CN111087612B - Phosphorus-containing flame-retardant nylon and preparation method and application thereof - Google Patents
Phosphorus-containing flame-retardant nylon and preparation method and application thereof Download PDFInfo
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- CN111087612B CN111087612B CN201811234499.7A CN201811234499A CN111087612B CN 111087612 B CN111087612 B CN 111087612B CN 201811234499 A CN201811234499 A CN 201811234499A CN 111087612 B CN111087612 B CN 111087612B
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention provides a phosphorus-containing flame-retardant nylon, and a preparation method and application thereof, namely, a macromolecular phosphine-containing component is introduced in the nylon polymerization process, the compatibility of a system is improved to the maximum extent, the problem which is easy to occur in blending modification is reduced, the flame retardance and the spinnability of the nylon can be obviously improved, and the method has simple process, is easy for large-scale production, and is more suitable for application in the spinning-fiber field, the wire and cable field and the 3D printing field.
Description
Technical Field
The invention relates to phosphorus-containing flame-retardant nylon and a preparation method and application thereof, in particular to a phosphorus-containing flame-retardant anti-dripping nylon material capable of being formed into fibers by a polymerization method.
Background
Polyamide (PA, commonly known as nylon) has good comprehensive performance, is an important raw material of synthetic fibers, and has the advantages of good wear resistance, high rebound resilience, high breaking strength, good dyeability and the like when used as fibers. However, when the polyamide is used for synthetic fibers, the polyamide has poor heat resistance and can be flammable in a harsh use environment, which limits the application of the polyamide in many fields, so that the flame retardant modification and the anti-dripping modification of the nylon are particularly important.
In the field of engineering plastics, the flame retardant modification is mainly carried out on nylon by a double-screw melt blending extrusion method, the flame retardant mainly comprises a bromine system, a nitrogen system, a phosphorus system and various compound systems, the research on the halogen-free flame retardant nylon fiber has not been broken through, and the large-scale commercialized flame retardant nylon fiber is rarely applied. The difficulty of flame retardant research of polyamide fiber is that: firstly, due to the fact that amido bonds of nylon are active, chemical reaction is easily generated between the amido bonds and a flame retardant at the spinning temperature of about 260-300 ℃, molecular chains are degraded, spinning difficulty is caused, and the mechanical property of fibers is deteriorated; secondly, a high dosage of the flame retardant is added to endow the nylon with sufficient flame retardance, which puts higher requirements on the distribution form and state of the flame retardant in the nylon. Therefore, a proper flame-retardant system, a flame retardant introduction mode and the interaction with amido bond are the keys for preparing the nylon with good spinnability.
The phosphorus flame retardant generates less toxic and corrosive gas in the combustion process, can simultaneously play a flame retardant role in a gas phase and a condensed phase, is one of the development directions of flame retardant materials, and is successively developed and introduced in companies such as Clariant, Albright & Wilson, FRX Polymers and the like in Germany, for example, diethyl aluminum phosphinate is an additive flame retardant widely applied to nylon, and can achieve a certain flame retardant effect when being compounded with a nitrogen flame retardant, but diethyl aluminum phosphinate has a large influence on the mechanical property of a base material, and the modified nylon does not have spinnability. With the development of flame retardants with low toxicity, low smoke, low addition and anti-dripping, macromolecular phosphine flame retardants are an important development direction, have good thermal stability, can be melted in the processing process, do not have the problems of poor dispersibility and the like, and are one of ideal flame retardants for flame-retardant fibers.
