CN115850200A - Polymerizable 3, 1-benzoxazine substituted phenol monomer, preparation method, cured product and application - Google Patents
Polymerizable 3, 1-benzoxazine substituted phenol monomer, preparation method, cured product and application Download PDFInfo
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- CN115850200A CN115850200A CN202211325484.8A CN202211325484A CN115850200A CN 115850200 A CN115850200 A CN 115850200A CN 202211325484 A CN202211325484 A CN 202211325484A CN 115850200 A CN115850200 A CN 115850200A
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- benzoxazine
- polymerizable
- substituted phenol
- phenol monomer
- cured product
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- 239000000178 monomer Substances 0.000 title claims abstract description 48
- GTYZDORKFFSTLS-UHFFFAOYSA-N 2h-3,1-benzoxazine Chemical group C1=CC=CC2=NCOC=C21 GTYZDORKFFSTLS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 150000002989 phenols Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 11
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 7
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000004103 aminoalkyl group Chemical group 0.000 claims abstract description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims abstract description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims abstract description 5
- 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 abstract description 5
- 125000002541 furyl group Chemical group 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- DYXWBIIIQALDGP-UHFFFAOYSA-N 2,4-dihydro-1h-3,1-benzoxazine Chemical group C1=CC=C2COCNC2=C1 DYXWBIIIQALDGP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 3
- 125000003368 amide group Chemical group 0.000 claims abstract description 3
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims abstract description 3
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 claims abstract description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 3
- 239000011347 resin Substances 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 27
- 239000011159 matrix material Substances 0.000 claims description 26
- -1 3, 1-benzoxazine-substituted phenol Chemical class 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 17
- 239000003063 flame retardant Substances 0.000 claims description 17
- 239000000853 adhesive Substances 0.000 claims description 16
- 230000001070 adhesive effect Effects 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
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- 238000002679 ablation Methods 0.000 claims description 13
- 238000004100 electronic packaging Methods 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 12
- 239000012772 electrical insulation material Substances 0.000 claims description 11
- 239000006249 magnetic particle Substances 0.000 claims description 11
- 239000000376 reactant Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052700 potassium Inorganic materials 0.000 claims description 8
- 239000011591 potassium Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002262 Schiff base Substances 0.000 claims description 6
- 150000004753 Schiff bases Chemical class 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001744 Polyaldehyde Polymers 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000007363 ring formation reaction Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 7
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 claims 1
- 239000000047 product Substances 0.000 description 116
- 238000000921 elemental analysis Methods 0.000 description 23
- 239000002994 raw material Substances 0.000 description 22
- 238000001819 mass spectrum Methods 0.000 description 21
- 239000002131 composite material Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- CGACGSHTSCXSSO-UHFFFAOYSA-N 2h-1,3-benzoxazine Chemical compound C1=CC=C2C=NCOC2=C1 CGACGSHTSCXSSO-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 8
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 238000007142 ring opening reaction Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 238000004088 simulation Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- 238000006731 degradation reaction Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
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- RSSICPKUBLFYGE-UHFFFAOYSA-N (2-amino-6-methoxyphenyl)methanol Chemical compound COC1=CC=CC(N)=C1CO RSSICPKUBLFYGE-UHFFFAOYSA-N 0.000 description 1
- 239000001431 2-methylbenzaldehyde Substances 0.000 description 1
- KGWNRZLPXLBMPS-UHFFFAOYSA-N 2h-1,3-oxazine Chemical group C1OC=CC=N1 KGWNRZLPXLBMPS-UHFFFAOYSA-N 0.000 description 1
- JJYPMNFTHPTTDI-UHFFFAOYSA-N 3-methylaniline Chemical compound CC1=CC=CC(N)=C1 JJYPMNFTHPTTDI-UHFFFAOYSA-N 0.000 description 1
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- YTHJCZRFJGXPTL-UHFFFAOYSA-N 4-hydroxy-3-nitrobenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1[N+]([O-])=O YTHJCZRFJGXPTL-UHFFFAOYSA-N 0.000 description 1
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- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention discloses a polymerizable 3, 1-benzoxazine substituted phenol monomer, a preparation method, a cured product and application, wherein the monomer comprises at least one phenol group and at least one 2H,4H-3, 1-benzoxazine group, and the chemical structures of the monomer are shown as formulas (Ia), (Ib) and (Ic):
R 1 and R 2 Respectively selected from one or more of hydrogen, alkyl, alkoxy, aryl, allyl, ethynyl, halogen, nitryl, sulfonyl, hydroxyl, hydroxyalkyl, amino, aminoalkyl, aldehyde group, carboxyl and amido; r 3 Selected from H, C1-C18 alkyl, ethenyl, ethynyl, cyclohexyl, phenyl, anthryl, benzyl and furyl. The cured product prepared from the polymerizable 3, 1-benzoxazine substituted phenol monomer has excellent thermodynamic property.
Description
Technical Field
The invention relates to the field of organic chemistry and high polymer materials, in particular to a polymerizable 3, 1-benzoxazine substituted phenol monomer, a preparation method, a cured substance and application.
