CN114437344B - Room-temperature phosphorescent polyamide copolymer, and preparation method and application thereof - Google Patents
Room-temperature phosphorescent polyamide copolymer, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114437344B CN114437344B CN202011201897.6A CN202011201897A CN114437344B CN 114437344 B CN114437344 B CN 114437344B CN 202011201897 A CN202011201897 A CN 202011201897A CN 114437344 B CN114437344 B CN 114437344B
- Authority
- CN
- China
- Prior art keywords
- comonomer
- polyamide copolymer
- groups
- formula
- polyamide
- 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
- 239000004952 Polyamide Substances 0.000 title claims abstract description 101
- 229920002647 polyamide Polymers 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 83
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 8
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 41
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- VWYQFZKTKAMCLU-UHFFFAOYSA-N 4-amino-3,5-dibromobenzoic acid Chemical compound NC1=C(Br)C=C(C(O)=O)C=C1Br VWYQFZKTKAMCLU-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- BFIVZIVVJNFTIQ-UHFFFAOYSA-N 4-amino-3-bromobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1Br BFIVZIVVJNFTIQ-UHFFFAOYSA-N 0.000 claims description 14
- 150000002430 hydrocarbons Chemical group 0.000 claims description 14
- 229960002684 aminocaproic acid Drugs 0.000 claims description 11
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- -1 4-amino-3-bromobenzoic acid butyl ester Chemical compound 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical compound [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 claims description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 238000006068 polycondensation reaction Methods 0.000 claims description 6
- QMQFFHSJUJDRPG-UHFFFAOYSA-N 3-amino-2,4,6-triiodobenzoic acid Chemical compound NC1=C(I)C=C(I)C(C(O)=O)=C1I QMQFFHSJUJDRPG-UHFFFAOYSA-N 0.000 claims description 5
- 230000005284 excitation Effects 0.000 claims description 5
- 238000006862 quantum yield reaction Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 239000002861 polymer material Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 22
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 21
- 229920002292 Nylon 6 Polymers 0.000 description 21
- 238000007599 discharging Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229920000299 Nylon 12 Polymers 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000009835 boiling Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 11
- 239000004677 Nylon Substances 0.000 description 10
- 229920001778 nylon Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005086 pumping Methods 0.000 description 8
- 229920000571 Nylon 11 Polymers 0.000 description 7
- 229920002302 Nylon 6,6 Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 3
- 239000004687 Nylon copolymer Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000000103 photoluminescence spectrum Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 238000000628 photoluminescence spectroscopy Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical group [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1425—Non-condensed systems
-
- 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
- C09K2211/14—Macromolecular compounds
- C09K2211/1408—Carbocyclic compounds
- C09K2211/1433—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyamides (AREA)
Abstract
The invention provides a polyamide copolymer, a preparation method and application thereof. The polyamide copolymer comprises structural units derived from comonomer a and comonomer B; the comonomer A has the structural formula: The R 1,R2,R3,R4,R5 and R 6 contain at least one-COOR 11, at least one-NH 2R12 and at least one heteroatom, and the rest substituent can be at least one of-H, -R and-OR; wherein R 11 is selected from-H and/or-R 13,R12 is selected from-H and/or-O (c=o) R 14, said R, R 13、R14 are each independently selected from at least one of alkanes and aromatics; the comonomer B is at least one polyamide monomer. The polyamide copolymer of the invention has simple preparation method, is easy to prepare high polymer material with room temperature phosphorescence effect and good comprehensive performance, and has great application potential in the fields of anti-counterfeiting, emergency lighting, light conversion and the like.
Description
Technical Field
The invention relates to the field of high molecular polymer luminescent materials, and further relates to a room temperature phosphorescent nylon copolymer, a preparation method and application thereof.
Background
Polyamide (nylon) is a linear polymer with amide groups on the main chain, and nylon has good comprehensive properties including mechanical properties, heat resistance, abrasion resistance, chemical resistance and self-lubricity, and has a low friction coefficient, a certain flame retardance, and self-extinguishing property once fire is not continuously combusted. Nylon materials have been widely paid attention to in industry because of their excellent properties, and with the progress of technology, nylon has been widely used in particular in the industries of automobiles, electronic appliances, and the like.
With the increasing demand for light weight automobiles, more and more metal materials are replaced with nylon. At the same time, these industries have also placed higher demands on the properties of nylon materials. Therefore, the development of nylon materials with high strength and high fluidity is a hot spot for the development of products in the automobile industry and the electric appliance market. But nylon materials are polar and have high crystallinity, resulting in increased toughness. Meanwhile, in the modification process, the nylon has high melt strength and high processing modification difficulty. These characteristics bring difficulty to the development and use of nylon materials.
Phosphorescent materials and fluorescent materials are two common luminescent materials. The fluorescence and phosphorescence are generated by the transition of a substance from an excited state and spontaneous emission. At present, the phosphorescent materials in the prior art are widely applied to the fields of RMB anti-counterfeiting, biological imaging and the like, but the application of the phosphorescent materials is greatly limited because many materials can only show phosphorescent performance at low temperature or doped with heavy metals such as iridium and platinum.
The organic material of room temperature phosphorescence can just overcome the limitations, for example, see paper (J. Zhang Liang, et al, chem. Theory, doi: 10.6023/A20060243) on the development of organic small molecule room temperature phosphorescence materials.
However, the phosphorescent material at the present stage still stays in the small molecular field, and (1) the small molecular luminescent material is easy to remain in the matrix and is not easy to remove, so that the phosphorescent material is not beneficial to repeated use for many times; (2) The small molecular luminescent material can destroy the original property of the system after being blended into the system, and the system is irreversibly influenced; (3) Small molecule luminescent materials are not easy to process and thus present difficulties in manufacturing a wide variety of products or devices using them. Therefore, how to improve the processability of the luminescent material and the compatibility with the medium, so that the organic luminescent material can be widely used, is a problem that needs to be solved in the prior art.
