CN111074373A - Flame-retardant antibacterial PTT fiber material and preparation method therefor - Google Patents

Flame-retardant antibacterial PTT fiber material and preparation method therefor Download PDF

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CN111074373A
CN111074373A CN201911300572.0A CN201911300572A CN111074373A CN 111074373 A CN111074373 A CN 111074373A CN 201911300572 A CN201911300572 A CN 201911300572A CN 111074373 A CN111074373 A CN 111074373A
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flame
ptt
raw materials
fiber material
ptt fiber
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CN111074373B (en
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张毅
夏镭
赵志刚
程方清
朱爱华
黄金华
岳同健
胡同云
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Shanghai Changwei Jinci Engineering Plastic Co ltd
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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
    • D01F6/92—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 polyesters
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the field of high polymer materials, in particular to a flame-retardant antibacterial PTT fiber material which comprises the following components in parts by weight: 80-98 parts of PTT, 1-5 parts of a toughening agent, 1-10 parts of a flame retardant, 0.1-5 parts of a nano composite material, 0.1-1 part of an antioxidant and 0.1-1 part of a lubricant. The PTT fiber nano composite material with good flame retardant, smoke suppression and antibacterial effects is prepared by compounding the flame retardant and the nano composite material, and is particularly suitable for producing fiber raw materials of curtain cloth and carpets.

Description

Flame-retardant antibacterial PTT fiber material and preparation method therefor
Technical Field
The invention relates to the field of high polymer materials, in particular to a flame-retardant antibacterial PTT fiber material and a preparation method thereof.
Background
The polymer material is easy to burn, and not only releases a large amount of heat, but also releases toxic smoke during burning. In a fire, casualties often die from the heat and toxic fumes produced during combustion. The fire hazard of materials is therefore mainly divided into: heat hazards and smoke hazards. Thermal hazards can be characterized primarily by the rate of heat release (HRR) and the peak rate of heat release (phHRR); smoke hazards can be characterized primarily by the total smoke generation (TSP).
Both the curtain cloth and the carpet are indoor products, so bacteria are easy to breed in a humid environment, and the curtain cloth and the carpet are not convenient to clean, so that the antibacterial performance of the fiber is high.
PTT is the abbreviation of polytrimethylene terephthalate, namely polytrimethylene terephthalate, and is a novel industrialized aromatic polyester. Because PTT has a lower flexural modulus and elastic recovery than PET, PTT is more suitable than PET for making fiber fillers and carpets. Currently, Shell and DuPont successively realize the industrial production of PTT. Therefore, the preparation of the flame-retardant antibacterial PTT material has great significance.
Chinese patent document CN106245156A discloses a flame-retardant antibacterial simulation wig and a preparation method thereof, which comprises the following components in parts by weight: 80-90% of polyester material, 5-11% of flame retardant, 2.5-6% of antibacterial agent, 0.3-3% of dispersing agent, 0.2-0.5% of antioxidant and 2-5% of color master batch. The patent mainly adds phosphate flame retardant, nano layered silicate or nano bentonite as flame retardant synergist and nano silver ions as antibacterial agent, and evaluates the flame retardant performance by evaluating the limit oxygen index, but does not explain the heat release rate and smoke amount.
However, no report is found about a flame-retardant antibacterial PTT fiber material suitable for preparing carpets and curtains and a preparation method thereof at present.
Disclosure of Invention
The invention aims to provide a flame-retardant antibacterial PTT fiber, which is prepared by compounding nano montmorillonite, tetrapod-like zinc oxide whiskers and a flame retardant, and is suitable for preparing fiber materials of carpets and curtains.
The invention provides a flame-retardant antibacterial PTT fiber material, which comprises the following components in parts by weight:
Figure BDA0002321659880000021
wherein the content of the first and second substances,
the PTT is poly (1, 3-propylene terephthalate) with the intrinsic viscosity of 0.7-1.1 dL/g. Preferably 2271 from dupont, usa.
The toughening agent is styrene-butadiene-styrene (SBS), ABS high rubber powder, polyurethane elastomer, ethylene-methyl methacrylate copolymer (EMA), ethylene-butyl methacrylate copolymer (EBA), polyolefin elastomer, silicon rubber with a core-shell structure or methyl methacrylate-butadiene-styrene (MBS) or ethylene-acrylate-glycidyl methacrylate copolymer. Ethylene-acrylate-glycidyl methacrylate copolymers are preferred. Specifically, AX8900 of Acoma can be selected.
The flame retardant is one or more than two of aromatic phosphate, phosphonate, cyclic alkyl phosphonate or phosphorus nitrogen flame retardant. Preferably, the content of phosphorus in the cyclic alkyl phosphonate is 18-22%. Specifically, FR-1012 in United America chemical industry can be selected.
The nano composite material is one or more than two of nano aluminum oxide, nano organic montmorillonite, nano aluminum hydroxide or nano zinc oxide, and the particle size is 10-1000 nm. Preferably, nano organic montmorillonite and tetrapod-like zinc oxide whisker (ZnOw) are compounded for use; the grain size of the nano organic montmorillonite is 10-30 nm, and the grain size of the tetrapod-like zinc oxide whisker is 10-100 nm. The specific optional nano organic montmorillonite is DK2 of Zhejiang Fenghong, and the particle size is 10-30 nm; the tetrapod-like zinc oxide whiskers are WZX5 of a Hangzhou Jikang new material, and the particle size is 10-100 nm.
The antioxidant is one or two of phosphite ester antioxidant 168, phosphite ester antioxidant S-9228, hindered phenol antioxidant 1010, hindered phenol antioxidant 1098 and hindered phenol antioxidant 1076. Preferably, the mixture of the phosphite antioxidant S-9228 with large molecular weight and the hindered phenol antioxidant 1076 is selected.
The lubricant is one or more than two of silicone powder, Pentaerythritol Ester (PETS) and ethylene distearamide. Pentaerythritol esters are preferred.
In a preferred embodiment of the invention, the flame-retardant antibacterial PTT fiber material consists of the following components in parts by weight:
Figure BDA0002321659880000031
in a preferred embodiment of the invention, the flame-retardant antibacterial PTT fiber material consists of the following components in parts by weight:
Figure BDA0002321659880000032
wherein, in the preferred embodiment, the selected PTT is 2271 of DuPont, USA;
the selected toughening agent is AX8900 of Achima;
the selected flame retardant cyclic alkyl phosphonate is FR-1012 of the United states chemical industry;
the selected nano organic montmorillonite is DK2 of Zhejiang Fenghong;
the four-needle zinc oxide crystal whisker is WZX5 of Hangzhou Jikang new material;
the selected antioxidant is compounded by antioxidant 1076 produced by CIBA company and S-9228 produced by Dover company;
the lubricant selected is Pentaerythritol Ester (PETS).
In a second aspect of the invention, a preparation method of the flame-retardant antibacterial PTT fiber is provided, which comprises the following steps:
s1, preparing raw materials according to the weight part ratio, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
The invention has the advantages that:
under the condition of adding the cyclic alkyl phosphonate, the nano organic montmorillonite and the tetrapod-like zinc oxide whisker (ZnOw) are compounded together to achieve the optimal flame-retardant and antibacterial effects. The cyclic alkyl phosphonate ester has good flame retardant performance, but the peak value of the heat release rate and the total smoke generation amount which are used independently do not meet the technical index requirements. The best performance requirement is achieved by the matching use of the organic montmorillonite and ZnOw. The reason is that the organic montmorillonite forms a state of stripping a part of intercalation in the PTT resin, thus hindering the heat transfer and the volatilization of pyrolysis products in the combustion process; in addition, the existence of the organic montmorillonite also stabilizes the structure of the carbon layer, and greatly reduces the heat release rate and the smoke release amount; ZnOw has a unique three-dimensional four-needle structure, so when the ZnOw is used with organic montmorillonite in a synergistic way, the organic montmorillonite is easier to form a stripped lamellar structure, the agglomeration among the organic montmorillonite is hindered, and the peak value of the heat release rate and the total smoke release amount are further reduced. On the other hand, the addition of ZnOw has obvious catalytic action on the carbon forming reaction and has good synergistic flame retardant effect. In the antibacterial aspect, ZnOw slowly releases zinc ions when in contact with bacteria. Because zinc ions have redox property, the zinc ions can be combined with cell membranes and membrane proteins, break enzymes of an electron transfer system after entering cells, and react with-SH groups to achieve the aim of antibiosis. After killing bacteria, zinc ions can be dissociated from cells, and the process is repeated, so that the antibacterial efficiency is improved. Therefore, the flame-retardant antibacterial PTT fiber material can be prepared by the scheme.
Detailed Description
The following examples are provided to illustrate specific embodiments of the present invention.
In the following examples and comparative examples, the following ingredients were used for each raw material:
the selected PTT is 2271 of DuPont in America;
the selected toughening agent is AX8900 of Achima;
the selected aromatic phosphate flame retardant is WSFR-BDP which is held in great abundance in Zhejiang, and the phosphorus content is 8-12%;
the selected flame retardant cyclic alkyl phosphonate is FR-1012 of the United America chemical industry, and the phosphorus content is 18-22%;
the selected nano organic montmorillonite is DK2 of Zhejiang Fenghong, and the particle size is 10-30 nm;
the four-needle zinc oxide whisker is WZX5 of a Hangzhou Jikang new material, and the particle size is 10-100 nm;
the selected antioxidant is compounded by antioxidant 1076 produced by CIBA company and S-9228 produced by Dover company;
the lubricant selected is Pentaerythritol Ester (PETS).
TABLE 1 Components and proportions of comparative examples 1 to 3 and examples 1 to 4
Figure BDA0002321659880000051
TABLE 2 Components and proportions of examples 5 to 11
Figure BDA0002321659880000052
TABLE 3 compositions and proportions of examples 12-15
Figure BDA0002321659880000053
Figure BDA0002321659880000061
Comparative example 1:
s1, preparing raw materials according to the weight part ratio in the table 1, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Comparative example 2:
s1, preparing raw materials according to the weight part ratio in the table 1, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Comparative example 3:
s1, preparing raw materials according to the weight part ratio in the table 1, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 1:
s1, preparing raw materials according to the weight part ratio in the table 1, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 2:
s1, preparing raw materials according to the weight part ratio in the table 1, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a hot roller is 80-120 ℃.
Example 3:
s1, preparing raw materials according to the weight part ratio in the table 1, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 4:
s1, preparing raw materials according to the weight part ratio in the table 1, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 5:
s1, preparing raw materials according to the weight part ratio shown in the table 2, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 6:
s1, preparing raw materials according to the weight part ratio shown in the table 2, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 7:
s1, preparing raw materials according to the weight part ratio shown in the table 2, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 8:
s1, preparing raw materials according to the weight part ratio shown in the table 2, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 9:
s1, preparing raw materials according to the weight part ratio shown in the table 2, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 10:
s1, preparing raw materials according to the weight part ratio shown in the table 2, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 11:
s1, preparing raw materials according to the weight part ratio shown in the table 2, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 12:
s1, preparing raw materials according to the weight part ratio shown in the table 2, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 13:
s1, preparing raw materials according to the weight part ratio shown in the table 2, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 14:
s1, preparing raw materials according to the weight part ratio shown in the table 2, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Example 15:
s1, preparing raw materials according to the weight part ratio shown in the table 2, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
Evaluation of the effects of the implementations
The PTT fibers prepared in the comparative examples 1 to 3 and the examples 1 to 15 are subjected to related tests: the breaking strength and elongation at break were tested according to GB/T27629; peak heat release rate (phHRR) and total smoke generation (TSP) were tested according to astm e1354 using a cone calorimeter; the sterilization rate is tested according to ASTM E2149-2001, using 1.5-3X 102(CFU/ml) was inoculated with the bacterial suspension concentration and cultured with shaking for 18 hours to evaluate the final sterilization rate. The test results are shown in tables 4-6 below:
TABLE 4 test results for comparative examples 1 to 3 and examples 1 to 4
Figure BDA0002321659880000101
TABLE 5 test results of examples 5 to 11
Figure BDA0002321659880000102
Figure BDA0002321659880000111
TABLE 6 test results of examples 12 to 15
Figure BDA0002321659880000112
As can be seen from comparative examples 1 to 3 and examples 1 to 3, the use of the cyclic alkyl phosphonate ester has a lower peak heat release rate and a lower total smoke generation amount than the aromatic phosphate ester flame retardant at the same addition amount; and the breaking strength and the breaking elongation of the fiber are higher, and the fiber has better fiber forming property.
As can be seen from examples 2 and 4 to 6, the peak value of the heat release rate and the total amount of the generated smoke are sharply decreased as the amount of the organic montmorillonite used is increased, because the lamellar structure of the organic montmorillonite forms a structure in which a part of the intercalation is partially peeled off in the PTT resin during the extrusion granulation process. During combustion, heat is blocked by the sheets of organized montmorillonite, so the peak heat release rate and the total smoke generation are reduced. However, when the amount of the organic montmorillonite added exceeds 0.5%, the spinneret holes are clogged, which has a certain influence on the spinning process and also sharply decreases the breaking strength and breaking elongation.
It can be seen from examples 7-9 that with the addition of tetrapod-like zinc oxide whiskers, the peak heat release rate and the total amount of smoke generated also decreased, because zinc oxide has a significant catalytic effect on carbon formation. In addition, when the tetrapod-like zinc oxide whiskers contact with bacteria, zinc ions are slowly released. Because zinc ions have redox property, the zinc ions can be combined with cell membranes and membrane proteins, break enzymes of an electron transfer system after entering cells, and react with-SH groups to achieve the aim of antibiosis. After killing bacteria, zinc ions can be dissociated from cells, and the process is repeated, so that a good sterilization effect can be achieved by a small amount of addition.
It can be seen from examples 10 to 12 that after the organic montmorillonite and the tetrapod-like zinc oxide whiskers are compounded, the heat release rate and the total amount of generated smoke are further reduced, mainly because the tetrapod-like zinc oxide whiskers further promote the organic montmorillonite to be peeled into a lamellar structure in the extrusion granulation process and hinder the agglomeration among the organic montmorillonite, so that the heat transfer and the smoke transfer path are further blocked.
It can be seen from examples 2, 10, 13 and 14 that the addition of only the organized montmorillonite and the tetrapod-like zinc oxide whiskers had no significant effect on the heat release rate and the amount of smoke generation without the addition of the cyclic alkyl phosphonate.
Therefore, in the case that the organic montmorillonite and the tetrapod-like zinc oxide whisker are used together under the condition of adding the cyclic alkyl phosphonate ester, the organic montmorillonite/tetrapod-like zinc oxide/zinc.
While the preferred embodiments of the present invention have been described in detail, it will be understood by those skilled in the art that the invention is not limited thereto, and that various changes and modifications may be made without departing from the spirit of the invention, and the scope of the appended claims is to be accorded the full range of equivalents.

Claims (10)

1. The flame-retardant antibacterial PTT fiber material is characterized by comprising the following components in parts by weight:
Figure FDA0002321659870000011
the nano composite material is one or more than two of nano aluminum oxide, nano organic montmorillonite, nano aluminum hydroxide or nano zinc oxide, and the particle size is 10-1000 nm.
2. The flame-retardant antibacterial PTT fiber material according to claim 1, characterized in that the PTT is poly (1, 3-propylene terephthalate) having an intrinsic viscosity of 0.7-1.1 dL/g.
3. The flame-retardant antibacterial PTT fiber material according to claim 1, wherein the toughening agent is styrene-butadiene-styrene (SBS), ABS high rubber powder, polyurethane elastomer, ethylene-methyl methacrylate copolymer (EMA), ethylene-butyl methacrylate copolymer (EBA), polyolefin elastomer, silicone rubber with a core-shell structure or methyl methacrylate-butadiene-styrene (MBS) or ethylene-methyl acrylate-glycidyl methacrylate copolymer.
4. The flame-retardant antibacterial PTT fiber material according to claim 1, characterized in that the flame retardant is one or more of aromatic phosphates, phosphonates, cyclic alkyl phosphonates or phosphorus-nitrogen flame retardants.
5. The flame-retardant antibacterial PTT fiber material according to claim 4, characterized in that the flame retardant is a cyclic alkyl phosphonate.
6. The flame-retardant antibacterial PTT fiber material according to claim 1, characterized in that the antioxidant is one or two of phosphite antioxidant 168, phosphite antioxidant S-9228, hindered phenol antioxidant 1010, hindered phenol antioxidant 1098 and hindered phenol antioxidant 1076; the lubricant is one or more than two of silicone powder, Pentaerythritol Ester (PETS) and ethylene distearamide.
7. The flame-retardant antibacterial PTT fiber material according to claim 1, wherein the nanocomposite is a mixture of nano-organic montmorillonite and tetrapod-like zinc oxide whiskers; the grain size of the nano organic montmorillonite is 10-30 nm, and the grain size of the tetrapod-like zinc oxide whisker is 10-100 nm.
8. The flame-retardant antibacterial PTT fiber material according to claim 1, characterized in that the flame-retardant antibacterial PTT fiber material comprises the following components in parts by weight:
Figure FDA0002321659870000021
9. the flame-retardant antibacterial PTT fiber material according to claim 1, characterized in that the flame-retardant antibacterial PTT fiber material comprises the following components in parts by weight:
Figure FDA0002321659870000022
10. a method for preparing a flame retardant antibacterial PTT fiber according to any one of claims 1 to 9, comprising the steps of:
s1, preparing raw materials according to the weight part ratio, putting the raw materials into a premixer to uniformly mix the raw materials, heating the raw materials to 60 ℃, and then preserving the heat for 15 minutes to obtain a premix;
s2, adding the premix obtained in the step S1 into a double-screw extruder, extruding and pelletizing to obtain a PTT material, wherein the rotating speed of a charging barrel of the double-screw extruder is 15-35rpm, and the temperature of the charging barrel is 220-270 ℃;
s3, melting and spinning the PTT material prepared in the step S2 to prepare PTT fibers, wherein the temperature of a material cylinder of the melting and spinning is 220-270 ℃, the stretching multiple is 4-5 times, and the temperature of a roller is 80-120 ℃.
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