CN109180889A - A kind of preparation method and applications of full biological source benzoxazine resin - Google Patents
A kind of preparation method and applications of full biological source benzoxazine resin Download PDFInfo
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- CN109180889A CN109180889A CN201811012544.4A CN201811012544A CN109180889A CN 109180889 A CN109180889 A CN 109180889A CN 201811012544 A CN201811012544 A CN 201811012544A CN 109180889 A CN109180889 A CN 109180889A
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- 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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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2244—Oxides; Hydroxides of metals of zirconium
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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Abstract
The present invention relates to a kind of preparation method and applications of full biological source polybenzoxazine.Full biological source benzoxazine prepolymer process provided by the invention is simple, and reaction efficiency is high, and product purity is high, narrow molecular weight distribution, the product structure after solidification is uniform, and network structure is complete.The full biological source benzoxazine solidified resin that the final temperature programming of the performed polymer solidifies has excellent heat resistance, mechanical property, flame retardant property and dielectric properties, especially there is excellent high-frequency dielectric performance, it can be applied to high frequency and high speed circuit board substrate, microwave and millimeter wave communication, the fields such as trailer-mounted radar.And since the resin after solidifying has flourishing cross-linked network, higher nitrogen content, the full biological source benzoxazine porous resin material after carbonization can be used as functional material application, can be applied to storage, drug loading, pollutant process, gas absorption etc..
Description
Technical field
The present invention relates to high-molecular organic material technical fields, and in particular to a kind of full biological source benzoxazine resin
Preparation method and applications.
Background technique
Benzoxazine is a kind of novel phenolic resin, be a kind of by phenolic compound, aminated compounds and aldehydes is original
Material is reacted through Mannich and the 6-membered heterocyclic compound of synthesis.It is maintaining the excellent hot property of traditional phenolic resin, fire-retardant
Property and while electrical insulating property, also possess the advantages of many traditional phenolic resin are not had such as in processing solidification process without small
Molecule release, products made thereby porosity is low, and volume is shunk close to zero, and material has more excellent high-temperature thermal stability performance, fire-retardant
Performance, mechanical property and chemical stability etc., and water imbibition is low and preparation process in be not necessarily to strong acid or strong base catalyst, subtract
The small damage to equipment.Therefore have in fields such as electronic information, aerospace, friction material, composite materials and widely answer
With prospect, the research interest of people is caused.With deep and thinking the continuous expansion of research, researcher is gradually by benzene
And oxazines resin develops from engineering material to functional material direction, is such as related to high frequency communications, energy storage, absorption, separation, shape note
Recall equal fields, has attracted extensive attention.
Into 21st century, information passes into the high frequency signal transmission epoch.In order to improve signaling rate, electronics
The high frequency of information products mentions the macromolecule resin of copper-clad plate (CCL) and its important component as information transmitting carrier
Higher requirement is gone out, its dielectric properties has both low-k and ultralow dielectric loss to matrix resin needs in high frequency.So
And the dielectric constant k of traditional benzoxazine resin is generally 3.5, dielectric loss f is generally 0.02 (1GHz), can not be fine
Meet high frequency communications to the high request of substrate resin.Therefore, how to be carried out using the flexible MOLECULE DESIGN of benzoxazine resin
Chemical structure design, to reduce resin polarity, this be the problem of being worth researcher to inquire into (Polymer Chemistry,
2018,9(21),2913-2925)。
In addition, benzoxazine resin is also used as the presoma of carbon material, benzoxazine porous carbon materials were both introduced
A variety of organic elements such as oxygen, nitrogen, and there is the pore structure of multiplicity.Large number of micropore and biggish specific surface area are not only
Be conducive to improve the performances such as absorption (fine particles such as electronics, ion, gas molecule), the ion transmission of material, be also beneficial to hold
Dopant of receiving improve composite material compatibility, thus make its gas absorption and storage, catalysis, inductor, photoelectron etc. very
It is multi-field that all there are application prospect (polymer material science and engineering, 2018,34 (1), 184-190).