The development of polyamide materials with excellent combination of properties and room temperature phosphorescence has been reported in the prior art.
Disclosure of Invention
Aiming at the problems of the room temperature phosphorescent materials in the prior art, the invention provides a polyamide copolymer with room temperature phosphorescence. The polyamide copolymer can be provided with phosphorescence effect by selecting and adjusting the type and proportion of the comonomer. The preparation method of the polyamide copolymer is simple, and the high polymer material with room temperature phosphorescence effect and good comprehensive performance can be easily prepared.
It is an object of the present invention to provide a room temperature phosphorescent polyamide copolymer.
A polyamide copolymer according to the invention comprises structural units derived from a comonomer A and from a comonomer B.
The polyamide copolymer of the present invention, wherein the monomer a is at least one of monomers having the following structure:
In the above formula (1), at least one-COOR 11, at least one-NH 2R12 and at least one heteroatom are contained in six substituents R 1、R2、R3、R4、R5 and R 6, and the remaining substituents can be at least one of-H, -R and-OR; wherein R 11 is selected from-H and/or-R 13,R12 is selected from-H and/or-O (c=o) R 14, and R, R 13、R14 is each independently selected from at least one of alkanes and aromatics;
preferably, the hetero atom of the substituent is at least one hetero atom such as fluorine (F), chlorine (Cl), bromine (Br), iodine (I), phosphorus (P), and silicon (Si), and more preferably at least one hetero atom such as Br and I.
Preferably, the above R, R 13、R14 carbon atoms are each independently selected from C1 to C10, more preferably C1 to C4.
According to a preferred embodiment of the present invention, the above monomer A is preferably a monomer in which R1 and R4 in the above formula (1) are carboxyl and amino groups, respectively, and more preferably a monomer in which the other groups in the formula (1) are at least one bromine-substituted.
According to a preferred embodiment of the present invention, the comonomer A is at least one of 4-amino-3-bromobenzoic acid or 4-amino-3, 5-dibromobenzoic acid, 3-amino-2, 4, 6-triiodobenzoic acid, 4-amino-3-bromobenzoic acid butyl ester.
The polyamide copolymer according to the invention, wherein the monomer B is a monomer of a polyamide, preferably at least one polyamide monomer having the following structure:
NH 3-R7-NH3 (2-1)
R 'OOC-R8-COOR' formula (2-2)
R' OOC-R9-NH 3 formula (2-3)
NH 3-R7'-NH4 +-- OOC-R8' -COOH formula (2-5).
In the above formulae (2-1) to (2-4), R7, R8, R7', R8', R9 and R10 are each independently preferably one of an aromatic hydrocarbon, a linear hydrocarbon or a branched alkane of C 1-C20, more preferably C 1～C18.
Wherein R7 and/or R7' above is further preferably a C 3-C12 aromatic hydrocarbon, linear hydrocarbon or branched alkane, more preferably a C 4-C10 aromatic hydrocarbon, linear hydrocarbon or branched alkane, most preferably- (CH 2)4-,-(CH2)6-,-(CH2)10 -.
Wherein R8 and/or R8' above is further preferably a C 1-C10 aromatic hydrocarbon, a straight-chain hydrocarbon or a branched chain, more preferably a C2-C8 straight-chain hydrocarbon, most preferably- (CH 2)2-,-(CH2)4-,-(CH2)8 -.
Wherein R9 and/or R10 above is more preferably a C 3-C12 linear hydrocarbon group, more preferably a C 5-C10 linear hydrocarbon group, most preferably- (CH 2)3-,--(CH2)8 -.
In the above formula (2-2), R 'and R' are each independently selected from one of a hydrogen atom (-H), a phenyl group, and an alkyl group of C 1～C4; preferably one of H and butyl.
R' "in the above formula (2-3) is selected from one of hydrogen atom (-H), phenyl, alkyl of C 1～C4; preferably one of H and butyl.
The above comonomer B may be particularly preferably at least one of the monomers of the formulae (2-3), (2-4) and (2-5); more preferably nylon 6, nylon 66, nylon 11, nylon 12 and other monomers; wherein the monomer of formula (2-3) is most preferably caprolactam, the monomer of formula (2-4) is most preferably aminocaproic acid, and the monomer of formula (2-5) is most preferably hexamethylenediamine adipate.
Further, the method comprises the steps of,
When the monomer B is selected from the group consisting of the formula (2-1) and the formula (2-2), the molar ratio between the two monomers of the formula (2-1) and the formula (2-2) (i.e., diamine monomer and diacid monomer) is not limited, and preferably 1: (0.9-1.1), more preferably 1:1.
When the monomer B is selected from the monomers of the formula (2-1) and the formula (2-3) and/or the formula (2-4), the molar ratio between the monomers of the formula (2-1) and the formula (2-3) and/or the formula (2-4) is not limited, and preferably 1: (50-5000).
When the monomer B is selected from the monomers of the formula (2-2) and the formula (2-3) and/or the formula (2-4), the molar ratio between the monomers of the formula (2-2) and the formula (2-3) and/or the formula (2-4) is not limited, and preferably 1: (0.01-100).
In a preferred embodiment of the polyamide copolymer according to the invention, the molar ratio of the two structural units in the polyamide copolymer, namely structural units derived from comonomer A to structural units derived from comonomer B, is preferably 1: (0.0001-5000), preferably 1: (0.005 to 5000), more preferably 1: (0.01 to 5000), most preferably 1: (0.10 to 2000), more preferably 1: (0.1-1000).
