CN108440561B - A kind of biology base benzoxazine presoma and its preparation method and application based on soybean derivatives - Google Patents
A kind of biology base benzoxazine presoma and its preparation method and application based on soybean derivatives Download PDFInfo
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- CN108440561B CN108440561B CN201810096831.1A CN201810096831A CN108440561B CN 108440561 B CN108440561 B CN 108440561B CN 201810096831 A CN201810096831 A CN 201810096831A CN 108440561 B CN108440561 B CN 108440561B
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- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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Abstract
The present invention provides a kind of biology base benzoxazine presoma based on soybean derivatives has the structure as shown in formula (I).Preparation method includes: that isoflavones, monoamine and paraformaldehyde are blended, and cyclization reaction occurs under heating, and the biology base benzoxazine presoma based on soybean derivatives is prepared.Preparation is simple, easy to operate, controllably makes, easy to implement, is suitable for large-scale industrial production.The present invention is based on the thermosetting polyphenylene of the biology base benzoxazine presoma ring-opening polymerisation of soybean derivatives preparation and oxazines resin has excellent corrosion resistance, mechanical property and thermal property, there is a possibility that substituting existing petroleum-based products, use scope is extensive.
Description
Technical field
The invention belongs to biological based thermoset applications, in particular to a kind of biology base benzoxazine based on soybean derivatives
Presoma and its preparation method and application.
Background technique
Benzoxazine resin is a kind of novel phenolic resin, because it is widely used in excellent comprehensive performance etc.
The fields such as anticorrosive paint, bonding agent, microelectronics, space flight and aviation are a kind of very important thermosetting materials.However, at this stage
Most of benzoxazine resin all derives from petroleum resources, and petroleum resources are a kind of unsustainable resources, along with its storage
The increasingly reduction of amount, necessarily will cause the continuous raising of the high molecular material cost from petroleum resources.Recently, in protection ring
Under the dual-pressure of border and saving petroleum resources, the view of people is entered using sustainable resource as the biology base high molecular material of raw material
Open country, correlative study and development and utilization are increasingly by the attention of people.Therefore, a large amount of biology base benzoxazine, which is developed, prepares
Come, the relatively traditional benzoxazine of these biology base benzoxazines there are various characteristics.But biology base benzoxazine
There is also many disadvantages as traditional benzoxazine resin for resin: the benzoxazine of single functionality exists in ring-opening polymerisation
Chain transfer reaction, the relative molecular mass of resulting polymers is relatively low, to limit its scope of application；The benzene of bifunctionality
And oxazines due to its molecular structure itself the characteristics of, polymer equally exist that crosslink density is low, elongation at break is low and
The drawbacks such as poor toughness.Therefore, how to improve the degree of cross linking of biology base benzoxazine has very to improve its thermodynamic property
Important meaning.
Isoflavones is flavone compound, is a kind of secondary metabolite formed in soybean growth, can be a large amount of
Obtained from plant, have the following structure:
Its structure is similar to petroleum-based chemicals bisphenol-A, it is known that bisphenol-A is under a cloud physiological-toxicity, and in Europe
It has been used by limitation Deng many countries, although isoflavones has the structure similar with bisphenol-A, it is a kind of couple of people
The beneficial substance of body has delaying female aging, improves menopause symptom, osteoporosis, blood lipid raising, breast cancer, prostate
Outstanding advantages of cancer, heart disease, osteoporosis, cardiovascular disease, this is also a kind of welfare of stealth to construction personnel.It is most important
A bit, have in isoflavones structure can amount incurred external crosslinking reaction functional group, final cured product can be increased
The degree of cross linking improves the whole thermomechanical property of material.
Summary of the invention
The present invention provides a kind of biology base benzoxazine presoma and its preparation method and application based on soybean derivatives,
Using bio-based source compound isoflavones, biology base benzoxazine presoma is obtained by reaction, preparation is simple, operation
Simplicity controllably makes, easy to implement, is suitable for large-scale industrial production.
The invention adopts the following technical scheme:
A kind of biology base benzoxazine presoma based on soybean derivatives has the structure as shown in formula (I):
In formula (I), R is selected from C2H5、C3H7、C4H9、C5H11、C5H5O、C6H5And C6H13At least one of.