Background
Phenol resin is a resin having good insulating and flame retardant properties, and thus has been widely used in the electrical and electronic industries since the invention as a first synthetic resin. However, the traditional phenolic resin is often required to be subjected to a polymerization reaction under catalysis of strong acid and strong base, and by-products such as small molecules and the like are generated in the curing process, so that defects are generated inside the material, and the mechanical property and the water absorption property of the material are seriously affected. The benzoxazine resin is a novel phenolic resin which is developed in recent years and cured through ring-opening polymerization, and the resin not only overcomes the defects of the phenolic resin, but also has the advantages of high mechanical strength, low water absorption, small curing shrinkage and the like, so the benzoxazine resin is widely concerned since the first report in 1994, and has important application value in the fields of metal coating corrosion prevention, electric equipment and electronic device packaging, high-temperature-resistant adhesives, aerospace composite materials and the like.
However, the currently mainstream reported benzoxazine resins also have some obvious disadvantages: firstly, because the benzoxazine with single functionality has low polarity and low molecular weight and weak intermolecular interaction force, the benzoxazine has obvious weight loss in the curing process; secondly, the key structure of the currently mainstream benzoxazine resin is 1, 3-benzoxazine, and a Mannich bridge structure formed after ring opening is greatly reduced in the aspect of thermal stability relative to phenolic resin, and structures such as alkynyl and the like are required to be additionally introduced to ensure the thermal property of the material; more importantly, the molecular weight of the obtained polymer is low due to the influence of chain transfer reaction in the polymerization process, so that the application range is limited, which is particularly obvious in the monofunctional benzoxazine resin. For the resin with higher functionality, the application of the material is limited due to the defects of low crosslinking density of the polymer, large brittleness of the material and the like caused by intramolecular hydrogen bonds formed by ring opening of 1, 3-benzoxazine.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polymerizable 3, 1-benzoxazine substituted phenol monomer, a preparation method, a cured product and application, and solves the technical problems of low polymer crosslinking density and high material brittleness caused by the formation of intramolecular hydrogen bonds due to the ring opening of 1, 3-benzoxazine in the prior art.
In order to achieve the purpose, the technical scheme is as follows:
a polymerizable 3, 1-benzoxazine substituted phenol monomer comprising at least one phenol group and at least one 2h,4h-3, 1-benzoxazine group having the chemical structure shown in formulae (ia), (ib) and (Ic):
wherein p is R 1 P is an integer of 0 to 4; q is R 2 Q is an integer of 0 to 5; p and q are not 0 at the same time;
R 1 and R 2 Are respectively selected from H, alkyl, alkoxy, aryl, allyl, ethynyl, halogen, nitryl, sulfonyl, hydroxyl, hydroxyalkyl, amino, aminoalkyl, aldehyde group, carboxyl and amido;
R 3 selected from H, C1-C18 alkyl, ethenyl, ethynyl, cyclohexyl, phenyl, anthryl, benzyl and furyl;
with the following conditions:
all R 1 And R 2 In which at least one hydroxyl group is present, and when p.gtoreq.2, each R 1 Same or different, when q is not less than 2, each R 2 The same or different;
when m1=1, X 1 ＝R 1 ；
When m1=2, X 1 = single bond (-), -O-, -S-),
/>
When m1=3, the number of the magnetic particles is,
when m1=4, the number of the magnetic particles is,
when m2=1, X 2 ＝R 2 ；
When m2=2, X 2 = single bond (-), -O-, -S-),
When m2=3, the number of the magnetic particles is,
when m2=4, the number of the magnetic particles is,
when m3=1, X 3 ＝R 3 ；
When m3=2, X 3 (= single bond) —),
When m3=3, the number of the magnetic particles is,
/>
when m3=4, the number of the magnetic particles is,
the invention discloses a method for preparing a polymerizable 3, 1-benzoxazine substituted phenol monomer,
the method comprises the following steps:
step 1: dissolving an anthranilic alcohol compound and an aldehyde reactant A in an organic solvent at the temperature of 0-120 ℃ to obtain a Schiff base solution containing at least one phenolic hydroxyl group and an alcoholic hydroxyl group;
step 2: adding a reducing agent into the Schiff base solution obtained in the step 1 at the temperature of 0-120 ℃ to obtain a Mannich base solution containing at least one phenolic hydroxyl group and at least one alcoholic hydroxyl group;
and step 3: and (3) adding an aldehyde reactant B into the Mannich base solution obtained in the step (2), performing cyclization reaction at room temperature-120 ℃, and performing reduced pressure distillation and drying to obtain the Mannich base.
Specifically, the chemical structural formula of the anthranilic alcohol compound in the step 1 is shown as the formula (II):
wherein j is R 11 J is an integer of 0 to 3;
R 11 selected from the group consisting of hydrogen, alkyl, alkoxy, aryl, allyl, ethynyl, halogen, nitro, sulfonyl, hydroxyl, hydroxyalkyl, amino, aminoalkyl, aldehyde, carboxyl, amide;
when j is greater than or equal to 2, each R 11 The same or different;
when n1=1, Z 1 ＝R 11 ；
When n1=2, Z 1 = single bond (-), -O-, -S-),
/>
When n1=3, the number of the active layers is increased,
when n1=4, the number of the bits is increased,
further, the aldehyde reactant a in step 1 has a chemical structural formula shown in formula (III):
R 12 selected from the group consisting of hydrogen, alkyl, alkoxy, aryl, allyl, ethynyl, halogen, nitro, sulfonyl, hydroxyl, hydroxyalkyl, amino, aminoalkyl, aldehyde, carboxyl, amide;
wherein k is R 12 K is an integer of 0 to 4;
when k is 2 or more, each R 12 The same or different;
when n2=1, Z 2 ＝R 12 ；
When n2=2, Z 2 = single bond (-), -O-, -S-),
When n2=3, the number of the active layers is increased,
when n2 is =4, the number of the nodes is set to zero,
/>
further, the reducing agent in step 2 includes sodium borohydride or potassium borohydride.