In a preferred embodiment of the polyamide copolymers according to the invention, the polyamide copolymers according to the invention have a relative viscosity of from 1.5 to 5.0, preferably from 2.0 to 4.5, more preferably from 2.3 to 4.3.
In a preferred embodiment of the polyamide copolymers of the present invention, the polyamide copolymers of the present invention have fluorescent and phosphorescent effects, which can generate fluorescence of 380 to 650nm, preferably 400 to 550nm, more preferably 400 to 500nm, under ultraviolet light excitation (e.g., 365nm ultraviolet light excitation); and can generate phosphorescence of 400-600 nm, preferably 500-600 nm, and the phosphorescence quantum yield is more than 1%; the phosphorescent lifetime of the polyamide copolymer is greater than 100ms.
It is another object of the present invention to provide a process for preparing said polyamide copolymer.
The preparation method of the polyamide copolymer comprises the step of polymerizing the components comprising the comonomer A and the comonomer B to obtain the polyamide copolymer. The polymerization may be at least one of polyamide polymerization methods known in the art, such as polycondensation (including hydrolytic ring-opening polymerization), anionic polymerization, and the like; the polymerization reaction may be in the form of solution polymerization, bulk polymerization, interfacial polymerization, or the like. The polymerization in the preparation method of the invention is preferably carried out by adopting a ring-opening polymerization mode of a body. The polymerization process of the present invention may be carried out in a continuous or batch mode.
In particular, the method comprises the steps of,
In a preferred embodiment of the method for producing a polyamide copolymer of the present invention, the method for producing a polyamide copolymer of the present invention comprises polycondensing the comonomer (including hydrolysis ring-opening reaction) to obtain the polyamide copolymer of the present invention. The reaction atmosphere is preferably an inert atmosphere, which is a common inert atmosphere in the prior art, preferably nitrogen.
In a preferred embodiment of the process for producing a polyamide copolymer of the present invention, the polycondensation reaction (including the hydrolytic ring-opening reaction) may employ the reaction conditions of a usual polycondensation reaction of polyamide.
The reaction temperature of the polycondensation reaction of the present invention may be preferably 180 to 300 ℃, more preferably 230 to 280 ℃; the reaction time is 0.5 to 24 hours, preferably 4 to 12.
The polycondensation reaction of the present invention has no special requirement on pressure, and can be maintained at 0 to 20 atm during the reaction.
The polymerization reaction of the present invention is preferably: maintaining the reaction temperature at 180-300 ℃, firstly, maintaining the reaction at high pressure (for example, the pressure is greater than or equal to normal pressure) for a period of time (for example, preferably 0-6 hours), then slowly reducing the pressure, and reacting at normal pressure or negative pressure or vacuum for a period of time (for example, preferably 0.5-3 hours); then vacuumizing, further reducing the vacuum degree to below 200Pa, and reacting (preferably 0.5-2 h). The slow depressurization by high vacuum in the reaction process is a consideration of the process and safety, and finally the high vacuum reaction is carried out, mainly for removing the byproduct water of the reaction.
In a preferred embodiment of the method for preparing a polyamide copolymer of the present invention, the mass ratio of the comonomer a to the comonomer B is 1: (0.0001-5000), preferably 1: (0.005 to 5000), more preferably 1: (0.01 to 5000), most preferably 1: (0.10 to 2000), more preferably 1: (0.1-1000).
In a preferred embodiment of the method for preparing a polyamide copolymer of the present invention, the comonomer a is preferably at least one of 4-amino-3-bromobenzoic acid and 4-amino-3, 5-dibromobenzoic acid, and the comonomer B is at least one of lactam, aminocaproic acid, and hexamethylenediammonium adipate.
In a preferred embodiment of the method for producing a polyamide copolymer of the present invention, the reaction system (including the reactor) may be subjected to an oxygen removal treatment prior to the polymerization reaction in order to reduce the generation of by-products and to improve the polymerization efficiency. The mode of the oxygen removal treatment according to the present invention is not particularly limited, and may be a mode of oxygen removal which is conventional in the art, for example, replacement with an inert gas, specifically oxygen removal by charging an inert gas into the system for 20 to 50 minutes, preferably for 20 to 30 minutes; it may also be preferred to include maintaining the reaction under an inert atmosphere while the polymerization reaction is in progress. The inert atmosphere mentioned above includes a usual inert atmosphere such as nitrogen.
In the preparation method of the polyamide copolymer, conventional auxiliary agents such as triphenylphosphine, triphenyl phosphite, triphenyl phosphate and the like can be added in the polymerization reaction, so that the color of the polymer is improved, and the polymerization reaction speed is improved.
In the preparation method of the polyamide copolymer, after the polymerization reaction is finished, the reaction product can be subjected to post-treatment in a common manner in the field to obtain the polyamide copolymer, for example, the reaction product is subjected to processes such as vacuum monomer removal or solvent digestion washing to remove monomers.
A third object of the present invention is to provide the use of said polyamide copolymers in phosphorescent materials.
The polyamide copolymer can be well applied to the technical fields of anti-counterfeiting, emergency lighting, light conversion and the like.
For example, the polyamide copolymer of the present invention may be used directly as phosphorescent material, or the polyamide copolymer with phosphorescent effect of the present invention may be used together with other polymer materials to prepare phosphorescent products for various phosphorescent material application fields by conventional polymer processing methods, such as melt blending process.
According to the technical scheme, the proper proportion relation between the comonomer A and the comonomer B can be determined by selecting the proper comonomer A and the proper comonomer B, so that the prepared polyamide copolymer has phosphorescence luminescence property. The invention enables phosphorescent molecules (such as comonomer A) to polymerize in a polymer main chain by a copolymerization method, thereby avoiding side effects such as exudation migration and the like and ensuring long-time stable use.
