CN107573334A - A kind of single function benzoxazine of the imide group containing alicyclic and preparation method thereof - Google Patents
A kind of single function benzoxazine of the imide group containing alicyclic and preparation method thereof Download PDFInfo
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- CN107573334A CN107573334A CN201710229092.4A CN201710229092A CN107573334A CN 107573334 A CN107573334 A CN 107573334A CN 201710229092 A CN201710229092 A CN 201710229092A CN 107573334 A CN107573334 A CN 107573334A
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- Prior art keywords
- alicyclic
- benzoxazine
- aminophenol
- reaction
- preparation
- Prior art date
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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 35
- 125000002723 alicyclic group Chemical group 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 125000005462 imide group Chemical group 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 150000002989 phenols Chemical class 0.000 claims abstract description 14
- 150000003949 imides Chemical class 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229930040373 Paraformaldehyde Chemical class 0.000 claims abstract description 9
- 229920002866 paraformaldehyde Chemical class 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 6
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 13
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 12
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 12
- -1 anhydrides compound Chemical class 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229940018563 3-aminophenol Drugs 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 238000004100 electronic packaging Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 9
- 239000000178 monomer Substances 0.000 abstract description 7
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 238000007493 shaping process Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 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 3
- QZVQQUVWFIZUBQ-UHFFFAOYSA-N 3-fluoroaniline Chemical compound NC1=CC=CC(F)=C1 QZVQQUVWFIZUBQ-UHFFFAOYSA-N 0.000 description 3
- 0 CC(CCC1C(N2C)=*)CC1C2=O Chemical compound CC(CCC1C(N2C)=*)CC1C2=O 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- LWMIDUUVMLBKQF-UHFFFAOYSA-N 4-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical class CC1CC=CC2C(=O)OC(=O)C12 LWMIDUUVMLBKQF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- UVARRZDJPDWVJL-UHFFFAOYSA-N CC(C1C(N2C)=O)C=CCC1C2=O Chemical compound CC(C1C(N2C)=O)C=CCC1C2=O UVARRZDJPDWVJL-UHFFFAOYSA-N 0.000 description 1
- VTVWGTIGJGYSJY-UHFFFAOYSA-N CN(C(C1C2C(C=C)C=CC1)=O)C2=O Chemical compound CN(C(C1C2C(C=C)C=CC1)=O)C2=O VTVWGTIGJGYSJY-UHFFFAOYSA-N 0.000 description 1
- PGHYPCPNTBGZLQ-UHFFFAOYSA-N CN(C(C1C2CCCC1)=O)C2=O Chemical compound CN(C(C1C2CCCC1)=O)C2=O PGHYPCPNTBGZLQ-UHFFFAOYSA-N 0.000 description 1
- ZXLYYQUMYFHCLQ-UHFFFAOYSA-N CN(C(c1ccccc11)=O)C1=O Chemical compound CN(C(c1ccccc11)=O)C1=O ZXLYYQUMYFHCLQ-UHFFFAOYSA-N 0.000 description 1
- VKXOJPZTGBRUCY-UHFFFAOYSA-N CN(C1OC1C1C2CC(Cl)=CC1)C2=O Chemical compound CN(C1OC1C1C2CC(Cl)=CC1)C2=O VKXOJPZTGBRUCY-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229960000250 adipic acid Drugs 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention provides single function benzoxazine of a kind of imide group containing alicyclic and preparation method thereof.This preparation method is made up of two steps.The first step：The phenolic compound of reaction synthesis imide structure containing alicyclic；Second step：So that containing the imido phenolic compound of alicyclic, aminated compounds and paraformaldehyde, as raw material, reaction synthesizes the monofunctional benzoxazine monomer of alicyclic imide group.The advantage of the invention is that：Using hexa-atomic alicyclic imide group, effectively increase the machinability of acid imide benzoxazine colophony, and part alicyclic contains carbon-carbon double bond structure, it is crosslinked benzoxazine Bu Jin oxazine rings open loop in elevated cure, END CAPPED GROUP with secondary cross-linking, can substantially increase the heat endurance of resin.The resin processing temperature window of gained of the invention is widened, and is advantageous to machine-shaping.The method preparation technology is simple, low for equipment requirements, can be with industrialized production.