Furthermore, the aldehyde reactant B in step 3 has a chemical structural formula shown in formula (IV):
when n3=1, X3= hydrogen, C1-C18 alkyl, vinyl, ethynyl, cyclohexyl, phenyl, anthracenyl, benzyl, furanyl;
when n3=2, X 3 (= single bond) —),
When n3=3, the number of the bits is increased,
when n3=4
Further, the aldehyde reactant B in step 3 further comprises a trimer aldehyde and a polyaldehyde.
Further, the organic solvent in step 1 includes methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, t-butanol, toluene, xylene, chlorinated hydrocarbon, ethyl acetate, butyl acetate, acetone, butanone, tetrahydrofuran, methyl t-butyl ether, dioxane, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide.
The invention also protects a cured product, which is prepared by heating and polymerizing the polymerizable 3, 1-benzoxazine substituted phenol monomer prepared by the preparation method of the polymerizable 3, 1-benzoxazine substituted phenol monomer, wherein the heating temperature of the heating and polymerization is 120-250 ℃, and the heating time is 1-24 hours.
The polymerizable 3, 1-benzoxazine substituted phenol monomer prepared by the preparation method of the polymerizable 3, 1-benzoxazine substituted phenol monomer is applied as an adhesive, a packaging material and a matrix resin.
Compared with the prior art, the invention has the beneficial technical effects that:
compared with the existing material, the polymerizable 3, 1-benzoxazine substituted phenol monomer reduces the ring-opening polymerization activation energy of 3, 1-benzoxazine due to the introduction of phenolic hydroxyl, so that the 3, 1-benzoxazine structure also has polymerization capability; the benzyl hydroxyl group formed after the ring opening reaction of the 3, 1-benzoxazine can be further condensed to form a diphenylmethane structure, so that the glass transition temperature, the thermal stability and the carbon residue rate of the material are obviously improved; the ring-opened 3, 1-benzoxazine structure can not form an intramolecular hydrogen bond structure of the ring-opened 1, 3-benzoxazine, and the reduction of the thermal property and the mechanical property of the material caused by the reduction of the crosslinking density is avoided, so that the polymerizable 3, 1-benzoxazine substituted phenol monomer has outstanding heat resistance, mechanical property and flame retardant property.
The preparation method provided by the invention is simple, simple and convenient to operate and easy to implement.
(III) the cured product provided by the invention has no obvious weight loss in the monomer curing process and has a more compact cross-linked network structure.
The cured product provided by the invention has wide application, and can be used as a high-temperature-resistant adhesive, a component electronic packaging material, an ablation-resistant flame-retardant material and a fiber reinforced electrical insulating material matrix resin in the fields of electrical industry, electronic industry, vehicle manufacturing and aerospace.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
FIG. 1 is an infrared spectrum of a 3, 1-benzoxazine-substituted phenol monomer obtained in example 1;
FIG. 2 is a chart showing a hydrogen nuclear magnetic resonance spectrum of a 3, 1-benzoxazine-substituted phenol monomer obtained in example 1;
FIG. 3 is a carbon nuclear magnetic resonance spectrum of a 3, 1-benzoxazine-substituted phenol monomer obtained in example 1;
FIG. 4 is a temperature differential scanning calorimetry spectrum of a 3, 1-benzoxazine-substituted phenol monomer prepared in example 1;
FIG. 5 shows simulation results of 3, 1-benzoxazine-substituted phenol monomers obtained in example 1;
FIG. 6 is a graph showing a change in an infrared spectrum during curing of a 3, 1-benzoxazine-substituted phenol monomer obtained in example 1;
FIG. 7 is a thermogravimetric plot of a cured 3, 1-benzoxazine-substituted phenol obtained in example 1, compared with a conventional cured 1, 3-benzoxazine.
The details of the present invention are explained in further detail below with reference to the drawings and examples.
Detailed Description
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
In the following examples, the infrared spectra were characterized using a Bruker sensor 27 apparatus, the nmr spectra were characterized using a Vario elii apparatus, the curing process was characterized using a differential scanning calorimeter TA Q2000, the thermogravimetry was characterized using a Mettler Toledo, the viscoelastometry spectra were characterized using a TA Q800, the mass spectra were characterized using an agilent 5973 mass spectrometer apparatus, and the elemental analysis was characterized using an Elementar Vario EL cube, germany.
Example 1:
preparation of polymerizable 3, 1-benzoxazine substituted phenol monomer:
step 1, dissolving 0.1mol of anthranilic alcohol and 0.1mol of salicylaldehyde in ethanol, and reacting for 6 hours at 80 ℃ to obtain a Schiff base solution;
step 2, adding 0.05mol of sodium borohydride into the Schiff base solution obtained in the step 1 at room temperature to react for 0.5 hour to obtain a Mannich base solution;
and 3, adding 0.1mol of paraformaldehyde into the Mannich base solution obtained in the step 2, reacting at 80 ℃ for 12 hours, and carrying out reduced pressure distillation and drying to obtain light yellow solid powder, wherein the yield of the target product (1-1) is 85%.