The polyamide copolymer with phosphorescence effect has the characteristics of simple synthesis steps, easily available monomers, cheap raw materials, adjustable optical performance and the like, and has great application potential in the fields of anti-counterfeiting, emergency lighting, light conversion and the like.
Drawings
FIG. 1 is a photoluminescence spectrum of the polyamide copolymerization product A1 of example 1;
in fig. 1, the ordinate indicates the phosphorescence intensity (a.u.), and the abscissa indicates the wavelength (nm); it can be seen that the polyamide copolymer A1 of example 1 emits both fluorescence at a wavelength of 431nm and phosphorescence at a wavelength of 539nm under photoluminescence spectroscopy.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
Experimental data in the following examples and comparative examples were measured using the following measurement methods and instruments:
(1) Optical performance test method (photoluminescence spectrum):
The test instrument was an FLS 980 steady state transient fluorescence spectrometer from Edinburgh, UK. The excitation light source for the fluorescence steady-state spectrum test is a xenon lamp, the fluorescence life test adopts an LED laser or a super-continuous laser as a light source, and the phosphorescence steady-state transient spectrum test adopts a microsecond lamp as the light source and cooperates with the gate control operation. The detectors all employ P928P PMT detectors. The photoluminescence total quantum yield and phosphorescence quantum yield were measured using FLS 980 with an integrating sphere attachment.
(2) Monomer composition: determination by Nuclear Magnetic Resonance (NMR). The instrument is Varian-300 MHz or Bruker AVANCE-400MHz nuclear magnetic resonance spectrometer, and is measured at room temperature. The deuterated reagent used is deuterated formic acid.
(3) Relative viscosity test of polyamide copolymer:
The molecular weight of the polyamide copolymer is characterized by using a relative viscosity test, weighing 0.25g of polymer sample, filling the polymer sample into a 25ml volumetric flask, adding concentrated sulfuric acid (not reaching the scale mark), adding the liquid level in the volumetric flask to the scale mark by using the concentrated sulfuric acid after the sample is completely dissolved, and shaking uniformly for measurement; 10ml of the prepared solution is measured by a pipette and added into a black-bone viscometer (4-1.0-1.1), the viscometer is vertically arranged in a constant-temperature water bath with the temperature of 25+/-0.5 ℃ for 20min, and the time of the solution flowing through two scale marks of the viscometer is the flowing time of the solution. Each sample was measured 3 times (no more than + 0.2S before and after error) and averaged.
The various monomers and starting materials used in the examples and comparative examples below were commercially available.
[ Example 1]
Comonomer a: 4-amino-3, 5-dibromobenzoic acid;
Comonomer B: nylon 6 monomer (caprolactam and aminocaproic acid);
taking 0.1 wt% of 4-amino-3, 5-dibromobenzoic acid of total weight of the nylon 6 monomer to synthesize a polyamide copolymer:
90g of caprolactam and 10g of aminocaproic acid, 0.1g of 4-amino-3, 5-dibromobenzoic acid are added into a 500mL three-port bottle, nitrogen is introduced to deoxidize for 30min, the temperature of a reaction kettle is raised to 240 ℃, the reaction temperature is controlled between 240 ℃ and 260 ℃, stirring is carried out for 3h under normal pressure, then vacuum pumping is carried out, the reaction temperature is controlled to be about 230 ℃, the vacuum pumping is continued after the reaction is carried out for 1h under 7000Pa, the vacuum degree is further reduced to be below 200Pa, and the reaction is carried out for 0.5h and then the material is discharged; and (3) discharging, and boiling the discharged material for 10 hours by using 1000g of deionized water at the temperature of 95 ℃ to remove unreacted monomers, thus obtaining the polyamide copolymer product A1.
The relative viscosity of the polyamide copolymer A1 of the present invention was 2.4. The monomer composition of the resulting polymer was determined by NMR and the molar ratio of monomer structural units derived from 4-amino-3, 5-dibromobenzoic acid to nylon 6 structural units was 1:1000.
[ Example 2]
Comonomer a: 4-amino-3-bromobenzoic acid;
comonomer B: monomer of nylon 6 (caprolactam)
Taking 1% wt of 4-amino-3-bromobenzoic acid of the total weight of the nylon 6 monomer to synthesize a polyamide copolymer:
100g of caprolactam, 5g of deionized water and 1g of 4-amino-3-bromobenzoic acid are introduced into a 1000mL autoclave, the mixture is heated under stirring at5 atm to a temperature of 260℃and maintained at this temperature and pressure for 4 hours; then reducing the pressure to normal pressure, and then purging with nitrogen for 1.5 hours while maintaining the temperature at 250-260 ℃; then placing the system under vacuum condition of 0.5 atmospheric pressure for 1h to discharge; and (3) discharging, and boiling the discharged material for 10 hours by using 1000g of deionized water at the temperature of 95 ℃ to remove unreacted monomers, thus obtaining the polyamide copolymer product A2.
The relative viscosity of the polyamide copolymer A2 according to the invention was 2.8. The monomer composition of the resulting polymer was determined by NMR and the molar ratio of monomer structural units derived from 4-amino-3, 5-dibromobenzoic acid to nylon 6 structural units was 1:90.
[ Example 3]
Comonomer a: 4-amino-3, 5-dibromobenzoic acid;
comonomer B: nylon 6 monomer (caprolactam and aminocaproic acid)
Taking 4.5% wt of 4-amino-3, 5-dibromobenzoic acid of total weight of nylon 6 monomer to synthesize polyamide copolymer:
90g of caprolactam and 10g of aminocaproic acid, 4.5g of 4-amino-3, 5-dibromobenzoic acid are added into a 500mL three-port bottle, nitrogen is introduced to deoxidize for 30min, the temperature of the reaction kettle is raised to 240 ℃, the reaction temperature is controlled between 240 and 260 ℃, stirring reaction is carried out for 3h under normal pressure, vacuum pumping is carried out, the reaction temperature is controlled to be about 230 ℃, the low vacuum reaction is carried out for 1h under 7000Pa, vacuum pumping is continued, the vacuum degree is further reduced to be below 200Pa, and the reaction is carried out for 0.5h and then discharging is carried out; and (3) discharging, and boiling the discharged material for 10 hours by using 1000g of deionized water at the temperature of 95 ℃ to remove unreacted monomers, thus obtaining the polyamide copolymer product A3.
