Flame-retardant nylon material as well as preparation method and application thereof

Abstract

The invention discloses a flame-retardant nylon material as well as a preparation method and application thereof, relates to the technical field of flame-retardant high polymer materials, and solves the problems that a flame-retardant nylon material prepared by a blending method is unstable in flame-retardant effect and a flame-retardant nylon material prepared by a copolymerization method is complex in process. The preparation method comprises the following steps: carrying out ring-opening copolymerization on a seven-membered ring lysine derivative monomer formed by ring formation of lysine and other lactam monomers to obtain copolyamide with a functional group on a side chain, and reacting a reagent containing a flame-retardant group with the functional group to prepare the flame-retardant nylon material. The flame-retardant nylon material prepared by the invention can effectively avoid migration and loss of the flame retardant, improve the dispersity of the flame retardant and enhance the flame-retardant effect. Meanwhile, a renewable lysine resource is used for partially replacing a petroleum resource, so that the method has the advantages of resource conservation, environmental friendliness, simple process, low production cost and the like. The flame-retardant nylon material disclosed by the invention has lasting and stable flame-retardant performance and can be widely applied to the fields of automobiles, textiles, electronics and electricity, buildings, packaging and the like.

Description

Technical Field

[0001] The invention relates to the technical field of flame retardant polymer materials, and in particular to a flame retardant nylon material and a preparation method and application thereof. Background Art

[0002] Polyamide (abbreviated as nylon) is a thermoplastic engineering plastic containing amide bonds in the main chain of the molecule. Since it was introduced by DuPont in the United States in 1930, it has become one of the engineering plastics with the most varieties, the largest output and the widest application range in the world. Unfortunately, however, most nylons have poor flame retardancy and are flammable polymer materials. When burning, they will generate a lot of heat and molten droplets, which can easily cause secondary fires and seriously threaten people's lives and property safety, which to a certain extent limits the application of nylon materials.

[0003] At present, the methods for flame retardant modification of nylon mainly include blending and copolymerization. Blending refers to dispersing flame retardants in nylon materials by melt blending to achieve flame retardant modification. It has the advantages of simple process, easy operation, low cost and wide application, and is the main method for producing flame retardant nylon. However, this method is difficult to control the distribution of flame retardants in the material, agglomeration will occur, and there is microscopic phase separation between the flame retardant and the nylon base material, which has a great impact on the mechanical properties of the material. At the same time, during use, problems such as migration and precipitation of flame retardants may occur, resulting in poor flame retardant durability and unstable effect. Copolymerization refers to directly combining flame retardants with the main chain or side chain of the polymer through monomer structure design to give flame retardant properties. This method can avoid problems such as uneven distribution, migration, precipitation of flame retardants and poor compatibility with base materials, has good flame retardant durability, and does not require secondary processing in the later stage, reducing the impact on material properties. It is an ideal method for flame retardant modification of nylon. However, this method usually requires a special monomer structure design, there are fewer types of copolymer monomers containing flame retardants, and the processing technology is complicated and the production cost is high. Currently, there is no widely used blended flame retardant modification method.

[0004] In addition, whether it is flame retardant modification of blends or flame retardant modification of copolymers, the raw materials used are mainly derived from non-renewable resources such as petroleum, which is not conducive to the stability and sustainable development of the nylon industry. Therefore, it is still of great significance to replace (or partially replace) petroleum resources with biomass resources to produce nylon materials and develop new processes to achieve flame retardant modification. Summary of the invention

[0005] In order to solve the technical problems that the flame retardant effect of flame retardant nylon materials prepared by blending method is unstable and the process of preparing nylon flame retardant materials by copolymerization method is complicated, the present invention proposes a flame retardant nylon material and its preparation method and application.

[0006] The technical solution of the present invention is as follows:

[0007] A flame retardant nylon material, the molecular structure of which comprises two different repeating units represented by the following formulas I and III or II and III:

[0008]

[0009] Wherein, n is any natural number selected from 1 to 8;

[0010] x and y represent the molar proportion of each part of the repeating unit, x is selected from 0.01 to 0.50, y is selected from 0.50 to 0.99, and x+y=1;

[0011] R 1 Selected from hydrogen, C 1～10 Substituted / unsubstituted, straight-chain / branched aliphatic hydrocarbon group, substituted / unsubstituted C 3～12 One of an alicyclic hydrocarbon group, a substituted / unsubstituted aryl group, and a substituted / unsubstituted aralkyl group;

[0012] R 2 and R 3 Each independently selected from C 1～10 Substituted / unsubstituted, straight-chain / branched aliphatic hydrocarbon group, substituted / unsubstituted C 3～12 One of an alicyclic hydrocarbon group, a substituted / unsubstituted aryl group, and a substituted / unsubstituted aralkyl group;

[0013] More preferably, R 1 Selected from hydrogen, C 1～5 Straight chain / branched aliphatic hydrocarbon group, substituted / unsubstituted C 3～6 One of alicyclic hydrocarbon group, substituted / unsubstituted aryl group, substituted / unsubstituted aralkyl group; R 2 and R 3 Each independently selected from C 1～5 Straight chain / branched aliphatic hydrocarbon group, substituted / unsubstituted C 3～6 One of an alicyclic hydrocarbon group, a substituted / unsubstituted aryl group, and a substituted / unsubstituted aralkyl group.

[0014] R is selected from one of the structures shown in the following formula IV:

[0015]

[0016] Among them, Z 1 , Z 2 are each independently selected from hydrogen, C 1～10 One of branched / branched aliphatic hydrocarbon group, hydroxyl group, methoxy group, tert-butoxy group, cyano group, boric acid, and boric acid ester;

[0017] Z 3 , Z 4 , Z 5Each independently selected from C 1～10 One of a linear / branched aliphatic hydrocarbon group, a substituted / unsubstituted aryl group, and a substituted / unsubstituted aralkyl group;

[0018] X 1 , X 2 Each is independently selected from an oxygen atom or an imino group.

[0019] More preferably, Z 1 , Z 2 are independently selected from hydrogen, C 1～5 One of linear / branched aliphatic hydrocarbon, methoxy, tert-butoxy, cyano, and boric acid; Z 3 , Z 4 , Z 5 Each independently selected from C 1～5 One of a linear / branched aliphatic hydrocarbon group, a substituted / unsubstituted aryl group, and a substituted / unsubstituted aralkyl group.

[0020] The present invention also provides a method for preparing the flame retardant nylon material, comprising the following steps:

[0021] Step 1: mixing a seven-membered cyclic lysine derivative monomer with a lactam monomer, and performing ring-opening copolymerization to obtain a copolyamide having a functional group on the side chain;

[0022] Step 2: using the copolyamide obtained in step 1 to react with a reagent containing a flame retardant group in a solvent to obtain a flame retardant nylon material;

[0023] Wherein, the structural formula of the seven-membered cyclic lysine derivative monomer is shown in the following formula V:

[0024]

[0025] Among them, R 4 and R 5 are each independently selected from hydrogen, C 1～10 Substituted / unsubstituted, straight-chain / branched aliphatic hydrocarbon group, substituted / unsubstituted C 3～12 One of an alicyclic hydrocarbon group, a substituted / unsubstituted aryl group, and a substituted / unsubstituted aralkyl group;

[0026] More preferably, R 4 and R 5 are each independently selected from hydrogen, C 1～5 Straight chain / branched aliphatic hydrocarbon group, substituted / unsubstituted C 3～6 One of an alicyclic hydrocarbon group, a substituted / unsubstituted aryl group, and a substituted / unsubstituted aralkyl group.

[0027] Specifically, when R 4 and R 5When both are hydrogen, it is referred to as an unprotected cyclic lysine monomer. The flame retardant nylon obtained is composed of the structural units shown in Formula I and Formula III, and R in Formula I 1 is hydrogen;

[0028] When R 4 and R 5 When one of them is hydrogen and the other is not hydrogen, it is referred to as a single protected cyclic lysine monomer. The flame retardant nylon obtained is composed of the structural units shown in Formula I and Formula III, and R in Formula I 1 With R in Formula V 4 , R 5 The same structure as the one in which hydrogen is not present;

[0029] When R 4 and R 5 When both are not hydrogen, it is referred to as a double protected cyclic lysine monomer. The flame retardant nylon obtained is composed of the structural units shown in formula II and formula III, and R in formula II 2 , R 3 With R in Formula V 4 , R 5 same.

[0030] The structural formula of the lactam is shown in the following formula VI:

[0031]

[0032] Wherein, n is any natural number selected from 1 to 8.

[0033] Preferably, the preparation method of the seven-membered cyclic lysine derivative monomer is as follows:

[0034] Lysine hydrochloride / lysine / aqueous solution containing lysine is mixed with methanol, an equimolar amount of sodium hydroxide is added / not added, and a dehydration cyclization reaction is carried out at 125°C to 200°C, and aminocaprolactam (unprotected cyclic lysine monomer, R in Formula V) is obtained after extraction with ethyl acetate. 4 , R 5 are hydrogen);

[0035] Or continue with R 4 and / or R 5 The corresponding aldehydes and / or halogenated hydrocarbons of the group are reacted to obtain a single-protected or double-protected cyclic lysine monomer.

[0036] Preferably, the ring-opening copolymerization method of the seven-membered cyclic lysine derivative monomer and the lactam monomer in step 1 is selected from one of hydrolysis polymerization and anion polymerization;

[0037] The hydrolysis polymerization method requires the addition of water and an optional molecular weight regulator, and the molar ratio of the seven-membered cyclic lysine derivative monomer, caprolactam, water and molecular weight regulator is (1-100):100:(0.1-5):(0-5); the polymerization temperature is 140° C. to 320° C., the polymerization time is 2 h to 96 h, and the polymerization pressure is -0.1 MPa to 5 MPa;

[0038] Furthermore, the hydrolysis polymerization can be divided into three stages: pressure reaction, normal pressure reaction and reduced pressure reaction. The reaction conditions of each stage are as follows:

[0039] Pressurized reaction stage: polymerization temperature is 140℃~230℃; polymerization time is 2h~24h; polymerization pressure is 0.3MPa~5MPa; Normal pressure reaction stage: polymerization temperature is 180℃~280℃; polymerization time is 0.5h~10h; polymerization pressure is -0.05MPa~0.1MPa; Reduced pressure reaction stage: polymerization temperature is 200℃~320℃; polymerization time is 2h~36h; polymerization pressure is -0.1MPa~0MPa.

[0040] The anionic polymerization method requires the addition of an activator and a catalyst, and the molar ratio of the seven-membered cyclic lysine derivative monomer, caprolactam, activator and catalyst is (1-100):100:(0.1-5):(0.1-5); the polymerization temperature is 140°C-230°C, and the polymerization time is 1h-6h.

[0041] Preferably, the molecular weight regulator is selected from one of acetic acid, adipic acid and benzoic acid.

[0042] Preferably, the catalyst in the anionic polymerization method is selected from one or a combination of at least two of alkali metals, alkali metal oxides, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides, alkaline earth metals, alkaline earth metal oxides, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal alkoxides, carbene reagents, guanidine reagents, amidine reagents, and phosphazene reagents;

[0043] More preferably, the catalyst is selected from one of sodium hydride, potassium hydride, phosphazene base, potassium tert-butoxide, sodium methoxide, potassium methoxide, sodium and potassium.

[0044] Preferably, the activator in the anionic polymerization method has a structure as shown in Formula VII:

[0045]

[0046] Among them, R 6 Selected from hydrogen, C 1～5 The substituted / unsubstituted, linear / branched aliphatic hydrocarbon group, substituted / unsubstituted aryl group is preferably one of methyl, ethyl, phenyl, tert-butylphenyl and trifluoromethylphenyl.

[0047] More preferably, R 6 It is one of methyl, ethyl, phenyl, tert-butylphenyl and trifluoromethylphenyl.

[0048] Preferably, the flame retardant group-containing reagent in step 2 has R-Hal or RR 7 -Hal structure, wherein R is selected from one of the structures shown in formula IV, R 7 Selected from C 1～10 An aliphatic hydrocarbon group, a substituted / unsubstituted aromatic group, and Hal is selected from a group consisting of chlorine, bromine and iodine; the reagent containing the flame retardant group can be directly purchased or synthesized by conventional chemical methods.

[0049] More preferably, R 7 Selected from C 1～6 The invention relates to an aliphatic hydrocarbon group, a substituted or unsubstituted aromatic group; Hal is selected from one of chlorine and bromine.

[0050] Preferably, the solvent in step 2 is selected from one or a combination of at least two of water, methanol, ethanol, trifluoroethanol, hexafluoroisopropanol, benzyl alcohol, ethylene glycol, and cyclohexanol; more preferably, it is one of methanol, ethanol, trifluoroethanol, and hexafluoroisopropanol. The reaction temperature is 20°C to 100°C, and the reaction time is 2h to 12h.

[0051] The present invention also provides an application of the flame retardant nylon material, which is specifically applied to the fields of automobile, textile, electrical and electronic, construction and packaging.

[0052] Compared with the prior art, the specific beneficial effects of the present invention are:

[0053] The present invention uses a seven-membered cyclic lysine derivative monomer formed by lysine ring formation to open-ring copolymerize with other lactam monomers to obtain a copolyamide with a functional group on the side chain, and then uses a reagent containing a flame retardant group to react with the functional group to prepare a flame retardant nylon material. Compared with the existing method of flame retardant modification of nylon by blending, the present invention uses the functional group of the polyamide side chain to react with the reagent containing the flame retardant group to directly connect the flame retardant group to the side chain of the polyamide, which can avoid the migration and loss of the flame retardant, improve the dispersibility of the flame retardant, and enhance the stability and durability of the flame retardant performance.

[0054] Compared with the existing method of flame-retardant modification of nylon by copolymerization, the preparation process provided by the present invention is simple, the production cost is low, and it is more suitable for the industrial production of flame-retardant nylon materials.

[0055] The present invention partially replaces petroleum resources with renewable lysine resources, has the characteristics of resource conservation and environmental friendliness, and is in line with the "dual carbon" strategy and sustainable development needs.

[0056] The flame-retardant nylon material of the present invention has a durable and stable flame-retardant property and can be widely used in the fields of automobile, textile, electrical and electronic, construction, packaging, etc. DETAILED DESCRIPTION

[0057] In order to make the technical solution of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below. It should be noted that the following embodiments are only used to better understand the technical solution of the present invention and should not be understood as limiting the present invention.

[0058] Example 1.

[0059] (1) aminocaprolactam (unprotected cyclic lysine, R in formula V) 4 , R 5 All are hydrogen) preparation:

[0060] In a 100L reactor, add 50mol of lysine hydrochloride, 50mol of sodium hydroxide and 50L of methanol, and react at 190°C for 3h under a nitrogen atmosphere. Cool to room temperature, filter, remove insoluble matter, evaporate to dryness and recover methanol, extract with ethyl acetate to obtain aminocaprolactam, with a yield of 94%, and a purity of 99% according to H-NMR analysis. 1 H NMR (300 MHz, D 2 O)δ3.69-3.72(dd,1H),3.22-3.26(m,2H),1.26-1.99(m,6H).

[0061] (2) Preparation of copolyamide:

[0062] Weigh 10 mmol of aminocaprolactam prepared in step (1) and 100 mmol of caprolactam into a reactor, then add 0.1 mmol of water, replace with nitrogen and maintain the nitrogen atmosphere, react under pressure at 190°C and 0.8 MPa for 6 h, then heat to 210°C and react at normal pressure for 1 h, and finally react under reduced pressure at 230°C and -0.1 MPa for 3 h to obtain copolyamide with a yield of 85%.

[0063] (3) Preparation of flame retardant nylon:

[0064] The copolyamide prepared in step (2) was dissolved in 100 mL of trifluoroethanol, 10 mmol of triethylamine and 10 mmol of diphenylphosphine chloride were added, and the mixture was stirred at room temperature for 24 h. The reaction solution was precipitated in methanol, and the flame retardant nylon material was obtained after centrifugation and drying, with a yield of 98%.

[0065] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1is hydrogen, R is the structure A in formula Ⅳ (Z 1 , Z 2 are all hydrogen); in formula III, n=4.

[0066] Example 2.

[0067] (1) aminocaprolactam (unprotected cyclic lysine, R in formula V) 4 , R 5 All are hydrogen) preparation:

[0068] In a 100L reactor, add 50mol of lysine and 50L of methanol, stir and react at 190°C for 3h. Cool to room temperature, evaporate to dryness and recover methanol, extract with ethyl acetate to obtain α-amino-ε-caprolactam with a yield of 95%. According to H-NMR analysis, the purity is 98%. 1 H NMR (300 MHz, D 2 O)δ3.69-3.72(dd,1H),3.22-3.26(m,2H),1.26-1.99(m,6H).

[0069] (2) Preparation of copolyamide:

[0070] Weigh 50 mmol of aminocaprolactam prepared in step (1) and 100 mmol of caprolactam into a reactor, then add 0.5 mmol of water, replace with nitrogen and maintain the nitrogen atmosphere, pressurize and react at 200°C and 0.5 MPa for 2 h, then heat to 210°C and react at normal pressure for 1 h, and finally react at 230°C and -0.1 MPa for 5 h to obtain copolyamide with a yield of 80%.

[0071] (3) Preparation of flame retardant nylon:

[0072] The copolyamide prepared in step (2) was dissolved in 120 mL of trifluoroethanol, 50 mmol of triethylamine and 50 mmol of methyl phenylchlorophosphonate were added, and the mixture was stirred at room temperature for 24 h. The reaction solution was precipitated in methanol, and the flame-retardant nylon material was obtained after centrifugation and drying, with a yield of 90%.

[0073] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1 is hydrogen, R is the B structure (Z 1 is methoxy, Z 2 is hydrogen); in formula III, n=4.

[0074] Example 3.

[0075] (1) aminocaprolactam (unprotected cyclic lysine, R in formula V) 4 , R 5 All are hydrogen) preparation:

[0076] In a 100L reactor, add 14.6kg of lysine fermentation liquid (lysine content is 50%) and 40L of methanol, stir and react at 190°C for 3h. Cool to room temperature, filter, remove insoluble matter, evaporate to dryness and recover methanol, extract with ethyl acetate to obtain α-amino-ε-caprolactam, the yield is 90%, and the purity is 98% according to nuclear magnetic hydrogen spectrum analysis. 1 H NMR (300 MHz, D 2 O)δ3.69-3.72(dd,1H),3.22-3.26(m,2H),1.26-1.99(m,6H).

[0077] (2) Preparation of copolyamide:

[0078] Weigh 20 mmol of aminocaprolactam prepared in step (1) and 100 mmol of caprolactam into a reactor, then add 0.2 mmol of water and 0.1 mmol of benzoic acid, replace with nitrogen and maintain the nitrogen atmosphere, react under pressure at 180°C and 0.3 MPa for 2 h, then heat to 200°C and react under normal pressure for 5 h, and finally react under reduced pressure at 250°C and -0.1 MPa for 5 h to obtain copolyamide with a yield of 88%.

[0079] (3) Preparation of flame retardant nylon:

[0080] The copolyamide prepared in step (2) was dissolved in 110 mL of trifluoroethanol, and 20 mmol of triethylamine and 20 mmol of phenylchlorophosphonate were added. The mixture was stirred at room temperature for 24 h. The reaction solution was precipitated in methanol, and the flame-retardant nylon material was obtained after centrifugation and drying. The yield was 92%.

[0081] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1 is hydrogen, R is the C structure (Z 2 is hydrogen, Z 3 is methoxy, X 1 is oxygen); in formula III, n=4.

[0082] Example 4.

[0083] (1) Preparation of copolyamide:

[0084] 80 mmol of aminocaprolactam prepared in step (1) of Example 1 and 100 mmol of caprolactam were weighed and added to a reactor, followed by addition of 1 mmol of water and 1 mmol of benzoic acid. The mixture was replaced with nitrogen and maintained under a nitrogen atmosphere. The mixture was reacted under pressure at 180° C. and 1.5 MPa for 5 h, then heated to 200° C. and reacted under normal pressure for 5 h. Finally, the mixture was reacted under reduced pressure at 230° C. and −0.1 MPa for 5 h to obtain copolyamide with a yield of 90%.

[0085] (2) Preparation of flame retardant nylon:

[0086] First, 2-amino-4,6-dichloro-S-triazine is reacted with aniline to obtain 2,4-diphenyl-melamine, which is then further reacted with phosphorus oxychloride to prepare an intermediate product R-Cl containing a flame retardant group.

[0087] The copolyamide prepared in step (1) was dissolved in 200 mL of trifluoroethanol, 80 mmol of triethylamine and 80 mmol of the prepared intermediate product R-Cl were added, and the mixture was stirred and reacted at room temperature for 24 h. The reaction solution was precipitated in methanol, and a flame-retardant nylon material was obtained after centrifugation and drying, with a yield of 93%.

[0088] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1 is hydrogen, R is the F structure (X 1 , X 2 is imino, Z 4 , Z 5 is phenyl); in formula III, n=4.

[0089] Example 5.

[0090] (1) Preparation of copolyamide:

[0091] 10 mmol of aminocaprolactam prepared in step (1) of Example 1 and 100 mmol of caprolactam were weighed and added to a reactor, followed by addition of 0.1 mmol of water and 0.1 mmol of adipic acid. The mixture was replaced with nitrogen and maintained under a nitrogen atmosphere. The mixture was reacted under pressure at 160° C. and 1.5 MPa for 2 h, then heated to 180° C. and reacted under normal pressure for 4 h. Finally, the mixture was reacted under reduced pressure at 210° C. and −0.1 MPa for 5 h to obtain copolyamide with a yield of 75%.

[0092] (2) Preparation of flame retardant nylon:

[0093] Firstly, 2,4,6-trichloro-1,3,5-triazine is reacted with aniline to prepare an intermediate product R-Cl containing a flame retardant group.

[0094] The copolyamide prepared in step (1) was dissolved in 100 mL of trifluoroethanol, 10 mmol of triethylamine and 10 mmol of the prepared intermediate product R-Cl were added, and the mixture was stirred and reacted at room temperature for 24 h. The reaction solution was precipitated in methanol, and a flame-retardant nylon material was obtained after centrifugation and drying, with a yield of 90%.

[0095] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1 is hydrogen, R is the M structure (X 1 , X2 is imino, Z 4 , Z 5 is phenyl); in formula III, n=4.

[0096] Example 6.

[0097] (1) Preparation of copolyamide:

[0098] 10 mmol of aminocaprolactam prepared in step (1) of Example 1 and 100 mmol of caprolactam were weighed and added to a reactor, followed by addition of 0.1 mmol of water and 0.1 mmol of adipic acid. The mixture was replaced with nitrogen and maintained under a nitrogen atmosphere. The mixture was reacted under pressure at 180°C and 0.8 MPa for 5 h, then heated to 210°C and reacted under normal pressure for 4 h. Finally, the mixture was reacted under reduced pressure at 230°C and -0.1 MPa for 5 h to obtain copolyamide with a yield of 86%.

[0099] (2) Preparation of flame retardant nylon:

[0100] Firstly, hexachlorocyclotriphosphine is reacted with aniline to prepare an intermediate product R-Cl containing a flame retardant group.

[0101] The copolyamide prepared in step (1) was dissolved in 100 mL of trifluoroethanol, 10 mmol of triethylamine and 10 mmol of the prepared intermediate product R-Cl were added, and the mixture was stirred and reacted at room temperature for 24 h. The reaction solution was precipitated in methanol, and a flame-retardant nylon material was obtained after centrifugation and drying, with a yield of 94%.

[0102] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1 is hydrogen, R is the N structure (X 1 , X 2 is imino, Z 4 , Z 5 is phenyl); in formula III, n=4.

[0103] Example 7.

[0104] (1) Preparation of copolyamide:

[0105] 10 mmol of aminocaprolactam prepared in step (1) of Example 1 and 100 mmol of caprolactam were weighed and added to a reactor, followed by addition of 0.1 mmol of water and 0.1 mmol of adipic acid. The mixture was replaced with nitrogen and maintained under a nitrogen atmosphere. The mixture was reacted under pressure at 180°C and 0.8 MPa for 5 h, then heated to 210°C and reacted under normal pressure for 4 h. Finally, the mixture was reacted under reduced pressure at 230°C and -0.1 MPa for 5 h to obtain copolyamide with a yield of 86%.

[0106] (2) Preparation of flame retardant nylon:

[0107] First, 3-chloropropylamine was reacted with benzaldehyde, and then further reacted with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) to prepare an intermediate product R-Cl containing a flame retardant group.

[0108] The copolyamide prepared in step (1) was dissolved in 100 mL of trifluoroethanol, 10 mmol of triethylamine and 10 mmol of the prepared intermediate product R-Cl were added, and the mixture was stirred and reacted at room temperature for 24 h. The reaction solution was precipitated in methanol, and a flame-retardant nylon material was obtained after centrifugation and drying, with a yield of 95%.

[0109] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1 is hydrogen, R is the H structure (Z 3 is phenyl); in formula III, n=4.

[0110] Example 8.

[0111] (1) Monomethyl seven-membered cyclic lysine derivative monomer (monoprotected cyclic lysine, R in formula V 4 is hydrogen, R 5 For methyl) preparation:

[0112] 1 mol of aminocaprolactam prepared in step (1) of Example 1 was weighed and added to a 5 L reactor, and then 2 L of methanol, 1 mol of paraformaldehyde and 6.4 g of Pd / C catalyst were added. After nitrogen replacement, hydrogen was charged to 3.0 MPa, and the mixture was stirred at 120° C. for 2 h. After cooling to room temperature, the Pd / C catalyst was recovered by suction filtration, and the filtrate was spin-dried and recrystallized from ethyl acetate to obtain monomethyl protected cyclic lysine with a yield of 95%. The purity was 98% according to H NMR analysis. 1 H NMR (300 MHz, CDCl 3 ): δ6.00(s,1H),3.50-3.54(m,1H),3.26-3.31(m,4H),2.87-2.90(m,1H),2.50(s,1H),2.06-2.12(m,1H),1.43-1.68(m,5H).

[0113] (2) Preparation of copolyamide:

[0114] Weigh 10 mmol of the monomethyl protected cyclic lysine prepared in step (1) and 100 mmol of caprolactam into a reactor, then add 0.1 mmol of water, replace with nitrogen and maintain the nitrogen atmosphere, react under pressure at 180°C and 0.8 MPa for 2 h, then heat to 210°C and react under normal pressure for 4 h, and finally react under reduced pressure at 230°C and -0.1 MPa for 5 h to obtain copolyamide with a yield of 82%.

[0115] (3) Preparation of flame retardant nylon:

[0116] The copolyamide prepared in step (2) was dissolved in 100 mL of trifluoroethanol, and 10 mmol of triethylamine and 10 mmol of N, N'-diphenylphosphoryl diammonium chloride were added. The mixture was stirred at room temperature for 24 h. The reaction solution was precipitated in methanol, and the flame-retardant nylon material was obtained after centrifugation and drying. The yield was 94%.

[0117] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1 is methyl, R is the D structure (Z 1 , Z 2 All are hydrogen, X 1 is an imino group); in formula III, n=4.

[0118] Example 9.

[0119] (1) Preparation of copolyamide:

[0120] Weigh 20 mmol of the monomethyl protected cyclic lysine prepared in step (1) of Example 7 and 100 mmol of caprolactam into a reactor, then add 0.2 mmol of water, replace with nitrogen and maintain the nitrogen atmosphere, react under pressure at 180°C and 0.8 MPa for 2 h, then heat to 210°C and react under normal pressure for 4 h, and finally react under reduced pressure at 230°C and -0.1 MPa for 5 h to obtain copolyamide with a yield of 80%.

[0121] (2) Preparation of flame retardant nylon:

[0122] Firstly, phosphorus oxychloride is reacted with pentaerythritol phosphate and aniline to prepare an intermediate product R-Cl containing a flame retardant group.

[0123] The copolyamide prepared in step (1) was dissolved in 110 mL of trifluoroethanol, 20 mmol of triethylamine and 20 mmol of the prepared intermediate product R-Cl were added, and the mixture was stirred and reacted at room temperature for 24 h. The reaction solution was precipitated in methanol, and a flame-retardant nylon material was obtained after centrifugation and drying, with a yield of 93%.

[0124] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1 is methyl, R is the structure E in formula IV (Z 1 is hydrogen, X 1 is an imino group, X 2 is oxygen); in formula III, n=4.

[0125] Example 10.

[0126] (1) Preparation of copolyamide:

[0127] 10 mmol of the monomethyl protected cyclic lysine prepared in step (1) of Example 7 and 100 mmol of caprolactam were weighed and added to the reactor, and then 0.1 mmol of water was added, and nitrogen was replaced and the nitrogen atmosphere was maintained. The reaction was carried out under pressure at 180°C and 0.8 MPa for 2 h, and then the temperature was raised to 210°C and normal pressure for 4 h. Finally, the reaction was carried out under reduced pressure at 230°C and -0.1 MPa for 5 h to obtain copolyamide with a yield of 83%.

[0128] (2) Preparation of flame retardant nylon:

[0129] Firstly, diphenylphosphine chloride is reacted with piperazine to obtain an intermediate, which is then reacted with phenylphosphine dichloride to prepare an intermediate product R-Cl containing a flame retardant group.

[0130] The copolyamide prepared in step (1) was dissolved in 100 mL of trifluoroethanol, 10 mmol of triethylamine and 10 mmol of the prepared intermediate product R-Cl were added, and the mixture was stirred and reacted at room temperature for 24 h. The reaction solution was precipitated in methanol, and a flame-retardant nylon material was obtained after centrifugation and drying, with a yield of 93%.

[0131] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1 is methyl, R is the G structure (Z 4 , Z 5 are all hydrogen); in formula III, n=4.

[0132] Example 11.

[0133] (1) Monobenzyl seven-membered cyclic lysine derivative monomer (monoprotected cyclic lysine, R in formula V 4 is hydrogen, R 5 is benzyl) preparation:

[0134] 1 mol of aminocaprolactam prepared in step (1) of Example 1 was weighed and added to a 5 L reactor, and then 2 L of methanol, 1 mol of benzaldehyde and 6.4 g of Pd / C catalyst were added. After nitrogen replacement, hydrogen was charged to 3.0 MPa, and the reaction was stirred at room temperature for 2 h. The Pd / C catalyst was recovered by suction filtration, and the filtrate was spin-dried and recrystallized from ethyl acetate to obtain monobenzyl-protected cyclic lysine with a yield of 93%. The purity was 98% according to H NMR analysis. 1 H NMR (300 MHz, CDCl 3 ): δ7.23-7.38(m,5H),6.37(s,1H),3.69-3.89(m,2H),3.11-3.33(m,3H),2.38(s,1H),1.96-2.02(m,2H),1.35-1.79(m,4H).

[0135] (2) Preparation of copolyamide:

[0136] 10 mmol of the monobenzyl protected cyclic lysine prepared in step (1) and 100 mmol of caprolactam were weighed and added to the reactor, and then 0.1 mmol of water was added, and nitrogen was replaced and the nitrogen atmosphere was maintained. The reaction was carried out under pressure at 180° C. and 0.8 MPa for 2 h, and then the temperature was raised to 210° C. and reacted under normal pressure for 4 h. Finally, the reaction was carried out under reduced pressure at 230° C. and -0.1 MPa for 5 h to obtain copolyamide with a yield of 82%.

[0137] (3) Preparation of flame retardant nylon:

[0138] Firstly, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) was reacted with dichlorothionyl to prepare an intermediate product R-Cl containing a flame retardant group.

[0139] The copolyamide prepared in step (2) was dissolved in 100 mL of trifluoroethanol, 10 mmol of triethylamine and 10 mmol of the prepared intermediate product R-Cl were added, and the mixture was stirred and reacted at room temperature for 24 h. The reaction solution was precipitated in methanol, and a flame-retardant nylon material was obtained after centrifugation and drying, with a yield of 93%.

[0140] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1 is benzyl, R is structure I in formula IV; and n=4 in formula III.

[0141] Example 12.

[0142] (1) Preparation of copolyamide:

[0143] 10 mmol of the monobenzyl-protected cyclic lysine prepared in step (1) of Example 10 and 100 mmol of caprolactam were weighed and added to the reactor, and then 0.1 mmol of water was added, and nitrogen was replaced and the nitrogen atmosphere was maintained. The reaction was carried out under pressure at 180° C. and 0.8 MPa for 2 h, and then the temperature was raised to 210° C. and reacted under normal pressure for 4 h. Finally, the reaction was carried out under reduced pressure at 230° C. and −0.1 MPa for 5 h to obtain copolyamide with a yield of 82%.

[0144] (3) Preparation of flame retardant nylon:

[0145] The copolyamide prepared in step (2) was dissolved in 100 mL of trifluoroethanol, and 10 mmol of triethylamine and 10 mmol of 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphahexanal phosphate were added. The mixture was stirred at room temperature for 24 h. The reaction solution was precipitated in methanol, and a flame-retardant nylon material was obtained after centrifugation and drying. The yield was 93%.

[0146] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1 is benzyl, R is the J structure in formula IV; and n=4 in formula III.

[0147] Example 13.

[0148] (1) Preparation of copolyamide:

[0149] 5 mmol of the monobenzyl-protected cyclic lysine prepared in step (1) of Example 10 and 100 mmol of caprolactam were weighed and added to the reactor, and then 0.1 mmol of water was added, and nitrogen was replaced and the nitrogen atmosphere was maintained. The reaction was carried out under pressure at 180° C. and 0.8 MPa for 2 h, and then the temperature was raised to 210° C. and reacted under normal pressure for 4 h. Finally, the reaction was carried out under reduced pressure at 230° C. and −0.1 MPa for 5 h to obtain copolyamide with a yield of 86%.

[0150] (3) Preparation of flame retardant nylon:

[0151] Firstly, o-phenylenediamine is reacted with phosphorus oxychloride to prepare an intermediate product R-Cl containing a flame retardant group.

[0152] The copolyamide prepared in step (2) was dissolved in 100 mL of trifluoroethanol, 5 mmol of triethylamine and 5 mmol of the prepared intermediate product R-Cl were added, and the mixture was stirred and reacted at room temperature for 24 h. The reaction solution was precipitated in methanol, and a flame-retardant nylon material was obtained after centrifugation and drying, with a yield of 90%.

[0153] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1 is benzyl, R is the L structure (X 1 , X 2 is an imino group); in formula III, n=4.

[0154] Example 14.

[0155] (1) Diethyl seven-membered cyclic lysine derivative monomer (double protected cyclic lysine, R in formula V 4 , R 5 All are ethyl) preparation:

[0156] Weigh 1 mol of aminocaprolactam prepared in step (1) of Example 1 and add it to a 5 L reactor, then add 2 L of acetonitrile, 2 mol of potassium carbonate and 1 mmol of potassium iodide, stir evenly, add 2 mol of ethyl bromide, stir at 85 ° C for 10 h, cool to room temperature, filter, spin-dry the filtrate, and recrystallize from ethyl acetate to obtain diethyl-protected cyclic lysine with a yield of 85%. The purity is 96% according to H NMR analysis. 1 H NMR (300 MHz, CDCl 3): δ6.18(s,1H),3.45-3.55(m,2H),3.30-3.35(m,1H),2.60-2.80(m,4H),1.45-2.05(m,6H),1.02(t,6H).

[0157] (2) Preparation of copolyamide:

[0158] Weigh 10 mmol of the diethyl protected cyclic lysine prepared in step (1) and 100 mmol of caprolactam into a reactor, then add 0.1 mmol of water, replace with nitrogen and maintain the nitrogen atmosphere, react under pressure at 180°C and 0.8 MPa for 4 h, then heat to 210°C and react under normal pressure for 4 h, and finally react under reduced pressure at 230°C and -0.1 MPa for 8 h to obtain copolyamide with a yield of 85%.

[0159] (3) Preparation of flame retardant nylon:

[0160] Firstly, 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane 3,9-dioxide is reacted with phenol to prepare an intermediate product R-Cl containing a flame retardant group.

[0161] The copolyamide prepared in step (2) was dissolved in 100 mL of trifluoroethanol, 10 mmol of the prepared intermediate product R-Cl was added, and the mixture was stirred at 70° C. for 12 h. The reaction solution was precipitated in methanol, and the flame-retardant nylon material was obtained after centrifugation and drying, with a yield of 90%.

[0162] The flame retardant nylon obtained comprises structural units shown in formula II and formula III, wherein R 2 , R 3 are all ethyl, R is the K structure (Z 4 is phenyl, X 1 is oxygen); in formula III, n=4.

[0163] Example 15.

[0164] (1) Preparation of copolyamide:

[0165] 10 mmol of the diethyl protected cyclic lysine prepared in step (1) of Example 14, 100 mmol of caprolactam, 1 mmol of N-benzoyl caprolactam and 1 mmol of sodium hydride (NaH) were weighed and added into a reaction kettle. Under a nitrogen atmosphere, the mixture was stirred at 180° C. for 3 h to obtain copolyamide with a yield of 90%.

[0166] (3) Preparation of flame retardant nylon:

[0167] The copolyamide prepared in step (2) was dissolved in 100 mL of trifluoroethanol, 10 mmol of diphenylphosphine chloride was added, and the mixture was stirred at 70° C. for 12 h. The reaction solution was precipitated in methanol, centrifuged and dried to obtain a flame retardant nylon material with a yield of 95%.

[0168] The flame retardant nylon obtained comprises structural units shown in formula II and formula III, wherein R 2 , R 3 are all ethyl, R is the structure A in formula Ⅳ (Z 1 , Z 2 are all hydrogen); in formula III, n=4.

[0169] Example 16.

[0170] (1) Preparation of copolyamide:

[0171] 5 mmol of the diethyl protected cyclic lysine prepared in step (1) of Example 14, 100 mmol of caprolactam, 1 mmol of N-benzoyl caprolactam and 1 mmol of sodium hydride (NaH) were weighed and added into a reaction kettle. Under a nitrogen atmosphere, the mixture was stirred at 180° C. for 3 h to obtain copolyamide with a yield of 92%.

[0172] (3) Preparation of flame retardant nylon:

[0173] Firstly, hexachlorocyclotriphosphine is reacted with 4-methoxyphenol to prepare an intermediate product R-Cl containing a flame retardant group.

[0174] The copolyamide prepared in step (2) was dissolved in 100 mL of trifluoroethanol, 10 mmol of the prepared intermediate product R-Cl was added, and the mixture was stirred at 70° C. for 12 h. The reaction solution was precipitated in methanol, and the flame-retardant nylon material was obtained after centrifugation and drying, with a yield of 90%.

[0175] The flame retardant nylon obtained comprises structural units shown in formula II and formula III, wherein R 2 , R 3 are all ethyl, R is the N structure (Z 4 , Z 4 All are 4-methoxyphenyl, X 1 , X 2 are all y oxygen); in formula III, n=4.

[0176] Example 17.

[0177] (1) a dibenzyl seven-membered cyclic lysine derivative monomer (double-protected cyclic lysine, R in formula V 4 , R 5 All are benzyl) preparation:

[0178] 1 mol of aminocaprolactam prepared in step (1) of Example 1 was weighed and added to a 5 L reactor, followed by the addition of 2 L of acetonitrile, 2 mol of potassium carbonate and 1 mmol of potassium iodide. After stirring evenly, 2 mol of benzyl chloride was added, and the mixture was stirred at 85 ° C for 6 h. The mixture was cooled to room temperature, filtered, and the filtrate was spin-dried. The filtrate was recrystallized from ethyl acetate to obtain dibenzyl-protected cyclic lysine with a yield of 80%. The purity was 96% according to H NMR analysis. 1 H NMR (300 MHz, CDCl 3 ): δ7.19-7.39(m,10H),5.66(s,1H),3.86-4.09(m,4H),3.41-3.43(d,1H),2.85-3.13(m,2H),1.32-2.00(m,6H).

[0179] (2) Preparation of copolyamide:

[0180] Weigh 10 mmol of the diethyl protected cyclic lysine prepared in step (1) and 100 mmol of caprolactam into a reactor, then add 0.1 mmol of water, replace with nitrogen and maintain the nitrogen atmosphere, react under pressure at 180°C and 0.8 MPa for 4 h, then heat to 210°C and react under normal pressure for 6 h, and finally react under reduced pressure at 230°C and -0.1 MPa for 8 h to obtain copolyamide with a yield of 80%.

[0181] (3) Preparation of flame retardant nylon:

[0182] The copolyamide prepared in step (2) was dissolved in 100 mL of trifluoroethanol, 10 mmol of methyl phenylchlorophosphonate was added, and the mixture was stirred at 70° C. for 12 h. The reaction solution was precipitated in methanol, centrifuged and dried to obtain a flame retardant nylon material with a yield of 93%.

[0183] The flame retardant nylon obtained comprises structural units shown in formula II and formula III, wherein R 2 , R 3 are all benzyl, R is the B structure (Z 1 is methoxy, Z 2 is hydrogen); in formula III, n=4.

[0184] Example 18.

[0185] (1) Preparation of copolyamide:

[0186] 10 mmol of the dibenzyl-protected cyclic lysine prepared in step (1) of Example 17, 100 mmol of caprolactam, 1 mmol of N-benzoyl caprolactam and 1 mmol of sodium hydride (NaH) were weighed and added into a reaction kettle. Under a nitrogen atmosphere, the mixture was stirred at 180° C. for 3 h to obtain copolyamide with a yield of 85%.

[0187] (3) Preparation of flame retardant nylon:

[0188] The copolyamide prepared in step (2) was dissolved in 100 mL of trifluoroethanol, 10 mmol of 5,5-dimethyl-2-chloro-1,3,2-dioxaphosphahexanoyl phosphate was added, and the mixture was stirred at 70° C. for 12 h. The reaction solution was precipitated in methanol, and the flame-retardant nylon material was obtained after centrifugation and drying, with a yield of 92%.

[0189] The flame retardant nylon obtained comprises structural units shown in formula II and formula III, wherein R 2 , R 3 They are all benzyl groups, R is the J structure in formula IV; and n=4 in formula III.

[0190] Example 19.

[0191] (1) Preparation of copolyamide:

[0192] 5 mmol of the dibenzyl-protected cyclic lysine prepared in step (1) of Example 17, 100 mmol of caprolactam, 1 mmol of N-benzoyl caprolactam and 1 mmol of sodium hydride (NaH) were weighed and added into a reaction kettle. Under a nitrogen atmosphere, the mixture was stirred at 180° C. for 3 h to obtain copolyamide with a yield of 90%.

[0193] (3) Preparation of flame retardant nylon:

[0194] Firstly, o-phenylenediamine is reacted with phosphorus oxychloride to prepare an intermediate product R-Cl containing a flame retardant group.

[0195] The copolyamide prepared in step (2) was dissolved in 100 mL of trifluoroethanol, 10 mmol of the prepared intermediate product R-Cl was added, and the mixture was stirred at 70° C. for 12 h. The reaction solution was precipitated in methanol, centrifuged and dried to obtain a flame retardant nylon material with a yield of 92%.

[0196] The flame retardant nylon obtained comprises structural units shown in formula II and formula III, wherein R 2 , R 3 are all benzyl, R is the L structure (X 1 , X 2 is an imino group); in formula III, n=4.

[0197] Comparative Example 1.

[0198] 100 mmol of caprolactam was weighed and added into the polymerization reactor, and then 2 mmol of water was added. The nitrogen atmosphere was replaced and maintained, and the reaction was carried out under pressure at 180°C and 1.5 MPa for 5 hours, then the temperature was raised to 200°C and normal pressure was reacted for 5 hours, and finally the reaction was carried out under reduced pressure at 230°C and -0.1 MPa for 5 hours to obtain copolyamide with a yield of 90%.

[0199] Comparative Example 2.

[0200] (1) Preparation of copolyamide:

[0201] 0.5 mmol of aminocaprolactam prepared in step (1) of Example 1 and 100 mmol of caprolactam were weighed and added to the reactor, and then 0.1 mmol of water was added, and nitrogen was replaced and the nitrogen atmosphere was maintained. The reaction was carried out under pressure at 200°C and 0.5 MPa for 2 h, and then the temperature was raised to 210°C and normal pressure for 1 h. Finally, the reaction was carried out under reduced pressure at 230°C and -0.1 MPa for 5 h to obtain copolyamide with a yield of 85%.

[0202] (2) Preparation of flame retardant nylon:

[0203] The copolyamide prepared in step (1) was dissolved in 120 mL of trifluoroethanol, and 0.5 mmol of triethylamine and 0.5 mmol of methyl phenylchlorophosphonate were added. The mixture was stirred and reacted at room temperature for 24 h. The reaction solution was precipitated in methanol, and the flame-retardant nylon material was obtained after centrifugation and drying. The yield was 90%.

[0204] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1 is hydrogen, R is the B structure (Z 1 is methoxy, Z 2 is hydrogen); in formula III, n=4.

[0205] Comparative Example 3.

[0206] (1) Preparation of copolyamide:

[0207] 200 mmol of aminocaprolactam prepared in step (1) of Example 1 and 100 mmol of caprolactam were weighed and added to a reactor, and then 0.5 mmol of water was added. The mixture was replaced with nitrogen and the nitrogen atmosphere was maintained. The mixture was pressurized and reacted at 200°C and 0.5 MPa for 2 h, then the temperature was raised to 210°C and normal pressure was reacted for 1 h, and finally the reaction was carried out at 230°C and -0.1 MPa under reduced pressure for 5 h to obtain copolyamide with a yield of 70%.

[0208] (2) Preparation of flame retardant nylon:

[0209] The copolyamide prepared in step (1) was dissolved in 200 mL of trifluoroethanol, and 200 mmol of triethylamine and 200 mmol of methyl phenylchlorophosphonate were added. The mixture was stirred and reacted at room temperature for 24 h. The reaction solution was precipitated in methanol, and the flame-retardant nylon material was obtained after centrifugation and drying. The yield was 88%.

[0210] The flame retardant nylon obtained comprises structural units shown in formula I and formula III, wherein R 1is hydrogen, R is the B structure (Z 1 is methoxy, Z 2 is hydrogen); in formula III, n=4.

[0211] In order to evaluate the flame retardant properties and tensile properties of the flame retardant nylon materials prepared in Examples 1-19 and the nylon materials prepared in Comparative Examples 1-3, the materials were made into specimens according to the standard, and then tested according to the following test method. The results are shown in Table 1:

[0212] Vertical burning test (UL-94): Test the samples in accordance with GB / T 2408-2021 standard;

[0213] Limiting oxygen index (LOI) test: Test the samples according to GB / T 2406.2-2009 standard;

[0214] Tensile performance test: Test the samples according to GB / T 1040.2-2022 standard

[0215] Table 1

[0216]

[0217]

[0218] As shown in the data of Table 1, the flame retardant nylon material of the present invention has a significant flame retardant effect and a tensile property substantially equivalent to that of the conventional nylon material (Comparative Example 1). In contrast, the flame retardant property of the nylon material of Comparative Example 2 is insufficient, and the tensile property of the nylon material of Comparative Example 3 is poor.

[0219] According to the present invention, at least a part of the applications in the fields of automobiles, textiles, electronics and electrical, construction and packaging is made of the flame-retardant nylon material of the present invention, for example, by injection molding, blow molding, extrusion, calendaring, etc. The specific operations and conditions are well known to those skilled in the art and can be selected according to actual needs, and will not be described in detail here.

[0220] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, and these simple modifications all belong to the protection scope of the present invention. It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

Claims

1. A flame retardant nylon material, characterized in that: The molecular structure comprises two different repeating units as shown in the following formula I and formula III or formula II and formula III: Wherein, n is any natural number selected from 1 to 8; x and y represent the molar proportion of each part of the repeating unit, x is selected from 0.01 to 0.50, y is selected from 0.50 to 0.99, and x+y=1; R1 is selected from hydrogen, C 1～10 Substituted / unsubstituted, straight-chain / branched aliphatic hydrocarbon group, substituted / unsubstituted C 3～12 One of an alicyclic hydrocarbon group, a substituted / unsubstituted aryl group, and a substituted / unsubstituted aralkyl group; R2 and R3 are each independently selected from C 1～10 Substituted / unsubstituted, straight-chain / branched aliphatic hydrocarbon group, substituted / unsubstituted C 3～12 One of an alicyclic hydrocarbon group, a substituted / unsubstituted aryl group, and a substituted / unsubstituted aralkyl group; R is selected from one of the structures shown in the following formula IV: Wherein, Z1 and Z2 are each independently selected from hydrogen, C 1～10 One of branched / branched aliphatic hydrocarbon group, hydroxyl group, methoxy group, tert-butoxy group, cyano group, boric acid, and boric acid ester; Z3, Z4, and Z5 are each independently selected from C 1～10 One of a linear / branched aliphatic hydrocarbon group, a substituted / unsubstituted aryl group, and a substituted / unsubstituted aralkyl group; X1 and X2 are each independently selected from an oxygen atom or an imino group.

2. A method for preparing the flame retardant nylon material according to claim 1, characterized in that: The following steps are involved: Step 1: mixing a seven-membered cyclic lysine derivative monomer with a lactam monomer, and performing ring-opening copolymerization to obtain a copolyamide having a functional group on the side chain; Step 2: using the copolyamide obtained in step 1 to react with a reagent containing a flame retardant group in a solvent to obtain a flame retardant nylon material; Wherein, the structural formula of the seven-membered cyclic lysine derivative monomer is shown in the following formula V: Wherein, R4 and R5 are each independently selected from hydrogen, C 1～10 Substituted / unsubstituted, straight-chain / branched aliphatic hydrocarbon group, substituted / unsubstituted C 3～12 One of an alicyclic hydrocarbon group, a substituted / unsubstituted aryl group, and a substituted / unsubstituted aralkyl group; The structural formula of the lactam is shown in the following formula VI: Wherein, n is any natural number selected from 1 to 8.

3. The method for preparing the flame retardant nylon material according to claim 2, characterized in that: The preparation method of the seven-membered cyclic lysine derivative monomer is as follows: Lysine hydrochloride / lysine / aqueous solution containing lysine is mixed with methanol, an equimolar amount of sodium hydroxide is added / not added, a dehydration ring reaction is carried out at 125°C to 200°C, and the mixture is extracted with ethyl acetate to obtain; Or further react with corresponding aldehydes and / or halogenated hydrocarbons having R4 and / or R5 groups to obtain.

4. The method for preparing the flame retardant nylon material according to claim 2, characterized in that: The ring-opening copolymerization method of the seven-membered cyclic lysine derivative monomer and the lactam monomer in step 1 is selected from one of a hydrolysis polymerization method and an anion polymerization method; The hydrolysis polymerization method requires the addition of water and an optional molecular weight regulator, and the molar ratio of the seven-membered cyclic lysine derivative monomer, caprolactam, water and molecular weight regulator is (1-100):100:(0.1-5):(0-5); the polymerization temperature is 140° C. to 320° C., the polymerization time is 2 h to 96 h, and the polymerization pressure is -0.1 MPa to 5 MPa; The anionic polymerization method requires the addition of an activator and a catalyst, and the molar ratio of the seven-membered cyclic lysine derivative monomer, caprolactam, activator and catalyst is (1-100):100:(0.1-5):(0.1-5); the polymerization temperature is 140°C-230°C, and the polymerization time is 1h-6h.

5. The method for preparing a flame retardant nylon material according to claim 4, characterized in that: The molecular weight regulator in the hydrolysis polymerization is selected from one of acetic acid, adipic acid and benzoic acid.

6. The method for preparing the flame retardant nylon material according to claim 4, characterized in that: The catalyst in the anionic polymerization method is selected from one or a combination of at least two of alkali metals, alkali metal oxides, alkali metal hydroxides, alkali metal hydrides, alkali metal alkoxides, alkaline earth metals, alkaline earth metal oxides, alkaline earth metal hydroxides, alkaline earth metal hydrides, alkaline earth metal alkoxides, carbene reagents, guanidine reagents, amidine reagents, and phosphazene reagents.

7. The method for preparing a flame retardant nylon material according to claim 4, characterized in that: The activator in the anionic polymerization method has a structure as shown in Formula VII: Wherein R6 is selected from hydrogen, C 1～5 substituted / unsubstituted, straight-chain / branched aliphatic hydrocarbon group, substituted / unsubstituted aromatic group.

8. The method for preparing a flame retardant nylon material according to claim 2, characterized in that: The flame retardant group-containing reagent in step 2 has a structure of R-Hal or R-R7-Hal, wherein R is selected from one of the structures shown in formula IV, and R7 is selected from C 1～10 The invention relates to an aliphatic hydrocarbon group, a substituted / unsubstituted aryl group, and Hal is selected from one of chlorine, bromine and iodine.

9. The method for preparing a flame retardant nylon material according to claim 2, characterized in that: The solvent in step 2 is selected from one or a combination of at least two of water, methanol, ethanol, trifluoroethanol, hexafluoroisopropanol, benzyl alcohol, ethylene glycol, and cyclohexanol; the reaction temperature is 20° C. to 100° C., and the reaction time is 2 h to 12 h.

10. Use of the flame-retardant nylon material according to claim 1 or the flame-retardant nylon material obtained by the preparation method according to any one of claims 2 to 9, characterized in that: Used in automotive, textile, electrical and electronic, construction and packaging fields.

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