The biology base benzoxazine presoma of the soybean derivatives has double benzoxazine structures, is opened based on the presoma
The resulting polybenzoxazine resin of cyclopolymerization is relative to traditional resulting polyphenyl of simple function benzoxazine presoma ring-opening polymerisation
And oxazines resin has huge raising, especially glass transition temperature and heat-staple improvement in performance, can be used as high-performance bonding
Agent.Due to the difference of R in structure, the glass transition temperature and thermostabilization also have very big difference, the knot of alkane less, rigid
Structure, the glass transition temperature and thermostabilization that polybenzoxazine resin is showed are higher.
Preferably, R is selected from C2H5、C3H7、C4H9、C5H11、C5H5O、C6H5Or C6H13At least one of；It is further excellent
Choosing, R C5H5O or C6H5, polybenzoxazine resin shows the glass transition temperature and excellent thermal stability of superelevation.
The preparation method of the above-mentioned biology base benzoxazine presoma based on soybean derivatives, comprising:
By isoflavones, monoamine and paraformaldehyde, cyclization reaction occurs under heating, obtains shown in structure such as formula (I)
Biology base benzoxazine presoma；Shown in the monoamine structural formula such as formula (II):
R—NH2(II)
R in formula (II) is consistent with the definition of R in formula (I)；
Preferably, the monoamine is at least one of ethamine, propylamine, butylamine, amylamine, hexylamine, aniline or chaff amine；Into
One step is preferred, and monoamine is one of aniline or chaff amine, and obtained polybenzoxazine resin shows the glass transition of superelevation
Temperature and excellent thermal stability.It is 390 DEG C that the glass transition temperature of isoflavones aniline polybenzoxazine resin, which is up to,
Td10It is 471 DEG C.It is 410 DEG C that the glass transition temperature of isoflavones chaff amine polybenzoxazine resin, which is up to, Td10It is 467
℃。
Preferably, the molar ratio of the isoflavones and monoamine, paraformaldehyde is 1:2:4-12；Under this ratio, energy
Enough guarantee that monoamine is completely complete by polyformaldehyde reaction, the yield highest for the benzoxazine monomer being prepared.
Preferably, the temperature of the cyclization reaction is 90~120 DEG C, and the reaction time is 24~72h；At this temperature, energy
Enough guarantee that reactant reaction is complete, the yield highest for the benzoxazine monomer being prepared.
The solvent of the cyclization reaction is at least one of dioxane, toluene, and dosage is the 1 of isoflavones quality
~20 times；Guarantee reactant under a certain concentration, be conducive to reaction speed and yield.
The present invention also provides the biology base benzoxazine presomas based on soybean derivatives to prepare polybenzoxazine tree
The application of rouge.
The biology base benzoxazine presoma based on soybean derivatives is heated at 160-220 DEG C of temperature
2-8 hours, obtain polybenzoxazine resin.
Biology base benzoxazine presoma based on soybean derivatives of the invention, directlys adopt the soybean of bio-based source
Isoflavones is prepared as raw material, and preparation method is simple and efficient, easy to operate, is controllably made, can using existing chemical industry equipment
With large-scale production, there is the advantages of yield is high, simple process, be suitable for large-scale industrial production, existing stone can also be reduced
Pollution of the oil base benzoxazine resin to the dependence of fossil resources and its to environment.
The biology base benzoxazine presoma based on soybean derivatives that the present invention obtains, finally obtained polybenzoxazine
Resin product has very high crosslink density and excellent thermal property, mechanical property.
Since isoflavones derives from biomass material, the exploitation energy of this biology base benzoxazine class product
The development for enough pushing bio-based materials, is of great significance to the sustainable development for promoting the fields such as entire high molecular material, is
A kind of biology base, green, environment-friendly products have the double effects saved petroleum resources and protect environment.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy of isoflavones chaff amine benzoxazine prepared by embodiment 11H-NMR。
Fig. 2 is the nuclear magnetic resonance spectroscopy of isoflavones aniline benzoxazine prepared by embodiment 21H-NMR。
Specific embodiment
Below with reference to embodiment, the present invention is further explained.It should be understood that these embodiments be merely to illustrate the present invention without
For limiting the scope of the invention.