The literature "noise and thermal stability students of PA66 stabilizing triaryl phosphine oxide [ J ]]Bulletin of Materials Science,2009,32(4): 374-containing 380 PA66 whose main chain contains triaryl phosphine oxide TPO was prepared by copolycondensation using cyclohexane adipate and bis (4-carboxyphenyl) phenylphosphine oxide (BCPPO) as raw Materials; chinese patent with application number CN201510624531.2 discloses a diphosphine flame-retardant copolymerized nylon and a preparation method thereof, which adopts diphosphine organic phosphine ammonium salt as an intermediate synthesized by phosphine oxide diamine and phosphine oxide dihydric alcohol to copolymerize with nylon 66 salt to prepare the diphosphine flame-retardant copolymerized nylon; chinese patent with application number CN201510163762.8 discloses a flame-retardant nylon 6 and a preparation method thereof, wherein the flame-retardant nylon 6 is prepared by polymerizing caprolactam, aminomethyl phenylphosphinic acid and a polymer catalyst, and relates to various flame-retardant nylon productsHarmful chemicals, namely aminomethyl phenylphosphinic acid monomer structure is completely polymerized to a nylon main chain after participating in reaction, and the flame-retardant nylon has a benzene ring structure, so that the flame-retardant nylon has poor physical properties such as melting point, crystallinity and the like; chinese patent with application number CN201310294502.5 discloses a preparation method of MCA flame-retardant polyamide material, which adopts melamine salt of dicarboxylic acid, cyanurate of organic diamine and water as medium, and nano SiO2And metal oxide as synergistic flame retardant, dispersing and mixing, and in-situ polymerizing to obtain flame-retardant polyamide, so that partial flame-retardant component can be connected to polyamide chain, MCA formed in-situ can be uniformly dispersed in polyamide matrix, and the synergistic flame retardant SiO2And the addition of the metal oxide can further improve the flame retardance, and finally the molecular weight of the polymer is increased by a solid-phase polycondensation method to prepare the flame-retardant polyamide material; the Chinese patent with the application number of CN201510483164.9 discloses a carboxyl-terminated phosphine-containing polyester, a preparation method and application thereof, wherein the carboxyl-terminated phosphine-containing polyester is synthesized by taking phenolic hydroxyl-terminated phosphine-containing polyester, alkylene oxide monomers and acid anhydrides as reaction raw materials, and the monomers are applied to the polymerization flame-retardant modification of nylon to obtain beneficial effects.
However, in the process of preparing nylon by the prior art, the consumption of the flame retardant is large, and the problems of melt dripping and poor spinnability of the flame retardant polymer exist, so that the preparation method of the phosphorus-containing nylon is urgently needed to be developed in the field, namely, a macromolecular phosphine-containing component is introduced in the nylon polymerization process, the compatibility of a system is improved to the maximum extent, the problem which is easy to occur in blending modification is reduced, especially, the spinnability of the nylon can be obviously improved, and the method has simple process and is easy for large-scale production.
Disclosure of Invention
In order to overcome the problems of large consumption of flame retardant, melt dripping and poor spinnability of flame retardant polymers in the prior art, the invention provides the phosphorus-containing flame retardant nylon, and the preparation method and the application thereof, namely, a macromolecular phosphine-containing component is introduced in the nylon polymerization process, the compatibility of a system is improved to the maximum extent, the problem which is easy to occur in blending modification is reduced, the flame retardance and the spinnability of the nylon can be obviously improved, and the method has simple process and is easy for large-scale production.
In order to achieve the above object, a first aspect of the present invention discloses a method for preparing a phosphorus-containing flame retardant nylon, comprising the steps of:
(1) providing a first mixture comprising 10 to 120 parts by weight (preferably 30 to 100 parts by weight, more preferably 50 to 95 parts by weight) of a nylon monomer, 2 to 15 parts by weight (preferably 4 to 10 parts by weight, more preferably 5 to 8 parts by weight) of a phosphine-containing flame retardant;
(2) providing 1-6 parts by weight (preferably 2-4 parts by weight) of water, carrying out polymerization reaction with the first mixture to obtain the phosphine-containing flame-retardant nylon,
wherein the phosphine-containing flame retardant is polyphosphonate shown as the following formula I and derivatives thereof, or polyphosphonate shown as the following formula II or phosphonate-carbonate copolymer;
wherein each R is1、R2Are respectively selected from the following groups:
R3selected from methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl or sec-butyl;
R4is selected from
R5Is selected from
Wherein，R1、R2、R3Each as described in formula I above;
n and m are positive integers of more than or equal to 1.
In another preferred embodiment, the nylon monomer is selected from the group consisting of: caprolactam, sebacic acid, dodecanedioic acid, dodecanoic acid, sebacic acid, ethylenediamine, adipic acid-1, 4 diaminobutylamine, or combinations thereof.