Diphenolic acid and chaff amine both are from natural resources, abundance, renewable, at low cost.Based on diphenolic acid and chaff amine
Prepare benzoxazine it has been reported that but existing preparation method carried out in nonpolar solvent, the reaction time is long (10-15h), Gu
Change high (230-250 DEG C) (CN201810013847- biomass diphenolic acid-chaff amine type benzoxazine resin and its preparation side of temperature
Method).Moreover, breaking through common engineering application other than using the good hot property of diphenolic acid chaff amine type benzoxazine, filling
Divide and search out the functionalized application in emerging fields such as high frequency communications, energy storage, absorption using the advantage of its structure and performance, this is right
In promoting its comprehensive performance and resin added value, then seem more urgent and important.
Summary of the invention
The technical problem to be solved by the present invention is to aiming at the above shortcomings existing in the prior art, provide a kind of full biology
Source benzoxazine performed polymer, the preparation method of polymer resin and polymer resin are as high-frequency dielectric material, adsorption function material
The application of material.
In order to solve the above technical problems, present invention provide the technical scheme that
A kind of full biological source benzoxazine performed polymer is provided, with following general formula:
The synthetic route of full biological source benzoxazine performed polymer are as follows:
The present invention also provides the preparation methods of above-mentioned full biological source benzoxazine performed polymer, are solventless method, step
It is as follows: under nitrogen atmosphere, aldehyde compound and chaff amine to be first added into reaction vessel, 115~160 DEG C under the conditions of high-speed stirred
0.25~1h is reacted, diphenolic acid is added the reaction was continued 0.75~3h.Wherein, in aldehyde compound in aldehyde radical and natural diphenolic acid
Phenolic hydroxyl group, the amido molar ratio in chaff amine be 1~2:1:0.5~1, post-processing obtains full biological source benzoxazine pre-polymerization
Body；
It or is mixed solvent method, step are as follows: aldehydes chemical combination is added into reaction vessel by way of repeatedly feeding step by step
Object, phenolic compound and binary amine compound, the mode that the substep repeatedly feeds are under nitrogen atmosphere, first by aldehydes
It closes object and chaff amine is added in reaction vessel, polar/non-polar mixed solvent is added, diphenolic acid is added after stirring sufficiently, wherein
Aldehyde radical and the phenolic hydroxyl group in natural diphenolic acid, the amido molar ratio in chaff amine are 1~2:1:0.5~1 in aldehyde compound, in 75
~115 DEG C of 4~8h of reaction, post-processing obtain full biological source benzoxazine performed polymer；
Reaction route are as follows:
According to the above scheme, the aldehyde compound is formaldehyde or paraformaldehyde.
According to the above scheme, the natural bis-phenol is diphenolic acid, and molecular structural formula is as follows:
According to the above scheme, nonpolar solvent: toluene, butanone, dimethylbenzene；Polar solvent: cyclohexanone, acetone, ethyl acetate,
Ether, N, N '-dimethyl formamide, dioxane, chloroform, ethyl alcohol, tetrahydrofuran etc..Volume ratio is 5:1-1:5.
According to the above scheme, the post-processing in the solventless method are as follows: poured into after reactant is pulverized after reaction
Except unreacted reactant and impurity is gone out in methanol solution, supernatant liquor is removed after standing and obtains yellow powder, after yellow powder drying
Obtain full biological source benzoxazine performed polymer.
Post-processing in the mixed solvent method are as follows: after reaction pour into reaction product or reaction solution in methanol solution
Except unreacted reactant and impurity out, will precipitating it is dry after grinding obtain benzoxazine oligomer.Preferably, the methanol solution is dense
Degree is 50~95wt%.
A kind of full biological source benzoxazine resin is will to solidify to obtain after the dissolution of benzoxazine performed polymer.
The resin that full biological source benzoxazine performed polymer solidifies has following general formula:
According to the above scheme, dissolution solvent can be toluene, dimethylbenzene, ethyl alcohol, chloroform, dimethyl methyl in above-mentioned solidification
Any one or more in amide, Isosorbide-5-Nitrae-dioxane.