In embodiment, nuclear magnetic resonance spectroscopy1H-NMR uses the III type wave spectrum of 400AVANCE of Brooker company (Bruker)
Instrument (Spectrometer) measurement, 400MHz, deuterated chloroform (CDCl3)。
The yield of biology base benzoxazine presoma based on soybean derivatives is calculated by the following formula to obtain:
Yield=benzoxazine presoma mass number/(the molal quantity of isoflavones × benzoxazine presoma mole
Quality) × 100%
Embodiment 1
By 1mol isoflavones, 2mol chaff amine, 6mol paraformaldehyde, be dissolved in 500mL dioxane and toluene
It in mixed solution (weight ratio 3:1), is reacted 32 hours at 90 DEG C, decompression rotary evaporation removes mixed solvent, washing and drying
After obtain isoflavones chaff amine benzoxazine presoma, yield 91.5%, nuclear magnetic resonance spectroscopy1H-NMR as shown in Figure 1,
The hydrogen atom above each peak and isoflavones chaff amine benzoxazine compound structure on figure is all one-to-one.
Isoflavones chaff amine benzoxazine presoma is heated in convection oven, finally solidifies to 260 DEG C, obtains
Isoflavones chaff amine polybenzoxazine resin.The glass transition of resulting cured product is 410 DEG C, Td10It is 467 DEG C, storage
Energy modulus is 3500MPa, and the salt spray resistance testing time reaches 400h.
Embodiment 2
By 1mol isoflavones, 2mol aniline, 7.5mol paraformaldehyde, be dissolved in 650mL dioxane and toluene
Mixed solution in (weight ratio 2:1), reacted 52 hours at 100 DEG C, decompression rotary evaporation removes mixed solvent, washing and dry
Isoflavones aniline benzoxazine presoma, yield 90.8% are obtained after dry.Nuclear magnetic resonance spectroscopy1H-NMR such as Fig. 2 institute
Show, the hydrogen atom above each peak and isoflavones aniline benzoxazine compound structure on figure is all one-to-one.
Isoflavones aniline benzoxazine presoma is heated in convection oven and is finally solidified to 260 DEG C, is obtained
Isoflavones aniline polybenzoxazine resin.The glass transition of resulting cured product is 390 DEG C, Td10It is 471 DEG C, storage
Energy modulus is 3700MPa, and the salt spray resistance testing time reaches 290h.
Embodiment 3
By 1mol isoflavones, 2mol ethamine, 6.1mol paraformaldehyde, be dissolved in 550mL dioxane and toluene
Mixed solution neutralize (weight ratio 3:2), react 24 hours at 120 DEG C, decompression rotary evaporation remove mixed solvent, wash and
Isoflavones ethamine benzoxazine presoma, yield 95.5% are obtained after drying.
Isoflavones ethamine benzoxazine presoma is heated in convection oven and is finally solidified to 260 DEG C, is obtained
Isoflavones ethamine polybenzoxazine resin.The glass transition of resulting cured product is 370 DEG C, Td10It is 441 DEG C, storage
Energy modulus is 3450MPa, and the salt spray resistance testing time reaches 250h.
Embodiment 4
By 1mol isoflavones, 2mol butylamine, 5.2mol paraformaldehyde, be dissolved in 650mL dioxane and toluene
Mixed solution in (weight ratio 1:1), reacted 72 hours at 90 DEG C, decompression rotary evaporation removes mixed solvent, washing and dry
Isoflavones butylamine benzoxazine presoma, yield 94.5% are obtained after dry.
Isoflavones butylamine benzoxazine presoma is heated in convection oven and is finally solidified to 260 DEG C, is obtained
Isoflavones ethamine polybenzoxazine resin.The glass transition of resulting cured product is 350 DEG C, Td10It is 440 DEG C, storage
Energy modulus is 3380MPa, and the salt spray resistance testing time reaches 200h.
Embodiment 5
By 1mol isoflavones, 2mol hexylamine, 6.1mol paraformaldehyde, be dissolved in 560mL dioxane and toluene
Mixed solution in (weight ratio 2:3), reacted 43 hours at 110 DEG C, decompression rotary evaporation removes mixed solvent, washing and dry
Isoflavones hexylamine benzoxazine presoma, yield 95.5% are obtained after dry.
Isoflavones hexylamine benzoxazine presoma is heated in convection oven and is finally solidified to 260 DEG C, is obtained
Isoflavones hexylamine polybenzoxazine resin.The glass transition of resulting cured product is 330 DEG C, Td10It is 438 DEG C, storage
Energy modulus is 3300MPa, and the salt spray resistance testing time reaches 180h.
Embodiment 6
By 1mol isoflavones, 2mol ethamine, 8.1mol paraformaldehyde, 360mL dioxane is dissolved in, 100
It is reacted 23 hours at DEG C, decompression rotary evaporation removes mixed solvent, and isoflavones ethamine benzo evil is obtained after washing and drying
Piperazine presoma, yield 97.5%.
Isoflavones ethamine benzoxazine presoma is heated in convection oven and is finally solidified to 260 DEG C, is obtained
Isoflavones ethamine polybenzoxazine resin.The glass transition of resulting cured product is 370 DEG C, Td10It is 441 DEG C, storage
Energy modulus is 3450MPa, and the salt spray resistance testing time reaches 250h.
Embodiment 7
By 1mol isoflavones, 2mol butylamine, 5.9mol paraformaldehyde, be dissolved in 450mL toluene, at 90 DEG C
Reaction 82 hours, decompression rotary evaporation removes mixed solvent, before obtaining isoflavones butylamine benzoxazine after washing and drying
Drive body, yield 96.5%.
Isoflavones butylamine benzoxazine presoma is heated in convection oven and is finally solidified to 260 DEG C, is obtained
Isoflavones ethamine polybenzoxazine resin.The glass transition of resulting cured product is 350 DEG C, Td10It is 444 DEG C, storage
Energy modulus is 3390MPa, and the salt spray resistance testing time reaches 210h.
Claims (6)
1. a kind of biology base benzoxazine presoma based on soybean derivatives is in the application for preparing polybenzoxazine resin, spy
Sign is: the biology base benzoxazine presoma based on soybean derivatives is heated at 160-220 DEG C of temperature
2-8 hours, obtain polybenzoxazine resin；The biology base benzoxazine presoma based on soybean derivatives has such as
Structure shown in formula (I):
In formula (I), R is selected from C2H5、C3H7、C4H9、C5H11、C5H5O、C6H5And C6H13At least one of.
2. the biology base benzoxazine presoma according to claim 1 based on soybean derivatives is preparing polybenzoxazine
The application of resin, which is characterized in that the preparation method of the biology base benzoxazine presoma, comprising:
Under heating by isoflavones, monoamine and paraformaldehyde, cyclization reaction occurs, it is raw as shown in formula (I) to obtain structure
Object base benzoxazine presoma；Shown in the monoamine structural formula such as formula (II):
R—NH2 (II)
In formula (II), R is consistent with the definition of R in formula (I).
3. the biology base benzoxazine presoma according to claim 2 based on soybean derivatives is preparing polybenzoxazine
The application of resin, which is characterized in that the monoamine be ethamine, propylamine, butylamine, amylamine, hexylamine, aniline or chaff amine at least
It is a kind of.
4. the biology base benzoxazine presoma according to claim 3 based on soybean derivatives is preparing polybenzoxazine
The application of resin, which is characterized in that the monoamine is one of aniline or chaff amine.
5. the biology base benzoxazine presoma according to claim 2 based on soybean derivatives is preparing polybenzoxazine
The application of resin, which is characterized in that the molar ratio of the isoflavones and monoamine, paraformaldehyde is 1:2:4~12.
6. the biology base benzoxazine presoma according to claim 2 based on soybean derivatives is preparing polybenzoxazine
The application of resin, which is characterized in that the cyclization reaction temperature is 90~120 DEG C, and the reaction time is 24~72h.
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| CN110054894B (en) * | 2019-05-13 | 2021-07-02 | 东华大学 | Bio-based polyimide film and preparation method and application thereof |
| CN110591091A (en) * | 2019-09-24 | 2019-12-20 | 常州市宏发纵横新材料科技股份有限公司 | Main chain type benzoxazine containing daidzein group and preparation method thereof |
| CN110894274B (en) * | 2019-11-27 | 2022-12-06 | 中国科学院宁波材料技术与工程研究所 | Daidzein-based bio-based main chain type benzoxazine resin and preparation method and application thereof |
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Non-Patent Citations (1)
| Title |
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| Polybenzoxazines—New high performance thermosetting resins: Synthesis and properties;N.N. Ghosh等;《Prog. Polym. Sci.》;20070802;第32卷;第1344-1391页 * |
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