CN108059701B - Biomass phenolphthalein-furfuryl amine type benzoxazine resin and preparation method thereof - Google Patents
Biomass phenolphthalein-furfuryl amine type benzoxazine resin and preparation method thereof Download PDFInfo
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- CN108059701B CN108059701B CN201810014012.8A CN201810014012A CN108059701B CN 108059701 B CN108059701 B CN 108059701B CN 201810014012 A CN201810014012 A CN 201810014012A CN 108059701 B CN108059701 B CN 108059701B
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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
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- 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
Abstract
The invention provides a biomass phenolphthalein-furfuryl amine type benzoxazine resin and a preparation method thereofThe preparation method comprises the following steps: adding a solvent, phenolphthalein and formaldehyde into a reaction container, then dropwise adding furfuryl amine into the reaction container, stirring and heating to a reflux state after dropwise adding is finished, and reacting for 20-25 h; after the reaction is finished, removing the solvent, washing and drying to obtain a biomass phenolphthalein-furfuryl amine type benzoxazine monomer; and placing the benzoxazine monomer in a mold for step curing to obtain the thermosetting biomass phenolphthalein-furfuryl amine benzoxazine resin. The biomass phenolphthalein-furfuryl amine benzoxazine resin has lower curing temperature, higher heat resistance and residual carbon retention rate, and is suitable for manufacturing high-performance high-temperature-resistant materials. The structure of the biomass phenolphthalein-furfuryl amine benzoxazine resin is as follows:
Description
Technical Field
The invention relates to the technical field of novel biomass thermosetting resin and preparation thereof, in particular to biomass phenolphthalein-furfuryl amine type benzoxazine resin and a preparation method thereof.
Background
The benzoxazine resin is a novel thermosetting engineering plastic, has better heat resistance, electrical property, low surface energy, low water absorption and dimensional stability compared with the traditional phenolic resin, is suitable for preparing fiber reinforced polymer matrix composite materials with low porosity, high performance and low cost, and can be used for preparing a plurality of novel composite materials with special physical properties by molecular design and compounding with phenolic resin, epoxy resin or bismaleimide resin. In addition, acid or alkali is not needed to be used as a catalyst in the curing process, no pollution is caused to the environment, no small molecules are emitted during curing, the volume shrinkage rate is zero, the comprehensive performance of the epoxy resin is superior to that of phenolic resin, epoxy resin and maleimide resin, and the epoxy resin is widely applied to the fields of aerospace materials, medical materials, electronic materials and the like.
In recent years, various industries are rapidly developed, the value of the biomass benzoxazine resin to society is more and more abundant, but the biomass benzoxazine resin is excessively dependent on petrochemical products, people pay more and more attention to environmental protection, bio-based compounds have attracted more and more attention, the gradual replacement of chemical products by the bio-based compounds becomes a necessary trend, and the research hotspot is provided for the benzoxazine resin prepared from biomass.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art, and provides a novel biomass phenolphthalein-furfuryl amine type benzoxazine resin and a preparation method thereof.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a biomass phenolphthalein-furfuryl amine type benzoxazine resin (Bio-PolyBoz-PF) has the following structural formula:
the biomass phenolphthalein-furfuryl amine type benzoxazine resin is prepared from a benzoxazine monomer (Bio-Boz-PF) with the following structure:
the phenolphthalein-furfuryl amine type benzoxazine resin of the present invention may be polymerized under heating and/or in the presence of a catalyst to form a nitrogen-containing network structure similar to a phenolic resin.
The preparation method of the phenolphthalein-furfuryl amine type benzoxazine resin comprises the following preparation steps:
(1) adding a solvent, phenolphthalein and formaldehyde into a reaction container, then dropwise adding furfuryl amine into the reaction container, stirring and heating to a reflux state after dropwise adding is finished, and reacting for 20-25 h; after the reaction is finished, removing the solvent, washing and drying to obtain a biomass phenolphthalein-furfuryl amine type benzoxazine monomer;
(2) and (2) placing the biomass phenolphthalein-furfuryl amine type benzoxazine monomer obtained in the step (1) in a mold for step curing to obtain the thermosetting biomass phenolphthalein-furfuryl amine type benzoxazine resin.
The solvent in the step (1) of the invention is at least one of three mixed solvents formed by mixing ethanol with toluene, dioxane and xylene respectively, and the volume ratio of the ethanol to the other components is 1: (3-5).
The formaldehyde in the step (1) is one of paraformaldehyde and formaldehyde aqueous solution.
The dripping time of the furfuryl amine in the step (1) is 0.5-1 h.
