CN110551140A - Benzoxazine resin containing spiro acetal structure and preparation method thereof - Google Patents
Benzoxazine resin containing spiro acetal structure and preparation method thereof Download PDFInfo
- Publication number
- CN110551140A CN110551140A CN201810557331.3A CN201810557331A CN110551140A CN 110551140 A CN110551140 A CN 110551140A CN 201810557331 A CN201810557331 A CN 201810557331A CN 110551140 A CN110551140 A CN 110551140A
- Authority
- CN
- China
- Prior art keywords
- hydroxybenzaldehyde
- acid
- pentaerythritol bis
- compound
- benzoxazine resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 68
- 239000011347 resin Substances 0.000 title claims abstract description 68
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- -1 bisphenol compound Chemical class 0.000 claims abstract description 70
- 238000000034 method Methods 0.000 claims abstract description 44
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 45
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 25
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 14
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 229920002866 paraformaldehyde Polymers 0.000 claims description 12
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 150000003973 alkyl amines Chemical class 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 150000001448 anilines Chemical class 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 claims description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
- KZZKOVLJUKWSKX-UHFFFAOYSA-N cyclobutanamine Chemical compound NC1CCC1 KZZKOVLJUKWSKX-UHFFFAOYSA-N 0.000 claims description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims 1
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- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 65
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- 238000004134 energy conservation Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229960003742 phenol Drugs 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- 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 discloses a benzoxazine resin containing a spiro acetal structure and a preparation method thereof, the benzoxazine resin is prepared from a bisphenol compound containing the spiro acetal structure, a primary amine compound and an aldehyde compound through a solution synthesis method, the preparation method has simple process and mild conditions, large-scale industrial production can be realized, and a cured product of the prepared benzoxazine resin after curing has good chemical degradation property and can be degraded under an acidic condition, so that a composite material product can be recycled, resources are saved, and good environmental benefits are achieved.
Description
Technical Field
The invention relates to benzoxazine resin and a preparation method thereof, in particular to benzoxazine resin containing a spiro acetal structure and a preparation method thereof
Background
Along with the development of society, the requirements of people on materials are more and more strict, and the recycling of composite material wastes has important significance on the sustainable development of resources and environment. In China, with the development of the industries such as aerospace, new energy, rail transit, wind power and the like, the application field of the thermosetting resin-based composite material is continuously expanded, and accordingly, the problem of recycling the thermosetting resin-based composite material waste is more and more prominent. Many research institutions at home and abroad have already proposed related problems and researched the recovery problem [ chemical information, Ningbo materials institute composite material green recovery research advances [ J ] chemical novel materials, 2013 (2): 168-168.].
at present, comprehensive treatment becomes a new direction for recycling composite materials, and the main research direction is roughly divided into two aspects: the method is characterized by comprising the following steps of firstly, researching a new treatment technology of non-renewable thermosetting composite material waste; second, a new renewable and degradable material is developed [ shixijun, shigeling, zuirqing, current recycling situation of composite materials at home and abroad [ J ] plastic industry, 2011, 39 (1): 14-18.].
3 4For the degradation and recovery of thermosetting resin, many experts and scholars at home and abroad have carried out relevant researches, the main methods comprise a physical method and a chemical method, wherein the physical method mainly adopts mechanical crushing recovery, and the chemical method mainly comprises a pyrolysis method and a solvent method [ creep, plum, Li Xiao ] the recovery method of thermosetting resin matrix composite material research progress [ J ] engineering plastic application, 2013, 41 (1): 100-104 ], Shanxi coal institute' S forestal team selectively breaks the carbon-nitrogen bond of epoxy resin by coordination unsaturated zinc ions, realizes high-efficiency degradation and recycling of carbon fiber reinforced epoxy resin, and realizes degradation and recovery of glass fiber reinforced unsaturated polyester resin [ Deng T S, Liu Y, Cui XJ, et al.
The disposal of thermosetting composite material waste in China mainly adopts landfill and incineration, and the landfill method occupies land resources and causes soil damage. Incineration does not cause land waste, but secondary pollution is caused due to a large amount of toxic gas generated in combustion, and potential and unknown dangers exist [ chemical. Ningbo material composite material green recovery research advances [ J ] novel chemical materials, 2013 (2): 168-168.].
Therefore, the development of a decomposable thermosetting resin system is an effective way for realizing recycling of waste thermosetting resin and adhesives, coating materials and composite materials thereof, and is also one of important directions for the development of the field of thermosetting resin.
The benzoxazine resin (BZ) is a novel thermosetting resin which is a compound containing a nitrogen-oxygen six-membered heterocycle obtained by condensation reaction of phenols, aldehydes and amine compounds serving as raw materials, and is cured to obtain the polybenzoxazine resin. Besides good heat resistance and flame retardance of the traditional phenolic resin, the benzoxazine resin has no volatile micromolecules released in the ring-opening curing process, the thermosetting shrinkage rate is nearly zero, the porosity of the cured polybenzoxazine resin is low, internal stress and cracks almost do not exist, and the benzoxazine resin is beneficial to processing and molding of finished products and maintaining the size of products. Meanwhile, benzoxazine resin almost has no free aldehyde and phenol, can be used as a flame retardant material of an engine room, and is widely applied to various fields of buildings, transportation, aerospace, electronics, ships, energy sources and the like [ guo army, domestic and foreign composite material waste recovery technology and development status [ J ] scientific and technological innovation guide, 2011 (33): 99-100.].
however, the crosslinked network structure of the benzoxazine resin after curing is insoluble and infusible, which greatly limits the application of the benzoxazine resin in the aspects of recycling and degradability. Therefore, the method for degrading and recycling the cured benzoxazine is important for recycling the composite material waste, building a resource-saving and environment-friendly harmonious society, and responding to the call of environment protection, energy conservation, emission reduction and sustainable development at home and abroad.
Therefore, a degradable benzoxazine resin is needed to realize the recycling and reusing of the benzoxazine resin.
disclosure of Invention
In order to overcome the above problems, the present inventors have conducted intensive studies and, as a result, found that: the benzoxazine resin containing the spiro acetal structure is prepared from the bisphenol compound containing the spiro acetal structure, a primary amine compound and an aldehyde compound through a solution synthesis method, the cured product of the prepared benzoxazine resin after curing has good chemical degradation property, the recycling and reutilization of waste materials are realized, and the preparation method is simple in process, mild in condition and environment-friendly, and is beneficial to large-scale industrial production, so that the invention is completed.
The invention aims to provide a benzoxazine resin containing a spiro acetal structure, wherein the benzoxazine resin contains a structure shown in a formula (I):
A, B is independently selected from one of formula (II) to formula (IV), A and B can be same or different;
Wherein, R 1, R 2 and R 3 are respectively and independently selected from H, alkyl, alicyclic group, aromatic group or derivatives thereof, and R 1, R 2 and R 3 can be the same or different.
Another aspect of the present invention is to provide a method for preparing a benzoxazine resin containing a spiro acetal structure, the method comprising the steps of:
step 1, adding a bisphenol compound containing a spiro acetal structure and a primary amine compound into a solvent, and mixing;
Step 2, adding an aldehyde compound into the system in the step 1 for reaction;
And 3, carrying out post-treatment on the product obtained in the step 2.
The invention further provides a decomposition method of the benzoxazine resin cured product containing the spiro acetal structure, and the benzoxazine resin cured product is soaked in an acid solution for 2-72 hours, preferably 8-48 hours.
