CN110128611A - Low-temperature setting biology base benzoxazine resin and preparation method thereof - Google Patents
Low-temperature setting biology base benzoxazine resin and preparation method thereof Download PDFInfo
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- CN110128611A CN110128611A CN201910287794.7A CN201910287794A CN110128611A CN 110128611 A CN110128611 A CN 110128611A CN 201910287794 A CN201910287794 A CN 201910287794A CN 110128611 A CN110128611 A CN 110128611A
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- phloroglucin
- biology base
- benzoxazine
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- temperature setting
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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
Abstract
The invention discloses a kind of low-temperature setting biology base benzoxazine resins and preparation method thereof.The benzoxazine resin monomer is prepared with the phloroglucin of bio-based source, chaff amine and paraformaldehyde, and under the conditions of the catalyst of phloroglucin, p-aminobenzoic acid and the paraformaldehyde preparation with bio-based source, 200 DEG C of low-temperature setting characteristics being fully cured are realized, are suitable for preparing the Green Composites of natural fiber enhancing.The synthesis technology of monomer and catalyst is reasonable, and purity is high, raw material is biomass material, environmentally protective, and yield is high and cost economical rationality, structural formula such as following formula (I) are shown:
Description
Technical field
The present invention relates to a kind of biological based thermoset applications and its preparation technical fields more particularly to a kind of low-temperature setting
(using 140 DEG C as initial cure temperature, terminating solidification temperature is 190 DEG C for solidification) biology base benzoxazine resin and its preparation side
Method.
Background technique
Polymer material is twentieth century material with the fastest developing speed, but almost all of polymer is all with fossil
Mineral resources production.With the rapid development of economy, the non-renewable resources such as petroleum are fewer and fewer, find it is new can be again
Production-goods source, and obtain from renewable resource the energy and chemicals has become our vital task.
Benzoxazine resin is to be reacted to generate monomer by phenolic compound, primary amine compound and formaldehyde, is then being heated
And/or crosslinking curing is made under the action of catalyst.Compared with conventional thermosetting resin, benzoxazine resin has unique excellent
Point: (1) volume change very little in solidification process；(2) water absorption rate is very low；(3) carbon yield is higher；(4) it is not needed in solidification process
Strong acid is as catalyst；(5) there is no by-product generation in solidification process；(6) flexibility of MOLECULE DESIGN is higher.Therefore, benzo
Oxazines resin obtains worldwide concern at present, it has also become the big hot spot in thermosetting resin research field.
Up to the present, the synthesis most important phenol source of benzoxazine resin is bisphenol-A (Bisphenol A, BPA), still
Bisphenol-A is mainly derived from oil product, causes the excessive dependence to oil product；And bisphenol-A can also cause dirt to environment
Dye；In addition, also will cause during existing material synthesis benzoxazine resin, polymerization temperature is high, curing process is undesirable not
Foot.Therefore, how to research and develop a kind of green and the high-performance oxazines resin with low-temperature setting characteristic is a urgent problem to be solved.
Summary of the invention
The technical problem to be solved by the present invention is to be directed to the above prior art, a kind of low-temperature setting biology base benzo is provided
Oxazines resin --- phloroglucin chaff amine/phloroglucin p-aminobenzoic acid type benzoxazine resin.
In order to solve the above-mentioned technical problem, a kind of the technical solution adopted by the present invention are as follows: low-temperature setting biology base benzo evil
Piperazine resin, shown in structural formula such as following formula (I):
The biology base phloroglucin chaff amine of above structure of the present invention/phloroglucin p-aminobenzoic acid type benzoxazine tree
Rouge, by the biology base phloroglucin chaff amine type benzoxazine monomer (PHG-F) (II) and biology base isophthalic three of following general structure
Phenol p-aminobenzoic acid type benzoxazine catalyst (PHG-P) (III) synthesis:
The above-mentioned benzoxazine monomer of the present invention and benzoxazine catalyst structure contain oxazines ring, therefore, can dislike in benzo
The net of nitrogenous and similar phenolic resin is generated in piperazine catalyst structure containing generation polymerization reaction under conditions of carboxyl catalysis heating
Shape structure.
