CN107460561A - A kind of antibacterial flame-retardant polyamide 66 fabric and preparation method thereof - Google Patents

A kind of antibacterial flame-retardant polyamide 66 fabric and preparation method thereof Download PDF

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Publication number
CN107460561A
CN107460561A CN201710707042.2A CN201710707042A CN107460561A CN 107460561 A CN107460561 A CN 107460561A CN 201710707042 A CN201710707042 A CN 201710707042A CN 107460561 A CN107460561 A CN 107460561A
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retardant
polyamide
flame
antibacterial
antibacterial flame
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CN107460561B (en
Inventor
冯新星
张华�
王修行
来侃
张长琦
潘凯
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Central Military Logistics Department Quartermaster Equipment Institute
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Central Military Logistics Department Quartermaster Equipment Institute
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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
    • 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
    • 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
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/04—Blended or other yarns or threads containing components made from different materials
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/449—Yarns or threads with antibacterial properties
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/13—Physical properties anti-allergenic or anti-bacterial

Abstract

The invention discloses a kind of antibacterial flame-retardant polyamide 66 fabric and preparation method thereof.The preparation method of the antibacterial flame-retardant polyamide 66 comprises the following steps：(1) phosphonium flame retardant, diamine and dihydric alcohol obtain fire retardant performed polymer through prepolymerization reaction and polymerisation successively in water；(2) the fire retardant performed polymer is added in the polymerization process of polyamide 66, obtains Flameproof polyamide 66；(3) Flameproof polyamide 66 is carried out into antimicrobial treatment to produce.Antibacterial flame-retardant nylon and fiber of the present invention, antibiotic property is strong, antibacterial efficacy is lasting, anti-microbial property is stable, and fire-retardant oxygen index (OI) is high, further increases the antibiotic property and anti-flammability of polyamide.Antibacterial flame-retardant nylon fiber and fabric of the present invention, it is not only fire-retardant good, also with antibacterial functions, communal facility, such as aircraft, high ferro seat-cover fabric are can be widely used for, can be applicable to the fields such as health care, clothes.

Description

A kind of antibacterial flame-retardant polyamide 66 fabric and preparation method thereof
Technical field
The present invention relates to a kind of antibacterial flame-retardant polyamide 66 fabric and preparation method thereof, belong to Polymer Synthesizing field.
Background technology
With the raising of people's living condition, for weaving face fabric health and the requirement more and more higher of security；Clothes The antibiotic property of health and garment material when wearing has close relationship, and security and the fire resistance of garment material have Antibiotic property and security are particularly important under important relationship, particularly special operation environment.It is well known that polyamide (popular name nylon) It is that kind is most complete, cost performance is best, a combination property fiber material, therefore proposes new modified polyamine fibre material.
Polyamide 66 is the kind that yield is maximum with consumption in polyamide, accounts for 50% or so of polyamide total amount.It is poly- Acid amides 66 has many premium properties such as high-strength, wear-resisting, be widely used in building, weave, chemical industry, the field such as military affairs.But The combustibility of polyamide 66 have impact on it and widely apply.Effective fire retardant and related synergistic flame retardant are added, makes polyamides The material of amine 66 has anti-flammability, is method more universal in current flame-retarded technology, typically there is blending and copolymerization two from technological angle Kind method.Most of research concentrates on polyamide 66 and is granulated to blending fire retardant and the blending of related synergistic flame retardant at present, This blending method exposes shortcomings, and such as fire retardant addition is more, bad dispersibility, polyamide 66 performance are limited, contracting The application of small blending class Flameproof polyamide 66.