The relative viscosity of the polyamide copolymer A3 according to the invention was 2.6. The monomer composition of the resulting polymer was determined by NMR and the molar ratio of monomer structural units derived from 4-amino-3, 5-dibromobenzoic acid to nylon 6 structural units was 1:18.
[ Comparative example 1]
Synthesis of nylon 6:
90g of caprolactam and 10g of aminocaproic acid are added into a 500mL three-port bottle, nitrogen is introduced to remove oxygen for 30min, the temperature of a reaction kettle is raised to 240 ℃, the reaction temperature is controlled to be between 240 and 260 ℃, after stirring reaction for 3h at normal pressure, vacuum pumping is performed, the reaction temperature is controlled to be about 230 ℃, vacuum pumping is continued after reaction for 1h at 7000Pa, the vacuum degree is further reduced to be below 200Pa, and then the reaction is performed for 0.5h and then discharging is performed; and (3) discharging, and boiling the discharged material for 10 hours by using 1000g of deionized water at the temperature of 95 ℃ to remove unreacted monomers, thus obtaining a nylon 6 product B1. The relative viscosity of nylon 6 product B1 was 2.6.
[ Example 4]
Comonomer a: 4-amino-3-bromobenzoic acid;
Comonomer B: nylon 66 monomer (hexamethylene diammonium adipate);
taking 0.1 wt% of 4-amino-3 bromobenzoic acid of the total weight of the nylon 66 monomer to synthesize a polyamide copolymer:
To a 1000mL autoclave were added 100g of hexamethylenediammonium adipate and 0.1g of 4-amino-3-bromobenzoic acid, and the mixture was heated to a temperature of 280℃under 7.5 atm with stirring, and maintained at this temperature and pressure for 2 hours; then the pressure was reduced to normal pressure, then purged with nitrogen for 1.5 hours while maintaining the temperature at 280 ℃; then placing the system under vacuum condition of 0.5 atmospheric pressure for 1h to discharge; and (3) discharging, and boiling the discharged material for 10 hours by using 1000g of deionized water at the temperature of 95 ℃ to remove unreacted monomers, thus obtaining the polyamide copolymer product A4.
The relative viscosity of the polyamide copolymer A4 according to the invention was 2.9. The monomer composition of the resulting polymer was determined by NMR and the molar ratio of monomer structural units derived from 4-amino-3-bromobenzoic acid to nylon 66 structural units was 1:800.
[ Comparative example 2]
Synthesis of nylon 66:
100g of hexamethylenediammonium adipate was added to a 1000mL autoclave, and the mixture was heated to a temperature of 280℃under 7.5 atm with stirring, and maintained at this temperature and pressure for 2 hours; the pressure was then reduced and then purged with nitrogen for 1.5 hours while maintaining the temperature at 280 ℃. Then placing the system under vacuum condition of 0.5 atmospheric pressure for 1h to discharge; and (3) discharging, and boiling the discharged material for 10 hours by using 1000g of deionized water at the temperature of 95 ℃ to remove unreacted monomers, thus obtaining a nylon 66 product B2. The relative viscosity of nylon 66 product B2 was 2.4.
[ Example 5]
Comonomer a: 4-amino-3, 5-dibromobenzoic acid;
comonomer B: nylon 11 monomer (aminoundecanoic acid);
Taking 11% wt of 4-amino-3, 5-dibromobenzoic acid of total weight of nylon 11 monomers to synthesize a polyamide copolymer:
90g of aminoundecanoic acid and 10g of 4-amino-3, 5-dibromobenzoic acid are added into a 500mL three-port bottle, nitrogen is introduced to deoxidize for 30min, the temperature of the reaction kettle is raised to 260 ℃, the reaction temperature is controlled between 260 and 280 ℃, stirring reaction is carried out for 3h under normal pressure, vacuum pumping is carried out, the reaction temperature is controlled to be about 230 ℃,7000Pa low vacuum reaction is carried out for 1h, vacuum pumping is continued, the vacuum degree is further reduced to be less than 200Pa, and the reaction is carried out for 0.5h and then discharging is carried out; and (3) discharging, and boiling the discharged material for 10 hours by using 1000g of deionized water at the temperature of 95 ℃ to remove unreacted monomers, thus obtaining the polyamide copolymer product A5.
The relative viscosity of the polyamide copolymer A5 of the invention was 2.5. The monomer composition of the resulting polymer was determined by NMR to have a molar ratio of monomer structural units derived from 4-amino-3, 5-dibromobenzoic acid to nylon 11 structural units of 1:8.5.
[ Comparative example 3]
Synthesis of nylon 11:
Adding 100g of aminoundecanoic acid into a 500mL three-port bottle, introducing nitrogen to deoxidize for 30min, heating a reaction kettle to 260 ℃, controlling the reaction temperature to 260-280 ℃, stirring under normal pressure to react for 3h, vacuumizing, controlling the reaction temperature to about 230 ℃ and 7000Pa, continuously vacuumizing after low-vacuum reaction for 1h, further reducing the vacuum degree to below 200Pa, and discharging after reacting for 0.5 h; and (3) discharging, and boiling the discharged material for 10 hours by using 1000g of deionized water at the temperature of 95 ℃ to remove unreacted monomers, thus obtaining a nylon 11 product B3. The relative viscosity of nylon 11 product B3 was 1.3.
