Caged molecule flame retardants, methods of making and use on recycled articles

Abstract

The present application relates to a kind of cage molecule-containing flame retardant and its preparation method and application on regenerated product, the molecular structure formula of cage molecule-containing flame retardant is: Or preparation method is: after cyanuric chloride, aminopropyl butyl POSS, acid binding agent and solvent are mixed, at 0~5 ℃, 2~2.5 h is reacted, and intermediate product is obtained, then intermediate product, ethylene glycol (or aniline), acid binding agent and solvent are mixed, at 40~45 ℃, 4~4.5 h is reacted;Application: BHET (or caprolactam obtained by waste polyamide hydrolysis) obtained by waste polyethylene glycol alcoholysis is copolymerized with cage molecule-containing flame retardant.The flame retardant of the present application has excellent flame retardant performance and anti-dripping performance, the method of the present application is simple and environmentally friendly, and can be widely used in industry, the polyester or polyamide fiber of the present application can form a dense carbon layer on the surface when burning, which can isolate oxygen and prevent melting and dripping, and has excellent flame retardant performance.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of flame retardants, and relates to a cage-containing molecule-containing flame retardant, a preparation method thereof and application of the flame retardant to regenerated products. BACKGROUND

[0002] The regenerated polyester is prepared from waste recycled polyester products by physical, physical-chemical and chemical methods, etc. Because the regenerated polyester has the characteristics of low raw material price, environmental protection and simple production, and in addition to the increasing shortage of petroleum resources, the social stock of polyester waste bottles is huge, and the demand for polyester fibers is increasing, more and more enterprises pay attention to it, and the products are mainly applied to the fields of automobiles, home textiles, filling materials, etc. Therefore, the flame-retardant regenerated polyester fiber and its products will become a new hotspot in China's textile market, and have good development prospects. The limiting oxygen index (LOI) of the regenerated polyester is about 22%, which makes the regenerated polyester a flammable product, and because the polyester has low melt viscosity at high temperature, it often accompanies the phenomenon of melt dripping during combustion, which is easy to cause secondary fire.

[0003] Generally, the flame-retardant modification of the regenerated polyester fiber is mainly adding phosphorus-based or halogen-based flame retardants in the polyester melt state to prepare regenerated polyester masterbatch, blending the masterbatch with the chip to spin, and then preparing the flame-retardant polyester fiber.

[0004] The application CN103215686A discloses a flame-retardant regenerated polyester fiber, which is prepared by adopting the masterbatch method to granulate the regenerated polyester chip and phosphorus-based flame retardant powder by double-screw extrusion, making flame-retardant regenerated polyester masterbatch, and blending the masterbatch with the chip to spin and prepare the flame-retardant regenerated polyester fiber. The product has good flame retardancy, and the limiting oxygen index is 30%, but the melt dripping condition is not considered.

[0005] The application CN104017195A discloses a production method of phosphorus-based copolymerized flame-retardant regenerated polyester chip and industrial yarn, and the phosphorus-based copolymerized flame-retardant regenerated polyester chip is prepared by adding the flame retardant into the polyester which has completed the polymerization process. The ES flame retardant is added into the polyester which has completed the polymerization process, and the flame retardant is grafted on the polymer molecule in the form of a side chain, but the flame-retardant effect is unstable, is easily affected by other additives and processing methods, etc., and the preparation process is complex, the cost is high, and the anti-melt dripping performance is not significantly improved.

[0006] Polyamide 6 has excellent physical and mechanical properties and textile processing performance since its advent, its output has been in the first place in the synthetic fiber family for a long time, and it is also widely used in various fields. With the continuous increase of production capacity, more and more solid waste is generated every year. Polyamide 6 is chemically stable and difficult to degrade in the natural environment. If it is not recycled, it will have a great impact on the environment. Therefore, people focus on recycled polyamide. With the development of the recycling industry, recycled polyamide fibers and their products have gradually entered the fashion. And with the gradual understanding of fire, the fire prevention awareness is gradually strengthened, and the flame retardant function of various functional fibers is paid more and more attention by the public. Therefore, the development of flame-retardant polyamide products is constantly being promoted.

[0007] At present, the research on flame-retardant modified virgin polyamide fibers and textiles is more common, which is generally through melt blending of flame retardant and spinning melt, and then made into flame-retardant fibers. There are also ways to introduce monomers or macromolecules with flame-retardant components into the polymer molecular chain through polymerization to modify the flame retardant.

[0008] Patent CN110923848A provides a kind of flame-retardant polyamide fiber preparation method, polyamide, melamine cyanurate, graphite-like carbon nitride, zinc compound and 9, 10-dihydro-9-oxa-10-phosphorus heterocyclic phenyl-10-oxide (DOPO) derivative melt blend is prepared into flame-retardant polyamide chip, and then spun into flame-retardant polyamide fiber.

[0009] Patent CN112048061A mixes flame retardant salt with polyamide 66 oligomer and / or polyamide 6 oligomer, and then performs polycondensation reaction to prepare copolymerized flame-retardant polyamide. The flame retardant salt is prepared by high temperature and high pressure reaction of N,N-di(6-aminohexyl) phenyl phosphorodiamide and dibasic acid HOOCR1COOH, wherein R1 is linear, branched or cyclic C2-C15 alkylene structure.

[0010] However, the phosphine oxide flame retardant used in patent CN112048061A has a large addition amount, and the produced polyamide is an oligomer and has no improvement on the dripping performance of polyamide. Patent CN110923848A uses a blending method to prepare flame-retardant polyamide, which requires high temperature and high shear force to achieve good dispersion effect. And DOPO itself is not completely non-flammable, and its combustion process will release some harmful substances, which will affect the environment.

[0011] Multi-element synergistic flame retardant has become one of the development directions of halogen-free flame retardant, such as silicon-nitrogen, silicon-phosphorus, etc. The inorganic silicon-oxygen skeleton structure of POSS makes it have excellent thermal stability, radiation resistance and oxidation resistance. On the one hand, because the bond energy of Si-O is much higher than that of C-C, when the POSS molecule is bonded to the main chain or side chain of the polymer, the hybrid material can still maintain stable structure and performance above the glass transition temperature (Tg) or even when the temperature reaches the beginning of melting; on the other hand, when the organic molecules on the surface of POSS are oxidized and decomposed at high temperature, because the Si-O-Si in POSS is very stable to oxygen free radicals, a SiO2 protective layer can be formed on the surface after the degradation of POSS, which has the effects of heat resistance, heat insulation and radiation resistance, and also plays the role of structural support. However, because of the compatibility problem between the POSS flame retardant and the regenerated polyamide, there are problems such as poor dispersion when blending, and currently there are few applications of the POSS flame retardant in the flame-retardant modification of regenerated polyamide fibers. SUMMARY

[0012] The purpose of the present application is to solve the problems existing in the prior art, and the present application provides a cage molecule-containing flame retardant, a preparation method thereof and an application thereof in regenerated products.