According to the above scheme, it is described be cured as being dissolved with organic solvent after 100~200 DEG C of curing reactions 4~for 24 hours, obtain
Full biological source benzoxazine resin.
A kind of full biological source benzoxazine porous resin material is by above-mentioned full biological source benzoxazine performed polymer
Solidification, or consolidated after above-mentioned full biological source benzoxazine performed polymer and nanoparticle in mass ratio 10%~30% are mixed
Change, then carbonization obtains the porous material based on full biological source benzoxazine resin under inert atmosphere, and the carbonization is
600~800 DEG C of processing 5-15h.
According to the above scheme, the nanoparticle is selected from zinc oxide, ferroso-ferric oxide, titanium dioxide, zirconium oxide or hydrogen-oxygen
Change aluminium etc..
The present invention also provides a kind of above-mentioned functionalized application of full biological source benzoxazine resin, specifically: as height
Frequency dielectric material is applied to high frequency and high speed circuit board substrate, microwave and millimeter wave communication, the fields such as trailer-mounted radar.
The present invention also provides the functionalized applications of above-mentioned full biological source benzoxazine porous resin material, specifically, will
Full biological source benzoxazine porous resin material after carbonization is applied to storage, drug loading, pollutant as functional material
Processing, gas absorption etc..
The beneficial effects of the present invention are:
1, full biological source benzoxazine prepolymer process provided by the invention is simple, environmentally protective, and reaction efficiency is high, system
Product purity is high, narrow molecular weight distribution, the product structure after solidification is uniform, and network structure is complete, and resin has in high frequency as a result,
Preferable dielectric properties and biggish high frequency communications application potential.
Compared to the dielectric constant 3.6 of common bisphenol-A aniline type benzoxazine resin, dielectric loss 0.03, the present invention
The high-frequency dielectric performance of benzoxazine resin is obviously improved, its dielectric constant is less than 3.0 under high frequency condition, under dielectric loss
It is down to 0.02~0.01.This aspect is since the introducing of carboxyl in diphenolic acid reacts away polarity phenolic hydroxyl group, so that setting after solidification
Rouge polar groups, which are consumed, causes polarity to reduce, moreover, the introducing of low polarity furan nucleus is also beneficial to reduce polarity, increases certainly
By volume, to improve dielectric properties.Additionally, there are the generation that extremely micro diphenolic acid decarboxylic reaction leads to said minuscule hole,
Dielectric properties are made to be further enhanced because of the introducing of air.In addition important one side is solventless method and polarity/non-
The product purity that polarized mixed solvent method preparation method obtains is high, and narrow molecular weight distribution, structure is uniform, and network structure is complete, makes
Obtain resin has preferable dielectric properties and biggish high frequency communications application potential in high frequency.
Specifically, present invention employs solventless method preparations: using diphenolic acid as phenol source, using chaff amine as amine source, by adjusting
The ratio of diphenolic acid and chaff amine controls raw material adition process, and temperature control, in a nitrogen atmosphere using the full biology of solventless method synthesis
Source benzoxazine performed polymer.Whole reactionless solvent addition, it is difficult to eliminate removal reaction dissolvent, overcomes when reacting in solvent
Between long disadvantage, combined coefficient is high, and the reaction time is short (1~4h), and the data of solidification temperature (100~200 DEG C) also relatively report are aobvious
Writing reduces, and the full biological source benzoxazine performed polymer purity is high synthesized, and side reaction is few, high income (> 99%), molecular weight
It is distributed small；Simple process, it is environmentally protective.
