CN108912068A - A kind of benzoxazine and preparation method thereof - Google Patents
A kind of benzoxazine and preparation method thereof Download PDFInfo
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- CN108912068A CN108912068A CN201810575066.1A CN201810575066A CN108912068A CN 108912068 A CN108912068 A CN 108912068A CN 201810575066 A CN201810575066 A CN 201810575066A CN 108912068 A CN108912068 A CN 108912068A
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- benzoxazine
- benzoxazine monomer
- monomer
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- GLBBMFNUETZTRQ-ZQTLJVIJSA-N CC(C)C1[F](C)[C@H](C)[C@@H]1C Chemical compound CC(C)C1[F](C)[C@H](C)[C@@H]1C GLBBMFNUETZTRQ-ZQTLJVIJSA-N 0.000 description 1
Classifications
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- 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
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
- C08G14/06—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols and monomers containing hydrogen attached to nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Benzoxazine colophony has wide practical use in fields such as copper-clad plate, laminate, refractory material, RTM, composite material, insulating materials, in the field for having special high request to dielectric properties, the Polybenzoxazine disadvantage not ideal enough there is also solidification temperature height, dielectric properties, the present invention is by introducing adamantane structure in benzoxazine colophony main chain, reduce benzoxazine colophony dielectric constant, further by introducing the phenol with electron-withdrawing group, system reactivity is improved.The resin is suitable for fields such as composite resin matrix, microelectronic packaging material and adhesive.
Description
Technical field
The present invention relates to a kind of benzoxazine monomers, resin and preparation method thereof, in particular to a kind of to have superior dielectric
The benzoxazine colophony of property.
Background technique
Benzoxazine colophony is the benzo hexa-member heterocycle using phenolic compound, primary amine compound and aldehyde as Material synthesis
Object -- benzoxazine monomer is raw material for conjunction, and benzoxazine monomer is formed by curing benzoxazine under the action of heating or catalyst
Resin.Compared with traditional phenolic resin, benzoxazine colophony has the advantages that many new, such as lower melting viscosity, is convenient for
Processing and forming；Strong acid catalyst is not needed, heat or its ring-opening polymerisation can be made using catalyst such as lewis acids；When polymerization without
Small molecule is released；Very little is shunk in polymerization process；It is heat-resist, glass transition temperature and thermal stability with higher；Tool
There are the comprehensive performances such as good mechanics, fire-retardant, and water absorption rate is extremely low；With flexible MOLECULE DESIGN etc..Thus Ben Bing Evil
Piperazine has wide practical use in fields such as copper-clad plate, laminate, refractory material, RTM, composite material, insulating materials.
As high-performance thermosetting resin, benzoxazine colophony application field is extensive, but has for some pairs of dielectric properties
How the field of special high request, the disadvantage that there is also solidification temperatures is high for benzoxazine, dielectric properties are not ideal enough etc., improve
Its comprehensive performance is to meet the emphasis that the application that more higher performances require is current Polybenzoxazine research.
Summary of the invention
In view of the deficiencies of the prior art, the present invention is by Molecular Design, provide a kind of high dielectric property, melt viscosity compared with
Low benzoxazine monomer and resin.
It furthers investigate by inventor, as a result, it has been found that adamantane monomer to be introduced to the main chain of benzoxazine, and has as follows
The benzoxazine colophony of structure has lower dielectric constant.The present invention provides a kind of benzoxazine comprising adamantane structure
Monomer has the following structure：
Wherein, R1、R2It may be the same or different, R1、R2ForOne of
Or two kinds, the integer that n is 0~7, when n is 0, nitrogen-atoms is directly connected on the C of adamantane ring, R3To be chosen as C atomicity
Measure one of the alkyl (including naphthenic base) for being 0~20, the aryl that C atomic quantity is 0~20, electron-withdrawing group or a variety of.
Further,The integer that middle n is 0~3.
Further, R3For electron-withdrawing group.
Further, R3For：Tertiary amine cation NR3, R is one or both of methyl, ethyl；Nitro NO2；Three halogen first
Base CX3, wherein X=F, Cl；Cyano CN；Sulfonic group SO3H；Formoxyl CHO；Acyl group COR, R are methyl, ethyl, n-propyl, isopropyl
One of base；One of carboxy CO OH or a variety of.Inventor is found through experiments that, by introducing adamantane structure, to anti-
It answers the reactivity of system to have an impact, works as R3Further preferably electron-withdrawing group when, can be improved benzoxazine colophony synthesis
Reactivity in the process reduces reaction cost so as to shorten the reaction time.