In another preferred embodiment, the first mixture further comprises 0.01 to 2 parts by weight of a ring-opening promoter selected from the group consisting of: aminocaproic acid, adipic acid hexamethylenediamine salt, NH2(CH2)XCOOH or a combination thereof, wherein x is a positive integer from 1 to 16.
In another preferred embodiment, the first mixture further comprises 0.01-1.0 part by weight of a synergistic flame retardant, and the synergistic flame retardant is montmorillonite.
In another preferred embodiment, the average molecular weight of the compound of formula II is 1400-5500, and the mass percentage of phosphorus element is 8.5-10.3 wt%.
In another preferred example, the method comprises the steps of: melting the nylon monomer at 130 ℃, adding the phosphine-containing flame retardant, adding the ring-opening accelerator after full dissolution, putting into a high-pressure polymerization kettle, adding water, heating for polymerization reaction, extracting, and vacuum-drying at 75-80 ℃ for 24h to obtain the phosphine-containing flame-retardant nylon.
In another preferred embodiment, the first mixture further comprises 0.01 to 0.5 weight parts of antioxidant, and the antioxidant is hindered phenols and/or phosphonites. Preferably, the hindered phenolic antioxidant is selected from the group consisting of 2, 8-di-tert-butyl-4-methylphenol, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, or combinations thereof; the phosphite antioxidant is selected from the following group: tris [ 2.4-di-tert-butylphenyl ] phosphite (phosphite 168), 3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dioctadecylpentaerythritol diphosphite, or a combination thereof.
In another preferred example, the method comprises the steps of:
(1) melting 10-120 parts by weight of the nylon monomer, adding 2-15 parts by weight of the phosphine-containing flame retardant, fully dissolving, and putting into a high-pressure polymerization kettle;
(2) adding 1-6 parts by weight of water into a high-pressure polymerization kettle, stirring, carrying out polymerization reaction at the temperature of 200-300 ℃ and under the pressure of 0.3-0.6MPa, finally standing, discharging, extracting and drying in vacuum to obtain the phosphine-containing flame-retardant nylon.
In another preferred embodiment, the polymerization reaction in the step (2) is carried out for 7 to 10 hours.
In a second aspect of the invention, there is provided a phosphine-containing flame retardant nylon prepared by the method of the first aspect.
In another preferred embodiment, the phosphine-containing flame-retardant nylon meets the spinning requirement of 800m/min, the diameter of a spinneret orifice is 0.3mm, the drafting magnification is 3-3.5 times, and the drafting speed is 500 m/min.
In another preferred embodiment, the phosphine containing flame retardant nylon has a limiting oxygen index in the range of 23 to 40, preferably 25 to 28.
In another preferred embodiment, the flame retardant grade of the phosphine-containing flame retardant nylon is V-0.
In another preferred example, the phosphine-containing flame-retardant nylon can be used for preparing electric wires and cables or used for 3D printing.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Compared with the prior art, the technical scheme provided by the invention has the following advantages:
1. the invention adopts the method of directly dissolving the phosphine-containing flame retardant such as polyphosphonate or derivatives thereof in a nylon monomer (such as caprolactam) or preparing the phosphine-containing flame retardant nylon by an amide exchange method, and can prepare the flame retardant copolymerized nylon which is halogen-free, has no molten drop and has higher mechanical property and textile property under the condition of adding a small amount of flame retardant, particularly improves the flame retardance and the elongation at break of the flame retardant copolymerized nylon, is more suitable for the application in the spinning-fiber field, the wire and cable field and the 3D printing field, has simple process, convenient production and lower cost, and is easy to realize the process.
2. The method adopts the polymerization method to prepare the halogen-free flame-retardant nylon, is different from the flame-retardant nylon prepared by double-screw blending, has the advantages that the dosage of the flame retardant is less than the addition amount of blending modification, the cost is low, the flame retardant efficiency is high, the flame retardant can be melted in the processing process, the influence on the mechanical property of a substrate material is small, and the application prospect is excellent.
3. The flame retardant exists in nylon in the form of macromolecular chains, the relative viscosity and spinnability of the nylon are improved to a certain extent, the flame retardant is not separated out, and the flame retardant effect can be maintained for a long time.
