CN107840934A - A kind of alkynyl-modified benzoxazine colophony and preparation method thereof - Google Patents
A kind of alkynyl-modified benzoxazine colophony and preparation method thereof Download PDFInfo
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- CN107840934A CN107840934A CN201711147950.7A CN201711147950A CN107840934A CN 107840934 A CN107840934 A CN 107840934A CN 201711147950 A CN201711147950 A CN 201711147950A CN 107840934 A CN107840934 A CN 107840934A
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- Prior art keywords
- alkynyl
- preparation
- benzoxazine colophony
- benzoxazine
- modified
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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
- C08G14/12—Chemically modified polycondensates
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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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention provides a kind of alkynyl-modified benzoxazine colophony and preparation method thereof, the molecular formula with following structure：Benzoxazine containing alkynyl prepared by the present invention, alkynes benzoxazine is crosslinked while solidification Guo Cheng Zhong oxazine rings are in open loop with alkynyl, it is more stable, alkynyl benzoxazine colophony also has higher temperature in use, glass transition temperature is higher than the similar resin without alkynyl, and glass transition temperature is 350 450 DEG C；Residual carbon is high, has preferable processing characteristics.
Description
Technical field
The present invention relates to a kind of thermosetting resin and its manufacture method, more particularly to a kind of alkynyl-modified benzoxazine tree
Fat and preparation method thereof.
Background technology
Benzoxazine is a kind of new thermosetting resin, can be polymerize by thermal induction ring-opening reaction.Ben Bing Evil
Piperazine has the advantages of many unique, such as cure shrinkage is small, and no coupling product generates during solidification, and water imbibition is low.Due to these advantages,
Benzoxazine has been a great concern in recent years.Benzoxazine can be closed by phenolic compound, primary amine and paraformaldehyde
Into because the species of raw material is various, benzoxazine has considerable MOLECULE DESIGN flexibility.
The report that Dui benzoxazines are modified has been studied, such as Chinese patent《Aromatic diamines type benzoxazine colophony containing alkynyl
And preparation method thereof》(publication number CN102516537B) discloses the preparation method of the benzoxazine colophony containing alkynyl, but operates
Step is relatively complicated, and reaction condition is more harsh；Chinese patent《A kind of bisphenol-A-bi-benzoxazine containing double DOPO and its
The preparation method of polymer》(publication number:CN106928279A a kind of bisphenol-A-bi-benzoxazine containing double DOPO) is disclosed
Preparation method, main purpose are the fire resistance for improving resin；It is but up to the present, also no to be directed to bisphenol-f type Ben Bing Evil
Piperazine resin carries out the relevant report of alkynyl modification.
The defects of existing in view of above-mentioned existing benzoxazine monomer, the present inventor are based on being engaged in such product design system
Abundant for many years practical experience and professional knowledge are made, and coordinates the utilization of scientific principle, is actively subject to research and innovation, to found one kind
Alkynyl-modified benzoxazine colophony and preparation method thereof, it is set to have more practicality.By constantly research, design, and pass through
After studying sample repeatedly and improving, the present invention having practical value is created finally.
The content of the invention
The invention provides a kind of alkynyl-modified benzoxazine colophony and preparation method thereof, improves benzoxazine colophony glass
Glass transition temperature.
The present invention is realized using following scheme：
Alkynyl-modified benzoxazine colophony proposed by the present invention, there is the molecular formula of following structure：
As preferable, alkynyl-modified benzoxazine colophony, glass transition temperature is 350-450 DEG C.
The preparation method of alkynyl-modified benzoxazine colophony, including following operating procedure：
Step 1, benzoxazine, its reaction equation are synthesized with solventless method with Bisphenol F, to acetylenylaniline and paraformaldehyde
It is shown below：
Step 2, reacted with the benzoxazine of gained in step 1 with 3- propargyl bromides, reaction is as follows：
Reactant is filtered, filtrate is poured into cold water, is precipitated, precipitation is filtered out and is dried in vacuo；
Step 3, gained solid in step 2 is warming up to 180 DEG C~280 DEG C 0.5~5h of solidification, obtains target product.