Description
Technical field
The invention belongs to thermosetting resin and its preparing technical field, specific description is related to a kind of acid imide containing alicyclic
Monofunctional benzoxazine of group and preparation method thereof.
Background technology
Traditional phenolic resin is because its raw material is easy to get, cheap, production technology and equipment are simple, the product being made
With excellent mechanical performance, weatherability, cold resistance, heat resistance, good stability of the dimension and be widely used.But with
The raising of application field and performance requirement, phenolic resin have been unsatisfactory for the requirement in some fields.To meet higher decomposition temperature
The requirement of degree, good hot restorability, enough coefficient of friction, preferable anti-wear performance and relatively low noise, benzoxazine
Had been surprisingly found that by Holly and Cope.Benzoxazine compound is a kind of intermediate containing heterocycle structure, typically by phenols chemical combination
Thing, primary amine compound and formaldehyde are made through condensation reaction, then the ring-opening polymerisation under heating or catalyst action, and generation is nitrogenous
And the network structure of similar phenolic resin, referred to as Polybenzoxazine.
There are many patents to be related to the benzoxazine containing acid imide or amide structure.Such as Patent No.
2009100975549.6 Chinese invention patent《Bi-benzoxazine containing imide structure and preparation method thereof》(Granted publication
Number：The A of CN 101857592), disclose a kind of bi-benzoxazine containing imide structure and preparation method thereof, the patent is by acyl
Imine structure is introduced into the strand of benzoxazine compound, adds the heat resistance and mechanical property of polymer, combination property
It is excellent, it is suitable for the resin matrix of high-performance composite materials；The patent of invention of Application No. 200610020900.8《It is a kind of
Benzoxazine containing maleimide and allyl ether and preparation method thereof》Shen Qing Publication is a kind of to contain maleimide and alkene
The benzoxazine of propyl ether, benzoxazine heat endurance greatly improves made from the patent, and preparation method reactions steps are few, raw
It is low to produce cost.
These patents, it is structurally-modified by Dui benzoxazine monomers, the heat resistance of polymer is improved, but manage not enough
Think, especially the process window of resin monomer, often spent only 50 more, be unfavorable for processing and forming.In addition, do not have also at present
Report is related to using alicyclic containing hexatomic ring and acid imide connected structure group phenol source to prepare benzoxazine monomer and performance.
The content of the invention
The present invention is directed to the defects of benzoxazine colophony is existing, introduces hexa-atomic alicyclic ring hydrocarbon structure, synthesized benzoxazine
Journey summary, and the hexatomic ring alicyclic ring hydrocarbon structure introduced compensate for traditional acid imide benzoxazine monomer by molecular weight is low, molecule
Performance deficiency caused by rigidity is high, and the machinability of benzoxazine colophony is improved, assign its particular characteristic.
It is as follows to reach a kind of benzoxazine of above-mentioned performance its molecular formula：
Wherein, R1- it is one of following：
R1In the ortho position of oxygen atom, meta or para position；
To be one of following：
To reach the monofunctional benzoxazine that another object of the present invention provides a kind of imide group containing alicyclic
Preparation method, it is characterised in that comprise the following steps：
(1) using one kind in o-aminophenol, m-aminophenol and para-aminophenol and anhydrides compound as raw material, instead
The phenolic compound of the imide structure containing alicyclic should be synthesized, reaction equation is as follows：
Wherein, R is one of following：
R1- it is one of following：
R1In the ortho position of phenolic hydroxyl group, meta or para position.