The invention has the following beneficial effects:
(1) the benzoxazine resin containing the spiro acetal structure has the spiro structure, so that the benzoxazine resin has excellent rigidity and heat resistance;
(2) The cured product of the benzoxazine resin containing the spiro acetal structure has good chemical degradation property and can be degraded under an acidic condition, so that the cyclic utilization of a composite material product can be realized;
(3) According to the preparation method of the benzoxazine resin containing the spiro acetal structure, the prepared benzoxazine resin has high purity and high yield, and the yield can reach 80% or even 85%;
(4) The preparation method of the benzoxazine resin containing the spiro acetal structure provided by the invention has the advantages of simple process, mild conditions, easily available raw materials, environmental friendliness and capability of large-scale industrial production.
drawings
FIG. 1 shows an IR spectrum of the product obtained in example 1 of the present invention; FIG. 2 shows the DSC curve of the product obtained in example 1 of the present invention; FIG. 3 shows the nuclear magnetic hydrogen spectrum of the product obtained in example 1 of the present invention; FIG. 4 shows an IR spectrum of the product obtained in example 8 of the present invention; FIG. 5 shows a DSC curve of the product obtained in example 8 of the present invention; FIG. 6 shows a nuclear magnetic hydrogen spectrum of a product obtained in example 8 of the present invention; FIG. 7 shows an IR spectrum of a product obtained in example 11 of the present invention; FIG. 8 shows a DSC curve of the product obtained in example 11 of the present invention; FIG. 9 shows a nuclear magnetic hydrogen spectrum of a product obtained in example 11 of the present invention; FIG. 10 shows an IR spectrum of a product obtained in example 12 of the present invention; FIG. 11 shows a DSC curve of the product obtained in example 12 of the present invention; FIG. 12 shows a nuclear magnetic hydrogen spectrum of a product obtained in example 12 of the present invention; FIG. 13 shows an IR spectrum of a product obtained in example 10 of the present invention; FIG. 14 shows a DSC curve of the product obtained in example 10 of the present invention; FIG. 15 shows a nuclear magnetic hydrogen spectrum of a product obtained in example 10 of the present invention; FIG. 16 shows an IR spectrum of a product obtained in example 13 of the present invention; FIG. 17 shows a DSC curve of the product obtained in example 13 of the present invention; FIG. 18 shows a nuclear magnetic hydrogen spectrum of a product obtained in example 13 of the present invention; FIG. 19 shows an IR spectrum of a product obtained in example 14 of the present invention; FIG. 20 shows a DSC curve of the product obtained in example 14 of the present invention; FIG. 21 shows a nuclear magnetic hydrogen spectrum of a product obtained in example 14 of the present invention; FIG. 22 shows an IR spectrum of a product obtained in example 15 of the present invention; FIG. 23 shows a DSC curve of the product obtained in example 15 of the present invention; FIG. 24 shows a nuclear magnetic hydrogen spectrum of a product obtained in example 15 of the present invention; FIG. 25 shows an IR spectrum of a product obtained in example 16 of the present invention; FIG. 26 shows an IR spectrum of a product obtained in example 17 of the present invention.
Detailed Description
The invention is explained in more detail below with reference to the drawings and preferred embodiments. The features and advantages of the present invention will become more apparent from the description.
According to an aspect of the invention, a benzoxazine resin containing a spiro acetal structure is provided, wherein the benzoxazine resin contains a structure shown in a formula (I)
A, B is independently selected from one of formula (II) to formula (IV), A and B can be same or different;
Wherein, R 1, R 2 and R 3 are respectively and independently selected from H, alkyl, substituted alkyl, alicyclic group, aromatic group or derivatives thereof, and R 1, R 2 and R 3 can be the same or different.
According to the invention, alkyl is C 1 -C 22 alkyl, preferably C 1 -C 18 alkyl, more preferably methyl, ethyl, n-butyl, n-pentyl, n-hexyl, dodecyl or octadecyl, for example n-butyl, n-pentyl or n-hexyl.
According to the invention, the substituted alkyl is selected from benzyl or β -phenylethyl.
according to the invention, the alicyclic group is a C 3 -C 8 alicyclic group, preferably a C 3 -C 6 alicyclic group, such as a cyclobutyl group, a cyclopentyl group or a cyclohexyl group, for example a cyclohexyl group.
According to the invention, the aryl is phenyl or substituted phenyl, the substituted phenyl is alkyl substituted phenyl or nitro substituted phenyl, and p-tolyl, o-tolyl or m-tolyl are preferred; the aryl derivative is selected from 3- (trifluoromethyl) phenyl.
In a particular embodiment according to the present invention, the benzoxazine resin containing a spiro acetal structure has a structure as shown in any one of the following (1) to (10),
(1) Pentaerythritol bis-p-hydroxybenzaldehyde-aniline type
(2) Pentaerythritol bis-p-hydroxybenzaldehyde-cyclohexylamine type
(3) Pentaerythritol bis-p-hydroxybenzaldehyde-n-hexylamine type
(4) pentaerythritol bis-p-hydroxybenzaldehyde-n-pentylamine type
(5) Pentaerythritol bis-p-hydroxybenzaldehyde n-butylamine type
(6) Pentaerythritol bis-m-hydroxybenzaldehyde-aniline type
(7) Pentaerythritol bis-m-hydroxybenzaldehyde-cyclohexylamine type
(8) Pentaerythritol bis-m-hydroxybenzaldehyde-n-hexylamine type
(9) Pentaerythritol bis-p-hydroxybenzaldehyde-dodecylamine type
(10) Pentaerythritol bis-p-hydroxybenzaldehyde-p-toluidine type
Another aspect of the present invention provides a method for preparing a benzoxazine resin containing a spiro acetal structure, preferably the above benzoxazine resin, comprising the steps of:
Step 1, adding a bisphenol compound containing a spiro acetal structure and a primary amine compound into a solvent, and mixing;
Step 2, adding an aldehyde compound into the system in the step 1 for reaction;
And 3, carrying out post-treatment on the reaction product obtained in the step 2.
According to the present invention, in step 1, the bisphenol compound containing a spiro acetal structure is selected from one or more of pentaerythritol bis (p-hydroxybenzaldehyde), pentaerythritol bis (m-hydroxybenzaldehyde), pentaerythritol bis (o-hydroxybenzaldehyde) or their derivatives, preferably pentaerythritol bis (p-hydroxybenzaldehyde) or pentaerythritol bis (m-hydroxybenzaldehyde).
Wherein, the molecular structures of the pentaerythritol bis-p-hydroxybenzaldehyde, the pentaerythritol bis-m-hydroxybenzaldehyde and the pentaerythritol bis-o-hydroxybenzaldehyde are respectively shown as formula (V), formula (VI) and formula (VII).
According to the invention, in step 1, primary amine compounds such as alkylamine, substituted alkylamine, alicyclic amine, aromatic amine and derivatives thereof are used.
According to the invention, the alkylamine is a C1-C22 alkylamine, preferably a C1-C18 alkylamine, more preferably methylamine, ethylamine, n-propylamine, n-butylamine, n-pentylamine, n-hexylamine, dodecylamine or octadecylamine, for example n-butylamine, n-pentylamine or n-pentylamine.
According to the invention, the substituted alkylamine is selected from benzylamine or β -phenylethylamine.
according to the invention, the alicyclic amine is a C3-C8 alicyclic amine, preferably a C3-C6 alicyclic amine, more preferably a cyclobutane amine, a cyclopentan-amine or a cyclohexylamine, such as cyclohexylamine.
according to the invention, the aromatic amine is selected from aniline or substituted aniline, preferably aniline; and/or, the derivative of the aromatic amine is selected from 3- (trifluoromethyl) phenyl.
According to the invention, the substituted aniline is an alkyl-substituted aniline or a nitro-substituted aniline, preferably p-toluidine, o-toluidine or m-toluidine.
according to the present invention, in step 2, the aldehyde compound is paraformaldehyde or an aqueous formaldehyde solution, preferably paraformaldehyde.
