CN116813909A - Flame retardant containing caged molecules, preparation method thereof and application of flame retardant to regenerated products - Google Patents
Flame retardant containing caged molecules, preparation method thereof and application of flame retardant to regenerated products Download PDFInfo
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- CN116813909A CN116813909A CN202310835635.2A CN202310835635A CN116813909A CN 116813909 A CN116813909 A CN 116813909A CN 202310835635 A CN202310835635 A CN 202310835635A CN 116813909 A CN116813909 A CN 116813909A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
- C08G63/6956—Dicarboxylic acids and dihydroxy compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
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Abstract
The invention relates to a flame retardant containing cage-shaped molecules, a preparation method thereof and application thereof in regenerated products, wherein the molecular structural formula of the flame retardant containing cage-shaped molecules is as follows:or (b)Preparation methodThe method comprises the following steps: mixing cyanuric chloride, aminopropyl butyl POSS, an acid binding agent and a solvent, reacting for 2-2.5 hours at 0-5 ℃ to obtain an intermediate product, mixing the intermediate product, glycol (or aniline), the acid binding agent and the solvent, and reacting for 4-4.5 hours at 40-45 ℃; application: and (3) carrying out copolymerization reaction on BHET (or caprolactam obtained by hydrolysis of waste polyamide) obtained by alcoholysis of waste polyester and a flame retardant containing cage molecules. The flame retardant disclosed by the invention has excellent flame retardant property and anti-dripping property, the method is simple and environment-friendly, industrial popularization can be realized, a compact carbon layer can be formed on the surface when the polyester or polyamide fiber is combusted, oxygen is isolated, melting is prevented from falling, and the flame retardant property is excellent.
Description
Technical Field
The invention belongs to the technical field of flame retardants, and relates to a flame retardant containing caged molecules, a preparation method thereof and application thereof in regenerated products.
Background
The regenerated polyester is prepared from waste recovered polyester products by physical method, physical and chemical method, and the like, and has the characteristics of low raw material price, environmental protection, simple production, and the like, and the increasingly shortage of natural resources such as petroleum, and the like, the social storage of the waste polyester bottles is huge, the demand of polyester fibers is continuously increased, and the waste polyester is valued by more and more enterprises, so that the regenerated polyester is mainly applied to the fields of automobiles, home textiles, filling materials, and the like. Therefore, the flame-retardant regenerated polyester fiber and the product thereof become a new hot spot of the textile market in China and have good development prospect. The Limiting Oxygen Index (LOI) of the regenerated polyester is about 22%, so that the regenerated polyester becomes a flammable product, and secondary fire is easy to cause due to the fact that the polyester is often accompanied with a molten drop phenomenon during combustion due to the low melt viscosity of the polyester at high temperature.
The general flame-retardant modification of recycled polyester fibers is mainly to prepare a recycled polyester master batch by adding a flame retardant such as phosphorus or halogen in a molten state of polyester, and to prepare a flame-retardant polyester fiber by blending and spinning the master batch and chips.
The invention CN103215686A discloses a flame-retardant regenerated polyester fiber, which is prepared by granulating a regenerated polyester slice in a phosphorus flame retardant powder by a masterbatch method through double screw extrusion, preparing a flame-retardant regenerated polyester masterbatch, and blending and spinning the masterbatch and the slice. The flame retardance of the product was good, the limiting oxygen index was 30%, but the melt drop was not considered.
The invention CN104017195A discloses a phosphorus copolymerized flame-retardant regenerated polyester chip and a production method of industrial yarn thereofThe ES flame retardant is added into polyester which has completed the polymerization process, and the flame retardant is grafted on polymer molecules in a side chain mode, but the flame retardant effect is unstable and is easily influenced by other additives, treatment methods and other factors, the preparation process is complex, the cost is high, and meanwhile, the anti-dripping performance is not obviously improved.
Polyamide 6, because of its excellent physical and mechanical properties and textile processability, has been widely used in various fields, since its production has been in the first place in the family of synthetic fibers for a considerable period of time. With the continuous increase of the productivity of polyamide 6, more and more solid waste is produced each year. Polyamide 6 is chemically stable and difficult to degrade in natural environments, and if it is not recycled, it will have a great influence on the environment. Thus, people put their eyes on the regenerated polyamide, and as the regeneration industry develops, the regenerated polyamide fiber and its products gradually step into popularity. And, along with the gradual clear understanding of people to the conflagration, the fire prevention consciousness is strengthened gradually, and the fire-retardant function of various functional fibers is more and more paid attention to by masses. The development of flame retardant polyamide products is therefore continually being advanced.
At present, a lot of research on flame-retardant modified virgin polyamide fibers and textiles is carried out, wherein a flame retardant is generally melt-blended with a spinning melt by a blending method, and then the flame-retardant fibers are manufactured, and a monomer or a macromolecule with a flame-retardant component is introduced into a polymer molecular chain by a polymerization method to carry out flame-retardant modification.
Patent CN110923848A provides a method for preparing flame-retardant polyamide fiber, which comprises the steps of melt blending polyamide, melamine cyanurate, graphite-like carbon nitride, zinc compound and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivative to prepare flame-retardant polyamide slice, and spinning to prepare the flame-retardant polyamide fiber.
The patent CN112048061A is prepared by mixing flame retardant salt with polyamide 66 oligomer and/or polyamide 6 oligomer and performing polycondensation reaction to obtain the copolymerized flame retardant polyamide, wherein the flame retardant salt comprises N, N-di (6-amino hexyl) phenyl phosphoryl diamine and dibasic acid HOOCR 1 COOH is prepared by high-temperature high-pressure reaction, wherein R 1 Is a linear, branched or cyclic C2-C15 alkylene structure.
However, the addition amount of the phosphine oxide flame retardant adopted in the patent CN112048061a is large, the produced polyamide is an oligomer and the melt dripping performance of the polyamide is not improved, the flame retardant polyamide is prepared in a blending mode in the patent CN110923848A, the dispersion of the flame retardant polyamide needs high temperature and high shearing force to achieve good dispersion effect, the DOPO itself is not completely incombustible, and the combustion process releases some harmful substances to affect the environment.
Multielement synergistic flame retardance has become one of the development directions of halogen-free flame retardants, such as silicon nitrogen, silicon phosphorus and the like. The POSS has an inorganic silica skeleton structure, so that the POSS has excellent thermal stability and resistanceOn the one hand, because the Si-O bond energy is far higher than the C-C bond energy, when POSS molecules are bonded to the main chain or side chains of the polymer, the structure and performance of the POSS molecules can still be kept stable when the hybrid material begins to melt above the glass transition temperature (Tg) and even when the temperature reaches the glass transition temperature (Tg); on the other hand, when organic molecules on the surface of POSS are oxidized and decomposed at high temperature, si-O-Si in POSS is very stable to oxygen free radical, and SiO can be formed on the surface after POSS is degraded 2 The protective layer has the functions of heat resistance, heat insulation, radiation protection and the like and plays a role of structural support, but the POSS flame retardant has the problems of poor dispersibility and the like in blending because of compatibility with the regenerated polyamide, so that the POSS flame retardant is freshly applied to flame retardant modification of the regenerated polyamide fiber.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a flame retardant containing caged molecules, a preparation method thereof and application thereof in regenerated products.
