CN106967001B - A kind of ternary benzoxazine-phthalonitrile intermediate, preparation method and its polymer - Google Patents
A kind of ternary benzoxazine-phthalonitrile intermediate, preparation method and its polymer Download PDFInfo
- Publication number
- CN106967001B CN106967001B CN201710224434.3A CN201710224434A CN106967001B CN 106967001 B CN106967001 B CN 106967001B CN 201710224434 A CN201710224434 A CN 201710224434A CN 106967001 B CN106967001 B CN 106967001B
- Authority
- CN
- China
- Prior art keywords
- benzoxazine
- phthalonitrile
- ternary
- phthalonitrile intermediate
- mixed solvent
- 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.)
- Active
Links
- MUAYXCWLPNRODA-UHFFFAOYSA-N 3-(2H-1,2-benzoxazin-3-yl)benzene-1,2-dicarbonitrile Chemical compound O1NC(=CC2=C1C=CC=C2)C=1C=CC=C(C=1C#N)C#N MUAYXCWLPNRODA-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920000642 polymer Polymers 0.000 title abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 15
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- WTSJLYWSCIPJNI-UHFFFAOYSA-N 3-(4-aminophenoxy)benzene-1,2-dicarbonitrile Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(C#N)=C1C#N WTSJLYWSCIPJNI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 125000000532 dioxanyl group Chemical group 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 229920006391 phthalonitrile polymer Polymers 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000010792 warming Methods 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 25
- 239000011347 resin Substances 0.000 description 25
- 238000001723 curing Methods 0.000 description 16
- 238000002390 rotary evaporation Methods 0.000 description 14
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 10
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000011417 postcuring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- RTYLDDVWAVEYEB-UHFFFAOYSA-N benzene-1,2-dicarbonitrile 2H-1,2-benzoxazine Chemical compound N#CC1=CC=CC=C1C#N.C1=CC=C2C=CNOC2=C1 RTYLDDVWAVEYEB-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- -1 amine compound Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 1
- DQNFPCOVVBRXOY-UHFFFAOYSA-N 4-amino-2-benzofuran-1,3-dione Chemical compound NC1=CC=CC2=C1C(=O)OC2=O DQNFPCOVVBRXOY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/16—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with only hydrogen or carbon atoms directly attached in positions 2 and 4
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
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)
Abstract
The present invention relates to a kind of ternary benzoxazine-phthalonitrile intermediate, preparation method and its polymer, preparation method includes the following steps: 1) addition II compound of formula, 4- amino phenoxy phthalonitrile, paraformaldehyde and mixed solvent into reactor, is warming up to 80~130 DEG C of reactions；The mixed solvent is dioxane and toluene；2) mixed solvent is removed, in a solvent by residue dissolution, and is poured onto lye, solid is precipitated, filter, washing obtains ternary benzoxazine-phthalonitrile intermediate after dry.Ternary benzoxazine-phthalonitrile intermediate the processability is good, the polymer excellent combination property solidified.
Description
Technical Field
The invention relates to the technical field of preparation of high-performance thermosetting resin, and particularly relates to a ternary benzoxazine-phthalonitrile intermediate, a preparation method and a polymer thereof.
Background
The bisphthalonitrile resin is a high-performance thermosetting resin, and is formed by curing bisphthalonitrile monomers through the addition polymerization reaction of cyano groups under a high-temperature condition, and a cured product is mainly of a triazine ring structure. The resin and the composite material thereof have the characteristics of high strength, high modulus, high temperature resistance, corrosion resistance, self-flame retardance, no release of small molecules in the curing process, low porosity of products, nearly zero shrinkage, low thermal expansion coefficient, stable size, low water absorption and the like. The Tg can reach more than 450 ℃ after complete curing. Although the bisphthalonitrile resin has a plurality of excellent application properties, the bisphthalonitrile resin has the defects of high curing temperature (the initial curing temperature is about 240 ℃) and narrow processing window.