In the invention, a bisphenol compound containing a spiro acetal structure, a primary amine compound and an aldehyde compound are subjected to condensation reaction to obtain the benzoxazine resin containing the spiro acetal structure, the synthesis method mainly comprises a solution method, a suspension method or a melting method, the benzoxazine resin is prepared by adopting a solution synthesis method, and phenolic hydroxyl, amino and aldehyde groups in the benzoxazine resin are reacted in the condensation reaction process, so that the amount of the bisphenol compound containing the spiro acetal structure, the primary amine compound and the aldehyde compound is calculated by the amount of the phenolic hydroxyl, the amino and the aldehyde compounds.
according to the invention, in the bisphenol compound, the primary amine compound and the aldehyde compound containing the spiro acetal structure, the ratio of the amount of the phenolic hydroxyl group, the amino group and the aldehyde group is 1: 1: (2.0-2.8), preferably 1: 2.0-2.4.
According to the present invention, in step 1, the solvent is selected from one of ethanol, methanol, isopropanol, butanol, tetrahydrofuran, dioxane, toluene, Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), preferably one of DMF, DMSO, NMP, more preferably DMF or NMP.
In the present invention, the bisphenol compound containing a spiro acetal structure and the primary amine compound are dissolved in a solvent and uniformly mixed, preferably, uniformly mixed by stirring. And then adding the aldehyde compound into the system in the step 1, wherein the reaction process for preparing the benzoxazine resin comprises an exothermic reaction, and in order to ensure that the reaction is sufficient and prevent other byproducts or exothermic reactions from being generated and influencing the yield of a final product, the aldehyde compound needs to be slowly added into the system in the step 1, and is preferably added into the system in the step 1 in portions.
According to the present invention, in step 2, the aldehyde compound is added to the system of step 1 one to many times, preferably 2 to 6 times, and more preferably 2 to 4 times.
According to the invention, because the early stage of the condensation reaction comprises an exothermic reaction, in order to prevent the heat released by the reaction from influencing the synthesis of a final product, the reaction system needs to be stirred at a low temperature of-10 ℃.
According to the invention, in the step 2, the reaction system is placed in a low-temperature constant-temperature water bath and stirred for 10-60 min, preferably 20-50 min, and more preferably 30 min.
according to the invention, in the step 2, the temperature of the reaction system is increased to carry out the reflux reaction at 80-120 ℃, preferably 90-110 ℃, more preferably 95-105 ℃, for example 95 ℃.
According to the invention, in the step 2, the temperature-rising reflux reaction time of the reaction system is 1-15 h, preferably 2-10 h, more preferably 5-12 h, most preferably 8-10 h, for example 10 h.
According to the invention, in step 3, the work-up comprises washing, filtering and drying of the reaction product obtained in step 2.
According to the invention, in the step 3, the reaction product obtained in the step 2 is washed by sodium hydroxide aqueous solution, filtered, washed by deionized water to be neutral and filtered, and the process can be repeated for multiple times, wherein the concentration of sodium hydroxide is preferably 1-3 mol/L.
According to the invention, in the step 3, the drying is to vacuum dry the washed and filtered product to constant weight, preferably the vacuum drying temperature is 40-60 ℃, preferably 50-60 ℃, for example 50 ℃.
In the present invention, the cured product can be prepared by curing the prepared benzoxazine resin containing a spiro acetal structure, and the preparation method preferably comprises the following steps: the benzoxazine resin containing the spiro acetal structure is treated for 2-16 hours at 100-240 ℃, preferably for 2-12 hours at 140-220 ℃, more preferably according to a programmed gradient temperature rise, and is treated for 1-2 hours at constant temperature of 140 ℃, 160 ℃, 180 ℃, 200 ℃ and 220 ℃.
In another aspect, the present invention provides a method for degrading a benzoxazine resin cured product containing a spiro acetal structure, the method specifically comprising: and (3) soaking the benzoxazine resin cured product containing the spiro acetal structure in an acid solution for 2-72 hours, preferably 8-48 hours.
According to the invention, the acidic solution comprises an acid compound, and the acid compound is an organic acid or an inorganic acid.
according to the invention, the organic acid is selected from one or more of formic acid, acetic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid and trichloroacetic acid, preferably acetic acid or p-toluenesulfonic acid, and more preferably acetic acid.
According to the invention, the inorganic acid is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
According to the invention, the acidic solution also comprises a polar solvent, preferably water, alcohol compounds, ketone compounds, ether compounds or amide compounds,
According to the invention, the alcohol compound is a compound containing one or more hydroxyl groups, and is selected from ethanol, methanol, isopropanol, butanol, isobutanol, phenethyl alcohol, benzyl alcohol, ethylene glycol, butylene glycol, 1, 3-propanediol, 1, 2-propanediol, glycerol, diethylene glycol, triethylene glycol; dipropylene glycol; furfuryl alcohol; tetrahydrofurfuryl alcohol, preferably methanol, ethanol, ethylene glycol, or diethylene glycol, more preferably ethanol or diethylene glycol.
According to the invention, the ketone compound is selected from butanone or cyclohexanone.
According to the invention, the ether compound is one or more selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Tetrahydrofuran (THF) and 1, 4-dioxane, preferably THF or 1, 4-dioxane.
according to the invention, the amide compound is selected from one of Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), sulfolane, N-methyl pyrrolidone (NMP), morpholine and N-methyl morpholine, preferably one or more of DMF, DMSO and NMP, preferably DMF or DMSO.
The benzoxazine resin containing the spirocyclic acetal structure provided by the invention is mixed with other thermosetting resins to obtain a composition, wherein the other thermosetting resins comprise one or more of epoxy resin, polyurethane resin, cyanate resin, furan resin, phenolic resin, unsaturated polyester resin, bismaleimide resin and other benzoxazine resin.
the benzoxazine resin containing the spiro acetal structure can be used for preparing various compositions with reinforcing materials, such as silicon dioxide, carbon nanotubes, glass fibers, carbon fibers, aramid fibers and the like, so as to obtain thermosetting resins with different purposes and products thereof. The obtained product has low porosity, small volume shrinkage, excellent heat resistance and mechanical property.
examples
The invention is further described below by means of specific examples. However, these examples are only illustrative and do not limit the scope of the present invention.
The following examples and comparative examples employ test methods:
Infrared spectroscopy test (FTIR): an IS-5 Fourier infrared spectrometer, wherein a KBr tabletting method IS adopted to prepare a test sample;
nuclear magnetic resonance hydrogen spectrum test (1H-NMR): adopting a 400MHz nuclear magnetic resonance instrument of Bruker Avance, wherein the testing temperature is 25 ℃, and the solvent is deuterated chloroform;
differential Scanning Calorimeter (DSC): model TQ100, test conditions: the temperature was raised from room temperature to 350 ℃ at a temperature raising rate of 10 ℃/min under a nitrogen atmosphere.
Example 1
Weighing raw materials according to the molar ratio of phenolic hydroxyl group, amino group and aldehyde group of 1: 2.1, sequentially adding 50mL of DMF, 3.44g (0.01mol) of pentaerythritol bis-p-hydroxybenzaldehyde and 1.83mL (0.02mol) of aniline into a 100mL three-neck flask, and uniformly stirring and mixing;
Adding 1.261g (0.042mol) of paraformaldehyde into a three-neck flask for 2-4 times, placing the three-neck flask in a low-temperature constant-temperature reaction bath, stirring for 30min, gradually heating to 95 ℃, and reacting at constant temperature for 10 h.
After the reaction is finished, washing a reaction product by using a sodium hydroxide aqueous solution with the concentration of 1mol/L, filtering, washing by using deionized water to be neutral, filtering, and drying in vacuum at 50 ℃ to be constant weight.