The IR spectrum of the objective product (1-1) obtained in this example is shown in FIG. 1: 3148 (-OH), 3035 (Ar-H), 2825 (-CH 2-), 1583, 1489 (C = C, ar), 1456 (-CH 2-), 1236, 1064, 1031 (C-O-C), 924 (3, 1-oxazine ring), 756 (1, 2-substituted aryl);
the hydrogen nuclear magnetic resonance spectrum (1H-NMR) of the objective product (1-1) is shown in FIG. 2: 9.12 (Ar-OH, 1H), 7.28-6.91 (Ar-H, 8H), 4.95 (N-CH 2-O, 2H), 4.62 (N-CH 2-Ar, 2H), 4.52 (O-CH 2-Ar, 2H);
the carbon nuclear magnetic resonance spectrum (13C-NMR) of the objective product (1-1) is shown in FIG. 3: 157.22 144.11, 129.37, 129.35, 127.59, 127.48, 125.22, 123.81, 122.52, 121.77, 120.07, 116.73 (Ar), 78.35 (N-CH 2-O), 67.27 (O-CH 2-Ar), 58.30 (N-CH 2-Ar).
Mass Spectrum (MS) M/Z =241[ M + ] of target product (1-1);
elemental Analysis (EA) result of the target product (1-1): found% (Calc.%): c:74.55 (74.67), H:6.16 (6.27), N:5.80 (5.81). The above results demonstrate that the monomer (1-1) was successfully prepared.
From the above structure identification result of the target product (1-1), the target product (1-1) prepared in this example is a 3, 1-benzoxazine substituted phenol monomer, and the structure of the target product (1-1) is as follows:
the synthesis route of the target product (1-1) is as follows:
the results of differential scanning calorimetry (FIG. 4) show that:
the target product has a distinct endothermic peak at 56 ℃ corresponding to the melting peak (melting point) of the monomer and an exothermic peak at 227 ℃ corresponding to the solidification polymerization peak of the monomer. The result not only shows that the monomer can be polymerized, but also shows that the monomer has a larger temperature range from melting to solidification, and a processing window with a wide temperature range is formed, so that the monomer is very beneficial to monomer solidification and molding.
The simulation results of curing simulation (fig. 5) performed on the target product prepared in this example further show that:
the key to the polymerization of the target product is that: the phenol forms intramolecular hydrogen bonds on the basis of oxazine rings, so that the bond energy of C-O in the oxazine rings is remarkably reduced, and the ring-opening polymerization reaction is facilitated.
The 3, 1-benzoxazine substituted phenol monomer prepared in the embodiment can be cured by distributed heating under the curing conditions of 120 ℃/1h,150 ℃/2h,180 ℃/2h,200 ℃/2h and 240 ℃/2h, and finally a cured product is prepared.
FIG. 6 is the change of the IR spectrum of the monomer during the step-by-step heating and curing process, and it can be clearly seen that the 3, 1-benzoxazine-substituted phenol monomer prepared in the present example has a molecular structure changed during the heating process, wherein the wave number is 924cm -1 The peak corresponding to the oxazine ring oscillation is significantly reduced. Meanwhile, originally 1489cm -1 The absorption peak of (2) was changed to 1502cm -1 Meaning that the original 1, 2-substituted benzene ring is changed into a tri-substituted structure, which proves that the monomer generates ring opening of oxazine ring during heating processAnd (4) carrying out polymerization reaction, and bonding short chains formed by ring opening and aromatic rings to form a polymer network.
The thermal weight loss analysis result shown in fig. 7 is used to determine the heat resistance and flame retardant performance of the material, and compared with the 1, 3-benzoxazine cured material with similar structure, the initial degradation temperature of the cured material prepared in the embodiment exceeds 350 ℃, and the 5% weight loss temperature reaches more than 400 ℃, while the initial degradation temperature of the currently general 1, 3-benzoxazine cured material is only about 250 ℃, and the 5% weight loss temperature is more than 310 ℃. This demonstrates that the monomeric cured product prepared in this example has a thermal stability far superior to that of the general-purpose 1, 3-benzoxazine cured product. In addition, compared with the commonly used 1, 3-benzoxazine cured product in the prior art, the carbon residue rate of the cured product prepared by the embodiment is higher than 10% and reaches 54%, the converted limiting oxygen index exceeds 40, and the cured product has good flame retardant property.
The thermodynamic property of the cured product prepared by compounding the monomer prepared in the embodiment with the glass fiber cloth is tested to obtain a dynamic visco-elastic spectrum, and according to the tan delta peak value, the glass transition temperature of the prepared material reaches above 217 ℃, and the glass transition temperature of the existing 1, 3-benzoxazine cured product is mostly between 150 ℃ and 180 ℃, so that the cured product prepared by curing the 3, 1-benzoxazine monomer prepared in the embodiment has excellent thermodynamic property.
The cured product prepared by the embodiment can be used as matrix resin raw materials of high-temperature-resistant adhesives, electronic packaging materials of components, ablation-resistant flame-retardant materials, fiber reinforced electrical insulating material composite material matrix resin raw materials and the like in the fields of electrical industry, electronic industry, vehicle manufacturing and aerospace, and can be used as high-power chip die attach adhesives, printed circuit board matrix resin, semiconductor device packaging molding compounds and the like.
Example 2
Dissolving 0.2mol of anthranilic alcohol and 0.2mol of 4-chloro-2-hydroxybenzaldehyde in isopropyl alcohol
In alcohol, in
Reacting at 90 ℃ for 8 hours, then adding 0.15mol of sodium borohydride, reacting at room temperature for 2 hours, then adding 0.22mol of formaldehyde solution, reacting at 80 ℃ for 20 hours, and distilling and drying under reduced pressure to obtain a light yellow solid powdery target product (1-2) with a yield of 77%.
And (3) structural identification:
the mass spectrum data of the target product (1-2) prepared in this example are: (MS) M/Z =275
[ M + ]; elemental analysis result (EA) of the objective product (1-2): found% (Calc.%):
C：65.12
(65.34)，H：5.00(5.12)，N：5.02(5.08)，O:11.67(11.60)。
the structure of the target product (1-2) is as follows:
the target product (1-2) prepared by the embodiment can be cured by heating step by step under the curing conditions of 120 ℃/1h,150 ℃/2h,180 ℃/2h,200 ℃/2h and 240 ℃/2h to prepare a cured product.
The test results of the properties of the target product (1-2) and the cured product in this example were substantially the same as those in example 1.
The cured product prepared by the embodiment can be used as matrix resin raw materials of high-temperature-resistant adhesives, electronic packaging materials of components and parts, ablation-resistant flame-retardant materials, fiber reinforced electrical insulation material composite matrix resin raw materials and the like in the fields of electrical industry, electronic industry, vehicle manufacturing and aerospace.
Example 3
Dissolving 0.15mol of 2-amino-6-methoxybenzyl alcohol and 0.15mol of vanillin in dimethyl sulfoxide, reacting for 5 hours at 110 ℃, then adding 0.1mol of sodium borohydride, reacting for 6 hours at 60 ℃, then adding 0.18mol of acetaldehyde solution, reacting for 24 hours at 80 ℃, washing and separating out, and then re-dissolving and drying by using ethanol to obtain a target product (1-3) of yellow solid powder with the yield of 82%.
And (3) structural identification:
mass spectrum data of the target product (1-3) obtained in this example: M/Z =315[ M + ];
elemental analysis result (EA) of the objective product (1-3) obtained in this example: found% (Calc.%): c:68.35 (68.55), H:6.66 (6.71), N:4.32 (4.44).
The structures of the target products (1-3) are as follows:
the test results of the properties of the target products (1-3) and the cured product of this example were substantially the same as those of example 1.
The target product (1-3) prepared by the embodiment can be cured by heating step by step under the curing conditions of 120 ℃/1h,150 ℃/2h,180 ℃/2h,200 ℃/2h and 240 ℃/2h to prepare a cured product.
The cured product prepared by the embodiment can be used as matrix resin raw materials of high-temperature-resistant adhesives, electronic packaging materials of components and parts, ablation-resistant flame-retardant materials, fiber reinforced electrical insulation material composite matrix resin raw materials and the like in the fields of electrical industry, electronic industry, vehicle manufacturing and aerospace.
Example 4
0.1mol of 3,3 '-dimethylol-4, 4' -diaminodiphenyl sulfone and 0.2mol of 4-hydroxybenzaldehyde are dissolved in butanone and reacted at 90 ℃ for 12 hours, then 0.1mol of potassium borohydride is added, 0.24mol of formaldehyde solution is added after the reaction at 60 ℃ for 6 hours, the reaction is carried out at 100 ℃ for 36 hours, and the target product (1-4) is obtained after reduced pressure distillation and drying, wherein the yield is 68 percent.
And (3) structure identification:
mass spectrum data (MS) of the target product (1-4) obtained in this example, M/Z =604 [ M + ];
elemental analysis result (EA) of the objective product (1-4) obtained in this example: found% (Calc.%): c:63.60 (63.56), H:5.31 (5.33), N:4.61 (4.63), S:5.24 (5.30).
The structures of the target products (1-4) are as follows:
the test results of the properties of the target products (1-4) and the cured product of this example were substantially the same as those of example 1.
The target product (1-4) prepared by the embodiment can be cured by heating step by step under the curing conditions of 180 ℃/2h,200 ℃/2h,240 ℃/2h and 250 ℃/4h to prepare a cured product.
The cured product prepared by the embodiment can be used as matrix resin raw materials of high-temperature-resistant adhesives, electronic packaging materials of components and parts, ablation-resistant flame-retardant materials, fiber reinforced electrical insulation material composite matrix resin raw materials and the like in the fields of electrical industry, electronic industry, vehicle manufacturing and aerospace.
Example 5
0.2mol of 3,3 '-dimethylol-4, 4' -diaminobenzophenone and 0.4mol of 3-nitro-4-hydroxybenzaldehyde are dissolved in toluene and reacted at 100 ℃ for 12 hours, then 0.22mol of potassium borohydride is added, 0.46mol of 4-methylbenzaldehyde is added after the reaction at 50 ℃ for 9 hours, the reaction is carried out at 110 ℃ for 36 hours, and the target product (1-5) is obtained as a yellow solid powder after distillation and drying under reduced pressure, with a yield of 58%.
Mass spectrum data of the target product (1-5) obtained in this example: M/Z =778[ M + ];
elemental analysis result (EA) of the objective product (1-5) obtained in this example: found% (Calc.%): c:69.02 (69.40), H:4.88 (4.92), N:7.08 (7.19).
The structures of the target products (1-5) are as follows:
the test results of the properties of the target products (1-5) and the cured product of this example were substantially the same as those of example 1.
The target product (1-5) prepared by the embodiment can be cured by heating step by step under the curing conditions of 180 ℃/2h,200 ℃/2h,240 ℃/2h and 250 ℃/4h to prepare a cured product.
The cured product prepared by the embodiment can be used as matrix resin raw materials of high-temperature-resistant adhesives, electronic packaging materials of components and parts, ablation-resistant flame-retardant materials, fiber reinforced electrical insulation material composite matrix resin raw materials and the like in the fields of electrical industry, electronic industry, vehicle manufacturing and aerospace.
Example 6
<xnotran> 0.01mol 3,3',3",3"' - -4,4',4",4"' - 0.04mol , 60 ℃ 24 , 0.022mol , 60 ℃ 24 0.05mol , 60 ℃ 48 , (1-6), 45%. </xnotran>
And (3) structural identification:
mass spectrum data (MS) of the objective product (1-6) obtained in this example, M/Z =1092[ M + ];
elemental analysis results (EA) of the objective products (1 to 6) obtained in this example: found% (Calc.%): c:71.12 (71.41), H:5.86 (5.90), N:5.11 (5.12).
The structures of the target products (1-6) are as follows:
the test results of the properties of the target products (1-6) and the cured product of this example were substantially the same as those of example 1.
The target product (1-6) prepared by the embodiment can be cured by heating step by step under the curing conditions of 180 ℃/2h,200 ℃/2h,240 ℃/2h and 250 ℃/4h to prepare a cured product.
The cured product prepared by the embodiment can be used as matrix resin raw materials of high-temperature-resistant adhesives, electronic packaging materials of components and parts, ablation-resistant flame-retardant materials, fiber reinforced electrical insulation material composite matrix resin raw materials and the like in the fields of electrical industry, electronic industry, vehicle manufacturing and aerospace.
Example 7
Dissolving 0.01mol of 3,3 '-dialdehyde-4, 4' -dihydroxydiphenylmethane and 0.02mol of anthranilic alcohol in ethanol, reacting for 12 hours at 60 ℃, then adding 0.011mol of potassium borohydride, reacting for 24 hours at 80 ℃, adding 0.024mol of formaldehyde solution, reacting for 20 hours at 60 ℃, and carrying out reduced pressure distillation and drying to obtain a pink solid powdery target product (1-7) with the yield of 73%.
And (3) structural identification:
mass spectrum data (MS) of the target product (1-7) prepared in this example (M/Z =494[ M + ]);
elemental analysis results (EA) of the objective products (1 to 7) obtained in this example: found% (Calc.%): c:75.13 (75.28), H:6.09 (6.11), N:5.62 (5.66).
The structures of the target products (1-7) are as follows:
the test results of the properties of the target products (1 to 7) and the cured product of this example were substantially the same as those of example 1.
The target product (1-7) prepared by the embodiment can be cured by heating step by step under the curing conditions of 120 ℃/1h,150 ℃/2h,180 ℃/2h,200 ℃/2h and 240 ℃/2h to prepare a cured product.
The cured product prepared by the embodiment can be used as matrix resin raw materials of high-temperature-resistant adhesives, electronic packaging materials of components and parts, ablation-resistant flame-retardant materials, fiber reinforced electrical insulation material composite matrix resin raw materials and the like in the fields of electrical industry, electronic industry, vehicle manufacturing and aerospace.
Example 8
Dissolving 0.02mol of 3,3 '-dialdehyde-4, 4' -dihydroxydiphenyl ether and 0.04mol of anthranilic alcohol in ethanol, reacting for 16 hours at 60 ℃, then adding 0.024mol of potassium borohydride, reacting for 24 hours at 60 ℃, adding 0.024mol of furfural, reacting for 30 hours at 80 ℃, and carrying out reduced pressure distillation and drying to obtain a target product (1-8) in the form of light pink solid powder with the yield of 73%.
And (3) structural identification:
mass spectrum data (MS) of the target product (1-8) obtained in this example, M/Z =628[ M + ];
elemental analysis results (EA) of the objective products (1 to 8) obtained in this example: found% (Calc.%): c:72.48 (72.60), H:5.09 (5.13), N:4.51 (4.46).
The structures of the target products (1-7) are as follows:
the test results of the properties of the target products (1 to 8) and the cured product of this example were substantially the same as those of example 1.
The target product (1-8) prepared by the embodiment can be cured by heating step by step under the curing conditions of 120 ℃/1h,150 ℃/2h,180 ℃/2h,200 ℃/2h and 240 ℃/2h to prepare a cured product.
The cured product prepared by the embodiment can be used as matrix resin raw materials of high-temperature-resistant adhesives, electronic packaging materials of components and parts, ablation-resistant flame-retardant materials, fiber reinforced electrical insulation material composite matrix resin raw materials and the like in the fields of electrical industry, electronic industry, vehicle manufacturing and aerospace.
Example 9
Dissolving 0.01mol of 3,3 '-trioxymethylene-4, 4' -trihydroxy triphenylmethane and 0.03mol of 4-methyl-2-aminobenzene in chloroform, reacting for 16 hours at 60 ℃, then adding 0.018mol of potassium borohydride, reacting for 24 hours at 80 ℃, adding 0.036mol of formaldehyde solution, reacting for 30 hours at 60 ℃, and distilling and drying under reduced pressure to obtain a white solid powdery target product (1-9) with the yield of 45%.
And (3) structural identification:
mass spectrum data (MS) of the target product (1-9) obtained in this example (M/Z =775[ M + ]);
elemental analysis results (EA) of the objective products (1 to 9) obtained in this example: found% (Calc.%): c:75.83 (75.85), H:6.45 (6.37), N:5.50 (5.42).
The structures of the target products (1-9) are as follows:
the test results of the properties of the target products (1 to 9) and the cured product of this example were substantially the same as those of example 1.
The target product (1-9) prepared by the embodiment can be cured by heating step by step under the curing conditions of 150 ℃/2h,180 ℃/2h,200 ℃/2h and 240 ℃/4h to prepare a cured product.
The cured product prepared in the embodiment can be used as a matrix resin raw material of a high-temperature-resistant adhesive, a component electronic packaging material, an ablation-resistant flame-retardant material, a fiber-reinforced electrical insulation material composite matrix resin raw material and the like in the fields of the electrical industry, the electronic industry, the vehicle manufacturing and the aerospace.
Example 10
Dissolving 0.06mol of salicylaldehyde and 0.06mol of anthranilic alcohol in ethyl acetate, reacting for 6 hours at 60 ℃, then adding 0.036mol of sodium borohydride, reacting for 12 hours at 60 ℃, adding 0.03mol of glyoxal solution, reacting for 30 hours at 60 ℃, and carrying out reduced pressure distillation and drying to obtain a light yellow solid powdery target product (1-10) with the yield of 63%.
And (3) structural identification:
mass spectrum data (MS) of the objective product (1-10) obtained in this example, M/Z =480[ M + ];
elemental analysis results (EA) of the objective products (1 to 10) obtained in this example: found% (Calc.%): c:75.09 (74.98), H:5.78 (5.87), N:5.77 (5.83).
The structures of the target products (1-10) are as follows:
the test results of the target products (1-10) and the cured product of this example were substantially the same as those of example 1.
The target product (1-10) prepared by the embodiment can be cured by heating step by step under the curing conditions of 120 ℃/1h,150 ℃/2h,180 ℃/2h,200 ℃/2h and 240 ℃/2h to prepare a cured product.
The cured product prepared by the embodiment can be used as matrix resin raw materials of high-temperature-resistant adhesives, electronic packaging materials of components and parts, ablation-resistant flame-retardant materials, fiber reinforced electrical insulation material composite matrix resin raw materials and the like in the fields of electrical industry, electronic industry, vehicle manufacturing and aerospace.
Example 11
0.04mol of syringaldehyde and 0.04mol of 4-methoxy-2-aminobenzol are dissolved in toluene and react for 8 hours at the temperature of 100 ℃, then 0.024mol of potassium borohydride is added, 0.02mol of furan dicarbaldehyde is added after 24 hours of reaction at the temperature of 60 ℃, then the reaction is carried out for 6 hours at the temperature of 100 ℃, and the white solid powdery target product (1-11) is obtained after reduced pressure distillation and drying, with the yield of 58%.
And (3) structural identification:
mass spectrum data (MS) of the aimed product (1-11) obtained in this example, M/Z =726[ M + ];
elemental analysis results (EA) of the objective products (1 to 11) obtained in this example: found% (Calc.%): c:66.23 (66.11), H:5.78 (5.83), N:3.80 (3.85).
The structures of the target products (1-11) are as follows:
the test results of the properties of the target products (1-11) and the cured product of this example were substantially the same as those of example 1.
The target product (1-11) prepared by the embodiment can be cured by heating step by step under the curing conditions of 180 ℃/2h,200 ℃/2h,240 ℃/2h and 250 ℃/4h to prepare a cured product.
The cured product prepared by the embodiment can be used as matrix resin raw materials of high-temperature-resistant adhesives, electronic packaging materials of components and parts, ablation-resistant flame-retardant materials, fiber reinforced electrical insulation material composite matrix resin raw materials and the like in the fields of electrical industry, electronic industry, vehicle manufacturing and aerospace.
The present invention is described in detail with reference to the embodiments, but the embodiments of the present invention are not limited by the embodiments, and any other changes, substitutions, combinations and simplifications made under the teaching of the patent core of the present invention are included in the protection scope of the present invention.
Claims (10)
1. A polymerizable 3, 1-benzoxazine-substituted phenol monomer comprising at least one phenol group and at least one 2h,4h-3, 1-benzoxazine group having the chemical structure according to formulae (ia), (ib) and (Ic):
wherein p is R 1 P is an integer of 0 to 4; q is R 2 Q is an integer of 0 to 5; p and q are not 0 at the same time;
R 1 and R 2 Are respectively selected from H, alkyl, alkoxy, aryl, allyl, ethynyl, halogen, nitryl, sulfonyl, hydroxyl, hydroxyalkyl, amino, aminoalkyl, aldehyde group, carboxyl and amido;
R 3 selected from H, C1-C18 alkyl, ethenyl, ethynyl, cyclohexyl, phenyl, anthryl, benzyl and furyl;
with the following conditions:
all of R 1 And R 2 In which at least one hydroxyl group is present, and when p.gtoreq.2, each R 1 Same or different, when q is not less than 2, each R 2 The same or different;
when m1=1, X 1 ＝R 1 ；
When m1=2, X 1 = single bond (-), -O-, -S-),
When m1=3, the number of the magnetic particles is,
/>
when m1=4, the number of the magnetic particles is,
when m2=1, X 2 ＝R 2 ；
When m2=2, X 2 = single bond (-), -O-, -S-),
When m2=3, the number of the magnetic particles is,
when the sum of m2=4 is greater than or equal to 4,
when m3=1, X 3 ＝R 3 ；
When m3=2, X 3 (= single bond) —),
When m3=3, the number of the magnetic particles is,
/>
when m3=4, the number of the magnetic particles is,
2. a preparation method of a polymerizable 3, 1-benzoxazine substituted phenol monomer is characterized by comprising the following steps:
step 1: dissolving an anthranilic alcohol compound and an aldehyde reactant A in an organic solvent at the temperature of 0-120 ℃ to obtain a Schiff base solution containing at least one phenolic hydroxyl group and an alcoholic hydroxyl group;
step 2: adding a reducing agent into the Schiff base solution obtained in the step (1) at the temperature of 0-120 ℃ to obtain a Mannich base solution containing at least one phenolic hydroxyl group and at least one alcoholic hydroxyl group;
and step 3: and (3) adding an aldehyde reactant B into the Mannich base solution obtained in the step (2), performing cyclization reaction at room temperature-120 ℃, and performing reduced pressure distillation and drying to obtain the Mannich base.
3. The method for preparing a polymerizable 3, 1-benzoxazine substituted phenol monomer according to claim 2, wherein the anthranilic alcohol compound in step 1 has a chemical formula shown in formula (II):
wherein j is R 11 J is an integer of 0 to 3;
R 11 selected from the group consisting of hydrogen, alkyl, alkoxy, aryl, allyl, ethynyl, halogen, nitro, sulfonyl, hydroxyl, hydroxyalkyl, amino, aminoalkyl, aldehyde, carboxyl, amide;
when j is greater than or equal to 2, each R 11 The same or different;
when n1=1, Z 1 ＝R 11 ；
When n1=2, Z 1 = single bond (-), -O-, -S-),
When n1=3, the number of the active layers is increased,
when n1=4, the number of the bits is increased,
4. a method for preparing a polymerizable 3, 1-benzoxazine substituted phenol monomer according to claim 2, wherein the aldehyde reactant a of step 1 has a chemical formula shown in formula (III):
r12 is selected from hydrogen, alkyl, alkoxy, aryl, allyl, ethynyl, halogen, nitro, sulfonyl, hydroxy, hydroxyalkyl, amino, aminoalkyl, aldehyde, carboxyl, amide;
wherein k is R 12 K is an integer of 0 to 4;
when k is 2 or more, each R 12 The same or different;
when n2=1, Z 2 ＝R 12 ；
When n2=2, Z 2 = single bond (-), -O-, -S-),
When n2=3, the number of the active layers is increased,
when n2=4, the number of the active layers is increased,
5. a method of preparing a polymerizable 3, 1-benzoxazine substituted phenol monomer according to claim 2 wherein the reducing agent in step 2 comprises sodium borohydride or potassium borohydride.
6. A method for preparing a polymerizable 3, 1-benzoxazine substituted phenol monomer according to claim 2, wherein the aldehyde reactant B of step 3 has a chemical formula shown in formula (IV):
when n3=1, X 3 Hydrogen, C1-C18 alkyl, vinyl, ethynyl, cyclohexyl, phenyl, anthracenyl, benzyl, furyl;
when n3=2, X 3 (= single bond) —),
When n3=3, the number of the bits is increased,
/>
when n3=4
7. A method of preparing a polymerizable 3, 1-benzoxazine substituted phenol monomer according to claim 2 wherein the aldehyde reactant B of step 3 further comprises a trioxymethylene and a polyaldehyde.
8. A method of preparing a polymerizable 3, 1-benzoxazine substituted phenol monomer according to claim 2 wherein the organic solvent of step 1 comprises methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, t-butanol, toluene, xylene, chlorinated hydrocarbons, ethyl acetate, butyl acetate, acetone, butanone, tetrahydrofuran, methyl t-butyl ether, dioxane, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide.
9. A cured product obtained by heating and polymerizing a polymerizable 3, 1-benzoxazine-substituted phenol monomer obtained by the method for preparing a polymerizable 3, 1-benzoxazine-substituted phenol monomer according to any one of claims 2 to 8 at a heating temperature of 120 ℃ to 250 ℃ for 1 to 24 hours.
10. The cured product of claim 9, which is used as a high temperature resistant adhesive, a component electronic packaging material, an ablation resistant flame retardant material, and a fiber reinforced electrical insulation material matrix resin.
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Citations (2)
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| CN105061417A (en) * | 2015-07-30 | 2015-11-18 | 哈尔滨工程大学 | Monoamine-bisphenol type asymmetric tri-functionality quinoxalinyl benzoxazine and preparation method thereof |
| KR20180003007A (en) * | 2016-06-30 | 2018-01-09 | 코오롱인더스트리 주식회사 | Benzoxazine compound and the usage thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105061417A (en) * | 2015-07-30 | 2015-11-18 | 哈尔滨工程大学 | Monoamine-bisphenol type asymmetric tri-functionality quinoxalinyl benzoxazine and preparation method thereof |
| KR20180003007A (en) * | 2016-06-30 | 2018-01-09 | 코오롱인더스트리 주식회사 | Benzoxazine compound and the usage thereof |
Non-Patent Citations (1)
| Title |
|---|
| LEI ZHANG ET AL.: "The first observation of 3, 1-benzoxazine polymerization for developing high performance thermosets", POLYMER CHEMISTRY, vol. 14, pages 754 - 762 * |
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