As the preparation method of preferable, alkynyl-modified benzoxazine colophony, Bisphenol F in the step 1, to acetylene
The mol ratio of base aniline and paraformaldehyde is 0.5~1.5：1~3：3~4.4.Formaldehyde is easily decomposed, it is necessary to appropriate excessive, at this
Material can react to greatest extent in proportion.
As the preparation method of preferable, alkynyl-modified benzoxazine colophony, the step 1 reaction is solvent-free
Under the conditions of carry out, reaction temperature be 60-120 DEG C, reaction time 1-5h.
As the preparation method of preferable, alkynyl-modified benzoxazine colophony, benzoxazine in the step 2,3- bromines
The mol ratio of propine and calcium carbonate is 1~5：1~6：1.2~6.8.The effect of calcium carbonate be neutralization reaction generation acid, it is necessary to
It is appropriate excessive.
As the preparation method of preferable, alkynyl-modified benzoxazine colophony, solvent, solvent are used in the step 2
For dimethylformamide or dimethyl acetamide.
As the preparation method of preferable, alkynyl-modified benzoxazine colophony, the step 2 reaction temperature be 60~
100 DEG C, the reaction time is 18~30h, pours into reaction solution in deionized water after reaction, and the precipitation of precipitation is washed, and is dried, i.e.,
Obtain target product.
As the preparation method of preferable, alkynyl-modified benzoxazine colophony, the step 2 uses Carbon Dioxide calcium,
Solvent is removed water with molecular sieve.
The beneficial functional of the present invention is：
Benzoxazine containing alkynyl prepared by the present invention, the presence of alkynyl can make the heat endurance of benzoxazine colophony
It can improve, benzoxazine is crosslinked while solidification Guo Cheng Zhong oxazine rings are in open loop with alkynyl, more stable, alkynyl
Benzoxazine colophony also has higher temperature in use, and glass transition temperature is higher than the similar resin without alkynyl, glass
It is 350-450 DEG C to change transition temperature.The presence of alkynyl can also reduce the solidification temperature of benzoxazine.In addition, alkynyl contains nitrogen
Element, the nitrogen content of benzoxazine solidfied material can be improved, so as to improve the anti-flammability of resin system.And the preparation of the present invention
Method operating method is relatively simple, requires not harsh to reaction condition, easily realizes, the yield of product is also higher.
Brief description of the drawings
Fig. 1 is the DMA curve maps of material after the solidification of the gained benzoxazine colophony of embodiment 1.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Concrete operation step：
The preparation method of the alkynyl-modified benzoxazine colophony of the present invention, in step 1, by Bisphenol F, to acetylenylaniline,
Paraformaldehyde is mixed in molar ratio, is added in flask, the stirring reaction in oil bath pan, and temperature is carried out after slowly being raised from room temperature
Reaction.
In step 2, by benzoxazine and 3- propargyl bromides, potassium carbonate is put into flask, is reacted in a heated condition, will be anti-
The mixture filtering that should be obtained, filtrate is poured into a large amount of cold water, dries, is produced in vacuum drying chamber after precipitation is filtered
Thing.
Embodiment 1
By 3.5g Bisphenol Fs, 4.095g is added in three-necked flask to acetylenylaniline, 2.310g paraformaldehydes, connects condensation
Pipe and agitating device, temperature is slowly raised to 110 DEG C, reacts 0.5 hour, reactant is taken out, obtains 7.862g benzoxazines
Solid.
By 2g benzoxazines, 0.505g 3- propargyl bromides, 0.683g Anhydrous potassium carbonates are placed in three-necked flask, add 30ml
Dimethylformamide, flask is placed in oil bath pan and stirred, reacted 24h at 80 DEG C, reacted product is filtered, filtrate is fallen
Enter in substantial amounts of water, solid product is filtered out, and wash several times, be placed in drying for one day in vacuum drying chamber, obtain 2.510g
Product.
After the resin is cured, the DMA curve maps that resulting materials measure are as shown in Figure 1.It can be seen that the tree
The glass transition temperature of fat material is up to 390 DEG C.
Embodiment 2
By 3.5g Bisphenol Fs, 4.095g is added in three-necked flask to acetylenylaniline, 2.310g paraformaldehydes, connects condensation
Pipe and agitating device, temperature is slowly raised to 90 DEG C, reacts 2 hours, reactant is taken out, 7.005g benzoxazines is obtained and consolidates
Body.
By 2g benzoxazines, 0.505g 3- propargyl bromides, 0.683g Anhydrous potassium carbonates are placed in three-necked flask, add 30ml
Dimethyl acetamide, flask is placed in oil bath pan and stirred, reacted 24h at 80 DEG C, reacted product is filtered, filtrate is fallen
Enter in substantial amounts of water, solid product is filtered out, and wash several times, be placed in drying for one day in vacuum drying chamber, obtain 2.443g
Product.Benzoxazine is crosslinked while solidification Guo Cheng Zhong oxazine rings are in open loop with alkynyl, more stable, is had good
Good heat resistance.
Embodiment 3
By 2.5g Bisphenol Fs, 2.925g is added in three-necked flask to acetylenylaniline, 1.650g paraformaldehydes, connects condensation
Pipe and agitating device, temperature is slowly raised to 110 DEG C, reacts 6 hours, reactant is taken out, 4.870g benzoxazines is obtained and consolidates
Body.
By 1g benzoxazines, 0.252g3- propargyl bromides, 0.341g Anhydrous potassium carbonates are placed in three-necked flask, add 30ml bis-
Methylacetamide, flask is placed in oil bath pan and stirred, reacted 24h at 80 DEG C, reacted product is filtered, filtrate is poured into
In substantial amounts of water, solid product is filtered out, and washed several times, is placed in drying for one day in vacuum drying chamber, obtains 1.168g productions
Thing.The resin Residual carbon of preparation is high, has preferable processing characteristics.
Embodiment 4
By 2.5g Bisphenol Fs, 2.925g is added in three-necked flask to acetylenylaniline, 1.650g paraformaldehydes, connects condensation
Pipe and agitating device, temperature is slowly raised to 90 DEG C, reacts 6 hours, reactant is taken out, 3.962g benzoxazines is obtained and consolidates
Body.
By 1g benzoxazines, 0.252g 3- propargyl bromides, 0.341g Anhydrous potassium carbonates are placed in three-necked flask, add 20ml
Dimethylformamide, flask is placed in oil bath pan and stirred, reacted 24h at 80 DEG C, reacted product is filtered, filtrate is fallen
Enter in substantial amounts of water, solid product is filtered out, and wash several times, be placed in drying for one day in vacuum drying chamber, obtain 1.236g
Product.
The benzoxazine monomer containing alkynyl prepared using the method for the present invention, yield is up to more than 79%, and has
Higher glass transition temperature, processing characteristics are excellent.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (9)
- A kind of 1. alkynyl-modified benzoxazine colophony, it is characterised in that：Molecular formula with following structure：
- 2. alkynyl-modified benzoxazine colophony according to claim 1, it is characterised in that：Glass transition temperature is 350-450℃。
- 3. the preparation method of alkynyl-modified benzoxazine colophony according to claim 1 or 2, it is characterised in that：Including Following operating procedure：Step 1, benzoxazine is synthesized with solventless method with Bisphenol F, to acetylenylaniline and paraformaldehyde, its reaction equation is as follows Shown in formula：Step 2, reacted with the benzoxazine of gained in step 1 with 3- propargyl bromides, reaction is as follows：Reactant is filtered, filtrate is poured into cold water, is precipitated, precipitation is filtered out and is dried in vacuo；Step 3, gained solid in step 2 is warming up to 180 DEG C~280 DEG C 0.5~5h of solidification, obtains target product.