The final product was weighed and the calculated yield was 40.1%.
And performing infrared and DSC tests and nuclear magnetic characterization on the obtained final product, wherein the obtained infrared spectrogram, DSC curve and nuclear magnetic hydrogen spectrum are respectively shown in figure 1, figure 2 and figure 3.
In FIG. 1, at 1600cm -1 and 1501cm -1, the stretching vibration peaks of C-C on a benzene ring are shown, at 1242cm -1 and 1031cm -1, the asymmetric stretching vibration peaks and the symmetric stretching vibration peaks of C-O-C bonds on an oxazine ring are shown respectively, at 947cm -1, the absorption vibration peaks of the oxazine ring are shown, at 1077cm -1 and 824cm -1, the vibration peaks of C-O-C on an acetal ring are shown, and at 824cm -1, the vibration peaks of C-N-C on the oxazine ring are shown.
as can be seen from FIG. 2, the first downward peak on the DSC curve is the melting endothermic peak, and the melting peak top temperature is about 155 ℃. The second upward peak is the exothermic curing peak of the oxazine, the initial curing temperature of the pentaerythritol bis-p-hydroxybenzaldehyde-aniline oxazine is 180 ℃, and the peak top temperature is about 227 ℃. Around 290 c, a downward endothermic peak begins to appear, probably because the oxazine ring is decomposed at high temperature.
In fig. 3, a new proton peak H a at a chemical shift δ of 4.60ppm belongs to hydrogen on the intermediate carbon of the oxazine ring N-C structure, a new proton peak H b and a new proton peak H c at a chemical shift δ of 5.38ppm belongs to the proton peaks S b and H c, corresponding peak areas S b+c: S a are 3: 2, and also satisfy the ratio of the corresponding hydrogen, chemical shifts at four positions d, e, f, and g on the intermediate spiro structure are also changed from 4.5ppm to 3.6ppm to 4.9ppm to 3.6ppm, and chemical shifts of two hydrogens overlap, and the overall integral of some peaks Sa: S b+ C: S d: Se: S f: Sg: S h+i+j+k+1+m is 2: 3: 1: 8, which is consistent with the ratio of hydrogens at the respective theoretical positions, and the obtained final product is pentaerythritol bis-condensed aniline (p-hydroxy benzaldehyde) at a high purity level of 7.29 ppm).
example 2
The procedure of example 1 was repeated except that paraformaldehyde was added in an amount of 1.321g (0.044mol), that is, a molar ratio of phenolic hydroxyl group, amine group and aldehyde group was 1: 2.2, and the obtained yield was 77.6%. The resulting final product was subjected to infrared, DSC testing and nuclear magnetic characterization, and the results were similar to example 1.
Example 3
The procedure of example 1 was repeated except that paraformaldehyde was added in an amount of 1.381g (0.046mol), that is, a molar ratio of phenolic hydroxyl group, amine group and aldehyde group was 1: 2.3, and the obtained yield was 85%. The resulting final product was subjected to infrared, DSC testing and nuclear magnetic characterization, and the results were similar to example 1.
example 4
The procedure of example 1 was repeated except that paraformaldehyde was added in an amount of 1.201g (0.04mol), that is, a molar ratio of phenolic hydroxyl group, amine group and aldehyde group was 1: 2.0, and the obtained yield was 35%. The resulting final product was subjected to infrared, DSC testing and nuclear magnetic characterization, and the results were similar to example 1.
Example 5
The procedure of example 1 was repeated except that paraformaldehyde was added in an amount of 1.441g (0.048mol), that is, a molar ratio of phenolic hydroxyl group, amine group and aldehyde group was 1: 2.4, and the obtained yield was 80%. The resulting final product was subjected to infrared, DSC testing and nuclear magnetic characterization, and the results were similar to example 1.
Example 6
The procedure in example 3 was repeated, except that the isothermal reaction time was 6h, and the yield was 80.7%. The resulting final product was subjected to infrared, DSC testing and nuclear magnetic characterization, and the results were similar to example 1.
Example 7
The procedure in example 3 was repeated, except that the isothermal reaction time was 2h, and the yield was 35.3%. The resulting final product was subjected to infrared, DSC testing and nuclear magnetic characterization, and the results were similar to example 1.
Example 8
Weighing raw materials according to the molar ratio of phenolic hydroxyl group, amino group and aldehyde group of 1: 2.3, sequentially adding 50ml of mixed solution of LDMF, 3.44g (0.01mol) of pentaerythritol bis-p-hydroxybenzaldehyde and 2.30ml (0.02mol) of cyclohexylamine into a 100ml three-neck flask, and uniformly stirring and mixing;
Adding 1.381g (0.046mol) of paraformaldehyde into a three-neck flask 2-4 times, placing the three-neck flask in a low-temperature constant-temperature reaction bath, stirring for 30min, gradually heating to 95 ℃, and reacting at constant temperature for 10 h.
after the reaction is finished, washing a reaction product by using a sodium hydroxide aqueous solution with the concentration of 1mol/L, filtering, washing by using deionized water to be neutral, filtering, and drying in vacuum at 50 ℃ to be constant weight.
The final product was weighed and the calculated yield was 33.2%.
And performing infrared and DSC tests and nuclear magnetic characterization on the obtained final product, wherein the obtained infrared spectrogram, DSC curve and nuclear magnetic hydrogen spectrum are respectively shown in figure 4, figure 5 and figure 6.
As can be seen from FIG. 4, the single peak at 1504cm -1 is the stretching vibration peak of C-C on the benzene ring, the stretching vibration peak of C-O-C bond on the oxazine ring is at 1230cm -1, the absorption vibration peak of the oxazine ring is at 891cm -1, the stretching vibration peaks of C-O-C on the acetal ring are at 823cm -1 and 1075cm -1, and 823cm -1 is also the vibration peak of C-N-C on the oxazine ring, and the molecular structure of the final product contains a spiro acetal structure and an oxazine ring.
As can be seen in fig. 5, the first downward peak is the melting endotherm and the melting peak top temperature is around 186 ℃. The second upward peak is the exothermic curing peak of the oxazine, the initial curing temperature of the pentaerythritol bis-p-hydroxybenzaldehyde-cyclohexylamine oxazine is about 190 ℃, and the peak top temperature is about 245 ℃. Around 278 ℃, a downward endothermic peak begins to appear, and the peak is broad, probably because the oxazine is decomposed at high temperature.
As can be seen from FIG. 6, a new proton peak H a at a chemical shift delta of 4.13ppm, which belongs to hydrogen on the intermediate carbon of the oxazine ring N-C-C structure, a proton peak H c at a chemical shift delta of 5.39ppm, a proton peak H b at a delta of 5.01ppm, chemical shifts at d, e, f and g on the intermediate spiro structure are also changed from 4.5ppm to 3.6ppm to 4.9ppm to 3.6ppm, and chemical shifts of two hydrogens are overlapped, while proton peaks H k to H p on cyclohexylamine appear in a range of 2.7ppm to 1.1ppm, the proton peaks on cyclohexylamine are not easily scored separately, and integral integration is performed on some peaks to obtain a ratio of S a: S b: S d: S f: S g: S h: S8284: S25: S892: S1: S2: S1: 6, and a ratio of S5391: 11: 1: 11 is determined on the synthetic pentaerythritol as a synthetic double-p-hydroxybenzene formaldehyde.
Example 9
Weighing the raw materials according to the molar ratio of phenolic hydroxyl group, amino group and aldehyde group of 1: 2.3, sequentially adding 50mL of dioxane, 3.44g (0.01mol) of pentaerythritol bis-p-hydroxybenzaldehyde and 2.30mL (0.02mol) of cyclohexylamine into a 100mL three-neck flask, and stirring and uniformly mixing;
Adding 1.381g (0.046mo1) of paraformaldehyde into a three-neck flask 2-4 times, placing the three-neck flask in a low-temperature constant-temperature reaction bath, stirring for 30min, gradually heating to 95 ℃, and reacting at constant temperature for 10 h.