[ Example 6]
Comonomer a: 4-amino-3-bromobenzoic acid butyl ester;
comonomer B: nylon 12 monomer (laurolactam);
taking 5.2 wt% of 4-amino-3-bromobutyl benzoate based on the total weight of the nylon 12 monomer to synthesize a polyamide copolymer:
Adding 95g of laurolactam and 5g of 4-amino-3-bromobutyl benzoate into a 500mL three-mouth bottle, introducing nitrogen to deoxidize for 30min, heating the reaction kettle to 260 ℃, controlling the reaction temperature between 260 and 280 ℃, stirring under normal pressure for 3h, vacuumizing, controlling the reaction temperature to about 230 ℃, carrying out 7000Pa low vacuum reaction for 1h, continuously vacuumizing, further reducing the vacuum degree to below 200Pa, carrying out reaction for 0.5h, and discharging; and (3) discharging, and boiling the discharged material for 10 hours by using 1000g of deionized water at the temperature of 95 ℃ to remove unreacted monomers, thus obtaining the polyamide copolymer product A6.
The relative viscosity of the polyamide copolymer A6 of the invention was 3.4. The monomer composition of the resulting polymer was determined by NMR and the molar ratio of the monomer structural unit derived from butyl 4-amino-3-bromobenzoate to the nylon 12 structural unit was 1/18.
[ Comparative example 4]
Synthesis of nylon 12:
Adding 95g of laurolactam into a 500mL three-port bottle, introducing nitrogen to deoxidize for 30min, heating the reaction kettle to 260 ℃, controlling the reaction temperature to 260-280 ℃, stirring and reacting for 3h under the condition of keeping 2 atmospheres, vacuumizing, controlling the reaction temperature to about 230 ℃ and carrying out 7000Pa low vacuum reaction for 1h, continuously vacuumizing, further reducing the vacuum degree to below 200Pa, reacting for 0.5h, and discharging; and (3) discharging, and boiling the discharged material for 10 hours by using 1000g of deionized water at the temperature of 95 ℃ to remove unreacted monomers, thus obtaining a nylon 12 product B4. The relative viscosity of nylon 12 product B4 was 4.0.
[ Example 7]
Comonomer a: 4-amino-3-bromobenzoic acid;
comonomer B: nylon 12 monomer and nylon 6 monomer;
Taking 0.1 wt% of 3-amino-2, 4, 6-triiodobenzoic acid based on the total weight of the nylon 12 monomer and the nylon 6 monomer to synthesize a polyamide copolymer:
45g of caprolactam, 5g of aminocaproic acid, 50g of laurolactam and 0.1g of 3-amino-2, 4, 6-triiodobenzoic acid are added into a 500mL three-port bottle, nitrogen is introduced into the bottle to deoxidize for 30min, the reaction kettle is heated to 260 ℃, stirred and reacted for 3h under normal pressure, vacuumizing is carried out, the reaction temperature is controlled to be about 230 ℃, the vacuum reaction is carried out for 1h under 7000Pa, vacuumizing is continued, the vacuum degree is further reduced to be less than 200Pa, and the reaction is carried out for 0.5h and then the material is discharged; and (3) discharging, and boiling the discharged material for 10 hours by using 1000g of deionized water at the temperature of 95 ℃ to remove unreacted monomers, thus obtaining a nylon copolymer product A7.
The relative viscosity of the polyamide copolymer A7 according to the invention was 4.2. The monomer composition of the resulting polymer was determined by NMR and the molar ratio of 3-amino-2, 4, 6-triiodobenzoic acid monomer structural units/nylon 6 structural units/nylon 12 structural units was 1:450:470.
[ Comparative example 5]
Synthesis of nylon 6 and nylon 12 copolymers:
Adding 45g of caprolactam, 5g of aminocaproic acid and 50g of laurolactam into a 500mL three-necked bottle, introducing nitrogen to deoxidize for 30min, heating the reaction kettle to 260 ℃, stirring and reacting for 3h under normal pressure, vacuumizing, controlling the reaction temperature to about 230 ℃, continuously vacuumizing after 7000Pa low vacuum reaction for 1h, further reducing the vacuum degree to below 200Pa, and discharging after reacting for 0.5 h; and (3) discharging, and boiling the discharged material for 10 hours by using 1000g of deionized water at the temperature of 95 ℃ to remove unreacted monomers, thus obtaining a nylon 6 and nylon 12 copolymer product B5.
The relative viscosity of nylon 6 and nylon 12 copolymer product B5 was 2.0.
[ Example 8]
Comonomer a: 4-amino-3-bromobenzoic acid;
comonomer B: nylon 12 monomer and nylon 6 monomer;
Adding 5g of aminocaproic acid, 5g of laurolactam and 90g of 4-amino-3-bromobenzoic acid into a 1000mL three-port bottle, introducing nitrogen to deoxidize for 30min, heating the reaction kettle to 280 ℃, stirring under normal pressure to react for 3h, vacuumizing, controlling the reaction temperature to be about 260 ℃, performing 7000Pa low vacuum reaction for 0.5h, continuously vacuumizing, further reducing the vacuum degree to be below 1000Pa, performing reaction for 0.5h, and discharging; and (3) discharging, and boiling the discharged material for 10 hours by using 1000g of deionized water at the temperature of 95 ℃ to remove unreacted monomers, thus obtaining a nylon copolymer product A8.
The relative viscosity of the polyamide copolymer A8 according to the invention was 2.8. The monomer composition of the resulting polymer was determined by NMR and the molar ratio of monomer structural units derived from 4-amino-3-bromobenzoic acid to nylon 6 structural units to nylon 12 structural units was 1:0.06:0.06.