[0013] To achieve the above-mentioned purpose, the present application adopts the following scheme:

[0014] The cage molecule-containing flame retardant A has the following molecular structure formula:

[0015]

[0016] As a preferred technical scheme:

[0017] The cage molecule-containing flame retardant A has the following molecular structure formula:

[0018] The application also provides a method for preparing the cage molecule-containing flame retardant A according to any one of the above, wherein cyanuric chloride, aminopropyl isobutyl POSS, an acid binding agent I and a solvent I are mixed, and then reacted at 0-5 DEG C for 2-2.5 hours, and then the intermediate product is obtained by water washing and filtration; the Cl element is difficult to react with the amino group at normal temperature, and the application combines the cyanuric chloride and the aminopropyl isobutyl POSS by the reaction of the amino group and the Cl element in the cyanuric chloride in a low-temperature solvent; then the intermediate product, ethylene glycol (EG), an acid binding agent II and a solvent II are mixed, and then reacted at 40-45 DEG C for 4-4.5 hours, and then the product is precipitated by adding into ethyl acetate, and then the cage molecule-containing flame retardant A is obtained by filtration, washing and vacuum drying; the molar ratio of the cyanuric chloride, the aminopropyl isobutyl POSS and the acid binding agent I is 1:1-1.2:1; and the molar ratio of the intermediate product, the ethylene glycol and the acid binding agent II is 1:1-1.2:1.

[0019] The reaction equation for preparing the cage molecule-containing flame retardant A is as follows.

[0020]

[0021] As a preferred technical scheme,

[0022] The method is as described above, the acid binding agent I and the acid binding agent II are both sodium hydroxide; the solvent I is tetrahydrofuran, chloroform, toluene or acetone; and the solvent II is N,N-dimethylformamide (DMF) or acetonitrile.

[0023] The application also provides the application of the cage molecule-containing flame retardant A according to any one of the above on the regenerated polyester, wherein the BHET obtained by alcoholysis of waste polyester is subjected to copolymerization with the cage molecule-containing flame retardant A, so as to prepare a cage molecule-containing modified flame-retardant copolymerized regenerated polyester; the flame retardant is combined on the molecular chain of the regenerated polyester by polymerization, so as to realize the flame-retardant and anti-dripping performance of the regenerated polyester; and the molecular structure formula of the cage molecule-containing modified flame-retardant copolymerized regenerated polyester is as follows:

[0024]

[0025] In the formula, the value range of n is 140-200.

[0026] As a preferred technical scheme,

[0027] The application is as described above, and the specific steps are as follows:

[0028] (1) alcoholysis of waste polyester;

[0029] The glycol and the waste polyester are mixed in a mass ratio of 1-3:1, a catalyst (Zn(Ac)2) accounting for 0.2% of the mass of the waste polyester is added, and the mixture is reacted at 160-200°C for 1-5h under the condition of continuous nitrogen supply;

[0030] (2) purification;

[0031] The substances other than BHET in the waste polyester alcoholysis product are removed; the regenerated polyester product after alcoholysis contains some catalysts and other impurities in addition to BHET, which will affect the polymerization reaction during the copolymerization process, the product is purified by a combination of fractional filtration and refrigeration recrystallization, thereby reducing the influence of impurities on the polymerization reaction, and the specific process is as follows: first, filtration at 170°C to obtain a filtrate, then a large amount of distilled water is added and heated to 90°C or above to quickly filter to obtain a filtrate, then refrigeration recrystallization at 4°C for 8h, and finally filtration and drying to obtain pure BHET;

[0032] (3) copolymerization;

[0033] The BHET obtained in step (2), the cage molecule-containing flame retardant A, and the catalyst (Sb2O3) are mixed, the molar proportion of the cage molecule-containing flame retardant A in the mixture is 1-10%, and the mass of the catalyst is 0.04wt% of the mass of the BHET, and the mixture is reacted at a temperature of 280-290°C and a pressure of 0.3-0.5MPa for 2-3h to obtain the cage molecule-containing modified flame-retardant copolymerized regenerated polyester.

[0034] As described above, the cage molecule-containing modified flame-retardant copolymerized regenerated polyester has a melt dripping resistance grade of V-0 level, an ultimate oxygen index of 30% or more, and a contact angle of the cage molecule-containing modified flame-retardant copolymerized regenerated polyester chip with water of 130° or more.

[0035] As described above, after the cage molecule-containing modified flame-retardant copolymerized regenerated polyester is prepared, it is subjected to melt spinning to obtain a cage molecule-containing modified flame-retardant copolymerized regenerated polyester fiber.

[0036] As described above, the process parameters of the melt spinning include: screw zone 1 temperature 250-270°C, screw zone 2 temperature 260-280°C, screw zone 3 temperature 255-275°C, screw zone 4 temperature 255-275°C, metering pump temperature 255-275°C, spinning speed 600m / min, and draw ratio 3.5.

[0037] As described above, the cage molecule-containing modified flame-retardant copolymerized regenerated polyester fiber has a melt dripping resistance grade of V-0 level, an ultimate oxygen index of 30% or more, and a breaking strength of 3.5cN / dtex or more.

[0038] The application also provides the cage molecule-containing flame retardant B with the following molecular structure formula:

[0039]

[0040] As a preferred technical scheme:

[0041] The cage molecule-containing flame retardant B has an initial decomposition temperature of 260 DEG C and a residual carbon content of 27% at 800 DEG C.

[0042] The application also provides a method for preparing the cage molecule-containing flame retardant B, which comprises the following steps: mixing cyanuric chloride, aminopropyl isobutyl POSS, an acid-binding agent III and a solvent III, and then reacting at 0-5 DEG C for 2-2.5 h, washing with water, filtering to obtain an intermediate product, mixing the intermediate product, aniline, an acid-binding agent IV and a solvent IV, and then reacting at 40-45 DEG C for 4-4.5 h, adding into ethyl acetate to precipitate the product, and then filtering, washing and vacuum drying to obtain the cage molecule-containing flame retardant B; wherein, the Cl and the amino group are difficult to react at room temperature, and the application combines the cyanuric chloride and the aminopropyl isobutyl POSS by reacting the Cl element in the cyanuric chloride with the amino group in the low-temperature solvent.

[0043] The molar ratio of the cyanuric chloride, the aminopropyl isobutyl POSS and the acid-binding agent III is 1:1-1.2:1, and the molar ratio of the intermediate product, the aniline and the acid-binding agent IV is 1:1-1.2:1.

[0044] The reaction equation for preparing the cage molecule-containing flame retardant B is as follows.

[0045]

[0046] The cage structure in the flame retardant can isolate air in the center of the molecule to form a physical barrier to block the contact between the fuel and oxygen, thereby reducing the combustion reaction rate and achieving the flame-retardant effect; on the other hand, the cage structure in the POSS has high thermal stability and is difficult to decompose at high temperatures, and can enhance the mechanical properties of the material.

[0047] As a preferred technical scheme:

[0048] In the method, the acid-binding agent III and the acid-binding agent IV are both sodium hydroxide; and the solvent III is tetrahydrofuran, chloroform, toluene or acetone; and the solvent IV is N,N-dimethylformamide (DMF) or acetonitrile.

[0049] The reason why the acid-binding agent III and the acid-binding agent IV are the same, and the single solvent III and the solvent IV are different, is that the acid-binding agent mainly reacts with active groups such as hydroxyl groups in the polymer molecules, and the selection mainly considers the reactivity and the compatibility with the polymer. The combination with the polymer can be realized through the reactivity, and is not affected by the solvent. The performance of the acid-binding agent can be regulated by changing the amount and the ratio of the acid-binding agent. On the contrary, the selection of the solvent mainly considers the compatibility and the dispersibility with the polymer. The solvent compatible with the polymer needs to be selected to ensure that the flame retardant can be uniformly dispersed in the polymer. The selection needs to consider various factors, such as the solubility of the polymer, the volatility, the toxicity, the price and the like.