The preparation method of the above-mentioned low-temperature setting biology base benzoxazine resin of the present invention, comprising the following steps:
(1) phloroglucin, chaff amine, formaldehyde and solvent are added into reaction vessel；Phloroglucin: chaff amine: formaldehyde: solvent=
0.01 mole: 0.03~0.04 mole: 0.06~0.08 mole: 100~150 milliliter, stirring is raised to reflux to after being completely dissolved
Petroleum ether is used in state, isothermal reaction 6~10 hours after reaction, and upper layer is taken to clarify phase, and revolving removal solvent obtains
Biology base phloroglucin chaff amine type benzoxazine resin monomer (PHG-F)；
(2) phloroglucin, p-aminobenzoic acid, formaldehyde and solvent are added into reaction vessel；Phloroglucin: p-aminophenyl
Formic acid: it formaldehyde: solvent=0.01 mole: 0.03~0.04 mole: 0.06~0.08 mole: 100~150 milliliters, stirs to complete
It is raised to reflux state, isothermal reaction 6~10 hours after fully dissolved, filters to obtain clear solution after reaction, revolving removes solvent,
Obtain biology base phloroglucin p-aminobenzoic acid type benzoxazine catalyst (PHG-P)；
(3) by the resulting biology base phloroglucin chaff amine type benzoxazine monomer of step (1) and step (2) resulting biology
Base phloroglucin p-aminobenzoic acid type benzoxazine catalyst is uniformly mixed, and is subsequently placed in stage curing in dry equipment, is obtained
Biology base phloroglucin chaff amine/phloroglucin p-aminobenzoic acid type benzoxazine resin.
Solvent described in above-mentioned steps (1) of the present invention and (2) is dioxane (1,4- dioxane).
Formaldehyde is paraformaldehyde in above-mentioned steps (1) of the present invention and step (2).
Biology base phloroglucin chaff amine type benzoxazine monomer and biology base phloroglucin pair in above-mentioned steps (3) of the present invention
The ratio of aminobenzoic acid type benzoxazine catalyst be 10:0~8:2 (0 not add catalyst be exactly pure PHG-F monomer,
It can also directly heat solidification, PHG-F solidification temperature can be made to be substantially reduced after a certain amount of PHG-P catalyst is added).
In above-mentioned steps (3) of the present invention it is stage curing specifically refer to 140 DEG C/1h, 150 DEG C/1h, 160 DEG C/2h, 170 DEG C/
1h、190℃/1h。
Compared with prior art, the present invention have following remarkable advantage and the utility model has the advantages that
(1) biomass benzoxazine resin of the present invention is to use phloroglucin for phenol source, and chaff amine and p-aminobenzoic acid are
Amine source, these three substances all derive from biomass, environmentally protective, reduce the dependence of petroleum resources.
(2) biology base phloroglucin chaff amine of the present invention/phloroglucin p-aminobenzoic acid type benzoxazine resin synthesis
Simple process is rationally, purity is high, yield are high and cost is relatively low；
(3) biology base phloroglucin chaff amine/phloroglucin p-aminobenzoic acid type benzoxazine of the method for the present invention preparation
Resin has good low-temperature setting characteristic, is suitable for preparing the Green Composites of natural fiber enhancing.
(4) biology base phloroglucin chaff amine/phloroglucin p-aminobenzoic acid type benzoxazine of the method for the present invention preparation
Resin heat resistance with higher and carbon yield are suitable for preparing the material of some high temperature resistants, resistance to ablation.
(5) phloroglucin of the invention (Phloroglucinol, PHG) molecule has 3 phenol hydroxyls similar with bisphenol-A
Based structures, so a kind of polymer monomer of the PHG as bio-based source, it is entirely possible to be used for benzoxazine instead of bisphenol-A
The preparation of the high molecular materials such as resin；Chaff amine (Furfurylamine, FA) of the invention is also a kind of in nature
The common biomass fine chemical material of the plant materials such as corncob, cotton seed hulls and bagasse production；By being with phloroglucin
Phenol source, chaff amine are amine source, get rid of excessive dependence of traditional benzoxazine resin to oil product；P-aminobenzoic acid (p-
Aminobenzoic acid, PABA) be also bio-based source compound, content is very in yeast, liver, wheat bran, malt
Height contains amino in structure, therefore can be used as amine source and be used to prepare benzoxazine resin monomer；Meanwhile PABA molecular structure
In also contain a carboxyl (- COOH), capable of promoting oxazines ring, ring-opening polymerisation is (industrial at present most common at a lower temperature
The solidification temperature of bisphenol-A aniline type benzoxazine resin is solidified at 250 DEG C, and completion of cure then needs higher temperature.And
Benzoxazine resin solidification temperature according to the present invention can be fully cured at 180 DEG C or so, and at 200 DEG C or so),
Improve the curing process of benzoxazine resin.
(6) present invention is that phenol source and amine source are prepared for full life compared to the traditional diphenolic acid for having used biology base and chaff amine
The scheme of the benzoxazine resin of object base is compared, and the biology base phloroglucin and chaff amine that the present invention uses are prepared for phenol source and amine source
Full biology base benzoxazine resin, be entirely different bio-based compounds as phenol source.In terms of solidification temperature, the present invention
Involved benzoxazine resin has lower solidification temperature, is in particular in that solidification peak is unimodal, cure peak temperature
For 160~180 DEG C (existing solidification peaks be bimodal, cure peak temperature is respectively 180 DEG C and 225 DEG C or so), and at 200 DEG C
Left and right, which realizes, is fully cured (prior art can just be realized at 250 DEG C or so and is fully cured).In terms of hot property, the present invention
Involved benzoxazine resin has good thermal stability.Specific manifestation: initial decomposition temperature is under a nitrogen atmosphere
302.0 DEG C, the slightly higher prior art, and the carbon residue at 800 DEG C is up to 53.3%, is much higher than the prior art.
(7) present invention to be using chaff amine and p-aminobenzoic acid be respectively benzoxazine tree that amine source prepares full biology base
Rouge, emphasis is three carboxyls of introducing in full biology base benzoxazine resin structure, solid to benzoxazine resin using carboxyl
The facilitation for changing reaction realizes the purpose of its low-temperature setting.The present invention is protecting the full biology base benzoxazine resin structure
Under the premise of selected solvent of the dioxane as the synthesis, be the synthesis temperature because if using chloroform, methanol as solvent
It is too low, influence whether the yield of resin.And toluene temperature is excessively high, will lead to partial monosomy ring-opening polymerisation in the synthesis process,
And then influence the purity of synthon；The polarity of ethyl alcohol is greater than dioxane, from the perspective of the yield of monomer and purity, two
Six ring of oxygen is most suitable solvent.In terms of curing process, pure PHG-F fusing point is 135 DEG C or so (as shown in Figure 5), PHG-
The fusing point of F/PHG-P mixed system is 120 DEG C or so, therefore the solidification of this patent is terminated using 140 DEG C as initial cure temperature
Solidification temperature is 190 DEG C, needs 6h (140 DEG C/1h, 150 DEG C/1h, 160 DEG C/2h, 170 DEG C/1h, 190 DEG C/1h) altogether；Therefore this hair
The bright curing process conventional curing process temperature that compares is low, and the time is short.
(8) have in the prior art using p-aminobenzoic acid is that amine source is prepared for benzoxazine resin monomer, and utilizes
DOPO prepares the technical solution of epoxy curing agent to its modification, and the DOPO of one of molecule is to pass through evil in this method
Piperazine ring open loop addition is introduced into molecular structure, in the structure of formation comprising a hydroxyl (- OH) and a carboxyl (- COOH),
Reaction can be crosslinked with the epoxy group in epoxy resin plays the role of curing agent；It follows that in the structure due to
Oxazines ring open loop addition leads to that oxazines ring structure is not present, and the carboxyl being also just far from being in p-aminobenzoic acid structure is to oxazines ring
The facilitation of Structured cured reaction；And it is prepared for using phloroglucin and p-aminobenzoic acid containing there are three carboxylics in the present invention
The full biology base benzoxazine monomer of base.Due to the presence of these three carboxyls, what is made itself oneself has very low solidification temperature
(147.8 DEG C of initial cure temperature, 160.8 DEG C of cure peak temperature, solidify 167.8 DEG C of final temperature), and also can be right
PHG-F resin has apparent facilitation.It follows that in the present invention, using p-aminobenzoic acid as the master in amine source
Syllabus is to reduce the solidification temperature of benzoxazine resin to introduce carboxyl.
Detailed description of the invention
Shown in FIG. 1 is the FTIR spectrum of biology base phloroglucin chaff amine type benzoxazine resin monomer (PHG-F) of the present invention
Figure；
Shown in Fig. 2 is biology base phloroglucin chaff amine type benzoxazine resin monomer (PHG-F) of the present invention1H NMR
Spectrogram；
Shown in Fig. 3 is biology base phloroglucin p-aminobenzoic acid type benzoxazine catalyst (PHG-P) of the present invention
FTIR spectrogram；
Shown in Fig. 4 is biology base phloroglucin p-aminobenzoic acid type benzoxazine catalyst (PHG-P) of the present invention1H NMR spectra；
Shown in fig. 5 is biology base phloroglucin chaff amine of the present invention/phloroglucin p-aminobenzoic acid type benzoxazine tree
DSC spectrogram of the rouge in the heating rate of 10K/min；
Shown in fig. 6 is biology base phloroglucin chaff amine of the present invention/phloroglucin p-aminobenzoic acid type benzoxazine tree
TG spectrogram under rouge condition of nitrogen gas.
Shown in Fig. 7 is biology base phloroglucin chaff amine of the present invention/phloroglucin p-aminobenzoic acid type benzoxazine tree
TG spectrogram under rouge air conditions.
Specific embodiment
The present invention is further described in detail with reference to embodiments.It is noted that detailed description below is all to illustrate
Property, it is intended to further instruction is provided to the present invention.Unless otherwise indicated, all scientific and technical terms that the present invention uses
With with the normally understood identical meanings of the technical field of the invention personnel.
Embodiment 1:
The preparation method of the present embodiment low-temperature setting biology base benzoxazine resin, comprising the following steps:
(1) in the three neck round bottom flask equipped with magnetic stirring apparatus and spherical condensation tube, sequentially add chaff amine 0.04mol,
Phloroglucin 0.01mol, polyformaldehyde 0.06mol and dioxane 100ml.Stirring is slowly raised to flow back to being completely dissolved rear temperature
State, isothermal reaction 8 hours.With petroleum ether clarifying reaction liquid, colourless transparent solution is obtained.Acquired solution revolving, obtains
The powder of white, i.e. biology base phloroglucin chaff amine type benzoxazine resin monomer (PHG-F), yield 82.7%, purity
98.2%.
(2) in the three neck round bottom flask equipped with magnetic stirring apparatus and spherical condensation tube, p-aminobenzoic acid is sequentially added
0.04mol, phloroglucin 0.01mol, polyformaldehyde 0.06mol and dioxane 100ml are stirred slow to rear temperature is completely dissolved
It is raised to reflux state, isothermal reaction 8 hours.Gained turbid solution filters to obtain clear solution, and solution is rotated, and obtains orange toner
End, i.e. biology base phloroglucin p-aminobenzoic acid type benzoxazine catalyst (PHG-P), yield 85.0%, purity 96.8%.
(3) with the product of step (1) and step (2) with 9.5:0.5,9:1,8:2 ratio mixes resulting fire-retardant group
Phloroglucin benzoxazine mix monomer, which is placed in inside the mold prepared in advance, is put in stage curing in air dry oven, segmentation
Solidify temperature-rise period are as follows: 140 DEG C/1h, 150 DEG C/1h, 160 DEG C/2h, 170 DEG C/1h, 190 DEG C/1h obtain the novel full biology base of heat
Phloroglucin chaff amine/phloroglucin p-aminobenzoic acid type benzoxazine resin.
Embodiment 2:
The preparation method of the present embodiment low-temperature setting biology base benzoxazine resin, comprising the following steps:
(1) in the three neck round bottom flask equipped with magnetic stirring apparatus and spherical condensation tube, sequentially add chaff amine 0.03mol,
Phloroglucin 0.01mol, polyformaldehyde 0.06mol and dioxane 100ml.Stirring is slowly raised to flow back to being completely dissolved rear temperature
State, isothermal reaction 6 hours.With petroleum ether clarifying reaction liquid, colourless transparent solution is obtained.Acquired solution revolving, obtains
The powder of white, i.e. biology base phloroglucin chaff amine type benzoxazine resin monomer (PHG-F), yield 51.6%, purity
97.8%.
(2) in the three neck round bottom flask equipped with magnetic stirring apparatus and spherical condensation tube, p-aminobenzoic acid is sequentially added
0.03mol, phloroglucin 0.01mol, polyformaldehyde 0.06mol and dioxane 100ml.It stirs slow to rear temperature is completely dissolved
It is raised to reflux state, isothermal reaction 6 hours.Gained turbid solution filters to obtain clear solution, and solution is rotated, and obtains orange toner
End, i.e. biology base phloroglucin p-aminobenzoic acid type benzoxazine catalyst (PHG-P), yield 60.3%, purity 96.1%.
(3) with the product of step (1) and step (2) with 9.5:0.5,9:1,8:2 ratio mixes resulting fire-retardant group
Phloroglucin benzoxazine mix monomer, which is placed in inside the mold prepared in advance, is put in stage curing in air dry oven, segmentation
Solidify temperature-rise period are as follows: 140 DEG C/1h, 150 DEG C/1h, 160 DEG C/2h, 170 DEG C/1h, 190 DEG C/1h obtains between novel full biology base
Benzenetriol chaff amine/phloroglucin p-aminobenzoic acid type benzoxazine resin.
Embodiment 3:
The preparation method of the present embodiment low-temperature setting biology base benzoxazine resin, comprising the following steps:
(1) in the three neck round bottom flask equipped with magnetic stirring apparatus and spherical condensation tube, sequentially add chaff amine 0.04mol,
Phloroglucin 0.01mol, polyformaldehyde 0.08mol and dioxane 150ml.Stirring is slowly raised to flow back to being completely dissolved rear temperature
State, isothermal reaction 10 hours.With petroleum ether clarifying reaction liquid, colourless transparent solution is obtained.Acquired solution revolving, obtains
The powder of white, i.e. biology base phloroglucin chaff amine type benzoxazine resin monomer (PHG-F), yield 93.2%, purity
99.1%.
(2) in the three neck round bottom flask equipped with magnetic stirring apparatus and spherical condensation tube, p-aminobenzoic acid is sequentially added
0.04mol, phloroglucin 0.01mol, polyformaldehyde 0.08mol and dioxane 150ml.It stirs slow to rear temperature is completely dissolved
It is raised to reflux state, isothermal reaction 10 hours.Gained turbid solution filters to obtain clear solution, and solution is rotated, and obtains crocus
Powder, i.e. biology base phloroglucin p-aminobenzoic acid type benzoxazine catalyst (PHG-P), yield 95.7%, purity
97.6%.
(3) with the product of step (1) and step (2) with 9.5:0.5,9:1,8:2 ratio mixes resulting fire-retardant group
Phloroglucin benzoxazine mix monomer, which is placed in inside the mold prepared in advance, is put in stage curing in air dry oven, segmentation
Solidify temperature-rise period are as follows: 140 DEG C/1h, 150 DEG C/1h, 160 DEG C/2h, 170 DEG C/1h, 190 DEG C/1h obtains between novel full biology base
Benzenetriol chaff amine/phloroglucin p-aminobenzoic acid type benzoxazine resin.
Embodiment 4:
The biology base phloroglucin chaff amine that embodiment 3 is obtained/phloroglucin p-aminobenzoic acid type benzoxazine resin
And intermediate product benzoxazine monomer carries out index of correlation detection, as a result as shown in figs. 1-7.
Fig. 1 is the FTIR spectrogram of biology base phloroglucin chaff amine type benzoxazine resin monomer (PHG-F).It can be with from figure
Find out: the characteristic absorption peak of benzoxazine structure appears in: 1224.1cm-1(the stretching vibration of C-O-C on benzoxazine ring
Peak), 1072.7cm-1(flexural vibrations peak of C-O-C on benzoxazine ring), 945.0cm-1(CH in oxazines ring2Out-of-plane bending vibration
It is dynamic), 1380.4cm-1(stretching vibration peak of C-N-C on benzoxazine ring), 1470.5cm-1(the flexible vibration of C=C in furan nucleus
Dynamic peak).
Fig. 2 is biology base phloroglucin chaff amine type benzoxazine resin monomer (PHG-F)1H NMR spectra.It can from figure
To find out: the Hydrogen Proton chemical shift in oxazines ring appears in 3.82ppm and 4.73ppm, is respectively belonging to-Ar-CH2- N- and-
O-CH2-N-；Hydrogen Proton chemical shift in furan nucleus appears in 6.18ppm, 6.27ppm and 7.34ppm；Area ratio is 1.96:
2.07:1.09:1.07:1.00 consistent with the number ratio of Hydrogen Proton in target product close to 2:2:1:1:1.
Therefore, the structure that can be seen that prepared product and target product from Fig. 1 and Fig. 2 is consistent, i.e., raw
The structure of object base phloroglucin chaff amine type benzoxazine resin monomer (PHG-F).
Fig. 3 is the FTIR spectrogram of biology base phloroglucin p-aminobenzoic acid type benzoxazine catalyst (PHG-P).From figure
In it can be seen that the characteristic absorption peak of benzoxazine structure appears in: 1257cm-1(the flexible vibration of C-O-C on benzoxazine ring
Dynamic peak), 1078cm-1(flexural vibrations peak of C-O-C on benzoxazine ring), 948cm-1(CH in oxazines ring2Out-of-plane bending vibration
It is dynamic), 1378cm-1(stretching vibration peak of C-N-C on benzoxazine ring), 1678cm-1(the C=O vibration peak of carboxyl), 3422cm-1
(the hydroxyl vibration peak to dissociate in carboxyl) and 2961cm-1、2662cm-1(the polymerization vibration peak of hydroxyl).
Fig. 4 is biology base phloroglucin p-aminobenzoic acid type benzoxazine catalyst (PHG-P)1H NMR spectra.From
It can be seen that the Hydrogen Proton chemical shift in oxazines ring appears in 3.57ppm and 5.16ppm in figure, it is respectively belonging to-Ar-
CH2- N- and-O-CH2-N-；Hydrogen Proton chemical shift in carboxyl appears in 12.42；The Hydrogen Proton of phenyl ring in p-aminobenzoic acid
Chemical shift appears in 7.12ppm and 7.75ppm, area ratio 1:0.97, close to Hydrogen Proton in 1:1 and target product
Number ratio is consistent.
Therefore, the structure that can be seen that prepared product and target product from Fig. 3 and Fig. 4 is consistent, i.e., raw
The structure of object base phloroglucin p-aminobenzoic acid type benzoxazine catalyst (PHG-P).
Fig. 5 is biology base phloroglucin chaff amine/phloroglucin p-aminobenzoic acid type benzoxazine resin 10K/min's
The DSC spectrogram of heating rate, characteristic temperature data are as shown in table 1.From Fig. 5 and table 1 it can be seen that PHG-F monomer
Beginning solidification temperature is 187.4 DEG C, and cure peak temperature is 202.5 DEG C.Solidifying final temperature is 217.9 DEG C.And PHG-P catalyst
Initial cure temperature only have 147.8 DEG C, cure peak temperature only has 160.8 DEG C.Solidification final temperature only has 167.8 DEG C, this
Illustrate that PHG-P catalyst has excellent low-temperature setting characteristic.Solidification temperature of the PHG-F after a certain amount of PHG-P is added has
It is decreased obviously, PHG-F monomer can be made to be fully cured at 200 DEG C or so 5% PHG-P is added, further relate to PHG-P pairs
The curing reaction of PHG-F has good catalysed promoted to act on.
1 biology base phloroglucin chaff amine of table/phloroglucin p-aminobenzoic acid type benzoxazine resin DSC curve feature
Temperature
Fig. 6 is under biology base phloroglucin chaff amine/phloroglucin p-aminobenzoic acid type benzoxazine resin condition of nitrogen gas
TG spectrogram.From Fig. 6 and table 2 it can be seen that under the conditions of nitrogen atmosphere, the initial decomposition temperature (T of novel PPHG-F5%)
It is 302.0 DEG C, at 800 DEG C, carbon residue retention rate is up to 53.0%.It is made PPHG-F/PPHG-P's adding a certain amount of PHG-P
T5%It is all little with carbon residue retention rate variation at 800 DEG C, especially the 800 of PPHG-F/PPHG-P is made in addition 10%PHG-P
DEG C when carbon residue retention rate and PPHG-F maintain an equal level, it is little that this illustrates that PHG-P catalyst influences the thermal stability of PPHG-F.
Fig. 7 is under biology base phloroglucin chaff amine/phloroglucin p-aminobenzoic acid type benzoxazine resin air conditions
TG spectrogram.From Fig. 7 and table 2 it can be seen that under the conditions of air atmosphere, the initial decomposition temperature (T of novel PPHG-F5%)
It is 297.8 DEG C, at 800 DEG C, carbon residue retention rate is up to 1.5%.It is made PPHG-F/PPHG-P's adding a certain amount of PHG-P
T5%Variation is less, but obviously slack-off in 450 DEG C or more of high temperature section decomposition rate, and carbon residue retention rate has centainly at 800 DEG C
The raising of degree.This illustrates that PHG-P catalyst does not reduce the thermo-oxidative stability of PPHG-F not only, has instead a degree of
Improve, especially in high temperature section.
2 biology base phloroglucin chaff amine of table/phloroglucin p-aminobenzoic acid type benzoxazine resin TG curve result
Data
The present embodiments relate to the material arrived, reagent and experimental facilities, are to meet thermosetting property tree unless otherwise instructed
The commercial product of rouge preparation technical field.
The above is merely a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, under the premise of not departing from core of the invention technology, improvements and modifications can also be made, these improvements and modifications are also answered
Belong to scope of patent protection of the invention.With any change in the comparable meaning and scope of claims of the present invention, all
It is considered as being included within the scope of the claims.
Claims (9)
1. a kind of low-temperature setting biology base benzoxazine resin, it is characterised in that: shown in its structural formula such as following formula (I):
2. low-temperature setting biology base benzoxazine resin according to claim 1, it is characterised in that: the benzoxazine
The synthon of resin includes biology base phloroglucin chaff amine type benzoxazine monomer and biology base phloroglucin p-aminophenyl first
Acid type benzoxazine catalyst.
3. low-temperature setting biology base benzoxazine resin according to claim 2, it is characterised in that: between the biology base
Shown in the structure such as following formula (II) of benzenetriol chaff amine type benzoxazine monomer:
4. low-temperature setting biology base benzoxazine resin according to claim 2, it is characterised in that: between the biology base
Shown in the structure such as following formula (III) of benzenetriol p-aminobenzoic acid type benzoxazine catalyst:
5. the preparation method of low-temperature setting biology base benzoxazine resin described in -4 any claims according to claim 1,
It is characterized by: step includes:
(1) phloroglucin, chaff amine, formaldehyde and solvent are added into reaction vessel；Phloroglucin: chaff amine: formaldehyde: solvent=0.01
Mole: 0.03~0.04 mole: 0.06~0.08 mole: 100~150 milliliters, stirring be raised to after being completely dissolved reflux state,
Isothermal reaction 6~10 hours, petroleum ether is used after reaction, upper layer is taken to clarify phase, and revolving removal solvent obtains biology base
Phloroglucin chaff amine type benzoxazine resin monomer；
(2) phloroglucin, p-aminobenzoic acid, formaldehyde and solvent are added into reaction vessel；Phloroglucin: p-aminophenyl first
Acid: it formaldehyde: solvent=0.01 mole: 0.03~0.04 mole: 0.06~0.08 mole: 100~150 milliliters, stirs to complete
It is raised to reflux state, isothermal reaction 6~10 hours after dissolution, filters to obtain clear solution after reaction, revolving removal solvent obtains
To biology base phloroglucin p-aminobenzoic acid type benzoxazine catalyst；
It (3) will be between the resulting biology base phloroglucin chaff amine type benzoxazine monomer of step (1) and step (2) resulting biology base
Benzenetriol p-aminobenzoic acid type benzoxazine catalyst is uniformly mixed, and is subsequently placed in stage curing in drying equipment, is given birth to
Object base phloroglucin chaff amine/phloroglucin p-aminobenzoic acid type benzoxazine resin.
6. the preparation method of low-temperature setting biology base benzoxazine resin according to claim 5, it is characterised in that: step
(1) and solvent described in (2) is dioxane.
7. the preparation method of low-temperature setting biology base benzoxazine resin according to claim 5, it is characterised in that: step
(1) and in step (2) formaldehyde is paraformaldehyde.
8. the preparation method of low-temperature setting biology base benzoxazine resin according to claim 5, it is characterised in that: step
(3) biology base phloroglucin chaff amine type benzoxazine monomer and biology base phloroglucin p-aminobenzoic acid type benzoxazine are urged in
The weight ratio of agent is 10:0~8:2.
9. the preparation method of low-temperature setting biology base benzoxazine resin according to claim 5, it is characterised in that: step
(3) stage curing in be specifically divided into following five sections: 140 DEG C/1h, 150 DEG C/1h, 160 DEG C/2h, 170 DEG C/1h, 190 DEG C/1h.
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| CN111138423A (en) * | 2019-12-20 | 2020-05-12 | 浙江大学宁波理工学院 | Monomer of benzoxazine resin, benzoxazine resin and preparation method thereof |
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| CN111057050A (en) * | 2019-12-20 | 2020-04-24 | 浙江大学宁波理工学院 | Monomer of bio-based benzoxazine resin, benzoxazine resin and preparation method thereof |
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| CN112500605B (en) * | 2020-11-16 | 2021-08-13 | 厦门大学 | MnO2fiber/CNT @ polybenzoxazine aerogel and preparation method thereof |
| CN113248673A (en) * | 2021-06-29 | 2021-08-13 | 中国科学院宁波材料技术与工程研究所 | Ultralow-temperature curing benzoxazine self-assembly composition, copolymer, preparation method and application |
| CN113248673B (en) * | 2021-06-29 | 2022-05-31 | 中国科学院宁波材料技术与工程研究所 | Ultralow-temperature curing benzoxazine self-assembly composition, copolymer, preparation method and application |
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