Test experiment
The optical properties of the polyamide polymers obtained in examples 1 to 8 and comparative examples 1 to 5 at room temperature were measured, and the fluorescence and phosphorescence effect data at room temperature were shown in Table 1.
TABLE 1
From the above data, it can be seen that the polyamide copolymer of the present invention has both fluorescent and phosphorescent effects, with a phosphorescent quantum yield greater than 1%; phosphorescent lifetime is greater than 100ms; can be well applied to the fields of anti-counterfeiting, emergency lighting, light conversion and the like.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various modifications can be made to the technical solutions of the present invention within the scope of the technical concept of the present invention, which all fall within the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (22)
1. A polyamide copolymer comprising structural units derived from comonomer a and comonomer B; wherein: the comonomer a is at least one of the monomers having the structure:
Formula (1);
In the above formula (1), at least one-COOR 11, at least one-NH 2R12 and at least one heteroatom are contained in six substituents R 1、R2、R3、R4、R5 and R 6, and the remaining substituents can be at least one of-H, -R and-OR; wherein R 11 is selected from-H and/or-R 13,R12 is selected from-H and/or-O (c=o) R 14, and R, R 13、R14 is each independently selected from at least one of alkanes and aromatics; the number of carbon atoms of R, R 13、R14 is independently selected from C1-C10;
The comonomer B is at least one of polyamide monomers; the heteroatom is at least one of F, cl, br, I, P and Si heteroatoms;
the molar ratio of structural units derived from comonomer a to structural units derived from comonomer B in the polyamide copolymer is 1: (0.0001-5000).
2. The polyamide copolymer according to claim 1, wherein:
The number of carbon atoms R, R 13、R14 in the substituent of the formula (1) is independently selected from C1-C4.
3. The polyamide copolymer according to claim 1, wherein:
Monomers of which R 1,R4 in the formula (1) of the comonomer A is carboxyl and amino respectively; and/or the number of the groups of groups,
The comonomer A is at least one of 4-amino-3-bromobenzoic acid or 4-amino-3, 5-dibromobenzoic acid, 3-amino-2, 4, 6-triiodobenzoic acid and 4-amino-3-bromobenzoic acid butyl ester.
4. The polyamide copolymer according to claim 1, wherein:
wherein the comonomer B is at least one of polyamide monomers having the structure:
NH 3-R7-NH3 formula (2-1);
R ' OOC-R8-COOR ' ' formula (2-2);
R ' ' ' OOC-R9-NH 3 formula (2-3);
Formula (2-4);
NH 3-R7'-NH4 +-- OOC-R8' -COOH formula (2-5);
In the above formulas (2-1) to (2-4), R7, R8, R7', R8', R9 and R10 are each independently one of aromatic hydrocarbons, linear hydrocarbon groups or branched alkane hydrocarbons of C 1-C20;
In the above formula (2-2), R ' and R ' ' are each independently selected from one of a hydrogen atom, a phenyl group, and an alkyl group of C 1~C4;
r ' ' ' in the above formula (2-3) is selected from one of a hydrogen atom, a phenyl group and an alkyl group of C 1~C4.
5. The polyamide copolymer as claimed in claim 4, wherein:
in the formula (2-2), R ' and R ' ' are independently one of H and butyl; and/or the number of the groups of groups,
R ' ' ' in the formula (2-3) is one of H and butyl.
6. The polyamide copolymer as claimed in claim 4, wherein:
The R7 and/or R7' is aromatic hydrocarbon, straight-chain hydrocarbon or branched alkane of C 3-C12; and/or the number of the groups of groups,
R8 and/or R8' are aromatic hydrocarbon, straight-chain hydrocarbon or branched chain of C 1-C10; and/or the number of the groups of groups,
R9 and/or R10 is a straight-chain hydrocarbon group of C 3-C12.
7. The polyamide copolymer of claim 6, wherein:
The R7 and/or R7' are C 4-C10 aromatic hydrocarbon, straight-chain hydrocarbon and branched alkane; and/or the number of the groups of groups,
R8 and/or R8' is a linear hydrocarbon group of C 2-C8; and/or the number of the groups of groups,
R9 and/or R10 is a straight-chain hydrocarbon group of C 5-C10.
8. The polyamide copolymer of claim 7, wherein:
R7 and/or R7' is one of- (CH 2)4-,-( CH2)6-,-( CH2)10 -, and/or,
R8 and/or R8' is one of- (CH 2)2-,-( CH2)4-,-( CH2)8 -, and/or,
R9 and/or R10 is one of- (CH 2)3 -and- (CH 2)8 -).
9. The polyamide copolymer as claimed in claim 4, wherein:
when the comonomer B is selected from the monomers of the formula (2-1) and the formula (2-2), the molar ratio between the two monomers of the formula (2-1) and the formula (2-2) is 1: (0.9-1.1).
10. The polyamide copolymer as claimed in claim 4, wherein:
The comonomer B is at least one of the monomers of the formulas (2-3), (2-4) and (2-5).
11. The polyamide copolymer of claim 10, wherein:
the comonomer B is at least one of caprolactam, aminocaproic acid and adipic acid hexamethylenediammonium salt.
12. The polyamide copolymer according to any one of claims 1 to 11, characterized in that:
The molar ratio of structural units derived from comonomer a to structural units derived from comonomer B in the polyamide copolymer is 1: (0.005-5000).
13. The polyamide copolymer of claim 12, wherein:
the molar ratio of structural units derived from comonomer a to structural units derived from comonomer B in the polyamide copolymer is 1: (0.01-5000).