Further, R3For cyano, nitro, trihalomethyl CX3, wherein X=F, Cl.
The present invention also provides a kind of preparation methods of benzoxazine monomer, pass through diamine monomer, phenol containing adamantane structure
Class monomer, aldehyde monomers, by reacting realization as follows：
Wherein, R1、R2It may be the same or different, R1、R2ForOne of
Or two kinds, the integer that n is 0~7, when n is 0, nitrogen-atoms is directly connected on the C of adamantane ring；R3To be chosen as C atomicity
Measure one of the alkyl (including naphthenic base) for being 0~20, the aryl that C atomic quantity is 0~20, electron-withdrawing group or a variety of；
WhereinN=2~100.
Further,The integer that middle n is 0~3.
Further, R3For electron-withdrawing group.
Further, R3For：Tertiary amine cation NR3, R is one or both of methyl, ethyl；Nitro NO2；Three halogen first
Base CX3, wherein X=F, Cl；Cyano CN；Sulfonic group SO3H；Formoxyl CHO；Acyl group COR, R are methyl, ethyl, n-propyl, isopropyl
One of base；One of carboxy CO OH or a variety of.Inventor is found through experiments that, by introducing adamantane structure, to anti-
It answers the reactivity of system to have an impact, when R3 is more preferably electron-withdrawing group, benzoxazine colophony synthesis can be improved
Reactivity in the process reduces reaction cost so as to shorten the reaction time.
Further, R3For cyano, nitro, trihalomethyl CX3, wherein X=F, Cl.
Further, the molar ratio of reactant is：Diamines, phenol and aldehyde containing adamantane structure：(0.8~1.25)：
(1.6~2.5)：(0.1~2.5).
Further, reaction temperature is：0~100 DEG C.
Further, synthesis process solvent for use is：Toluene, dimethylbenzene, methyl phenyl ethers anisole, monochloro methane, methylene chloride, trichlorine
The mixture of one or more of methane, dioxane, tetrahydrofuran, methanol, ethyl alcohol, isopropanol, acetone, butanone etc..
Containing the benzoxazine of adamantane structure obtained by the present invention, can be used alone or with other kinds of Ben Bing Evil
Piperazine monomer or phenolic resin or epoxy resin or inorganic filler are used in mixed way.
The present invention also provides a kind of benzoxazine colophony, benzoxazine colophony is solidified to obtain by benzoxazine monomer, described
Contain above-mentioned at least one benzoxazine monomer in benzoxazine monomer.
Further, solidification temperature is 100~250 DEG C.
Adamantane structure, which is introduced into benzoxazine main chain, can reduce its dielectric constant, so that it is specific to assign benzoxazine colophony
Functionality, expand the application field of benzoxazine.Further by introducing there is the phenol of electron-withdrawing group reaction work can be improved
Property, reaction temperature is reduced, the reaction time is shortened.
Detailed description of the invention
Fig. 1 is the chemical equation of benzoxazine preparation method of the invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, the embodiments of the present invention are carried out below
Detailed elaboration.The given examples are served only to explain the present invention, is not intended to limit the scope of the present invention.
Embodiment 1
Be added in the there-necked flask of 500mL 100mL dioxane, 100mL butanone and 0.15molA1 (as follows) and
0.3mol is to carboxylic phenol, and controlled at 10 DEG C, 0.35mol formaldehyde is instilled in there-necked flask, after be warming up to 80 DEG C, and in this
At a temperature of react 8h, after cooling, reaction solution is poured into distilled water and is precipitated, filtered, washed, vacuum drying is obtained containing adamantane
The benzoxazine monomer of group.
Benzoxazine monomer is poured into mold, 160~250 DEG C stage curing, obtains benzoxazine colophony.
The glass transition temperature of the resin is：213 DEG C, melt viscosity (100 DEG C)：300mPa.s is kept at 100 DEG C
3h, the melt viscosity of resin are (100 DEG C)：350mPa.s；Dielectric constant 2.1.
Embodiment 2
The dioxane and 0.16mol A2 (as follows) and 0.3mol pairs of 200mL are added in the there-necked flask of 500mL
Trichloromethyl phenol, controlled at 30 DEG C hereinafter, 0.38mol formaldehyde is instilled in there-necked flask, after be warming up to 90 DEG C, and in this
At a temperature of react 6h, after cooling, reaction solution is poured into distilled water and is precipitated, filtered, washed, vacuum drying is obtained containing adamantane
The benzoxazine monomer of group.