Copolyreaction is carried out using the fire retardant and polyamide 66 monomer of reactivity, introduced on polyamide 66 macromolecular chain Fire-retardant unit, the permanent fire retardant of polyamide 66 is realized, be the emphasis studied in recent years on Flameproof polyamide 66.At present, gush A large amount of patent report copoly type Flameproof polyamides 66 are showed：Patent of invention CN104211954B is such as authorized to disclose a kind of Halogen resistance The preparation method of nylon66 fiber polymer is fired, is generated using the fire retardant DOPO derivatives and binary acid or binary amine copolymer of reactivity Salt, then be copolymerized with nylon salt, obtain halogen-free flame-proof nylon 66.Patent of invention 201510435341.6 discloses a kind of copolymerization resistance The preparation method of the fiber of retardant polyamide 66, the fire-retardant polyamides of block is made in a kind of phosphorous reactive flame retardant, aggregated reaction by it The copolymer of amine 66, then by polyamide 66 copolymer pelletizing, after drying, melt spinning prepares the fiber of Flameproof polyamide 66.China Patent (publication number CN1266445A) obtains fire-retardant nylon using the fire retardant CEPPA of reactivity and the monomer copolymerization of nylon66 fiber 66 polymer, flame retardant molecule are keyed in polymer molecular chain so that the fire resistance of product is effective for a long time.Using reactivity Fire retardant or fire-retardant performed polymer and polyamide 66 monomer copolymerization and to obtain the polymer of Flameproof polyamide 66 be a kind of effective Improve the scheme of polyamide 66 product fire resistance, but be copolymerized in Flameproof polyamide 66, due to the introducing of fire retardant, formed a large amount of Steric effect, make the viscosity of copolymerization Flameproof polyamide 66 relatively low, it is necessary to the process viscosified again, easily cause jaundice or end The problems such as amino mismatches, made troubles for following process or spinning.
Chinese patent CN103774265B discloses a kind of preparation method of anti-bacterial fibre, and it is micro- to prepare antiseptic zinc oxide Grain is added in polymer, and anti-bacterial fibre is obtained by melt electrostatic spinning technology spinning, and this kind of method is larger using antibacterial dosage, The mechanical property of fiber is had influence on, and antibacterial effect is limited.Chinese patent CN101705614B discloses a kind of nickel-plated and silver-plated virtue Fragrant polyamide conductive fiber preparation method, its process include：Washing and oil removing, remove fiber surface impurity after, take sensitization, Activation plates last layer catalyst activity layer in fiber surface, distinguishes nickel plating, silver plating process using immersion process, this method operates Carry out the numerous and diverse difficult control of process, and metal and fiber binding force of cladding material are poor, the coat of metal easily comes off.Chinese patent CN102877287B discloses the preparation method that a kind of antibacterial cellulose of halogen amine is knitted, and fabric is immersed in the solution of periodate In be selectively oxidized, in the Surface Creation aldehyde radical of fabric, antiseptic, fabric face grafting cost are added by being grafted method Compare high, and the mechanical property of the addition degree fabric of peroxide initiator causes to damage in grafting process.
The content of the invention
It is an object of the invention to provide a kind of antibacterial flame-retardant polyamide 66 fabric and preparation method thereof, the inventive method letter Single, reaction is easily controlled, reactive flame retardant species is more.
Present invention firstly provides a kind of antibacterial flame-retardant polyamide 66 (nylon copolymer), it has preferable antibiotic property and resistance Combustion property, and there is good mechanical property, melt spinning can manufacture antibacterial flame-retardant Nylon66.
The preparation method of antibacterial flame-retardant polyamide 66 provided by the present invention, comprises the following steps：
(1) phosphonium flame retardant, diamine and dihydric alcohol obtain fire retardant through prepolymerization reaction and polymerisation successively in water Performed polymer；
(2) the fire retardant performed polymer is added in the polymerization process of polyamide 66, obtains Flameproof polyamide 66；
(3) Flameproof polyamide 66 is subjected to antimicrobial treatment, produces the antibacterial flame-retardant polyamide 66.
In above-mentioned preparation method, in step (1), the weight average molecular weight of the fire retardant performed polymer can be 2000~ 4000。
In above-mentioned preparation method, in step (1), before the prepolymerization reaction, methods described also includes will be described phosphorous Fire retardant, the diamine, the dihydric alcohol and the water mix the step of 0.5~1h；
The prepolymerization reaction and the polymerisation are carried out in an inert atmosphere.