Or use polar/non-polar mixed solvent: using diphenolic acid as phenol source, using chaff amine as amine source, by adjusting diphenolic acid
And the ratio of chaff amine, raw material adition process, and temperature control are controlled, is synthesized under nitrogen atmosphere using polar/non-polar mixed solvent method
Full biological source benzoxazine performed polymer.Reaction efficiency is high, and the reaction time, (4~8h) significantly shortened compared with usual vehicle method, solidification
The data of temperature (100~200 DEG C) relatively report significantly reduce.And because benzoxazine is first formed in nonpolar solvent, then
It being transferred in polar solvent, polar solvent plays the role of Purification by filtration, so that the benzoxazine performed polymer purity is high of synthesis,
Molecular weight distribution is small.Preparation process is simple, and reaction efficiency is high, product purity is high.
2, this performed polymer is not only containing the carboxyl functional group of diphenolic acid, but also the furan nucleus containing chaff amine, in view of carboxyl-functional
Group and furan nucleus make pair that performed polymer cure peak temperature (184 DEG C) is more typical to the cured open loop catalytic action of benzoxazine
The cure peak temperature (244 DEG C) of phenol A aniline type benzoxazine resin reduces 60 DEG C, and the process industrial art performance of resin significantly mentions
High (BA is bisphenol-A aniline type benzoxazine, and FD is full biological source benzoxazine, sees attached drawing 1).
3, prepared full biological source benzoxazine performed polymer is when solidifying ring-opening reaction, in addition to benzoxazine itself
Open loop crosslinking is outer, additionally it is possible to which further progress is chemically crosslinked (see solidified resin general formula).The furan nucleus of one side chaff amine can be with
The nitrogen-atoms on Mannich bridge that benzoxazine open loop is formed forms chemical bonding effect, on the other hand, the carboxyl energy of diphenolic acid
The phenolic hydroxyl group that enough and benzoxazine open loop is formed forms ester bond.In addition to chemical bonding acts on, full biological source benzoxazine resin
In also form rich and varied chemical hydrogen bond action, these are also beneficial to intermolecular interaction in Strengthens network structure,
Improve its hot property.The full biological source benzoxazine resin with three branched structures can be obtained by finally solidifying, and be had higher
Crosslink density, excellent heat resistance (Residual carbon (30~40%), glass transition temperature (240~303 DEG C) and anti-flammability
Energy (limit oxygen index 30.3)) (PBA is bisphenol-A aniline type benzoxazine resin, and PFD is full biological source benzoxazine tree
Rouge, glass transition temperature are shown in attached drawing 2, and thermal stability is shown in attached drawing 3).
4, due to the furan nucleus of chaff amine and the carboxyl of diphenolic acid in full biological source benzoxazine resin provided by the invention
Introducing so that the resin after carbonization has many electroactive functional groups, and increases of resin material crosslink density makes after being carbonized
Resin is easily formed porous structure, thus make full biological source benzoxazine resin in storage, pollutant process, drug loading,
Gas absorption etc. also has good application prospect.
Detailed description of the invention
Fig. 1 is the solidification polymerization behavior that differential scanning calorimetry (DSC) characterizes benzoxazine.In view of carboxyl functional group and furan
Ring mutter to the cured open loop catalytic action of benzoxazine, makes the cure peak temperature of full biological source benzoxazine performed polymer (FD)
The cure peak temperature (244 DEG C) of (184 DEG C) more typical bisphenol-A aniline type benzoxazine (BA) reduces 60 DEG C, resin
Process industrial art performance significantly improves.
Fig. 2 is the hot property that dynamic thermomechanical analysis method (DMA) tests resin, the peak temperature of loss angle tangent in figure
Represent the glass transition temperature of resin.The glass transition temperature of common bisphenol-A aniline type benzoxazine resin (PBA) is
167 DEG C, and the glass transition temperature of full biological source benzoxazine resin is 303 DEG C, hot property significantly improves.
Fig. 3 is the high high-temp stability that gravitational thermal analysis method (TGA) tests resin.At 800 DEG C of high temperature, bisphenol-A aniline
The Residual carbon of type benzoxazine resin (PBA) is 27%, and the Residual carbon of full biological source benzoxazine resin is 40%, high temperature
Thermal stability significantly improves.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention further retouches present invention work in detail
It states.
