CN109438382A - It is a kind of based on deoxidation to double benzoxazine monomers and preparation method thereof of anisoin - Google Patents
It is a kind of based on deoxidation to double benzoxazine monomers and preparation method thereof of anisoin Download PDFInfo
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- CN109438382A CN109438382A CN201811316253.4A CN201811316253A CN109438382A CN 109438382 A CN109438382 A CN 109438382A CN 201811316253 A CN201811316253 A CN 201811316253A CN 109438382 A CN109438382 A CN 109438382A
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- Prior art keywords
- deoxidation
- anisoin
- double
- preparation
- benzoxazine
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- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 50
- LRRQSCPPOIUNGX-UHFFFAOYSA-N 2-hydroxy-1,2-bis(4-methoxyphenyl)ethanone Chemical compound C1=CC(OC)=CC=C1C(O)C(=O)C1=CC=C(OC)C=C1 LRRQSCPPOIUNGX-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000000178 monomer Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 claims abstract description 16
- OTKCEEWUXHVZQI-UHFFFAOYSA-N 1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1=CC=CC=C1 OTKCEEWUXHVZQI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 13
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 10
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 10
- 150000005130 benzoxazines Chemical class 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000000047 product Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 230000004580 weight loss Effects 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 239000000706 filtrate Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 3
- 239000002798 polar solvent Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 239000003063 flame retardant Substances 0.000 description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 150000000183 1,3-benzoxazoles Chemical class 0.000 description 3
- NNKQLUVBPJEUOR-UHFFFAOYSA-N 3-ethynylaniline Chemical group NC1=CC=CC(C#C)=C1 NNKQLUVBPJEUOR-UHFFFAOYSA-N 0.000 description 3
- -1 Benzoxazine compound Chemical class 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- NJXPYZHXZZCTNI-UHFFFAOYSA-N 3-aminobenzonitrile Chemical compound NC1=CC=CC(C#N)=C1 NJXPYZHXZZCTNI-UHFFFAOYSA-N 0.000 description 2
- MWKAGZWJHCTVJY-UHFFFAOYSA-N 3-hydroxyoctadecan-2-one Chemical compound CCCCCCCCCCCCCCCC(O)C(C)=O MWKAGZWJHCTVJY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 150000004893 oxazines Chemical class 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HLCPWBZNUKCSBN-UHFFFAOYSA-N 2-aminobenzonitrile Chemical compound NC1=CC=CC=C1C#N HLCPWBZNUKCSBN-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- 125000004217 4-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C([H])([H])* 0.000 description 1
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 1
- 240000006927 Foeniculum vulgare Species 0.000 description 1
- 235000004204 Foeniculum vulgare Nutrition 0.000 description 1
- 235000003332 Ilex aquifolium Nutrition 0.000 description 1
- 235000002296 Ilex sandwicensis Nutrition 0.000 description 1
- 235000002294 Ilex volkensiana Nutrition 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical group C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000001831 conversion spectrum Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
-
- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
Abstract
The invention belongs to thermosetting resin technical fields, provide a kind of double benzoxazines and preparation method thereof based on deoxidation to anisoin structure, preparation method includes two steps, (1) deoxidation mixes anisoin and pyridine hydrochloride, in 200 DEG C of 3~10h of reaction, it is post-treated, obtain 4,4'- dihydroxy deoxybezoin, desoxybenzoin；(2) 4,4'- dihydroxy deoxybezoin, desoxybenzoin and aminated compounds are mixed with paraformaldehyde, low polar solvent is added as reaction dissolvent, in 80~110 DEG C of 3~6h of reaction；It is filtered after reaction, filtrate water is washed 1~3 time, then by rotating, being dried to obtain product.It is an advantage of the invention that introducing deoxidation in benzoxazine molecule obtains novel benzoxazine monomer to anisoin structure, synthesis step is simple, yield is high, has very excellent heat, mechanical property after solidifying benzoxazine resin, and gained resin material has excellent anti-flammability；Synthesis technology is simple, lower to equipment requirement, is suitable for large-scale production.
Description
Technical field
The invention belongs to thermosetting resin technical fields, and in particular to it is a kind of based on deoxidation to double benzene of anisoin structure
And oxazines and preparation method thereof.
Background technique
Benzoxazine compound is to be found in synthesis Mannich reaction product in nineteen forty-four by Holly and Cope earliest
's.Then, Burke et al. compares in-depth study to the synthesis of benzoxazine.The country to the research of benzoxazine most
Before this since Gu Yi of Sichuan University et al., since 1993, Gu Yi et al. is in benzoxazine ring-opening polymerization mechanism, solidification
Dynamics, ablative mechanism etc. have done systematic research, have pushed benzoxazine in laminate, tellite, friction
The utilization in the fields such as material.As a kind of novel thermosetting phenolic resin, benzoxazine not only has traditional phenolic resin
Advantage, and there is no small molecule releasing in forming and hardening, cure shrinkage is practically negligible, has low product porosity.In addition, logical
It crosses and selects different phenols and amine, can be designed that the benzoxazine monomer for meeting different demands, so benzoxazine also has
There is very strong designability.Based on the above feature, benzoxazine receives the enthusiasm research of numerous scientific research personnel.
With the enhancing of awareness of safety, people especially propose the performance of material higher at heat-resisting and fire-retardant aspect
It is required that.But most of resin matrixes be all it is inflammable, how to improve the heat resistance and anti-flammability of benzoxazine resin, thus
Expand benzoxazine uses field, it has also become research hotspot in recent years.In this regard, domestic and international researcher has carried out a series of grind
Study carefully: in " Development of a DOPO-containing benzoxazine and its high-performance
flame retardant copolybenzoxazines”(Polymer Degradation and Stability,2009,
94,1693-1699) synthesis that the benzoxazine containing DOPO is reported in a text introduces P elements, higher limit oxygen index table
Bright this contains DOPO benzoxazine with good flame retardant property；In " Benzoxazine-containing branched
polysiloxanes:Highly efficient reactive-type flame retardants and property
It reports in enhancement agents for polymers " (Polymer, 2013,54,2945-2951) article based on silicon
The synthesis of the branched polysiloxane reactive flame retardant containing benzoxazine of nitrogen synergistic effect MOLECULE DESIGN theory, this is a kind of
Novel efficient flame-retarding agent and polymer performance reinforcing agent, but the addition of fire retardant inevitably generates mechanical performance of polymer etc.
Adverse effect；In entitled " Rheological and curing behaviors of high heat-resistant
It is reported in the article of benzoxazine resin " (Polymer Testing, 2018,69,214-218) a kind of with high burnt
The synthesis of the novel simple function benzoxazine resin of charcoal yield, the coke yield at 800 DEG C is 42.7%, but is managed not enough
Think.Currently, not having been reported that the synthesis being related to based on deoxidation to double benzoxazines of anisoin also.
Summary of the invention
Based on the present Research of flame retardant type benzoxazine, the present invention introduces deoxidation to fennel in benzoxazine monomer molecule
Fragrant benzoin structures make benzoxazine resin have excellent anti-flammability, at 800 DEG C of atmosphere of inert gases, carbon yield 65-
80%, and gained resin material has very excellent heat, mechanical property；Synthesis technology is simple, lower to equipment requirement, is suitable for
Large-scale production.
It is an object of the invention to improve the heat resistance of benzoxazine and fire-retardant to anisoin structure by introducing deoxidation
Property, a kind of double benzoxazines and preparation method thereof based on deoxidation to anisoin structure are provided.
The purpose of the present invention is what is be achieved through the following technical solutions:
An object of the present invention is to provide a kind of double benzoxazine monomers based on deoxidation to anisoin, molecularization
It is as follows to learn structural formula:
Wherein,For with one of flowering structure:
The second object of the present invention is to provide a kind of preparation side based on deoxidation to double benzoxazine monomers of anisoin
Method,
The first step is original to anisoin (alias: 4- methoxy-benzyl -4- acetophenone) and pyridine hydrochloride with deoxidation
Material, reaction preparation 4,4'- dihydroxy deoxybezoin, desoxybenzoin, chemical equation are as follows:
Second step is prepared with 4,4'- dihydroxy deoxybezoin, desoxybenzoin, aminated compounds and paraformaldehyde by Solvent method
Based on deoxidation to double benzoxazines of anisoin structure, chemical equation is as follows:
The aminated compounds structural formula is R-NH2, for one of flowering structure:
Concrete operation step is:
(1) reaction vessel is added to anisoin and pyridine hydrochloride in deoxidation to be uniformly mixed, then heating stirring, 160
DEG C~220 DEG C between react 3~10 hours；Reactant is poured into water after stopping reaction, precipitates, filter, obtain yellow powder,
It is recrystallized to give 4,4'- dihydroxy deoxybezoin, desoxybenzoin in acetone；
The deoxidation is 1: 2~1: 6 to anisoin and pyridine hydrochloride in molar ratio；Preferred molar ratio is 1: 4；
(2) in a solvent by 4,4'- dihydroxy deoxybezoin, desoxybenzoin made from step (1) and aminated compounds and paraformaldehyde
Mixing, then heats up, reacts 3~6 hours between 80 DEG C~110 DEG C；Reactant is filtered after stopping reaction, by filtrate water
It is rotated after washing 1~3 time, isolates solvent, then drying obtains solid product, as based on deoxidation to the double of anisoin structure
Benzoxazine monomer.
4,4'- dihydroxy deoxybezoin, desoxybenzoin, aniline and the paraformaldehyde is 1: 1: 2~1: 4: 6 in molar ratio；It is preferred that
Molar ratio is 1: 2: 4.4；
The solvent is one of toluene, dimethylbenzene, dioxane or mixture.
Compared with prior art, present invention has an advantage that
Deoxidation is introduced in benzoxazine molecule, and prepared by double benzoxazine monomers, synthesis step letter to anisoin structure
Single, yield is high, resin excellent workability, and benzoxazine resin after solidifying is made to have very excellent heat, mechanical property, and
Gained resin material has excellent anti-flammability；Synthesis technology is simple, lower to equipment requirement, is suitable for large-scale production.
Detailed description of the invention
The hydrogen nuclear magnetic resonance spectrogram for the benzoxazoles resin that Fig. 1 embodiment 1 obtains；
The infrared spectrogram for the benzoxazoles resin that Fig. 2 embodiment 1 obtains；
The DSC spectrogram for the benzoxazine resin that Fig. 3 embodiment 1 obtains；
The TGA spectrogram of material after the benzoxazine resin that Fig. 4 embodiment 1 obtains solidifies.
Specific embodiment
The present invention presented below it is a kind of based on deoxidation to the tool of double benzoxazines of anisoin structure and preparation method thereof
Body embodiment.It is important to point out that: following instance is only used for that the present invention will be described in more detail, rather than reduces this
The protection scope of invention.The professional of the art after reading this disclosure, under the premise of not departing from present inventive concept
The modifications and adaptations made are all within the scope of protection of present invention.
Embodiment 1
It is a kind of based on deoxidation to double benzoxazines and preparation method thereof of anisoin structure, specific steps are as follows:
(1) 5.183g (0.02mol) deoxidation is added to and is equipped with to anisoin and 9.348g (0.08mol) pyridine hydrochloride
Stirrer, condenser pipe reaction flask in, be heated to 200 DEG C and be stirred, reaction 5 hours after terminate.Be cooled to 80 DEG C hereinafter,
Reactant is poured into the 500ml beaker equipped with enough water, and is stirred with glass bar, is largely precipitated.After suction filtration, obtain
To yellow powder, product is put into vacuum drying oven drying, obtains 4,4'- dihydroxy deoxybezoin, desoxybenzoin 3.92g, yield 85%.
Chemical equation is as follows:
(2) 4, the 4'- dihydroxy deoxybezoin, desoxybenzoin 0.996g (4.4mmol) and benzene reacted by previous step is weighed
Amine 0.813g (8.7mmol), paraformaldehyde 0.566g (18.8mmol) are added separately to the reaction equipped with stirrer, condenser pipe
In bottle, 36ml dimethylbenzene being added as solvent, 80 DEG C is warming up to and is stirred, reaction was completed after 5 hours for reaction, will react
Object filtering, obtained filtrate are washed 3 times, are isolated dimethylbenzene by revolving, are dried, obtain product 1.77g, yield 88%.Change
It is as follows to learn reaction equation:
In the present embodiment, obtained oxazines product structure are as follows:
The hydrogen nuclear magnetic resonance spectrogram of the product, the infrared conversion spectrum figure of Fourier, DSC curve figure and thermogravimetric curve figure are shown in
Attached drawing 1, attached drawing 2, attached drawing 3 and attached drawing 4.
1 hydrogen nuclear magnetic resonance spectrogram of attached drawing.Chemical shift 5.36,5.44ppm and 4.62,4.68ppm are methylene on oxazines ring
Base characteristic peak.Fig. 2 is infrared spectrogram, wherein 924 and 1238cm-1Place is the characteristic absorption peak of benzoxazine ring.Attached drawing 3 is
DSC curve figure, the benzoxazine monomer cure exothermic peak temperature are 217 DEG C.Attached drawing 3 is as can be seen that benzoxazoles resin warm
Carbon yield when temperature when weightlessness 5% is 403 DEG C, 800 DEG C is 68%.In addition, the benzoxazine resin that the present embodiment obtains
The heat release of flame retardant test result can be 55Jg after solidification-1K-1。
Embodiment 2
Aniline in the reaction of 1 second step of embodiment is replaced with into m-aminophenyl formonitrile HCN, other steps are the same as the step in embodiment 1
Suddenly.
The particular chemical of in-between anthranilo nitrile are as follows:
In second step reaction, the amount of reactant is changed to: weighing 4, the 4'- dihydroxy deoxidation benzene reacted by previous step
Acyloin 1.560g (6.8mmol) and m-aminophenyl formonitrile HCN 1.615g (13.7mmol), paraformaldehyde 0.886g
(29.5mmol)。
The structural formula of the double benzoxazines of gained are as follows:
Double benzoxazine monomer yields 90% that the present embodiment obtains, further after solidification crosslinking, polybenzoxazine resin
When in thermal weight loss 5%, temperature is 435 DEG C, 800 DEG C of atmosphere of inert gases, the heat of carbon yield 73%, flame retardant test result is released
Exoergic is 50Jg-1K-1。
Embodiment 3
Aniline in the reaction of 1 second step of embodiment is replaced with into 3-aminophenylacetylene, other steps are the same as the step in embodiment 1
Suddenly.
The wherein particular chemical of 3-aminophenylacetylene are as follows:
In second step reaction, the amount of reactant is changed to: weighing 4, the 4'- dihydroxy deoxidation benzene reacted by previous step
Acyloin 1.575g (6.9mmol) and 3-aminophenylacetylene 1.616g (13.8mmol), paraformaldehyde 0.895g
(29.8mmol)。
The structural formula of the double benzoxazines of gained are as follows:
Double benzoxazine monomer yields 92% that the present embodiment obtains.Further after solidification crosslinking, polybenzoxazine resin
When in thermal weight loss 5%, temperature is 443 DEG C, 800 DEG C of atmosphere of inert gases, carbon yield 75%, flame retardant test heat, which discharges, to be
48Jg-1K-1。
Claims (9)
1. it is a kind of based on deoxidation to double benzoxazine monomers of anisoin, which is characterized in that molecular formula is as follows:
Wherein,For with one of flowering structure:
2. it is according to claim 1 based on deoxidation to double benzoxazine monomers of anisoin, which is characterized in that the base
Polybenzoxazine resin, polybenzoxazine are obtained after double benzoxazine monomers of the deoxidation to anisoin further solidify crosslinking
Resin in thermal weight loss 5% temperature be 400-460 DEG C, 800 DEG C of atmosphere of inert gases when, carbon yield 65-80%.
3. it is according to claim 1 based on deoxidation to the preparation method of double benzoxazine monomers of anisoin, feature
It is, specifically includes the following steps:
(1) synthesis of 4,4'- dihydroxy deoxybezoin, desoxybenzoin
Reaction vessel is added to anisoin and pyridine hydrochloride in deoxidation to be uniformly mixed, then heating stirring, 160 DEG C~220
DEG C, it reacts 3~10 hours, product is poured into water washing after reaction, is dried after refiltering, product 4,4'- dihydroxy are obtained
Base deoxybezoin, desoxybenzoin；
(2) synthesis based on deoxidation to double benzoxazines of anisoin structure
4, the 4'- dihydroxy deoxybezoin, desoxybenzoin of step (1) preparation and aminated compounds and paraformaldehyde are mixed in a solvent,
80 DEG C~110 DEG C are then heated to, is reacted 3~6 hours, after stopping reaction, is washed with water and rotates solvent, then drying obtains
Solid product, as based on deoxidation to double benzoxazine monomers of anisoin structure.
4. as claimed in claim 3 based on deoxidation to the preparation method of double benzoxazine monomers of anisoin, feature exists
In in step (2), the aminated compounds structural formula is R-NH2, for one of flowering structure:
5. as claimed in claim 3 based on deoxidation to the preparation method of double benzoxazine monomers of anisoin, feature exists
In in step (1), the deoxidation is 1: 2~1: 6 to the molar ratio of anisoin and pyridine hydrochloride.
6. as claimed in claim 5 based on deoxidation to the preparation method of double benzoxazine monomers of anisoin, feature exists
In the deoxidation is 1: 4 to the molar ratio of anisoin and pyridine hydrochloride.
7. as claimed in claim 3 based on deoxidation to the preparation method of double benzoxazine monomers of anisoin, feature exists
In in step (2), the molar ratio of 4, the 4'- dihydroxy deoxybezoin, desoxybenzoin, aminated compounds and paraformaldehyde is 1: 2: 4
~1: 2: 5.
8. as claimed in claim 7 based on deoxidation to the preparation method of double benzoxazine monomers of anisoin, feature exists
In the molar ratio of 4, the 4'- dihydroxy deoxybezoin, desoxybenzoin, aminated compounds and paraformaldehyde is 1: 2: 4.4.
9. as claimed in claim 3 based on deoxidation to the preparation method of double benzoxazine monomers of anisoin, feature exists
In in step (2), the solvent is one of toluene, dimethylbenzene, dioxane or mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811316253.4A CN109438382B (en) | 2018-11-07 | 2018-11-07 | Dibenzoxazine monomer based on deoxyp-anisoin and preparation method thereof |
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| CN111100120A (en) * | 2019-11-04 | 2020-05-05 | 江苏大学 | Bio-based bis-benzoxazine monomer and preparation method thereof |
| CN111234211A (en) * | 2020-03-16 | 2020-06-05 | 淮北绿洲新材料有限责任公司 | Benzoxazine intrinsic flame-retardant resin and preparation method thereof |
| CN114195803A (en) * | 2021-08-24 | 2022-03-18 | 镇江利德尔复合材料有限公司 | Coumarin-based bio-based bifunctional benzoxazine resin and preparation method thereof |
| CN114836005A (en) * | 2022-06-16 | 2022-08-02 | 南京工业大学 | Preparation method of para-aminobenzonitrile derivative flame-retardant epoxy resin composite material |
| CN116396477A (en) * | 2023-04-14 | 2023-07-07 | 中国人民解放军国防科技大学 | High-temperature-resistant polybenzoxazine aerogel and preparation method thereof |
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| CN106366079A (en) * | 2016-08-30 | 2017-02-01 | 常州市宏发纵横新材料科技股份有限公司 | Dibenzoxazine monomer containing ortho-position maleimide groups and preparation method thereof |
| CN107129493A (en) * | 2017-04-10 | 2017-09-05 | 江苏大学 | A kind of two amine type bi-benzoxazines of the imide containing alicyclic and preparation method thereof |
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| CN106366079A (en) * | 2016-08-30 | 2017-02-01 | 常州市宏发纵横新材料科技股份有限公司 | Dibenzoxazine monomer containing ortho-position maleimide groups and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111100120A (en) * | 2019-11-04 | 2020-05-05 | 江苏大学 | Bio-based bis-benzoxazine monomer and preparation method thereof |
| CN111100120B (en) * | 2019-11-04 | 2022-08-23 | 江苏大学 | Bio-based bis-benzoxazine monomer and preparation method thereof |
| CN111234211A (en) * | 2020-03-16 | 2020-06-05 | 淮北绿洲新材料有限责任公司 | Benzoxazine intrinsic flame-retardant resin and preparation method thereof |
| CN114195803A (en) * | 2021-08-24 | 2022-03-18 | 镇江利德尔复合材料有限公司 | Coumarin-based bio-based bifunctional benzoxazine resin and preparation method thereof |
| CN114195803B (en) * | 2021-08-24 | 2024-04-02 | 镇江利德尔复合材料有限公司 | Difunctional benzoxazine resin based on coumarin bio-base and preparation method thereof |
| CN114836005A (en) * | 2022-06-16 | 2022-08-02 | 南京工业大学 | Preparation method of para-aminobenzonitrile derivative flame-retardant epoxy resin composite material |
| CN116396477A (en) * | 2023-04-14 | 2023-07-07 | 中国人民解放军国防科技大学 | High-temperature-resistant polybenzoxazine aerogel and preparation method thereof |
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