[0050] The application also provides the application of the cage molecule-containing flame retardant B in the regenerated polyamide as described in any one of the above. Caprolactam obtained by hydrolysis of waste polyamide is subjected to copolymerization with the cage molecule-containing flame retardant B to prepare a cage molecule-containing modified flame-retardant copolymerized regenerated polyamide. The flame retardant is combined on the molecular chain of the regenerated polyamide through polymerization to realize the flame-retardant and anti-dripping performance of the regenerated polyamide. The molecular structural formula of the cage molecule-containing modified flame-retardant copolymerized regenerated polyamide is as follows:

[0051]

[0052] In the formula, the value range of n is 140-200.

[0053] As a preferred technical scheme:

[0054] The application is as described above, and the specific steps are as follows:

[0055] (1) Waste polyamide hydrolysis;

[0056] The cut waste polyamide (nylon 6) is subjected to depolymerization reaction in subcritical water with a temperature of 340-350 DEG C and a pressure of 9 MPa for 60-90 min. The mass ratio of the subcritical water to the polyamide fiber waste is 20-50:1.

[0057] (2) Purification;

[0058] The application discloses a method for removing substances other than caprolactam from waste polyamide hydrolysate, and purifying a regenerated polyamide product after hydrolysis.

[0059] (3) copolymerization;

[0060] The caprolactam obtained in step (2) is mixed with the cage molecule-containing flame retardant B, the molar proportion of the cage molecule-containing flame retardant B in the mixture is 1-10%, and the mixture is reacted under the conditions of a temperature of 220-280 DEG C, normal pressure and nitrogen protection for 6-14 h, so as to obtain the cage molecule-containing modified flame-retardant copolymerized regenerated polyamide.

[0061] As described above, the cage molecule-containing modified flame-retardant copolymerized regenerated polyamide has a melt dripping resistance grade of V-0, an ultimate oxygen index of 30% or more, and a contact angle of the polyamide chip to water of 130 DEG or more.

[0062] As described above, the cage molecule-containing modified flame-retardant copolymerized regenerated polyamide is prepared, and then melt spinning is performed to obtain the cage molecule-containing modified flame-retardant copolymerized regenerated polyamide fiber.

[0063] As described above, the process parameters of the melt spinning include: the screw feeding section temperature is 255-265 DEG C, the screw melting section temperature is 270-280 DEG C, the screw pressure relief section temperature is 260-270 DEG C, the metering pump temperature is 260-270 DEG C, the spinning speed is 1000 m / min, and the draft ratio is 2.0-2.6.

[0064] As described above, the cage molecule-containing modified flame-retardant copolymerized regenerated polyamide fiber has a melt dripping resistance grade of V-0, an ultimate oxygen index of 30% or more, and a breaking strength of 4 cN / dtex or more.

[0065] Advantages

[0066] (1) The cage molecule-containing flame retardant A has good flame retardancy.

[0067] (2) The preparation method of the application has simple process;

[0068] (3) When the cage molecule-containing flame retardant A of the application is applied to polyester, when the organic molecules on the surface of POSS are oxidized and decomposed at high temperature, the Si-O-Si in POSS is very stable to oxygen radicals, and a SiO2 protective layer can be formed on the surface after the degradation of POSS, which has the effects of heat resistance, heat insulation, radiation resistance and structural support, thereby improving the anti-dripping performance of the polyester;

[0069] (4) When the cage molecule-containing flame retardant A of the application is applied to polyester, the POSS with organic-inorganic hybrid structure can promote the increase of the nanometer roughness of the material surface and the reduction of the surface energy due to its special nanometer cage structure, thereby endowing the material with certain hydrophobic and oleophobic properties and improving the surface antifouling ability of the material;

[0070] (5) The preparation method of the cage molecule-containing flame retardant B of the application has simple process and is convenient to prepare;

[0071] (6) The cage molecule-containing flame retardant B of the application uses the POSS structure and the phosphorus element to be compounded, improves the stability of the polymer at high temperature, reduces the emission of toxic gas when the polymer burns, and can achieve the effects of flame retardation and anti-dripping;

[0072] (7) The cage molecule-containing flame retardant B of the application has good compatibility when applied to regenerated polyamide, and the product obtained has excellent flame retardation effect, anti-dripping performance and certain stain resistance. BRIEF DESCRIPTION OF DRAWINGS

[0073] Figure 1 is the infrared spectrum of the cage molecule-containing flame retardant A of the application;

[0074] Figure 2 is the infrared spectrum of the cage molecule-containing flame retardant B of the application. DETAILED DESCRIPTION

[0075] The application will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the application and not to limit the scope of the application. In addition, it should be understood that those skilled in the art can make various modifications or changes to the application after reading the content taught by the application, and these equivalent forms also fall within the scope defined by the claims attached to the application.

[0076] Sources of related substances in the examples:

[0077] Cyanoformyl chloride: the manufacturer is Luo En Reagent, and the model is R020254;

[0078] Aminopropylbutyl POSS: manufacturer is Bide Pharmatech, and the model number is BD01136948;

[0079] Ethylene glycol: manufacturer is Infsci, and the model number is H29138;

[0080] Sodium hydroxide: manufacturer is Luo En Reagent, and the model number is R033306;

[0081] Tetrahydrofuran: manufacturer is Macklin, and the model number is T818764;

[0082] Chloroform: brand is Greagent, and the model number is 01104470;

[0083] Toluene: brand is Greagent, and the model number is 01006984;

[0084] Acetone: manufacturer is Yonghua Chemical Co., Ltd., and the model number is 100702162;

[0085] N,N-dimethylformamide: manufacturer is Luo En Reagent, and the model number is R004209;

[0086] Acetonitrile: manufacturer is Luo En Reagent, and the model number is R033065;

[0087] Zinc acetate: manufacturer is Bide Pharmatech, and the model number is BD157154;

[0088] Sb2O3: manufacturer is Araldin, and the model number is A102834;

[0089] Ethyl acetate: manufacturer is Greagent, and the model number is 01022547;

[0090] Waste polyester: manufacturer is Ningbo Dafa Co., Ltd.

[0091] Aniline: manufacturer is Araldin, and the model number is A112120;

[0092] Waste polyamide: manufacturer is Zhejiang Taihua New Material Co., Ltd.

[0093] The molecular structure formula of the cage molecule-containing flame retardant A prepared in the examples is as follows:

[0094]

[0095] The molecular structure formula of the cage molecule-containing modified flame-retardant copolymerized regenerated polyester prepared in the examples is as follows:

[0096]

[0097] In the formula, the value range of n is 140-200.

[0098] The molecular structure of the flame retardant B containing cage molecules prepared in the embodiment is as follows:

[0099]

[0100] The molecular structure of the flame-retardant copolymerized recycled polyamide containing cage molecules prepared in the embodiment is as follows:

[0101]

[0102] In the formula, n ranges from 140 to 200.

[0103] The detection method of the related properties of the substance prepared in the embodiment is as follows:

[0104] The detection method of the residual carbon content of the flame retardant is as follows: The thermal analyzer TG209 F1 Iris produced by the German Nianchi Instrument Manufacturing Co., Ltd. is used for testing, the temperature is raised to 800 DEG C at a rate of 10 DEG C / min, the weight of the sample is 7 mg, and the test process is under N2 protection, and the high-temperature carbon residue of the sample is studied.