Embodiment 1
The preparation of full biological source benzoxazine performed polymer:
In solvent-free situation, 5.82g (0.06mol) chaff amine, 3.60g (0.12mol) paraformaldehyde are added for nitrogen atmosphere
It is stirred, in the three-necked flask of the 250mL of thermometer equipped with condenser pipe, magneton, is heated to 160 DEG C of reaction 0.25h after mixing,
8.58g (0.03mol) natural diphenolic acid is added, after mixing 160 DEG C of reaction 0.75h, aldehyde radical, phenolic hydroxyl group and amido function
Group's molar ratio is 2:1:1, pours into methanol solution (concentration 85wt%) reaction solution stand for 24 hours after reaction, remove after standing
It goes supernatant liquor to obtain yellow powder, 8h will be dried in vacuo at 60 DEG C of yellow powder, the product finally dried is that full biology comes
Source benzoxazine performed polymer.Yield 99.5%, molecular weight distribution 1.16.
Embodiment 2
The preparation of full biological source benzoxazine performed polymer:
In solvent-free situation, 4.85g (0.05mol) chaff amine, 3.00g (0.10mol) paraformaldehyde are added for nitrogen atmosphere
It is stirred, in the three-necked flask of the 250mL of thermometer equipped with condenser pipe, magneton, is heated to 115 DEG C of reaction 1h after mixing, then
8.58g (0.03mol) natural diphenolic acid is added, after mixing 115 DEG C of reaction 3h, aldehyde radical, phenolic hydroxyl group and amidine functional group rub
Reaction solution is poured into methanol solution (concentration 50wt%) stand for 24 hours, after standing after reaction by you than being 1.67:1:0.83
It removes supernatant liquor and obtains yellow powder, 8h will be dried in vacuo at 60 DEG C of yellow powder, the product finally dried is full biology
Source benzoxazine performed polymer.Yield 99.2%, molecular weight distribution 1.12.
Embodiment 3
The preparation of full biological source benzoxazine performed polymer:
In solvent-free situation, 3.88g (0.04mol) chaff amine, 2.4g (0.08mol) paraformaldehyde are added for nitrogen atmosphere
It is stirred, in the three-necked flask of the 250mL of thermometer equipped with condenser pipe, magneton, is heated to 140 DEG C of reaction 0.75h after mixing,
8.58g (0.03mol) natural diphenolic acid is added, after mixing 140 DEG C of reaction 2h, aldehyde radical, phenolic hydroxyl group and amidine functional group
Molar ratio is 1.33:1:0.67, pours into methanol solution (concentration 95wt%) reaction solution stand for 24 hours after reaction, stand
Supernatant liquor is removed afterwards and obtains yellow powder, will be dried in vacuo 8h at 60 DEG C of yellow powder, and the product finally dried is complete raw
Object source benzoxazine performed polymer.Yield 99.6%, molecular weight distribution 1.14.
Embodiment 4
The preparation of full biological source benzoxazine performed polymer:
In solvent-free situation, 2.91g (0.03mol) chaff amine, 1.8g (0.06mol) paraformaldehyde are added for nitrogen atmosphere
It is stirred, in the three-necked flask of the 250mL of thermometer equipped with condenser pipe, magneton, is heated to 130 DEG C of reaction 0.5h after mixing,
8.58g (0.03mol) natural diphenolic acid is added, after mixing 130 DEG C of reaction 2.5h, aldehyde radical, phenolic hydroxyl group and amido function
Group's molar ratio is 1:1:0.5, pours into methanol solution (concentration 65wt%) reaction solution stand for 24 hours, after standing after reaction
It removes supernatant liquor and obtains yellow powder, 8h will be dried in vacuo at 60 DEG C of yellow powder, the product finally dried is full biology
Source benzoxazine performed polymer.Yield 99.3%, molecular weight distribution 1.21.
Embodiment 5
The preparation of full biological source benzoxazine performed polymer:
5.82g (0.06mol) chaff amine, 3.60g (0.12mol) paraformaldehyde are added equipped with condenser pipe, magneton stirring, temperature
It spends in the three-necked flask of meter, 75mL toluene/ethanol mixed solvent (toluene and ethyl alcohol volume ratio 2:1) is added, is heated to 80 DEG C and stirs
It is passed through nitrogen after mixing 60min, 8.58g (0.03mol) natural bis-phenol is added, aldehyde radical, phenolic hydroxyl group and amidine functional group molar ratio are
Reaction solution is poured into methanol solution (concentration 85wt%) stand for 24 hours after reaction, obtained by 2:1:1, the reaction was continued later 7h
Precipitating, will be deposited at 60 DEG C and is dried in vacuo 6h, and the powder for the brown color for finally grinding the product of drying is complete raw
Object source benzoxazine performed polymer.Yield 95%, molecular weight distribution 1.15.
Embodiment 6
The preparation of full biological source benzoxazine performed polymer:
2.91g (0.03mol) chaff amine, 1.8g (0.06mol) paraformaldehyde are added equipped with condenser pipe, magneton stirring, temperature
It spends in the three-necked flask of meter, 60mL toluene/N is added, N '-dimethyl formamide mixed solvent (volume ratio 1:1) is heated to
It is passed through nitrogen after 115 DEG C of stirring 30min, 8.58g (0.03mol) natural diphenolic acid, aldehyde radical, phenolic hydroxyl group and amidine functional group is added
Molar ratio is 1:1:0.5, the reaction was continued later 3.5h, after reaction pours into reaction solution in methanol solution (concentration 50wt%)
It stands for 24 hours, is precipitated, will be deposited at 60 DEG C and be dried in vacuo 6h, the brown color for finally grinding the product of drying
Powder is full biological source benzoxazine performed polymer.Yield 96%, molecular weight distribution 1.19.
Embodiment 7
The preparation of full biological source benzoxazine performed polymer:
4.85g (0.05mol) chaff amine, 3.00g (0.10mol) paraformaldehyde are added equipped with condenser pipe, magneton stirring, temperature
It spends in the three-necked flask of meter, is added 60mL toluene/ethanol mixed solvent (volume ratio 1:5), after being heated to 80 DEG C of stirring 30min
It is passed through nitrogen, 8.58g (0.03mol) natural diphenolic acid is added, aldehyde radical, phenolic hydroxyl group and amido functional group molar ratio are 1.67:1:
Reaction solution is poured into methanol solution (concentration 95wt%) stand for 24 hours after reaction, obtained by 0.83, the reaction was continued later 5h
Precipitating, will be deposited at 60 DEG C and is dried in vacuo 6h, and the powder for the brown color for finally grinding the product of drying is complete raw
Object source benzoxazine performed polymer.Yield 95%, molecular weight distribution 1.17.
Embodiment 8
The preparation of full biological source benzoxazine performed polymer:
3.88g (0.04mol) chaff amine, 2.4g (0.08mol) paraformaldehyde are added equipped with condenser pipe, magneton stirring, temperature
It spends in the three-necked flask of meter, is added 60mL toluene/ethyl acetate mixed solvent (volume ratio 5:1), be heated to 75 DEG C of stirrings
It is passed through nitrogen after 60min, 8.58g (0.03mol) natural bis-phenol is added, aldehyde radical, phenolic hydroxyl group and amido functional group molar ratio are
Reaction solution is poured into methanol solution (concentration 60wt%) stand after reaction by 1.33:1:0.67, the reaction was continued later 4h
For 24 hours, it is precipitated, will be deposited at 60 DEG C and be dried in vacuo 6h, the powder for the brown color for finally grinding the product of drying
As full biological source benzoxazine performed polymer.Yield 95%, molecular weight distribution 1.20.
Embodiment 9
The preparation of full biological source polybenzoxazine resin:
Full biological source benzoxazine performed polymer prepared by embodiment 1, which is dissolved in after solvent dimethylformamide, to be poured into admittedly
Change in mold, is placed in vacuum oven in 80 DEG C of heating 12h, later at 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C, 180 DEG C,
Solidify 2h at 200 DEG C respectively and obtain full biological source benzoxazine resin, glass transition temperature is 303 DEG C, 800 DEG C of carbon residues
Rate is up to 40%, and limit oxygen index is up to 33.5, dielectric constant 2.8, dielectric loss 0.01.
