CN110923848B - Flame-retardant polyamide fiber and preparation method thereof - Google Patents
Flame-retardant polyamide fiber and preparation method thereof Download PDFInfo
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- CN110923848B CN110923848B CN201911104177.5A CN201911104177A CN110923848B CN 110923848 B CN110923848 B CN 110923848B CN 201911104177 A CN201911104177 A CN 201911104177A CN 110923848 B CN110923848 B CN 110923848B
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
- D01D5/30—Conjugate filaments; Spinnerette packs therefor
- D01D5/34—Core-skin structure; Spinnerette packs therefor
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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
Abstract
The invention relates to a flame-retardant polyamide fiber and a preparation method thereof, wherein the preparation method comprises the following steps: melting and blending polyamide, melamine cyanurate, graphite-like carbon nitride and zinc compounds and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives to prepare flame-retardant polyamide chips, and then carrying out melt spinning and drafting winding or carrying out melt spinning and drafting winding by adopting a skin-core composite spinning method and taking flame-retardant polyamide as a skin layer and polyamide as a core layer; the prepared flame-retardant polyamide fiber material is flame-retardant polyamide, and the flame-retardant polyamide mainly comprises, by mass, 92-96.8 parts of polyamide, 2-5 parts of melamine cyanurate, 0.1-0.5 part of graphite-like carbon nitride, 0.1-0.5 part of zinc compound and 1-2 parts of DOPO derivative. The preparation method is simple, and the prepared product has low addition of the flame retardant and has good mechanical property and flame retardant property.
Description
Technical Field
The invention belongs to the technical field of flame-retardant fibers, and relates to a flame-retardant polyamide fiber and a preparation method thereof.
Background
Polyamide fibers are widely used in the fields of home textiles, apparel, and industrial rope nets. In these fields, the flame retardant property of the product is increasingly emphasized, and the development of a flame retardant polyamide fiber which is easy for industrial production and has good mechanical properties is a trend of industry development.
Polyamide fiber flame retardance currently takes two major technical routes: the first is post-finishing method, and the second is flame retardant blending method. The flame-retardant fiber of the after-finishing method is not resistant to washing, the flame-retardant performance is easy to lose, the procedures of grafting, rolling, baking, coating, spraying and the like are generally needed in production, the process is long, the energy consumption is large, and the environment is not protected; the blending method of the flame retardant is easy to cause the problems of poor fiber spinnability, frequent filament breakage in industrial production, short continuous startup time, low strength and the like.
In addition, in the current research on flame-retardant polyamide fibers, the blending method usually has a large addition amount of a flame retardant in order to improve the flame-retardant performance, which further aggravates the defects of poor spinnability and low mechanical strength of the flame-retardant fibers prepared by the blending method, and a small addition amount often causes the flame-retardant performance of the core of the product to be not up to the standard. For example, in document 1 (Flame of N-, P-and Si-based Flame Retardant Polymers on Flame, Thermal Behavior and Mechanical Properties of PA6 Composite Fibers [ J ]. Fibers and Polymers,2018, Vol.19(6), 1194-channels 1206.) and document 2 (Flame Retardant polyamide and fiber preparation and performance study [ D ]. Donghua university, 2015.), the Flame Retardant is added in a small amount and has good Mechanical Properties, but the Flame Retardant effect is poor, the limit oxygen index value is lower than 30%, and the dripping phenomenon is severe during combustion.
Therefore, the development of a flame-retardant polyamide fiber with low addition of a flame retardant, good spinnability and good flame-retardant performance is a technical problem to be solved at present.
Disclosure of Invention
The invention aims to solve the problems that the mechanical property and the flame retardant property of the flame retardant polyamide fiber prepared by a blending method in the prior art cannot be considered at the same time, and the flame retardant polyamide fiber is difficult to industrially apply due to poor spinnability, and provides the flame retardant polyamide fiber and the preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a flame-retardant polyamide fiber is made of flame-retardant polyamide, and the flame-retardant polyamide mainly comprises, by mass, 92-96.8 parts of polyamide, 2-5 parts of melamine cyanurate, 0.1-0.5 part of graphite-like phase carbon nitride, 0.1-0.5 part of a zinc compound, and 1-2 parts of a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative.
As a preferred technical scheme:
the limit oxygen index of the flame-retardant polyamide fiber is more than or equal to 30.5 percent.