After the reaction is finished, washing a reaction product by using a sodium hydroxide aqueous solution with the concentration of 1mol/L, filtering, washing by using deionized water to be neutral, filtering, and drying in vacuum at 50 ℃ to be constant weight. The calculated yield was 54.3%.
example 10
The procedure in example 9 was repeated except that 1.977ml (0.02mol) of n-butylamine was used in place of 2.30ml (0.02mol) of cyclohexylamine, to calculate the yield to be 43.1%.
and performing infrared and DSC tests and nuclear magnetic characterization on the obtained final product, wherein the obtained infrared spectrogram, DSC curve and nuclear magnetic hydrogen spectrum are respectively shown in figure 13, figure 14 and figure 15.
From FIG. 13, it can be seen that 1504cm -1 is the peak of stretching vibration of C-C on the benzene ring, 1232cm -1 is the peak of stretching vibration of C-O-C bond on the oxazine ring, 923cm -1 is the peak of absorption vibration of the oxazine ring, 824cm -1 and 1079cm -1 are the peaks of stretching vibration of C-O-C on the acetal ring, and 824cm -1 is also the peak of vibration of C-N-C on the oxazine ring, and 2947cm -1 and 2856cm -1 are the peaks of vibration of CH 2 and CH 3 on N-butylamine, and thus, from FIG. 13, oxazine is generated.
As can be seen in FIG. 14, the first downward peak is the melting endotherm and the melting peak top temperature is around 107 ℃. The second upward peak is the exothermic curing peak of oxazine, which has an initial curing temperature of about 150 deg.C and a peak top temperature of about 228 deg.C. Around 255 ℃, a downward endothermic peak begins to appear, and the oxazine is decomposed probably at high temperature.
From fig. 15, it can be seen that a proton peak Ha appears at δ of 4.02pm, which is hydrogen on the middle carbon of the N-C structure of oxazine ring, a proton peak Hc appears at δ of 5.39ppm, a proton peak Hb appears at δ of 4.86ppm, chemical shifts of d, e, f, and g on the middle spiro structure change to 4.9ppm to 3.6ppm, and some proton peaks overlap with H b, proton peaks H k to H o on N-butylamine appear in the interval of 0.9ppm to 2.9ppm, integration of peak areas results in S a: S b: S c: S d+e+f+g: S h: S i: S j: S k: S l: S m: S n: S2: 1: 4.6: 1: 2: 2.2: 3.2: 2, and a theoretical difference from N-butyl amine to N-p-hydroxyamine can result in a long-N-butyl amine condensation reaction time, which may result in a high purity of final benzoxazine formaldehyde.
Example 11
The procedure in example 9 was repeated except that 2.642ml (0.02mol) of n-hexylamine was used in place of 2.30ml (0.02mol) of cyclohexylamine, and the calculated yield was 22.6%.
And performing infrared and DSC tests and nuclear magnetic characterization on the obtained final product, wherein the obtained infrared spectrogram, DSC curve and nuclear magnetic hydrogen spectrum are respectively shown in figure 7, figure 8 and figure 9.
As can be seen from FIG. 7, 1504cm -1 is the stretching vibration peak of C-C on the benzene ring, 1231cm -1 is the stretching vibration peak of C-O-C bond on the oxazine ring, 929cm -1 is the absorption vibration peak of the oxazine ring, 824cm -1 and 1077cm -1 are the stretching vibration peaks of C-O-C on the acetal ring, 824cm -1 is also the vibration peak of C-N-C in the oxazine ring, and 929cm -1 is the vibration peak of the benzene ring connected with the oxazine ring.
As can be seen from FIG. 8, the first downward peak is the melting endotherm and the melting peak top temperature is around 105 ℃. The second upward peak is the exothermic curing peak of the oxazine, the initial curing temperature of the pentaerythritol bis-p-hydroxybenzaldehyde-n-hexylamine oxazine is about 155 ℃, and the peak top temperature is about 240 ℃. After which no endothermic peak appeared.
As can be seen from FIG. 9, the peak area of H a, hydrogen on the intermediate carbon belonging to the oxazine ring N-C-C structure, is shown at delta-4.02 ppm, the peak area of H c, the peak area of H b is shown at delta-4.89 ppm, the chemical shifts of d, e, f and g on the intermediate spiro structure are also changed from 4.5ppm-3.6ppm to 4.9ppm-3.6ppm, and some proton peaks overlap with H b, the peak areas of Hk to H p, which belong to N-hexyl amine, appear in the range of 0.89ppm to 2.75ppm, peak area integration is carried out to obtain S a: S b: S c: S d: S e: S f: S g: S h: S i: S j: S k: S6866: S m+n+o: S c: S d: S e: S f: S g: S3: 1, and the final product of parahydroxyben-1H 1: 1H 1, 1: 1, and 1: 1.
Example 12
The procedure in example 9 was repeated except that 2.32ml (0.02mol) of n-pentylamine was used in place of 2.30ml (0.02mol) of cyclohexylamine, and the calculated yield was 56.6%.
And performing infrared and DSC tests and nuclear magnetic characterization on the obtained final product, wherein the obtained infrared spectrogram, DSC curve and nuclear magnetic hydrogen spectrum are respectively shown in figure 10, figure 11 and figure 12.
From FIG. 10, it can be found that 1504cm -1 is the stretching vibration peak of C-C on the benzene ring, 1230cm -1 is the stretching vibration peak of C-O-C bond on the oxazine ring, 929cm -1 is the absorption vibration peak of the oxazine ring, 824cm -1 and 1079cm -1 are the stretching vibration peaks of C-O-C on the acetal ring, and 824cm -1 is also the vibration peak of C-N-C in the oxazine ring, and 2941cm -1 and 2858cm -1 are the vibration peaks of CH 2 and CH 3 carried by N-pentylamine, therefore, it can be seen from FIG. 10 that oxazine is generated.
As can be seen from FIG. 11, the first downward peak is the melting endotherm and the melting peak top temperature is around 113 ℃. The second upward peak is the exothermic curing peak of the oxazine, the initial curing temperature of the pentaerythritol bis-p-hydroxybenzaldehyde-n-pentylamine oxazine is about 155 ℃, and the peak top temperature is about 240 ℃. Around 286 c, a downward endothermic peak begins to appear, probably because at high temperatures, oxazines decompose.
It can be seen from fig. 12 that the proton peak Ha, hydrogen belonging to the intermediate carbon of the oxazine ring N-C structure, appears at a δ of 4.01ppm, the proton peak Hc appears at a δ of 5.38ppm, the proton peak Hb appears at a δ of 4.88ppm, the oxazine ring is formed, the chemical shift and split of hydrogen on the benzene ring are changed, the proton peaks Hj, Hh, Hi all appear in the chemical shift δ range of 6.77ppm to 7.29ppm, besides, the chemical shifts at d, e, f, g on the intermediate spiro structure are also changed from 4.5ppm to 3.6ppm to 4.9ppm to 3.6ppm, and some proton peaks overlap Hb, the proton peaks H k to H o belonging to N-pentylamine appear in the range of 0.9ppm to 2.9ppm, the integral of p-pentylamine peak area H563568 to H a: 3528, the p-pentylamine area H a: 736: 3, the p-pentylamine area H357: 3: 493, the final product has a higher molar ratio of 1: 3, 3.
Example 13
Weighing raw materials according to the molar ratio of phenolic hydroxyl group, amino group and aldehyde group of 1: 2.3, sequentially adding 50mL of dioxane, 3.44g (0.01mol) of pentaerythritol bis-m-hydroxybenzaldehyde and 1.83mL (0.02mol) of aniline into a 100mL three-neck flask, and uniformly stirring and mixing;
Adding 1.381g (0.046mol) of paraformaldehyde into a three-neck flask 2-4 times, placing the three-neck flask in a low-temperature constant-temperature reaction bath, stirring for 30min, gradually heating to 95 ℃, and reacting at constant temperature for 10 h.
After the reaction is finished, washing a reaction product by using a sodium hydroxide aqueous solution with the concentration of 1mol/L, filtering, washing by using deionized water to be neutral, filtering, and drying in vacuum at 50 ℃ to be constant weight. The calculated yield was 23.4%.
And performing infrared and DSC tests and nuclear magnetic characterization on the obtained final product, wherein the obtained infrared spectrogram, DSC curve and nuclear magnetic hydrogen spectrum are respectively shown in figure 16, figure 17 and figure 18.
From FIG. 16, it can be found that the peak positions at 1599cm -1 and 1498cm -1 are stretching vibration peaks of C-C on the benzene ring, the peak positions at 1229cm -1 and 1032cm -1 are respectively asymmetric stretching vibration peaks and symmetric stretching vibration peaks of C-O-C bonds on the oxazine ring, the peak position at 932cm -1 is an absorption vibration peak of the oxazine ring, the peak positions at 1078cm -1 and 803cm -1 are stretching vibration peaks of C-O-C on the acetal ring, and the peak position at 803cm -1 is also a vibration peak of C-N-C in the oxazine ring.
From FIG. 17, it can be seen that two melting peaks appear, the first melting peak having a peak top temperature of about 130 ℃ and the second melting peak having a peak top temperature of 190 ℃. The third upward peak is the exothermic curing peak of oxazine, the initial curing temperature is about 230 ℃, and the peak top temperature is about 260 ℃. Around 295 c, a small endothermic peak appears, probably because at high temperatures partial decomposition of oxazines occurs.
As can be seen from fig. 18, the newly appearing proton peak Ha at δ of 4.65ppm belongs to hydrogen on the intermediate carbon of the N-C structure of the oxazine ring, the proton peaks Hb and Hc at δ of 5.38ppm belongs to the proton peaks S b+c: S a of 3: 2, and the ratio of the corresponding hydrogen is also satisfied, because the oxazine ring is generated, the chemical shift and split of hydrogen on the original benzene ring are changed, and in addition to the benzene ring brought by aniline on the oxazine ring, the proton peaks of hydrogen on all benzene rings are present in the chemical shift δ of 6.95-7.3ppm and the phenomenon of chemical shift overlap occurs, besides, the chemical shifts d, e, f and g on the intermediate spiro structure are also changed from 4.5ppm-3.6ppm to 4.85ppm-3.6ppm and the chemical shifts of two hydrogens are overlapped, the integral of d, e, f and g on the intermediate spiro structure are also changed from 4.5ppm-3.6ppm to 4.85ppm-3.6ppm and the integral of two hydrogens on the intermediate spiro structure is found to be similar to the chemical shift of the acetal, and the chemical shift of the acetal is difficult to synthesize the benzoxazine ring, but the synthetic double acetal is found to the synthetic acetal, and the chemical shift of the acetal is found to the acetal, the molar ratio of the acetal is similar to the acetal is found to the molar ratio of the acetal is similar to the acetal which is found to the benzoxazine ring which is similar to the molar ratio of the benzoxazine ring, but the molar ratio of the benzoxazine ring is found to the molar ratio of the.
Example 14
The procedure in example 13 was repeated, except that 2.30ml (0.02mol) of cyclohexylamine was used in place of 1.83ml (0.02mol) of aniline, to give a yield of 68.8%.
and performing infrared and DSC tests and nuclear magnetic characterization on the obtained final product, wherein the obtained infrared spectrogram, DSC curve and nuclear magnetic hydrogen spectrum are respectively shown in figure 19, figure 20 and figure 21.
From FIG. 19, it can be found that 1247cm -1 is the stretching vibration peak of C-O-C bond on oxazine ring, 924cm -1 is the absorption vibration peak belonging to oxazine ring, 1079cm -1 is the stretching vibration peak of C-O-C on acetal ring, 873cm -1 is the vibration peak of C-N-C on oxazine ring, 2928cm -1 and 2852cm -1 are the vibration peaks of CH 2 carried by cyclohexylamine.
From FIG. 20, it can be seen that the first downward melting peak top temperature is around 148 ℃. The first upward peak is the exothermic curing peak of oxazine, which has an initial curing temperature of about 185 deg.C and a peak top temperature of about 242 deg.C. At around 270 ℃, an endothermic peak appears, probably because partial decomposition of oxazines occurs at high temperatures.
as can be seen from fig. 21, the newly-appearing proton peak Ha at δ ═ 4.10ppm belongs to the hydrogen on the middle carbon of the oxazine ring N-C structure. The proton peak Hc is at 5.38ppm δ, and the proton peak Hb is at 5.00ppm δ. Because oxazine rings are generated, chemical shifts and splits of hydrogen on the original benzene ring are changed, and proton peaks Hh, Hi and Hj all appear in a chemical shift delta range of 6.76-7.29 ppm. Chemical shifts of four positions of d, e, f and g on the intermediate spiro structure are also changed to 4.9ppm-3.6 ppm. And the proton peaks Hk to Hp belonging to cyclohexylamine appear in the interval of 2.7ppm to 1.1 ppm. In the figure, we can find that the peak is much, the raw material is not removed completely, or the reaction time is too long to cause partial ring opening of oxazine, and the acetal of m-hydroxyl has two reaction sites and byproducts. The method can ensure that the pentaerythritol bis-m-hydroxybenzaldehyde-cyclohexylamine oxazine is successfully synthesized.
Example 15
The procedure in example 13 was repeated except that 2.64ml (0.02mol) of n-hexylamine was used in place of 1.83ml (0.02mol) of aniline, to obtain a yield of 35.6%.
and performing infrared and DSC tests and nuclear magnetic characterization on the obtained final product, wherein the obtained infrared spectrogram, DSC curve and nuclear magnetic hydrogen spectrum are respectively shown in figure 22, figure 23 and figure 24.
As can be seen from FIG. 22, there is a stretching vibration peak of C-O-C bond on oxazine ring at 1244cm-1, an absorption vibration peak belonging to oxazine ring at 931cm -1, a stretching vibration peak of C-O-C bond on acetal ring at 1072cm -1, a vibration peak of C-N-C bond on oxazine ring at 879cm -1, vibration peaks of CH 2 and CH 3 carried by N-hexylamine at 2929cm -1 and 2856cm -1, and thus, it can be seen from FIG. 22 that oxazine ring is generated.
It can be seen from FIG. 23 that the first downward melting peak has a peak top temperature of about 86 deg.C, the second downward melting peak has a peak top temperature of 190 deg.C, an initial solidification temperature of about 225 deg.C, and a peak top temperature of about 249 deg.C.
as can be seen from fig. 24, the proton peak Ha appears at 6 ═ 4.00 ppm. The chemical shift δ is 5.39ppm, the proton peak Hc, and the chemical shift δ is 4.88ppm, the proton peak Hb. Because oxazine rings are generated, chemical shifts and splits of hydrogen on the original benzene ring are changed, and proton peaks Hh, Hi and Hj all appear in a chemical shift delta range of 6.76-7.00 ppm. Chemical shifts of four positions of d, e, f and g on the intermediate spiro structure are also changed to 4.9ppm-3.6 ppm. While the proton peak belonging to n-hexylamine appears in the interval of 2.7ppm to 0.9 pm. FIG. 24 was integrated Sa: Sb: Sc: Sd + e + f + g: Sh + i + j 2: 3: 1, in accordance with the theoretical ratio. More hetero-peaks can be found in the figure, which may be the partial ring opening of oxazines caused by too long reaction time or the by-products caused by two reaction sites of m-hydroxy acetal. The successful synthesis of pentaerythritol bis-m-hydroxybenzaldehyde-n-hexylamine oxazine can be determined.