In order to achieve the above purpose, the invention adopts the following scheme:
the molecular structural formula of the flame retardant A containing cage-shaped molecules is as follows:
as a preferable technical scheme:
the flame retardant A containing the cage-like molecules has an initial decomposition temperature of 260 ℃ and a carbon residue at 800 ℃ of 27%.
The invention also provides a method for preparing the cage-like molecular flame retardant A, which is characterized in that after cyanuric chloride (Cyanuric chloride), aminopropyl butyl POSS (AminopropylIsobutyl POSS), an acid binding agent I and a solvent I are mixed, the mixture is reacted for 2 to 2.5 hours at the temperature of 0 to 5 ℃, an intermediate product is obtained by water washing and filtration, cl and amino are difficult to react at normal temperature, the cyanuric chloride is combined with aminopropyl butyl pos through the reaction of the amino and Cl element in the cyanuric chloride in a low-temperature solvent, the intermediate product, ethylene Glycol (EG), the acid binding agent II and the solvent II are mixed and then reacted for 4 to 4.5 hours at the temperature of 40 to 45 ℃, the mixture is added into ethyl acetate to separate out the product, and the product is filtered, washed and dried in vacuum to obtain the cage-like molecular flame retardant A; the molar ratio of cyanuric chloride to aminopropyl butyl POSS to the acid binding agent I is 1:1-1.2:1; the mol ratio of the intermediate product to the glycol to the acid-binding agent II is 1:1-1.2:1.
The reaction equation for preparing the flame retardant A containing the cage molecule is as follows.
As a preferable technical scheme:
in the method, the acid binding agent I and the acid binding agent II are sodium hydroxide; the solvent I is tetrahydrofuran, chloroform, toluene or acetone; solvent II is N, N-Dimethylformamide (DMF) or acetonitrile.
The invention also provides application of the flame retardant A containing the caged molecules in regenerated polyester, and the BHET obtained by alcoholysis of waste polyester and the flame retardant A containing the caged molecules are subjected to copolymerization reaction to prepare the flame-retardant copolymerized regenerated polyester containing the caged molecules; the invention combines the flame retardant on the molecular chain of the regenerated polyester by polymerization to realize the flame retardant and anti-dripping performance of the regenerated polyester; the molecular structural formula of the flame-retardant copolymerized regenerated polyester containing the cage molecule modification is as follows:
wherein n is 140 to 200.
As a preferred technical scheme;
the application as described above comprises the following specific steps:
(1) Alcoholysis of waste polyester;
mixing glycol with the mass ratio of 1-3:1 with waste polyester, and adding a catalyst (Zn (Ac) accounting for 0.2% of the mass of the waste polyester into the mixture 2 ) Reacting for 1-5 h at 160-200 ℃ under the condition of continuously introducing nitrogen;
(2) Purifying;
Removing substances except BHET in the waste polyester alcoholysis product; the recycled polyester product after alcoholysis has some catalyst and other impurities besides BHET, and can influence the polymerization reaction in the copolymerization reaction process, the invention adopts a mode of combining fractional suction filtration and refrigeration recrystallization phase to purify the product, thereby reducing the influence of impurities on the polymerization reaction, and the specific process is as follows: firstly, rapidly filtering at 170 ℃ to obtain filtrate, then adding a large amount of distilled water, heating to above 90 ℃ to rapidly filter to obtain filtrate, then refrigerating at 4 ℃ for 8 hours to recrystallize, and finally filtering and drying to obtain pure BHET;
(3) Copolymerizing;
BHET obtained in the step (2), flame retardant A containing cage molecule, and catalyst (Sb 2 O 3 ) The mixture is mixed, the mole ratio of the flame retardant A containing the caged molecule in the mixture is 1 to 10 percent, the mass of the catalyst is 0.04 weight percent of the mass of the BHET, and the mixture is reacted for 2 to 3 hours under the conditions that the temperature is 280 to 290 ℃ and the pressure is 0.3 to 0.5MPa, thus obtaining the flame-retardant copolymerized regenerated polyester containing the caged molecule modification.
By the application, the anti-dripping grade of the flame-retardant co-recycled polyester containing the cage-like molecules reaches the V-0 grade, the limiting oxygen index is more than 30%, and the contact angle of the flame-retardant co-recycled polyester chip containing the cage-like molecules to water reaches more than 130 degrees.
After the application is carried out, the flame-retardant copolymerized regenerated polyester fiber containing the cage-shaped molecule modification is prepared by melt spinning.
For the applications described above, the process parameters of melt spinning include: the temperature of the first area of the screw is 250-270 ℃, the temperature of the second area of the screw is 260-280 ℃, the temperature of the third area of the screw is 255-275 ℃, the temperature of the fourth area of the screw is 255-275 ℃, the temperature of the metering pump is 255-275 ℃, the spinning speed is 600m/min, and the draft multiple is 3.5.
By the application, the melt drop resistance grade of the flame-retardant copolymerized regenerated polyester fiber containing the cage-shaped molecule modification reaches the V-0 grade, the limiting oxygen index is more than 30%, and the breaking strength reaches more than 3.5 cN/dtex.
The invention also provides a flame retardant B containing cage-shaped molecules, which has the following molecular structural formula:
as a preferable technical scheme:
the flame retardant B containing the cage-like molecules has an initial decomposition temperature of 260 ℃ and a residual carbon content of 27% after 800 ℃.
The invention also provides a method for preparing the flame retardant B containing cage molecules, which comprises the steps of mixing cyanuric chloride (Cyanuric chloride), aminopropyl butyl POSS (AminopropylIsobutyl POSS), an acid binding agent III and a solvent III, reacting for 2-2.5 hours at 0-5 ℃, washing with water, filtering to obtain an intermediate product, mixing the intermediate product, aniline (Aniline), the acid binding agent IV and the solvent IV, reacting for 4-4.5 hours at 40-45 ℃, adding the mixture into ethyl acetate to precipitate a product, filtering, washing and vacuum drying to obtain the flame retardant B containing cage molecules; wherein, cl and amino are difficult to react at normal temperature, the invention combines cyanuric chloride with aminopropyl butyl POSS through the reaction of amino and Cl element in cyanuric chloride in a low-temperature solvent;
The molar ratio of cyanuric chloride to aminopropyl butyl POSS to the acid binding agent III is 1:1-1.2:1, and the molar ratio of the intermediate product to the aniline to the acid binding agent IV is 1:1-1.2:1.
The reaction equation for preparing the flame retardant B containing the cage molecule is as follows.
The cage structure in the flame retardant can isolate air in the molecular center to form a physical barrier, so that the contact of fuel and oxygen is blocked, the combustion reaction rate is reduced, and a flame-retardant effect is formed.
As a preferable technical scheme:
in the method, the acid binding agent III and the acid binding agent IV are sodium hydroxide; the solvent III is tetrahydrofuran, chloroform, toluene or acetone; solvent IV is N, N-Dimethylformamide (DMF) or acetonitrile.
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, because the acid binding agent mainly reacts with active groups such as hydroxyl groups in polymer molecules, the reactivity and the compatibility with the polymer are mainly considered, the combination with the polymer can be realized through the reactivity, the acid binding agent is not influenced by the solvent, and the regulation and control of the performance can be realized through changing the dosage, the proportion and the like of the acid binding agent. Instead, the choice of solvent is made to pay more attention to the compatibility and dispersibility with the polymer, and the choice of solvent compatible with the polymer is made to ensure that the flame retardant is uniformly dispersed in the polymer, and various factors such as solubility, volatility, toxicity, price, etc. of the polymer are considered.
The invention also provides an application of the flame retardant B containing the caged molecule on regenerated polyamide, wherein caprolactam obtained by hydrolyzing waste polyamide and the flame retardant B containing the caged molecule are subjected to copolymerization reaction to prepare the flame-retardant copolymerized regenerated polyamide containing the caged molecule; the invention combines the flame retardant on the molecular chain of the regenerated polyamide by polymerization to realize the flame retardant and anti-dripping performance of the regenerated polyamide; the molecular structural formula of the flame-retardant copolymerized regenerated polyamide containing the cage molecule modification is as follows:
wherein n is 140 to 200.
As a preferable technical scheme:
the application as described above comprises the following specific steps:
(1) Hydrolyzing the waste polyamide;
carrying out depolymerization reaction on the chopped waste polyamide (nylon 6) in subcritical water with the temperature of 340-350 ℃ and the pressure of 9MPa for 60-90 min, wherein the mass ratio of subcritical water to polyamide fiber waste is 20-50:1;
(2) Purifying;
removing substances except caprolactam in the waste polyamide hydrolysate; the hydrolyzed regenerated polyamide product has some catalyst and other impurities except caprolactam, which can affect the polymerization reaction in the copolymerization reaction process, and the invention adopts a combination mode of suction filtration, extraction and reduced pressure distillation to purify the product, thereby reducing the influence of impurities on the polymerization reaction, wherein the purification process is as follows: firstly adding a 32wt% sodium hydroxide aqueous solution into a substance to be purified, then performing reduced pressure distillation treatment to remove residual water (the product is named as crude amide oil), then performing benzene extraction, namely taking benzene as an extractant, effectively extracting caprolactam in the crude amide oil (the product is named as benzene hexyl liquid), treating the rest part by a condensate stripping tower, recovering a small amount of benzene, and finally performing water extraction, namely selecting process water condensate as the extractant, effectively extracting caprolactam in the benzene hexyl liquid, and promoting the smooth removal of various benzene-soluble impurities in the caprolactam;
(3) Copolymerizing;
mixing caprolactam obtained in the step (2) with a flame retardant B containing caged molecules, wherein the molar ratio of the flame retardant B containing caged molecules in the mixture is 1-10%, and reacting for 6-14 h under the conditions of 220-280 ℃ and normal pressure and nitrogen protection to obtain the flame-retardant copolyamide containing caged molecules.
By the application, the molten drop resistance grade of the flame-retardant co-polyamide with the caged molecular modification reaches the V-0 grade, the limiting oxygen index is more than 30%, and the contact angle of the slice of the flame-retardant co-polyamide with the caged molecular modification reaches more than 130 degrees.
After the application is carried out, the flame-retardant copolymerization regenerated polyamide fiber containing the cage-shaped molecule modification is prepared by melt spinning.
For the applications described above, the process parameters of melt spinning include: 255-265 ℃ of screw feeding section temperature, 270-280 ℃ of screw melting section temperature, 260-270 ℃ of screw pressure release section temperature, 260-270 ℃ of metering pump temperature, 1000m/min of spinning speed and 2.0-2.6 of draft multiple.
By the application, the melt drop resistance grade of the flame-retardant co-regenerated polyamide fiber containing the caged molecule modification reaches the V-0 grade, the limiting oxygen index is more than 30%, and the breaking strength reaches more than 4 cN/dtex.
Advantageous effects
(1) The flame retardant A containing the cage-shaped molecules has good flame retardance;
(2) The preparation method has simple process;
(3) When the flame retardant A containing cage molecules is applied to polyester, si-O-Si in POSS is very stable to oxygen free radicals when organic molecules on the surface of POSS are subjected to high-temperature oxidative decomposition, and an SiO2 protective layer can be formed on the surface after POSS is degraded, so that the flame retardant A has the functions of heat resistance, heat insulation, radiation resistance and the like, plays a structural supporting role, and has a certain improvement on the anti-dripping performance of the polyester;
(4) When the flame retardant A containing cage-shaped molecules is applied to polyester, POSS with an organic-inorganic hybridization structure can promote the increase of the nano roughness of the surface of a material and reduce the surface energy after being introduced due to the special nano cage-shaped structure, so that the material is endowed with certain hydrophobic and oleophobic properties, and the surface antifouling capacity of the material is improved;
(5) The preparation method of the flame retardant B containing cage-shaped molecules has the advantages of simple process and convenient preparation;
(6) According to the flame retardant B containing cage-shaped molecules, the POSS structure is adopted to be compounded with the phosphorus element, so that the stability of the polymer at high temperature is improved, the emission of toxic gas during the combustion of the polymer is reduced, and the flame-retardant and anti-dripping effects can be realized;
(7) The flame retardant B containing the cage-shaped molecules is applied to the regenerated polyamide, has good compatibility, and the obtained product has excellent flame retardant effect, molten drop resistance and certain stain resistance.
Drawings
FIG. 1 is an infrared spectrum of a flame retardant A containing caged molecules according to the present application;
FIG. 2 is an infrared spectrum of a flame retardant B containing caged molecules according to the present application.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
Sources of related substances in the examples:
cyanuric chloride: the manufacturer is Roen reagent with the mark of R020254;
aminopropyl butyl POSS: the manufacturer is Bi-get medicine, and the brand is BD01136948;
ethylene glycol: manufacturer is infsci, and the trade name is H29138;
sodium hydroxide: the manufacturer is Roen reagent with the mark of R033306;
tetrahydrofuran: the manufacturer is microphone with the brand of T818764;
Chloroform: the brand is great, the product number is 01104470;
toluene: the brand is great, the product number is 01006984;
acetone: the manufacturer is Yonghua chemical Co., ltd, and the brand is 100702162;
n, N-dimethylformamide: the manufacturer is Roen reagent with the mark of R004209;
acetonitrile: the manufacturer is Roen reagent with the mark of R033065;
zinc acetate: the manufacturer is Bi-get medicine, and the brand is BD157154;
antimony trioxide: vendor is Alatine with brand A102834;
ethyl acetate: manufacturer is great, model 01022547;
waste polyester: the manufacturer is Ningbo Dafa limited company.
Aniline: vendor is Alatine with brand A112120;
waste polyamide: the manufacturer is Zhejiang Taihua New Material Co., ltd.
The molecular structural formula of the flame retardant A containing the cage-shaped molecules prepared in the example is as follows:
the molecular structural formula of the cage molecule-containing modified flame-retardant copolymerized recycled polyester prepared in the example is as follows:
wherein n is 140 to 200.
The molecular structural formula of the flame retardant B containing the cage-shaped molecules prepared in the example is as follows:
the molecular structural formula of the cage-shaped molecule-containing modified flame-retardant copolymerization regenerated polyamide prepared in the example is as follows:
wherein n is 140 to 200.
The detection method of the related performance of the prepared substance in the example comprises the following steps:
the method for detecting the residual carbon content of the flame retardant comprises the following steps: the thermal analyzer TG 209 F1 Iris test manufactured by German Chi instruments, inc. was used, the temperature was raised to 800℃at 10℃per minute, the sample weight was 7mg, and the test procedure was N 2 Under the protection, the high-temperature carbon residue of the sample is studied;
the detection method of the anti-dripping grade of the resin comprises the following steps: detecting according to a standard GB/T2408-2021;
the method for detecting the limiting oxygen index comprises the following steps: detection is carried out by reference to standard GB/T5454-1997;
the detection method of the fiber anti-dripping grade comprises the following steps: detecting according to a standard GB/T5456-2009;
the detection method of the fiber breaking strength comprises the following steps: measuring the breaking strength of the fiber by using a monofilament yarn extensometer C (XQ-1A) produced by Shanghai Kopu application science;
the detection method of the water contact angle comprises the following steps: and measuring the contact angle of the water by using a contact angle measuring instrument OCA40Micro to obtain the flame-retardant copolymer regenerated polyester chip containing the caged molecule or the flame-retardant copolymer regenerated polyamide chip containing the caged molecule.
Example 1
The preparation method of the flame retardant A containing cage-shaped molecules comprises the following specific steps:
(1) Preparing raw materials:
cyanuric chloride;
aminopropyl butyl POSS;
ethylene glycol;
Acid binding agent I: sodium hydroxide;
acid binding agent II: sodium hydroxide;
solvent I: tetrahydrofuran;
solvent II: n, N-dimethylformamide;
(2) Preparing a flame retardant A containing caged molecules:
mixing cyanuric chloride, aminopropyl butyl POSS, an acid binding agent I and a solvent I, reacting for 2.5 hours at 0 ℃, washing with water, filtering to obtain an intermediate product, mixing the intermediate product, glycol, the acid binding agent II and the solvent II, reacting for 4.5 hours at 40 ℃, adding the mixture into ethyl acetate to separate out a product, and filtering, washing and vacuum drying to obtain the flame retardant A containing cage molecules; wherein, the mol ratio of cyanuric chloride to aminopropyl butyl POSS to acid binding agent I is 1:1:1; the molar ratio of the intermediate product, the ethylene glycol and the acid-binding agent II is 1:1:1.
The initial decomposition temperature of the prepared flame retardant A containing cage-like molecules is 260 ℃, and the carbon residue at 800 ℃ is 27%; the infrared spectrum of the flame retardant A containing the caged molecule is shown in FIG. 1, and a peak exists at 1114 wave number, and the peak is a peak of Si-O-Si bond in POSS, which indicates that the POSS structure of the main body of the flame retardant still exists.
Example 2
The preparation method of the flame retardant A containing cage-shaped molecules comprises the following specific steps:
(1) Preparing raw materials:
cyanuric chloride;
aminopropyl butyl POSS;
Ethylene glycol;
acid binding agent I: sodium hydroxide;
acid binding agent II: sodium hydroxide;
solvent I: chloroform;
solvent II: acetonitrile;
(2) Preparing a flame retardant A containing caged molecules:
mixing cyanuric chloride, aminopropyl butyl POSS, an acid binding agent I and a solvent I, reacting for 2 hours at 5 ℃, washing with water, filtering to obtain an intermediate product, mixing the intermediate product, glycol, the acid binding agent II and the solvent II, reacting for 4 hours at 45 ℃, adding the mixture into ethyl acetate to separate out a product, filtering, washing and drying the product containing the cage-shaped molecular flame retardant A in vacuum; wherein, the mol ratio of cyanuric chloride to aminopropyl butyl POSS to acid binding agent I is 1:1.1:1; the molar ratio of the intermediate product, the ethylene glycol and the acid-binding agent II is 1:1:1.
The initial decomposition temperature of the prepared flame retardant A containing cage-like molecules is 260 ℃, and the carbon residue at 800 ℃ is 27%.
Example 3
The preparation method of the flame retardant A containing cage-shaped molecules comprises the following specific steps:
(1) Preparing raw materials:
cyanuric chloride;
aminopropyl butyl POSS;
ethylene glycol;
acid binding agent I: sodium hydroxide;
acid binding agent II: sodium hydroxide;
solvent I: toluene;
solvent II: n, N-dimethylformamide;
(2) Preparing a flame retardant A containing caged molecules:
mixing cyanuric chloride, aminopropyl butyl POSS, an acid binding agent I and a solvent I, reacting for 2.5 hours at 0 ℃, washing with water, filtering to obtain an intermediate product, mixing the intermediate product, glycol, the acid binding agent II and the solvent II, reacting for 4.5 hours at 40 ℃, adding the mixture into ethyl acetate to separate out a product, and filtering, washing and vacuum drying to obtain the flame retardant A containing cage molecules; wherein, the mol ratio of cyanuric chloride to aminopropyl butyl POSS to acid binding agent I is 1:1:1; the molar ratio of the intermediate product, the ethylene glycol and the acid-binding agent II is 1:1.1:1.
The initial decomposition temperature of the prepared flame retardant A containing cage-like molecules is 260 ℃, and the carbon residue at 800 ℃ is 27%.
Example 4
The preparation method of the flame retardant A containing cage-shaped molecules comprises the following specific steps:
(1) Preparing raw materials:
cyanuric chloride;
aminopropyl butyl POSS;
ethylene glycol;
acid binding agent I: sodium hydroxide;
acid binding agent II: sodium hydroxide;
solvent I: acetone;
solvent II: acetonitrile;
(2) Preparing a flame retardant A containing caged molecules:
mixing cyanuric chloride, aminopropyl butyl POSS, an acid binding agent I and a solvent I, reacting for 2 hours at 5 ℃, washing with water, filtering to obtain an intermediate product, mixing the intermediate product, glycol, the acid binding agent II and the solvent II, reacting for 4 hours at 45 ℃, adding the mixture into ethyl acetate to separate out a product, filtering, washing and drying the product containing the cage-shaped molecular flame retardant A in vacuum; wherein, the mol ratio of cyanuric chloride to aminopropyl butyl POSS to acid binding agent I is 1:1.2:1; the molar ratio of the intermediate product, the ethylene glycol and the acid-binding agent II is 1:1.2:1.
The initial decomposition temperature of the prepared flame retardant A containing cage-like molecules is 260 ℃, and the carbon residue at 800 ℃ is 27%.
Example 5
The application of the flame retardant A containing the caged molecules is as follows:
(1) Preparing flame-retardant copolymerized regenerated polyester:
(1.1) alcoholysis of waste polyester;
mixing ethylene glycol with the mass ratio of 1:1 with waste polyester, adding zinc actinide accounting for 0.2% of the mass of the waste polyester, and reacting for 5 hours at 160 ℃ under the condition of continuously introducing nitrogen;
(1.2) purification;
removing substances except BHET in the waste polyester alcoholysis product;
(1.3) copolymerizing;
mixing BHET obtained in the step (1.2), a flame retardant A containing caged molecules (prepared in the embodiment 1) and antimony trioxide, wherein the molar ratio of the flame retardant A containing caged molecules in the mixture is 1%, the mass of the antimony trioxide is 0.04wt% of the mass of the BHET, and reacting for 3 hours at the temperature of 280 ℃ and the pressure of 0.5MPa to obtain the flame-retardant copolymerized regenerated polyester containing caged molecules;
the prepared flame-retardant copolymerized regenerated polyester containing the cage-shaped molecules has the anti-dripping grade reaching the V-0 grade, the limiting oxygen index being 30.2 percent, and the contact angle of the flame-retardant copolymerized regenerated polyester chip containing the cage-shaped molecules to water being 130.2 degrees;
(2) Preparing flame-retardant copolymerized regenerated polyester fibers:
carrying out melt spinning on the flame-retardant copolymerized regenerated polyester containing the cage-shaped molecule modification prepared in the step (1) to prepare a flame-retardant copolymerized regenerated polyester fiber containing the cage-shaped molecule modification; wherein, the technological parameters of melt spinning comprise: the temperature of the first area of the screw is 250 ℃, the temperature of the second area of the screw is 260 ℃, the temperature of the third area of the screw is 255 ℃, the temperature of the fourth area of the screw is 255 ℃, the temperature of a metering pump is 255 ℃, the spinning speed is 600m/min, and the draft multiple is 3.5.
The finally prepared flame-retardant copolymerized regenerated polyester fiber containing cage-shaped molecules has the anti-molten drop grade reaching V-0 grade, the limiting oxygen index of 30.2 percent and the breaking strength of 3.7cN/dtex.
Example 6
The application of the flame retardant A containing the caged molecules is as follows:
(1) Preparing flame-retardant copolymerized regenerated polyester:
(1.1) alcoholysis of waste polyester;
mixing ethylene glycol with the mass ratio of 2:1 with waste polyester, adding zinc actinide accounting for 0.2% of the mass of the waste polyester, and reacting for 4 hours at 180 ℃ under the condition of continuously introducing nitrogen;
(1.2) purification;
removing substances except BHET in the waste polyester alcoholysis product;
(1.3) copolymerizing;
mixing BHET obtained in the step (1.2), a flame retardant A containing caged molecules (prepared in the example 2) and antimony trioxide, wherein the molar ratio of the flame retardant A containing caged molecules in the mixture is 4%, the mass of the antimony trioxide is 0.04% of the mass of the BHET, and reacting for 2.5h under the conditions of the temperature of 285 ℃ and the pressure of 0.4MPa to obtain the flame-retardant copolymerized regenerated polyester containing caged molecules;
the prepared flame-retardant copolymerized regenerated polyester containing the cage-shaped molecules has the anti-dripping grade reaching the V-0 grade, the limiting oxygen index being 31.2 percent, and the contact angle of the flame-retardant copolymerized regenerated polyester chip containing the cage-shaped molecules to water being 131.1 degrees;
(2) Preparing flame-retardant copolymerized regenerated polyester fibers:
carrying out melt spinning on the flame-retardant copolymerized regenerated polyester containing the cage-shaped molecule modification prepared in the step (1) to prepare a flame-retardant copolymerized regenerated polyester fiber containing the cage-shaped molecule modification; wherein, the technological parameters of melt spinning comprise: 255 ℃ for the first area of the screw, 265 ℃ for the second area of the screw, 260 ℃ for the third area of the screw, 260 ℃ for the fourth area of the screw, 260 ℃ for the metering pump, 600m/min of spinning speed and 3.5 of draft multiple.
The finally prepared flame-retardant copolymerized regenerated polyester fiber containing cage-shaped molecules has the anti-molten drop grade reaching V-0 grade, the limiting oxygen index being 31.5% and the breaking strength being 3.5cN/dtex.
Example 7
The application of the flame retardant A containing the caged molecules is as follows:
(1) Preparing flame-retardant copolymerized regenerated polyester:
(1.1) alcoholysis of waste polyester;
mixing ethylene glycol with the mass ratio of 2.5:1 with waste polyester, adding zinc actinide accounting for 0.2% of the mass of the waste polyester, and reacting for 2 hours at 190 ℃ under the condition of continuously introducing nitrogen;
(1.2) purification;
removing substances except BHET in the waste polyester alcoholysis product;
(1.3) copolymerizing;
mixing BHET obtained in the step (1.2), a flame retardant A containing caged molecules (prepared in the example 3) and antimony trioxide, wherein the molar ratio of the flame retardant A containing caged molecules in the mixture is 8%, the mass of the antimony trioxide is 0.04% of the mass of the BHET, and reacting for 2.5h under the conditions of the temperature of 287 ℃ and the pressure of 0.4MPa to obtain the flame-retardant co-regenerated polyester containing caged molecules;
The prepared flame-retardant copolymerized regenerated polyester containing the cage-shaped molecules has the anti-dripping grade reaching the V-0 grade, the limiting oxygen index being 32.5 percent, and the contact angle of the flame-retardant copolymerized regenerated polyester chip containing the cage-shaped molecules to water being 130.8 degrees;
(2) Preparing flame-retardant copolymerized regenerated polyester fibers:
carrying out melt spinning on the flame-retardant copolymerized regenerated polyester containing the cage-shaped molecule modification prepared in the step (1) to prepare a flame-retardant copolymerized regenerated polyester fiber containing the cage-shaped molecule modification; wherein, the technological parameters of melt spinning comprise: the temperature of the first area of the screw is 260 ℃, the temperature of the second area of the screw is 270 ℃, the temperature of the third area of the screw is 265 ℃, the temperature of the fourth area of the screw is 265 ℃, the temperature of a metering pump is 265 ℃, the spinning speed is 600m/min, and the draft multiple is 3.5.
The finally prepared flame-retardant copolymerized regenerated polyester fiber containing cage-shaped molecules has the anti-molten drop grade reaching V-0 grade, the limiting oxygen index being 32.4% and the breaking strength being 3.8cN/dtex.
Example 8
The application of the flame retardant A containing the caged molecules is as follows:
(1) Preparing flame-retardant copolymerized regenerated polyester:
(1.1) alcoholysis of waste polyester;
mixing ethylene glycol with the mass ratio of 3:1 with waste polyester, adding zinc actinide accounting for 0.2% of the mass of the waste polyester, and reacting for 1h at 200 ℃ under the condition of continuously introducing nitrogen;
(1.2) purification;
removing substances except BHET in the waste polyester alcoholysis product;
(1.3) copolymerizing;
mixing BHET obtained in the step (1.2), a flame retardant A containing caged molecules (prepared in the example 4) and antimony trioxide, wherein the molar ratio of the flame retardant A containing caged molecules in the mixture is 10%, the mass of the antimony trioxide is 0.04% of the mass of the BHET, and reacting for 2 hours at the temperature of 290 ℃ and under the pressure of 0.3MPa to obtain the flame-retardant copolymerized regenerated polyester containing caged molecules;
the prepared flame-retardant copolymerized regenerated polyester containing the cage-shaped molecules has the anti-dripping grade reaching the V-0 grade, the limiting oxygen index being 33.4 percent, and the contact angle of the flame-retardant copolymerized regenerated polyester chip containing the cage-shaped molecules to water being 131.2 degrees;
(2) Preparing flame-retardant copolymerized regenerated polyester fibers:
carrying out melt spinning on the flame-retardant copolymerized regenerated polyester containing the cage-shaped molecule modification prepared in the step (1) to prepare a flame-retardant copolymerized regenerated polyester fiber containing the cage-shaped molecule modification; wherein, the technological parameters of melt spinning comprise: 270 ℃ in the first area of the screw, 280 ℃ in the second area of the screw, 275 ℃ in the third area of the screw, 275 ℃ in the fourth area of the screw, 275 ℃ in the metering pump, 600m/min of spinning speed and 3.5 of draft multiple.
The finally prepared flame-retardant copolymerized regenerated polyester fiber containing cage-shaped molecules has the anti-molten drop grade reaching V-0 grade, the limiting oxygen index being 33.3% and the breaking strength being 3.7cN/dtex.
Example 9
The preparation method of the flame retardant B containing cage-shaped molecules comprises the following specific steps:
(1) Preparing raw materials:
cyanuric chloride;
aminopropyl butyl POSS;
aniline;
acid binding agent III: sodium hydroxide;
acid binding agent IV: sodium hydroxide;
solvent III: tetrahydrofuran;
solvent IV: n, N-dimethylformamide;
(2) Preparing a flame retardant B containing cage-like molecules:
mixing cyanuric chloride, aminopropyl butyl POSS, an acid binding agent III and a solvent III, reacting for 2.5 hours at 0 ℃, washing with water, filtering to obtain an intermediate product, mixing the intermediate product, aniline, the acid binding agent IV and the solvent IV, reacting for 4 hours at 40 ℃, adding the mixture into ethyl acetate to separate out a product, filtering, washing and drying in vacuum to obtain the flame retardant B containing cage-shaped molecules; wherein, the mol ratio of cyanuric chloride, aminopropyl butyl POSS and acid binding agent III is 1:1.2:1, and the mol ratio of intermediate product, aniline and acid binding agent IV is 1:1.2:1.
The initial decomposition temperature of the finally prepared flame retardant B containing cage-like molecules is 260 ℃, and the residual carbon content after 800 ℃ is 27%; the infrared spectrum of the flame retardant B containing the caged molecule is shown in FIG. 2, which shows that a peak exists at wavenumber 1114, which is the peak of the Si-O-Si bond in POSS, indicating that the host POSS structure of the flame retardant is still present.
Example 10
The preparation method of the flame retardant B containing cage-shaped molecules comprises the following specific steps:
(1) Preparing raw materials:
cyanuric chloride;
aminopropyl butyl POSS;
aniline;
acid binding agent III: sodium hydroxide;
acid binding agent IV: sodium hydroxide;
solvent III: chloroform;
solvent IV: n, N-dimethylformamide;
(2) Preparing a flame retardant B containing cage-like molecules:
mixing cyanuric chloride, aminopropyl butyl POSS, an acid binding agent III and a solvent III, reacting for 2 hours at 5 ℃, washing with water, filtering to obtain an intermediate product, mixing the intermediate product, aniline, the acid binding agent IV and the solvent IV, reacting for 4.5 hours at 45 ℃, adding the mixture into ethyl acetate to separate out a product, filtering, washing and drying in vacuum to obtain the flame retardant B containing cage-shaped molecules; wherein, the mol ratio of cyanuric chloride to aminopropyl butyl POSS to acid binding agent III is 1:1:1, and the mol ratio of intermediate product to aniline to acid binding agent IV is 1:1:1.
The final prepared flame retardant B containing cage-like molecules has an initial decomposition temperature of 260 ℃ and a carbon residue after 800 ℃ of 27%.
Example 11
The preparation method of the flame retardant B containing cage-shaped molecules comprises the following specific steps:
(1) Preparing raw materials:
cyanuric chloride;
aminopropyl butyl POSS;
aniline;
acid binding agent III: sodium hydroxide;
Acid binding agent IV: sodium hydroxide;
solvent III: toluene;
solvent IV: acetonitrile;
(2) Preparing a flame retardant B containing cage-like molecules:
mixing cyanuric chloride, aminopropyl butyl POSS, an acid binding agent III and a solvent III, reacting for 2 hours at 0 ℃, washing with water, filtering to obtain an intermediate product, mixing the intermediate product, aniline, the acid binding agent IV and the solvent IV, reacting for 4.5 hours at 40 ℃, adding the mixture into ethyl acetate to separate out a product, filtering, washing and drying in vacuum to obtain the flame retardant B containing cage-shaped molecules; wherein, the mol ratio of cyanuric chloride, aminopropyl butyl POSS and acid binding agent III is 1:1.2:1, and the mol ratio of intermediate product, aniline and acid binding agent IV is 1:1.2:1.
The final prepared flame retardant B containing cage-like molecules has an initial decomposition temperature of 260 ℃ and a carbon residue after 800 ℃ of 27%.
Example 12
The preparation method of the flame retardant B containing cage-shaped molecules comprises the following specific steps:
(1) Preparing raw materials:
cyanuric chloride;
aminopropyl butyl POSS;
aniline;
acid binding agent III: sodium hydroxide;
acid binding agent IV: sodium hydroxide;
solvent III: acetone;
solvent IV: acetonitrile;
(2) Preparing a flame retardant B containing cage-like molecules:
mixing cyanuric chloride, aminopropyl butyl POSS, an acid binding agent III and a solvent III, reacting for 2.5 hours at 5 ℃, washing with water, filtering to obtain an intermediate product, mixing the intermediate product, aniline, the acid binding agent IV and the solvent IV, reacting for 4 hours at 45 ℃, adding the mixture into ethyl acetate to separate out a product, filtering, washing and drying in vacuum to obtain the flame retardant B containing cage-shaped molecules; wherein, the mol ratio of cyanuric chloride to aminopropyl butyl POSS to acid binding agent III is 1:1:1, and the mol ratio of intermediate product to aniline to acid binding agent IV is 1:1:1.
The final prepared flame retardant B containing cage-like molecules has an initial decomposition temperature of 260 ℃ and a carbon residue after 800 ℃ of 27%.
Example 13
The application of the flame retardant B containing cage-shaped molecules comprises the following specific steps:
(1) Preparation of a recycled polyamide:
(1.1) hydrolysis of waste polyamides:
carrying out depolymerization reaction on the chopped waste polyamide (nylon 6) in subcritical water with the temperature of 340 ℃ and the pressure of 9MPa for 90min, wherein the mass ratio of subcritical water to polyamide fiber waste is 30:1;
(1.2) purification:
removing substances except caprolactam in the waste polyamide hydrolysate;
(1.3) copolymerization:
mixing caprolactam obtained in the step (1.2) with a flame retardant B containing caged molecules (prepared in the embodiment 9), wherein the molar ratio of the flame retardant B containing caged molecules in the mixture is 1%, and reacting for 10 hours under the conditions of 240 ℃ and normal pressure and nitrogen protection to obtain the flame-retardant copolyregenerated polyamide containing caged molecules;
the prepared flame-retardant copolymerization regenerated polyamide containing the caged molecule modified has the anti-dripping grade reaching the V-0 grade, the limiting oxygen index being 30.5 percent, and the contact angle of the slice of the flame-retardant copolymerization regenerated polyamide containing the caged molecule modified is 131 degrees;
(2) Preparation of regenerated polyamide fibers:
The flame-retardant copolymerization regenerated polyamide containing the caged molecule modification prepared in the step (1) is subjected to melt spinning to prepare a flame-retardant copolymerization regenerated polyamide fiber containing the caged molecule modification; wherein, the technological parameters of melt spinning comprise: the temperature of the screw feeding section is 255 ℃, the temperature of the screw melting section is 270 ℃, the temperature of the screw decompression section is 260 ℃, the temperature of the metering pump is 260 ℃, the spinning speed is 1000m/min, and the draft multiple is 2.
The finally prepared flame-retardant copolymerized regenerated polyamide fiber containing the caged molecule has the anti-molten drop grade reaching V-0 grade, the limiting oxygen index being 31.5% and the breaking strength being 4cN/dtex.
Example 14
The application of the flame retardant B containing cage-shaped molecules comprises the following specific steps:
(1) Preparation of a recycled polyamide:
(1.1) hydrolysis of waste polyamides:
carrying out depolymerization reaction on the chopped waste polyamide (nylon 6) in subcritical water with the temperature of 350 ℃ and the pressure of 9MPa for 60min, wherein the mass ratio of subcritical water to polyamide fiber waste is 40:1;
(1.2) purification:
removing substances except caprolactam in the waste polyamide hydrolysate;
(1.3) copolymerization:
mixing caprolactam obtained in the step (1.2) with a flame retardant B containing caged molecules (prepared in the embodiment 10), wherein the mole ratio of the flame retardant B containing caged molecules in the mixture is 4%, and reacting for 8 hours under the conditions of 260 ℃ and normal pressure and nitrogen protection to obtain the flame retardant copolyregenerated polyamide containing caged molecules;
The prepared flame-retardant copolymerization regenerated polyamide containing the caged molecule modification has the anti-dripping grade reaching the V-0 grade, the limiting oxygen index being 31.2 percent, and the contact angle of the slice of the flame-retardant copolymerization regenerated polyamide containing the caged molecule modification to water being 130 degrees;
(2) Preparation of regenerated polyamide fibers:
the flame-retardant copolymerization regenerated polyamide containing the caged molecule modification prepared in the step (1) is subjected to melt spinning to prepare a flame-retardant copolymerization regenerated polyamide fiber containing the caged molecule modification; wherein, the technological parameters of melt spinning comprise: the temperature of the screw feeding section is 260 ℃, the temperature of the screw melting section is 275 ℃, the temperature of the screw decompression section is 265 ℃, the temperature of the metering pump is 265 ℃, the spinning speed is 1000m/min, and the draft multiple is 2.
The finally prepared flame-retardant copolymerized regenerated polyamide fiber containing the caged molecule has the anti-molten drop grade reaching V-0 grade, the limiting oxygen index being 30.5% and the breaking strength being 4.2cN/dtex.
Example 15
The application of the flame retardant B containing cage-shaped molecules comprises the following specific steps:
(1) Preparation of a recycled polyamide:
(1.1) hydrolysis of waste polyamides:
carrying out depolymerization reaction on the chopped waste polyamide (nylon 6) in subcritical water with the temperature of 340 ℃ and the pressure of 9MPa for 80 minutes, wherein the mass ratio of subcritical water to polyamide fiber waste is 20:1;
(1.2) purification:
removing substances except caprolactam in the waste polyamide hydrolysate;
(1.3) copolymerization:
mixing caprolactam obtained in the step (1.2) with a flame retardant B containing caged molecules (prepared in the embodiment 11), wherein the mole ratio of the flame retardant B containing caged molecules in the mixture is 8%, and reacting for 14 hours under the conditions of 220 ℃ and normal pressure and nitrogen protection to obtain the flame-retardant copolyregenerated polyamide containing caged molecules;
the prepared flame-retardant copolymerization regenerated polyamide containing the caged molecule modified has the anti-dripping grade reaching the V-0 grade, the limiting oxygen index being 32.4 percent, and the contact angle of the slice of the flame-retardant copolymerization regenerated polyamide containing the caged molecule modified is 132 degrees;
(2) Preparation of regenerated polyamide fibers:
the flame-retardant copolymerization regenerated polyamide containing the caged molecule modification prepared in the step (1) is subjected to melt spinning to prepare a flame-retardant copolymerization regenerated polyamide fiber containing the caged molecule modification; wherein, the technological parameters of melt spinning comprise: the temperature of the screw feeding section is 265 ℃, the temperature of the screw melting section is 280 ℃, the temperature of the screw decompression section is 270 ℃, the temperature of the metering pump is 270 ℃, the spinning speed is 1000m/min, and the draft multiple is 2.6.
The finally prepared flame-retardant copolymerized regenerated polyamide fiber containing the caged molecule has the anti-molten drop grade reaching V-0 grade, the limiting oxygen index being 32.5% and the breaking strength being 4.5cN/dtex.
Example 16
The application of the flame retardant B containing cage-shaped molecules comprises the following specific steps:
(1) Preparation of a recycled polyamide:
(1.1) hydrolysis of waste polyamides:
carrying out depolymerization reaction on the chopped waste polyamide (nylon 6) in subcritical water with the temperature of 350 ℃ and the pressure of 9MPa for 70min, wherein the mass ratio of subcritical water to polyamide fiber waste is 50:1;
(1.2) purification:
removing substances except caprolactam in the waste polyamide hydrolysate;
(1.3) copolymerization:
mixing caprolactam obtained in the step (1.2) with a flame retardant B containing caged molecules (prepared in the embodiment 12), wherein the molar ratio of the flame retardant B containing caged molecules in the mixture is 10%, and reacting for 6 hours under the conditions of 280 ℃ and normal pressure and nitrogen protection to obtain the flame-retardant copolyregenerated polyamide containing caged molecules;
the prepared flame-retardant copolymerization regenerated polyamide containing the caged molecule modified has the anti-dripping grade reaching the V-0 grade, the limiting oxygen index being 33.5 percent, and the contact angle of the slice of the flame-retardant copolymerization regenerated polyamide containing the caged molecule modified to water being 131 degrees;
(2) Preparation of regenerated polyamide fibers:
the flame-retardant copolymerization regenerated polyamide containing the caged molecule modification prepared in the step (1) is subjected to melt spinning to prepare a flame-retardant copolymerization regenerated polyamide fiber containing the caged molecule modification; wherein, the technological parameters of melt spinning comprise: the temperature of the screw feeding section is 270 ℃, the temperature of the screw melting section is 258 ℃, the temperature of the screw decompression section is 275 ℃, the temperature of the metering pump is 275 ℃, the spinning speed is 1000m/min, and the draft multiple is 2.6.
The finally prepared flame-retardant copolymerized regenerated polyamide fiber containing the caged molecule has the anti-molten drop grade reaching V-0 grade, the limiting oxygen index being 30.5% and the breaking strength being 4.3cN/dtex.
Claims (9)
1. The flame retardant containing the caged molecule is characterized by comprising a flame retardant A containing the caged molecule or a flame retardant B containing the caged molecule; the molecular structural formula of the flame retardant A containing cage molecules is as follows:
the molecular structural formula of the flame retardant B containing cage molecules is as follows:
2. the flame retardant containing cage molecules according to claim 1, wherein the initial decomposition temperature of the flame retardant A containing cage molecules is 260 ℃ and the carbon residue at 800 ℃ is 27%; the initial decomposition temperature of the flame retardant B containing the cage-like molecules is 260 ℃, and the carbon residue after 800 ℃ is 27%.
3. A method for preparing the flame retardant containing the caged molecule according to claim 1 or 2, wherein the preparation method of the flame retardant A containing the caged molecule comprises the following steps: mixing cyanuric chloride, aminopropyl butyl POSS, an acid binding agent I and a solvent I, reacting for 2-2.5 hours at 0-5 ℃ to obtain an intermediate product, mixing the intermediate product, glycol, the acid binding agent II and the solvent II, and reacting for 4-4.5 hours at 40-45 ℃ to obtain the flame retardant A containing cage molecules; the molar ratio of cyanuric chloride to aminopropyl butyl POSS to the acid binding agent I is 1:1-1.2:1; the mol ratio of the intermediate product to the glycol to the acid-binding agent II is 1:1-1.2:1;
The preparation method of the flame retardant B containing cage-shaped molecules comprises the following steps: mixing cyanuric chloride, aminopropyl butyl POSS, an acid binding agent III and a solvent III, reacting for 2-2.5 hours at 0-5 ℃ to obtain an intermediate product, mixing the intermediate product, aniline, the acid binding agent IV and the solvent IV, and reacting for 4-4.5 hours at 40-45 ℃ to obtain the flame retardant B containing cage molecules; the molar ratio of cyanuric chloride to aminopropyl butyl POSS to the acid binding agent III is 1:1-1.2:1, and the molar ratio of the intermediate product to the aniline to the acid binding agent IV is 1:1-1.2:1.
4. The use of the flame retardant containing caged molecules according to claim 1 or 2 for recycling polyester, wherein BHET obtained by alcoholysis of waste polyester and the flame retardant containing caged molecules are subjected to copolymerization reaction to obtain the flame retardant copolyrecycled polyester containing caged molecules.
5. The use according to claim 4, characterized by the specific steps of:
(1) Alcoholysis of waste polyester;
mixing ethylene glycol with the mass ratio of 1-3:1 with waste polyester, adding a catalyst accounting for 0.2% of the mass of the waste polyester, and reacting for 1-5 h at 160-200 ℃ under the condition of continuously introducing nitrogen;
(2) Purifying;
removing substances except BHET in the waste polyester alcoholysis product;
(3) Copolymerizing;
and (3) mixing the BHET obtained in the step (2), the flame retardant containing the caged molecules and the catalyst, wherein the molar ratio of the flame retardant containing the caged molecules in the mixture is 1-10%, the mass of the catalyst is 0.04wt% of the mass of the BHET, and the mixture reacts for 2-3 hours under the conditions that the temperature is 280-290 ℃ and the pressure is 0.3-0.5 MPa, so that the flame-retardant copolymerized regenerated polyester containing the caged molecules is obtained.
6. The method according to claim 4, wherein after the regenerated flame-retardant copolymerized polyester containing the caged molecule is prepared, melt spinning is further performed to prepare the regenerated flame-retardant copolymerized polyester fiber containing the caged molecule; the melt drop resistance grade of the flame-retardant copolymerized regenerated polyester fiber containing the cage-shaped molecule modification reaches the V-0 grade, the limiting oxygen index is more than 30%, and the breaking strength reaches more than 3.5 cN/dtex.
7. The use of a flame retardant containing caged molecules according to claim 1 or 2 for regenerating polyamide, wherein caprolactam obtained by hydrolysis of waste polyamide is copolymerized with the flame retardant containing caged molecules to obtain the flame retardant copolyamide containing caged molecules.
8. The use according to claim 7, characterized by the specific steps of:
(1) Hydrolyzing the waste polyamide;
Depolymerizing waste polyamide in subcritical water at 340-350 ℃ and under 9MPa for 60-90 min, wherein the mass ratio of subcritical water to polyamide fiber waste is 20-50:1;
(2) Purifying;
removing substances except caprolactam in the waste polyamide hydrolysate;
(3) Copolymerizing;
mixing caprolactam obtained in the step (2) with a flame retardant containing caged molecules, wherein the molar ratio of the flame retardant containing caged molecules in the mixture is 1-10%, and reacting for 6-14 h under the conditions of 220-280 ℃ and normal pressure and nitrogen protection to obtain the flame-retardant copolyamide containing caged molecules.
9. The method according to claim 7, wherein after the regenerated polyamide containing the modified flame-retardant copolyamide with the caged molecule is prepared, melt spinning is further performed to obtain the regenerated polyamide fiber containing the modified flame-retardant copolyamide with the caged molecule; the melt drop resistance grade of the flame-retardant copolymerized regenerated polyamide fiber containing the cage-shaped molecule modification reaches the V-0 grade, the limiting oxygen index is more than 30%, and the breaking strength reaches more than 4 cN/dtex.
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| CN118373982A (en) * | 2024-06-21 | 2024-07-23 | 江苏文凤化纤集团有限公司 | Flame-retardant polycaprolactam composite material prepared by in-situ polymerization, and preparation method and application thereof |
| CN118440327A (en) * | 2024-05-17 | 2024-08-06 | 湖北君邦新材料科技有限公司 | Novel POSS flame retardant containing phosphorus and nitrogen elements, preparation method and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2949434A (en) * | 1956-10-12 | 1960-08-16 | Union Carbide Corp | Silicon-containing compounds |
| WO1999028382A1 (en) * | 1997-12-03 | 1999-06-10 | Chisso Corporation | Flame retardant for styrene resins and flame-retardant styrene resin composition |
| JP2002363414A (en) * | 2001-06-12 | 2002-12-18 | Asahi Kasei Corp | Cage-like silsesquioxane-containing composition |
| CN107868255A (en) * | 2017-11-17 | 2018-04-03 | 厦门大学 | The preparation method and applications of POSS DOPO triazine derivative flame retardants with self assembly humidification |
| CN110408032A (en) * | 2019-06-28 | 2019-11-05 | 中北大学 | A kind of silsesquioxane modified melamine flame retardant and preparation method thereof |
-
2023
- 2023-07-10 CN CN202310835635.2A patent/CN116813909B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2949434A (en) * | 1956-10-12 | 1960-08-16 | Union Carbide Corp | Silicon-containing compounds |
| WO1999028382A1 (en) * | 1997-12-03 | 1999-06-10 | Chisso Corporation | Flame retardant for styrene resins and flame-retardant styrene resin composition |
| JP2002363414A (en) * | 2001-06-12 | 2002-12-18 | Asahi Kasei Corp | Cage-like silsesquioxane-containing composition |
| CN107868255A (en) * | 2017-11-17 | 2018-04-03 | 厦门大学 | The preparation method and applications of POSS DOPO triazine derivative flame retardants with self assembly humidification |
| CN110408032A (en) * | 2019-06-28 | 2019-11-05 | 中北大学 | A kind of silsesquioxane modified melamine flame retardant and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JUN LIU，等: ""POSS-based microporous polymers: Efficient Friedel-Crafts synthesis, CO2 capture and separation properties"", 《MICROPOROUS AND MESOPOROUS MATERIALS》, vol. 250, 22 May 2017 (2017-05-22), pages 203 - 209, XP085074326, DOI: 10.1016/j.micromeso.2017.05.043 * |
| OMER N，等: ""Preparation and Properties of Water-Soluble Fluorescent Multifunction Nanohybrid Probes"", 《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY APPLICATIONS》, vol. 3, no. 3, 31 December 2019 (2019-12-31), pages 1 - 9 * |
| 吴海洋: ""POSS基多元素阻燃剂设计及其阻燃环氧树脂的研究"", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, no. 2, 15 February 2022 (2022-02-15), pages 016 - 75 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118440327A (en) * | 2024-05-17 | 2024-08-06 | 湖北君邦新材料科技有限公司 | Novel POSS flame retardant containing phosphorus and nitrogen elements, preparation method and application |
| CN118373982A (en) * | 2024-06-21 | 2024-07-23 | 江苏文凤化纤集团有限公司 | Flame-retardant polycaprolactam composite material prepared by in-situ polymerization, and preparation method and application thereof |
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