2007-01-24 | 电子科技大学 | 苯并噁嗪树脂中间体、树脂、固化物及其制备方法和用途 |
CN101235131A (zh) * | 2008-02-27 | 2008-08-06 | 山东大学 | 含炔丙基醚的新型苯并噁嗪中间体及其树脂的制备方法 |
US20090240006A1 (en) * | 2008-03-24 | 2009-09-24 | Case Western Reserve University | Novel naphthoxazine composition |
CN102516194A (zh) * | 2011-10-18 | 2012-06-27 | 广东生益科技股份有限公司 | 苯并噁嗪中间体及其制备方法 |
Also Published As
Publication number | Publication date |
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EP2769975B1 (en) | 2017-05-31 |
KR20140067006A (ko) | 2014-06-03 |
KR101579387B1 (ko) | 2015-12-21 |
EP2769975A4 (en) | 2015-04-15 |
US20140206864A1 (en) | 2014-07-24 |
EP2769975A1 (en) | 2014-08-27 |
US9062011B2 (en) | 2015-06-23 |
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