CN104693134B - 一种均三嗪衍生物单体及聚芳醚荧光材料的制备方法 - Google Patents
一种均三嗪衍生物单体及聚芳醚荧光材料的制备方法 Download PDFInfo
- Publication number
- CN104693134B CN104693134B CN201510133998.7A CN201510133998A CN104693134B CN 104693134 B CN104693134 B CN 104693134B CN 201510133998 A CN201510133998 A CN 201510133998A CN 104693134 B CN104693134 B CN 104693134B
- Authority
- CN
- China
- Prior art keywords
- fluorescent material
- polyarylether
- monomer
- fluorophenyls
- 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.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims abstract description 46
- 229920000090 poly(aryl ether) Polymers 0.000 title claims abstract description 31
- 239000000178 monomer Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000010276 construction Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 125000001207 fluorophenyl group Chemical group 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
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 238000000944 Soxhlet extraction Methods 0.000 claims description 2
- MVPPADPHJFYWMZ-IDEBNGHGSA-N chlorobenzene Chemical group Cl[13C]1=[13CH][13CH]=[13CH][13CH]=[13CH]1 MVPPADPHJFYWMZ-IDEBNGHGSA-N 0.000 claims description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 14
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 abstract description 12
- -1 fluorobenzene formamidine compound Chemical class 0.000 abstract description 12
- AEKVBBNGWBBYLL-UHFFFAOYSA-N 4-fluorobenzonitrile Chemical compound FC1=CC=C(C#N)C=C1 AEKVBBNGWBBYLL-UHFFFAOYSA-N 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 229920000642 polymer Polymers 0.000 abstract description 5
- 238000003486 chemical etching Methods 0.000 abstract description 4
- 230000000977 initiatory effect Effects 0.000 abstract description 4