- 4. the preparation method of alkynyl-modified benzoxazine colophony according to claim 3, it is characterised in that：The step Bisphenol F in one, it is 0.5~1.5 to the mol ratio of acetylenylaniline and paraformaldehyde：1~3：3~4.4.
- 5. the preparation method of alkynyl-modified benzoxazine colophony according to claim 4, it is characterised in that：The step One reaction is carried out in the absence of a solvent, and reaction temperature is 60-120 DEG C, reaction time 1-5h.
- 6. the preparation method of alkynyl-modified benzoxazine colophony according to claim 3, it is characterised in that：The step The mol ratio of benzoxazine in two, 3- propargyl bromides and calcium carbonate is 1~5：1~6：1.2~6.8.
- 7. the preparation method of alkynyl-modified benzoxazine colophony according to claim 6, it is characterised in that：The step Solvent is used in two, solvent is dimethylformamide or dimethyl acetamide.
- 8. the preparation method of alkynyl-modified benzoxazine colophony according to claim 3, it is characterised in that：The step Two reaction temperatures are 60~100 DEG C, and the reaction time is 18~30h.
- 9. the preparation method of alkynyl-modified benzoxazine colophony according to claim 3, it is characterised in that：The step Two use Carbon Dioxide calcium, and solvent is removed water with molecular sieve.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711147950.7A CN107840934A (en) | 2017-11-17 | 2017-11-17 | A kind of alkynyl-modified benzoxazine colophony and preparation method thereof |
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| CN201711147950.7A CN107840934A (en) | 2017-11-17 | 2017-11-17 | A kind of alkynyl-modified benzoxazine colophony and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818868A (en) * | 2019-11-29 | 2020-02-21 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric-property main chain benzoxazine copolymer oligomer, copolymer resin and preparation method thereof |
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| US5543516A (en) * | 1994-05-18 | 1996-08-06 | Edison Polymer Innovation Corporation | Process for preparation of benzoxazine compounds in solventless systems |
| US20070191555A1 (en) * | 2004-03-30 | 2007-08-16 | Hatsuo Ishida | Thermosetting resin composition and its article |
| US8802846B1 (en) * | 2013-04-22 | 2014-08-12 | Chung Shan Institute Of Science And Technology, Armaments Bureau, M.N.D | Preparation and application of propargyl ether-containing benzoxazine with high-TG characteristic |
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2017
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| US5543516A (en) * | 1994-05-18 | 1996-08-06 | Edison Polymer Innovation Corporation | Process for preparation of benzoxazine compounds in solventless systems |
| US20070191555A1 (en) * | 2004-03-30 | 2007-08-16 | Hatsuo Ishida | Thermosetting resin composition and its article |
| US8802846B1 (en) * | 2013-04-22 | 2014-08-12 | Chung Shan Institute Of Science And Technology, Armaments Bureau, M.N.D | Preparation and application of propargyl ether-containing benzoxazine with high-TG characteristic |
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|---|
| VERNON M. RUSSELL ET AL.: ""Study of the Characterization and Curing of a Phenyl Benzoxazine Using 15N Solid-State Nuclear Magnetic Resonance Spectroscopy"", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| XIN NLNG ET AL.: ""Phenolic Materials via Ring- Opening Polymerization of Benzoxazines: Effect of Molecular Structure on Mechanical and Dynamic Mechanical Properties"", 《JOURNAL OF POLYMER SCIENCE: PART B:POLYMER PHYSICS》 * |
| 刘彩召 等: ""苯并噁嗪树脂耐热改性研究进展"", 《中国胶粘剂》 * |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818868A (en) * | 2019-11-29 | 2020-02-21 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric-property main chain benzoxazine copolymer oligomer, copolymer resin and preparation method thereof |
| CN110818868B (en) * | 2019-11-29 | 2023-12-12 | 淮北绿洲新材料有限责任公司 | Monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer oligomer, monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer resin and preparation method of monoamine-terminated ultrahigh-frequency low-dielectric main chain benzoxazine copolymer oligomer |
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Application publication date: 20180327 |