The polyamide is one of nylon 6, nylon 66, nylon 56, nylon 11, nylon 12, nylon 1010 and nylon 1212, or a mixture or copolymer of two or more of the above.
In the flame-retardant polyamide fiber, the zinc compound is one or more of zinc sulfide, zinc diethylphosphinate, zinc 2-carboxyethylphenylphosphinate and zinc cyanurate.
The structural formula of the flame-retardant polyamide fiber, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is (a), (b) or (c), and the flame-retardant polyamide fiber is specifically as follows:
the invention also provides a method for preparing the flame-retardant polyamide fiber, which comprises the steps of carrying out melt spinning and drafting winding on the flame-retardant polyamide fiber after the flame-retardant polyamide chip is prepared by melt blending of polyamide, melamine cyanurate, graphite-like phase carbon nitride and zinc compounds and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives.
As a preferred technical scheme:
in the above-mentioned method, the flame-retardant polyamide chips are dried and pre-crystallized before melt spinning, and the process is as follows: firstly, increasing the temperature from 15-25 ℃ to 50-80 ℃ within 0.5-1 h, preserving the heat for 5-10 h, then continuously increasing the temperature to 90-100 ℃ within 0.5-1 h, preserving the heat for 4-8 h, then continuously increasing the temperature to 110-120 ℃ within 0.5-1 h, preserving the heat for 8-15 h, and finally reducing the temperature to 50-80 ℃ within 0.5-1 h.
The method has the advantages that the temperature of melt blending is 260-280 ℃, the temperature of melt spinning is 260-290 ℃, the speed of drawing and winding is 300-3000 m/min, and the drawing multiple is 1.5-6.0.
The invention also provides another method for preparing the flame-retardant polyamide fiber, which is characterized in that a skin-core composite spinning method is adopted, the flame-retardant polyamide is used as a skin layer, the polyamide is used as a core layer, and melt spinning and drafting winding are carried out to prepare the flame-retardant polyamide fiber, wherein the flame-retardant polyamide is prepared by melt blending of polyamide, melamine cyanurate, graphite-like phase carbon nitride, a zinc compound and a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative.
As a preferred technical scheme:
the method has the advantages that the temperature of melt blending is 260-280 ℃, the temperature of melt spinning is 260-290 ℃, the speed of drawing and winding is 300-3000 m/min, and the drawing multiple is 1.5-6.0.
The invention mechanism is as follows:
the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives are dispersed in the fibers in a sea-like form, not only play a role of a dispersing agent to fully disperse melamine cyanurate, graphite-like carbon nitride and zinc compounds, but also can permeate into the layers of the melamine cyanurate and the graphite-like carbon nitride in a lubricant form, promote a large amount of slippage of lamella of the melamine cyanurate and the graphite-like carbon nitride in the spinning and stretching process, solve the problems of easy agglomeration, large particles, poor dispersibility and the like of inorganic flame retardants, and directly improve the spinnability and mechanical properties of the fibers. In addition, the surface area of the flame retardant after the sliding of the sheet layer is increased, so that the heat transfer can be effectively prevented, the heat exchange rate is reduced, the better flame retardant property is exerted, and the using amount of the flame retardant is greatly reduced. Meanwhile, after the polymer base material is heated and decomposed, the zinc compound with the island-shaped structure plays a role of a central point, can be complexed with terminal amino groups generated by decomposition of the base body and amino groups of graphite-like carbon nitride, promotes the decomposed base body to be crosslinked into carbon, enables the base body material to be condensed near the central point, is not easy to transfer, and plays a role in molten drop resistance.
When the flame-retardant polyamide fiber prepared by the invention is ignited, the melamine cyanurate can generate a large amount of nitrogen-containing non-combustible gas and water vapor, so that the concentration of the combustible gas in a combustion environment is diluted and the expansion of a carbon layer is promoted. Melamine cyanurate is used as a gas source, graphite-like phase carbon nitride is used as a carbonization induction and promotion agent, and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives are heated and decomposed to generate strong acid (such as polyphosphoric acid, pyrophosphoric acid and the like) with water absorption or dehydration effects, and can be used as an acid source to form a ternary composite synergistic flame retardant effect, so that the flame retardant effect is enhanced.
Has the advantages that:
(1) the preparation method of the flame-retardant polyamide fiber has the advantages of simple process and low cost, and is suitable for industrialization;
(2) the flame-retardant polyamide fiber has the ternary synergistic effect of an air source, a carbon source and an acid source and the dual flame-retardant effect of an air phase and a condensed phase, and can achieve the purposes of no melting and dripping and good flame-retardant property;
(3) the flame-retardant polyamide fiber disclosed by the invention is low in flame retardant addition, has good mechanical properties and flame retardance, and is wide in application range.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of flame-retardant polyamide fiber comprises the following specific steps:
(1) preparing flame-retardant polyamide chips by melt blending of 94 parts of nylon 6, 3.5 parts of melamine cyanurate, 0.5 part of graphite-like carbon nitride, 0.5 part of zinc sulfide and 1.5 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, wherein the melt blending temperature is 270 ℃, and the structural formula of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives is as follows:
(2) drying and pre-crystallizing the flame-retardant polyamide chips by the following steps: firstly, the temperature is increased from 20 ℃ to 65 ℃ within 0.75h, the temperature is kept for 6h, then the temperature is continuously increased to 95 ℃ within 0.75h, the temperature is kept for 6h, then the temperature is continuously increased to 115 ℃ within 0.68h, the temperature is kept for 12h, and finally the temperature is reduced to 60 ℃ within 0.56 h;
(3) carrying out melt spinning and drafting winding on the polyamide chips treated in the step (2) to obtain flame-retardant polyamide fibers; the temperature of melt spinning is 276 ℃, the speed of drawing and winding is 2000m/min, and the drawing multiple is 3.5;
the limit oxygen index of the prepared flame-retardant polyamide fiber is 30.9%.
Example 2
A preparation method of flame-retardant polyamide fiber comprises the following specific steps:
(1) 92 parts of nylon 66, 5 parts of melamine cyanurate, 0.5 part of graphite-like carbon nitride, 0.5 part of zinc diethylphosphinate and 2 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative are subjected to melt blending to prepare the flame-retardant polyamide slice, wherein the melt blending temperature is 260 ℃, and the structural formula of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is as follows:
(2) drying and pre-crystallizing the flame-retardant polyamide chips, wherein the process comprises the following steps: firstly, increasing the temperature from 15 ℃ to 50 ℃ within 0.5h, preserving the heat for 10h, then continuously increasing the temperature to 90 ℃ within 0.5h, preserving the heat for 8h, then continuously increasing the temperature to 110 ℃ within 0.5h, preserving the heat for 15h, and finally reducing the temperature to 50 ℃ within 0.5 h;
(3) carrying out melt spinning and drafting winding on the polyamide chips treated in the step (2) to obtain flame-retardant polyamide fibers; the temperature of melt spinning is 260 ℃, the speed of drafting and winding is 300m/min, and the drafting multiple is 1.6;
the limiting oxygen index of the prepared flame-retardant polyamide fiber is 32.5%.
Example 3
A preparation method of flame-retardant polyamide fiber comprises the following specific steps:
(1) melting and blending 95.5 parts of nylon 56, 3 parts of melamine cyanurate, 0.4 part of graphite-like phase carbon nitride, 0.4 part of 2-carboxyethyl phenyl zinc phosphinate and 1.7 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative to prepare the flame-retardant polyamide slice, wherein the temperature of the melting and blending is 280 ℃, and the structural formula of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is as follows:
(2) drying and pre-crystallizing the flame-retardant polyamide chips by the following steps: firstly, heating from 25 ℃ to 80 ℃ within 1h, preserving heat for 5h, then continuously heating to 100 ℃ within 1h, preserving heat for 4h, then continuously heating to 120 ℃ within 1h, preserving heat for 8h, and finally cooling to 80 ℃ within 1 h;
(3) carrying out melt spinning and drafting winding on the polyamide chips treated in the step (2) to obtain flame-retardant polyamide fibers; the temperature of melt spinning is 290 ℃, the speed of drawing and winding is 3000m/min, and the drawing multiple is 5.6;
the limit oxygen index of the prepared flame-retardant polyamide fiber is 30.6%.
Example 4
A preparation method of flame-retardant polyamide fiber comprises the following specific steps:
(1) the flame-retardant polyamide chip is prepared by melt blending 93.5 parts of nylon 11, 4.3 parts of melamine cyanurate, 0.3 part of graphite-like carbon nitride, 0.3 part of zinc cyanurate and 1.6 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, wherein the melt blending temperature is 265 ℃, and the structural formula of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is as follows:
(2) drying and pre-crystallizing the flame-retardant polyamide chips, wherein the process comprises the following steps: firstly, the temperature is increased from 21 ℃ to 70 ℃ within 0.66h, the temperature is kept for 7.5h, then the temperature is continuously increased to 97 ℃ within 0.76h, the temperature is kept for 7h, then the temperature is continuously increased to 114 ℃ within 0.55h, the temperature is kept for 13h, and finally the temperature is reduced to 70 ℃ within 0.88 h;
(3) carrying out melt spinning and drafting winding on the polyamide chips treated in the step (2) to obtain flame-retardant polyamide fibers; the temperature of melt spinning is 271 ℃, the speed of drawing and winding is 1500m/min, and the drawing multiple is 3;
the limiting oxygen index of the prepared flame-retardant polyamide fiber is 31.8%.
Example 5
A preparation method of flame-retardant polyamide fiber comprises the following specific steps:
(1) the flame-retardant polyamide is prepared by melt blending nylon 12, melamine cyanurate, graphite-like phase carbon nitride and a zinc compound and a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, wherein the zinc compound is a mixture of zinc sulfide and zinc cyanurate in a mass ratio of 1:1, the melt blending temperature is 275 ℃, and the structural formula of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is as follows:
(2) adopting a skin-core composite spinning method, taking the flame-retardant polyamide prepared in the step (1) as a skin layer and nylon 12 as a core layer, and carrying out melt spinning and drafting winding to prepare the flame-retardant polyamide fiber, wherein the temperature of the melt spinning is 278 ℃, the speed of the drafting winding is 2500m/min, and the drafting multiple is 4.8;
the prepared flame-retardant polyamide fiber consists of 93.5 parts by mass of nylon 12, 4.6 parts by mass of melamine cyanurate, 0.3 part by mass of graphite-like phase carbon nitride, 0.3 part by mass of a zinc compound and 1.3 parts by mass of a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative; and its limiting oxygen index was 31.2%.
Example 6
A preparation method of flame-retardant polyamide fiber comprises the following specific steps:
(1) the flame-retardant polyamide is prepared by melt blending nylon 1010, melamine cyanurate, graphite-like phase carbon nitride, a zinc compound and a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, wherein the zinc compound is a mixture of zinc sulfide, zinc diethylphosphinate and zinc 2-carboxyethyl phenyl phosphinate in a mass ratio of 1:1:1, the melt blending temperature is 280 ℃, and the structural formula of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is as follows:
(2) performing melt spinning and drafting winding by adopting a skin-core composite spinning method and taking the flame-retardant polyamide prepared in the step (1) as a skin layer and nylon 1010 as a core layer to prepare the flame-retardant polyamide fiber, wherein the temperature of the melt spinning is 290 ℃, the speed of the drafting winding is 2800m/min, and the drafting multiple is 6;
the prepared flame-retardant polyamide fiber consists of 96.8 parts by mass of nylon 1010, 2 parts by mass of melamine cyanurate, 0.1 part by mass of graphite-like phase carbon nitride, 0.1 part by mass of a zinc compound and 1 part by mass of a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative; and its limiting oxygen index is 30.5%.
Example 7
A preparation method of flame-retardant polyamide fiber comprises the following specific steps:
(1) the flame-retardant polyamide is prepared by melt blending nylon 1212, melamine cyanurate, graphite-like phase carbon nitride, zinc sulfide and a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, wherein the melt blending temperature is 260 ℃, and the structural formula of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is as follows:
(2) performing melt spinning and drafting winding by using the flame-retardant polyamide prepared in the step (1) as a skin layer and nylon 1212 as a core layer by adopting a skin-core composite spinning method to prepare the flame-retardant polyamide fiber, wherein the temperature of the melt spinning is 260 ℃, the speed of the drafting winding is 350m/min, and the drafting multiple is 1.5;
the prepared flame-retardant polyamide fiber consists of 92.5 parts by mass of nylon 1212, 5 parts by mass of melamine cyanurate, 0.5 part by mass of graphite-like phase carbon nitride, 0.5 part by mass of zinc sulfide and 1.5 parts by mass of a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative; and its limiting oxygen index is 32.1%.
Example 8
A preparation method of flame-retardant polyamide fiber comprises the following specific steps:
(1) the flame-retardant polyamide is prepared by melt blending of copolymerized nylon 6/66, melamine cyanurate, graphite-like carbon nitride, zinc sulfide and a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, wherein the melt blending temperature is 270 ℃, and the structural formula of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is as follows:
(2) performing melt spinning and drafting winding by adopting a skin-core composite spinning method and taking the flame-retardant polyamide prepared in the step (1) as a skin layer and the copolymerized nylon 6/66 as a core layer to prepare the flame-retardant polyamide fiber, wherein the temperature of the melt spinning is 275 ℃, the speed of the drafting winding is 1200m/min, and the drafting multiple is 2.5;
the prepared flame-retardant polyamide fiber consists of 95 parts of copolymerized nylon 6/66, 3 parts of melamine cyanurate, 0.4 part of graphite-like phase carbon nitride, 0.4 part of zinc sulfide and 1.2 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative in parts by mass; and its limiting oxygen index is 31%.
Example 9
A preparation method of flame-retardant polyamide fiber comprises the following specific steps:
(1) the flame-retardant polyamide is prepared by melt blending of a mixture of nylon 6, nylon 66 and nylon 56, melamine cyanurate, graphite-like phase carbon nitride, zinc sulfide and a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative in a mass ratio of 1:1:1, wherein the melt blending temperature is 265 ℃, and the structural formula of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is as follows:
(2) performing melt spinning and drafting winding by using the flame-retardant polyamide prepared in the step (1) as a skin layer and a mixture of nylon 6, nylon 66 and nylon 56 in a mass ratio of 1:1:1 as a core layer by adopting a skin-core composite spinning method to prepare the flame-retardant polyamide fiber, wherein the temperature of the melt spinning is 275 ℃, the speed of the drafting winding is 1200m/min, and the drafting multiple is 2.5;
the prepared flame-retardant polyamide fiber consists of 94.5 parts by mass of a mixture of nylon 6, nylon 66 and nylon 56 in a mass ratio of 1:1:1, 2.5 parts by mass of melamine cyanurate, 0.5 part by mass of graphite-like carbon nitride, 0.5 part by mass of zinc sulfide and 2 parts by mass of a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative; and its limiting oxygen index was 32.7%.
Comparative example 1
A flame-retardant polyamide fiber was prepared in the same manner as in example 1, except that melamine cyanurate was not added in the step (1), and the flame-retardant polyamide fiber was obtained to have a limiting oxygen index of 28.8%.
Comparative example 2
A flame retardant polyamide fiber was prepared in substantially the same manner as in example 1, except that graphite-like phase carbon nitride was not added in the step (1), and the limited oxygen index of the flame retardant polyamide fiber was 30.0%.
Comparative example 3
A flame retardant polyamide fiber was prepared in substantially the same manner as in example 1, except that no zinc sulfide was added in the step (1), and the limited oxygen index of the flame retardant polyamide fiber was 29.4%.
Comparative example 4
A flame-retardant polyamide fiber was prepared in the same manner as in example 1, except that no 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative was added in the step (1), and the limited oxygen index of the resulting flame-retardant polyamide fiber was 29.3%.
As can be seen from comparison of comparative example 1 with example 1, the flame retardant property is much worse because the melamine cyanurate in example 1 can generate a large amount of nitrogen-containing non-combustible gas and water vapor, dilute the concentration of combustible gas in the combustion environment and promote the expansion of the char layer; the melamine cyanurate is used as a gas source, and forms a ternary composite synergistic flame retardant effect with graphite-phase carbon nitride as a carbonization induction and promoter and a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative as an acid source, so that the flame retardant effect is enhanced; in contrast, the melamine cyanurate in comparative example 1 is absent, and the flame retardant effect is weakened if the flame retardant effect caused by the gas source generated in the combustion process is absent;
as can be seen from comparison between comparative example 2 and example 1, the flame retardant performance is worse because the graphite-like carbon nitride in example 1, as a carbonization inducing and accelerating agent, can form a ternary composite synergistic flame retardant effect with melamine cyanurate as a gas source and a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative as an acid source, thereby enhancing the flame retardant effect; in contrast, the comparative example 2 lacks graphite-like phase carbon nitride, and cannot form a synergistic flame-retardant effect in the combustion process, so that the flame-retardant effect is weakened;
as can be seen by comparing the comparative example 3 with the example 1, the flame retardant performance is poorer, because when the polymer substrate is heated and decomposed, the zinc sulfide existing in an island-shaped structure in the example 1 plays a role of a central point, and can perform a complexing action with terminal amino groups generated by the decomposition of the matrix and amino groups of graphite-like carbon nitride, so that the decomposed matrix is promoted to be crosslinked into carbon, the matrix material is condensed near the central point and is not easy to transfer, and the anti-dripping effect is achieved;
comparing the comparative example 4 with the example 1, it can be seen that the flame retardant property is worse, wherein the worse flame retardant property is that the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivative is dispersed in the fiber in a sea form, which not only plays a role of a dispersant to fully disperse the melamine cyanurate, the graphite-like carbon nitride and the zinc compound, but also can permeate into the interlayer of the melamine cyanurate and the graphite-like carbon nitride in a form of a lubricant to promote a large amount of slippage of the lamella of the melamine cyanurate and the graphite-like carbon nitride, thereby solving the problems of easy agglomeration, large particles, poor dispersibility and the like of the inorganic flame retardant and directly improving the spinnability of the fiber. In addition, the surface area of the flame retardant after the sliding of the sheet layer is increased, so that the heat transfer can be effectively prevented, the heat exchange rate is reduced, the better flame retardant property is exerted, and the using amount of the flame retardant is greatly reduced; the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is used as an acid source, and forms a ternary composite synergistic flame retardant effect with melamine cyanurate and graphite-like phase carbon nitride, so that the flame retardant effect is enhanced; in comparative example 4, no 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative was added, so that the interlayer slip phenomenon of melamine cyanurate and graphite-like carbon nitride was not caused, and the acid source could not be provided to form a synergistic flame retardant effect with melamine cyanurate and graphite-like carbon nitride.
Claims (7)
1. A flame retardant polyamide fiber characterized by: the material is flame-retardant polyamide which mainly comprises, by mass, 92-96.8 parts of polyamide, 2-5 parts of melamine cyanurate, 0.1-0.5 part of graphite-like phase carbon nitride, 0.1-0.5 part of zinc compound and 1-2 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative;
the limit oxygen index of the flame-retardant polyamide fiber is more than or equal to 30.5 percent;
the zinc compound is more than one of zinc sulfide, zinc diethyl phosphinate, zinc 2-carboxyethyl phenyl phosphinate and zinc cyanurate;
the structural formula of the 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative is (a), (b) or (c), and the structural formula is as follows:
2. the flame-retardant polyamide fiber according to claim 1, wherein the polyamide is one or a mixture or a copolymer of two or more of nylon 6, nylon 66, nylon 56, nylon 11, nylon 12, nylon 1010 and nylon 1212.
3. A process for preparing a flame-retardant polyamide fiber as claimed in any one of claims 1 to 2, characterized in that: melting and blending polyamide, melamine cyanurate, graphite-like carbon nitride, zinc compound and 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative to obtain flame-retardant polyamide chip, and then carrying out melt spinning and drafting winding to obtain the flame-retardant polyamide fiber.
4. The method according to claim 3, wherein the flame retardant polyamide chips are dried and pre-crystallized prior to melt spinning by: firstly, increasing the temperature from 15-25 ℃ to 50-80 ℃ within 0.5-1 h, preserving the heat for 5-10 h, then continuously increasing the temperature to 90-100 ℃ within 0.5-1 h, preserving the heat for 4-8 h, then continuously increasing the temperature to 110-120 ℃ within 0.5-1 h, preserving the heat for 8-15 h, and finally reducing the temperature to 50-80 ℃ within 0.5-1 h.
5. The method according to claim 3, wherein the melt-blending temperature is 260 to 280 ℃, the melt-spinning temperature is 260 to 290 ℃, the speed of the drawing and winding is 300 to 3000m/min, and the drawing ratio is 1.5 to 6.0.
6. A process for preparing a flame-retardant polyamide fiber as claimed in any one of claims 1 to 2, characterized in that: the flame-retardant polyamide fiber is prepared by adopting a sheath-core composite spinning method, taking flame-retardant polyamide as a sheath layer and polyamide as a core layer, and carrying out melt spinning and drafting winding, wherein the flame-retardant polyamide is prepared by melt blending of polyamide, melamine cyanurate, graphite-like phase carbon nitride, a zinc compound and a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative.
7. The method according to claim 6, wherein the melt-blending temperature is 260 to 280 ℃, the melt-spinning temperature is 260 to 290 ℃, the speed of the drawing and winding is 300 to 3000m/min, and the drawing ratio is 1.5 to 6.0.
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| CN112779765A (en) * | 2020-12-31 | 2021-05-11 | 宁波三邦超细纤维有限公司 | Flame-retardant micron-silk composite superfine fiber and preparation method thereof |
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