The ratio of phenolphthalein, furfuryl amine, formaldehyde and solvent in the step (1) is 0.02-0.10 mol: 0.04-0.20 mol: 0.088-0.44 mol: 30-80 ml. The above-mentioned proportion is not limited by a specific unit, and an equal reduction or increase in the proportion on the basis of the above-mentioned numerical proportion is considered to fall within the above-mentioned range of proportion.
The invention is characterized in that the step (2) comprises the following steps of: 170 ℃ and 180 ℃ for 0.5-1.5h, 185 ℃ and 495 ℃ for 1.5-2.5h, 200 ℃ and 220 ℃ for 1.5-2.5h, 230 ℃ and 240 ℃ for 0.5-1.5h, 24,5-255 ℃ and 0.5-1.5 h. Preferably, the step curing (step curing) in the step (2) of the present invention is: 175 ℃, 1h, 190 ℃, 2h, 210 ℃, 2h, 235 ℃, 1h, 250 ℃ and 1 h.
Compared with the prior art, the invention has the following remarkable advantages and beneficial effects:
(1) the synthetic process of the Bio-based phenolphthalein-furfuryl amine benzoxazine resin (Bio-PolyBoz-PF) is simple and reasonable, the cost is low, the purity is high, and the yield is high;
(2) the amine source used in the invention is furfuryl amine, which is a common fine chemical raw material produced from plant raw materials such as corncobs, cottonseed hulls, bagasse and the like in nature, and gets rid of excessive dependence on petroleum products.
(3) The biomass phenolphthalein-furfuryl amine benzoxazine resin prepared by the method has the advantages of low curing temperature, high heat resistance and residual carbon retention rate, and is suitable for manufacturing high-performance high-temperature-resistant materials.
(4) The initial decomposition temperature (T) of the biomass phenolphthalein-furfuryl amine type benzoxazine resin (Bio-PolyBoz-PF) of the invention5％) The temperature is up to 372 ℃, and the carbon residue retention rate is up to 65% at 800 ℃. While the initial decomposition temperature (T) of the conventional bisphenol A-aniline type benzoxazine resin (PolyBoz-BA)5％) 343 ℃ CThe carbon residue retention rate at 800 ℃ is only 34%. As can be seen, the initial decomposition temperature (T) of Bio-PolyBoz-PF vs PolyBoz-BA5％) And the carbon residue retention rate at 800 ℃ is respectively improved by 29 ℃ and 31%. The TG result can show that the novel biomass benzoxazine resin has good heat resistance.
Drawings
Fig. 1 shows an FTIR spectrum of a biomass phenolphthalein-furfuryl amine benzoxazine monomer according to the present invention.
FIG. 2 shows the preparation of biomass phenolphthalein-furfuryl amine type benzoxazine monomer1H NMR spectrum.
FIG. 3 shows DSC spectra of biomass phenolphthalein-furfuryl amine type benzoxazine monomer of the present invention and comparative example conventional bisphenol A-aniline type benzoxazine monomer.
Fig. 4 shows TG spectra of biomass phenolphthalein-furfuryl amine type benzoxazine resin according to the present invention and comparative example conventional bisphenol a-aniline type benzoxazine resin.
Detailed Description
The present invention will be described in further detail with reference to examples. It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all scientific and technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
Comparative example:
directly placing a commercial bisphenol A-aniline benzoxazine monomer in a prepared mould in advance, and then placing the mould in a forced air drying oven for step curing: maintaining at 175 deg.C for 1h, then heating to 190 deg.C for 2h, then heating to 210 deg.C for 2h, then heating to 235 deg.C for 1h, then heating to 250 deg.C for 1 h. Obtaining the thermosetting traditional bisphenol A-aniline benzoxazine resin.
Example 1:
the preparation method of the biomass phenolphthalein-furfuryl amine benzoxazine resin comprises the following steps:
(1) a mixed solution of 0.02mol of phenolphthalein, 0.088mol of polyformaldehyde, 5ml of ethanol and 25ml of toluene is sequentially added into a four-neck round-bottom flask provided with a magnetic stirrer, a spherical condenser tube, a thermometer and a constant-pressure dropping funnel, stirred and heated to a reflux state, then 0.04mol of furfurylamine is dropwise added into the flask by the constant-pressure dropping funnel for 5min, and then a constant-temperature reaction is carried out for 23 hours. Removing excessive solvent by rotary evaporation to obtain yellowish white powder, and washing with anhydrous ethanol to remove a small amount of unreacted raw materials. Vacuum drying for 24 hours (65 ℃), obtaining the biomass phenolphthalein-furfuryl amine benzoxazine monomer with 86.5% yield.
(2) And (2) placing the phenolphthalein-furfuryl amine type benzoxazine monomer obtained in the step (1) into a prepared mold in advance, and placing the mold into an air-blast drying oven for segmented curing (the step curing temperature is the same as the comparative example) to obtain the thermosetting biomass phenolphthalein-furfuryl amine type benzoxazine resin.