[0105] The detection method of the resin anti-dripping grade is as follows: The detection is carried out according to the standard GB / T 2408-2021;

[0106] The detection method of the limiting oxygen index is as follows: The detection is carried out according to the standard GB / T 5454-1997;

[0107] The detection method of the fiber anti-dripping grade is as follows: The detection is carried out according to the standard GB / T 5456-2009;

[0108] The detection method of the fiber breaking strength is as follows: The filament yarn strength meter C(XQ-1A) produced by Shanghai Kepu Applied Science Institute is used to measure the breaking strength of the fiber;

[0109] The detection method of the water contact angle is as follows: The contact angle measuring instrument OCA40Micro is used to measure the water contact angle of the flame-retardant copolymerized recycled polyester chip containing cage molecules or the flame-retardant copolymerized recycled polyamide chip containing cage molecules.

[0110] Embodiment 1

[0111] The preparation method of the flame retardant A containing cage molecules is as follows:

[0112] (1) Prepare raw materials:

[0113] Tricyanuric chloride;

[0114] Aminopropylbutyl POSS;

[0115] Ethylene glycol;

[0116] Acid acceptor I: sodium hydroxide;

[0117] Base II: sodium hydroxide;

[0118] Solvent I: tetrahydrofuran;

[0119] Solvent II: N,N-dimethylformamide;

[0120] (2) Preparation of cage molecule-containing flame retardant A:

[0121] After mixing cyanuric chloride, aminopropyl butyl POSS, base I and solvent I, reacting at 0°C for 2.5h, washing with water, filtering to obtain an intermediate product, then mixing the intermediate product, ethylene glycol, base II and solvent II, reacting at 40°C for 4.5h, adding to ethyl acetate to precipitate the product, and then filtering, washing, and vacuum drying to obtain cage molecule-containing flame retardant A; wherein the molar ratio of cyanuric chloride, aminopropyl butyl POSS and base I is 1:1:1; the molar ratio of the intermediate product, ethylene glycol and base II is 1:1:1.

[0122] The initial decomposition temperature of the prepared cage molecule-containing flame retardant A is 260°C, and the carbon residue at 800°C is 27%; the infrared spectrum of the cage molecule-containing flame retardant A is shown in Figure 1 As shown in the figure, there is a peak at a wave number of 1114, which is the peak of Si-O-Si bond in POSS, indicating that the main POSS structure of the flame retardant still exists.

[0123] Example 2

[0124] The preparation method of the cage molecule-containing flame retardant A is as follows:

[0125] (1) Preparation of raw materials:

[0126] Cyanuric chloride;

[0127] Aminopropyl butyl POSS;

[0128] Ethylene glycol;

[0129] Base I: sodium hydroxide;

[0130] Base II: sodium hydroxide;

[0131] Solvent I: chloroform;

[0132] Solvent II: acetonitrile;

[0133] (2) Preparation of cage molecule-containing flame retardant A:

[0134] The cyanuric chloride, the aminopropylbutyl POSS, the acid-binding agent I and the solvent I are mixed, and then reacted at 5 DEG C for 2 hours, and then washed with water and filtered to obtain an intermediate product; then the intermediate product, the ethylene glycol, the acid-binding agent II and the solvent II are mixed, and then reacted at 45 DEG C for 4 hours, and then added into ethyl acetate to precipitate the product, and then filtered, washed and vacuum dried to obtain the cage molecule-containing flame retardant A; wherein the molar ratio of the cyanuric chloride, the aminopropylbutyl POSS and the acid-binding agent I is 1:1.1:1; and the molar ratio of the intermediate product, the ethylene glycol and the acid-binding agent II is 1:1:1.

[0135] The initial decomposition temperature of the prepared cage molecule-containing flame retardant A is 260 DEG C, and the carbon residue at 800 DEG C is 27%.

[0136] Example 3

[0137] The preparation method of the cage molecule-containing flame retardant A comprises the following specific steps:

[0138] (1) Preparation of raw materials:

[0139] Cyanuric chloride;

[0140] Aminopropylbutyl POSS;

[0141] Ethylene glycol;

[0142] The acid-binding agent I is sodium hydroxide;

[0143] The acid-binding agent II is sodium hydroxide;

[0144] The solvent I is toluene;

[0145] The solvent II is N,N-dimethylformamide;

[0146] (2) Preparation of the cage molecule-containing flame retardant A:

[0147] The cyanuric chloride, the aminopropylbutyl POSS, the acid-binding agent I and the solvent I are mixed, and then reacted at 0 DEG C for 2.5 hours, and then washed with water and filtered to obtain an intermediate product; then the intermediate product, the ethylene glycol, the acid-binding agent II and the solvent II are mixed, and then reacted at 40 DEG C for 4.5 hours, and then added into ethyl acetate to precipitate the product, and then filtered, washed and vacuum dried to obtain the cage molecule-containing flame retardant A; wherein the molar ratio of the cyanuric chloride, the aminopropylbutyl POSS and the acid-binding agent I is 1:1:1; and the molar ratio of the intermediate product, the ethylene glycol and the acid-binding agent II is 1:1.1:1.

[0148] The initial decomposition temperature of the prepared cage molecule-containing flame retardant A is 260 DEG C, and the carbon residue at 800 DEG C is 27%.

[0149] Example 4

[0150] The preparation method of the cage molecule-containing flame retardant A comprises the following specific steps:

[0151] (1) Preparation of raw materials:

[0152] cyanuric chloride;

[0153] ammoniopropylbutyl POSS;

[0154] ethylene glycol;

[0155] Base I: sodium hydroxide;

[0156] Base II: sodium hydroxide;

[0157] Solvent I: acetone;

[0158] Solvent II: acetonitrile;

[0159] (2) Preparation of cage molecule-containing flame retardant A:

[0160] After mixing cyanuric chloride, ammoniopropylbutyl POSS, Base I and Solvent I, reacting at 5°C for 2h, washing with water, filtering to obtain an intermediate product, then mixing the intermediate product, ethylene glycol, Base II and Solvent II, reacting at 45°C for 4h, adding to ethyl acetate to precipitate the product, and then filtering, washing, vacuum drying cage molecule-containing flame retardant A; wherein the molar ratio of cyanuric chloride, ammoniopropylbutyl POSS and Base I is 1:1.2:1; the molar ratio of the intermediate product, ethylene glycol and Base II is 1:1.2:1.

[0161] The prepared cage molecule-containing flame retardant A has an initial decomposition temperature of 260°C and a carbon residue at 800°C of 27%.

[0162] Example 5

[0163] Application of cage molecule-containing flame retardant A, specifically as follows:

[0164] (1) Preparation of flame-retardant copolymerized regenerated polyester:

[0165] (1.1) Alcoholysis of waste polyester;

[0166] Mix ethylene glycol and waste polyester at a mass ratio of 1:1, then add 0.2% of the mass of waste polyester of zinc acetate to the mixture, and react at 160°C for 5h under the condition of continuous nitrogen flow;

[0167] (1.2) Purification;

[0168] Remove substances other than BHET from the alcoholysis product of waste polyester;

[0169] (1.3) Copolymerization;

[0170] The BHET obtained in step (1.2), the cage molecule-containing flame retardant A (prepared by Example 1), and antimony trioxide were mixed, the molar ratio of the cage molecule-containing flame retardant A in the mixture was 1%, and the mass of the antimony trioxide was 0.04wt% of the mass of the BHET, and the mixture was reacted at a temperature of 280℃ and a pressure of 0.5MPa for 3h to obtain the cage molecule-containing modified flame-retardant copolymerized regenerated polyester;

[0171] The cage molecule-containing modified flame-retardant copolymerized regenerated polyester prepared has a melt dripping resistance level of V-0, an limiting oxygen index of 30.2%, and a contact angle of the cage molecule-containing modified flame-retardant copolymerized regenerated polyester chip with water of 130.2°;

[0172] (2) Preparation of flame-retardant copolymerized regenerated polyester fiber:

[0173] The cage molecule-containing modified flame-retardant copolymerized regenerated polyester prepared in step (1) was subjected to melt spinning to obtain the cage molecule-containing modified flame-retardant copolymerized regenerated polyester fiber; wherein the process parameters of the melt spinning include: screw zone 1 temperature 250℃, screw zone 2 temperature 260℃, screw zone 3 temperature 255℃, screw zone 4 temperature 255℃, metering pump temperature 255℃, spinning speed 600m / min, and draw ratio 3.5.