Benzoxazine monomer is poured into mold, 140~220 DEG C stage curing, obtains benzoxazine colophony.
The glass transition temperature of the resin is：184 DEG C, melt viscosity (100 DEG C)：330mPa.s is kept at 100 DEG C
3h, the melt viscosity of resin are (100 DEG C)：400mPa.s；Dielectric constant 2.3.
Embodiment 3
The butanone and 0.18mol A3 (as follows) and 0.3mol that 200mL is added in the there-necked flask of 500mL are to nitro
Phenol, controlled at 30 DEG C hereinafter, 0.3mol formaldehyde is instilled in there-necked flask, after be warming up to 90 DEG C, and it is anti-at a temperature of this
8h is answered, after cooling, reaction solution is poured into distilled water and is precipitated, is filtered, is washed, vacuum drying obtains the benzene of the group containing adamantane
Bing oxazine monomer.
Benzoxazine monomer is poured into mold, 150~230 DEG C stage curing, obtains benzoxazine colophony.
The glass transition temperature of the resin is：209 DEG C, melt viscosity (100 DEG C)：280mPa.s is kept at 100 DEG C
3h, the melt viscosity of resin are (100 DEG C)：340mPa.s；Dielectric constant 2.1.
Embodiment 4
Be added in the there-necked flask of 500mL 100mL dioxane, 100mL butanone and 0.15mol p-phenylenediamine and
0.3mol is to carboxylic phenol, and controlled at 10 DEG C, 0.35mol formaldehyde is instilled in there-necked flask, after be warming up to 80 DEG C, and in this
At a temperature of react 8h, after cooling, reaction solution is poured into distilled water and is precipitated, filter, wash, vacuum drying, obtain benzoxazine
Monomer.
Benzoxazine monomer is poured into mold, 160~250 DEG C stage curing, obtains benzoxazine colophony.
The glass transition temperature of the resin is：160℃；Melt viscosity (100 DEG C)：290mPa.s is kept at 100 DEG C
3h, the melt viscosity of resin are (100 DEG C)：381mPa.s；Dielectric constant 3.5.
The above embodiments merely illustrate the technical concept and features of the present invention, it will be understood by those skilled in the art that
The respective embodiments described above are realization specific embodiments of the present invention, and in practical applications, it can be right in the form and details
Various changes can be made for it, without departing from the spirit and scope of the present invention.
Claims (10)
1. a kind of benzoxazine monomer comprising adamantane structure, it is characterised in that have the following structure：
Wherein, R1、R2It may be the same or different, R1、R2ForOne of or two
Kind, the integer that n is 0~7, when n is 0, nitrogen-atoms is directly connected on the C of adamantane ring, R3It is 0~20 for C atomic quantity
One of alkyl (including naphthenic base), the aryl that C atomic quantity is 0~20, electron-withdrawing group are a variety of.
2. benzoxazine monomer as described in claim 1, which is characterized in thatThe integer that middle n is 0~3.
3. benzoxazine monomer as described in claim 1, which is characterized in that R3For electron-withdrawing group.
4. benzoxazine monomer as described in claim 1, which is characterized in that R3For：Tertiary amine cation NR3, R is methyl, ethyl
One or both of；Nitro NO2；Trihalomethyl CX3, wherein X=F, Cl；Cyano CN；Sulfonic group SO3H；Formoxyl CHO；Acyl
Base COR, R are one of methyl, ethyl, n-propyl, isopropyl；One of carboxy CO OH or a variety of.
5. benzoxazine monomer as described in claim 1, which is characterized in that R3For cyano, nitro, trihalomethyl CX3, wherein X
=F, Cl.
6. a kind of preparation method of benzoxazine monomer, which is characterized in that pass through diamine monomer, phenols list containing adamantane structure
Body, aldehyde monomers, by reacting realization as follows：
Wherein, R1、R2It may be the same or different, R1、R2ForOne of or two
Kind, the integer that n is 0~7, when n is 0, nitrogen-atoms is directly connected on the C of adamantane ring；R3It is 0 to be chosen as C atomic quantity
One of~20 alkyl (including naphthenic base), the aryl that C atomic quantity is 0~20, electron-withdrawing group are a variety of；WhereinN=2~100.
7. the preparation method of benzoxazine monomer as claimed in claim 6, which is characterized in thatMiddle n is 0~3
Integer.