Benzoxazine is a six-membered heterocyclic compound synthesized by condensation reaction of a phenolic compound, an amine compound and an aldehyde compound, and is subjected to ring opening polymerization under the action of heating or a catalyst to generate a nitrogen-containing network structure similar to phenolic resin. The benzoxazine resin is used as a novel phenolic resin, has the thermal property, the mechanical property, the electrical property, the flame retardance and the corrosion resistance of the traditional phenolic resin, and has the advantages of small shrinkage rate, no release of small molecules and low water absorption rate during curing and molding. Compared with the bisphthalonitrile resin, the benzoxazine resin has low curing temperature, the initial curing temperature is about 150 ℃, but the initial decomposition temperature is mostly lower than 350 ℃.
The Chinese invention patent (CN 102816127A) discloses a double-end-group phthalonitrile-benzoxazine resin intermediate and a synthesis method thereof, the double-end-group phthalonitrile-benzoxazine resin intermediate is prepared by adopting aromatic dihydric phenol, 4-aminophthalidone and paraformaldehyde as raw materials, the double-end-group phthalonitrile-benzoxazine resin intermediate is pre-cured at the temperature of 150-200 ℃, and is post-treated for 4-8 hours at the temperature of 200-250 ℃ to obtain a resin polymer, the glass transition temperature is 378 ℃, and the decomposition temperature (5%) is 488 ℃. How to improve the glass transition temperature (Tg), the thermal property, the mechanical property and the flame retardant property of resin of benzoxazine resin becomes a technical problem to be solved urgently in the field.
Disclosure of Invention
The invention aims to provide a ternary benzoxazine-phthalonitrile intermediate, a preparation method and a polymer thereof aiming at the defects of the prior art, wherein the ternary benzoxazine-phthalonitrile intermediate has good processability, and the polymer obtained by curing has excellent comprehensive performance.
The technical scheme provided by the invention for solving the technical problems is as follows: a ternary benzoxazine-phthalonitrile intermediate has the following structural formula:
wherein,R1～R6each independently selected from hydrogen or C1～C4An alkyl group.
The invention also provides a preparation method of the ternary benzoxazine-phthalonitrile intermediate, which comprises the following steps:
1) adding a compound of formula II, 4-aminophenoxy phthalonitrile, paraformaldehyde and a mixed solvent into a reactor, and heating to 80-130 ℃ for reaction; the mixed solvent is dioxane and toluene;
wherein R is1～R6Each independently selected from hydrogen or C1～C4Alkyl, and the ortho-position of the phenolic hydroxyl group cannot be simultaneously alkyl;
2) and removing the mixed solvent, dissolving the residue in the solvent, pouring into alkali liquor, separating out solid, filtering, washing and drying to obtain the ternary benzoxazine-phthalonitrile intermediate.
The reaction equation involved is as follows:
wherein R is1～R6As described above; (CH)2O)nIs paraformaldehyde.
According to the technical scheme, a bisphthalonitrile structure is introduced into a ternary benzoxazine molecule, and complementation is formed in the aspects of curing temperature and high-temperature resistance of resin, so that the benzoxazine intermediate has the characteristic of low-temperature curing of a benzoxazine intermediate, and has high-temperature resistance compared with that of the bisphthalonitrile resin.
Moreover, the intermediate prepared by the invention contains three benzoxazine-phthalonitrile structures in a single molecule, compared with the existing unitary or binary benzoxazine-phthalonitrile intermediate, the crosslinking density of the resin can be improved, and the cured resin has higher Tg, better heat resistance, mechanical property, flame retardant property, corrosion resistance and cohesiveness.
The reaction in the step 1) is a light-shielding reaction. Because the 4-aminophenoxy phthalonitrile is easy to deteriorate under the action of light, a light-shielding reaction is adopted, the generation of byproducts is reduced, and the yield is improved.
Preferably, the reaction time in the step 1) is 3-8 h away from light.
Preferably, the mixed solvent is removed in the step 2) by rotary evaporation.