(2), as raw material, to react synthetic fat containing the imido phenolic compound of alicyclic, aminated compounds and paraformaldehyde
The monofunctional benzoxazine of cyclic hydrocarbon imide group, reaction equation are as follows：
Wherein, R1- it is one of following：
R1In the ortho position of oxygen atom, meta or para position；
To be one of following：
Concrete operation step is as follows：
(1) by one kind in o-aminophenol, m-aminophenol and para-aminophenol and anhydrides compound by suitably rubbing
You are added using glacial acetic acid in the reaction system of solvent, then will to be full of nitrogen in reaction system or other inertia are protected than mixing
Gas is protected, for system from room temperature to 100~120 DEG C, total reaction time is 6~8 hours.After stopping reaction, reaction solution is passed through
Deionized water precipitating, washing, the phenolic compound for filtering, being dried to obtain the imide group containing alicyclic.
One kind in described o-aminophenol, m-aminophenol and para-aminophenol with anhydrides compound in molar ratio
For 1：1~1：1.3；It is preferably in a proportion of 1：1.1.
(2) phenolic compound, aminated compounds and the paraformaldehyde of the alicyclic containing acid imide are pressed into appropriate mixed in molar ratio,
It is added in low polar solvent, then heat temperature raising, reaction system is reacted 8~12 hours at 100~120 DEG C, stops reaction
Afterwards, reaction solution is washed 2-3 times with alkali lye A, the outstanding solvent that steams is precipitated, and obtains monofunctional benzoxazine.
The described phenolic compound of acid imide containing alicyclic, aminated compounds and paraformaldehyde is 1 in molar ratio:1:2~
1:1:2.2, it is preferably in a proportion of 1:1:2.1.
Described low polar solvent is toluene or dimethylbenzene.
Described alkali lye A is one in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acid carbonate, potassium carbonate, saleratus
Kind.
Compared with prior art, the advantage of the invention is that：Using hexa-atomic alicyclic imide group, acyl is effectively increased
The machinability of imines benzoxazine colophony, and part alicyclic contains carbon-carbon double bond structure, makes benzoxazine solid in heating
Only oxazine ring open loop is not crosslinked during change, and END CAPPED GROUP with secondary cross-linking, can substantially increase the heat endurance of resin.The present invention
The resin processing temperature window of gained is widened, and is advantageous to machine-shaping.The method preparation technology is simple, low for equipment requirements,
Can be with industrialized production.
Brief description of the drawings
Fig. 1 is the infrared spectrogram for the benzoxazine monomer that embodiment 1 obtains；
Fig. 2 is the DSC curve figure for the benzoxazine colophony that embodiment 1 obtains.
Embodiment
The present invention is described further below in conjunction with instantiation.It is important to point out that：Following instance is simply to this
Invention is described further, and is not limited solely to protection scope of the present invention.Those skilled in the art are readding
After reader invention, do not depart from the present invention concept thereof under, can also change to do various modifications and adaptations, these improve and
Adjustment belongs to the scope of protection of present invention.
Embodiment one
Ortho-Aminophenol 10.91g, THPA 15.22g, acetic acid 250.00ml are added to containing agitator, thermometer
And in the reaction bulb of condenser pipe, reaction unit is vacuumized with vavuum pump, is filled with nitrogen afterwards, repeatedly for three times.It is being passed through nitrogen
Under conditions of being protected, progressively heating be heated to 120 DEG C react 6 hours.Then 300ml deionized waters are added, are obtained a large amount of
Precipitation.After suction filtration, washed three times with a large amount of water and ethanol, be put into 50 DEG C of vacuum tanks and dry, obtain product 21.63g, yield
89%.Reaction equation is as follows：
Weigh as the phenolic compound 12.16g of the imide group containing alicyclic obtained by previous step, and aniline 4.66g,
Paraformaldehyde 3.13g, dimethylbenzene 100ml are added separately to be equipped with agitator, in the reaction bulb of thermometer and condenser pipe, with 10
DEG C/h speed is heated to 120 DEG C of reaction 8h.After reaction terminates, solution is cooled to room temperature, with the carbonic acid of mass concentration 5%
Hydrogen sodium solution washs 3 times, then is dried to obtain product 16.38g, yield 91% through outstanding steaming.Reaction equation is as follows：
The thermal weight loss characterization result of resin is shown in after the FTIR spectrum of the product, differential scanning calorimetry and solidification
Accompanying drawing 1, accompanying drawing 2.Accompanying drawing 1 is infrared spectrogram, wherein 935cm-1The characteristic peak of Chu Wei oxazine rings.Accompanying drawing 2 is differential scanning amount
DSC figures obtained by hot method, it can be seen that the maximum cure peak temperature of the resin is 249.8 DEG C.