[0174] The cage molecule-containing modified flame-retardant copolymerized regenerated polyester fiber finally prepared has a melt dripping resistance level of V-0, a limiting oxygen index of 30.2%, and a breaking strength of 3.7cN / dtex.

[0175] Example 6

[0176] Application of the cage molecule-containing flame retardant A, specifically as follows:

[0177] (1) Preparation of flame-retardant copolymerized regenerated polyester:

[0178] (1.1) Alcoholysis of waste polyester;

[0179] The waste polyester was mixed with ethylene glycol at a mass ratio of 2:1, then 0.2% of the mass of the waste polyester of zinc diacetate was added thereto, and the mixture was reacted at 180℃ for 4h under the condition of continuous nitrogen gas flow;

[0180] (1.2) Purification;

[0181] The substances other than BHET in the alcoholysis product of the waste polyester were removed;

[0182] (1.3) Copolymerization;

[0183] The BHET obtained in step (1.2), the cage molecule-containing flame retardant A (obtained from Example 2), and antimony trioxide are mixed, the molar ratio of the cage molecule-containing flame retardant A in the mixture is 4%, and the mass of the antimony trioxide is 0.04wt% of the mass of the BHET, and the mixture is reacted at a temperature of 285°C and a pressure of 0.4MPa for 2.5h to obtain the cage molecule-containing modified flame-retardant copolymerized regenerated polyester;

[0184] The prepared cage molecule-containing modified flame-retardant copolymerized regenerated polyester has a melt dripping resistance level of V-0 level, an limiting oxygen index of 31.2%, and a contact angle of the cage molecule-containing modified flame-retardant copolymerized regenerated polyester chip with water of 131.1°;

[0185] (2) Preparation of flame-retardant copolymerized regenerated polyester fiber:

[0186] The cage molecule-containing modified flame-retardant copolymerized regenerated polyester prepared in step (1) is subjected to melt spinning to obtain the cage molecule-containing modified flame-retardant copolymerized regenerated polyester fiber; wherein the process parameters of the melt spinning include: screw zone 1 temperature 255°C, screw zone 2 temperature 265°C, screw zone 3 temperature 260°C, screw zone 4 temperature 260°C, metering pump temperature 260°C, spinning speed 600m / min, and draw ratio 3.5.

[0187] The finally prepared cage molecule-containing modified flame-retardant copolymerized regenerated polyester fiber has a melt dripping resistance level of V-0 level, a limiting oxygen index of 31.5%, and a breaking strength of 3.5cN / dtex.

[0188] Example 7

[0189] Application of the cage molecule-containing flame retardant A, specifically as follows:

[0190] (1) Preparation of flame-retardant copolymerized regenerated polyester:

[0191] (1.1) Alcoholysis of waste polyester;

[0192] After the ethylene glycol and the waste polyester are mixed at a mass ratio of 2.5:1, 0.2% of zinc diacetate based on the mass of the waste polyester is added thereto, and the mixture is reacted at 190°C for 2h under the condition of continuous nitrogen gas blowing;

[0193] (1.2) Purification;

[0194] Removal of substances other than BHET from the alcoholysis product of the waste polyester;

[0195] (1.3) Copolymerization;

[0196] The BHET obtained in step (1.2), the cage molecule-containing flame retardant A (prepared in Example 3), and antimony trioxide were mixed, the molar ratio of the cage molecule-containing flame retardant A in the mixture was 8%, and the mass of the antimony trioxide was 0.04wt% of the mass of the BHET, and then the mixture was reacted at a temperature of 287°C and a pressure of 0.4MPa for 2.5h to obtain the cage molecule-containing modified flame-retardant copolymerized regenerated polyester;

[0197] The prepared cage molecule-containing modified flame-retardant copolymerized regenerated polyester had a melt dripping resistance level of V-0, an limiting oxygen index of 32.5%, and a contact angle of the cage molecule-containing modified flame-retardant copolymerized regenerated polyester chip with water of 130.8°;

[0198] (2) Preparation of flame-retardant copolymerized regenerated polyester fiber:

[0199] The cage molecule-containing modified flame-retardant copolymerized regenerated polyester prepared in step (1) was subjected to melt spinning to obtain the cage molecule-containing modified flame-retardant copolymerized regenerated polyester fiber; wherein the process parameters of the melt spinning included: screw zone 1 temperature 260°C, screw zone 2 temperature 270°C, screw zone 3 temperature 265°C, screw zone 4 temperature 265°C, metering pump temperature 265°C, spinning speed 600m / min, and draw ratio 3.5.

[0200] The finally obtained cage molecule-containing modified flame-retardant copolymerized regenerated polyester fiber had a melt dripping resistance level of V-0, a limiting oxygen index of 32.4%, and a breaking strength of 3.8cN / dtex.

[0201] Example 8

[0202] Application of the cage molecule-containing flame retardant A, specifically as follows:

[0203] (1) Preparation of flame-retardant copolymerized regenerated polyester:

[0204] (1.1) Alcoholysis of waste polyester;

[0205] After the ethylene glycol and the waste polyester were mixed at a mass ratio of 3:1, 0.2% of the zinc diacetate based on the mass of the waste polyester was added thereto, and the mixture was reacted at 200°C for 1h under the condition of continuous nitrogen gas flow;

[0206] (1.2) Purification;

[0207] Removal of substances other than BHET from the alcoholysis product of the waste polyester;

[0208] (1.3) Copolymerization;

[0209] The BHET obtained in step (1.2), the cage molecule-containing flame retardant A (prepared by Example 4), and antimony trioxide were mixed, the mole percentage of the cage molecule-containing flame retardant A in the mixture was 10%, and the mass of the antimony trioxide was 0.04wt% of the mass of the BHET, and then the mixture was reacted at a temperature of 290℃ and a pressure of 0.3MPa for 2h to obtain the cage molecule-containing modified flame-retardant copolymerized regenerated polyester;

[0210] The prepared cage molecule-containing modified flame-retardant copolymerized regenerated polyester had a melt dripping resistance level of V-0 level, an limiting oxygen index of 33.4%, and a contact angle of the cage molecule-containing modified flame-retardant copolymerized regenerated polyester chip to water of 131.2°;

[0211] (2) Preparation of the flame-retardant copolymerized regenerated polyester fiber:

[0212] The cage molecule-containing modified flame-retardant copolymerized regenerated polyester prepared in step (1) was subjected to melt spinning to obtain the cage molecule-containing modified flame-retardant copolymerized regenerated polyester fiber; wherein the process parameters of the melt spinning included: screw zone 1 temperature 270℃, screw zone 2 temperature 280℃, screw zone 3 temperature 275℃, screw zone 4 temperature 275℃, metering pump temperature 275℃, spinning speed 600m / min, and draw ratio 3.5.