Drawings
The advantages and spirit of the present invention can be further understood by the following detailed description of the invention and the accompanying drawings.
FIG. 1 shows the temperature-rising melting curves of pure nylon 6 and flame-retardant nylon V obtained in example 5 of the present invention;
FIG. 2 shows the cooling melting curves of pure nylon 6 and flame retardant nylon V prepared in example 5 of the present invention.
Detailed Description
Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. However, the present invention should be understood not to be limited to such an embodiment described below, and the technical idea of the present invention may be implemented in combination with other known techniques or other techniques having the same functions as those of the known techniques.
Description of the terms
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
As used herein, the term "about" when used in reference to a specifically recited value means that the value may vary by no more than 1% from the recited value. For example, as used herein, the expression "about 100" includes 99 and 101 and all values in between (e.g., 99.1, 99.2, 99.3, 99.4, etc.).
As used herein, the term "comprising" or "includes" can be open, semi-closed, and closed. In other words, the term also includes "consisting essentially of …," or "consisting of ….
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the subject matter claimed. As used herein, the singular is intended to include the plural unless the context specifically indicates otherwise. It must be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. It should also be noted that the use of "or", "or" means "and/or" unless stated otherwise. Furthermore, the terms "comprising" or "including" can be open, semi-closed, and closed. In other words, the term also includes "consisting essentially of …," or "consisting of ….
Definitions for the terms of the standardization sector can be found in the literature references including Carey and Sundberg "ADVANCED ORGANIC CHEMISTRY 4TH ED." Vols.A (2000) and B (2001), Plenum Press, New York. Unless otherwise indicated, conventional methods within the skill of the art are employed, such as mass spectrometry, NMR, IR and UV/VIS spectroscopy, and pharmacological methods. Unless a specific definition is set forth, the terms used herein in the pertinent description of analytical chemistry, organic synthetic chemistry, and pharmaceutical chemistry are known in the art. Standard techniques can be used in chemical synthesis, chemical analysis, pharmaceutical preparation, formulation and delivery, and treatment of patients. For example, the reaction and purification can be carried out using the instructions of the kit from the manufacturer, or according to the methods known in the art or the instructions of the present invention. The techniques and methods described above can generally be practiced according to conventional methods well known in the art, as described in various general and more specific documents referred to and discussed in this specification. In the present specification, groups and substituents thereof may be selected by one skilled in the art to provide stable moieties and compounds.
When a substituent is described by a general formula written from left to right, the substituent also includes chemically equivalent substituents obtained when the formula is written from right to left. For example, -CH2O-is equivalent to-OCH2-。
The section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described. All documents, or portions of documents, cited in this application, including but not limited to patents, patent applications, articles, books, operating manuals, and treatises, are hereby incorporated by reference in their entirety.
Certain chemical groups defined herein are preceded by a shorthand notation to indicate the total number of carbon atoms present in the group. For example, C1-C6 alkyl refers to an alkyl group as defined below having a total of 1 to 6 carbon atoms. The total number of carbon atoms in the shorthand notation excludes carbons that may be present in a substituent of the group.
In addition to the foregoing, the following terms, when used in the specification and claims of this application, have the meanings indicated below, unless otherwise specifically indicated.
As used herein, the term "halogen" refers to fluorine, chlorine, bromine or iodine. The terms "halogen" and "halo" are synonymous.
As used herein, the term "alkyl" as a group or as part of another group (e.g., as used in halo-substituted alkyl and the like groups) refers to a fully saturated straight or branched hydrocarbon chain radical consisting only of carbon and hydrogen atoms, having, for example, 1 to 7 carbon atoms, and attached to the remainder of the molecule by a single bond, including, but not limited to, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 2-methylbutyl, 2-dimethylpropyl, n-hexyl, heptyl, and the like.
As used herein, the term "alkenyl" as a group or part of another group means consisting of only carbon and hydrogen atoms, containing at least one double bond, having, for example, 2 to 8 (preferably 2 to 6) carbon atoms and bonded to the molecule by single bondsAnd the remainder of the chain, straight or branched hydrocarbon chain groups such as, but not limited to, vinyl, propenyl, allyl, but-1-enyl, but-2-enyl, pent-1, 4-dienyl, and the like. As used herein, "C" is2-C6Straight or branched alkenyl "includes a single double bond, or a plurality of discrete double bonds. As used herein, the term "alkynyl" as a group or part of another group refers to a straight or branched hydrocarbon chain group consisting solely of carbon and hydrogen atoms, containing at least one triple bond, optionally containing at least one double bond, having, for example, 2 to 6 carbon atoms, and attached to the rest of the molecule by a single bond, such as, but not limited to, ethynyl, prop-1-ynyl, but-1-ynyl, pent-1-en-4-ynyl, and the like. As used herein, "C" is2-C6Straight or branched alkynyl "includes a single triple bond, or a plurality of discrete triple bonds.
As used herein, "optionally" or "optionally" means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not. For example, "optionally substituted aryl" means that the aryl group is substituted or unsubstituted, and the description includes both substituted and unsubstituted aryl groups. The "optionally" substituents described in the claims and the description section of the present invention are selected from alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl, cyano, nitro, optionally substituted aryl, optionally substituted heteroaryl, optionally substituted cycloalkyl, optionally substituted heterocycloalkyl.
The terms "moiety," "structural moiety," "chemical moiety," "group," "chemical group" as used herein refer to a specific fragment or functional group in a molecule. Chemical moieties are generally considered to be chemical entities that are embedded in or attached to a molecule.
As used herein, "flame retardant" refers to any compound that inhibits, prevents, or reduces the spread of a fire.
As used in the invention, the synergistic flame retardant is compounded with the phosphine-containing flame retardant, has excellent flame retardant performance, low price, good stability and small addition amount, and can maintain the original physical and chemical properties and mechanical properties of the material.
As used herein, the terms "nylon", "polyamide" have the same meaning and, alternatively, "polyamide" may be nylon 1010, nylon 612, nylon 12, nylon 610, nylon 66, nylon 46, or nylon 6.
The terms "flame retardant", "fire resistant", "flame resistant", "fire resistant" as used herein means that the compound or composition exhibits a Limiting Oxygen Index (LOI) of at least 23. The fire resistance can be measured according to the UL test, and the tested materials are given a UL-94V-0, UL-94V-1 and UL-94V-2 rating, the standards for each UL-94V-rating being as follows:
UL-94V-0: none of the samples burned for more than 10 seconds after the test flame was removed; the total time for flaming combustion does not exceed 50 seconds for each set of 5 samples after 10 ignitions. None of the test specimens released any droplets that ignited the absorbent cotton.
UL-94V-1: none of the samples burned for more than 30 seconds after the test flame was removed; the total time for flaming combustion does not exceed 250 seconds for each set of 5 samples after 10 ignitions. None of the test specimens released any droplets that ignited the absorbent cotton.
UL-94V-2: none of the samples burned for more than 30 seconds after the test flame was removed; the total time for flaming combustion after 10 ignitions for each set of 5 samples did not exceed 250 seconds. The test specimen may release a droplet of liquid that ignites the cotton wool.
The implementation mode is as follows:
the first embodiment is as follows: flame-retardant nylon I
1880g of solid caprolactam are melted at 130 ℃, 120g of polyphosphonate (Nofia OL1001, FRX Polymer) is added, after complete dissolution, the material is put into a 5L high-pressure polymerization kettle, and 60g of deionized water is added. Replacing air in the kettle with nitrogen, starting stirring, heating to 250 ℃, keeping the pressure in the kettle at 0.5MPa, carrying out ring opening reaction for 3 hours, then decompressing, introducing nitrogen, carrying out polycondensation for 5 hours, gradually reducing the temperature to 240 ℃ in the polycondensation process, reducing the stirring speed to 200rpm, finally vacuumizing for 0.5 hour, standing, discharging, casting a belt, granulating, extracting with 90 ℃ deionized water for 12 hours, and vacuum-drying at 80 ℃ for 12 hours to obtain the flame-retardant nylon 6 slice.
The second embodiment: flame-retardant nylon II
1840g of solid caprolactam was melted at 130 ℃ and 160g of polyphosphonate (Nofia OL1001, FRX Polymer Co.) was added and, after sufficient dissolution, the batch was put into a 5L autoclave and 60g of deionized water was added. Replacing air in the kettle with nitrogen, starting stirring, heating to 250 ℃, keeping the pressure in the kettle at 0.5MPa, carrying out ring opening reaction for 3 hours, then decompressing, introducing nitrogen, carrying out polycondensation for 5 hours, gradually reducing the temperature to 240 ℃ in the polycondensation process, reducing the stirring speed to 200rpm, finally vacuumizing for 0.5 hour, standing, discharging, casting a belt, granulating, extracting with 90 ℃ deionized water for 12 hours, and vacuum-drying at 80 ℃ for 12 hours to obtain the flame-retardant nylon 6 slice.
Example three: flame-retardant nylon III
1800g of solid caprolactam are melted at 130 ℃,200 g of polyphosphonate (Nofia OL1001, FRX Polymer Co.) is added and, after being sufficiently dissolved, the material is put into a 5L high-pressure polymerization kettle, and 60g of deionized water is added. Replacing air in the kettle with nitrogen, starting stirring, heating to 250 ℃, keeping the pressure in the kettle at 0.5MPa, carrying out ring opening reaction for 3 hours, then decompressing, introducing nitrogen, carrying out polycondensation for 5 hours, gradually reducing the temperature to 240 ℃ in the polycondensation process, reducing the stirring speed to 200rpm, finally vacuumizing for 0.5 hour, standing, discharging, casting a belt, granulating, extracting with 90 ℃ deionized water for 12 hours, and vacuum-drying at 80 ℃ for 12 hours to obtain the flame-retardant nylon 6 slice.
Example four: flame-retardant nylon IV
1860g of solid caprolactam was melted at 130 deg.C, 100g of phosphonate-carbonate copolymer (Nofia OL5000, FRX Polymer Co.) was added, after it was sufficiently dissolved, 40g of aminocaproic acid was added, and the material was charged into a 5L autoclave, followed by addition of 120g of deionized water. Replacing air in the kettle with nitrogen, starting stirring, heating to 250 ℃, keeping the pressure in the kettle at 0.65MPa, carrying out ring opening reaction for 3 hours, then decompressing, introducing nitrogen, carrying out polycondensation for 5 hours, gradually reducing the temperature to 240 ℃ in the polycondensation process, reducing the stirring speed to 200rpm, finally vacuumizing for 0.5 hour, standing, discharging, casting a belt, granulating, extracting with 90 ℃ deionized water for 12 hours, and vacuum-drying at 80 ℃ for 12 hours to obtain the flame-retardant nylon 6 slice.
Example five: flame-retardant nylon V
1780g of solid caprolactam are melted at 130 ℃, 180g of phosphonate-carbonate copolymer (Nofia OL5000, FRX Polymer Co.) is added, after it is fully dissolved, 40g of aminocaproic acid is added, the batch is put into a 5L high-pressure polymerization kettle, and then 120g of deionized water is added. Replacing air in the kettle with nitrogen, starting stirring, heating to 250 ℃, keeping the pressure in the kettle at 0.65MPa, carrying out ring opening reaction for 3 hours, then decompressing, introducing nitrogen, carrying out polycondensation for 5 hours, gradually reducing the temperature to 240 ℃ in the polycondensation process, reducing the stirring speed to 200rpm, finally vacuumizing for 0.5 hour, standing, discharging, casting a belt, granulating, extracting with 90 ℃ deionized water for 12 hours, and vacuum-drying at 80 ℃ for 12 hours to obtain the flame-retardant nylon 6 slice.
Examples one to five raw material formulations are shown in table 1 below:
table 1 examples first to fifth raw material ratios
Product Performance analysis
Spinnability:
the flame retardant nylon V obtained in example 5 was used as a test sample, in which the amount of the flame retardant was about 9%. The flame-retardant nylon V can meet the spinning requirement of 800m/min, the diameter of a spinneret orifice is 0.3mm, the drafting multiplying power is 3-3.5 times, and the drafting speed is 500 m/min.
In the prior art, the flame-retardant nylon prepared by other methods or other flame retardants has poor spinnability, extremely high yarn breakage rate in the spinning process, and almost no continuous spinning due to overhigh pressure of a spinning assembly in a short time. Compared with the flame-retardant nylon prepared in the prior art, the flame-retardant nylon prepared in the patent has excellent spinnability.
Thermal performance analysis:
FIG. 1 shows the temperature-rising melting curves of pure nylon 6 and flame-retardant nylon V obtained in example 5 of the present invention, and the thermal analysis results show that the melting point of flame-retardant nylon V is 221 ℃ which is almost equivalent to that of pure nylon 6.
FIG. 2 shows the temperature-decreasing melting curve of pure nylon 6 and the flame-retardant nylon V obtained in example 5 of the present invention, the crystallization temperature of the flame-retardant nylon V is higher than that of pure nylon 6, and the introduction of the phosphine-containing flame retardant (OL5000) makes it easier to crystallize.
The above shows that the introduction of the phosphine-containing flame retardant does not degrade the thermal performance of the phosphine-containing nylon product, almost the same as or better than pure nylon 6.
And (3) flame retardant test results:
in the invention, the flame retardant test is carried out by the following steps:
the test was carried out on an oxygen index tester (HC-2, Jiangnin district analytical instruments, Nanjing), the test specimens were placed vertically on support (top lit), ignited for 20s, and tested to maintain a minimum oxygen concentration for flame combustion for at least 30s, with the specimen dimensions 100mm by 10mm by 3.2 mm.
Vertical burning test (UL94)
The vertical burning method is used for testing the burning behavior of a vertically placed material after a flame is applied to the material, so as to measure the flammability of the material. The test was carried out according to the GB 4096-84 standard, and the test was carried out on a horizontal vertical combustion tester (CZF-3, Jiangning district analytical Instrument works, Nanjing), the specimens were ignited for 10s, the flame source was removed, and the flaming combustion time was recorded. If the cotton is self-extinguished within 30s, the cotton is re-ignited for 10s, the flame and flameless afterflame time is recorded, and whether flame molten drops are generated or not and whether the molten drops ignite the cotton wool or not are observed. The specimen size was 125mm X13 mm X3.2 mm.
The flame retardant nylon prepared by the embodiment of the invention has the following flame retardant test results as shown in the following table 2:
TABLE 2 flame retardance test results
Generally, the limit oxygen index of pure nylon 6 without flame retardant is between 21.5 and 22, while the limit oxygen index of the flame retardant nylon prepared by the method can reach 23 to 28, and the flame retardant property is excellent.
Therefore, the phosphine-containing flame retardant nylon prepared by the method disclosed by the invention can be fully combined with polyamide by adding the phosphine-containing flame retardant in the polymerization process, the addition amount is small, the flame retardant property is excellent, and the problems of performance reduction and cost increase caused by flame retardant modification of a nylon material are effectively solved.
In addition, the phosphine-containing flame-retardant nylon prepared by the method can also be used in the fields of electric wires, cables, 3D printing and the like, the traditional flame-retardant 3D printing consumable uses the additive flame retardant, the wire diameter of the consumable is not stably controlled, and the flame retardant is very easy to precipitate due to the very thin layer thickness in the melt deposition process.
Claims (14)
1. A method for preparing phosphorus-containing flame-retardant nylon, comprising the steps of:
(1) providing a first mixture comprising 10-120 parts by weight of a nylon monomer, 2-15 parts by weight of a phosphine-containing flame retardant;
(2) providing 1-6 parts by weight of water, carrying out polymerization reaction with the first mixture to obtain the phosphine-containing flame-retardant nylon,
wherein the phosphine-containing flame retardant is polyphosphonate shown as the following formula I, or polyphosphonate or phosphonate-carbonate copolymer shown as the following formula II;
wherein each R is1、R2Are respectively selected from the following groups:
R3selected from methyl, ethyl, n-propyl, isopropyl, n-butyl,Tert-butyl or sec-butyl;
R4is selected from
R5Is selected from
Wherein R is1、R2、R3Each as described above in formula I;
n is a positive integer greater than or equal to 1;
the phosphonate-carbonate copolymer is Nofia OL5000, a product of FRX Polymer Co.
2. The method of claim 1, wherein the nylon monomer is selected from the group consisting of: caprolactam, sebacic acid, dodecanedioic acid, dodecalactam, sebacic acid, ethanediamine, adipic acid-1, 4-diaminobutylamine, or combinations thereof.
3. The method of claim 1, wherein the first mixture further comprises 0.01 to 2 parts by weight of a ring-opening promoting agent selected from the group consisting of: adipic acid hexamethylenediamine salt, NH2(CH2) XCOOH, or a combination thereof, wherein x is a positive integer from 1 to 16.
4. The method of claim 1, wherein the first mixture further comprises 0.01 to 1.0 parts by weight of a synergistic flame retardant, and the synergistic flame retardant is montmorillonite.
5. The method of claim 1, wherein the compound of formula II has an average molecular weight of 1400 to 5500, and wherein the phosphorus is present in an amount of 8.5 to 10.3 wt%.
6. The method of claim 1, wherein the method comprises the steps of: melting the nylon monomer at 130 ℃, adding the phosphine-containing flame retardant, adding a ring-opening accelerator after full dissolution, putting into a high-pressure polymerization kettle, adding water, heating for polymerization reaction, extracting, and vacuum-drying at 75-80 ℃ for 24h to obtain the phosphine-containing flame-retardant nylon.
7. The method of claim 1, wherein the first mixture further comprises 0.01 to 0.5 parts by weight of an antioxidant which is a hindered phenol and/or a phosphite, wherein the hindered phenol antioxidant is selected from the group consisting of 2, 8-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, or a combination thereof; the phosphite antioxidant is selected from the following group: tris [ 2.4-di-tert-butylphenyl ] phosphite, 3, 9-bis (2, 4-dicumylphenoxy) -2,4,8, 10-tetraoxa-3, 9-diphosphaspiro [5.5] undecane, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, dioctadecylpentaerythritol diphosphite, or a combination thereof.
8. The method of claim 1, wherein the method comprises the steps of:
(1) melting 10-120 parts by weight of the nylon monomer, adding 2-15 parts by weight of the phosphine-containing flame retardant, fully dissolving, and putting into a high-pressure polymerization kettle;
(2) adding 1-6 parts by weight of water into a high-pressure polymerization kettle, stirring, carrying out polymerization reaction at the temperature of 200-300 ℃ and under the pressure of 0.3-0.6MPa, finally standing, discharging, extracting and drying in vacuum to obtain the phosphine-containing flame-retardant nylon.
9. A phosphine-containing flame retardant nylon made by the process of any of claims 1-8.
10. The phosphine-containing flame retardant nylon of claim 9, wherein the phosphine-containing flame retardant nylon meets the spinning requirement of 800m/min, the diameter of a spinneret orifice is 0.3mm, the drafting magnification is 3-3.5 times, and the drafting speed is 500 m/min.
11. The phosphine-containing flame retardant nylon of claim 9 wherein the phosphine-containing flame retardant nylon has a limiting oxygen index in the range of 23 to 40.
12. The phosphine-containing flame retardant nylon of claim 9 wherein the limiting oxygen index of the phosphine-containing flame retardant nylon is in the range of 25 to 28.
13. The phosphine-containing flame retardant nylon of claim 9 wherein the flame retardant rating of the phosphine-containing flame retardant nylon is V-0.
14. The phosphine-containing flame retardant nylon of claim 9 wherein the phosphine-containing flame retardant nylon is useful for making wire and cable or for 3D printing.
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| CN107033345A (en) * | 2017-05-17 | 2017-08-11 | 东华大学 | A kind of resin of Environmentally-frieflame-retardant flame-retardant nylon 6 and preparation method thereof |
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| CN101497741A (en) * | 2009-02-27 | 2009-08-05 | 中北大学 | Phosphine copolyamide / nano montmorillonite flame-retardant composite material and preparation thereof |
| JP2011174051A (en) * | 2010-01-29 | 2011-09-08 | Toray Ind Inc | Flame-retardant polyamide resin composition and molded article made of the same |
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