Embodiment 10
The preparation of all natural type polybenzoxazine resin:
All natural type benzoxazine performed polymer prepared by embodiment 2 is put into curing mold and is placed in vacuum oven
200 DEG C of solidification 4h obtain all natural type benzoxazine resin, and glass transition temperature is 290 DEG C, and 800 DEG C of carbon yields are reachable
37%, limit oxygen index is up to 32.3, dielectric constant 2.85, dielectric loss 0.016.
Embodiment 11
The preparation of full biological source polybenzoxazine resin:
Full biological source benzoxazine performed polymer prepared by embodiment 5 be dissolved in toluene/ethanol mixed solvent (toluene with
Ethyl alcohol volume ratio 2:1) after pour into curing mold, be placed in vacuum oven in 80 DEG C of heating 12h, later at 100 DEG C, 120
DEG C, solidify 2h at 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C respectively and obtains full biological source benzoxazine resin, glass transition
Temperature is 300 DEG C, and 800 DEG C of carbon yields are up to 40%, and limit oxygen index is up to 33, dielectric constant 2.83, and dielectric loss is
0.019。
Embodiment 12
The preparation of full biological source polybenzoxazine resin:
Full biological source benzoxazine performed polymer prepared by embodiment 8 pours into curing mold after being dissolved in toluene solvant
In, solidify at 100 DEG C obtain full biological source benzoxazine resin for 24 hours later, glass transition temperature be 265 DEG C, 800
DEG C carbon yield is up to 27%, and limit oxygen index is up to 28.7, dielectric constant 2.95, dielectric loss 0.019.
Embodiment 13
By improving preparation process, which can also be prepared into porous carbon materials for Magneto separate water pollutant, and light is urged
Change degradation of contaminant etc..
Full biological source benzoxazine performed polymer and ferroso-ferric oxide prepared by embodiment 1 are dissolved in dimethyl formyl
In amine solvent (its concentration is 20%) thermal response of falling back kettle, it is placed in vacuum oven in 130 DEG C of heating 8h, Zhi Hou
Solidify 2h at 140 DEG C, 160 DEG C, 180 DEG C, 200 DEG C respectively and obtain full biological source benzoxazine resin/zinc oxide porous material,
Resin is placed in the lower 700 DEG C of carbonizations 2h of nitrogen protection in tube furnace, is obtained based on full biological source benzoxazine resin and four oxygen
Change the porous material of three-iron, specific surface area 51m2/g.Obtained porous material is pulverized and puts into water and can effectively inhale
The pollutants such as attached solution water Methylene Blue.
Embodiment 14
Full biological source benzoxazine performed polymer and zinc oxide prepared by embodiment 5 are dissolved in dimethylformamide
In solvent (its concentration is 30%) thermal response of falling back kettle, it is placed in vacuum oven in 130 DEG C of heating 8h, later 140
DEG C, solidify 2h at 160 DEG C, 180 DEG C, 200 DEG C respectively and obtain full biological source benzoxazine resin/zinc oxide porous material,
Resin is placed in the middle lower 700 DEG C of carbonizations 1h of nitrogen protection in tube furnace, obtain based on complete full biological source benzoxazine resin and
The porous material of zinc oxide, specific surface area 66m2/g.Obtained porous material is pulverized and is put into water through ultraviolet light
The pollutants such as formaldehyde in the water that can effectively degrade are irradiated, removal rate is 96% in the formalin of 12ppm.
Claims (10)
1. the preparation method of full biological source benzoxazine performed polymer, is solventless method, steps are as follows: under nitrogen atmosphere, first
Addition aldehyde compound and chaff amine into reaction vessel, 115~160 DEG C of 0.25~1h of reaction under the conditions of high-speed stirred, then plus
Enter diphenolic acid the reaction was continued 0.75~3h, wherein aldehyde radical and phenolic hydroxyl group in natural diphenolic acid in aldehyde compound, in chaff amine
Amido molar ratio is 1~2:1:0.5~1, and post-processing obtains full biological source benzoxazine performed polymer；
It or is mixed solvent method, step are as follows: aldehyde compound, phenol is added into reaction vessel by way of repeatedly feeding step by step
Class compound and binary amine compound, the mode that the substep repeatedly feeds are under nitrogen atmosphere, first by aldehyde compound
It is added in reaction vessel with chaff amine, polar/non-polar mixed solvent is added, diphenolic acid is added after stirring sufficiently, wherein aldehydes
Phenolic hydroxyl group in compound in aldehyde radical and natural diphenolic acid, the amido molar ratio in chaff amine are 1~2:1:0.5~1, in 75~
115 DEG C of 4~8h of reaction, post-processing obtain full biological source benzoxazine performed polymer.
2. preparation method according to claim 1, it is characterised in that: the aldehyde compound is formaldehyde or paraformaldehyde；
The natural bis-phenol is diphenolic acid, and molecular structural formula is as follows:
3. preparation method according to claim 1, it is characterised in that: the nonpolar solvent: toluene, butanone, diformazan
Benzene；Polar solvent: cyclohexanone, acetone, ethyl acetate, ether, N, N '-dimethyl formamide, dioxane, chloroform, ethyl alcohol, four
Hydrogen furans, the two volume ratio are 5:1-1:5.
4. preparation method according to claim 1, it is characterised in that: the post-processing in the solventless method are as follows: reaction knot
It is poured into after reactant is pulverized after beam in methanol solution except unreacted reactant and impurity is gone out, removes supernatant liquor after standing and obtain
Yellow powder will obtain full biological source benzoxazine performed polymer after yellow powder drying.
Post-processing in the mixed solvent method are as follows: after reaction pour into reaction product or reaction solution in methanol solution except out
Grinding after precipitating drying is obtained benzoxazine oligomer by unreacted reactant and impurity.Preferably, the concentration of methanol solution is
50~95wt%.
5. a kind of full biological source benzoxazine resin, it is characterised in that: it is to prepare preparation method described in claim 1
Solidify after obtained full biological source benzoxazine performed polymer dissolution and obtains, structure are as follows:
6. full biological source benzoxazine resin according to claim 5, it is characterised in that: it is by claim 1 institute
Solidify after the dissolution of full biological source benzoxazine performed polymer that the preparation method stated is prepared and to obtain；
Solvent for use is dissolved in solidification in toluene, dimethylbenzene, ethyl alcohol, chloroform, dimethylformamide, Isosorbide-5-Nitrae-dioxane
Any one or more.
7. full biological source benzoxazine resin according to claim 5, it is characterised in that: described is cured as with organic
100~200 DEG C of curing reactions 4~for 24 hours after solvent dissolution, obtain full biological source benzoxazine resin.
8. the application of full biological source benzoxazine resin described in claim 5, it is characterised in that: as high-frequency dielectric material
Applied to high frequency and high speed circuit board substrate, microwave and millimeter wave communication, trailer-mounted radar field.
9. a kind of full biological source benzoxazine porous resin material is to consolidate above-mentioned full biological source benzoxazine performed polymer
Change, or is consolidated after above-mentioned full biological source benzoxazine performed polymer and nanoparticle in mass ratio 10%~30% are mixed
Change, then carbonization obtains the porous material based on full biological source benzoxazine resin under inert atmosphere, and the carbonization is
600~800 DEG C of processing 5-15h；The nanoparticle is selected from zinc oxide, ferroso-ferric oxide, titanium dioxide, zirconium oxide or hydrogen-oxygen
Change aluminium.
10. the application of full biological source benzoxazine porous resin material according to any one of claims 8, specifically, by after carbonization
Full biological source benzoxazine porous resin material is applied to storage, drug loading, pollutant process, gas as functional material
Absorption aspect.
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