Example 16
The procedure in example 9 was repeated except that 3.707g (0.02mol) of dodecylamine was used in place of 2.30ml (0.02mol) of cyclohexylamine, the yield was 40.3%. The obtained product was subjected to infrared test, and the results are shown in fig. 25.
As can be seen from FIG. 25, 1504cm -1 is the C-C stretching vibration peak on the benzene ring, 1238cm -1 is the C-O-C stretching vibration peak on the oxazine ring, 918cm -1 is the absorbing vibration peak of the oxazine ring, 1072cm -1 and 829cm -1 are the C-O-C stretching vibration peaks on the acetal ring, and further 829cm -1 is the C-N-C vibration peak on the oxazine ring, 2924cm -1 and 2850cm -1 are the vibration peaks of CH 2 and CH 3 on dodecylamine.
Example 17
the synthesis was carried out in the same manner as in example 9 except that 2.143g (0.02mol) of p-toluidine was used in place of 2.30ml (0.02mol) of cyclohexylamine, giving a yield of 30.9%. The obtained product was subjected to infrared test, and the results are shown in fig. 25.
As can be seen from FIG. 26, 1518cm -1 is a C-C stretching vibration peak on a benzene ring, 1238cm -1 is a C-O-C stretching vibration peak on an oxazine ring, 949cm -1 is an absorbing vibration peak of an oxazine ring, 1072cm -1 and 814cm -1 are C-O-C stretching vibration peaks on an acetal ring, 879cm -1 is a C-N-C vibration peak on an oxazine ring, 2858cm -1 is a vibration peak of CH 3 carried on p-toluidine, and the existence of an oxazine ring indicates that the pentaerythritol bis-p-hydroxybenzaldehyde-p-toluidine type benzoxazine is synthesized.
Comparative example 1
Weighing raw materials according to the molar ratio of phenolic hydroxyl group, amino group and aldehyde group of 1: 2.1, sequentially adding 50mL of toluene, 2.28g (0.01mol) of bisphenol A and 1.83mL (0.02mol) of aniline into a 100mL three-neck flask, and uniformly stirring and mixing;
Adding 1.261g (0.042mol) of paraformaldehyde into a three-neck flask for 2-4 times, placing the three-neck flask in a low-temperature constant-temperature reaction bath, stirring for 30min, gradually heating to 95 ℃, and reacting at constant temperature for 10 h.
after the reaction is finished, the reaction product is washed by sodium hydroxide aqueous solution with the concentration of 1mol/L, filtered, washed by deionized water to be neutral, filtered and dried in vacuum at the temperature of 50 ℃ to be constant weight. The final product was weighed to give a yield of 75.2%.
And (3) curing the obtained final product, specifically, respectively carrying out constant temperature treatment for 1h at 140 ℃, 160 ℃, 180 ℃ and 200 ℃ according to the programmed temperature rise, and naturally cooling to the room temperature after the constant temperature treatment to obtain the cured product.
Examples of the experiments
Experimental example 1
Comparative example 1 the cured product and the cured product of example 1 were placed in an acidic solution, degraded by heating for a certain period of time, filtered, dried to a constant weight, and tested for the degree of degradation, with the results shown in table 1. Wherein,
TABLE 1 degradation of the cured products of comparative example 1 and example 1 in acidic solution
| sample (I) | Kinds of solution (volume ratio) | Temperature/. degree.C | Reaction time/h | Degree of degradation/%) |
| Comparative example 1 | Ethanol, water and acetic acid are 1: 1 | 85 | 9 | 0 |
| Example 1 | Ethanol, water and acetic acid are 1: 1 | 85 | 9 | 54.1 |
| Example 1 | Ethanol, water and acetic acid are 1: 1 | 85 | 24 | 81.2 |
| Example 1 | Ethanol, water and acetic acid are 1: 1 | 85 | 48 | 90 |
| Example 1 | Ethanol, water and acetic acid are 1: 2 | 85 | 48 | 100 |
| Example 1 | 50ml of ethanol: 0.025mol of p-toluenesulfonic acid | 85 | 9 | 52.3 |
| Example 1 | Nitric acid, water, DMF and ethanol in the ratio of 1 to 2 | 75 | 12 | 60.0 |
| Example 1 | Sulfuric acid, water, DMF and ethanol in the ratio of 1 to 2 | 65 | 12 | 16.5 |
| example 1 | Ethanol, water and hydrochloric acid are 1: 2 | 85 | 8 | 60.2 |
| Example 1 | Glycol, water and acetic acid are 1: 1 | 100 | 10 | 65.2 |
| Example 1 | Diethylene glycol, water and acetic acid are 1: 1 | 100 | 10 | 63.5 |
| Example 1 | DMSO, water and acetic acid are 1: 2 | 120 | 48 | 100 |
| Example 1 | NMP, water and acetic acid are 1: 2 | 120 | 48 | 100 |
| example 1 | THF, ethanol, water and acetic acid are 1: 2 | 60 | 48 | 55.7 |
as can be seen from table 1, the cured products of comparative example 1 and example 1 were placed in a solution of ethanol, water and acetic acid in a volume ratio of 1: 1, and after degradation at the same temperature for the same time, the degree of degradation of the cured product of comparative example 1 was 0, i.e., no degradation occurred, and the degree of degradation of the cured product of example 1 was 54.1%. The spirocyclic acetal structure is demonstrated to endow the polybenzoxazine resin with degradability under acidic conditions. As can be seen from Table 1, the cured products of example 1 were degraded to different degrees in the above solutions, and the longer the degradation time and the stronger the acidity, the higher the degradation degree, at the same solution and temperature. The cured product of the benzoxazine resin containing the helical acetal structure can be degraded under acidic conditions, and has the property of chemical degradation, namely the polybenzoxazine resin containing the helical acetal structure can be recycled.
The invention has been described in detail with reference to the preferred embodiments and illustrative examples. It should be noted, however, that these specific embodiments are only illustrative of the present invention and do not limit the scope of the present invention in any way. Various modifications, equivalent substitutions and alterations can be made to the technical content and embodiments of the present invention without departing from the spirit and scope of the present invention, and these are within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A benzoxazine resin containing a spiro acetal structure, wherein the benzoxazine resin contains a structure represented by formula (I):
A, B is independently selected from one of formula (II) to formula (IV), A and B can be same or different;
Wherein, R 1, R 2 and R 3 are respectively and independently selected from H, alkyl, substituted alkyl, alicyclic group, aromatic group or derivatives thereof, and R 1, R 2 and R 3 can be the same or different.
2. The benzoxazine resin according to claim 1,
The alkyl is C 1 -C 22 alkyl, preferably C 1 -C 18 alkyl, such as methyl, ethyl, n-butyl, n-pentyl, n-hexyl, dodecyl or octadecyl, and/or
The alicyclic group is C 3 -C 8, preferably C 3 -C 6 alicyclic group, such as cyclobutyl, cyclopentyl or cyclohexyl, and/or
The aryl is phenyl or substituted phenyl, the substituted phenyl is alkyl substituted phenyl or nitro substituted phenyl, and p-tolyl, o-tolyl or m-tolyl are preferable.
3. The benzoxazine resin according to claim 1 or 2, wherein the benzoxazine resin has a structure as shown in any one of the following (1) to (10),
(1) Pentaerythritol bis-p-hydroxybenzaldehyde-aniline type
(2) pentaerythritol bis-p-hydroxybenzaldehyde-cyclohexylamine type
(3) Pentaerythritol bis-p-hydroxybenzaldehyde-n-hexylamine type
(4) Pentaerythritol bis-p-hydroxybenzaldehyde-n-pentylamine type
(5) Pentaerythritol bis-p-hydroxybenzaldehyde n-butylamine type
(6) Pentaerythritol bis-m-hydroxybenzaldehyde-aniline type
(7) Pentaerythritol bis-m-hydroxybenzaldehyde-cyclohexylamine type
(8) Pentaerythritol bis-m-hydroxybenzaldehyde-n-hexylamine type
(9) Pentaerythritol bis-p-hydroxybenzaldehyde-dodecylamine type
(10) Pentaerythritol bis-p-hydroxybenzaldehyde-p-toluidine type
4. A preparation method of benzoxazine resin containing a spiro acetal structure is characterized by comprising the following steps:
step 1, adding a bisphenol compound containing a spiro acetal structure and a primary amine compound into a solvent, and mixing;
Step 2, adding an aldehyde compound into the system in the step 1 for reaction;
And 3, carrying out post-treatment on the product obtained in the step 2.
5. The method according to claim 4, wherein the bisphenol compound containing a spiro acetal structure is selected from one or more of pentaerythritol bis-p-hydroxybenzaldehyde, pentaerythritol bis-m-hydroxybenzaldehyde, pentaerythritol bis-o-hydroxybenzaldehyde or derivatives thereof, preferably pentaerythritol bis-p-hydroxybenzaldehyde or pentaerythritol bis-m-hydroxybenzaldehyde.
6. The method of claim 4, wherein the primary amine compound is an alkylamine, a substituted alkylamine, an alicyclic amine, an aromatic amine, or a derivative thereof,
The alkylamine is C 1 -C 22 alkylamine, preferably C 1 -C 18 alkylamine, such as methylamine, ethylamine, n-butylamine, n-pentylamine, n-hexylamine, dodecylamine or octadecylamine, and/or
The alicyclic amine is C 3 -C 8 alicyclic amine, preferably C 3 -C 6 alicyclic amine, such as cyclobutane amine, cyclopentane amine or cyclohexane amine, and/or
The aromatic amine is selected from aniline or substituted aniline, the substituted aniline is selected from alkyl substituted aniline or nitro substituted aniline, preferably p-toluidine, o-toluidine or m-toluidine,
the aldehyde compound is paraformaldehyde or a formaldehyde aqueous solution.
7. the method according to claim 4, wherein the solvent is selected from one or more of ethanol, methanol, isopropanol, butanol, tetrahydrofuran, dioxane, toluene, dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone.
8. The method of claim 4,
In the bisphenol compound, the primary amine compound and the aldehyde compound containing the spiro acetal structure, the ratio of the amount of phenolic hydroxyl, amino and aldehyde is 1: 1: (2.0 to 2.8), preferably 1: 1: (2.0 to 2.4),
In the step 2, the reaction is carried out for 10-60 min at-10 ℃, and then the reaction is carried out for 1-15 h at 80-120 ℃.
9. a decomposition method of a benzoxazine resin cured product containing a spiro acetal structure is characterized in that the benzoxazine resin cured product is soaked in an acid solution for 2-72 hours, preferably 8-48 hours,
The acid solution comprises an acid compound which is an organic acid or an inorganic acid,
The organic acid is selected from formic acid, acetic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid or trichloroacetic acid;
The inorganic acid is selected from hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
10. The method according to claim 9, wherein the acidic solution further comprises a polar solvent, wherein the polar solvent is preferably one or more of water, alcohol compounds, ketone compounds, ether compounds or amide compounds,
The alcohol compound is a compound containing one or more hydroxyl groups, such as one or more of ethanol, methanol, glycerol, diethylene glycol and furfuryl alcohol,
The ketone compound is selected from one or two of butanone and cyclohexanone,
the ether compound is one or more selected from ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, tetrahydrofuran and 1, 4-dioxane,
The amide compound is selected from one or more of dimethylformamide, dimethyl sulfoxide, sulfolane, N-methyl pyrrolidone, morpholine and N-methyl morpholine.
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| US20210309838A1 (en) * | 2020-04-01 | 2021-10-07 | The Goodyear Tire & Rubber Company | Rubber composition and a rubber product |
| CN113637132A (en) * | 2020-05-11 | 2021-11-12 | 中国石油化工股份有限公司 | Benzoxazine resin, preparation method and application |
| CN113698418A (en) * | 2020-05-21 | 2021-11-26 | 北京化工大学 | Bisacetamide compound containing spiro structure, and preparation method and application thereof |
| US20220195153A1 (en) * | 2020-12-17 | 2022-06-23 | The Goodyear Tire & Rubber Company | Rubber composition offering high stiffness and low hysteresis |
| CN115403724A (en) * | 2021-05-27 | 2022-11-29 | 中国石油化工股份有限公司 | Main chain type benzoxazine resin, preparation method thereof, and bisphthalonitrile-based composite material and composite cured resin containing same |
| CN115433334A (en) * | 2021-06-02 | 2022-12-06 | 北京化工大学 | Main chain type benzoxazine resin with di (trimethylolpropane) acetal structure |
| CN115433333A (en) * | 2021-06-02 | 2022-12-06 | 北京化工大学 | Benzoxazine resin with erythritol acetal structure |
| CN115490824A (en) * | 2021-06-17 | 2022-12-20 | 中国石油化工股份有限公司 | End-capped benzoxazine resin, bisphthalonitrile-based composite material containing end-capped benzoxazine resin and composite cured resin |
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| US20210309838A1 (en) * | 2020-04-01 | 2021-10-07 | The Goodyear Tire & Rubber Company | Rubber composition and a rubber product |
| CN113637132A (en) * | 2020-05-11 | 2021-11-12 | 中国石油化工股份有限公司 | Benzoxazine resin, preparation method and application |
| CN113637132B (en) * | 2020-05-11 | 2023-10-13 | 中国石油化工股份有限公司 | Benzoxazine resin and preparation method and application thereof |
| CN113698418A (en) * | 2020-05-21 | 2021-11-26 | 北京化工大学 | Bisacetamide compound containing spiro structure, and preparation method and application thereof |
| US20220195153A1 (en) * | 2020-12-17 | 2022-06-23 | The Goodyear Tire & Rubber Company | Rubber composition offering high stiffness and low hysteresis |
| US12018154B2 (en) * | 2020-12-17 | 2024-06-25 | The Goodyear Tire & Rubber Company | Rubber composition offering high stiffness and low hysteresis |
| CN115403724A (en) * | 2021-05-27 | 2022-11-29 | 中国石油化工股份有限公司 | Main chain type benzoxazine resin, preparation method thereof, and bisphthalonitrile-based composite material and composite cured resin containing same |
| CN115433334A (en) * | 2021-06-02 | 2022-12-06 | 北京化工大学 | Main chain type benzoxazine resin with di (trimethylolpropane) acetal structure |
| CN115433333A (en) * | 2021-06-02 | 2022-12-06 | 北京化工大学 | Benzoxazine resin with erythritol acetal structure |
| CN115433333B (en) * | 2021-06-02 | 2023-12-15 | 北京化工大学 | Benzoxazine resin with erythritol acetal structure |
| CN115433334B (en) * | 2021-06-02 | 2023-12-15 | 北京化工大学 | Main chain type benzoxazine resin with bis (trimethylol) propane acetal structure |
| CN115490824A (en) * | 2021-06-17 | 2022-12-20 | 中国石油化工股份有限公司 | End-capped benzoxazine resin, bisphthalonitrile-based composite material containing end-capped benzoxazine resin and composite cured resin |
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