In above-mentioned preparation method, in step (1), the temperature of the prepolymerization reaction is 50~90 DEG C, the time is 0.5~ 1.5h；
The temperature of the polymerisation is 180~190 DEG C, and the time is 1~2h；
The polymerisation is carried out under 0.15~0.3MPa pressure, concretely 0.2MPa.
In above-mentioned preparation method, in step (1), the phosphonium flame retardant, the diamine, the dihydric alcohol with it is described The mol ratio of water is 1：1.1~1.2：1：50~100；
The phosphonium flame retardant is CEPPA, DDP or their derivative；
The structural formula of the CEPPA is as shown in formula I：
The derivative of the CEPPA is the sodium salt or sylvite of the CEPPA；
The structural formula of the DDP is as shown in formula II：
The derivative of the DDP is the sodium salt or sylvite of the DDP；
The diamine is one or both of ethylenediamine, propane diamine, butanediamine and pentanediamine；
The dihydric alcohol is the dihydric alcohol that carbon number is 2~10.
In above-mentioned preparation method, in step (2), the polymerization process of the polyamide 66 is as follows：
The aqueous solution of polyamide 66 salt is carried out under conditions of temperature is 200~210 DEG C, pressure is 1.7~2.2MPa Heat-insulation pressure keeping processing；After pressure release to normal pressure, the fire retardant performed polymer is added, is reacted after heating；
The mass fraction of the aqueous solution of the polyamide 66 salt is 70~85%, concretely 80%；
The addition of the fire retardant performed polymer is the 4 of the gross weight of the fire retardant performed polymer and the polyamide 66 salt ~15%；
The time of the heat-insulation pressure keeping processing is 50min~1.5h；
The temperature of the reaction is 250~265 DEG C, and the time is 0.5~1h.
In above-mentioned preparation method, after the copolyreaction terminates, methods described also includes heating up and the step of vacuumize；
Temperature after the heating is 270~285 DEG C, and the extraction time is 30~50min, and the vacuum after extraction is 0.01 ~50KPa.
It is as follows the step of the antimicrobial treatment in step (3) in above-mentioned preparation method：
1) section of the Flameproof polyamide 66 is added into silver plating reaction liquid and reacted；
2) and then D/W and ethanol water is added dropwise continues to react.
In above-mentioned preparation method, in step 1), the silver plating reaction liquid is AgNO3, ammoniacal liquor and NaOH the aqueous solution, The concentration of each component is according to as follows：
AgNO31~2g/L of 2~4g/L, ammoniacal liquor 10~15ml/L, NaOH；
Concretely：
AgNO32g/L, ammoniacal liquor 10ml/L, NaOH 1g/L, AgNO33g/L, ammoniacal liquor 13ml/L, NaOH 2g/L, AgNO3 3g/L, ammoniacal liquor 12ml/L, NaOH 1.5g/L, AgNO33g/L, ammoniacal liquor 11ml/L, NaOH 1.5g/L or AgNO34g/L, ammoniacal liquor 15ml/L, NaOH 2g/L.
In step 1), the temperature of the reaction is 20~30 DEG C, and the time is 30~60min；
In step 2), the concentration of the D/W is 5~10g/L, the concentration of the ethanol water for 15~ 25ml/L；
In step 2), the time of the reaction is 20~30min.
The antibacterial flame-retardant polyamide 66 that the above method is prepared falls within protection scope of the present invention.
The section and the section (not silver-plated fire-retardant slice) of the Flameproof polyamide 66 of the antibacterial flame-retardant polyamide 66 After mixing antibacterial flame-retardant nylon fiber is obtained through spinning；
The weight ratio of section with the section of the Flameproof polyamide 66 of the antibacterial flame-retardant polyamide 66 is 20~50：80 ~50.
The antibacterial flame-retardant nylon fiber and other fiber blends can prepare antibacterial flame-retardant fabric, such as retardant cotton, fire-retardant Terylene, anti-flaming viscose, Flame Vinylon or fire-retardant cyanogen polyvinyl chloride fibre etc., its blending weight ratio are 20~30：80~70.