14. The polyamide copolymer according to claim 1, wherein:
the relative viscosity of the polyamide copolymer is 1.5-5.0; and/or the number of the groups of groups,
Under the excitation of ultraviolet light, the polyamide copolymer can generate 380-650 nm fluorescence; and/or the number of the groups of groups,
Under the excitation of ultraviolet light, the polyamide copolymer can generate phosphorescence of 400-600 nm; and/or the number of the groups of groups,
The phosphorescent quantum yield of the polyamide copolymer is more than 1%; and/or the number of the groups of groups,
The phosphorescent lifetime of the polyamide copolymer is greater than 100ms.
15. The polyamide copolymer of claim 14, wherein:
the polyamide copolymer has a relative viscosity of 2.0 to 4.5.
16. The method for producing a polyamide copolymer according to any one of claims 1 to 15, comprising polymerizing the components including the comonomer to obtain the polyamide copolymer.
17. The method of claim 16, wherein the process comprises,
The mass ratio of the comonomer A to the comonomer B is 1: (0.0001-5000).
18. The method of claim 17, wherein the process comprises,
The mass ratio of the comonomer A to the comonomer B is 1: (0.005-5000).
19. The method of claim 18, wherein the process comprises,
The mass ratio of the comonomer A to the comonomer B is 1: (0.01-5000).
20. The method according to claim 16, wherein the polymerization conditions are:
The polymerization is polycondensation under an inert atmosphere, and/or,
The polymerization temperature is 180-300 ℃; and/or the number of the groups of groups,
The reaction time is 0.5-24 hours; and/or the number of the groups of groups,
The reaction pressure is 0-20 atm.
21. The method of manufacturing according to claim 20, wherein:
The polymerization reaction temperature is 230-280 ℃.
22. Use of a polyamide copolymer according to any one of claims 1 to 15 or prepared according to the preparation method of any one of claims 16 to 21 in the field of phosphorescent materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011201897.6A CN114437344B (en) | 2020-11-02 | 2020-11-02 | Room-temperature phosphorescent polyamide copolymer, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011201897.6A CN114437344B (en) | 2020-11-02 | 2020-11-02 | Room-temperature phosphorescent polyamide copolymer, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114437344A CN114437344A (en) | 2022-05-06 |
| CN114437344B true CN114437344B (en) | 2024-08-02 |
Family
ID=81358382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011201897.6A Active CN114437344B (en) | 2020-11-02 | 2020-11-02 | Room-temperature phosphorescent polyamide copolymer, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114437344B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115572340B (en) * | 2022-10-25 | 2023-06-13 | 重庆理工大学 | Imide polymer room-temperature phosphorescent material with crystallization performance, and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109957106A (en) * | 2019-03-13 | 2019-07-02 | 北京大学 | A kind of room temperature phosphorimetry nylon copolymer and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5102973A (en) * | 1989-10-13 | 1992-04-07 | Mitsubishi Petrochemical Co., Ltd. | Conjugated system-containing organic high molecular compound |
-
2020
- 2020-11-02 CN CN202011201897.6A patent/CN114437344B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109957106A (en) * | 2019-03-13 | 2019-07-02 | 北京大学 | A kind of room temperature phosphorimetry nylon copolymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Phosphorescence Properties of p-Aminobenzoic Acid Immobilized on a Nylon Membrane;GRACIELA M. ESCANDAR;《APPLIED SPECTROSCOPY》;20031231;第 58卷(第7期);836-842 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114437344A (en) | 2022-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5422418A (en) | Polyamides and objects obtained from them | |
| SE429134B (en) | PROCEDURE FOR THE PREPARATION OF POLYETER ESTERAMIDS | |
| US5917004A (en) | Weather-resistant polyamides and method of their production | |
| CN110218311B (en) | Flame-retardant semi-aromatic polyamide and preparation method thereof | |
| JP6377146B2 (en) | Process for the preparation of aliphatic or partially aromatic polyamides including solid phase polymerization | |
| CN114437344B (en) | Room-temperature phosphorescent polyamide copolymer, and preparation method and application thereof | |
| KR900007762B1 (en) | Process for the preparation of copolyamides based on hexamethylene diamine apidic acid and dimeric acid | |
| WO2020224377A1 (en) | Flame-retardant semi-aromatic polyamide and preparation method therefor | |
| US20230079764A1 (en) | Polymerization Process | |
| KR20150135737A (en) | Copolymerized polyamide resin, method for preparing the same and article comprising the same | |
| CN107325278A (en) | A kind of toughness nylon material and preparation method thereof | |
| CN114437340B (en) | Nylon copolymer, preparation method thereof and phosphorescent material thereof | |
| US5824763A (en) | Process for the manufacture of nylon compositions with improved flow | |
| US3627736A (en) | Polyamides from isophorone diamine, hexamethylene diamine, isophthalic acid and terephthalic acid | |
| JP3347545B2 (en) | Random copolymerized polyamide resin and method for producing the same | |
| JP4096446B2 (en) | Transparent polyamide resin and method for producing the same | |
| US20020183480A1 (en) | Polyamide elastomer | |
| KR101987540B1 (en) | Copolymerized polyamide resin, method for preparing the same and article comprising the same | |
| KR20160017197A (en) | Copolymerized polyamide resin, method for preparing the same and article comprising the same | |
| KR20220092108A (en) | Process for Preparing a Polyamide by Copolymerization of Multiple Components, Polyamide Prepared Thereby, and Composition Comprising the Same | |
| EP3290459A1 (en) | Polyamide resin, polyamide resin composition containing same, preparation method therefor, and molded product including same | |
| Russo et al. | Direct synthesis of aromatic polyamides | |
| EP3778710A1 (en) | Semi-aromatic polyamide resin and method for manufacturing same | |
| US4212965A (en) | Polyamides with elastomeric character from 5-methylnonamethylene diamine | |
| JP3601384B2 (en) | Novel polyamide and process for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |