Copolyamide, and preparation method therefor and use thereof

Abstract

The present disclosure relates to a copolyamide, and a preparation method therefor and the use thereof. The copolyamide has an adjustable melting point, hardness and other properties, and has photoluminescence and an improved molding processability. By modifying the adjustment of the main chain and side groups, the copolyamide can also exhibit additional functional benefits, such as antistatic, antibacterial, flame retardant and other properties. The method of the present disclosure is simple and efficient, and the selected comonomer can be derived from renewable biological resources, such that the dependence on petroleum resources is effectively reduced, thereby reducing production costs and improving the overall economic benefits.

Description

Copolyamide and preparation method and application thereof TECHNICAL FIELD

[0001] The present disclosure relates to the technical field of polyamide polymers, in particular, to a novel multi-component copolyamide and a preparation method and application thereof. BACKGROUND

[0002] Nylon 6 (polycaprolactam) is widely used in the fields of textiles, engineering plastics, automobile parts, etc. due to its high strength, excellent toughness, good wear resistance and corrosion resistance, and moisture absorption performance. However, the melting point of traditional nylon 6 is difficult to adjust, and the functional modification is limited, and the raw material caprolactam mainly depends on petrochemical industry, which faces challenges in sustainable development and environmental protection. Therefore, the development of bio-based or partially bio-based alternative materials has become a research hotspot.

[0003] Lysine, as a bio-based source of amino acid, has the potential to replace fossil raw materials such as petroleum-based monomers. However, due to its instability at high temperatures, it is difficult to be directly used for polymerization, and it is usually first cyclized into aminocaprolactam (see CN111116472A, Seven-membered cyclic lysine derivative monomer and its preparation method and antibacterial poly(epsilon-lysine)), and then copolymerized with caprolactam to prepare semi-bio-based nylon 6 (see CN115707727A, An antibacterial nylon 6 material and its preparation method and application). However, in the copolymerization process, if an anionic polymerization method is used, the cost is high, and it is difficult to be compatible with the existing nylon 6 production device for production. On the other hand, if the traditional hydrolysis ring-opening polymerization method is used, it is difficult to achieve effective copolymerization of aminocaprolactam and caprolactam or control the copolymerization structure, and even may lead to copolymerization failure.

[0004] Traditional homopolymer aromatic polyamides, such as PA6T and PA10T, etc., have excellent heat resistance due to the rigidity of the aromatic ring and the hydrogen bonding of the amide bond. This kind of material is usually obtained by polycondensation of aromatic diacid and aliphatic diamine, and when the number of carbon atoms in the aliphatic chain is ≤6, the melting point is significantly higher than that of aliphatic polyamides. This kind of material often decomposes at a small amount at 350℃ or above, so it can only be processed by melting when the melting point is reduced to below 350℃, which greatly limits the development of commercial homopolymer aromatic polyamides.

[0005] Therefore, it is urgent to develop a new type of sustainable bio-based polyamide material with adjustable properties (such as melting point, hardness, antistatic property, antibacterial property, optical property, flame retardant property, molding processing property, etc.). SUMMARY

[0006] The purpose of the present disclosure is to provide a novel multi-component copolyamide and its preparation method and application, which has adjustable properties (such as melting point, hardness, etc.), photoluminescence and improved forming processing performance. By selecting and / or quaternizing the side groups of the comonomer, the polyamide material can be flexibly modified to have functional benefits (such as antibacterial performance, flame retardant performance, etc.). By adjusting the main chain structure of the comonomer, the properties of the polyamide material can be transformed, for example, from plastic to elastomer, thereby adapting to different application requirements. The present application realizes efficient copolymerization of different reactive monomers by optimizing the copolymerization system, and can flexibly adjust the performance of the copolyamide, while reducing energy consumption and production cost, promoting the development of multifunctional and sustainable polyamide materials.

[0007] To achieve the above purpose, the first aspect of the present disclosure provides a copolyamide comprising a copolymerization structural unit represented by the following formula (1) to formula (4):

[0008] wherein,

[0009] represents a chemical bond;

[0010] R1is selected from substituted or unsubstituted C 1-20 alkylene;

[0011] R2is selected from substituted or unsubstituted C 1-12 alkylene, substituted or unsubstituted C 3-10 cycloalkylene, substituted or unsubstituted 3-10 membered heterocyclylene, substituted or unsubstituted C 6-10 arylene, substituted or unsubstituted 5-10 membered heteroarylene, substituted or unsubstituted -R a '-NH-(R a -NH) n -R a '-, substituted or unsubstituted -R b '-O-(R b -O) n' -R b '-, substituted or unsubstituted -R c "-O-(C(O)-R c -C(O)-O-R c '-O) n” -C(O)-R c -C(O)-O-R c ", substituted or unsubstituted -R d '-(Si(R d )2-O) n”' -Si(R d )2-R d '-, wherein Ra , R a , R b , R b , R d each independently selected from substituted or unsubstituted C 2-10 alkylene, substituted or unsubstituted C 6-10 arylene, R c , R c , R c each independently selected from C 1-10 alkylene, substituted or unsubstituted C 6-10 arylene, R d each independently selected from C 1-5 alkyl, C 1-5 alkoxy, C 6-10 aryl, n, n', n", n'" each independently represents an integer from 1 to 500;

[0012] the nitrogen-containing pendant group R3 is selected from one or more of substituted or unsubstituted amine group, quaternary ammonium cation, quaternary ammonium-type zwitterion;

[0013] R4 is selected from one or more of substituted or unsubstituted C 2-12 alkylene, substituted or unsubstituted C 3-10 cycloalkylene, substituted or unsubstituted 3-10 membered heterocyclylene, substituted or unsubstituted C 6-10 arylene, substituted or unsubstituted 5-10 membered heteroarylene;

[0014] R1, R2 and R4 are optionally each independently substituted with one or more substituents selected from C 1-10 alkyl, C 1-10 alkoxy, C 3- 10 cycloalkyl, 3-10 membered heterocyclyl, C 6-10 aryl and 5-10 membered heteroaryl.

[0015] A second aspect of the present disclosure provides a method for preparing a copolyamide, the method comprising: contacting a lactam compound, a caprolactam having a nitrogen-containing pendant group, a dibasic acid and a dibasic amine under an inert atmosphere to perform a copolymerization reaction,

[0016] wherein the lactam compound has a structure shown in the following formula (I), the caprolactam having a nitrogen-containing pendant group has a structure shown in the following formula (II), the dibasic amine has a structure shown in the following formula (III), and the dibasic acid has a structure shown in the following formula (IV),

[0017] wherein,

[0018] R1 is selected from substituted or unsubstituted C1-20 alkylene;

[0019] R2is selected from substituted or unsubstituted C 1-12 alkylene, substituted or unsubstituted C 3-10 cycloalkylene, substituted or unsubstituted 3-10 membered heterocyclylene, substituted or unsubstituted C 6-10 arylene, substituted or unsubstituted 5-10 membered heteroarylene, substituted or unsubstituted -R a '-NH-(R a -NH) n -R a '-, substituted or unsubstituted -R b '-O-(R b -O) n' -R b '-, substituted or unsubstituted -R c "-O-(C(O)-R c -C(O)-O-R c '-O) n” -C(O)-R c -C(O)-O-R c "-, substituted or unsubstituted -R d '-(Si(R d )2-O) n”' -Si(R d )2-R d '- wherein R a , R a ', R b , R b ', R d ' are each independently selected from substituted or unsubstituted C 2-10 alkylene, substituted or unsubstituted C 6-10 arylene, R c , R c ', R c " are each independently selected from C 1-10 alkylene, substituted or unsubstituted C 6- 10 arylene, R d are each independently selected from C 1-5 alkyl, C 1-5 alkoxy, C 6-10 aryl, n, n', n", n'" each independently represents an integer from 1 to 500;

[0020] the nitrogen-containing pendant group R3is a substituted amine group;

[0021] R4is selected from substituted or unsubstituted C 2-12 alkylene, substituted or unsubstituted C 3-10cycloalkylene, substituted or unsubstituted 3-10 membered heterocyclylidene, substituted or unsubstituted C 6-10 one or more of arylene, substituted or unsubstituted 5-10 membered heteroarylene;

[0022] R1, R2and R4are each independently optionally substituted with one or more substituents selected from C 1-10 alkyl, C 1-10 alkoxy, C 3- 10 cycloalkyl, 3-10 membered heterocyclyl, C 6-10 aryl and 5-10 membered heteroaryl.

[0023] A third aspect of the present disclosure provides a copolyamide prepared by the method of the second aspect of the present disclosure.

[0024] A fourth aspect of the present disclosure provides use of the copolyamide of the first aspect of the present disclosure and / or the third aspect of the present disclosure.

[0025] The present disclosure prepares a multi-copolyamide by using a lactam compound, caprolactam with a nitrogen-containing side group, a dibasic acid and a dibasic amine in a one-step copolymerization process. The copolyamide has controllable properties (such as melting point, hardness, etc.), photoluminescence and improved forming processing performance; and the side group thereof can be selected and / or quaternized, thereby achieving flexible modification; and the main chain structure thereof can be adjusted, thereby adapting to different application fields of polyamide materials. The method of the present disclosure is simple and efficient, the selected copolymer monomers can be derived from renewable biological resources, effectively reducing the dependence on petroleum resources, thereby reducing production costs and improving overall economic benefits; the obtained copolyamide has a lower melting point than traditional aromatic polyamides, improves the forming processing performance, and can exhibit photoluminescence, antistatic, anti-counterfeiting, antibacterial, good biocompatibility, and / or flame retardant properties, etc.

[0026] Other features and advantages of the present disclosure will be described in detail in the following specific embodiments section. BRIEF DESCRIPTION OF DRAWINGS

[0027] The accompanying drawings are included to provide a further understanding of the present disclosure and constitute a part of the specification, and together with the specific embodiments below, serve to explain the present disclosure but do not constitute a limitation thereof. In the drawings:

[0028] FIG. 1 is a two-dimensional fluorescence spectrum of a polymer film made of the copolyamide obtained in Example I-1 of the present disclosure.

[0029] FIG. 2 is an infrared spectrum of the copolyamides obtained in Example I-1 and Comparative Example I-2 of the present disclosure.

[0030] Figure 3 is a two-dimensional fluorescence spectrum of a polymer film made of the copolyamide elastomer obtained in Example II-1 of the present disclosure.

[0031] Figure 4 is an infrared spectrum of the copolyamide elastomer obtained in Example II-1 of the present disclosure.

[0032] Figure 5 is a test chart of the ultraviolet-visible light transmittance of a polymer film made of the copolyamide elastomer obtained in Example II-1 of the present disclosure.

[0033] Figure 6 is an infrared spectrum of the quaternized copolyamide obtained in Example IV-1 of the present disclosure.

[0034] Figure 7 is a photograph showing the antibacterial effect of Example IV-1 and Comparative Example IV-1 against Staphylococcus aureus. DETAILED DESCRIPTION

[0035] The specific embodiments of the present disclosure will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative and are not intended to limit the present disclosure.

[0036] Any specific numerical values (including the endpoints of numerical ranges) disclosed herein are not limited to the precise values recited as essentially approximate values for the exact values are also intended. And, for ranges recited as being between two endpoints, it is intended that every number or value between the endpoints is also included in the range. Also, the endpoints of the ranges are not limited to the precise values recited as essentially approximate values for the exact values are also intended. And, for ranges recited as being between two endpoints, it is intended that every number or value between the endpoints is also included in the range.

[0037] Unless otherwise defined, all terms used in disclosing the application, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. If any term is defined differently or used differently in the present disclosure, the definition of that term in this document prevails.

[0038] In the present application, except for the explicitly stated content, any matter or item not mentioned is directly applicable to those known in the art without any change. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are all considered as part of the original disclosure or original description of the present application, and should not be considered as new content that has not been disclosed or anticipated herein, unless the combination is considered to be obviously unreasonable by those skilled in the art.

[0039] In the present application, the term "alkyl" refers to a saturated aliphatic hydrocarbon group, including, for example, 1 to 20 carbon atoms (C 1-20 alkyl), 1 to 12 carbon atoms (C 1-12 alkyl), 1 to 8 carbon atoms (C1- 8alkyl), 1 to 6 carbon atoms (C 1-6 alkyl), or 1 to 4 carbon atoms (C 1-4 alkyl). Examples of alkyl groups include methyl, ethyl, propyl, 2-propyl, n-butyl, isobutyl, t-butyl, pentyl, neopentyl, and the like. Alkyl groups can be substituted or unsubstituted. Typical substituents include cycloalkyl, aryl, heteroaryl, heteroalicyclyl, hydroxy, alkoxy, aryloxy, thiohydroxy, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, aminyl, carboxy, nitro, silyl, amino, and the like. "Haloalkyl", for example, C 1-5 haloalkyl, refers to an alkyl group having one or more halogen substituents. "Alkylene" refers to the divalent form of an alkyl group, for example methylene, ethylene, propylene, butylene, pentylene, hexylene, isopropylene, isobutylene, sec-butylene, t-butylene, isopentylene. "Alkoxy", for example, C 1-5 alkoxy, refers to -O-alkyl, where alkyl is preferably C 1-5 , C 1-4 , C 1-3 , C 1-2 , or C1alkyl.

[0040] "Alkenyl" refers to unsaturated aliphatic hydrocarbon radicals including at least one carbon-carbon double bond, including straight, branched, and cyclic saturation, and including, for example, 2 to 5 carbon atoms (C 2-5 alkenyl). Representative examples include, but are not limited to, ethenyl, 1- propenyl, 2-propenyl, 1-, 2-, or 3-butenyl, and the like.

[0041] "C 3-10 ycloalkyl" refers to 3- to 10-membered all-carbon monocyclic, 3- to 10-membered all- carbon bicyclic, all-carbon 5-membered / 6-membered or 6-membered / 6-membered fused rings, polycyclic fused ring ("fused" ring systems refer to each ring in the system sharing one adjacent pair of carbon atoms with each other ring in the system) groups, wherein one or more rings can include one or more double bonds, but none of which have a completely conjugated pi-electron system, and bridged all-carbon ring systems. Examples of cycloalkyl groups include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, cyclohexene, cyclohexadiene, adamantane, cycloheptane, cycloheptatriene, and the like. Cycloalkyl groups can be substituted or unsubstituted. Typical substituents include alkyl, aryl, heteroaryl, heteroalicyclyl, hydroxy, alkoxy, aryloxy, thiohydroxy, alkylthio, arylthio, cyano, halogen, carbonyl, thiocarbonyl, carboxy, O-carbamyl, N-carbamyl, amido, nitro, amino, and the like. "Cycloalkylene" refers to the divalent form of a cycloalkyl group, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, or cyclodecylene, decahydronaphthyl.

[0042] "3-10 membered heterocyclyl" refers to a 3-10 membered ring radical, saturated or unsaturated, containing 1, 2, 3, or 4 ring heteroatoms selected from N, O, and S. 3-10 The carbon atoms in the cycloalkyl group are replaced in 1, 2, 3, or 4 positions by a heteroatom selected from N, O, and S. Examples of heterocyclyl groups include, but are not limited to, azetidinyl, pyrrolidinyl, imidazolinyl, pyrazolidinyl, thiazolidinyl, tetrahydrothienyl, tetrahydrofuranyl, dioxolanyl, and the like.

[0043] "C 6-10 "Aryl" refers to a fully carbon monocyclic or fused polycyclic ring radical of 6 to 10 carbon ring atoms having a completely conjugated pi-electron system. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, and the like. The aryl group can be substituted or unsubstituted. Typical substituents include halo, trihalomethyl, alkyl, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio, cyano, nitro, carbonyl, thiocarbonyl, carboxy, amido, amino, and the like. "Aryloxy" refers to the group -O-aryl, e.g., phenoxy. "Arylamine" refers to the group -NR'aryl, where R' is hydrogen or alkyl. 6-10 "Aryloxy" refers to the group -O-aryl, e.g., phenoxy.

[0044] "5-10 membered heteroaryl" refers to a monocyclic or fused polycyclic ring radical of 5 to 10 ring atoms containing 1, 2, 3, or 4 ring heteroatoms selected from N, O, and S, and having a completely conjugated pi-electron system. Examples of unsubstituted heteroaryl groups include, but are not limited to, pyrrolyl, pyrazolyl, triazolyl, tetrazolyl, furanyl, thiophenyl, imidazolyl, oxazolyl, thiazolyl, pyridyl, pyrimidyl, quinolyl, isoquinolyl, purinyl, triazinyl. The heteroaryl group can be substituted or unsubstituted. Typical substituents include alkyl, cycloalkyl, halo, trihalomethyl, hydroxy, alkoxy, aryloxy, mercapto, alkylthio, arylthio, cyano, nitro, carbonyl, thiocarbonyl, carboxy, amido, amino, and the like.

[0045] "Halo" or "halogen" refers to fluoro, chloro, bromo, and iodo.

[0046] "Ester" refers to the group -C(O)-O-R' or R'-C(O)-O-, where R is substituted or unsubstituted alkyl or aryl as defined herein.

[0047] "Ureido" refers to the group -NR'-C(O)-NR"R"' where R', R", R'" are each independently substituted or unsubstituted alkyl or aryl as defined herein.

[0048] "Amido" refers to C- or N-amido, i.e., -C(O)-NR'R" and -NR'C(O)R" groups, respectively, where R', R" are each independently hydrogen, or substituted or unsubstituted alkyl or aryl as defined herein.

[0049] "Amino" or "amido" means an -NR'2 group, where each R' is independently selected from hydrogen, substituted or unsubstituted alkyl, or aryl, as defined herein.

[0050] "Hydroxy" means an -OH group.

[0051] "Carboxy" means a -C(O)-O-H group.

[0052] "Nitro" means a -NO2 group.

[0053] "Cyano" means a -C≡N group.

[0054] "Cyanate" means an -O-C≡N group.

[0055] In a first aspect, the present disclosure provides a copolyamide including a copolymerization structural unit represented by the following formula (1) to (4);

[0056] wherein,

[0057] represents a chemical bond;

[0058] R1is selected from substituted or unsubstituted C 1-20 alkylene;

[0059] R2is selected from substituted or unsubstituted C 1-12 alkylene, substituted or unsubstituted C 3-10 cycloalkylene, substituted or unsubstituted 3-10 membered heterocyclylene, substituted or unsubstituted C 6-10 arylene, substituted or unsubstituted 5-10 membered heteroarylene, substituted or unsubstituted -R a '-NH-(R a -NH) n -R a '-, substituted or unsubstituted -R b '-O-(R b -O) n' -R b '-, substituted or unsubstituted -R c "-O-(C(O)-R c -C(O)-O-R c '-O) n” -C(O)-R c -C(O)-O-R c "-, substituted or unsubstituted -R d '-(Si(R d )2-O) n”' -Si(R d )2-R d '-, wherein Ra , R a , R b , R b , R d each independently selected from substituted or unsubstituted C 2-10 alkylene, substituted or unsubstituted C 6-10 arylene, R c , R c , R c each independently selected from C 1-10 alkylene, substituted or unsubstituted C 6- 10 arylene, R d each independently selected from C 1-5 alkyl, C 1-5 alkoxy, C 6-10 aryl, n, n', n", n'" each independently represents an integer from 1 to 500;

[0060] the nitrogen-containing pendant group R3 is selected from one or more of substituted or unsubstituted amine group, quaternary ammonium cation, quaternary ammonium type zwitterion;

[0061] R4 is selected from one or more of substituted or unsubstituted C 2-12 alkylene, substituted or unsubstituted C 3-10 cycloalkylene, substituted or unsubstituted 3-10 membered heterocyclylene, substituted or unsubstituted C 6-10 arylene, substituted or unsubstituted 5-10 membered heteroarylene;

[0062] R1, R2 and R4 are optionally each independently substituted with one or more substituents selected from C 1-10 alkyl, C 1-10 alkoxy, C 3- 10 cycloalkyl, 3-10 membered heterocyclyl, C 6-10 aryl and 5-10 membered heteroaryl.

[0063] The present disclosure prepares a multi-copolyamide having the above structure by using a lactam compound, a caprolactam having a nitrogen-containing pendant group, a dibasic acid and a dibasic amine in a one-step copolymerization, which has tunable properties (such as melting point, hardness, etc.), photoluminescence (which can convert part of 350-400 nm ultraviolet light into 450 nm blue light) and improved forming processing performance; and its pendant group can be selected and / or quaternized, thereby realizing flexible modification; its main chain structure can be adjusted, thereby adapting to different application fields of polyamide materials.

[0064] According to some embodiments of the present disclosure, R1is selected from one or more of ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene; preferably one or more of ethylene, butylene, nonylene, decylene, undecylene; more preferably butylene.

[0065] According to some embodiments of the present disclosure, R2is selected from one or more of ethylene, propylene, butylene, pentylene, hexylene, octylene, nonylene, furanylene, phenylene, -R a -NH-(R a -NH) n -R a '-, -R b '-O-(R b -O) n' -R b '-, -R d '-(Si(R d )2-O) n ” ' -Si(R d )2-R d '-, wherein R a , R a , R b , R b , R d are each independently selected from substituted or unsubstituted C 2-10 alkylene, substituted or unsubstituted C 6-10 arylene, preferably from one or more of ethylene, propylene, butylene, pentylene, phenyl, benzyl, R d are each independently selected from C 1-5 alkyl, C 1-5 alkoxy, C 6-10aryl, preferably one or more selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, phenyl, benzyl, n, n', n", n'" each independently represents an integer from 1 to 500, preferably an integer from 2 to 100. For example, n, n', n", n'" can each independently be selected from the group consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 1 1, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, 1 10, 120, 130, 140, 150, 160, 170, 180, 190, 200, 250, 300, 350, 400, 450, 500, or in a range consisting of any two of the aforementioned values.

[0066] According to some embodiments of the present disclosure, R2is selected from one or more of hexylene, phenylene, -R a -NH-(R a -NH) n -R a '-, -R b '-O-(R b -O) n' -R b '-, -R d '-(Si(R d )2-O) n”' -Si(R d )2-R d '-, wherein R a , R a , R b , R b , R d , R d , n, n', n'" are each as defined herein.

[0067] According to some embodiments of the present disclosure, R2has a molecular weight of 10-20000, preferably 50-3000. For example, R2may have a molecular weight of 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 15000, 20000, or in a range consisting of any two of the aforementioned values.

[0068] According to some embodiments of the present disclosure, R4 is selected from one or more of ethylene, propylene, butylene, pentylene, hexylene, octylene, nonylene, furanylene, phenylene.

[0069] According to some embodiments of the present disclosure, the nitrogen-containing pendant group R3 has a structure as shown in formula (5) or formula (6),

[0070] wherein L1 and L2 are the same or different, and each is independently selected from hydrogen, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted C 2-12 alkenyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted 3-20 membered heterocyclyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted 5-20 membered heteroaryl, -CHR a1 P(O)R a2 R a3 alkyl, C 1-5 alkenyl, C 1-5 alkoxy, C 2-5 alkyl, C 3-20 cycloalkyl, 3-20 membered heterocyclyl, C 6-20 aryl, 5-20 membered heteroaryl, C 1-10 ester, urea, C 1-10 amide, amine, hydroxyl, carboxyl, cyano, cyanate; or L1 and L2, together with the N atom to which they are attached, form a 5-20 membered saturated or unsaturated heterocyclic ring; L1 and L2 are optionally each independently substituted with one or more substituents selected from halogen, C

[0071] R a1 alkyl, substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted C 2-12 alkenyl, substituted or unsubstituted C 3-20 cycloalkyl, substituted or unsubstituted 3-20 membered heterocyclyl, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted 5-20 membered heteroaryl; R a1 alkyl, C 1-5 alkyl, C 1-5 alkoxy, C 1-5 haloalkyl, C 1-5 hydroxyalkyl, C 1- 5haloalkoxy, C 2-5 alkenyl, C 3-20 cycloalkyl, 3-20 membered heterocyclyl, C 6-20 aryl, C 6- 20 aryloxy, C 6-20 haloaryl, C6-20 Hydroxyaryl, C 6-20 The substituted group is one or more of the following: haloaryloxy, 5-20 heteroaryl, amino, hydroxyl, carboxyl, cyano, (2-oxo-3-azacycloheptane-1-ylamino)(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl)methimide;

[0072] R a2 and R a3 Each was independently selected from C 1-5 Alkoxy, C 6-10 aryloxy group, or R a2 and R a3 Together with the attached phosphoryl group P(O), it forms 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl;

[0073] L1' and L2' may be the same or different, and each is independently selected from substituted or unsubstituted C. 1-12 Alkyl, substituted or unsubstituted C 3-10 Cycloalkyl, substituted or unsubstituted 3-10 membered heterocyclic groups, substituted or unsubstituted C 6-10 One or more of aryl, substituted or unsubstituted 5-10 heteroaryl groups; L1' and L2' are each optionally independently selected from C 1-5 Alkyl, C 1-5 Alkoxy, C 3-10 Cycloalkyl, 3-10 membered heterocyclic groups, C 6-10 The aryl group is substituted by one or more substituents from 5-10 heteroaryl groups;

[0074] L3' is selected from hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-10 Cycloalkyl, substituted or unsubstituted 3-10 membered heterocyclic groups, substituted or unsubstituted C 6-10 One or more of aryl, substituted or unsubstituted 5-10 heteroaryl groups; L3' is optionally selected from C 1-5 Alkyl, C 1-5 Alkoxy, C 3-10 Cycloalkyl, 3-10 membered heterocyclic groups, C 6-10 Aryl, 5-10 heteroaryl, sulfonate group -SO 3- One or more substituents are replaced by L3'. When L3' has a sulfonate group, the nitrogen-containing side group R3 is a quaternary ammonium zwitterion.

[0075] According to some embodiments of the present disclosure, L1and L2are the same or different and each is independently selected from one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, benzyl, furanyl. Preferably, L1and L2are the same and selected from one or more of methyl, ethyl, propyl, butyl, benzyl.

[0076] According to some embodiments of the present disclosure, one of L1and L2is hydrogen and the other is selected from one or more of -CHR a1 P(O)R a2 R a3 , wherein R a1 , R a2 , R a3 are each as defined herein. Preferably, R a1 is selected from methyl, phenyl, benzyl, naphthyl, anthryl, phenanthryl, pyrenyl, furanyl, R a1 is optionally substituted with one or more substituents selected from methyl, phenyl, amino, dimethylamino, hydroxyl, hydroxymethyl, (2-oxo-3-azacycloheptan-l-ylamino)(9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide-10-yl)methylidene, R a2 and R a3 together with the attached phosphoryl P(O) form a 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide-10-yl group. For example, R a1 may be selected from one or more of phenyl, phenyl-substituted methyl, methyl- substituted phenyl, anthryl, dimethylamino-substituted phenyl, hydroxyl-substituted benzyl, furanyl, hydroxymethyl-substituted furanyl, (2-oxo-3-azacycloheptan-l-ylamino)(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl)methylidene-substituted phenyl; and R a2 and R a3 may together with the attached phosphoryl P(O) form a 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide-10-yl group.

[0077] According to some embodiments of the present disclosure, L1and L2are the same or different and each is independently selected from one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, benzyl, furanyl; L3is selected from one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, phenyl, L3is optionally substituted with one or more substituents selected from methyl, ethyl, propyl, a sulfonate group -SO 3-

[0078] ​According to some embodiments of the present disclosure, when the nitrogen-containing pendant group R3is a quaternary ammonium cation, the copolyamide further comprises a counter anion selected from one or more of a halide ion, a sulfonate ion; preferably, the halide ion is selected from a bromide ion and / or a chloride ion.

[0079] By introducing a nitrogen-containing pendant group into the copolyamide structure, it is possible to impart photoluminescent properties to the copolyamide, and to reduce the melting point of the copolyamide, improving its processability. By selecting and / or quaternising the substituent group on the nitrogen-containing pendant group, the copolyamide can be flexibly modified to impart additional functional benefits to the polyamide material, for example by selecting a phosphorus-containing substituent group to impart flame retardant properties to the polyamide material; by quaternising the copolyamide, a quaternised copolyamide can be obtained which has alcohol solubility, antibacterial properties and antistatic properties.

[0080] According to some embodiments of the present disclosure, the copolymerisation units of formulae (1) to (4) are bound together by amide bonds.

[0081] According to some embodiments of the present disclosure, the weight percentage of the copolymerisation unit of formula (1) is 1 to 50 wt%, preferably 1 to 40 wt%, based on the weight of the copolyamide. For example, the weight percentage of the copolymerisation unit of formula (1) can be 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, or within a range formed by any two of the aforementioned values.

[0082] According to some embodiments of the present disclosure, the weight percentage of the copolymerisation unit of formula (2) is 1 to 95 wt%, preferably 5 to 90 wt%, based on the weight of the copolyamide. For example, the weight percentage of the copolymerisation unit of formula (2) can be 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, or within a range formed by any two of the aforementioned values.

[0083] According to some embodiments of the present disclosure, the weight percentage of the copolymerized structural unit represented by formula (3) is 1-90 wt%, preferably 1-70 wt%, based on the weight of the copolyamide. For example, the weight percentage of the copolymerized structural unit represented by formula (3) can be 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or within a range consisting of any two of the aforementioned values.

[0084] According to some embodiments of the present disclosure, the weight percentage of the copolymerized structural unit represented by formula (4) is 1-50 wt%, preferably 1-40 wt%, based on the weight of the copolyamide. For example, the weight percentage of the copolymerized structural unit represented by formula (4) can be 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, or within a range consisting of any two of the aforementioned values.

[0085] In the present disclosure, the weight percentage of each copolymerized structural unit in the copolyamide is calculated based on the feeding ratio in the reaction. Since the content of small molecule substances in the product obtained by the present disclosure is less than 10% of the feeding amount, those skilled in the art can understand that each copolymerized monomer substantially participates in the copolymerization reaction.

[0086] According to some embodiments of the present disclosure, R2in formula (3) is selected from substituted or unsubstituted C 1-12 alkylene, substituted or unsubstituted C 3-10 cycloalkylene, substituted or unsubstituted 3-10 membered heterocyclylene, substituted or unsubstituted C 6-10 arylene, substituted or unsubstituted 5-10 membered heteroarylene, substituted or unsubstituted -R a '-NH-(R a -NH) n -R a '-, substituted or unsubstituted -R b '-O-(R b -O) n' -R b '-, substituted or unsubstituted -R c "-O-(C(O)-R c -C(O)-O-R c '-O) n” -C(O)-R c -C(O)-O-R c "-, substituted or unsubstituted -Rd '-(Si(R d )2-O) n”' -Si(R d )2-R d '-, where R a R a '、R b R b '、R c R c '、R c "、R d R d Each of the following is defined in this paper: n, n', n”, n”' each independently represents an integer from 1 to 4;

[0087] Wherein, the weight of the copolyamide is used as a basis,

[0088] The weight percentage of the copolymer structural unit shown in formula (1) is 1–50 wt%, preferably 1–40 wt%.

[0089] The copolymer structural unit shown in formula (2) has a weight percentage of 1–95 wt%, preferably 5–90 wt%.

[0090] The weight percentage of the copolymer structural unit shown in formula (3) is 1–50 wt%, preferably 1–40 wt%.

[0091] The weight percentage of the copolymer structural unit shown in formula (4) is 1 to 50 wt%, preferably 1 to 40 wt%.

[0092] According to other embodiments of this disclosure, the copolymer structural unit shown in formula (3) forms a soft segment of the copolyamide, and the copolymer structural units shown in formulas (1) and (2) form a hard segment of the copolyamide, thereby enabling the copolyamide to form an elastomer structure having both soft and hard segments, wherein R2 in formula (3) is selected from substituted or unsubstituted -R a '-NH-(R a -NH) n -R a '-, substituted or unsubstituted -R b '-O-(R b -O) n' -R b '-, substituted or unsubstituted -R c "-O-(C(O)-R c -C(O)-OR c '-O) n” -C(O)-R c -C(O)-OR c "-, substituted or unsubstituted -R d '-(Si(Rd )2-O) n”' -Si(R d )2-R d '-, where R a R a '、R b R b '、R c R c '、R c "、R d R d Each of the following is defined as follows: n, n', n”, n”' each independently represents an integer from 5 to 500, preferably an integer from 10 to 100.

[0093] According to some preferred embodiments of this disclosure, the hard segment can be a random copolymer segment, block copolymer segment, or alternating copolymer segment of a lactam compound and caprolactam having nitrogen-containing side groups.

[0094] According to some preferred embodiments of this disclosure, the hard segment may have the following structure.

[0095] In this context, x and y may be the same or different, and each is independently selected from any integer from 1 to 50.

[0096] According to some preferred embodiments of this disclosure, the number-average molecular weight of the soft segments is 800 to 20,000, preferably 900 to 3,000; for example, the number-average molecular weight of the soft segments can be 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 15000, 20000, or within a range consisting of any two of the above values. The number-average molecular weight of the hard segments is 800 to 10,000, preferably 1,000 to 5,000; for example, the number-average molecular weight of the hard segments can be 800, 900, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, or within a range consisting of any two of the above values.

[0097] According to some preferred embodiments of the present disclosure, the weight percentage of the soft segment is 20-90 wt%, preferably 40-80 wt%, more preferably 50-70 wt%, based on the weight of the copolyamide; for example, the weight percentage of the soft segment can be 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or within a range consisting of any two of the aforementioned values. The weight percentage of the hard segment is 10-80 wt%, preferably 20-60 wt%, more preferably 30-50 wt%; for example, the weight percentage of the hard segment can be 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, or within a range consisting of any two of the aforementioned values.

[0098] According to some preferred embodiments of the present disclosure, the molar ratio of the copolymerized structural unit represented by formula (1) to the copolymerized structural unit represented by formula (2) in the hard segment is 0.01-100:1, preferably 0.02-50:1. For example, the molar ratio of the copolymerized structural unit represented by formula (1) to the copolymerized structural unit represented by formula (2) in the hard segment can be 0.01:1, 0.02:1, 0.05:1, 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 5:1, 10:1, 20:1, 50:1, 100:1, or within a range consisting of any two of the aforementioned values.

[0099] By introducing the soft segment structure into the main chain of the copolyamide, a copolyamide elastomer material with special properties can be formed, thereby adapting to different application fields of polyamide materials. The copolyamide elastomer material of the present disclosure has adjustable melting point and hardness and other properties, and exhibits photoluminescence, antistatic, high light transmission and other performances. The optical performance of the copolyamide elastomer material is to block the transmission of ultraviolet light below 400 nm, convert ultraviolet light of 350-400 nm into blue light, and has a high transmittance to visible light. The introduction of the soft segment structure also helps to reduce the crystallinity of the copolyamide, further reduce the melting point, and significantly improve the molding processing performance.

[0100] According to some embodiments of the present disclosure, the copolyamide is a linear copolyamide. Preferably, the copolyamide is a linear random copolymer or a linear block copolymer. According to some embodiments of the present disclosure, the linear copolyamide can be further crosslinked due to the presence of reactive substituents on the main chain or side groups.

[0101] In a second aspect, the present disclosure provides a method for preparing a copolyamide, the method comprising: contacting a lactam compound, a caprolactam having a nitrogen-containing pendant group, a diacid and a diamine under an inert atmosphere to perform a copolymerization reaction,

[0102] wherein the lactam compound has a structure as shown in formula (I) below, the caprolactam having a nitrogen-containing pendant group has a structure as shown in formula (II) below, the diamine has a structure as shown in formula (III) below, and the diacid has a structure as shown in formula (IV) below,

[0103] wherein,

[0104] R1, R2, R4 are each as defined above, and the nitrogen-containing pendant group R3 is a substituted amine group.

[0105] According to some embodiments of the present disclosure, the caprolactam having a nitrogen-containing pendant group has a structure as shown in formula (II),

[0106] wherein L3 and L4 are each as defined above for L1 and L2, with the proviso that L3 and L4 are not hydrogen at the same time. The presence of L3 and / or L4 can allow the nitrogen-containing pendant group R3 to not undergo amidation reaction during the copolymerization process.

[0107] According to some embodiments of the present disclosure, the caprolactam having a nitrogen-containing pendant group is selected from one or more of dimethylaminocaprolactam, diethylaminocaprolactam, dipropylaminocaprolactam, dibutylaminocaprolactam, dibenzylaminocaprolactam, and phosphorus group-substituted aminocaprolactam. The specific structures are shown as follows:

[0108] wherein the phosphorus group-substituted aminocaprolactam can be selected from one or more of the following compounds:

[0109] The caprolactam having a nitrogen-containing pendant group used in the present disclosure can be prepared from lysine, preferably bio-based lysine, which has a molecular structure as shown below,

[0110] The caprolactam having a nitrogen-containing pendant group can be prepared by methods known in the art, which are not specifically limited in the present disclosure. Herein, the present disclosure exemplarily and non-restrictively provides a method for preparing the phosphorus group-substituted aminocaprolactam as described above from an aminocaprolactam, an aldehyde compound and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), which comprises the following steps:

[0111] S1: amino caprolactam and aldehyde compound are added into a reactor with temperature control device and stirring device in a molar ratio of 1:1, solvent is added, and the reaction is carried out under stirring at a temperature of 0-100°C, after the reaction is completed, cooling, filtration, drying, and an imine intermediate product is obtained;

[0112] S2: the imine intermediate product obtained in step S1 and 9,10-dihydro-9-oxa-10- phosphaphenanthrene-10-oxide (DOPO) are added into a reactor with temperature control device and stirring device in a molar ratio of 1:1, solvent is added, and the reaction is carried out under stirring at a temperature of 0-80°C, after the reaction is completed, cooling, filtration, washing, drying, and a solid form of amino caprolactam substituted with phosphorus group is obtained;

[0113] The reaction process in the above steps S1 and S2 is as follows:

[0114] The aldehyde compound is selected from one or more of benzaldehyde, phenylacetaldehyde, m-methylbenzaldehyde, 9-anthracenaldehyde, 4-dimethylaminobenzaldehyde, salicylaldehyde, furfural, hydroxymethylfurfural, p-xylylene and m-xylylene.

[0115] The solvent is selected from one or more of DMF, toluene, xylene, ethanol, ethylene glycol, DMSO, dioxane, tetrahydrofuran, dichloromethane and water.

[0116] According to some embodiments of the present disclosure, the lactam compound can be selected from one or more of butyrolactam, valerolactam, caprolactam, heptalactam, octalactam, nonalactam, decalactam, undecalactam, dodecalactam and tridecalactam, preferably one or more of butyrolactam, caprolactam, undecalactam, dodecalactam and tridecalactam, and more preferably caprolactam.

[0117] According to some embodiments of the present disclosure, the diacid is one or more of phthalic acid, adipic acid, azelaic acid, oxalic acid, sebacic acid, suberic acid, and furandicarboxylic acid.

[0118] According to some embodiments of the present disclosure, the diacid is one or more of phthalic acid, adipic acid, azelaic acid, oxalic acid, sebacic acid, suberic acid, and furandicarboxylic acid.

[0119] According to some embodiments of the present disclosure, the conditions of the copolymerization reaction include: being carried out under stirring, a reaction temperature of 180-280°C, preferably 200-260°C, for example, the reaction temperature can be 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, or within a range consisting of any two of the aforementioned values; a reaction time of 1-10h, preferably 3-8h, for example, the reaction time can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or within a range consisting of any two of the aforementioned values.

[0120] According to some embodiments of the present disclosure, the inert atmosphere includes one or more of nitrogen, helium, and argon, preferably nitrogen.

[0121] According to some embodiments of the present disclosure, the method further includes a premixing step, the temperature of the premixing being 80-120°C, preferably 90-110°C; the time of the premixing being 0.5-3h, preferably 1-2h. The premixing step is advantageous for further improving the reaction efficiency.

[0122] According to some embodiments of the present disclosure, in the method, no anionic initiator or anionic catalyst and water are added.

[0123] According to some embodiments of the present disclosure, the weight percentage of the caprolactam having a nitrogen-containing pendant group is 1-50 wt%, preferably 1-40 wt%, for example, it can be 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, or within a range consisting of any two of the above values; the weight percentage of the lactam compound is 1-95 wt%, preferably 5-90 wt%, for example, it can be 1 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, or within a range consisting of any two of the above values; the weight percentage of the dibasic acid is 1-50 wt%, preferably 1-40 wt%, for example, it can be 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, or within a range consisting of any two of the above values; the weight percentage of the dibasic amine is 1-90 wt%, preferably 1-70 wt%, for example, it can be 1 wt%, 3 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, or within a range consisting of any two of the above values.

[0124] According to some embodiments of the present disclosure, the molar ratio of the dibasic acid to the dibasic amine is 1:0.9-1.1, preferably 1:1.

[0125] According to some embodiments of the present disclosure, the molar ratio of the lactam compound to the caprolactam having a nitrogen-containing pendant group is 0.01-100:1, preferably 0.02-50:1. For example, the molar ratio of the lactam compound to the caprolactam having a nitrogen-containing pendant group can be 0.01:1, 0.02:1, 0.05:1, 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 5:1, 10:1, 20:1, 50:1, 100:1, or within a range consisting of any two of the above values.

[0126] According to some embodiments of the present disclosure, the method further comprises: contacting the copolyamide with a quaternary ammonium reagent in a solvent to perform a quaternary ammonium reaction, to obtain a quaternized copolyamide.

[0127] According to some embodiments of the present disclosure, the quaternary ammonium reagent is selected from a halogenated hydrocarbon and / or a sulfolane compound.

[0128] According to some embodiments of the present disclosure, the halogenated hydrocarbon has a structural formula of L3'-X, L3' is selected from one or more of hydrogen, a substituted or unsubstituted C 1-20 alkyl, a substituted or unsubstituted C 3-10 cycloalkyl, a substituted or unsubstituted 3-10 membered heterocyclyl, a substituted or unsubstituted C 6-10 aryl, a substituted or unsubstituted 5-10 membered heteroaryl; L3' is optionally substituted with one or more substituents selected from C 1-5 alkyl, C 1-5 alkoxy, C 3-10 cycloalkyl, 3-10 membered heterocyclyl, C 6-10 aryl, 5-10 membered heteroaryl; X is selected from one or more of chlorine, bromine and iodine.

[0129] According to some embodiments of the present disclosure, the halogenated hydrocarbon is selected from one or more of methyl bromide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, hexyl bromide, heptyl bromide, octyl bromide, nonyl bromide, decyl bromide, dodecyl bromide, tetradecyl bromide, hexadecyl bromide, benzyl chloride.

[0130] According to some embodiments of the present disclosure, the sulfolane compound is selected from one or more of C 2-7 sulfolane, preferably one or more of 1,3-propane sulfolane, cyclopropane sulfolane, 1,4-butane sulfolane.

[0131] According to some embodiments of the present disclosure, the quaternary ammonium reaction has a reaction temperature of 0-60°C, preferably 20-60°C, for example, the reaction temperature can be 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, or within a range consisting of any two of the aforementioned values; and a reaction time of 1-10h, preferably 2-9h, for example, the reaction time can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, or within a range consisting of any two of the aforementioned values.

[0132] According to some embodiments of the present disclosure, the solvent for the quaternary ammonium reaction is selected from one or more of N,N-dimethylformamide, toluene, xylene, ethanol, ethylene glycol, dimethyl sulfoxide, dioxane, tetrahydrofuran, dichloromethane and water.

[0133] According to some embodiments of the present disclosure, the molar ratio of the quaternary ammonium reagent to the caprolactam having a nitrogen-containing pendant group is 0.1-1:1, preferably 0.5-1:1. For example, the molar ratio of the quaternary ammonium reagent to the caprolactam having a nitrogen-containing pendant group can be 0.1:1, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, or within a range consisting of any two of the aforementioned values.

[0134] The method of the present disclosure realizes efficient copolymerization of different reactive monomers to prepare a multi-copolyamide by using a lactam compound, a caprolactam having a nitrogen-containing pendant group, a diacid and a diamine, wherein the diacid on one hand catalyzes the copolymerization of the caprolactam having a nitrogen-containing pendant group and the lactam compound, and on the other hand participates in the reaction as a monomer; the diamine on one hand initiates the reaction, and on the other hand serves as a main chain structure regulator to enable the formation of copolymers with different properties. By simultaneously introducing the diamine and the diacid, the ratio of carboxyl groups to amino groups is balanced, and a copolymer with high molecular weight is prepared. The method of the present disclosure is a one-step process, simple and efficient, and the selected copolymerization monomers can be derived from renewable biological resources, effectively reducing the dependence on petroleum resources, thereby reducing production costs and improving overall economic efficiency.

[0135] In a third aspect, the present disclosure provides a copolyamide prepared by the method of the second aspect of the present disclosure.

[0136] According to some embodiments of the present disclosure, the copolyamide of the first aspect and / or the third aspect of the present disclosure can be a semi-crystalline polymer or an amorphous polymer. When the copolyamide is a semi-crystalline polymer, it is opaque, and when the copolyamide is an amorphous polymer, it is transparent; when the copolyamide is transparent, the material prepared therefrom has the property of preventing ultraviolet light from penetrating and allowing visible light to penetrate.

[0137] According to some embodiments of the present disclosure, the crystallization temperature of the copolyamide is 70-230°C. For example, the crystallization temperature of the copolyamide can be 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, or within a range consisting of any two of the aforementioned values. In the present disclosure, the crystallization temperature can be measured, for example, according to the standard method ASTM D3418-21.

[0138] According to some embodiments of the present disclosure, the melting point of the copolyamide is 80-250 °C. For example, the melting point of the copolyamide can be 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C, 180 °C, 190 °C, 200 °C, 210 °C, 220 °C, 230 °C, 240 °C, 250 °C, or within a range consisting of any two of the aforementioned values. In the present disclosure, the melting point may, for example, be measured according to the ASTM D3418-21 standard method.

[0139] According to some embodiments of the present disclosure, the thermal decomposition temperature of the copolyamide is 300-450 °C, preferably 350-400 °C. For example, the thermal decomposition temperature of the copolyamide can be 300 °C, 310 °C, 320 °C, 330 °C, 340 °C, 350 °C, 360 °C, 370 °C, 380 °C, 390 °C, 400 °C, 410 °C, 420 °C, 430 °C, 440 °C, 450 °C, or within a range consisting of any two of the aforementioned values. In the present disclosure, the thermal decomposition temperature may, for example, be measured according to the ASTM E1131-08(2014) standard method.

[0140] According to some embodiments of the present disclosure, the biochar content of the copolyamide is 1 wt% or more, preferably 1-50 wt%, more preferably 10-40 wt%. In the present disclosure, biochar refers to a substance derived from a bio-based source, and the biochar content in the present disclosure can be calculated according to the feed ratio of caprolactam having a nitrogen-containing side group in the preparation method.

[0141] According to some embodiments of the present disclosure, the number average molecular weight of the copolyamide is 5000 or more, for example, 5000-100000. For example, the number average molecular weight of the copolyamide can be 5000, 6000, 7000, 8000, 9000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, or within a range consisting of any two of the aforementioned values. In the present disclosure, the number average molecular weight may, for example, be calculated by gel permeation chromatography.

[0142] According to some embodiments of the present disclosure, the molecular weight distribution of the copolyamide is 1-5, for example, 1.2-3.5. For example, the molecular weight distribution of the copolyamide can be 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, 3, 3.2, 3.5, 3.8, 4, 4.2, 4.5, 5, or within a range consisting of any two of the aforementioned values. In the present disclosure, the molecular weight distribution may, for example, be calculated by gel permeation chromatography.

[0143] In a fourth aspect, this disclosure provides for the application of the copolyamides described in the first aspect and / or the third aspect of this disclosure.

[0144] According to some embodiments of this disclosure, the copolyamide possesses tunable melting point, hardness, and other properties, photoluminescence, and improved molding and processing performance. For example, the copolyamide of this disclosure exhibits photoluminescence properties, blocking the transmission of ultraviolet light below 400 nm and converting ultraviolet light in the 350–400 nm range into blue light. Further functional benefits can be achieved by modifying the main chain and side groups of the copolyamide. On one hand, by introducing soft segment structures into the main chain, a copolyamide elastomer can be formed, which helps reduce the crystallinity of the copolyamide, further lowers the melting point, significantly improves molding and processing performance, and also improves antistatic properties. On the other hand, by introducing phosphorus-containing groups through substituents of nitrogen-containing side groups, polyamide materials with excellent flame-retardant properties can be obtained. Furthermore, by quaternizing the copolyamide, polyamide materials with excellent antibacterial properties can be obtained. Therefore, the copolyamide disclosed herein can be used in the preparation of engine materials, circuit board materials, composite materials for transportation, anti-counterfeiting materials, UV-resistant coatings, optical materials, medical devices, high-transparency polyamide products, antibacterial materials, antistatic materials and / or flame-retardant materials.

[0145] According to some embodiments of this disclosure, the application of the copolyamide elastomer of this disclosure in optical materials, antistatic materials, toughening fillers, and highly transparent polyamide products is provided.

[0146] According to some embodiments of this disclosure, the application of the phosphorus-containing copolyamide of this disclosure in flame-retardant materials is provided.

[0147] According to some embodiments of this disclosure, the application of the quaternized copolyamide of this disclosure in antistatic and / or antimicrobial materials is provided.

[0148] The present invention also discloses the following embodiments:

[0149] I-1. A linear copolyamide, characterized in that it comprises a copolymer formed from a lactam compound, caprolactam having a nitrogen-containing side group, a diacid, and a diamine; the linear copolyamide comprises a first repeating unit as shown in formula (1) and a second repeating unit as shown in formula (2).

[0150] Where R1 is C 1～20 The substituted or unsubstituted alkylene group of R1; the substituents of R1 include C 1～5 alkyl, C 6～10 aryl and C 3～10 One or more of the heteroaryl groups; the nitrogen-containing side group R3 is an amino group with a substituent.

[0151] I-2. The linear co-polyamide according to aspect I-1, wherein the nitrogen-containing pendant group R3 has a structure as shown in formula (a),

[0152] wherein L1and L2are the same or different, each independently comprising one or more of hydrogen, C 1～12 substituted or unsubstituted alkyl, C 3～20 substituted or unsubstituted cycloalkyl, C 6～20 substituted or unsubstituted aryl, C 3～20 substituted or unsubstituted heteroaryl; and at most only one of L1and L2is hydrogen;

[0153] the substituents of L1and L2each independently comprise one or more of C 1～5 alkyl, C 6～10 aryl, C 4～10 furyl.

[0154] I-3. The linear co-polyamide according to aspect I-1, wherein L1and L2are the same or different, each independently one or more of methyl, ethyl, propyl, butyl, and benzyl.

[0155] I-4. The linear co-polyamide according to aspect I-1, wherein the linear co-polyamide comprises a third repeating unit as shown in formula (3),

[0156] wherein R2is one or more of C 1～12 substituted or unsubstituted alkylene, C 2～30 substituted or unsubstituted ether, C 2～60 substituted or unsubstituted imine, C 3～20 substituted or unsubstituted cycloalkylene, C 6～20 substituted or unsubstituted arylene, and C 3～20 substituted or unsubstituted heteroarylene; 1～5 alkyl, C 6～10 aryl, and C 3～10 heteroaryl.

[0157] Preferably, R2comprises one or more of ethylene, propylene, butylene, pentylene, hexylene, furanylene, and phenylene.

[0158] I-5. The linear co-polyamide according to aspect I-4, wherein the weight percentage of the third repeating unit is 1-50%, preferably 1-40%, based on the weight of the linear co-polyamide.

[0159] I-6. The linear co-polyamide according to solution I-1, wherein the linear co-polyamide comprises a fourth repeating unit represented by the following formula (4),

[0160] wherein R4 is one or more of a substituted or unsubstituted alkylene, a substituted or unsubstituted arylene, and a substituted or unsubstituted heteroarylene; the substituents of R4 each independently comprise one or more of an alkyl, an aryl, and a heteroaryl; 2～12 6～20 3～20 1～5 6～10 3～10

[0161] Preferably, R4 comprises one or more of an ethylene, a propylene, a butylene, a hexylene, an octylene, a nonylene, a furanylene, and a phenylene.

[0162] I-7. The linear co-polyamide according to solution I-6, wherein the weight percentage of the fourth repeating unit is 5-50%, preferably 5-40%, based on the weight of the linear co-polyamide.

[0163] I-8. The linear co-polyamide according to solution I-1, wherein the weight percentage of the first repeating unit is 1-50%, preferably 10-40%, and the weight percentage of the second repeating unit is 1-95%, preferably 5-80%, based on the weight of the linear co-polyamide.

[0164] I-9. A method for preparing a linear co-polyamide, the method comprising: contacting a lactam compound, a caprolactam having a nitrogen-containing pendant group, a diacid, and a diamine in an inert atmosphere to perform a co-polymerization reaction,

[0165] wherein the lactam compound has a structure represented by the following formula (I), and the caprolactam having a nitrogen-containing pendant group has a structure represented by the following formula (II),

[0166] wherein R1 is one or more of a substituted or unsubstituted alkylene, the substituents of R1 comprising one or more of an alkyl, an aryl, and a heteroaryl; and the nitrogen-containing pendant group R3 is an amine group having a substituent. 1～20 1～5 6～10 3～10

[0167] I-10. The method according to solution I-9, wherein the caprolactam having a nitrogen-containing pendant group has a structure represented by the following formula,

[0168] ​​​​​​​​​​wherein L1and L2are the same or different and each independently comprises one or more of hydrogen, C 1～12 substituted or unsubstituted alkyl, C 3～20 substituted or unsubstituted cycloalkyl, C 6～20 substituted or unsubstituted aryl, C 4～20 substituted or unsubstituted furanyl; and at most only one of L1and L2is hydrogen;

[0169] substituents of L1and L2each independently comprise one or more of C 1～5 alkyl, C 6～10 aryl, and C 4～10 heteroaryl.

[0170] I-11. The method of aspect I-9, wherein the caprolactam having a pendant nitrogen-containing group comprises one or more of methylaminocaprolactam, dimethylaminocaprolactam, ethylaminocaprolactam, diethylaminocaprolactam, propylaminocaprolactam, dipropylaminocaprolactam, butylaminocaprolactam, dibutylaminocaprolactam, benzylaminocaprolactam, and dibenzylaminocaprolactam.

[0171] Optionally, the caprolactam having a pendant nitrogen-containing group is prepared from lysine.

[0172] I-12. The method of aspect I-9, wherein the diamine has a structure according to Formula (III), H2N— R2— NH2

[0173] Formula (III),

[0174] R2is C 1～12 substituted or unsubstituted alkylene, C 2～30 substituted or unsubstituted ether, C 2～60 substituted or unsubstituted imine, C 3～20 substituted or unsubstituted cycloalkylene, C 6～20 substituted or unsubstituted arylene, and C 3～20 substituted or unsubstituted heteroarylene. Substituents of R2comprise one or more of C 1～5 alkyl, C 6～10 aryl, and C 3～10 heteroaryl.

[0175] I-13. The method of aspect I-9, wherein the diamine is one or more of a polyetheramine, a polyethyleneimine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, hexylenediamine, furandiamine, and p-phenylenediamine, preferably hexylenediamine and / or p-phenylenediamine.

[0176] I-14. The method of aspect I-9, wherein the dibasic acid has a structure of formula (IV),

[0177] wherein R4 is one or more of substituted or unsubstituted alkylene, C 2～12 substituted or unsubstituted arylene, and C 6～20 substituted or unsubstituted heteroarylene; each substituent of R4 independently comprises one or more of C 3～20 alkyl, C 1～5 aryl, and C 6～10 heteroaryl. 3～10

[0178] I-15. The method of aspect I-9, wherein the dibasic acid is one or more of phthalic acid, adipic acid, azelaic acid, oxalic acid, sebacic acid, suberic acid, and furandicarboxylic acid.

[0179] I-16. The method of aspect I-9, wherein the inert atmosphere comprises one or more of nitrogen, argon, preferably nitrogen; the mixing temperature is 80-120°C, preferably 90-110°C; and the mixing time is 0.5-3h, preferably 1-2h.

[0180] I-17. The method of aspect I-9, wherein the copolymerization conditions comprise a reaction temperature of 180-280°C and a reaction time of 1-10h; preferably, a reaction temperature of 200-260°C and a reaction time of 2-9h.

[0181] I-18. The method of aspect I-9, wherein the weight percentage of the caprolactam having a nitrogen-containing pendant group is 1-50%, preferably 5-40%, based on the total weight of the reaction raw materials; the weight percentage of the lactam compound is 1-95%, preferably 5-90%; the weight percentage of the dibasic acid is 5-50%, preferably 5-40%; and the weight percentage of the dibasic amine is 1-50%, preferably 3-40%.

[0182] I-19. A linear copolyamide prepared by the method of any one of aspects I-9 to I-18.

[0183] I-20. The linear copolyamide of aspect I-19, wherein the linear copolyamide has a crystallization temperature of 100-230°C and a thermal decomposition temperature of 300-450°C.

[0184] I-21. The linear copolyamide of aspect I-19, wherein the linear copolyamide has a melting point of 100-250°C.

[0185] ​I-22. The linear co-polyamide according to any one of the preceding items I-19, wherein the linear co-polyamide has a biochar content of 1 wt% or more, preferably 1 to 50 wt%.

[0186] I-23. Use of the linear co-polyamide according to any one of the preceding items I-1 to I-8 and I-19 to I-22.

[0187] II-1. A co-polyamide elastomer having a nitrogen-containing pendant group, wherein the co-polyamide elastomer comprises a co-polymer having hard segments and soft segments, the soft segments being polyether soft segments and / or polyester soft segments; the hard segments comprising repeating units of formula (1) and formula (2) below,

[0188] wherein the nitrogen-containing pendant group R3 is a substituted or unsubstituted amine group.

[0189] II-2. The co-polyamide elastomer according to item II-1, wherein the nitrogen-containing pendant group R3 has a structure of formula (3) below,

[0190] In formula (3), L1 and L2 are the same or different, and each is independently selected from one of hydrogen, a substituted or unsubstituted alkyl group having a carbon number of 1 to 12, a substituted or unsubstituted cycloalkyl group having a carbon number of 3 to 20, a substituted or unsubstituted aryl group having a carbon number of 6 to 20, and a substituted or unsubstituted furanyl group having a carbon number of 4 to 20; the substituents of L1 and L2 are each selected from one or more of an alkyl group having a carbon number of 1 to 5, an aryl group having a carbon number of 6 to 10, and a furanyl group having a carbon number of 4 to 10.

[0191] II-3. The co-polyamide elastomer according to item II-2, wherein L1 and L2 are the same or different, and each is independently selected from one or more of a methyl group, an ethyl group, a propyl group, a butyl group, and a benzyl group.

[0192] II-4. The co-polyamide elastomer according to item II-1, wherein the soft segments are bonded to the hard segments via amide bonds.

[0193] II-5. The co-polyamide elastomer according to item II-1, wherein the co-polymer further comprises a structural unit of formula (4) below,

[0194] wherein R4 is selected from a substituted or unsubstituted alkylene group having a carbon number of 2 to 12, a substituted or unsubstituted arylene group having a carbon number of 6 to 20, and a substituted or unsubstituted furanylene group having a carbon number of 4 to 20; the substituents of R4 are selected from one or more of an alkyl group having a carbon number of 1 to 5, an aryl group having a carbon number of 6 to 10, and a benzyl group.

[0195] II-6. The copolyamide elastomer according to aspect II-1, wherein the soft segment has a structure according to formula (5):

[0196] wherein R2 is a substituted or unsubstituted ether linkage having a carbon atom number of 10 to 500; the substituents of R2 are selected from one or more of an alkyl group having a carbon atom number of 1 to 5, an aryl group having a carbon atom number of 6 to 10, and a furanyl group having a carbon atom number of 4 to 10;

[0197] R2 has a number average molecular weight of 800 to 20,000, preferably 900 to 3,000;

[0198] R1 has a number average molecular weight of 800 to 10,000.

[0199] II-7. The copolyamide elastomer according to aspect II-1, wherein the copolymer has a structure according to formula (6):

[0200] wherein R1 comprises the repeating units according to formula (1) and formula (2); R2 is a substituted or unsubstituted ether linkage having a carbon atom number of 10 to 500; the substituents of R2 are selected from one or more of an alkyl group having a carbon atom number of 1 to 5, an aryl group having a carbon atom number of 6 to 10, and a furanyl group having a carbon atom number of 4 to 10; R4 is selected from a substituted or unsubstituted alkylene group having a carbon atom number of 2 to 12, a substituted or unsubstituted arylene group having a carbon atom number of 6 to 20, and a substituted or unsubstituted furanylene group having a carbon atom number of 4 to 20; the substituents of R4 are selected from one or more of an alkyl group having a carbon atom number of 1 to 5, an aryl group having a carbon atom number of 6 to 10, and a benzyl group.

[0201] II-8. A method of preparing a copolyamide elastomer having a nitrogen-containing pendant group, the method comprising: contacting a soft segment prepolymer and a hard segment monomer;

[0202] wherein the hard segment monomer comprises caprolactam and caprolactam having a nitrogen-containing pendant group, the nitrogen-containing pendant group being a substituted or unsubstituted amine group; the soft segment prepolymer is a polyether prepolymer or a polyester prepolymer, the soft segment prepolymer having at least one amine group.

[0203] II-9. The method according to aspect II-8, wherein the soft segment prepolymer has a structure according to formula, H2N— R2— NH2,

[0204] R2 is a substituted or unsubstituted ether linkage having a carbon atom number of 10 to 500; the substituents of R2 are selected from one or more of an alkyl group having a carbon atom number of 1 to 5, an aryl group having a carbon atom number of 6 to 10, and a furanyl group having a carbon atom number of 4 to 10;

[0205] II-10. The method of aspect II-9, wherein the soft segment prepolymer is selected from one or more of a polyetheramine, a diamino polysiloxane, a polyoxyethylene diamine, a polyoxypropylene diamine, a diamino poly(ethylene oxide-co-propylene oxide), and a poly(tetramethylene ether) diamine.

[0206] The soft segment prepolymer has a number average molecular weight of 800 to 20,000, preferably 900 to 3,000.

[0207] Optionally, the polyetheramine is selected from one or more of a polyetheramine D900, a polyetheramine D1000, and a polyetheramine D2000.

[0208] II-11. The method of aspect II-8, wherein the caprolactam having a nitrogen-containing pendant group has a structure according to the following formula,

[0209] wherein L3and L4are the same or different and each is independently selected from hydrogen, a substituted or unsubstituted alkyl group having a carbon atom number of 1 to 12, a substituted or unsubstituted cycloalkyl group having a carbon atom number of 3 to 20, a substituted or unsubstituted aryl group having a carbon atom number of 6 to 20, and a substituted or unsubstituted furanyl group having a carbon atom number of 4 to 20; the substituents of L3and L4are each selected from one or more of an alkyl group having a carbon atom number of 1 to 5, an aryl group having a carbon atom number of 6 to 10, and a furanyl group having a carbon atom number of 4 to 10.

[0210] II-12. The method of aspect II-11, wherein the caprolactam having a nitrogen-containing pendant group is selected from one or more of an aminocaprolactam, a methylaminocaprolactam, a dimethylaminocaprolactam, an ethylaminocaprolactam, a diethylaminocaprolactam, a propylaminocaprolactam, a dipropylaminocaprolactam, a butylaminocaprolactam, a dibutylaminocaprolactam, a benzylaminocaprolactam, and a dibenzylaminocaprolactam.

[0211] II-13. The method of aspect II-8, wherein the method further comprises adding a diacid compound to the reaction system for the contacting reaction; the diacid compound has a structure according to the following formula,

[0212] wherein R4is selected from a substituted or unsubstituted alkylene group having a carbon atom number of 2 to 12, a substituted or unsubstituted arylene group having a carbon atom number of 6 to 20, and a substituted or unsubstituted furanylene group having a carbon atom number of 4 to 20; the substituents of R4are selected from one or more of an alkyl group having a carbon atom number of 1 to 5 and an aryl group having a carbon atom number of 6 to 10.

[0213] II-14. The method according to the scheme II-13, wherein the dibasic acid compound is selected from one or more of phthalic acid, adipic acid, azelaic acid, oxalic acid, sebacic acid, suberic acid, and furandicarboxylic acid.

[0214] II-15. The method according to the scheme II-8, wherein the conditions of the contact reaction include: being carried out under an inert atmosphere, a reaction temperature of 180-280 °C, preferably 200-260 °C; a reaction time of 1-10 h, preferably 3-8 h.

[0215] The inert atmosphere includes one or more of nitrogen and argon.

[0216] II-16. The method according to the scheme II-8, wherein the weight of the soft segment prepolymer is 10-80 %, preferably 20-60 %, further preferably 30-50 %, based on the total weight of the reaction raw materials.

[0217] The molar ratio of the caprolactam to the caprolactam having a nitrogen-containing pendant group is 0.01-100:1, preferably 0.2-50:1.

[0218] II-17. The copolyamide elastomer having a nitrogen-containing pendant group prepared by the method according to any one of the schemes II-8-16.

[0219] II-18. The use of the copolyamide elastomer having a nitrogen-containing pendant group according to any one of the schemes II-1-7 and II-17 in the preparation of anti-counterfeiting materials, ultraviolet-resistant coatings, medical devices, high-transparency polyamide products, and anti-static materials.

[0220] III-1. A flame retardant, characterized in that it comprises a copolyamide, the copolyamide comprising a first repeating unit represented by formula (1), a second repeating unit represented by formula (2), a third repeating unit represented by formula (3), and a fourth repeating unit represented by formula (4),

[0221] wherein R is one or more of hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group; R1 is a substituted or unsubstituted alkylene group; R2 is a substituted or unsubstituted ether group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted heteroarylene group. 1～20 3～30 6～30 3～30 1～12 2～200 2～20 6～20 3～20 ​​​​​​​​one or more of substituted or unsubstituted alkyl, C 2～20 one or more of substituted or unsubstituted alkylene, C 6～20 one or more of substituted or unsubstituted arylene, and C 3～20 one or more of substituted or unsubstituted heteroarylene; the substituents of R1, R2, and R4 are each independently one or more of C 1～10 one or more of alkyl, C 6～20 one or more of aryl, and C 3～20 one or more of heteroaryl.

[0222] III-2, the flame retardant of aspect III-1, wherein, wherein R is hydrogen, C 1～12 one or more of substituted or unsubstituted alkyl, C 3～20 one or more of substituted or unsubstituted cycloalkyl, C 6～20 one or more of substituted or unsubstituted aryl, C 4～20 one or more of substituted or unsubstituted furanyl; the substituents of R are one or more of C 1～8 one or more of alkyl, C 6～10 one or more of aryl, C 4～10 one or more of furanyl, amine, hydroxyl; preferably, R is one or more of phenyl, benzyl, furanyl, anthracenyl, p-dimethylaminophenyl, phenol, furanyl, hydroxymethyl furanyl, dimethylphenyl; the substituents of R are one or more of methyl, ethyl, amine, hydroxyl.

[0223] preferably, R is one or more of benzyl, ethylphenyl, anthracenyl, p-dimethylaminophenyl, phenol, furanyl, hydroxymethyl furanyl, dimethylphenyl.

[0224] III-3, the flame retardant of aspect III-1, wherein R2 is C 2～150 one or more of substituted or unsubstituted alkylene, C 2～10 one or more of substituted or unsubstituted alkylene, C 6～15 one or more of substituted or unsubstituted arylene, and C 4～15 one or more of substituted or unsubstituted furanylene; the substituents of R2 include one or more of methyl, ethyl, propyl, butyl, and phenyl;

[0225] preferably, R2 includes one or more of ethylene, propylene, butylene, pentylene, hexylene, furanylene, and phenylene.

[0226] III-4, the flame retardant of aspect III-1, wherein R4 is C 2～10 one or more of substituted or unsubstituted alkylene, C 6～10 one or more of substituted or unsubstituted arylene, and C 4～10 one or more of substituted or unsubstituted furanylene; the substituents of R4 include one or more of methyl, ethyl, propyl, butyl, and phenyl;

[0227] Preferably, R4 includes one or more of ethylene, butylene, hexylene, octylene, nonylene, decylene, furanylene, and phenylene.

[0228] III-5. The flame retardant according to scheme III-1, wherein R1 is one or more of propylene, butylene, pentylene, hexylene, heptylene.

[0229] III-6. The flame retardant according to scheme III-1, wherein the weight percentage of the first repeating unit is 0.1-50%, the weight percentage of the second repeating unit is 0.1-99%, the weight percentage of the third repeating unit is 0.1-80 wt%, and the weight percentage of the fourth repeating unit is 0.1-50%, based on the weight of the copolyamide.

[0230] III-7. A method for preparing a flame retardant, the method comprising:

[0231] mixing a lactam compound, an amino caprolactam having a phosphorus-containing derivative, a dibasic acid, and a dibasic amine under an inert atmosphere, and then performing a copolymerization reaction;

[0232] wherein the lactam compound has a structure shown in formula (I), the amino caprolactam having a phosphorus-containing derivative has a structure shown in formula (II), the dibasic amine has a structure shown in formula (III), and the dibasic acid has a structure shown in formula (IV),

[0233] wherein R is one or more of hydrogen, C 1～20 substituted or unsubstituted alkyl, C 3～30 substituted or unsubstituted cycloalkyl, C 6～30 substituted or unsubstituted aryl, C 3～30 substituted or unsubstituted heteroaryl; R1 is one or more of C 1～12 substituted or unsubstituted alkylene, R2 is one or more of C 2～200 substituted or unsubstituted ether, C 2～20 substituted or unsubstituted alkylene, C 6～20 substituted or unsubstituted arylene, and C 3～20 substituted or unsubstituted heteroarylene; R4 is one or more of C 2～12 substituted or unsubstituted alkylene, C 6～20 substituted or unsubstituted arylene, and C 3～20 substituted or unsubstituted heteroarylene; the substituents of R1, R2, and R4 are each independently C 1～10 alkyl, C 6～20 aryl, and C3～20 one or more of the following: heteroaryl, heterocyclyl, aryl, and cycloalkyl.

[0234] III-8. The method of scheme III-7, wherein the amino caprolactam with phosphorus-containing derivative comprises one or more of the following compounds,

[0235] III-9. The method of scheme III-7, wherein the lactam compound comprises one or more of the following: caprolactam, caprylactam, undecanolactam, and laurolactam.

[0236] III-10. The method of scheme III-7, wherein the diamine comprises one or more of the following: polyether amine, ethylenediamine, propylenediamine, butylenediamine, pentylenediamine, furan diamine, p-phenylenediamine, butylenediamine, and hexamethylenediamine; preferably one or more of the following: hexamethylenediamine, polyether amine, and p-phenylenediamine.

[0237] III-11. The method of scheme III-7, wherein the diacid comprises one or more of the following: phthalic acid, adipic acid, azelaic acid, oxalic acid, sebacic acid, suberic acid, and furandicarboxylic acid.

[0238] III-12. The method of scheme III-7, wherein the inert atmosphere comprises one or more of the following: nitrogen, argon; preferably nitrogen; the mixing temperature is 80-120 °C, preferably 90-110 °C; the mixing time is 0.5-3 h, preferably 1-2 h.

[0239] III-13. The method of scheme III-7, wherein the copolymerization conditions comprise: reaction temperature is 180-280 °C, reaction time is 1-10 h; preferably, reaction temperature is 200-260 °C, reaction time is 2-9 h.

[0240] III-14. The method of scheme III-7, wherein in the copolymerization system, the weight content of the amino caprolactam with phosphorus-containing derivative is 0.1-50%, preferably 1-30%; the weight content of the lactam compound is 0.1-99%, preferably 1-90%; the weight content of the diacid is 0.1-50%, preferably 1-30 wt%; the weight content of the diamine is 0.1-80%, preferably 10-70%.

[0241] III-15. The flame retardant prepared by the method of any one of schemes III-7-14.

[0242] III-16. The flame retardant of scheme III-15, wherein the limiting oxygen index of the flame retardant is 30% or more, preferably 40% or more.

[0243] III-17. The flame retardant according to Scheme III-15, wherein the UL-94 fire rating of the flame retardant is V-0.

[0244] The application of flame retardants described in any one of schemes III-18, III-1 to III-6, and III-15 to III-17.

[0245] IV-1. A copolyamide quaternary ammonium compound, characterized in that the quaternary ammonium compound is a quaternary ammonium salt containing a copolyamide quaternary ammonium cation, or a quaternary ammonium salt-type zwitterionic compound;

[0246] The copolyamide quaternary ammonium cation includes a first copolymer structural unit as shown in formula (1-1), a second copolymer structural unit as shown in formula (2), a third copolymer structural unit as shown in formula (3), and a fourth copolymer structural unit as shown in formula (4);

[0247] The quaternary ammonium salt zwitterionic compound includes a first copolymer structural unit as shown in formula (1-2), a second copolymer structural unit as shown in formula (2), a third copolymer structural unit as shown in formula (3), and a fourth copolymer structural unit as shown in formula (4);

[0248] In formula (1-1), R3 is a quaternary ammonium cation; in formula (1-2), R3' is a quaternary ammonium zwitterion; and R1 is a C 1～12 The substituted or unsubstituted alkylene group; R2 contains a polyether segment; R4 is C 2～20 Substituted or unsubstituted alkylene, C 6～20 Substituted or unsubstituted aryl and C 3～20 One or more of the substituted or unsubstituted heteroaryl groups; the substituents of R1, R2 and R4 are each independently C1. 1～10 alkyl, C 6～20 aryl and C 3～20 One or more of the heteroaryl groups.

[0249] IV-2. The copolyamide quaternary ammonium compound according to scheme IV-1, wherein R3 has the structure shown in formula (5) and R3' has the structure shown in formula (6).

[0250] L1 and L2 may be the same or different, and each independently includes C. 1～12 Substituted or unsubstituted alkyl groups, C 3～20 Substituted or unsubstituted cycloalkyl, C 6～20 Substituted or unsubstituted aryl, C 3～20 One or more of the substituted or unsubstituted heteroaryl groups;

[0251] each substituent of L1and L2independently includes one or more of C 1～5 alkyl, C 6～10 aryl, C 4～10 furyl;

[0252] L3includes one or more of H, C 1～30 substituted or unsubstituted alkyl, C 3～20 substituted or unsubstituted cycloalkyl, C 6～20 substituted or unsubstituted aryl, C 3～20 substituted or unsubstituted heteroaryl; each substituent of L3includes one or more of C 1～5 alkyl, C 6～10 aryl, C 4～10 furyl;

[0253] L3' is one or more of C 1～12 substituted or unsubstituted alkylene, C 6～20 substituted or unsubstituted arylene; each substituent of L3' is one or more of C 1～5 alkyl.

[0254] IV-3, the copolyamide quaternary ammonium compound according to aspect IV-2, wherein, wherein L1and L2are the same or different, each independently one or more of methyl, ethyl, propyl, butyl, and benzyl;

[0255] L3is one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, phenyl;

[0256] L3' is one of ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, L3'substituent is one of methyl, ethyl, propyl.

[0257] IV-4, the copolyamide quaternary ammonium compound according to aspect IV-1, wherein R2has the following structure:

[0258] R' is C 1～10 substituted or unsubstituted alkylene; R'substituent includes one or more of methyl, ethyl, propyl, butyl, and phenyl; n is any number of 2 or more;

[0259] R2has a molecular weight of 200 to 10,000, preferably 1,000 to 5,000.

[0260] IV-5, the copolyamide quaternary ammonium compound according to aspect IV-1, wherein R4is C 2～10 substituted or unsubstituted alkylene, C6～10 substituted or unsubstituted arylene and C 3～10 substituted or unsubstituted heteroarylene; the substituents of R4include one or more of methyl, ethyl, propyl, butyl and phenyl;

[0261] Preferably, R4includes one or more of ethylene, propylene, butylene, hexylene, octylene, nonylene, furanylene and phenylene.

[0262] IV-6, the copolyamide quaternary ammonium compound according to the scheme IV-1, wherein the weight percentage of the first copolymerized structural unit is 0.1-50%, preferably 3-30%, the weight percentage of the second copolymerized structural unit is 0.1-50%, preferably 5-30%, the weight percentage of the third copolymerized structural unit is 50-99%, preferably 50-90%, and the weight percentage of the fourth copolymerized structural unit is 0.1-50%, preferably 5-30%, based on the weight of the copolyamide quaternary ammonium compound.

[0263] IV-7, the copolyamide quaternary ammonium compound according to the scheme IV-1, wherein the anion of the quaternary ammonium salt includes one or more of halide ion and sulfonate ion; the halide ion includes bromide ion and / or chloride ion.

[0264] IV-8, a method for preparing a copolyamide quaternary ammonium compound, characterized in that the method comprises:

[0265] S1: contacting a lactam compound, caprolactam with side groups, a dibasic acid and a dibasic amine under an inert atmosphere to perform a copolymerization reaction to obtain a copolyamide;

[0266] S2: contacting the copolyamide with a quaternization reagent in a solvent to perform a reaction;

[0267] wherein the lactam compound has a structure shown in the following formula (I), the caprolactam with side groups has a structure shown in the following formula (II), the dibasic amine has a structure shown in the following formula (III), and the dibasic acid has a structure shown in the following formula (IV),

[0268] wherein R1is C 1～12 substituted or unsubstituted alkylene, R2includes a polyether segment; R4is C 2～12 substituted or unsubstituted alkylene, C 6～20 substituted or unsubstituted arylene and C 3～20 substituted or unsubstituted heteroarylene; the substituents of R4include one or more of methyl, ethyl, propyl, butyl and phenyl; 1～10 alkyl, C 6～20 aryl and C4～20 one or more of substituted or unsubstituted alkyl, C

[0269] IV-9. The method of scheme IV-8, wherein the caprolactam with pendant groups has a structure according to the following formula,

[0270] wherein L1and L2are the same or different and each independently comprises C 1～12 one or more of substituted or unsubstituted alkyl, C 3～20 one or more of substituted or unsubstituted cycloalkyl, C 6～20 one or more of substituted or unsubstituted aryl, C 3～20 one or more of substituted or unsubstituted heteroaryl.

[0271] the substituents of L1and L2each independently comprise one or more of C 1～5 alkyl, C 6～10 aryl, C 4～10 furyl.

[0272] IV-10. The method of scheme IV-8, wherein in step S1, the caprolactam with pendant groups comprises one or more of dimethylaminocaprolactam, diethylaminocaprolactam, dipropylaminocaprolactam, dibutylaminocaprolactam, and dibenzylaminocaprolactam.

[0273] the lactam compound comprises one or more of caprolactam, undecanolactam, and dodecanolactam.

[0274] IV-11. The method of scheme IV-8, wherein in step S1, the diamine is a polyetheramine; the molecular weight of the polyetheramine is 200-10000, preferably 1000-5000; and the diacid is one or more of phthalic acid, adipic acid, azelaic acid, oxalic acid, sebacic acid, suberic acid, and furandicarboxylic acid.

[0275] IV-12. The method of scheme IV-8, wherein in step S1, the inert atmosphere comprises one or more of nitrogen, argon, preferably nitrogen; the temperature of the contacting is 80-120°C, preferably 90-110°C; and the time of the relieving is 0.5-3h, preferably 1-2h.

[0276] IV-13. The method of scheme IV-8, wherein in step S1, the conditions of the copolymerization reaction comprise a reaction temperature of 180-280°C and a reaction time of 1-10h; preferably, the reaction temperature is 200-260°C and the reaction time is 2-9h.

[0277] IV-14. The method of any one of embodiments IV-8, wherein in step S1, the caprolactam having a pendant nitrogen-containing group is present in the copolymerization reaction system in an amount of 0.1 to 50% by weight, preferably 3 to 30% by weight; the lactam compound is present in the copolymerization reaction system in an amount of 0.1 to 50% by weight, preferably 1 to 50% by weight; the diacid is present in the copolymerization reaction system in an amount of 0.1 to 50% by weight, preferably 5 to 30% by weight; and the diamine is present in the copolymerization reaction system in an amount of 50 to 99% by weight, preferably 50 to 90% by weight.

[0278] IV-15. The method of any one of embodiments IV-8, wherein in step S2, the reaction is carried out at a temperature of 0 to 60 °C for a time period of 1 to 10 hours; preferably, the reaction is carried out at a temperature of 20 to 60 °C for a time period of 2 to 9 hours; and the solvent comprises one or more of N,N-dimethylformamide, toluene, xylene, ethanol, ethylene glycol, dimethyl sulfoxide, dioxane, tetrahydrofuran, dichloromethane, and water.

[0279] The molar ratio of the quaternizing agent to the caprolactam having a pendant group is 0.1 to 1:1.

[0280] IV-16. The method of any one of embodiments IV-8, wherein in step S2, the halogenated hydrocarbon has a structure of L3-X, L3 comprises one or more of a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group; each substituent of L3 independently comprises one or more of an alkyl group, an aryl group, a heteroaryl group, a cycloalkyl group, a furanyl group; preferably a substituted or unsubstituted alkyl group; and X comprises one or more of chlorine, bromine, and iodine. 1～30 3～20 6～20 3～20 1～5 6～10 4～10 11～20

[0281] The lactone compound comprises a C 2～7 lactone, preferably one or more of 1,3-propane sultone, cyclopropane sultone, 1,4-butane sultone.

[0282] IV-17. A copolyamide quaternary ammonium compound prepared by the method of any one of embodiments IV-8 to IV-16.

[0283] IV-18. The copolyamide compound of any one of embodiments IV-17, wherein the copolyamide quaternary ammonium compound has a surface resistance of 1 x 10 6 to 1 x 10 8 ​​​​​​​​Ω, preferably 1 x 10 6 ~ 1 x 10 7 Ω.

[0284] IV-19, Use of the copolyamide quaternized compound according to any one of embodiments IV-1 to 7 and 17 to 18.

[0285] The above detailed the preferred embodiments of the present application, but the present application is not limited to the specific details of the above-described embodiments, within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, and these simple modifications all belong to the protection scope of the present application.

[0286] Examples

[0287] The present disclosure will be described in detail below with specific examples. The following examples will help those skilled in the art to further understand the present disclosure, but do not limit the present disclosure in any form. Unless otherwise specified, the reagents used in the present disclosure are commercially available.

[0288] The caprolactam used in the present disclosure is purchased from Sinopec Hunan Petrochemical Company. The diacid and diamine monomer part used in the present disclosure is purchased from Inokai Reagent Company. The polyetheramine D2000 used in the present disclosure is purchased from Huntsman Company, product number and The molecular weight is 2000; the polyetheramine D1000 is purchased from Huntsman Company, product number The molecular weight is 1000; the polyetheramine D900 is purchased from Huntsman Company, product number The molecular weight is 900.

[0289] The amino caprolactam used in the present disclosure is α-amino-ε-caprolactam, purchased from Alpha Aesar Company, product number Y11268.

[0290] The preparation method of dimethylaminocaprolactam used in the present disclosure is as follows:

[0291] Step 1a: Dissolve lysine salt in methanol, add concentrated sulfuric acid dropwise at room temperature, and react; Step 1b: Add methanol to the reaction liquid obtained in step 1a, then dissolve NaOH with methanol and add dropwise to it for overnight reaction, then evaporate the methanol, and then add ethyl acetate for reflux reaction; Step 1c: Recrystallize the product obtained in step 1b to obtain white solid amino caprolactam; Step 1d: Dissolve the amino caprolactam obtained in step 1c in methanol, add palladium-carbon, add formaldehyde under hydrogen atmosphere, and react to obtain the crude product, and column chromatography to obtain dimethylaminocaprolactam.

[0292] The preparation method of dibenzylaminocaprolactam used in the present disclosure is as follows:

[0293] The amino caprolactam is heated to reflux under alkaline conditions to undergo substitution reaction with halogenated reagent; the solvent of the reaction solution is removed by distillation under reduced pressure, dissolved with organic solvent, washed with saturated brine, separated, and the organic layer is concentrated and crystallized to obtain dibenzyl amino caprolactam. Alternatively, the amino caprolactam is first reacted with benzaldehyde compound under alkaline conditions; a reducing agent is added to the reaction solution under low temperature conditions to obtain dibenzyl amino caprolactam.

[0294] The preparation method of the phosphorus group substituted amino caprolactam a used in the present disclosure is as follows:

[0295] The amino caprolactam (12.8 g) and benzaldehyde (10.6 g) are added to a reactor with temperature control device and stirring device in a molar ratio of 1:1, ethanol (40 g) is added, and the reaction is carried out at 50°C for 4 hours. After the reaction is completed, cooling, filtration, and drying are performed to obtain a yellowish imine intermediate product with a yield of 93%; then, 9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide (DOPO, CAS No.: 35948-25-5) (21.6 g) is added, and ethanol (40 g) is added, and the reaction is carried out at 50°C. After 10 hours of reaction, the product is cooled, filtered, washed, and dried to obtain phosphorus group substituted amino caprolactam a in the form of a yellowish solid with a yield of 94%.

[0296] Other phosphorus group substituted amino caprolactams b-j are prepared by the same method, except that benzaldehyde is replaced by equimolar benzeneacetaldehyde (b), m-tolualdehyde (c), 9-anthracene aldehyde (d), 4-dimethylamino benzaldehyde (e), salicylaldehyde (f), furfural (g), hydroxymethyl furfural (h), p-xylylene aldehyde (i), and m-xylylene aldehyde (j).

[0297] The test characterization method in the present disclosure is as follows:

[0298] Infrared spectrum: Fourier transform infrared spectrum (FTIR) is measured by Perkin-Elmer 2000 FT-IR spectrophotometer with a resolution of 4 cm -1 -1, and the sample is scanned for 32 times; KBr (potassium bromide) is used for tabletting, and the test is performed by attenuated total reflection (ATR) mode with a scanning wave number range of 4000-450 cm -1 .

[0299] Photoluminescence (fluorescence): fluorescence characteristics and quantum yield are tested on an OLYMPUS BX51 (Olympus) fluorescence microscope; the quantum yield is calculated by integrating sphere.

[0300] Visible light transmittance: tested on a UV-Vis spectrophotometer, PerkinElmer, Lambda 25.

[0301] Hardness: measured according to ASTM D2240 standard, using a Shore hardness tester. Shore A hardness is used for softer materials, and Shore D hardness is used for harder materials.

[0302] Surface resistance: measured using a Sigmaread AS982 surface resistance tester, with the test material placed on an insulating pad, at a test temperature of 25℃.

[0303] Glass transition temperature, crystallization temperature and melting temperature (melting point): analyzed using a Mettler differential scanning calorimeter, according to ASTM D3418-21 standard, with a heating rate of 10℃ / min-40℃ / min, under a nitrogen atmosphere.

[0304] Thermal decomposition temperature: measured using a Mettler thermogravimetric analyzer, according to ASTM E1131-08(2014) standard, with a heating rate of 10℃ / min, under a nitrogen atmosphere. Since aminocaproamide and derivatives have a thermal weight loss peak at about 200℃, the conversion rate of aminocaproamide derivatives participating in polymerization can be characterized by this method.

[0305] Relative viscosity: a 96% concentrated sulfuric acid dilute solution of the copolyamide is prepared, filtered and used. The relative viscosity is measured at room temperature (about 25℃) using an Ubbelohde viscometer.

[0306] UL94 vertical burning test: according to GB / T 2408-2021 "Plastics - Determination of the flammability of plastics - Horizontal and vertical method", the obtained copolyamide is made into a 125mm*13.0mm*10mm sample, with 10 parallel samples in each group, for vertical burning test. According to the UL94 standard, the material sample is divided into three levels of V-0, V-1 and V-2 according to the combustion performance. Among them, V-0 level represents the best flame retardant performance, with a combustion rate lower than the specified value, a flame tip height lower than the specified value, and a smoke amount also lower than the specified value. V-1 level and V-2 level are in turn less good.

[0307] Test level explanation:

[0308] V-2: after two 10-second combustion tests on the sample, the flame is extinguished within 60 seconds, and there can be burning material falling down.

[0309] V-1: after two 10-second combustion tests on the sample, the flame is extinguished within 60 seconds, and there can be no burning material falling down, with better flame retardant performance than V-2.

[0310] V-0: After two 10 seconds burning test of the sample, the flame is extinguished within 30 seconds, and no burning material falls, which is the highest level of flame retardant performance in conventional materials, and is often used in fields with extremely high fire safety requirements.

[0311] Limiting Oxygen Index (OI) test: According to GB / T 2406.2-2009 standard "Plastics - Determination of the burning behavior in an oxygen index test - Part 2: Test in room temperature", the obtained copolyamide is made into 80mm*10mm*4mm sample, 15 parallel samples per group, and limiting oxygen index test is carried out. The higher the oxygen index, the better the flame retardant performance of the material.

[0312] Antibacterial test: According to GB / T 20944.3-2008 standard, Escherichia coli and Staphylococcus aureus are detected by oscillation method. By rapidly oscillating the sample in the bacterial suspension, the contact between the microorganism and the sample is increased to detect its antibacterial activity. By comparing the viable bacterial concentration of the control sample and the antibacterial sample, the antibacterial rate is calculated.

[0313] Example I-1

[0314] Caprolactam (86.5g), dimethylaminocaprolactam (5g), terephthalic acid (5g) and hexanediamine (3.5g) are pre-mixed in a reaction kettle at 100°C until uniform, the mixing temperature is 100°C, the mixing time is 1h, after nitrogen replacement for three times, the temperature is raised to 230°C, the pressure is 0.3MPa, and the quaternary copolyamide is obtained after 8h of reaction. Among them, based on the total weight of the reaction raw materials, the addition amount of caprolactam accounts for 86.5wt%, the addition amount of dimethylaminocaprolactam accounts for 5wt%, the addition amount of terephthalic acid accounts for 5wt%, and the addition amount of hexanediamine accounts for 3.5wt%; the molar ratio of diamine to diacid is 1:1.

[0315] The quaternary copolyamide obtained in Example 1 is dissolved in concentrated sulfuric acid and the relative viscosity is measured. The dissolution of the quaternary copolyamide in concentrated sulfuric acid indicates that the obtained copolyamide is a linear copolyamide, and the measured relative viscosity is 2.2. The content of biochar in the quaternary copolyamide of Example 1 is 5wt%.

[0316] Examples I-2 to 16

[0317] The preparation method of Examples I-2 to 16 is the same as that of Example I-1, and the specific conditions are shown in Table 1.

[0318] Table 1

[0319] Comparative Example I-1

[0320] Caprolactam (91.5 g), terephthalic acid (5 g) and hexamethylenediamine (3.5 g) were pre-mixed at 100 °C in a reaction kettle until homogeneous. After three times of nitrogen replacement, the temperature was raised to 230 °C, and the pressure was 0.3 MPa. After 8 h of reaction, a terpolyamide was obtained. The glass transition temperature of the terpolyamide was 50 °C, the crystallization temperature was 177 °C, the melting point was 211 °C, the thermal decomposition temperature was 351 °C, and the terpolyamide had no photoluminescence property.

[0321] Comparative Example I-2

[0322] Caprolactam (91.5 g), terephthalic acid (5 g) and hexamethylenediamine (3.5 g) were pre-mixed at 100 °C in a reaction kettle until homogeneous. After three times of nitrogen replacement, the temperature was raised to 230 °C, and the pressure was 0.3 MPa. After 8 h of reaction, a terpolyamide was obtained. The glass transition temperature of the terpolyamide was 50 °C, the crystallization temperature was 177 °C, the melting point was 211 °C, the thermal decomposition temperature was 351 °C, and the terpolyamide had no photoluminescence property.

[0323] Comparative Example I-3

[0324] Comparative Example I-3

[0325] Test Example I-1

[0326] The copolyamides obtained in Example I-1 and Comparative Example I-2 were characterized by infrared spectroscopy. As shown in FIG. 2, the characteristic peak at 1638 cm -1 corresponds mainly to the vibration of carbon-oxygen double bond (C=0); the characteristic peak at 1542 cm -1 corresponds mainly to the bending vibration of amino group (N-H) and the vibration of carbon-nitrogen single bond (C-N); the characteristic peak at 3300 cm -1 corresponds mainly to the stretching vibration of free amine group (N-H); the characteristic peaks at 3070 cm -1 , 2938 cm -1 , and 2867 cm -1 correspond mainly to the stretching vibration of methylene (-CH2-).

[0327] Compared with Comparative Example I-2, the stretching vibration of C-N bond of the nitrogen atom directly connected to the carbon atom in Example I-1 appears at 1000-1300 cm -1 . In combination with the infrared spectrum of Comparative Example I-2 and the photoluminescence property test results of Comparative Example I-3, it can be confirmed that the dimethylaminocaprolactam in Example I-1 participates in the quaternary copolymerization reaction.

[0328] Test Example I-2

[0329] The copolyamides obtained in Examples I-1 to I-16 and Comparative Example I-2 were tested for crystallization temperature, melting point, thermal decomposition temperature, glass transition temperature, and relative viscosity. The copolyamides obtained were made into polymer films of about 0.5 mm in thickness, and the films were tested for luminescence performance and quantum yield. The results are shown in Table 2 and FIG. 1.

[0330] Table 2

[0331] As can be seen from the data in Table 2 and FIG. 1, the films prepared from the copolyamides of the present disclosure have photoluminescence performance and can convert part of the ultraviolet light of 350-400 nm into blue light of 450 nm. The copolyamides prepared in the present disclosure have a crystallization temperature of 80-230°C, a thermal decomposition temperature of 300-450°C, a melting point of below 250°C, a glass transition temperature of 40-50°C, and a relative viscosity of 1.6-2.8.

[0332] As can be seen from the comparison between Example I-1 and Example I-16, within the preferred weight percentage range of caprolactam having a nitrogen-containing side group in the present disclosure, the copolyamides obtained have better photoluminescence performance and higher quantum yield.

[0333] Test Example I-3

[0334] The products obtained in Examples I-3 to I-4 and Comparative Example I-1 were subjected to hot water extraction and drying, and the mass percentage of hot water extractables (extractable rate) was tested to evaluate the utilization efficiency of monomers. The extractables mainly include caprolactam, aminocaprolactam derivatives, and caprolactam cyclic oligomers with a polymerization degree of 2-5.

[0335] The test results show that the mass percentage of extractables in Example I-3 is 7.2 wt%, the mass percentage of extractables in Example I-4 is 9.1 wt%, and the mass percentage of extractables in Comparative Example I-1 is 12.3 wt%. Compared with Comparative Example I-1, the hot water extractable rate of the copolyamides obtained by the present disclosure is significantly reduced by adding diamines and diacids to participate in copolymerization, thereby improving the utilization rate of monomers in polymerization, and the four types of reactants in the method of the present disclosure can all participate in copolymerization well.

[0336] Comparative Example I-1 uses a hydrolysis polymerization method and cannot effectively copolymerize caprolactam having a nitrogen-containing side group with caprolactam to obtain a multi-component copolyamide.

[0337] As can be seen from the comparison between Example I-1 and Comparative Examples I-1, I-2, and I-3, the method of the present disclosure can effectively copolymerize caprolactam, caprolactam having a nitrogen-containing side group, diacids, and diamines to obtain a multi-component copolyamide, and the copolyamides obtained have adjustable melting points, photoluminescence, and improved molding processing performance.

[0338] Example II - Copolyamide elastomer

[0339] Example II-1

[0340] After the caprolactam (22 g), dimethylaminocaprolactam (2 g), terephthalic acid (3.32 g) and polyetheramine D2000 (40 g) were pre-mixed in a reaction kettle at 100 °C to be uniform, the reaction kettle was replaced with nitrogen for three times and then heated to 230 °C, the pressure was 0.3 MPa, and the copolyamide elastomer was obtained after 8 h of reaction.

[0341] The copolyamide elastomer obtained in Example II-1 was characterized by infrared spectroscopy. As shown in Figure 4, the characteristic peak at 3300 cm -1 corresponds to the stretching vibration of -NH-, the characteristic peak at 2860 cm -1 corresponds to the symmetric stretching vibration of -CH2-, the characteristic peak at 2930 cm -1 corresponds to the anti-symmetric stretching vibration of -CH2-, the characteristic peak at 1640 cm -1 corresponds to the amide carbonyl stretching vibration of secondary amide, the characteristic peak at 1550 cm -1 corresponds to the N-H bending vibration of secondary amide, the characteristic peak at 1110 cm -1 and a group of peaks nearby correspond to -C-O- ether bond, the characteristic peak at 2880 cm -1 corresponds to the characteristic absorption peak of -CH2- on the aliphatic ether.

[0342] The obtained copolyamide elastomer was made into a polymer film with a thickness of about 0.5 mm, and the fluorescence properties, fluorescence intensity (quantum yield) and visible light transmittance of the polymer film were tested. As shown in Figure 3 and Table 4, the polymer film has photoluminescence performance, can absorb ultraviolet light of 350-400 nm and release blue light of 450 nm, and the quantum yield is 25%. As shown in Figure 5, the polymer film can effectively block the transmission of ultraviolet light below 400 nm, and the transmittance of visible light is 95%. The melting point, thermal degradation temperature, surface resistance and hardness of the copolyamide elastomer were also tested, and the specific results are shown in Table 4.

[0343] Examples II-2-26

[0344] The preparation method of Examples II-2-26 is the same as that of Example II-1, and the specific conditions are shown in Table 3.

[0345] Table 3

[0346] Comparative Example II-1

[0347] Caprolactam (24 g), terephthalic acid (3.32 g) and polyetheramine (40 g) were pre-mixed in a reaction kettle at 100 ℃ until uniform, and then the temperature was raised to 230 ℃ after nitrogen replacement for three times, and the pressure was 0.3 MPa, and the copolyamide elastomer was obtained after 8 h of reaction. The copolyamide elastomer of Comparative Example 1 did not emit light under ultraviolet lamp irradiation, and did not have photoluminescence performance.

[0348] Comparative Example II-2

[0349] The copolyamide elastomer obtained from Comparative Example II-1 and dimethylaminocaprolactam were physically mixed, and the obtained mixture did not emit light under ultraviolet lamp irradiation, indicating that the physical mixture did not have photoluminescence performance.

[0350] The melting point, thermal decomposition temperature and surface resistance of the copolyamide elastomers obtained from Comparative Example II-1 and Examples II-1 to II-26 were tested, and the quantum yield and visible light transmittance of the polymer film of about 0.5 mm thick made from the copolyamide elastomer of Examples II-1 to II-26 were tested, and the results are shown in Table 4.

[0351] Table 4

[0352] According to the data in Table 4 and Figure 3, the copolyamide elastomer obtained by the present disclosure has photoluminescence performance, can block the transmission of ultraviolet light below 400 nm, convert ultraviolet light of 350-400 nm into blue light, and the quantum yield can reach 28%, and has a high transmittance of visible light, and the transmittance can reach 95%; the melting point of the copolyamide elastomer prepared by the present disclosure is below 200 ℃, the thermal decomposition temperature is 320-370 ℃, and the surface resistance is 0.1×10 9 ~ 20×10 9 Ω, and the Shore hardness is adjustable between 5.5A and 90.5A. The present disclosure can obtain a copolyamide elastomer with a significantly reduced melting point compared to the melting point of polyamide 6, which is 220 ℃.

[0353] As can be seen by comparing Examples II-1 to II-26 with Comparative Examples II-1 and II-2, the method of the present disclosure can effectively copolymerize caprolactam, caprolactam with nitrogen-containing side groups, and long-chain polyether diamine or amino-terminated polysiloxane to obtain copolyamide elastomers, and the obtained copolyamide elastomers have adjustable melting point and hardness, photoluminescence, antistatic and other properties.

[0354] Example III - Flame-retardant modified copolyamides

[0355] The amino caprolactams a-j with phosphorus group substitution used in this example were prepared according to the method described above.

[0356] Example III-1

[0357] Caprolactam (88.5 g), phosphorus group-substituted aminocaprolactam a (3 g), terephthalic acid (5 g), and hexanediamine (3.5 g) were mixed uniformly in a reaction kettle at 100°C, and then replaced with nitrogen three times, and then heated to 230°C, and the pressure was 0.3 MPa. After 8 h of reaction, a copolyamide was obtained. Among them, based on the total weight of the reaction raw materials, the amount of caprolactam added accounted for 88.5 wt%, the amount of phosphorus group-substituted aminocaprolactam a added accounted for 3 wt%, the amount of diacid added accounted for 5 wt%, the amount of diamine added accounted for 3.5%, and the molar ratio of diacid to diamine was 1:1.

[0358] The preparation method of Examples III-2 to 25 was the same as that of Example III-1, and the specific conditions are shown in Table 5. The number of the phosphorus group-substituted aminocaprolactam class is shown in the specific embodiment part of the present disclosure. The vertical burning test and limiting oxygen index test results of Examples III-1 to 25 are shown in Table 5.

[0359] Table 5

[0360] Comparative Example III-1

[0361] The limiting oxygen index and vertical burning test were tested by using nylon 6 purchased from Sinopec Hunan Petrochemical. The limiting oxygen index was 26.11%, and the vertical burning was V-2 level.

[0362] The phosphorus-containing copolyamide prepared by the present disclosure contains a P-C-N structure. According to the data in Table 5, the phosphorus-containing copolyamide has a synergistic flame-retardant effect of phosphorus and nitrogen in the combustion process, and significantly improves the flame-retardant properties of the polyamide material.

[0363] Example IV-Quaternized copolyamide

[0364] Example IV-1

[0365] (1) Caprolactam (38.4 g), dimethylaminocaprolactam (3.6 g), terephthalic acid (6 g), and polyetheramine D2000 (72 g) were pre-mixed uniformly in a reaction kettle at 100°C, and then replaced with nitrogen three times, and then heated to 230°C, and the pressure was 0.3 MPa. After 8 h of reaction, a copolyamide was obtained; among them, based on the total weight of the reaction raw materials, the amount of caprolactam added accounted for 32 wt%, the amount of dimethylaminocaprolactam added accounted for 3 wt%, the amount of diacid added accounted for 5 wt%, the amount of diamine added accounted for 60 wt%, and the molar ratio of diacid to diamine was 1:1.

[0366] (2) The copolyamide obtained in step (1) was soaked in ethanol, 2.8 g of 1,3-propane sultone was added, wherein the molar ratio of dimethylamino caprolactam to 1,3-propane sultone was 1:1, then the temperature was raised to 50°C, and an alcoholic solution of the quaternized copolyamide was obtained after stirring for 6 h.

[0367] The quaternized copolyamide obtained in Example IV-1 was tested by infrared spectroscopy. As shown in Figure 6, the characteristic peak at 1638 cm -1 corresponds to the amide carbonyl stretching vibration of secondary amide, the characteristic peak at 1542 cm -1 corresponds to the N-H bending vibration and C-N stretching vibration of secondary amide, the characteristic peak at 3300 cm -1 corresponds to the stretching vibration of -NH-, the characteristic peak at 1200-1300 cm -1 corresponds to the stretching vibration of ether bond; the characteristic peak in the range of 2900 cm -1 to 3000 cm -1 corresponds to the stretching vibration of methyl (CH3) and methylene (CH2) groups in the fatty chain of quaternary ammonium salt; the characteristic peak at 1176 cm -1 corresponds to the symmetric stretching vibration of sulfonic acid group S=0, the characteristic peak at 1041 cm - 1 corresponds to the asymmetric stretching vibration of sulfonic acid group S=0.

[0368] Examples IV-2 to 9

[0369] The method of Examples IV-2 to 9 is the same as that of Example IV-1, except that different quaternization reagents are selected. The specific conditions are shown in Table 1.

[0370] Comparative Example IV-1

[0371] The method of this comparative example is the same as that of Example IV-1, except that only step (1) in Example 1 is performed, and no quaternization modification is performed with a quaternization reagent. The obtained copolyamide cannot be dissolved in alcohol and has no antibacterial property.

[0372] Test Example IV

[0373] After the quaternized copolyamides obtained in Examples IV-1 to 9 and Comparative Example IV-1 were granulated, the antibacterial property was tested; after the obtained quaternized copolyamides were cast into films and fully dried, the surface resistance was tested. The test results of antibacterial property and surface resistance are shown in Table 6. The comparison photos of antibacterial effect of Example IV-1 and Comparative Example IV-1 on Staphylococcus aureus are shown in Figure 7.

[0374] Table 6

[0375] The quaternary ammonium copolyamides obtained by the embodiments IV-1 to IV-9 of the present disclosure can all be soluble in alcohol, indicating that the quaternary ammonium copolyamides have alcohol solubility; the surface resistance of the obtained quaternary ammonium copolyamides is below 10^8 Ω, indicating that the quaternary ammonium copolyamides have antistatic property; the quaternary ammonium copolyamides have significant antibacterial property against Escherichia coli and Staphylococcus aureus. The present disclosure can obtain quaternary ammonium copolyamides having alcohol solubility, antibacterial property and antistatic property at the same time by quaternary ammonium modification of the copolyamides, thereby broadening the range of application fields of the polyamide material in functionalized applications and further improving the comprehensive practical value of the material.

[0376] The preferred embodiments of the present disclosure are described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details in the above-described embodiments. Within the technical concept range of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all belong to the protection range of the present disclosure.

[0377] It should be noted that each specific technical feature described in the above-described specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combination manners.

[0378] In addition, various different embodiments of the present disclosure can also be combined in any manner, as long as it does not deviate from the idea of the present disclosure, and it should also be considered as disclosed by the present disclosure.​​​

Claims

1. A copolyamide, characterized in that, The copolyamide comprises the copolymer structural units shown in formulas (1) to (4) below; in, Indicates a chemical bond; R1 is selected from substituted or unsubstituted C. 1-20 Alkylene, preferably substituted or unsubstituted C 2-10 Alkylene, more preferably substituted or unsubstituted C 3-6 Alkylene; preferably, R1 is selected from one or more of ethylene, butylene, nonylene, decylene, and undecylene; R2 is selected from substituted or unsubstituted C. 1-12 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted 3-10 membered heterocyclic alkylene, substituted or unsubstituted C 6-10 arylene, substituted or unsubstituted 5-10 heteroarylene, substituted or unsubstituted -R a '-NH-(R a -NH) n -R a '-, substituted or unsubstituted -R b '-O-(R b -O) n' -R b '-, substituted or unsubstituted -R c "-O-(C(O)-R c -C(O)-OR c '-O) n” -C(O)-R c -C(O)-OR c "-, substituted or unsubstituted -R d '-(Si(R d )2-O) n”' -Si(R d )2-R d '-, where R a R a '、R b R b '、R d Each is independently selected from substituted or unsubstituted C 2-10 Alkylene, substituted or unsubstituted C 6-10 Alpha-aryl, R c R c '、R c Each independently selected from C 1-10 Alkylene, substituted or unsubstituted C 6- 10 Alpha-aryl, R d Each was independently selected from C 1-5 Alkyl, C 1-5 Alkoxy, C 6-10 Aryl group, n, n', n”, n”' each independently represents an integer from 1 to 500; preferably, R2 is selected from ethylidene, propylidene, butylidene, pentylene, hexylidene, octylidene, nonylidene, furanylidene, phenylidene, -R a '-NH-(R a -NH) n -R a '-、-R b '-O-(R b -O) n' -R b '-、-R d '-(Si(R d )2-O) n”' -Si(R d )2-R d One or more of '-, where R a R a '、R b R b '、R d R d '、n、n'、n”' are each defined as above; The nitrogen-containing side group R3 is selected from one or more of the following: substituted or unsubstituted amino groups, quaternary ammonium cations, and quaternary ammonium zwitterions; R4 is selected from substituted or unsubstituted C4. 2-12 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted 3-10 membered heterocyclic alkylene, substituted or unsubstituted C 6-10 One or more of arylene, substituted or unsubstituted 5-10 member heteroarylene; preferably, R4 is selected from one or more of ethylidene, propylidene, butylidene, pentylene, hexylidene, octylidene, nonylidene, furanylidene, and phenylidene. R1, R2, and R4 are each independently selected from C. 1-10 Alkyl, C 1-10 Alkoxy, C 3- 10 Cycloalkyl, 3-10 membered heterocyclic groups, C 6-10 It is substituted by one or more substituents in aryl and 5-10 heteroaryl groups.

2. The copolyamide according to claim 1, wherein, The nitrogen-containing side group R3 has a structure as shown in formula (5) or formula (6). L1 and L2 may be the same or different, and each is independently selected from hydrogen, substituted or unsubstituted C. 1-12 Alkyl, substituted or unsubstituted C 2-12 alkenyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted 3-20 membered heterocyclic groups, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted 5-20 quinone heteroaryl, -CHR a1 P(O)R a2 R a3 One or more of the following, or L1 and L2 together with the attached N atom to form a 5-20 member saturated or unsaturated heterocycle; L1 and L2 may be independently selected from halogens, C 1-5 Alkyl, C 1-5 Alkoxy, C 2-5 alkenyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic groups, C 6-20 Aryl, 5-20 heteroaryl, C 1-10 Ester group, urea group, C 1-10 The substance is substituted by one or more substituents selected from amide, amino, hydroxyl, carboxyl, cyano, and cyanate groups; R a1 Selected from hydrogen, substituted or unsubstituted C 1-12 Alkyl, substituted or unsubstituted C 2-12 alkenyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted 3-20 membered heterocyclic groups, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted 5-20 membered heteroaryl; R a1 Optionally selected from halogen, C 1-5 Alkyl, C 1-5 Alkoxy, C 1-5 Haloalkyl, C 1-5 Hydroxyalkyl, C 1- 5-Haloalkoxy, C 2-5 alkenyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic groups, C 6-20 Aryl, C 6- 20 aryloxy group, C 6-20 Halogenated aryl, C 6-20 Hydroxyaryl, C 6-20 The substituted group is one or more of the following: haloaryloxy, 5-20 heteroaryl, amino, hydroxyl, carboxyl, cyano, (2-oxo-3-azacycloheptane-1-ylamino)(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl)methimide; R a2 and R a3 Each was independently selected from C 1-5 Alkoxy, C 6-10 aryloxy group, or R a2 and R a3 Together with the attached phosphoryl group P(O), it forms 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl; L1' and L2' may be the same or different, and each is independently selected from substituted or unsubstituted C. 1-12 Alkyl, substituted or unsubstituted C 3-10 Cycloalkyl, substituted or unsubstituted 3-10 membered heterocyclic groups, substituted or unsubstituted C 6-10 One or more of aryl, substituted or unsubstituted 5-10 heteroaryl groups; L1' and L2' are each optionally independently selected from C 1-5 Alkyl, C 1-5 Alkoxy, C 3-10 Cycloalkyl, 3-10 membered heterocyclic groups, C 6-10 The aryl group is substituted by one or more substituents from 5-10 heteroaryl groups; L3' is selected from hydrogen, substituted or unsubstituted C. 1-20 Alkyl, substituted or unsubstituted C 3-10 Cycloalkyl, substituted or unsubstituted 3-10 membered heterocyclic groups, substituted or unsubstituted C 6-10 One or more of aryl, substituted or unsubstituted 5-10 heteroaryl groups; L3' is optionally selected from C 1-5 Alkyl, C 1-5 Alkoxy, C 3-10 Cycloalkyl, 3-10 membered heterocyclic groups, C 6-10 Aryl, 5-10 heteroaryl, sulfonate group -SO3 - One or more substituents in it are replaced; Preferably, L1 and L2 may be the same or different, and each is independently selected from one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, benzyl, and furanyl; or one of L1 and L2 is hydrogen, and the other is selected from -CHR. a1 P(O)R a2 R a3 One or more of them, wherein R a1 R a2 R a3 Each as defined above; Preferably, L1' and L2' are the same or different, and each is independently selected from one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, phenyl, benzyl, and furanyl; L3' is selected from one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, and phenyl, and L3' is optionally surrounded by a methyl, ethyl, propyl, or sulfonate group -SO3. - One or more substituents in it are replaced.

3. The copolyamide according to any one of the preceding claims, wherein, The copolymer structural units shown in formulas (1) to (4) are bonded together by amide bonds.

4. The copolyamide according to any one of the preceding claims, wherein, R2 is selected from substituted or unsubstituted -R a '-NH-(R a -NH) n -R a '-, substituted or unsubstituted -R b '-O-(R b -O) n' -R b '-, substituted or unsubstituted -R c "-O-(C(O)-R c -C(O)-OR c '-O) n” -C(O)-R c -C(O)-OR c "-, substituted or unsubstituted -R d '-(Si(R d )2-O) n”' -Si(R d )2-R d '-, where R a R a '、R b R b '、R d Each is independently selected from substituted or unsubstituted C 2-10 Alkylene, substituted or unsubstituted C 6-10 Alpha-aryl, R c R c '、R c Each independently selected from C 1-10 Alkylene, substituted or unsubstituted C 6- 10 Alpha-aryl, R d Each was independently selected from C 1-5 Alkyl, C 1-5 Alkoxy, C 6-10 Aryl, n, n', n”, n”' each independently represent an integer from 5 to 500, the copolymer structural unit shown in formula (3) forms the soft segment of the copolyamide, and the number average molecular weight is 800 to 20000, preferably 900 to 3000; the copolymer structural units shown in formulas (1) and (2) form the hard segment of the copolyamide, and the number average molecular weight is 800 to 10000, preferably 1000 to 5000.

5. The copolyamide according to claim 4, wherein, Based on the weight of the copolyamide, the soft segment comprises 20–90 wt%, preferably 40–80 wt%, more preferably 50–70 wt%, and the hard segment comprises 10–80 wt%, preferably 20–60 wt%, more preferably 30–50 wt%; and / or The molar ratio of the copolymer structural unit shown in formula (1) to the copolymer structural unit shown in formula (2) in the hard segment is 0.01 to 100:1, preferably 0.02 to 50:

1.

6. The copolyamide according to any one of claims 1-3, wherein, R2 is selected from substituted or unsubstituted C. 1-12 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted 3-10 membered heterocyclic alkylene, substituted or unsubstituted C 6-10 arylene, substituted or unsubstituted 5-10 heteroarylene, substituted or unsubstituted -R a '-NH-(R a -NH) n -R a '-, substituted or unsubstituted -R b '-O-(R b -O) n' -R b '-, substituted or unsubstituted -R c "-O-(C(O)-R c -C(O)-OR c '-O) n” -C(O)-R c -C(O)-OR c "-, substituted or unsubstituted -R d '-(Si(R d )2-O) n”' -Si(R d )2-R d '-, where R a R a '、R b R b '、R d Each is independently selected from substituted or unsubstituted C 2-10 Alkylene, substituted or unsubstituted C 6-10 Alpha-aryl, R c R c '、R c Each independently selected from C 1-10 Alkylene, substituted or unsubstituted C 6- 10 Alpha-aryl, R d Each was independently selected from C 1-5 Alkyl, C 1-5 Alkoxy, C 6-10 Aryl groups n, n', n”, and n”' each independently represent integers from 1 to 4; Wherein, the weight of the copolyamide is used as a basis, The copolymer structural unit shown in formula (1) has a weight percentage of 1–50 wt%, preferably 1–40 wt%. The copolymer structural unit shown in formula (2) has a weight percentage of 1–95 wt%, preferably 5–90 wt%. The copolymer structural unit shown in formula (3) has a weight percentage of 1–50 wt%, preferably 1–40 wt%. The weight percentage of the copolymer structural unit shown in formula (4) is 1 to 50 wt%, preferably 1 to 40 wt%.

7. The copolyamide according to any one of the preceding claims, wherein, The copolyamide is a linear copolyamide; preferably, the copolyamide is a linear random copolymer or a linear block copolymer.

8. A method for preparing copolyamide, characterized in that, The method includes: contacting a lactam compound, caprolactam with a nitrogen-containing side group, a diacid, and a diamine in an inert atmosphere to carry out a copolymerization reaction, thereby obtaining a copolyamide. The lactam compound has the structure shown in formula (I), the caprolactam with a nitrogen-containing side group has the structure shown in formula (II), the diamine has the structure shown in formula (III), and the diacid has the structure shown in formula (IV). in, R1 is selected from substituted or unsubstituted C. 1-20 Alkylene, preferably substituted or unsubstituted C 2-10 Alkylene, more preferably substituted or unsubstituted C 3-6 Alkylene; preferably, R1 is selected from one or more of ethylene, butylene, nonylene, decylene, and undecylene; R2 is selected from substituted or unsubstituted C. 1-12 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted 3-10 membered heterocyclic alkylene, substituted or unsubstituted C 6-10 arylene, substituted or unsubstituted 5-10 heteroarylene, substituted or unsubstituted -R a '-NH-(R a -NH) n -R a '-, substituted or unsubstituted -R b '-O-(R b -O) n' -R b '-, substituted or unsubstituted -R c "-O-(C(O)-R c -C(O)-OR c '-O) n” -C(O)-R c -C(O)-OR c "-, substituted or unsubstituted -R d '-(Si(R d )2-O) n”' -Si(R d )2-R d '-, where R a R a '、R b R b '、R d Each is independently selected from substituted or unsubstituted C 2-10 Alkylene, substituted or unsubstituted C 6-10 Alpha-aryl, R c R c '、R c Each independently selected from C 1-10 Alkylene, substituted or unsubstituted C 6- 10 Alpha-aryl, R d Each was independently selected from C 1-5 Alkyl, C 1-5 Alkoxy, C 6-10 Aryl group, n, n', n”, n”' each independently represents an integer from 1 to 500; preferably, R2 is selected from ethylidene, propylidene, butylidene, pentylene, hexylidene, octylidene, nonylidene, furanylidene, phenylidene, -R a '-NH-(R a -NH) n -R a '-、-R b '-O-(R b -O) n' -R b '-、-R d '-(Si(R d )2-O) n”' -Si(R d )2-R d One or more of '-, where R a R a '、R b R b '、R d R d '、n、n'、n”' are each defined as above; The nitrogen-containing side group R3 is a substituted amino group; R4 is selected from substituted or unsubstituted C4. 2-12 Alkylene, substituted or unsubstituted C 3-10 Cycloalkylene, substituted or unsubstituted 3-10 membered heterocyclic alkylene, substituted or unsubstituted C 6-10 One or more of arylene, substituted or unsubstituted 5-10 member heteroarylene; preferably, R4 is selected from one or more of ethylidene, propylidene, butylidene, pentylene, hexylidene, octylidene, nonylidene, furanylidene, and phenylidene. R1, R2, and R4 are each independently selected from C. 1-10 Alkyl, C 1-10 Alkoxy, C 3- 10 Cycloalkyl, 3-10 membered heterocyclic groups, C 6-10 It is substituted by one or more substituents in aryl and 5-10 heteroaryl groups.

9. The method according to claim 8, wherein, The caprolactam having nitrogen-containing side groups has the structure shown in the following formula. L3 and L4 may be the same or different, and each is independently selected from hydrogen, substituted or unsubstituted C. 1-12 Alkyl, substituted or unsubstituted C 2-12 alkenyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted 3-20 membered heterocyclic groups, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted 5-20 quinone heteroaryl, -CHR a1 P(O)R a2 R a3 One or more of the following, or L1 and L2 together with the attached N atom to form a 5-20 member saturated or unsaturated heterocycle; L1 and L2 may be independently selected from halogens, C 1-5 Alkyl, C 1-5 Alkoxy, C 2-5 alkenyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic groups, C 6-20 Aryl, 5-20 heteroaryl, C 1-10 Ester group, urea group, C 1-10 The substance is substituted by one or more substituents selected from amide, amino, hydroxyl, carboxyl, cyano, and cyanate groups; R a1 Selected from hydrogen, substituted or unsubstituted C 1-12 Alkyl, substituted or unsubstituted C 2-12 alkenyl, substituted or unsubstituted C 3-20 Cycloalkyl, substituted or unsubstituted 3-20 membered heterocyclic groups, substituted or unsubstituted C 6-20 aryl, substituted or unsubstituted 5-20 membered heteroaryl; R a1 Optionally selected from halogen, C 1-5 Alkyl, C 1-5 Alkoxy, C 1-5 Haloalkyl, C 1-5 Hydroxyalkyl, C 1- 5-Haloalkoxy, C 2-5 alkenyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic groups, C 6-20 Aryl, C 6- 20 aryloxy group, C 6-20 Halogenated aryl, C 6-20 Hydroxyaryl, C 6-20 The substituted group is one or more of the following: haloaryloxy, 5-20 heteroaryl, amino, hydroxyl, carboxyl, cyano, (2-oxo-3-azacycloheptane-1-ylamino)(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl)methimide; R a2 and R a3 Each was independently selected from C 1-5 Alkoxy, C 6-10 aryloxy group, or R a2 and R a3 Together with the attached phosphoryl group P(O), it forms 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl. The condition is that L3 and L4 are not both hydrogen; Preferably, the caprolactam having a nitrogen-containing side group is selected from dimethylaminocaprolactam, diethylaminocaprolactam, dipropylaminocaprolactam, dibutylaminocaprolactam, dibenzylaminocaprolactam, and -CHR. a1 P(O)R a2 R a3 One or more of the aminocaprolactams with substituent groups; Preferably, the caprolactam having nitrogen-containing side groups is prepared from lysine.

10. The method according to claim 8 or 9, wherein, The diamine is selected from one or more of polyether diamine, polyester diamine, diamino-terminated polysiloxane, polyoxyethylene diamine, polyoxypropylene diamine, diamino-terminated polyethylene oxide-propylene oxide copolymer, polytetramethylene ether diamine, polyethyleneimine, ethylenediamine, propylenediamine, butanediamine, pentanediamine, hexamethylenediamine, furan diamine, and p-phenylenediamine, preferably one or more of hexamethylenediamine, p-phenylenediamine, polyether diamine, diamino-terminated polysiloxane, and polyethyleneimine; preferably, the polyether diamine is selected from polyetheramine D50 to 20000, more preferably from polyetheramine D200 to 3000, and even more preferably from one or more of polyetheramine D230, polyetheramine D400, polyetheramine D900, polyetheramine D1000, and polyetheramine D2000; and / or The dicarboxylic acid is one or more of phthalic acid, adipic acid, azelaic acid, oxalic acid, sebacic acid, octanoic acid, and furanyl dicarboxylic acid.

11. The method according to any one of claims 8-10, wherein, The conditions for the copolymerization reaction include: a reaction temperature of 180–280°C, preferably 200–260°C; and a reaction time of 1–10 h, preferably 3–8 h. The inert atmosphere includes one or more of nitrogen and argon, preferably nitrogen.

12. The method according to any one of claims 8-11, wherein, Based on the total weight of the reactants, the caprolactam having nitrogen-containing side groups comprises 1–50 wt%, preferably 1–40 wt%; the lactam compound comprises 1–95 wt%, preferably 5–90 wt%; the diacid comprises 1–50 wt%, preferably 1–40 wt%; the diamine comprises 1–90 wt%, preferably 1–70 wt%; and / or The molar ratio of the lactam compound to the caprolactam having a nitrogen-containing side group is 0.01 to 100:1, preferably 0.02 to 50:

1.

13. The method according to any one of claims 8-12, further comprising: The copolyamide is brought into contact with a quaternizing agent in a solvent to carry out a quaternization reaction, thereby obtaining a quaternized copolyamide; Preferably, the quaternizing agent is selected from halogenated hydrocarbons and / or sulfonate lactones; Preferably, the conditions for the quaternization reaction include: a reaction temperature of 0–60°C, more preferably 20–60°C; and a reaction time of 1–10 h, more preferably 2–9 h. Preferably, the solvent is selected from one or more of N,N-dimethylformamide, toluene, xylene, ethanol, ethylene glycol, dimethyl sulfoxide, dioxane, tetrahydrofuran, dichloromethane, and water; Preferably, the molar ratio of the quaternizing agent to the caprolactam having nitrogen-containing side groups is 0.1 to 1:

1.

14. The copolyamide according to any one of claims 1-7 or the copolyamide prepared by the method according to any one of claims 8-13, wherein, The crystallization temperature of the copolyamide is 70℃~230℃; and / or The melting point of the copolyamide is 80℃~250℃; and / or The thermal decomposition temperature of the copolyamide is 300–450°C; and / or The biochar content of the copolyamide is 1 wt% or more, preferably 1 to 50 wt%.

15. The use of the copolyamide according to any one of claims 1-7 or the copolyamide prepared by the method according to any one of claims 8-13 in the preparation of anti-counterfeiting materials, UV-resistant coatings, optical materials, medical devices, highly transparent polyamide products, antibacterial materials, antistatic materials and / or flame-retardant materials.

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