The present invention has the advantages that：
Antibacterial flame-retardant nylon and fiber of the present invention, antibiotic property is strong, antibacterial efficacy is lasting, anti-microbial property is stable, and fire-retardant oxygen refers to Number is high, further increases the antibiotic property and anti-flammability of polyamide.
Antibacterial flame-retardant nylon fiber and fabric of the present invention, it is not only fire-retardant good, also with antibacterial functions, can be widely used for public Facility, such as aircraft, high ferro seat-cover fabric, can be applicable to the fields such as health care, clothes.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material used, reagent etc., unless otherwise specified, are commercially obtained in following embodiments.
The preparation of embodiment 1, antibacterial flame-retardant polyamide 66
1st, fire retardant performed polymer is prepared：
1) by fire retardant CEPPA, ethylenediamine, ethylene glycol and water 1:1.1:1:100 (mole) ratios mix, and incorporation time is 0.5h；
2) after being well mixed, the stirring reaction 1h at nitrogen protection, 50 DEG C；
3) after stirring reaction, 0.2MPa is pressurized to, is further heated up under nitrogen protection to 180 DEG C of progress polymerisations, Fire retardant performed polymer is prepared after reaction 1h；
4) weight average molecular weight of the fire retardant performed polymer prepared is 2000.
2nd, antibacterial flame-retardant polyamide 66 is prepared
1) 52% nylon salt is concentrated to 80% at 150 DEG C；
2) 200 DEG C of reactions are warming up to, polymerization pressure 1.7MPa, pressurize reaction 50min, unloads and is depressed into normal pressure；
3) startup agitator, high-speed stirred, the fire retardant performed polymer added in 1, addition account for the 4% of percentage by weight, Continue to be heated to 240 DEG C, react 1h；
4) 260 DEG C and then are again warming up to, and is evacuated to 0.01KPa, extracts 30min；
5) cut into slices, pack, obtain Flameproof polyamide 66 and cut into slices.
3rd, antibacterial flame-retardant nylon fiber is prepared
1) fire-retardant nylon section is put into silver-plated AgNO3In 2g/L, ammoniacal liquor 10ml/L, NaOH 1g/L reaction solutions, 20 DEG C of reaction 60min；
2) and then D/W 5g/L, ethanol water 15ml/L solution is added dropwise, reacts 20min；
3) silver-plated section is taken out and dried under vacuo, secondly by silver-plated section and not silver-plated fire-retardant slice by weight 30：70 blend spinnings, antibacterial flame-retardant nylon fiber is obtained, its mechanical property is shown in Table 6, has preferable mechanical property；
4) finally by antibacterial flame-retardant fiber and flame retardant polyester fiber by weight percentage 20：80 blending systems, most standby antibacterial Flame-retardant textile, its fire resistance are shown in Table 7, have preferable anti-flammability.
The antibacterial effect of the antibacterial flame-retardant Fypro of table 1
No matter fiber or antibacterial fabric are strong, antibacterial efficacy is lasting, anti-microbial property is steady it can be seen from data in table 1 It is fixed.
The preparation of embodiment 2, antibacterial flame-retardant polyamide 66
1st, fire retardant performed polymer is prepared
1) will be by fire retardant DDP, ethylenediamine, ethylene glycol and water with 1:1.2:1:50 (mole) ratios mix, when mixing equal Between be 1h；
2) after being well mixed, the stirring reaction 1.5h at nitrogen protection, 90 DEG C；
3) after stirring reaction, 0.2MPa is pressurized to, is further heated up under nitrogen protection to 190 DEG C of progress polymerisations, Fire retardant performed polymer is prepared after reaction 2h；
4) weight average molecular weight of the fire retardant performed polymer prepared is 3000.
2nd, antibacterial flame-retardant polyamide 66 is prepared
1) 52% nylon salt is concentrated to 80% at 150 DEG C；
2) 210 DEG C of reactions are warming up to, polymerization pressure 2.2MPa, pressurize reaction 1.5h, unloads and is depressed into normal pressure；
3) startup agitator, high-speed stirred, the fire retardant performed polymer added in 1, addition account for the 15% of percentage by weight, Continue to be heated to 250 DEG C, react 2h；
4) 275 DEG C and then are again warming up to, and is evacuated to 50KPa, extracts 50min；
5) cut into slices, pack, obtain Flameproof polyamide 66 and cut into slices.
3rd, antibacterial flame-retardant nylon fiber is prepared
1) fire-retardant nylon section is put into silver-plated AgNO3In 4g/L, ammoniacal liquor 15ml/L, NaOH 2g/L reaction solutions, 30 DEG C of reaction 30min；
2) and then D/W 10g/L, ethanol water 25ml/L solution is added dropwise, reacts 30min；
3) silver-plated section is taken out and dried under vacuo, secondly press silver-plated section and antibacterial flame-retardant polyamide 66 section piece Weight is than 20：80 blend spinnings, antibacterial flame-retardant nylon fiber is obtained, its mechanical property is shown in Table 6, has preferable mechanical property；
4) finally by antibacterial flame-retardant fiber and FRC by weight percentage 30：70 blending systems, most standby antibacterial Flame-retardant textile, its fire resistance are shown in Table 7, have preferable anti-flammability.
The antibacterial effect of the antibacterial flame-retardant Fypro of table 2
No matter fiber or antibacterial fabric are strong, antibacterial efficacy is lasting, anti-microbial property is steady it can be seen from data in table 2 It is fixed.
The preparation of embodiment 3, antibacterial flame-retardant polyamide 66
1st, fire retardant performed polymer is prepared
1) by fire retardant DDP sodium salts, propane diamine, propane diols and water 1:1.18:1:80 (mole) ratios mix, incorporation time For 0.5h；
2) after being well mixed, the stirring reaction 1h at nitrogen protection, 55 DEG C；
3) after stirring reaction, 0.2MPa is pressurized to, is further heated up under nitrogen protection to 182 DEG C of progress polymerisations, Fire retardant performed polymer is prepared after reaction 1.5h；
4) weight average molecular weight of the fire retardant performed polymer prepared is 2500.
2nd, antibacterial flame-retardant polyamide 66 is prepared
1) 52% nylon salt is concentrated to 80% at 150 DEG C；
2) 205 DEG C of reactions are warming up to, polymerization pressure 2MPa, pressurize reaction 1h, unloads and is depressed into normal pressure；
3) startup agitator, high-speed stirred, the fire retardant performed polymer added in 1, addition account for the 10% of percentage by weight, Continue to be heated to 245 DEG C, react 1.5h；
4) 265 DEG C and then are again warming up to, and is evacuated to 40KPa, extracts 45min；
5) cut into slices, pack, obtain Flameproof polyamide 66 and cut into slices.
3rd, antibacterial flame-retardant nylon fiber is prepared
1) fire-retardant nylon section is put into silver-plated AgNO3In 3g/L, ammoniacal liquor 11ml/L, NaOH 1.5g/L reaction solutions, 40min is reacted at 25 DEG C；
2) and then D/W 6g/L, ethanol water 17ml/L solution is added dropwise, reacts 25min；
3) silver-plated section is taken out and dried under vacuo, secondly by silver-plated section and the section of antibacterial flame-retardant polyamide 66 by weight Measure ratio 50：50 blend spinnings, antibacterial flame-retardant nylon fiber is obtained, its mechanical property is shown in Table 6, has preferable mechanical property；
4) finally by antibacterial flame-retardant fiber and flame-retardant cotton fiber by weight percentage 25：75 blending systems, most standby antibacterial hinder Combustible fabric, its fire resistance are shown in Table 7, have preferable anti-flammability.
The antibacterial effect of the antibacterial flame-retardant Fypro of table 3
No matter fiber or antibacterial fabric are strong, antibacterial efficacy is lasting, anti-microbial property is steady it can be seen from data in table 3 It is fixed.
The preparation of embodiment 4, antibacterial flame-retardant polyamide 66
1st, fire retardant performed polymer is prepared
1) by fire retardant DDP sylvite, butanediamine, pentanediamine, butanediol and water with 1:0.6:0.55:1:60 (mole) ratios Mixing, incorporation time 50min；
2) after being well mixed, the stirring reaction 1.5h at nitrogen protection, 60 DEG C；
3) after stirring reaction, 0.2MPa is pressurized to, is further heated up under nitrogen protection to 185 DEG C of progress polymerisations, Fire retardant performed polymer is prepared after reaction 1.5h；
4) weight average molecular weight of the fire retardant performed polymer prepared is 4000.
2nd, antibacterial flame-retardant polyamide 66 is prepared
1) 52% nylon salt is concentrated to 80% at 150 DEG C；
2) 208 DEG C of reactions are warming up to, polymerization pressure 1.9MPa, pressurize reaction 1.2h, unloads and is depressed into normal pressure；
3) startup agitator, high-speed stirred, the fire retardant performed polymer added in 1, addition account for the 8% of percentage by weight, Continue to be heated to 248 DEG C, react 1.5h；
4) 270 DEG C and then are again warming up to, and is evacuated to 30KPa, extracts 35min；
5) cut into slices, pack, obtain the section of antibacterial flame-retardant polyamide 66.
3rd, antibacterial flame-retardant nylon fiber is prepared
1) fire-retardant nylon section is put into silver-plated AgNO3In 3g/L, ammoniacal liquor 12ml/L, NaOH 1.5g/L reaction solutions, 45min is reacted at 25 DEG C；
2) and then D/W 7g/L, ethanol water 19ml/L solution is added dropwise, reacts 25min；
3) silver-plated section is taken out and dried under vacuo, secondly silver-plated section and Flameproof polyamide 66 are cut into slices by weight For 40：60 blend spinnings, antibacterial flame-retardant nylon fiber is obtained, its mechanical property is shown in Table 6, has preferable mechanical property；
4) finally by antibacterial flame-retardant fiber and aramid fiber by weight percentage 20：80 blending systems, most standby antibacterial flame-retardant Fabric, its fire resistance are shown in Table 7, have preferable anti-flammability.
The antibacterial effect of the antibacterial flame-retardant Fypro of table 4
No matter fiber or antibacterial fabric are strong, antibacterial efficacy is lasting, anti-microbial property is steady it can be seen from data in table 4 It is fixed.
The preparation of embodiment 5, antibacterial flame-retardant polyamide 66：
1st, fire retardant performed polymer is prepared
1) by fire retardant CEPPA sylvite, ethylenediamine, propane diamine, decanediol and water with 1:0.5:0.55:1:100 (moles) Ratio mixing, incorporation time 1h；
2) after being well mixed, the stirring reaction 1.2h at nitrogen protection, 70 DEG C；
3) after stirring reaction, 0.2MPa is pressurized to, is further heated up under nitrogen protection to 188 DEG C of progress polymerisations, Fire retardant performed polymer is prepared after reaction 1.5h；
4) weight average molecular weight of the fire retardant performed polymer prepared is 3600.
2nd, antibacterial flame-retardant polyamide 66 is prepared：
1) 52% nylon salt is concentrated to 80% at 150 DEG C；
2) 203 DEG C of reactions are warming up to, polymerization pressure 2.1MPa, pressurize reaction 1.5h, unloads and is depressed into normal pressure；
3) startup agitator, high-speed stirred, the fire retardant performed polymer added in 1, addition account for the 10% of percentage by weight, Continue to be heated to 248 DEG C, react 1.5h；
4) 272 DEG C and then are again warming up to, and is evacuated to 20KPa, extracts 25min；
5) cut into slices, pack, obtain Flameproof polyamide 66 and cut into slices.
3rd, antibacterial flame-retardant nylon fiber is prepared
1) fire-retardant nylon section is put into silver-plated AgNO3In 3g/L, ammoniacal liquor 13ml/L, NaOH 2g/L reaction solutions, 27 DEG C of reaction 50min；
2) and then it is added dropwise that D/W 9g/L, ethanol water be flourish and 23ml/L solution, reacts 28min；
3) silver-plated section is taken out and dried under vacuo, secondly silver-plated section and Flameproof polyamide 66 are cut into slices by weight For 30：70 blend spinnings, antibacterial flame-retardant nylon fiber is obtained, its mechanical property is shown in Table 6, has preferable mechanical property；
4) finally by antibacterial flame-retardant fiber and fire-retardant cyanogen polyvinyl chloride fibre fiber by weight percentage 30：70 blending systems, most standby resist Bacterium flame-retardant textile, its fire resistance are shown in Table 7, have preferable anti-flammability.
The antibacterial effect of the antibacterial flame-retardant Fypro of table 5
No matter fiber or antibacterial fabric are strong, antibacterial efficacy is lasting, anti-microbial property is steady it can be seen from data in table 5 It is fixed.
The mechanical property (2D*38mm) of the antibacterial flame-retardant fiber of table 6
The fire resistance of the antibacterial flame-retardant fabric of table 7
Above example is only to introduce the preferred case of the present invention, to those skilled in the art, without departing substantially from this Any obvious changes and improvements carried out in the range of spirit, it is regarded as the part of the present invention.

Claims (10)

1. a kind of preparation method of antibacterial flame-retardant polyamide 66, comprises the following steps：
(1) phosphonium flame retardant, diamine and dihydric alcohol obtain fire retardant pre-polymerization through prepolymerization reaction and polymerisation successively in water Body；
(2) the fire retardant performed polymer is added in the polymerization process of polyamide 66, obtains Flameproof polyamide 66；
(3) Flameproof polyamide 66 is subjected to antimicrobial treatment, produces the antibacterial flame-retardant polyamide 66.
2. preparation method according to claim 1, it is characterised in that：It is described before the prepolymerization reaction in step (1) The step of method also includes the phosphonium flame retardant, the diamine, the dihydric alcohol and the water mixing 0.5~1h；
The prepolymerization reaction and the polymerisation are carried out in an inert atmosphere.
3. preparation method according to claim 1 or 2, it is characterised in that：In step (1), the temperature of the prepolymerization reaction For 50~90 DEG C, the time is 0.5~1.5h；
The temperature of the polymerisation is 180~190 DEG C, and the time is 1~2h；
The polymerisation is carried out under 0.15~0.3MPa pressure.
4. according to the preparation method any one of claim 1-3, it is characterised in that：In step (1), the phosphor-containing flame-proof Agent, the diamine, the mol ratio of the dihydric alcohol and the water are 1：1.1~1.2：1：50~100；
The phosphonium flame retardant is CEPPA, DDP or their derivative；
The structural formula of the CEPPA is as shown in formula I：
The derivative of the CEPPA is the sodium salt or sylvite of the CEPPA；
The structural formula of the DDP is as shown in formula II：
The derivative of the DDP is the sodium salt or sylvite of the DDP；
The diamine is one or both of ethylenediamine, propane diamine, butanediamine and pentanediamine；
The dihydric alcohol is the dihydric alcohol that carbon number is 2~10.
5. according to the preparation method any one of claim 1-4, it is characterised in that：In step (2), the polyamide 66 Polymerization process it is as follows：
The aqueous solution of polyamide 66 salt is incubated under conditions of temperature is 200~210 DEG C, pressure is 1.7~2.2MPa Pressurize is handled；After pressure release to normal pressure, the fire retardant performed polymer is added, is reacted after heating；
The mass fraction of the aqueous solution of the polyamide 66 salt is 70~85%；
The addition of the fire retardant performed polymer be the gross weight of the fire retardant performed polymer and the polyamide 66 salt 4~ 15%；
The time of the heat-insulation pressure keeping processing is 50min~1.5h；
The temperature of the reaction is 250~265 DEG C, and the time is 0.5~1h.
6. the preparation method according to claim 4 or 5, it is characterised in that：After the copolyreaction terminates, methods described is also The step of including heating up and vacuumizing；
Temperature after the heating is 270~285 DEG C, and the extractions time is 30~50min, the vacuum after extraction for 0.01~ 50KPa。
7. according to the preparation method any one of claim 1-6, it is characterised in that：In step (3), the antimicrobial treatment The step of it is as follows：
1) section of the Flameproof polyamide 66 is added into silver plating reaction liquid and reacted；
2) and then D/W and ethanol water is added dropwise continues to react.
8. preparation method according to claim 7, it is characterised in that：In step 1), the silver plating reaction liquid is AgNO3, ammonia The aqueous solution of water and NaOH, the concentration of each component are as follows：
AgNO31~2g/L of 2~4g/L, ammoniacal liquor 10~15ml/L, NaOH；
In step 1), the temperature of the reaction is 20~30 DEG C, and the time is 30~60min；
In step 2), the concentration of the D/W is 5~10g/L, and the concentration of the ethanol water is 15~25ml/ L；
In step 2), the time of the reaction is 20~30min.
9. antibacterial flame-retardant polyamide 66 prepared by method any one of claim 1-8.
10. a kind of antibacterial flame-retardant nylon fiber or antibacterial flame-retardant nylon fabric, it is characterised in that：The antibacterial flame-retardant nylon Fiber obtains after the section of antibacterial flame-retardant polyamide 66 mixes with the section of Flameproof polyamide 66 as described in claim 9 through spinning Arrive；
The weight ratio of section with the section of the Flameproof polyamide 66 of the antibacterial flame-retardant polyamide 66 is 20~50：80~ 50；
The antibacterial flame-retardant nylon fabric is obtained by the antibacterial flame-retardant nylon fiber and other fiber blends；
The blending weight ratio of the antibacterial flame-retardant nylon fiber and other fibers is 20~30：80~70；
Other fibers are retardant cotton, flame-resistant terylene, anti-flaming viscose, Flame Vinylon or fire-retardant cyanogen polyvinyl chloride fibre.
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CN111764163A (en) * 2020-07-23 2020-10-13 浙江乐森科技有限公司 Production process of antibacterial flame-retardant composite fabric
CN113981691A (en) * 2021-10-26 2022-01-28 成都海蓉特种纺织品有限公司 Special fabric with flame-retardant and antibacterial functions and preparation method and application thereof
CN115928245A (en) * 2022-12-30 2023-04-07 徐州天虹银丰纺织有限公司 Preparation method of polymer fiber for antibacterial textile and antibacterial fabric
CN117107388A (en) * 2023-09-27 2023-11-24 东莞信鸿工程塑料有限公司 Antibacterial flame-retardant polyamide fiber material and preparation method thereof

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CN105155033A (en) * 2015-07-22 2015-12-16 东华大学 Flame-retardant polyamide 6 composite fiber and preparation method thereof
CN105155018A (en) * 2015-07-22 2015-12-16 东华大学 Copolymerized flame-retardant polyamide 66 fiber and preparation method thereof

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CN104630918A (en) * 2013-11-08 2015-05-20 昶尚国际贸易有限公司 Manufacturing method of antibacterial fiber filament and manufacturing method of antibacterial textile
CN105040154A (en) * 2015-07-22 2015-11-11 东华大学 Flame-retardant polyamide 66 complex fiber and preparation method thereof
CN105155033A (en) * 2015-07-22 2015-12-16 东华大学 Flame-retardant polyamide 6 composite fiber and preparation method thereof
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CN111764163A (en) * 2020-07-23 2020-10-13 浙江乐森科技有限公司 Production process of antibacterial flame-retardant composite fabric
CN113981691A (en) * 2021-10-26 2022-01-28 成都海蓉特种纺织品有限公司 Special fabric with flame-retardant and antibacterial functions and preparation method and application thereof
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CN117107388B (en) * 2023-09-27 2024-03-26 东莞信鸿工程塑料有限公司 Antibacterial flame-retardant polyamide fiber material and preparation method thereof

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