Example 2:
the preparation method of the biomass phenolphthalein-furfuryl amine benzoxazine resin comprises the following steps:
(1) a mixed solution of 0.05mol of phenolphthalein, 0.22mol of polyformaldehyde, 10ml of ethanol and 40ml of dioxane is sequentially added into a four-neck round-bottom flask provided with a magnetic stirrer, a spherical condenser tube, a thermometer and a constant-pressure dropping funnel, stirred and heated to a reflux state, then 0.10mol of furfurylamine is dropwise added into the flask by the constant-pressure dropping funnel for 10min, and then the reaction is carried out for 20 hours at constant temperature. Removing excessive solvent by rotary evaporation to obtain yellowish white powder, and washing with anhydrous ethanol to remove a small amount of unreacted raw materials. Vacuum drying for 24 hours (65 ℃), obtaining the biomass phenolphthalein-furfuryl amine benzoxazine monomer with 80.5% yield.
(2) And (2) placing the phenolphthalein-furfuryl amine type benzoxazine monomer obtained in the step (1) into a prepared mold in advance, and placing the mold into an air-blast drying oven for segmented curing (the step curing temperature is the same as the comparative example) to obtain the thermosetting biomass phenolphthalein-furfuryl amine type benzoxazine resin.
Example 3:
the preparation method of the biomass phenolphthalein-furfuryl amine benzoxazine resin comprises the following steps:
(1) the method comprises the steps of sequentially adding a mixed solution of 0.075mol of phenolphthalein, 0.33mol of polyformaldehyde, 20ml of ethanol and 60ml of xylene into a four-neck round-bottom flask provided with a magnetic stirrer, a spherical condenser, a thermometer and a constant-pressure dropping funnel, stirring and heating to a reflux state, then dropwise adding 0.15mol of furfurylamine into the flask by using the constant-pressure dropping funnel, finishing dropping for 15min, and reacting at constant temperature for 25 hours. Removing excessive solvent by rotary evaporation to obtain yellowish white powder, and washing with anhydrous ethanol to remove a small amount of unreacted raw materials. Vacuum drying for 24 hours (65 ℃) to obtain the biomass phenolphthalein-furfuryl amine type benzoxazine monomer with 89.5 percent of yield.
(2) And (2) placing the phenolphthalein-furfuryl amine type benzoxazine monomer obtained in the step (1) into a prepared mold in advance, and placing the mold into an air-blast drying oven for segmented curing (the step curing temperature is the same as the comparative example) to obtain the thermosetting biomass phenolphthalein-furfuryl amine type benzoxazine resin.
Example 4:
the biomass phenolphthalein-furfuryl amine type benzoxazine resin obtained in example 1, the intermediate product benzoxazine monomer and the conventional bisphenol a-aniline type benzoxazine resin obtained in the comparative example were subjected to correlation index detection, and the results are shown in fig. 1 to 4.
FIG. 1 is an FTIR spectrum of a biomass phenolphthalein-furfuryl amine benzoxazine monomer. As can be seen from the figure, the characteristic absorption peaks of the benzoxazine structure appear in: 1761cm-1(peak of carbonyl group in five-membered cyclic lactone in phenolphthalein Structure), 1235cm-1(stretching vibration peak of Ar-O-C on oxazine ring), 1154cm-1(peak of C-N-C in oxazine Ring), 932cm-1(oxazine Ring CH2Out-of-plane bending vibration).
FIG. 2 is a diagram of a biomass phenolphthalein-furfuryl amine type benzoxazine monomer1H NMR spectrum. As can be seen from the figure: the chemical shift of hydrogen protons in the oxazine ring is now 3.90ppm and 4.80ppm, respectively assigned to-Ar-CH2-N-and-O-CH2N-the chemical shift of the hydrogen protons of the methylene group to which N is attached to the furan ring is now 3.80ppm, the area ratio is 0.93: 1.00: 0.97, close to 1: 1: 1, and the number proportion of hydrogen protons in the target product.
Thus, from FTIR and1and H NMR spectrum shows that the prepared product has the same structure with the target product, namely the structure of the biological phenolphthalein-furfuryl amine type benzoxazine monomer.
FIG. 3 is a DSC spectra of biomass phenolphthalein-furfuryl amine type benzoxazine monomers and comparative example conventional bisphenol A-aniline type benzoxazine monomers. As can be seen from the figure: the initial curing temperature of the biomass phenolphthalein-furfuryl amine type benzoxazine monomer (Bio-Boz-PF) is 174.1 ℃, the curing peak temperature is 203.9 ℃, and the curing peak temperature is far lower than that of the traditional bisphenol A-aniline type benzoxazine monomer (Boz-BA) (the initial curing temperature and the curing peak temperature of the bisphenol A-aniline type benzoxazine resin are 212.0 ℃ and 252.4 ℃ respectively).
Fig. 4 is TG spectra of cured biomass phenolphthalein-furfuryl amine type benzoxazine resin and comparative example conventional bisphenol a-aniline type benzoxazine resin. As can be seen from the figure: initial decomposition temperature (T) of biomass phenolphthalein-furfuryl amine type benzoxazine resin (Bio-PolyBoz-PF)5％) The temperature is up to 372 ℃, and the carbon residue retention rate is up to 65% at 800 ℃. While the initial decomposition temperature (T) of the conventional bisphenol A-aniline type benzoxazine resin (PolyBoz-BA)5％) The carbon residue retention rate is only 34% at 800 ℃ and 343 ℃. As can be seen, the initial decomposition temperature (T) of Bio-PolyBoz-PF vs PolyBoz-BA5％) And the carbon residue retention rate at 800 ℃ is respectively improved by 29 ℃ and 31%. The TG result can show that the novel biomass benzoxazine resin has good heat resistance.
Example 5:
the biomass benzoxazine resin obtained in example 2 and the benzoxazine monomer as an intermediate product are subjected to related index detection, and the result is similar to that of example 4, so that the lists are not repeated.
Example 6:
the biomass benzoxazine resin obtained in example 3 and the benzoxazine monomer as an intermediate product are subjected to related index detection, and the result is similar to that of example 4, so that the lists are not repeated.
Materials, reagents and experimental equipment related to the embodiment of the invention are all commercial products which accord with the technical field of thermosetting resin preparation if no special description is provided.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, modifications and decorations can be made without departing from the core technology of the present invention, and these modifications and decorations shall also fall within the protection scope of the present invention. Any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (6)
1. The biomass phenolphthalein-furfuryl amine type benzoxazine resin is characterized in that: the structural formula is as follows:
the biomass phenolphthalein-furfuryl amine benzoxazine resin is prepared from monomers with the following structures:
the preparation method comprises the following steps:
(1) adding a solvent, phenolphthalein and formaldehyde into a reaction container, then dropwise adding furfuryl amine into the reaction container, stirring and heating to a reflux state after dropwise adding is finished, and reacting for 20-25 h; after the reaction is finished, removing the solvent, washing and drying to obtain a biomass phenolphthalein-furfuryl amine type benzoxazine monomer;
(2) and (2) placing the biomass phenolphthalein-furfuryl amine type benzoxazine monomer obtained in the step (1) in a mold for step curing to obtain the thermosetting biomass phenolphthalein-furfuryl amine type benzoxazine resin.
2. The biomass phenolphthalein-furfuryl amine-type benzoxazine resin according to claim 1, wherein: the solvent in the step (1) is at least one of three mixed solvents formed by mixing ethanol with toluene, dioxane and xylene respectively, and the volume ratio of the ethanol to the other components is 1: (3-5).
3. The biomass phenolphthalein-furfuryl amine-type benzoxazine resin according to claim 1, wherein: the formaldehyde in the step (1) is one of paraformaldehyde and formaldehyde aqueous solution.
4. The biomass phenolphthalein-furfuryl amine-type benzoxazine resin according to claim 2, wherein: the dripping time of the furfuryl amine in the step (1) is 0.5-1 h.
5. The biomass phenolphthalein-furfuryl amine-type benzoxazine resin according to claim 2, wherein: the ratio of phenolphthalein, furfuryl amine, formaldehyde and solvent in the step (1) is 0.02-0.10 mol: 0.04-0.20 mol: 0.088-0.44 mol: 30-80 mL.
6. The biomass phenolphthalein-furfuryl amine-type benzoxazine resin according to claim 2, wherein: step curing in the step (2): 175 ℃, 1h, 190 ℃, 2h, 210 ℃, 2h, 235 ℃, 1h, 250 ℃ and 1 h.
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| CN1733760A (en) * | 2005-08-08 | 2006-02-15 | 北京化工大学 | Phenolphthalein type benzoxazine intermediate and composition and method of making the same |
| CN101899155A (en) * | 2010-05-21 | 2010-12-01 | 北京化工大学 | Benzoxazine resin based on furfuryl amine, composition and preparation method thereof |
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| CN1733760A (en) * | 2005-08-08 | 2006-02-15 | 北京化工大学 | Phenolphthalein type benzoxazine intermediate and composition and method of making the same |
| CN101899155A (en) * | 2010-05-21 | 2010-12-01 | 北京化工大学 | Benzoxazine resin based on furfuryl amine, composition and preparation method thereof |
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