In the step 1), feeding 4-aminophenoxy phthalonitrile and paraformaldehyde according to the molar ratio of amino to aldehyde groups of 1: 1.7-2.5.
The molar ratio of the compound of the formula II in the step 1) to 4-aminophenoxy phthalonitrile is 1: 2.5-3.3.
R in the step 1)1～R6Are all hydrogen. The compound of formula II is preferably 1,1, 1-tris (4-hydroxyphenyl) ethane (THPE).
The volume ratio of dioxane to toluene in the mixed solvent is 2-5: 1.
The solvent in the step 2) is at least one selected from N, N-dimethylacetamide, N-dimethylformamide and N-methylpyrrolidone.
The alkaline solution in the step 2) is selected from one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
The invention also provides a ternary benzoxazine-phthalonitrile polymer, which is prepared by heating and curing the ternary benzoxazine-phthalonitrile intermediate.
The curing step is preferably: precuring at 160-200 ℃, and post-curing for 4-8h at 200-250 ℃ to obtain the ternary benzoxazine-phthalonitrile polymer.
Compared with the prior art, the invention has the beneficial effects that:
(1) the intermediate prepared by the invention increases the number of benzoxazine-phthalonitrile structures in a single molecule, thereby increasing reaction points and improving the resin crosslinking density, and the resin cured by the intermediate has higher Tg, and better heat resistance, mechanical property, flame retardant property, corrosion resistance and cohesiveness.
(2) The method has the advantages of mild reaction conditions, simplicity, practicability, recyclable solvent, high purity of the prepared ternary benzoxazine-phthalonitrile intermediate and guarantee of excellent performance of the resin in terms of raw material quality.
(3) The curing temperature of the prepared ternary benzoxazine-phthalonitrile intermediate is obviously lower than that of bisphthalonitrile resin, and the service temperature and the heat resistance of the polymer are obviously higher than those of benzoxazine resin.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
Molar ratio of massage type II1The compound APN, paraformaldehyde and toluene are sequentially fed into a reactor in a volume ratio of 1:3:6 to be measured, heated to 110 ℃, stirred in the dark for 6 hours, the solvent is removed by rotary evaporation, and the rotary evaporation product is dissolved in DMF and poured to 0And (3) precipitating a solid from a 1mol/L sodium hydroxide solution, filtering, washing with water, and drying in vacuum at 70 ℃ for 5 hours to obtain a ternary benzoxazine-phthalonitrile intermediate.
Formula II1The structural formula of the compound is as follows:
and (3) pre-curing the ternary benzoxazine-phthalonitrile intermediate at 160-200 ℃, and post-curing for 4-8 hours at 200-250 ℃ to obtain the ternary benzoxazine-phthalonitrile polymer.
Fourier infrared spectrum test is carried out on the ternary benzoxazine-phthalonitrile intermediate prepared in example 1, and the infrared spectrum of the ternary benzoxazine-phthalonitrile intermediate is 944cm-1And 1225cm-1A characteristic peak of benzoxazine, 2225cm, appears nearby-1The characteristic peak of phthalonitrile appears nearby, and the polymer is 944cm-1And 1225cm-1The signal in the vicinity disappears, indicating that the oxazine ring is completely ring-opening polymerized.
The nuclear magnetic hydrogen spectrum of the ternary benzoxazine-phthalonitrile intermediate shows signals of oxazine methylene hydrogen at 4.59 and 5.43 ppm.
Example 2
Molar ratio of massage type II1The compound APN is 1:3, the APN is paraformaldehyde is 1:2.1, the dioxane and the toluene with volume ratio of 5:1 are sequentially added into a reactor, the temperature is raised to 120 ℃, the mixture is stirred away from light and reacted for 5 hours, the solvent is removed by rotary evaporation, DMF dissolves rotary evaporation products, the rotary evaporation products are poured into 0.2mol/L sodium hydroxide solution, solid is separated out, the solid is filtered and washed, and the ternary benzoxazine-phthalonitrile intermediate is obtained after vacuum drying for 5 hours at 70 ℃.