[0213] The finally obtained cage molecule-containing modified flame-retardant copolymerized regenerated polyester fiber had a melt dripping resistance level of V-0 level, a limiting oxygen index of 33.3%, and a breaking strength of 3.7cN / dtex.

[0214] Example 9

[0215] The preparation method of the cage molecule-containing flame retardant B included the following specific steps:

[0216] (1) Preparation of raw materials:

[0217] cyanuric chloride;

[0218] aminopropylbutyl POSS;

[0219] aniline;

[0220] acid-binding agent III: sodium hydroxide;

[0221] acid-binding agent IV: sodium hydroxide;

[0222] solvent III: tetrahydrofuran;

[0223] solvent IV: N,N-dimethylformamide;

[0224] (2) Preparation of the cage molecule-containing flame retardant B:

[0225] The cyanuric chloride, the aminopropylbutyl POSS, the acid-binding agent III and the solvent III are mixed, and then reacted at 0°C for 2.5 hours, and then washed with water and filtered to obtain an intermediate product; then the intermediate product, aniline, the acid-binding agent IV and the solvent IV are mixed, and then reacted at 40°C for 4 hours, and then added into ethyl acetate to precipitate the product, and then filtered, washed and vacuum dried to obtain the cage molecule-containing flame retardant B; wherein the molar ratio of the cyanuric chloride, the aminopropylbutyl POSS and the acid-binding agent III is 1:1.2:1, and the molar ratio of the intermediate product, the aniline and the acid-binding agent IV is 1:1.2:1.

[0226] The cage molecule-containing flame retardant B prepared finally has an initial decomposition temperature of 260°C, and a residual carbon content of 27% at 800°C; the infrared spectrum of the cage molecule-containing flame retardant B is shown in Figure 2 The figure shows that there is a peak at a wave number of 1114, which is the peak of the Si-O-Si bond in the POSS, indicating that the main POSS structure of the flame retardant still exists.

[0227] Example 10

[0228] The preparation method of the cage molecule-containing flame retardant B includes the following specific steps:

[0229] (1) Preparation of raw materials:

[0230] cyanuric chloride;

[0231] aminopropylbutyl POSS;

[0232] aniline;

[0233] the acid-binding agent III: sodium hydroxide;

[0234] the acid-binding agent IV: sodium hydroxide;

[0235] the solvent III: chloroform;

[0236] the solvent IV: N,N-dimethylformamide;

[0237] (2) Preparation of the cage molecule-containing flame retardant B:

[0238] The cyanuric chloride, the aminopropylbutyl POSS, the acid-binding agent III and the solvent III are mixed, and then reacted at 0°C for 2.5 hours, and then washed with water and filtered to obtain an intermediate product; then the intermediate product, aniline, the acid-binding agent IV and the solvent IV are mixed, and then reacted at 40°C for 4 hours, and then added into ethyl acetate to precipitate the product, and then filtered, washed and vacuum dried to obtain the cage molecule-containing flame retardant B; wherein the molar ratio of the cyanuric chloride, the aminopropylbutyl POSS and the acid-binding agent III is 1:1.2:1, and the molar ratio of the intermediate product, the aniline and the acid-binding agent IV is 1:1.2:1.

[0239] The initial decomposition temperature of the cage molecule-containing flame retardant B prepared finally is 260 DEG C, and the carbon residue after 800 DEG C is 27%.

[0240] Example 11

[0241] The preparation method of the cage molecule-containing flame retardant B is as follows:

[0242] (1) Preparation of raw materials:

[0243] cyanuric chloride;

[0244] aminopropylbutyl POSS;

[0245] aniline;

[0246] base III: sodium hydroxide;

[0247] base IV: sodium hydroxide;

[0248] solvent III: toluene;

[0249] solvent IV: acetonitrile;

[0250] (2) Preparation of the cage molecule-containing flame retardant B:

[0251] After mixing cyanuric chloride, aminopropylbutyl POSS, base III and solvent III, reaction is carried out at 0 DEG C for 2h, and then the intermediate product is obtained by water washing and filtration; then the intermediate product, aniline, base IV and solvent IV are mixed, and reaction is carried out at 40 DEG C for 4.5h, and then the product is precipitated by adding into ethyl acetate; and then the cage molecule-containing flame retardant B is obtained by filtration, washing and vacuum drying; wherein the molar ratio of cyanuric chloride, aminopropylbutyl POSS and base III is 1:1.2:1, and the molar ratio of the intermediate product, aniline and base IV is 1:1.2:1.

[0252] The initial decomposition temperature of the cage molecule-containing flame retardant B prepared finally is 260 DEG C, and the carbon residue after 800 DEG C is 27%.

[0253] Example 12

[0254] The preparation method of the cage molecule-containing flame retardant B is as follows:

[0255] (1) Preparation of raw materials:

[0256] cyanuric chloride;

[0257] aminopropylbutyl POSS;

[0258] aniline;

[0259] base III: sodium hydroxide;

[0260] Base-acceptor IV: sodium hydroxide;

[0261] Solvent III: acetone;

[0262] Solvent IV: acetonitrile;

[0263] (2) Preparation of cage molecule-containing flame retardant B:

[0264] After mixing cyanuric chloride, aminopropylbutyl POSS, base-acceptor III and solvent III, reaction was carried out at 5℃ for 2.5h, and then the intermediate product was obtained by water washing and filtration. Then, the intermediate product, aniline, base-acceptor IV and solvent IV were mixed, and reaction was carried out at 45℃ for 4h. The product was precipitated by adding into ethyl acetate, and then was obtained by filtration, washing and vacuum drying. The cage molecule-containing flame retardant B was obtained. The molar ratio of cyanuric chloride, aminopropylbutyl POSS and base-acceptor III was 1:1:1, and the molar ratio of the intermediate product, aniline and base-acceptor IV was 1:1:1.

[0265] The initial decomposition temperature of the finally prepared cage molecule-containing flame retardant B was 260℃, and the residual carbon content after 800℃ was 27%.

[0266] Example 13

[0267] Application of the cage molecule-containing flame retardant B, the specific steps are as follows:

[0268] (1) Preparation of regenerated polyamide:

[0269] (1.1) Hydrolysis of waste polyamide:

[0270] The cut waste polyamide (nylon 6) was depolymerized in subcritical water at a temperature of 340℃ and a pressure of 9MPa for 90min, wherein the mass ratio of subcritical water to polyamide fiber waste was 30:1;

[0271] (1.2) Purification:

[0272] The substances other than caprolactam in the hydrolysis product of waste polyamide were removed;

[0273] (1.3) Copolymerization:

[0274] The caprolactam obtained in step (1.2) was mixed with the cage molecule-containing flame retardant B (prepared by the above-mentioned example 9), and the molar proportion of the cage molecule-containing flame retardant B in the mixture was 1%. The mixture was reacted at a temperature of 240℃, under normal pressure and under nitrogen protection for 10h, and a cage molecule-containing modified flame-retardant copolymerized regenerated polyamide was obtained.

[0275] The prepared flame-retardant copolymerized reclaimed polyamide containing cage molecules has a melt dripping resistance grade of V-0, an ultimate oxygen index of 30.5%, and a contact angle of 131° with water;

[0276] (2) Preparation of the reclaimed polyamide fiber:

[0277] The flame-retardant copolymerized reclaimed polyamide containing cage molecules prepared in step (1) is used to prepare a flame-retardant copolymerized reclaimed polyamide fiber containing cage molecules by melt spinning, wherein the process parameters of the melt spinning include: a screw feeding section temperature of 255°C, a screw melting section temperature of 270°C, a screw pressure relief section temperature of 260°C, a metering pump temperature of 260°C, a spinning speed of 1000 m / min, and a draw ratio of 2.

[0278] The flame-retardant copolymerized reclaimed polyamide fiber containing cage molecules finally prepared has a melt dripping resistance grade of V-0, an ultimate oxygen index of 31.5%, and a breaking strength of 4 cN / dtex.

[0279] Example 14

[0280] Application of the flame retardant containing cage molecules B, and the specific steps are as follows:

[0281] (1) Preparation of the reclaimed polyamide:

[0282] (1.1) Hydrolysis of the waste polyamide:

[0283] The cut waste polyamide (nylon 6) is subjected to depolymerization reaction in subcritical water at a temperature of 350°C and a pressure of 9 MPa for 60 min, wherein the mass ratio of the subcritical water to the polyamide fiber waste is 40:1.

[0284] (1.2) Purification:

[0285] The substances other than caprolactam in the hydrolysis product of the waste polyamide are removed.

[0286] (1.3) Copolymerization:

[0287] The caprolactam obtained in step (1.2) is mixed with the flame retardant containing cage molecules B (prepared in the above example 10), and the mole percentage of the flame retardant containing cage molecules B in the mixture is 4%, and the mixture is reacted at a temperature of 260°C, under normal pressure, and under nitrogen protection for 8 h, to obtain the flame-retardant copolymerized reclaimed polyamide containing cage molecules.

[0288] The prepared flame-retardant copolymerized reclaimed polyamide containing cage molecules has a melt dripping resistance grade of V-0, an ultimate oxygen index of 31.2%, and a contact angle of 130° with water;

[0289] (2) Preparation of the regenerated polyamide fiber:

[0290] The cage molecule-containing modified flame-retardant copolymerized regenerated polyamide prepared in step (1) is prepared into a cage molecule-containing modified flame-retardant copolymerized regenerated polyamide fiber by melt spinning; wherein the process parameters of the melt spinning include: the temperature of the screw feeding section is 260℃, the temperature of the screw melting section is 275℃, the temperature of the screw pressure relief section is 265℃, the temperature of the metering pump is 265℃, the spinning speed is 1000m / min, and the draw ratio is 2.

[0291] The anti-melt dripping grade of the finally prepared cage molecule-containing modified flame-retardant copolymerized regenerated polyamide fiber reaches V-0 grade, the limiting oxygen index is 30.5%, and the breaking strength is 4.2cN / dtex.

[0292] Example 15

[0293] Application of the cage molecule-containing flame retardant B, the specific steps are as follows:

[0294] (1) Preparation of the regenerated polyamide:

[0295] (1.1) Hydrolysis of the waste polyamide:

[0296] The cut waste polyamide (nylon 6) is subjected to depolymerization reaction in subcritical water at a temperature of 340℃ and a pressure of 9MPa for 80min, wherein the mass ratio of the subcritical water to the polyamide fiber waste is 20:1;

[0297] (1.2) Purification:

[0298] The substances other than caprolactam in the hydrolysis product of the waste polyamide are removed;

[0299] (1.3) Copolymerization:

[0300] The caprolactam obtained in step (1.2) is mixed with the cage molecule-containing flame retardant B (prepared in the above example 11), the molar proportion of the cage molecule-containing flame retardant B in the mixture is 8%, and the mixture is reacted at a temperature of 220℃, under normal pressure, and under the protection of nitrogen for 14h, to obtain the cage molecule-containing modified flame-retardant copolymerized regenerated polyamide;

[0301] The anti-melt dripping grade of the prepared cage molecule-containing modified flame-retardant copolymerized regenerated polyamide reaches V-0 grade, the limiting oxygen index is 32.4%, and the contact angle of the cage molecule-containing modified flame-retardant copolymerized regenerated polyamide chip to water is 132°;

[0302] (2) Preparation of the regenerated polyamide fiber:

[0303] The cage molecule-containing modified flame-retardant copolymerized regenerated polyamide prepared in step (1) is prepared into a cage molecule-containing modified flame-retardant copolymerized regenerated polyamide fiber by melt spinning; wherein the process parameters of melt spinning include: the temperature of the screw feeding section is 265°C, the temperature of the screw melting section is 280°C, the temperature of the screw pressure relief section is 270°C, the temperature of the metering pump is 270°C, the spinning speed is 1000 m / min, and the draw ratio is 2.6.

[0304] The prepared cage molecule-containing modified flame-retardant copolymerized regenerated polyamide fiber has a melt dripping resistance level of V-0, an ultimate oxygen index of 32.5%, and a breaking strength of 4.5 cN / dtex.

[0305] Example 16

[0306] Application of the cage molecule-containing flame retardant B, the specific steps are as follows:

[0307] (1) Preparation of a regenerated polyamide:

[0308] (1.1) Hydrolysis of waste polyamide:

[0309] The cut waste polyamide (nylon 6) is subjected to depolymerization reaction in subcritical water at a temperature of 350°C and a pressure of 9 MPa for 70 min, wherein the mass ratio of subcritical water to polyamide fiber waste is 50:1;

[0310] (1.2) Purification:

[0311] The substances other than caprolactam in the hydrolysis product of the waste polyamide are removed;

[0312] (1.3) Copolymerization:

[0313] The caprolactam obtained in step (1.2) is mixed with the cage molecule-containing flame retardant B (prepared in the above example 12), and the molar proportion of the cage molecule-containing flame retardant B in the mixture is 10%, and the mixture is reacted at a temperature of 280°C, under normal pressure, and under nitrogen protection for 6 h, to obtain a cage molecule-containing modified flame-retardant copolymerized regenerated polyamide;

[0314] The prepared cage molecule-containing modified flame-retardant copolymerized regenerated polyamide has a melt dripping resistance level of V-0, an ultimate oxygen index of 33.5%, and a contact angle of the cage molecule-containing modified flame-retardant copolymerized regenerated polyamide chip to water of 131°;

[0315] (2) Preparation of a regenerated polyamide fiber:

[0316] The cage molecule-containing modified flame-retardant copolymerized regenerated polyamide prepared in step (1) is prepared into a cage molecule-containing modified flame-retardant copolymerized regenerated polyamide fiber through melt spinning; wherein the process parameters of melt spinning include: the temperature of the screw feeding section is 270°C, the temperature of the screw melting section is 258°C, the temperature of the screw pressure relief section is 275°C, the temperature of the metering pump is 275°C, the spinning speed is 1000 m / min, and the draw ratio is 2.6.

[0317] The cage molecule-containing modified flame-retardant copolymerized regenerated polyamide fiber prepared finally has a melt dripping resistance grade of V-0, an ultimate oxygen index of 30.5%, and a breaking strength of 4.3 cN / dtex.

Claims

1. Use of a caged molecule flame retardant on recycled polyesters, characterized in that, The BHET obtained by alcoholysis of waste polyester is subjected to copolymerization with a cage molecule-containing flame retardant to prepare a cage molecule-containing modified flame-retardant copolymerized regenerated polyester; The cage molecule-containing flame retardant is cage molecule-containing flame retardant A or cage molecule-containing flame retardant B; the cage molecule-containing flame retardant A has the following molecular structure formula: ； The cage molecule-containing flame retardant B has the following molecular structure formula: 。 2. Use of a caged molecule-containing flame retardant on recycled polyester according to claim 1, characterized in that, The cage molecule-containing flame retardant A has an initial decomposition temperature of 260 DEG C and a residual carbon content of 27% at 800 DEG C; the cage molecule-containing flame retardant B has an initial decomposition temperature of 260 DEG C and a residual carbon content of 27% after 800 DEG C.

3. Use of a caged molecule-containing flame retardant on recycled polyester according to claim 1, characterized in that, The cage molecule-containing flame retardant A is prepared by mixing cyanuric chloride, aminopropyl butyl POSS, an acid-binding agent I and a solvent I, and then reacting at 0-5 DEG C for 2-2.5 h to obtain an intermediate product, and then mixing the intermediate product, ethylene glycol, an acid-binding agent II and a solvent II, and then reacting at 40-45 DEG C for 4-4.5 h to obtain the cage molecule-containing flame retardant A; the molar ratio of cyanuric chloride, aminopropyl butyl POSS and the acid-binding agent I is 1:1-1.2:1; the molar ratio of the intermediate product, ethylene glycol and the acid-binding agent II is 1:1-1.2:1; The cage molecule-containing flame retardant B is prepared by mixing cyanuric chloride, aminopropyl butyl POSS, an acid-binding agent III and a solvent III, and then reacting at 0-5 DEG C for 2-2.5 h to obtain an intermediate product, and then mixing the intermediate product, aniline, an acid-binding agent IV and a solvent IV, and then reacting at 40-45 DEG C for 4-4.5 h to obtain the cage molecule-containing flame retardant B; the molar ratio of cyanuric chloride, aminopropyl butyl POSS and the acid-binding agent III is 1:1-1.2:1, and the molar ratio of the intermediate product, aniline and the acid-binding agent IV is 1:1-1.2:

1.

4. Use of a caged molecule-containing flame retardant on recycled polyester according to claim 1, characterized in that, The specific steps are as follows: (1) alcoholysis of waste polyester; The ethylene glycol and the waste polyester are mixed at a mass ratio of 1-3:1, and then a catalyst is added in an amount of 0.2% of the mass of the waste polyester, and then the mixture is reacted at 160-200 DEG C for 1-5 h under the condition of continuous nitrogen blowing; (2) purification; The substances other than BHET in the alcoholysis product of the waste polyester are removed; (3) copolymerization; The BHET obtained in step (2), the cage molecule-containing flame retardant and the catalyst are mixed, the molar ratio of the cage molecule-containing flame retardant in the mixture is 1-10%, and the mass of the catalyst is 0.04 wt% of the mass of the BHET, and then the mixture is reacted at a temperature of 280-290 DEG C and a pressure of 0.3-0.5 MPa for 2-3 h to obtain the cage molecule-containing modified flame-retardant copolymerized regenerated polyester.

5. Use of a caged molecule-containing flame retardant on recycled polyester according to claim 1, characterized in that, After the cage molecule-containing modified flame-retardant copolymerized regenerated polyester is prepared, it is subjected to melt spinning to obtain cage molecule-containing modified flame-retardant copolymerized regenerated polyester fibers; the cage molecule-containing modified flame-retardant copolymerized regenerated polyester fibers have a melt dripping resistance grade of V-0, an ultimate oxygen index of 30% or more and a breaking strength of 3.5 cN / dtex or more.

6. Use of a caged molecule flame retardant on recycled polyamide, characterized in that, The caprolactam obtained by hydrolysis of waste polyamide is subjected to copolymerization with a cage molecule-containing flame retardant to prepare a cage molecule-containing modified flame-retardant copolymerized regenerated polyamide; The cage-containing molecule flame retardant is cage-containing molecule flame retardant A or cage-containing molecule flame retardant B; the molecular structural formula of the cage-containing molecule flame retardant A is as follows: ； The molecular structural formula of the cage-containing molecule flame retardant B is as follows: 。 7. Use of a caged molecule-containing flame retardant according to claim 6 on recycled polyamide, characterized in that, The initial decomposition temperature of the cage-containing molecule flame retardant A is 260 DEG C, and the residual carbon content at 800 DEG C is 27%; the initial decomposition temperature of the cage-containing molecule flame retardant B is 260 DEG C, and the residual carbon content after 800 DEG C is 27%.

8. Use of a caged molecule-containing flame retardant according to claim 6 on recycled polyamide, characterized in that, The preparation method of the cage-containing molecule flame retardant A is as follows: the cyanuric chloride, the aminopropyl butyl POSS, the acid binding agent I and the solvent I are mixed, and then reacted at 0-5 DEG C for 2-2.5 h to obtain an intermediate product; the intermediate product, the ethylene glycol, the acid binding agent II and the solvent II are mixed, and then reacted at 40-45 DEG C for 4-4.5 h to obtain the cage-containing molecule flame retardant A; the molar ratio of the cyanuric chloride, the aminopropyl butyl POSS and the acid binding agent I is 1:1-1.2:1; the molar ratio of the intermediate product, the ethylene glycol and the acid binding agent II is 1:1-1.2:1; The preparation method of the cage-containing molecule flame retardant B is as follows: the cyanuric chloride, the aminopropyl butyl POSS, the acid binding agent III and the solvent III are mixed, and then reacted at 0-5 DEG C for 2-2.5 h to obtain an intermediate product; the intermediate product, the aniline, the acid binding agent IV and the solvent IV are mixed, and then reacted at 40-45 DEG C for 4-4.5 h to obtain the cage-containing molecule flame retardant B; the molar ratio of the cyanuric chloride, the aminopropyl butyl POSS and the acid binding agent III is 1:1-1.2:1, and the molar ratio of the intermediate product, the aniline and the acid binding agent IV is 1:1-1.2:

1.

9. Use of a caged molecule-containing flame retardant according to claim 6 on recycled polyamide, characterized in that, The specific steps are as follows: (1) hydrolysis of waste polyamide; The waste polyamide is subjected to depolymerization reaction in subcritical water at a temperature of 340-350 DEG C and a pressure of 9 MPa for 60-90 min, wherein the mass ratio of the subcritical water to the polyamide fiber waste is 20-50:1; (2) purification; The substances other than caprolactam in the hydrolysis product of the waste polyamide are removed; (3) copolymerization; The caprolactam obtained in step (2) is mixed with the cage-containing molecule flame retardant, and the molar proportion of the cage-containing molecule flame retardant in the mixture is 1-10%; the mixture is reacted at a temperature of 220-280 DEG C, under normal pressure, under the protection of nitrogen, for 6-14 h, to obtain the cage-containing molecule modified flame-retardant copolymerized regenerated polyamide.

10. Use of a caged molecule-containing flame retardant according to claim 6 on recycled polyamide, characterized in that, After the cage-containing molecule modified flame-retardant copolymerized regenerated polyamide is prepared, it is subjected to melt spinning to obtain the cage-containing molecule modified flame-retardant copolymerized regenerated polyamide fiber; the melt dripping resistance grade of the cage-containing molecule modified flame-retardant copolymerized regenerated polyamide fiber reaches V-0 grade, the limiting oxygen index is 30% or more, and the breaking strength reaches 4 cN / dtex or more.

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