After the hot curing reaction of benzoxazine obtained by the present embodiment, its glass transition temperature is measured as 278 DEG C, 5%
Thermal weight loss temperature is that the carbon yield at 368 DEG C, 800 DEG C is 55%.
Embodiment two
THPA in embodiment 1 is replaced with into 1,2- ring hexanedioic acid acid anhydrides, aniline replaces with m-fluoroaniline, reactant
Amount makes corresponding change, and other operating procedures are the same as the step in embodiment 1.
Wherein, the concrete structure formula of 1,2- cyclohexane diacids acid anhydride is：
The concrete structure formula of m-fluoroaniline is：
In first step reaction, the amount of reactant is changed to：1,2- cyclohexane diacid acid anhydride is 15.42g, Ortho-Aminophenol
10.91g, acetic acid 250.00ml, obtain product 20.85g, yield 85%.
In second step reaction, the amount of reactant is changed to：The phenol for reacting to obtain by previous step is 12.26g, and poly
Formaldehyde is 3.13g, m-fluoroaniline 4.66g, obtains product 1.77g, yield 83%.
The structural formula of Suo get oxazine monomers is：
After the hot curing reaction of benzoxazine obtained by the present embodiment, 267 DEG C of its glass transition temperature, 5% heat are measured
Weightless temperature is that the carbon yield at 359 DEG C, 800 DEG C is 51%.
Embodiment three
THPA in embodiment 1 is replaced with into 3- methyl tetrahydro phthalic anhydrides, the amount of reactant makes corresponding change, other
Operating procedure is the same as the step in embodiment 1.
Wherein, the particular chemical formula of 3- methyl tetrahydro phthalic anhydrides is：
In first step reaction, the amount of reactant is changed to：3- methyl tetrahydro phthalic anhydrides are 16.62g, Ortho-Aminophenol
10.91g, acetic acid 250.00ml, obtain product 23.67g, yield 92%.
In second step reaction, the amount of reactant is changed to：The phenol for reacting to obtain by previous step is 12.86g, and poly
Formaldehyde is 3.13g, aniline 5.56g, obtains product 16.47g, yield 88%.
Products therefrom structural formula is：
After the hot curing reaction of benzoxazine obtained by the present embodiment, its glass transition temperature is measured as 289 DEG C, 5%
Thermal weight loss temperature is that the carbon yield at 379 DEG C, 800 DEG C is 60%.
Claims (9)
- A kind of 1. single function benzoxazine of imide group containing alicyclic, it is characterised in that：Single function benzoxazine point Minor is as follows：Wherein, R1- it is one of following：R1In the ortho position of oxygen atom, meta or para position；To be one of following：
- 2. a kind of preparation method of the monofunctional benzoxazine of imide group containing alicyclic according to claim 1, It is characterized in that comprise the following steps：(1) using one kind in o-aminophenol, m-aminophenol and para-aminophenol and anhydrides compound as raw material, reaction is closed It is as follows into the phenolic compound of the imide structure containing alicyclic, reaction equation：Wherein, R is one of following：R1- it is one of following：R1In the ortho position of phenolic hydroxyl group, meta or para position；(2) so that containing the imido phenolic compound of alicyclic, aminated compounds and paraformaldehyde, as raw material, reaction synthesizes alicyclic The monofunctional benzoxazine of imide group, reaction equation are as follows：Wherein, R1- it is one of following：R1In the ortho position of oxygen atom, meta or para position；To be one of following：
- 3. preparation method according to claim 2, it is characterised in that comprise the following steps that：(1) one kind in o-aminophenol, m-aminophenol and para-aminophenol and anhydrides compound are pressed into appropriate mol ratio Mixing, add using glacial acetic acid in the reaction system of solvent, then will to be full of nitrogen in reaction system or other inertia protect gas Body, for system from room temperature to 100~120 DEG C, total reaction time is 6~8 hours, after stopping reaction, by reaction solution through go from Sub- water precipitating, washing, the phenolic compound for filtering, being dried to obtain the imide group containing alicyclic；(2) phenolic compound, aminated compounds and the paraformaldehyde of the alicyclic containing acid imide are pressed into appropriate mixed in molar ratio, added Into low polar solvent, then heat temperature raising, makes reaction system be reacted 8~12 hours at 100~120 DEG C, will after stopping reaction Reaction solution is washed 2-3 times with alkali lye A, and the outstanding solvent that steams is precipitated, and obtains monofunctional benzoxazine.
- 4. preparation method according to claim 3, it is characterised in that：In step (1), described o-aminophenol, an ammonia One kind and anhydrides compound mole ratio in base phenol and para-aminophenol are 1：1~1：1.3.
- 5. preparation method according to claim 4, it is characterised in that：Described o-aminophenol, m-aminophenol and right One kind and anhydrides compound mole ratio in amino-phenol are 1：1.1.
- 6. preparation method according to claim 3, it is characterised in that：In step (2), described acid imide containing alicyclic phenol Class compound, aminated compounds and paraformaldehyde mol ratio are 1:1:2~1:1:2.2.
- 7. preparation method according to claim 6, it is characterised in that：The described phenolic compound of acid imide containing alicyclic, Aminated compounds and paraformaldehyde mol ratio are 1:1:2.1.
- 8. preparation method according to claim 3, it is characterised in that：In step (2), described low polar solvent is toluene Or dimethylbenzene；Described alkali lye A is one in sodium hydroxide, potassium hydroxide, sodium carbonate, sodium acid carbonate, potassium carbonate, saleratus Kind.
- 9. a kind of monofunctional benzoxazine of imide group containing alicyclic according to claim 1 is as polymer matrix Matrix material is applied to the purposes of automobile, space flight and aviation and Electronic Packaging field.
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| CN109293648A (en) * | 2018-08-03 | 2019-02-01 | 江苏大学 | Benzoxazine monomer containing ethynyl and norbornene, preparation method and application thereof |
| CN111269395A (en) * | 2020-04-14 | 2020-06-12 | 镇江利德尔复合材料有限公司 | Benzoxazine epoxy resin copolymer containing phenolic hydroxyl 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 |
| CN117362285A (en) * | 2023-12-06 | 2024-01-09 | 成都科宜高分子科技有限公司 | Benzoxazine derivative and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109293648A (en) * | 2018-08-03 | 2019-02-01 | 江苏大学 | Benzoxazine monomer containing ethynyl and norbornene, preparation method and application thereof |
| CN109293648B (en) * | 2018-08-03 | 2021-05-25 | 江苏大学 | Benzoxazine monomer containing ethynyl and norbornene, preparation method and application thereof |
| CN111269395A (en) * | 2020-04-14 | 2020-06-12 | 镇江利德尔复合材料有限公司 | Benzoxazine epoxy resin copolymer containing phenolic hydroxyl 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 |
| CN117362285A (en) * | 2023-12-06 | 2024-01-09 | 成都科宜高分子科技有限公司 | Benzoxazine derivative and preparation method thereof |
| CN117362285B (en) * | 2023-12-06 | 2024-02-09 | 成都科宜高分子科技有限公司 | Benzoxazine derivative and preparation method thereof |
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