8. the preparation method of benzoxazine monomer as claimed in claim 6, which is characterized in that R3For：Tertiary amine cation NR3, R
For one or both of methyl, ethyl；Nitro NO2；Trihalomethyl CX3, wherein X=F, Cl；Cyano CN；Sulfonic group SO3H；First
Acyl group CHO；Acyl group COR, R are one of methyl, ethyl, n-propyl, isopropyl；One of carboxy CO OH or a variety of.
9. the molar ratio of the preparation method of benzoxazine monomer as claimed in claim 6, reactant is：Knot containing adamantane
The diamine monomer of structure：Phenolic monomers：Aldehyde monomers=(0.8~1.25)：(1.6~2.5)：(0.1~2.5).
10. a kind of benzoxazine colophony is solidified to obtain by benzoxazine monomer, which is characterized in that in the benzoxazine monomer
Contain one of benzoxazine monomer as described in claim 1-5 or a variety of.
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| CN201810575066.1A CN108912068B (en) | 2018-06-06 | 2018-06-06 | Benzoxazine and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713691A (en) * | 2019-09-19 | 2020-01-21 | 长沙新材料产业研究院有限公司 | Benzoxazine and preparation method thereof |
| CN112778292A (en) * | 2020-12-25 | 2021-05-11 | 长沙新材料产业研究院有限公司 | Benzoxazine compound and preparation method thereof |
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| JP2004123742A (en) * | 2002-10-03 | 2004-04-22 | Choshun Jinzo Jushisho Kofun Yugenkoshi | Method for manufacturing benzoxazine compound |
| CN101128514A (en) * | 2004-12-28 | 2008-02-20 | 住友电木株式会社 | Benzoxazole resin precursor, polybenzoxazole resin, resin film and semiconductor device |
| CN101265322A (en) * | 2008-05-08 | 2008-09-17 | 山东大学 | Cyano-containing benzoxazine intermediate and resin thereof |
| US9631053B1 (en) * | 2015-11-24 | 2017-04-25 | National Chung Shan Institute Of Science And Technology | Polymeric benzoxazine resin structure with adamantane-containing main chain |
| CN107522831A (en) * | 2017-09-29 | 2017-12-29 | 西南石油大学 | A kind of containing silicon benzoxazine of the low dielectric of novel fire resistant and preparation method thereof |
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2018
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Patent Citations (5)
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| JP2004123742A (en) * | 2002-10-03 | 2004-04-22 | Choshun Jinzo Jushisho Kofun Yugenkoshi | Method for manufacturing benzoxazine compound |
| CN101128514A (en) * | 2004-12-28 | 2008-02-20 | 住友电木株式会社 | Benzoxazole resin precursor, polybenzoxazole resin, resin film and semiconductor device |
| CN101265322A (en) * | 2008-05-08 | 2008-09-17 | 山东大学 | Cyano-containing benzoxazine intermediate and resin thereof |
| US9631053B1 (en) * | 2015-11-24 | 2017-04-25 | National Chung Shan Institute Of Science And Technology | Polymeric benzoxazine resin structure with adamantane-containing main chain |
| CN107522831A (en) * | 2017-09-29 | 2017-12-29 | 西南石油大学 | A kind of containing silicon benzoxazine of the low dielectric of novel fire resistant and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110713691A (en) * | 2019-09-19 | 2020-01-21 | 长沙新材料产业研究院有限公司 | Benzoxazine and preparation method thereof |
| CN110713691B (en) * | 2019-09-19 | 2022-10-21 | 航天科工(长沙)新材料研究院有限公司 | Benzoxazine and preparation method thereof |
| CN112778292A (en) * | 2020-12-25 | 2021-05-11 | 长沙新材料产业研究院有限公司 | Benzoxazine compound and preparation method thereof |
| CN112778292B (en) * | 2020-12-25 | 2022-09-02 | 长沙新材料产业研究院有限公司 | Benzoxazine compound and preparation method thereof |
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Address after: 410205 East of the first floor, 2nd floor, 7th floor, 8th floor, Building B8, Luguyuyuan, No. 27 Wenxuan Road, Changsha High-tech Development Zone, Changsha, Hunan Province Patentee after: Aerospace Science and Industry (Changsha) New Materials Research Institute Co.,Ltd. Address before: 410205 7th floor, building B8, Lugu Enterprise Square, Yuelu District, Changsha City, Hunan Province Patentee before: CHANGSHA ADVANCED MATERIALS INDUSTRIAL RESEARCH INSTITUTE Co.,Ltd. |
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