- 230000035484 reaction time Effects 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000010792 warming Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 150000000182 1,3,5-triazines Chemical class 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- AAILEWXSEQLMNI-UHFFFAOYSA-N 1h-pyridazin-6-one Chemical compound OC1=CC=CN=N1 AAILEWXSEQLMNI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical group [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- QXAITBQSYVNQDR-ZIOPAAQOSA-N amitraz Chemical compound C=1C=C(C)C=C(C)C=1/N=C/N(C)\C=N\C1=CC=C(C)C=C1C QXAITBQSYVNQDR-ZIOPAAQOSA-N 0.000 description 2
- 229960002587 amitraz Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical class CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- YKYMGFHOJJOSEB-UHFFFAOYSA-N butan-1-ol;potassium Chemical compound [K].CCCCO YKYMGFHOJJOSEB-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- AFDQGRURHDVABZ-UHFFFAOYSA-N n,n-dimethylformamide;sulfur trioxide Chemical compound O=S(=O)=O.CN(C)C=O AFDQGRURHDVABZ-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000004893 oxazines Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011175 product filtration Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- PRLPAGCIZDCPKE-UHFFFAOYSA-N pyridine;sulfur monoxide Chemical compound S=O.C1=CC=NC=C1 PRLPAGCIZDCPKE-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/14—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom
- C07D251/24—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hydrogen or carbon atoms directly attached to at least one ring carbon atom to three ring carbon atoms
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
本发明涉及一种均三嗪衍生物单体及聚芳醚荧光材料的制备方法,属于有机合成、高分子合成、荧光材料、转光技术领域,本发明的技术方案为:以对氟苯甲腈为起始原料,与对氟苯甲脒类化合物经两步法合成2,4,6‑三(4‑氟苯基)‑1,3,5‑三嗪单体,均三嗪单体经一步法与一种或几种类双酚单体制备出聚芳醚类荧光材料。本发明的特点是单体合成收率高,纯度高,反应时间短,能耗低,节约成本。聚芳醚类荧光材料的制备特点是收率高,荧光强度高,热稳定性好,耐化学腐蚀等。
Description
技术领域
本发明属于有机合成、高分子合成、荧光材料、转光技术领域,尤其涉及一种均三嗪衍生物单体及聚芳醚荧光材料的制备方法。
背景技术
聚(三芳基-1,3,5-均三嗪)具有独特的均三嗪环及芳环平面共轭结构,使之展现出优异的综合性能,如热稳定性、光电性质、耐化学腐蚀、高强度,高模量等,因而在阻燃、光电、吸附材料等领域有广阔的应用前景。其中,体型聚(三芳基-1,3,5-均三嗪)因其独特的空间立体结构和共轭结构,可应用于吸附材料和光电材料等领域。体型聚(三芳基-1,3,5-均三嗪)的合成一般是通过含三芳基均三嗪结构的活性单体与其他活性单体通过加成、取代等反应实现。2,4,6-三(4-卤代苯基)-1,3,5-三嗪与多酚类或卤代单体反应是重要的聚合途径。
2,4,6-三(4-氟苯基)-1,3,5-三嗪作为重要的聚合单体,其合成方法在国内外文献中少有报道,以对氟苯甲腈为起始原料合成2,4,6-三(4-氟苯基)-1,3,5-三嗪的报道,目前只有一步法。该法是以氯化锌作催化剂,由对氟苯甲腈在270℃反应64h制得,产率为40%(Ricarda Berger,Jürg Hauser,et al.New symmetrically substituted 1,3,5-triazines as host compounds for channel-type inclusionformation.CrystEngComm,2014,14:768-770.)。该法虽然合成步骤简单,但反应温度高,反应时间长,能耗高,而且产率偏低,成本较高。
含三芳基-1,3,5-均三嗪结构的聚芳醚类化合物有很好的热稳定性,光电性质,耐化学腐蚀等优点,但对这方面的研究报道却极少,其应用主要受制于2,4,6-三(4-氟苯基)-1,3,5-三嗪单体的复杂制备过程及较低的产率。
发明内容
本发明的目的在于,克服现有技术的不足,提供了一种高收率、高纯度、低能耗、低成本合成2,4,6-三(4-氟苯基)-1,3,5-三嗪单体的方法,并提供了一种制备高收率、强荧光性、优异热稳定性聚芳醚类荧光材料的方法。
本发明的特点是单体合成收率高,纯度高,反应时间短,能耗低,节约成本。聚芳醚类荧光材料的制备特点是收率高,荧光强度高,热稳定性好,耐化学腐蚀等。
为解决上述技术问题,本发明的技术方案为:以对氟苯甲腈为起始原料,与对氟苯甲脒类化合物经两步法合成2,4,6-三(4-氟苯基)-1,3,5-三嗪单体,均三嗪单体经一步法与一种或几种类双酚单体制备出聚芳醚类荧光材料。本发明涉及的2,4,6-三(4-氟苯基)-1,3,5-三嗪的分子结构式以及聚芳醚类荧光材料的通式分别为:
其中,A表示结构单元: 中的一种或几种;
B表示结构单元:
一种均三嗪衍生物的制备方法,具体包括两个步骤:
(1)将对氟苯甲腈溶于硝基甲烷,加入三氧化硫复合物,制得环状中间体4,6-二(4-氟苯基)-2-氧代1,2,3,5-氧杂硫代二嗪;反应式如下:
(2)中间体和对氟苯甲脒类化合物按摩尔比为1:(1-3)溶于非质子极性溶剂,在有机碱催化下,于0-50℃搅拌0-3h,在温度为50-150℃加热0-3h,冷却至室温,加入溶剂,沉淀出产物并抽滤,洗涤,干燥,制得2,4,6-三(4-氟苯基)-1,3,5-三嗪,反应式如下:
本发明步骤(1)中,首先将对氟苯甲腈溶于硝基甲烷溶液中,加入三氧化硫复合物,反应生成4,6-二(4-氟苯基)-2-氧代1,2,3,5-氧杂硫代二嗪中间体。这是一个放热反应,高温容易导致原料发生磺化反应。因此,应控制反应在0-50℃;反应时间0-3h。然后,抽滤,洗涤,干燥,得中间体。洗涤滤液中可回收原料对氟苯甲腈和***、醇类溶剂。
本发明步骤(2)中,将中间体与对氟苯甲脒类化合物溶于非质子极性溶剂,加入有机碱,使反应体系呈碱性环境,有利于中和反应中产生的酸性物质,利于反应正向进行。在0-50℃搅拌0-3h,然后在50-150℃回流0-3h,使反应更充分,提高产率。冷却到室温,抽滤,醇类洗涤即可,无需重结晶,液相检测纯度100%。
本发明所述步骤(1)中对氟苯甲腈的质量用量为硝基甲烷的0.2-3倍;步骤(1)中对氟苯甲脒类化合物为对氟苯甲脒或对氟苯甲脒盐酸盐。步骤(1)中三氧化硫复合物为三氧化硫-吡啶复合物、三氧化硫-三甲胺复合物、三氧化硫-N,N-二甲基甲酰胺络合物或三氧化硫,其摩尔用量为对氟苯甲腈的1-3倍。
本发明所述步骤(2)中非质子极性溶剂为丙酮、N,N-二甲基甲酰胺或四氢呋喃,其质量用量为溶质的1-5倍;步骤(2)中的溶剂为水、甲醇或乙腈,其质量用量为硝基甲烷的1-5倍。步骤(2)中有机碱为甲醇钠,乙醇钾或叔丁醇钾,其摩尔用量为反应物的1-5倍。
一种由均三嗪衍生物制备的聚芳醚类荧光材料,结构通式如下:
其中
A表示结构单元: 中的一种或几种;
B表示结构单元:
所述聚芳醚类荧光材料的制备方法,具体步骤为:将2,4,6-三(4-氟苯基)-1,3,5-三嗪和类双酚单体按摩尔比2:(1-5)溶于溶剂及带水剂中,加催化剂,在温度为100-160℃除水1-5h,在150-220℃下反应1-12h,倒入含有盐酸和醇的水中,抽滤,磨碎,用索氏提取法除杂质,真空干燥,制得聚芳醚类荧光材料。反应式如下:
上述聚芳醚类荧光材料的制备方法中所述溶剂为N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜或环丁砜中的一种或任意几种,其质量用量为反应物的5-20倍。2,4,6-三(4-氟苯基)-1,3,5-三嗪单体和类双酚单体溶于溶剂及带水剂中,所用溶剂对反应物有良好的溶解性,对反应体系有良好的相配性,有利于提高聚合物的分子量。
所述带水剂为氯苯、甲苯或二甲苯,其体积用量为溶剂的1-10倍。加入带水剂,有利于促进反应正向进行。
所述催化剂为碳酸钠、碳酸钾或碳酸氢钠,其摩尔用量为反应物的1-3倍。
本体系为碱性亲核取代反应,碱在反应中作为催化剂,夺取类双酚单体与三卤代单体反应所生成的H+和F-,有利于加快反应速率和提高反应程度。
本发明的有益效果是:本发明描述的2,4,6-三(4-氟苯基)-1,3,5-三嗪合成的两步法,是以对氟苯甲腈为起始原料,经三氧化硫复合物催化合成4,6-二(4-氟苯基)-2-氧代1,2,3,5-氧杂硫代二嗪,然后与对氟苯甲脒类化合物反应制得的,反应特点是收率高,纯度高,反应时间短,能耗低,节约成本。发明中描述的聚芳醚荧光材料制备的一步法,是以2,4,6-三(4-氟苯基)-1,3,5-三嗪与类双酚单体进行亲核取代反应制得,该类材料的特点是收率高,荧光性强,热稳定性好,耐化学腐蚀。本发明人尚未发现现有的技术中公开有本发明的两步法制备2,4,6-三(4-氟苯基)-1,3,5-三嗪和一步法制备聚芳醚荧光材料的方法。
下面结合具体实施例子对本发明做进一步说明。
附图说明
图1为2,4,6-三(4-氟苯基)-1,3,5-三嗪单体的1H NMR谱图。该谱图显示只有两组峰,而且与该均三嗪单体中的质子氢种类以及核磁氢谱理论出峰位置一致,说明了所合成均三嗪单体的高纯度和化学结构的正确性。
图2为含6-(4-羟基苯基)哒嗪-3(2H)-酮结构的聚芳醚荧光材料的固体13C NMR谱图。通过该谱图能够分辨出不同位置的质子碳产生的峰,与该材料化学结构中的碳谱理论出峰位置相吻合,证明了材料结构的正确性。
图3为含6-(4-羟基苯基)哒嗪-3(2H)-酮结构的聚芳醚荧光材料的荧光光谱图。该荧光谱图展示了材料发射光谱的分布情况,可以确定该材料具有荧光性,且发射出的光为蓝光。
图4为含6-(4-羟基苯基)哒嗪-3(2H)-酮结构的聚芳醚荧光材料在氮气及空气氛围下的热失重图。图中显示材料在升温至400℃左右才开始出现明显失重现象,表明了该材料具有很好的热稳定性和热氧化稳定性。
具体实施方式
为更好理解本发明的技术方案,通过以下具体实施例作进一步详细描述。
原料说明
实施例中所用的6-(4-羟基苯基)哒嗪-3(2H)-酮,二氮杂萘酮参考文献J.Xu,Y.Z.Meng,S.J.Wang,A.S.Hay.Journal of Polymer Science Part A:PolymerChemistry.2006,44,10中所述方法合成。
实施例1
室温下将对氟苯甲腈(12.11g,0.1mol)溶于20mL硝基甲烷中,冰水浴冷却到10℃,加入三氧化硫-吡啶复合物(23.87g,0.15mol),在室温下搅拌1h,加入无水***,抽滤,***和乙醇洗涤数次,真空干燥,制得4,6-二(4-氟苯基)-2-氧代1,2,3,5-氧杂硫代二嗪,收率为75%。熔点:132.2-133.9℃。FTIR(KBr):1680cm-1(C=N伸缩振动峰),1586cm-1,1530cm-1,1477cm-1(苯环骨架产生的伸缩振动),1215cm-1(S=O伸缩振动),851cm-1(C-H弯曲振动峰)。
将4,6-二(4-氟苯基)-2-氧代1,2,3,5-氧杂硫代二嗪(3.22g,0.01mol)和对氟苯甲脒盐酸盐(1.75g,0.01mol)溶于50mL丙酮中,加入正丁醇钾(3.37,0.03mol),常温搅拌1h,加热到50℃并反应1h。冷却到室温,加入去离子水,抽滤,甲醇洗涤,干燥得3.09g 2,4,6-三(4-氟苯基)-1,3,5-三嗪,收率85%,纯度100%(高效液相测试)。熔点:261.6-262.5℃。FTIR(KBr):1602cm-1,1523cm-1,1507cm-1(苯环骨架产生的伸缩振动),859cm-1,861cm-1(C-H弯曲振动峰)。Anal.calcd for C21H12N3F3:C 69.42,H 3.33,N 11.57;found:C 68.90,H3.36,N 11.46.(单体的元素分析数据)1H NMR(400MHz,CDCl3):δ8.86–8.69(m,1H),7.40–7.17(m,1H),如图1所示。
实施例2
在配有分水器,回流冷凝管,机械搅拌及氮气导管的100mL圆底烧瓶中将2,4,6-三(4-氟苯基)-1,3,5-三嗪(1.82g,0.005mol)和6-(4-羟基苯基)哒嗪-3(2H)-酮(1.41g,0.0075mol)溶于20mL N,N-二甲基乙酰胺中,加入甲苯50mL,加入碳酸钾(1.38g,0.01mol),升温至150℃除水2h,移除甲苯和水,升温至170℃反应至不能搅拌,并保温1h。产物倒入含有盐酸和甲醇的水溶液中,抽滤,甲醇及水洗涤,干燥。球磨机磨碎,索氏提取除去溶剂和未反应原料,真空干燥,得3.04g聚芳醚均三嗪产物。产率为94%。FTIR:3446cm-1(O-H,N-H伸缩振动峰),1679cm-1(C=O,C=N伸缩振动峰),1596cm-1,1540cm-1,1499cm-1(苯环骨架产生的伸缩振动),1239cm-1(C-O-C伸缩振动峰),874cm-1,819cm-1(C-H弯曲振动峰),如图2所示。
将实施例所得聚芳醚荧光材料分散到去离子水中,以370nm激发波长激发,测量其发射波长400-600nm处的荧光强度,如图3所示。
将实施例所得聚芳醚荧光材料以20℃/min的升温速率,于50-800℃进行热重测试。氮气及空气氛围下热重谱图,如图4所示。
实施例3
在配有分水器,回流冷凝管,机械搅拌及氮气导管的100mL圆底烧瓶中将2,4,6-三(4-氟苯基)-1,3,5-三嗪(1.82g,0.005mol)和联苯二酚(1.49g,0.008mol)溶于25mL N,N-二甲基乙酰胺中,加入甲苯60mL,加入碳酸钾(1.38g,0.01mol),升温至150℃除水2h,移除甲苯和水,升温至170℃反应至不能搅拌,并保温1h。产物倒入含有盐酸和甲醇的水溶液中,抽滤,甲醇及水洗涤,干燥。球磨机磨碎,索氏提取除去溶剂和未反应原料,真空干燥,得2.93g聚芳醚均三嗪产物。产率为91%。FTIR:3390cm-1(O-H,N-H伸缩振动峰),1600cm-1,1550cm-1,1490cm-1(苯环骨架产生的伸缩振动),1239cm-1(C-O-C伸缩振动峰),874cm-1,819cm-1(C-H弯曲振动峰)。固态13C NMR(400MHz,H2SO4-d2,ppm):178.7,170.5,165.2,159.6,143.9,128.6,119.4,78.3,29.8。
将实施例所得聚芳醚荧光材料进行荧光测试,在最大激发波长390nm条件下,测得其发射波长在420-640nm范围内,最大发射波长为490nm。
热重分析测试,空气氛围下,初始分解温度为340℃,残炭率为5%;氮气氛围下,初始分解温度为370℃,残炭率为21%。
实施例4
在配有分水器,回流冷凝管,机械搅拌及氮气导管的100mL圆底烧瓶中将2,4,6-三(4-氟苯基)-1,3,5-三嗪(1.82g,0.005mol)和二氮杂萘酮(1.79g,0.0075mol)溶于25mL N,N-二甲基乙酰胺中,加入甲苯60mL,加入碳酸钾(1.38g,0.01mol),升温至150℃除水2h,移除甲苯和水,升温至170℃反应至不能搅拌,并保温1h。产物倒入含有盐酸和甲醇的水溶液中,抽滤,甲醇及水洗涤,干燥。球磨机磨碎,索氏提取除去溶剂和未反应原料,真空干燥,得3.15g聚芳醚均三嗪产物。产率为87%。产率为94%。FTIR:3460cm-1(O-H,N-H伸缩振动峰),1685cm-1(C=O,C=N伸缩振动峰),1590cm-1,1530cm-1,1496cm-1(苯环骨架产生的伸缩振动),1245cm-1(C-O-C伸缩振动峰),890cm-1,826cm-1(C-H弯曲振动峰),固态13C NMR(400MHz,H2SO4-d2,ppm):219.5,206.2,181.4,172.4,166.1,163.4,156.7,147.2,135.9,119.7,82.3,45.2。
将实施例所得聚芳醚荧光材料分散到去离子水中,以370nm激发波长激发,测得其发射波长在410-600nm范围内,最大发射波长为450nm。
将实施例所得聚芳醚荧光材料以20℃/min的升温速率,于50-800℃进行热重测试。测得空气氛围下,初始分解温度为320℃,残炭率为0%;氮气氛围下,初始分解温度为350℃,残炭率为17%。
Claims (1)
1.一种由均三嗪衍生物制备的聚芳醚类荧光材料,其特征在于,结构通式如下:
其中
A表示结构单元: 中的一种或几种;
B表示结构单元:
所述聚芳醚类荧光材料的制备为:将2,4,6-三(4-氟苯基)-1,3,5-三嗪和类双酚单体按摩尔比2:(1-5)溶于溶剂及带水剂中,加催化剂,在温度为100-160℃除水1-5h,在150-220℃下反应1-12h,倒入含有盐酸和醇的水中,抽滤,磨碎,用索氏提取法除杂质,真空干燥,制得聚芳醚类荧光材料;
反应式如下:
所述溶剂为N,N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜或环丁砜中的一种或任意几种,其质量用量为反应物的5-20倍;
所述带水剂为氯苯、甲苯或二甲苯,其体积用量为溶剂的1-10倍;
所述催化剂为碳酸钠、碳酸钾或碳酸氢钠,其摩尔用量为反应物的1-3倍。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510133998.7A CN104693134B (zh) | 2015-03-26 | 2015-03-26 | 一种均三嗪衍生物单体及聚芳醚荧光材料的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201510133998.7A CN104693134B (zh) | 2015-03-26 | 2015-03-26 | 一种均三嗪衍生物单体及聚芳醚荧光材料的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104693134A CN104693134A (zh) | 2015-06-10 |
CN104693134B true CN104693134B (zh) | 2017-05-31 |
Family
ID=53340729
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201510133998.7A Expired - Fee Related CN104693134B (zh) | 2015-03-26 | 2015-03-26 | 一种均三嗪衍生物单体及聚芳醚荧光材料的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104693134B (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106866563B (zh) * | 2015-12-11 | 2020-02-14 | 中国科学院大连化学物理研究所 | 一种制备2,4-二取代-1,3,5三嗪衍生物的方法 |
CN115612435B (zh) * | 2022-10-20 | 2023-09-12 | 唯万科技有限公司 | 一种密封用耐高温聚氨酯胶及其制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3211698A (en) * | 1961-07-13 | 1965-10-12 | Monsanto Res Corp | Polymeric chelates of bivalent metals and tris(hydroxyaryl)-s-triazines |
CN102382069A (zh) * | 2011-08-11 | 2012-03-21 | 大连理工大学 | 一种二卤代和二硝基三芳基-1,3,5-三嗪的单体制备方法 |
CN103539751A (zh) * | 2013-10-17 | 2014-01-29 | 南京大学 | 一类均三嗪衍生物及其在有机电致发光器件中的应用 |
-
2015
- 2015-03-26 CN CN201510133998.7A patent/CN104693134B/zh not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3211698A (en) * | 1961-07-13 | 1965-10-12 | Monsanto Res Corp | Polymeric chelates of bivalent metals and tris(hydroxyaryl)-s-triazines |
CN102382069A (zh) * | 2011-08-11 | 2012-03-21 | 大连理工大学 | 一种二卤代和二硝基三芳基-1,3,5-三嗪的单体制备方法 |
CN103539751A (zh) * | 2013-10-17 | 2014-01-29 | 南京大学 | 一类均三嗪衍生物及其在有机电致发光器件中的应用 |
Non-Patent Citations (5)
Title |
---|
New symmetrically substituted 1,3,5-triazines as host compounds for channel-type inclusion formation;Ricarda Berger,等;《CrystEngComm》;20111108;第14卷(第3期);第768-770页 * |
New Usage for Cyclotrimerization Reaction: a Facile Synthesis of 1,3,5-Triazine Derivatives;Mi Ouyang等;《Key Engineering Materials》;20121227;第531-532卷;第32-35页,尤其是第33页方案1 * |
Synthesis and Properties of Poly ( Arylene Ether Phenyl-s-triazine) s;SHICERU MATSUO;《Journal of Polymer Science, Part A: Polymer Chemistry》;19941231;第32卷(第11期);第2094页左栏最后一段-右栏第3段,第2095页方案1 * |
含二氮杂萘酮结构聚芳醚腈酮酮的合成及表征;王明晶,等;《高分子学报》;20070930(第9期);第833-837页 * |
含芳基均三嗪环耐高温聚合物的研究;喻桂朋;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20111115(第11期);全文 * |
Also Published As
Publication number | Publication date |
---|---|
CN104693134A (zh) | 2015-06-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102382069B (zh) | 一种二卤代和二硝基三芳基-1,3,5-三嗪的单体制备方法 | |
CN105037383A (zh) | 高纯度蝶烯四酸二酐及其合成方法以及基于蝶烯四酸二酐合成的聚酰亚胺 | |
CN106397778B (zh) | 一种提高聚合型磷氮膨胀阻燃剂产率和聚合度的方法 | |
CN105646260B (zh) | 含二苯胺‑芴的二酸单体、制备方法及其在制备聚酰胺中的应用 | |
CN103483206A (zh) | 一种含不对称非共平面结构的二胺单体及其制备方法 | |
CN104448311A (zh) | 一种基于2,3,6,7-三蝶烯四酸二酐的聚酰亚胺及其制备方法 | |
CN104693134B (zh) | 一种均三嗪衍生物单体及聚芳醚荧光材料的制备方法 | |
CN103012297A (zh) | 一种含均三嗪结构的氰酸酯和聚合物及制备方法 | |
CN105175218B (zh) | 一种二氯代对二甲苯环二体的制备方法 | |
KR100667967B1 (ko) | 신규한 β-술폰 이미드 화합물 및 이의 제조방법 | |
CN115260205B (zh) | 双芘基掺杂的扩展卟啉、其双钯金属络合物、其制备方法及其应用 | |
CN106496545A (zh) | 含有吲哚基团的聚芳醚酮及其制备方法 | |
CN105061464B (zh) | 单酚‑二胺型不对称三官能度喹喔啉基苯并噁嗪及其制备方法 | |
CN105061417A (zh) | 单胺-双酚型不对称三官能度喹喔啉基苯并噁嗪及其制备方法 | |
JP2019218659A (ja) | 超耐熱性を有する繊維、及び布 | |
CN111533706B (zh) | 一种1,4,6-三取代1,2-二氢-三嗪类化合物的制备方法 | |
CN102827370A (zh) | 一种含磷聚酰亚胺材料及其制备方法 | |
JP6483481B2 (ja) | トルキシン酸系ポリマーおよびその製造中間体 | |
CN102584610B (zh) | 双酚二(间氨基对羟基苯基)醚盐酸盐及其制备方法和用途 | |
CN107151324A (zh) | 热响应荧光型聚芳亚胺醚砜及其制备方法 | |
KR101652699B1 (ko) | 플루오르계 치환체가 치환된 폴리히드록시아미드 및 이의 제조방법 | |
CN101899014B (zh) | 2,4-二(4-甲羧基苯基)-6-苯基-1,3,5-三嗪及其衍生物和制备方法 | |
Banihashemi et al. | Synthesis and properties of novel aromatic polyamides derived from benzofuro [2, 3-b] benzofuran-2, 9-dicarboxylic acid and aromatic diamines | |
CN103012087B (zh) | 一种α,α'-双亚苄基环烷酮化合物的绿色合成方法 | |
CN115322173B (zh) | 一种多功能受阻胺类光稳定剂及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170531 |
|
CF01 | Termination of patent right due to non-payment of annual fee |