Example 3
Molar ratio of massage type II1The compound APN is 1:2.9, APN is paraformaldehyde is 1:2.1, the materials are sequentially added into a reactor according to the volume ratio of dioxane to toluene being 3:1, the temperature is raised to 100 ℃, the mixture is stirred away from light and reacted for 7 hours, the solvent is removed by rotary evaporation, DMF dissolves the rotary evaporation and is poured into 0.3mol/L sodium hydroxide solution, the solid is separated out, the solid is filtered and washed, and the ternary benzoxazine-phthalonitrile intermediate is obtained after vacuum drying for 5 hours at 70 ℃.
Example 4
Molar ratio of massage type II1And (3) sequentially feeding APN (N-methyl-N-propylidene) and paraformaldehyde into a reactor, heating to 120 ℃, keeping out of the sun, stirring for 5 hours, removing the solvent by rotary evaporation, dissolving the rotary evaporation product in DMF, pouring the solution into 0.1mol/L sodium hydroxide solution, separating out a solid, filtering, washing with water, and vacuum-drying at 70 ℃ for 5 hours to obtain the ternary benzoxazine-phthalonitrile intermediate, wherein the volume ratio of the paraformaldehyde to the toluene is 5: 1.
Example 5
Molar ratio of massage type II2And (2) sequentially feeding APN (N-methyl-N-propylidene) and paraformaldehyde into a reactor, heating to 110 ℃, stirring in the dark for 6 hours, removing the solvent by rotary evaporation, dissolving the rotary evaporation product in DMF (dimethyl formamide), pouring the solution into 0.1mol/L sodium hydroxide solution, separating out a solid, filtering, washing with water, and drying in vacuum at 70 ℃ for 5 hours to obtain the ternary benzoxazine-phthalonitrile intermediate, wherein the volume ratio of the paraformaldehyde to the toluene is 5: 1.
Formula II2The structural formula of the compound is as follows:
and (3) pre-curing the ternary benzoxazine-phthalonitrile intermediate at 160-200 ℃, and post-curing for 4-8 hours at 200-250 ℃ to obtain the ternary benzoxazine-phthalonitrile polymer.
Comparative example 1
Sequentially feeding bisphenol A, APN, paraformaldehyde and toluene according to a molar ratio of 1:2:4, heating to 110 ℃, stirring in the dark for 6 hours, removing the solvent by rotary evaporation, dissolving the rotary evaporation product in DMF, pouring into 0.1mol/L sodium hydroxide solution, separating out a solid, filtering, washing with water, and vacuum drying at 70 ℃ for 5 hours to obtain the bisphenol A binary benzoxazine-phthalonitrile intermediate.
And (3) pre-curing the bisphenol A type binary benzoxazine-phthalonitrile intermediate at 160-200 ℃, and post-curing for 4-8 hours at 200-250 ℃ to obtain the bisphenol A type binary benzoxazine-phthalonitrile polymer.
Performance testing
The polymers in examples 1, 5 and comparative example 1 were tested and the relevant data are shown in table 1.
Table 1 comparison of Tg, thermal Properties and limiting oxygen index of the polymers in examples and comparative examples
As can be seen from Table 1, the Tg, thermal (oxygen) stability, char yield and flame retardant properties of the polymers of examples 1 and 5 are superior to those of comparative example 1. Compared with the bisphenol A type binary benzoxazine-phthalonitrile intermediate and the polymer thereof in the comparative example 1, the intermediate prepared in the embodiment increases the number of benzoxazine-phthalonitrile structures in a single molecule, so that reaction points are increased, the resin crosslinking density is improved, and the Tg, the thermal (oxygen) stability, the carbon residue rate and the flame retardant property of the polymer can be obviously improved.
Claims (9)
1. The ternary benzoxazine-phthalonitrile intermediate is characterized in that the structural formula is as follows:
wherein,
2. a preparation method of a ternary benzoxazine-phthalonitrile intermediate is characterized by comprising the following steps:
1) adding a compound of formula II, 4-aminophenoxy phthalonitrile, paraformaldehyde and a mixed solvent into a reactor, and heating to 80-130 ℃ for reaction; the mixed solvent is dioxane and toluene;
2) and removing the mixed solvent, dissolving the residue in the solvent, pouring into alkali liquor, separating out solid, filtering, washing and drying to obtain the ternary benzoxazine-phthalonitrile intermediate.
3. The method for preparing the ternary benzoxazine-phthalonitrile intermediate according to claim 2, wherein the reaction in the step 1) is a reaction protected from light.
4. The method for preparing the ternary benzoxazine-phthalonitrile intermediate according to claim 2, wherein in the step 1), the 4-aminophenoxy phthalonitrile and paraformaldehyde are fed in a molar ratio of amino to aldehyde groups of 1: 1.7-2.5.
5. The method for preparing the ternary benzoxazine-phthalonitrile intermediate according to claim 2, wherein the molar ratio of the compound of formula II in the step 1) to 4-aminophenoxy phthalonitrile is 1: 2.5-3.3.
6. The preparation method of the ternary benzoxazine-phthalonitrile intermediate according to claim 2, wherein the volume ratio of dioxane to toluene in the mixed solvent is 2-5: 1.
7. The method for preparing a ternary benzoxazine-phthalonitrile intermediate according to claim 2, wherein the solvent in step 2) is at least one selected from the group consisting of N, N-dimethylacetamide, N-dimethylformamide, and N-methylpyrrolidone.
8. The method for preparing a ternary benzoxazine-phthalonitrile intermediate according to claim 2, wherein the alkali solution in the step 2) is one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
9. A ternary benzoxazine-phthalonitrile polymer produced by curing the ternary benzoxazine-phthalonitrile intermediate according to claim 1 by heating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710224434.3A CN106967001B (en) | 2017-04-07 | 2017-04-07 | A kind of ternary benzoxazine-phthalonitrile intermediate, preparation method and its polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710224434.3A CN106967001B (en) | 2017-04-07 | 2017-04-07 | A kind of ternary benzoxazine-phthalonitrile intermediate, preparation method and its polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106967001A CN106967001A (en) | 2017-07-21 |
| CN106967001B true CN106967001B (en) | 2019-06-18 |
Family
ID=59336445
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710224434.3A Active CN106967001B (en) | 2017-04-07 | 2017-04-07 | A kind of ternary benzoxazine-phthalonitrile intermediate, preparation method and its polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106967001B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107400359B (en) * | 2017-08-22 | 2020-06-16 | 哈尔滨工程大学 | Phthalonitrile, benzoxazine and tetra-amino phthalocyanine lead-based anti-radiation composite material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816127A (en) * | 2012-08-20 | 2012-12-12 | 成都德美精英化工有限公司 | Double-terminal group phthalonitrile-benzoxazine resin intermediate and its synthesis method |
| CN102976972A (en) * | 2012-12-03 | 2013-03-20 | 电子科技大学 | Nitrile resin monomer, nitrile resin polymer and preparation method of nitrile resin monomer and nitrile resin polymer |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB201322758D0 (en) * | 2013-12-20 | 2014-02-05 | Cytec Ind Inc | Multifunctional benzoxazines and composite materials incorporating then same |
| TWI685534B (en) * | 2014-12-29 | 2020-02-21 | 美商塞特工業公司 | Benzoxazines and compositions containing the same |
| CN105254879B (en) * | 2015-10-20 | 2018-11-09 | 中科院广州化学有限公司南雄材料生产基地 | A kind of side chain phthalonitrile modifying benzoxazine resin and preparation method and application |
-
2017
- 2017-04-07 CN CN201710224434.3A patent/CN106967001B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816127A (en) * | 2012-08-20 | 2012-12-12 | 成都德美精英化工有限公司 | Double-terminal group phthalonitrile-benzoxazine resin intermediate and its synthesis method |
| CN102976972A (en) * | 2012-12-03 | 2013-03-20 | 电子科技大学 | Nitrile resin monomer, nitrile resin polymer and preparation method of nitrile resin monomer and nitrile resin polymer |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis and characterization of a novel bisphthalonitrile containing benzoxazine;G.P.Cao，等;《eXPRESS Polymer Letters》;20071231;第1卷(第8期);第513页右栏第一段及图1 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106967001A (en) | 2017-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101619131B (en) | O-phthalodinitrile end-blocked soluble polyarylether resin with phthalazinone structure and condensate and preparation method thereof | |
| CN106750289A (en) | A kind of benzoxazine oligomer of maleimide base group end-sealed type and preparation method thereof | |
| CN102634019B (en) | Hybrid bisphenol copolymer fluorenyl benzoxazine prepolymer and preparation method thereof | |
| CN112442158A (en) | Bio-based degradable benzoxazine resin, preparation method thereof, cured resin thereof, compound thereof and degradation method | |
| CN103936686B (en) | N-semiaromatic alkyl diamine-bisphenol type four degree of functionality fluorenyl benzoxazine and preparation methods | |
| CN103936764B (en) | N-semiaromatic alkyl bis-phenol-diamine type four degree of functionality fluorenyl benzoxazines and preparation method thereof | |
| CN111269395A (en) | Benzoxazine epoxy resin copolymer containing phenolic hydroxyl and preparation method thereof | |
| CN107793566B (en) | Thermoplastic polybenzimidazole imide and preparation method thereof | |
| CN105254878A (en) | Polybenzoxazine connected bisphthalonitrile monomer as well as preparation method and application thereof | |
| CN106967001B (en) | A kind of ternary benzoxazine-phthalonitrile intermediate, preparation method and its polymer | |
| Yu et al. | Soluble and curable poly (phthalazinone ether amide) s with terminal cyano groups and their crosslinking to heat resistant resin | |
| CN102659526A (en) | Tetraphenolic hydroxyfluorene compound and preparation method thereof | |
| CN102702128B (en) | Ether bond-containing diamine flourenyl benzoxazine | |
| CN117164532B (en) | A biomass recyclable shape memory epoxy resin and its monomer and preparation method | |
| CN107573334B (en) | Monofunctional benzoxazine containing alicyclic hydrocarbon imide group and preparation method thereof | |
| CN114349954B (en) | Phthalonitrile-terminated polyaryl ether nitrile containing methylene/methylene, crosslinked cured modified polyaryl ether nitrile and preparation method thereof | |
| CN118852557B (en) | Allylated maleimido phenolic resin and preparation method thereof | |
| CN103492449A (en) | Epoxy resin and method for manufacturing same, and epoxy resin composition | |
| CN103896867B (en) | N-full aryl radical diamine-bisphenol type four functionality fluorenyl benzoxazine and preparation method thereof | |
| CN105061417B (en) | Monoamine bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine and preparation method thereof | |
| CN119060332A (en) | A halogen-free and phosphorus-free flame-retardant modified benzoxazine resin and its preparation method and application | |
| EP1670864A2 (en) | Thermally stable anthrapyridone compositions | |
| CN106967002A (en) | A kind of ternary benzoxazine intermediate, preparation method and its polymer | |
| CN109810235B (en) | Ethylene glycol modified melamine formaldehyde resin and preparation method thereof | |
| CN101857592A (en) | Dibenzoxazine containing imide structure and its preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180809 Address after: 310012 1802, room 1, Changdi Torch Hotel, 259 Xihu District Wensanlu Road, Hangzhou, Zhejiang Applicant after: HANGZHOU ZHONGYI TECHNOLOGY CO., LTD. Address before: 213022 Hengshan Road, Xinbei District, Changzhou, Jiangsu Province, No. 35 Applicant before: CHANGZHOU YANJING TECHNOLOGY CO., LTD. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |