CN113774510B - Preparation method of expanded graphite polyester flame-retardant fabric - Google Patents
Preparation method of expanded graphite polyester flame-retardant fabric Download PDFInfo
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- CN113774510B CN113774510B CN202110989607.7A CN202110989607A CN113774510B CN 113774510 B CN113774510 B CN 113774510B CN 202110989607 A CN202110989607 A CN 202110989607A CN 113774510 B CN113774510 B CN 113774510B
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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
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
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- 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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- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to the field of functional fibers, and discloses a preparation method of an expanded graphite polyester flame-retardant fabric, which comprises the following steps: (1) preparing a polyester chip: adding the expanded graphite nano powder into ethylene glycol, and uniformly stirring to obtain a dispersion liquid; adding terephthalic acid, ethylene glycol and a catalyst into the dispersion liquid, pulping, and performing esterification and polycondensation reaction to obtain the expanded graphite flame-retardant polyester chip; the mass of the expanded graphite nano powder is 3.5-6% of that of the expanded graphite flame-retardant polyester chip; (2) spinning: drying the expanded graphite flame-retardant polyester chips, and then carrying out melt spinning, and obtaining the stretched elasticized yarn after cross-air cooling, bundling oiling, drafting and elasticizing; (3) staining. According to the invention, the nano-scale expanded graphite is added in the polyester synthesis process, so that the prepared polyester fabric has excellent flame retardant property, does not have the phenomenon of melting and dripping, has good spinning condition in the spinning process, and does not have the phenomenon of filter blockage.
Description
Technical Field
The invention relates to the field of functional fibers, in particular to a preparation method of an expanded graphite terylene flame-retardant fabric.
Background
Among all synthetic fiber types, polyester (polyester) fiber accounts for more than 60% of the world synthetic fiber yield, and is the most widely used synthetic fiber type. The fiber is mainly applied to special textile fabrics of clothing fabrics, decorative materials, automobile roofs, medical antibacterial curtains, national defense and military industry and other industrial fiber products. Along with the continuous and rapid increase of the economy of China and the continuous increase of the consumption capability of domestic residents, the demand of polyester staple fibers in domestic areas is also continuously increased. However, as the polyester itself has no flame retardance, the oxygen index of the polyester is only about 20, the fiber product belongs to the inflammable grade, and along with the expansion of the application field of the polyester industrial yarn, the demand for flame-retardant products of the polyester industrial yarn is increasing.
At present, three solutions to the terylene flame-retardant field are respectively that a flame retardant is added as a monomer for copolymerization flame retardance, a flame retardant coating is added for post treatment to flame retardant on the surface of the fiber, and an inorganic flame-retardant master batch or a flame retardant and polyester are added for blending flame retardance, wherein the former is a chemical method, and the latter two are physical methods.
For example, the application number is CN201410240063.4, a preparation method of phosphorus copolymerized flame-retardant regenerated polyester chips is that foam materials obtained by melting polyester waste materials are dried and melted by a screw to obtain regenerated polyester melt, a flame-retardant regulating agent is added into the regenerated polyester melt, then a homogenization polymerization reaction is carried out in a homogenization reaction kettle, then the melt is filtered, discharged and granulated to obtain flame-retardant regenerated polyester chips, and then the chips are melted and spun by a screw extrusion spinneret plate, drawn and heat-set to obtain flame-retardant polyester. However, the viscosity of the regenerated slices is not easy to control in the traditional slices, and the addition amount of the flame retardant has a large influence on polymerization, so that the polymerization is not easy to be performed when the addition amount is higher.
For example, the paint of the flame-retardant PVC coating cloth of the polyester filaments, which is related to the application number CN201110318064.2, comprises 70-78 parts of polyvinyl chloride paste resin, 2-6 parts of acetyl tributyl citrate, 20-30 parts of light calcium carbonate, 21-32 parts of reinforcing agent, 80-120 parts of epoxidized soybean oil, 220-280 parts of dioctyl ester, 150-260 parts of paraffin, 120-180 parts of solution polymerized styrene-butadiene rubber and 80-140 parts of flame retardant to increase the flame retardance of the flame retardant. The defects are that the polyester surface has fewer reactive groups, the flame retardant coating only forms a flame retardant film, the fastness is poor, the polyester surface is greatly influenced by external conditions, and the polyester surface has a certain service life.
Compared with the problems in the former two flame-retardant methods, the blending flame retardant is a flame-retardant polyester yarn prepared by physically mixing polyester chips with inorganic flame-retardant master batches or flame retardants, drying, melting, extruding by a screw rod to a spinneret plate for spinning, drafting and heat setting, and blending and spinning. The method has the characteristics of simple operation, no need of large adjustment in the traditional spinning process, high flame retardant property and fastness and the like, and is widely applied to the production of flame retardant polyester. For example, a graphene terylene flame retardant fabric with the patent number of CN201810040880.3 has the graphene content of 1.5-3.5 percent, and is used for preparing a silicon dioxide-graphene composite porous material, preparing a graphene dispersion suspension, preparing a mixed functional master batch, melt spinning, cooling, forming and drafting. The defect is that graphene is high in cost and not easy to mass produce, and secondly, the problem of melting and dripping of PET polyester exists.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and provides a preparation method of an expanded graphite terylene flame-retardant fabric, wherein nano-scale expanded graphite is added in the polyester synthesis process, so that the prepared terylene fabric has excellent flame-retardant property, does not have the phenomenon of melting and dripping, has good spinning condition in the spinning process, and does not have the phenomenon of filter blockage.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method of an expanded graphite terylene flame retardant fabric comprises the following steps:
(1) Preparing polyester chips: adding the expanded graphite nano powder into ethylene glycol, and uniformly stirring to obtain a dispersion liquid; adding terephthalic acid, ethylene glycol and a catalyst into the dispersion liquid, pulping, and performing esterification and polycondensation reaction to obtain the expanded graphite flame-retardant polyester chip; the mass of the expanded graphite nano powder is 3.5-6% of that of the expanded graphite flame-retardant polyester chip;
(2) Spinning: drying the expanded graphite flame-retardant polyester chips, and then carrying out melt spinning, and obtaining the stretched elasticized yarn after cross-air cooling, bundling oiling, drafting and elasticizing;
(3) Dyeing: weaving the stretched elasticized yarn, dyeing, reducing and cleaning, and finally performing heat setting to obtain the terylene flame retardant fabric.
According to the invention, nano-scale expanded graphite is added in the polyester synthesis process, the adding mode and the adding time point of the expanded graphite nano-powder are controlled, so that the expanded graphite nano-powder can be uniformly dispersed and blended in the polyester, when the fabric is heated to a certain degree, the expanded graphite can start to expand, so that a very thick porous carbonized layer is formed, and the carbonized layer has enough thermal stability to separate the fabric from a heat source, so that the decomposition of the polymer is delayed and stopped, and a good flame retardant effect is achieved; and the expanded graphite is nontoxic, does not generate toxic and corrosive gas when heated, can greatly reduce the smoke amount, and does not have the phenomenon of melting and dripping. Meanwhile, the dispersion performance of the expanded graphite nano powder added in the mode of the invention in the polyester is well controlled, the spinning condition is good in the spinning process, and the filter is not blocked.
Preferably, the ratio of the total amount of ethylene glycol added in step (1) to the amount of terephthalic acid is 1.15-1.35:1; the addition amount of the catalyst is 0.02-0.06% of the mass of terephthalic acid.
Preferably, the reaction conditions for the esterification and polycondensation reactions in step (1) are:
esterification reaction: heating to 230-270 ℃ at a heating rate of 1.5-2.5 ℃/min for esterification reaction for 3-5 h;
pre-polycondensation: heating to 245-255 ℃ after the esterification reaction, vacuumizing in 50-60 min until the vacuum degree is 1800-2200 Pa, and reacting for 1.5-3 h;
and (3) final polycondensation: heating to 273-282 deg.c after pre-polycondensation, vacuum pumping to 60-80 Pa and polycondensation for 2-3 hr.
Preferably, the drying conditions of the expanded graphite flame-retardant polyester chips in the step (2) are as follows: drying at 135-145 deg.c for 10-20 min and then at 145-155 deg.c for 8-10 hr.
Preferably, the size of the filter screen in the spinning pack used in the melt spinning in the step (2) is 200 to 250 mesh. The invention ensures the uniform dispersion of the expanded graphite nano powder in the polyester fiber by controlling the mesh number of the filter screen, and improves the flame retardant property of the fiber while ensuring good spinning condition.
Preferably, the oiling agent used in the step (2) for cluster oiling comprises the following components in parts by weight: 40-50 parts of high-temperature resistant smoothing agent, 44.5-55 parts of degradable environment-friendly emulsifier, 5-7 parts of degradable antistatic agent and 0.1-0.5 part of oil stabilizer; the high-temperature-resistant smoothing agent comprises the components of polyol ester, fatty acid ester and refined vegetable oil in a mass ratio of 17-20:15-20:5-10; the components of the degradable environment-friendly emulsifier comprise cardanol polyoxyethylene ether with HLB values of 4.5, 7, 7.5, 9, 9.5 and 13 respectively; the mass ratio of the cardanol polyoxyethylene ether with the HLB value of 4.5, 7, 7.5, 9, 9.5 and 13 is 7-9:14-17:4.5-5:4-5:7-9:8-11; the degradable antistatic agent comprises cardanol polyoxyethylene ether phosphate.
In the polyester spinning oil in the prior art, raw materials are generally nondegradable or have low degradation degree in a short period, so that the oil is directly high in treatment cost, large in treatment period and high in treatment technical requirement; therefore, the oil agent of the invention selects the polyol ester, the fatty acid ester and the refined vegetable oil as the smoothing agent, does not contain mineral oil which is difficult to degrade, has no toxicity, low smell and strong biodegradability, and simultaneously has excellent lubricity and stability, high flash point, high temperature resistance, low volatility and good wear resistance.
The cardanol polyoxyethylene ether with specific HLB value is selected as the degradable environment-friendly emulsifier, and compared with the traditional fatty alcohol polyoxyethylene ether emulsifier, the cardanol polyoxyethylene ether has the advantages of higher cloud point, lower foam performance, better detergency, lower toxicity and easier biodegradation, and the emulsifying power and the hard water resistance are equivalent; meanwhile, the research of the invention discovers that the HLB value of the cardanol polyoxyethylene ether has a great influence on the stability of the oiling agent, when the cardanol polyoxyethylene ether with a single HLB value is adopted as an emulsifier, the oiling agent cannot have good stability, and the oiling agent with good stability can be obtained only by proportioning the cardanol polyoxyethylene ethers with different HLB values according to a specific proportion, so that the oiling agent meets the spinning requirement.
The cardanol polyoxyethylene ether phosphate is selected as the degradable antistatic agent in the oiling agent, compared with the traditional alkyl phosphate and fatty alcohol polyoxyethylene ether phosphate antistatic agent, the biodegradability of the agent is improved, so that the oiling agent is more environment-friendly, the moisture absorption of fibers can be improved, the dynamic friction coefficient between the fibers can be better adjusted, the agent can be adsorbed on the surfaces of the fibers in the high-speed spinning process, the conductivity is improved, and the accumulation of static electricity is reduced.
Preferably, the preparation method of the cardanol polyoxyethylene ether phosphate comprises the following steps:
a) Heating cardanol polyoxyethylene ether to 40-50 ℃, then adding phosphorus pentoxide under stirring, and reacting for 2-4 h at 60-70 ℃; adding water and hydrogen peroxide with the mass fraction of 20-30%, reacting for 1-3 h at 70-80 ℃, and cooling to room temperature to obtain an intermediate; the mass ratio of the added cardanol polyoxyethylene ether to the phosphorus pentoxide is 58-62:11-12; the mass volume ratio of the cardanol polyoxyethylene ether to the added water is 58-62 kg:4L; the volume ratio of the added water to the hydrogen peroxide is 4:2.5-3.8;
b) Heating the intermediate to 40-50 ℃, then dropwise adding phosphorus pentoxide and cardanol polyoxyethylene ether in a stirring state, and reacting for 2-4 h at 60-70 ℃; adding water and hydrogen peroxide with the mass fraction of 20-30%, reacting for 1-3 hours at 70-80 ℃, and cooling to room temperature to obtain the cardanol polyoxyethylene ether phosphate; wherein the mass ratio of the added intermediate to the phosphorus pentoxide to the cardanol polyoxyethylene ether is 34-36:21-22:97-98; the mass volume ratio of the intermediate to the added water is 34-36 kg:3L; the volume ratio of the added water to the hydrogen peroxide is 3:2-3.
The traditional polyoxyethylene ether phosphate is generally prepared by directly carrying out phosphorylation reaction on polyoxyethylene ether and phosphorus pentoxide, but because the reaction emits a large amount of heat, the product is easy to coke and has darker color, and the color of the prepared polyester fiber can be influenced when the polyoxyethylene ether phosphate is used in spinning oil. The preparation method comprises the steps of carrying out two-step reaction in the preparation of the cardanol polyoxyethylene ether phosphate, firstly reacting a part of cardanol polyoxyethylene ether with phosphorus pentoxide to obtain an intermediate, and then reacting the intermediate with cardanol polyoxyethylene ether and phosphorus pentoxide to finally obtain the cardanol polyoxyethylene ether phosphate. The cardanol polyoxyethylene ether phosphate monoester prepared by the method has the content of 77%, the conversion rate of 97%, and can effectively avoid coking of products and control the color of the products, thereby avoiding the influence of the color of the oiling agent on the color of the fiber and being beneficial to the subsequent dyeing of the fabric.
Preferably, the dye dosage in the step (3) is 3-7% of the fabric weight, the bath ratio is 1:8-10, the degreasing agent dosage is 0.8-1.2 g/L, and the pH of the dye liquor is 4-5; the dyeing condition is that the dyeing is started from 25-35 ℃, the temperature is raised to 85-95 ℃ at the temperature raising rate of 1.5-2.5 ℃/min, the temperature is kept for 20-30 min, the temperature is raised to 125-135 ℃ at the temperature raising rate of 0.5-1.5 ℃/min, the temperature is kept for 35-45 min, and the dyeing pressure is 0.3-0.5 MPa.
Preferably, the reduction cleaning conditions in step (3) are: the bath ratio is 1:8-10, naOH with the concentration of 1.5-2.5 g/L and sodium hydrosulfite with the concentration of 1.5-2.5 g/L are added, the temperature is 75-85 ℃ and the time is 20-40 min.
Preferably, the heat setting temperature in the step (3) is 165-175 ℃, and the heat setting time is 0.5-1.5 min.
Therefore, the invention has the following beneficial effects:
(1) The nano-scale expanded graphite is added in the polyester synthesis process, so that the prepared polyester fabric has excellent flame retardant property, does not have the phenomenon of melting and dripping, has good spinning condition in the spinning process, and does not have the phenomenon of filter blockage;
(2) Most of raw materials in the oiling agent used in the spinning process have the characteristic of easy biodegradation, so that the oiling agent not only meets the requirement of on-machine production, but also can improve the degradation degree of the oiling agent, reduce the treatment cost of the oiling agent and greatly improve the environmental protection property of the oiling agent;
(3) The preparation method of the antistatic agent in the oiling agent is optimized, and the color of the product is controlled, so that the influence of the color of the oiling agent on the color of the fiber is avoided, and the subsequent dyeing of the fabric is facilitated.
Detailed Description
The invention is further described below in connection with the following detailed description.
In the present invention, all the equipment and raw materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
a preparation method of an expanded graphite terylene flame retardant fabric comprises the following steps:
(1) Preparing polyester chips: adding expanded graphite nano powder (Qingdao Tianyuan graphite Co., ltd.) into ethylene glycol, and stirring uniformly to obtain a dispersion; adding terephthalic acid, ethylene glycol and an Sb catalyst into the dispersion liquid, pulping, and performing esterification and polycondensation reaction to obtain the expanded graphite flame-retardant polyester chip; wherein the mass of the expanded graphite nano powder is 5% of the mass of the expanded graphite flame-retardant polyester chip, and the ratio of the total amount of added ethylene glycol to the amount of terephthalic acid is 1.25:1; the addition amount of the Sb catalyst is 0.04% of the mass of terephthalic acid;
the reaction conditions are specifically as follows: esterification reaction: heating to 250 ℃ at a heating rate of 2 ℃/min for esterification reaction for 4 hours; pre-polycondensation: heating to 250 ℃ after the esterification reaction, vacuumizing to the vacuum degree of 2000Pa within 55min, and reacting for 2h; and (3) final polycondensation: after pre-polycondensation, the temperature is raised to 280 ℃, the vacuum is pumped to 70Pa, and the polycondensation reaction is carried out for 2.5 hours.
(2) Spinning: drying the expanded graphite flame-retardant polyester chips, and then carrying out melt spinning, and obtaining the stretched elasticized yarn after cross-air cooling, bundling oiling, drafting and elasticizing;
wherein the slice drying conditions are as follows: drying at 140 ℃ for 15min, and then drying at 150 ℃ for 9h;
the spinning process comprises the following steps: screw temperature (screw one zone temperature: 290 ℃, two zone temperature: 293 ℃, three zone temperature: 296 ℃, four zone temperature: 299 ℃, five zone temperature: 302 ℃, six zone temperature: 305 ℃), filter (filtration size: 200 mesh), box (spinning box temperature: 285 ℃), side blow (wind speed: 0.4m/s, nozzle tip: cluster oiling), pre-wire netting device (0.08 MPa), -first hot roller (90 ℃) -second hot roller (125 ℃) -main wire netting device (0.35 MPa), winding forming (4800 m/min); the oiling agent used in the cluster oiling process comprises the following raw materials in parts by weight:
40 parts of high-temperature resistant smoothing agent, wherein 20 parts of environment-friendly polyol ester (Shandong Rui, neopentyl glycol dioleate), 15 parts of fatty acid ester (sea-safe petrochemical, isooctyl stearate) and 5 parts of refined vegetable oil (Shanghai Chen-expensive canola oil);
54.9 parts of degradable environment-friendly emulsifier, 8.6 parts of cardanol polyoxyethylene ether with an HLB value of 4.5 and 17 parts of cardanol polyoxyethylene ether with an HLB value of 7; 5 parts of cardanol polyoxyethylene ether with an HLB value of 7.5; 5 parts of cardanol polyoxyethylene ether with an HLB value of 9, 8.6 parts of cardanol polyoxyethylene ether with an HLB value of 9.5 and 10.7 parts of cardanol polyoxyethylene ether with an HLB value of 13;
the preparation method of the cardanol polyoxyethylene ether comprises the following steps: pressing cashew nut shells to obtain cashew nut shell oil; refining the cashew nut shell oil to obtain cardanol; 157kg of cardanol is put into a stainless steel reaction kettle, and 2.5kg of sodium hydroxide solution prepared by dissolving sodium hydroxide in 30kg of water is added; after the materials are added, electric induction heating is used, and after water vapor and air are pumped out under reduced pressure, nitrogen is introduced to replace the air in the kettle; and (3) filling nitrogen into the kettle, pressing ethylene oxide into the kettle, uniformly heating the kettle to 135 ℃, reacting the kettle at 135 ℃ for 5 hours, cooling the kettle to 80 ℃ after the reaction is finished, and neutralizing the product with acetic acid to obtain the cardanol polyoxyethylene ether. The cardanol polyoxyethylene ether with different HLB values is obtained by adjusting the adding proportion of the ethylene oxide and the cardanol;
7 parts of degradable antistatic agent, namely cardanol polyoxyethylene ether phosphate is adopted as the degradable antistatic agent, and the preparation method comprises the following steps: a) Heating 60kg of cardanol polyoxyethylene ether to 45 ℃, then adding 11.7kg of phosphorus pentoxide under stirring, and reacting for 3 hours at 65 ℃; then adding 4L of water and 30wt% of hydrogen peroxide solution 2.5L, carrying out hydrolysis reaction for 2 hours at 75 ℃, and cooling to room temperature to obtain an intermediate; b) Heating 35kg of intermediate to 45 ℃, then dropwise adding 21.3kg of phosphorus pentoxide and 97.8kg of cardanol polyoxyethylene ether under stirring, and reacting for 3h at 65 ℃; adding 3L of water and 30wt% of hydrogen peroxide 2L, reacting for 2 hours at 75 ℃, and cooling to room temperature to obtain the cardanol polyoxyethylene ether phosphate;
0.1 part of oil stabilizer (Dow chemical, triethanolamine).
(3) Dyeing: the stretched textured yarn was woven to a grammage of 150g/m 2 The weft jersey is dyed, reduced and cleaned, and finally heat-set to obtain the terylene flame retardant fabric;
the dyeing process comprises the following steps: the dosage of the SHF-BRS reactive blue dye is 5% of the weight of the fabric, the bath ratio is 1:9, the dosage of the degreasing agent DS-1130 is 1.0g/L, and the pH of the dye liquor is 4.5; the dyeing condition is that the dyeing is started from 30 ℃, the temperature is increased to 90 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 25min, the temperature is increased to 130 ℃ at the heating rate of 2 ℃/min, the temperature is kept for 40min, and the dyeing pressure is 0.4MPa;
the reduction cleaning process comprises the following steps: the bath ratio is 1:9, naOH 2g/L and sodium hydrosulfite 2g/L are added, the temperature is 80 ℃, and the time is 30min; and (3) heat setting process: the temperature is 170 ℃, and the heat setting time is 1min.
Example 2:
a preparation method of an expanded graphite terylene flame retardant fabric comprises the following steps:
(1) Preparing polyester chips: adding expanded graphite nano powder (Qingdao Tianyuan graphite Co., ltd.) into ethylene glycol, and stirring uniformly to obtain a dispersion; adding terephthalic acid, ethylene glycol and an Sb catalyst into the dispersion liquid, pulping, and performing esterification and polycondensation reaction to obtain the expanded graphite flame-retardant polyester chip; wherein the mass of the expanded graphite nano powder is 3.5% of the mass of the expanded graphite flame-retardant polyester chip, and the ratio of the total amount of added ethylene glycol to the amount of terephthalic acid is 1.15:1; the addition amount of the Sb catalyst is 0.02% of the mass of terephthalic acid;
the reaction conditions are specifically as follows: esterification reaction: heating to 230 ℃ at a heating rate of 1.5/min ℃ for esterification reaction for 5h; pre-polycondensation: heating to 245 ℃ after the esterification reaction, vacuumizing to 1800Pa within 50min, and reacting for 3h; and (3) final polycondensation: after pre-polycondensation, the temperature is raised to 273 ℃, the vacuum is pumped to 60Pa, and the polycondensation reaction is carried out for 3 hours.
(2) Spinning: drying the expanded graphite flame-retardant polyester chips, and then carrying out melt spinning, and obtaining the stretched elasticized yarn after cross-air cooling, bundling oiling, drafting and elasticizing;
wherein the slice drying conditions are as follows: drying at 135 deg.C for 20min, and then at 145 deg.C for 10 hr;
the spinning process comprises the following steps: screw temperature (screw one zone temperature: 290 ℃, two zone temperature: 293 ℃, three zone temperature: 296 ℃, four zone temperature: 299 ℃, five zone temperature: 302 ℃, six zone temperature: 305 ℃), filter (filtration size: 200 mesh), box (spinning box temperature: 285 ℃), side blow (wind speed: 0.4m/s, nozzle tip: cluster oiling), pre-wire netting device (0.08 MPa), -first hot roller (90 ℃) -second hot roller (125 ℃) -main wire netting device (0.35 MPa), winding forming (4800 m/min); the oiling agent used in the cluster oiling process comprises the following raw materials in parts by weight:
44 parts of high-temperature resistant smoothing agent, wherein 17 parts of environment-friendly polyol ester (Shandong Rui Jie, pentaerythritol), 20 parts of fatty acid ester (sea-Anpetrifaction, trimethylolpropane oleate) and 7 parts of refined vegetable oil (Shanghai Chen-expensive canola oil);
49.9 parts of degradable environment-friendly emulsifier, wherein 7.8 parts of cardanol polyoxyethylene ether with an HLB value of 4.5 and 15.5 parts of cardanol polyoxyethylene ether with an HLB value of 7; 4.7 parts of cardanol polyoxyethylene ether with an HLB value of 7.5; 4.7 parts of cardanol polyoxyethylene ether with an HLB value of 9, 7.7 parts of cardanol polyoxyethylene ether with an HLB value of 9.5 and 9.5 parts of cardanol polyoxyethylene ether with an HLB value of 13; the preparation method of cardanol polyoxyethylene ether was the same as in example 1;
7 parts of degradable antistatic agent, namely cardanol polyoxyethylene ether phosphate is adopted as the degradable antistatic agent, and the preparation method comprises the following steps: a) 58kg of cardanol polyoxyethylene ether is heated to 40 ℃, then 11kg of phosphorus pentoxide is added under stirring, and the mixture reacts for 4 hours at 60 ℃; then adding 4L of water and 25wt% of hydrogen peroxide solution 3L, carrying out hydrolysis reaction for 3 hours at 70 ℃, and cooling to room temperature to obtain an intermediate; b) 34kg of intermediate is heated to 40 ℃, 21kg of phosphorus pentoxide and 97kg of cardanol polyoxyethylene ether are then added dropwise under stirring, and the mixture is reacted for 4 hours at 60 ℃; adding 3L of water and 25wt% of hydrogen peroxide solution 2.4L, reacting for 3 hours at 70 ℃, and cooling to room temperature to obtain the cardanol polyoxyethylene ether phosphate;
0.3 part of oil stabilizer (Dow chemical, triethanolamine).
(3) Dyeing: the stretched textured yarn was woven to a grammage of 150g/m 2 The weft jersey is dyed, reduced and cleaned, and finally heat-set to obtain the terylene flame retardant fabric;
the dyeing process comprises the following steps: the dosage of the SHF-BRS reactive blue dye is 3% of the weight of the fabric, the bath ratio is 1:8, the dosage of the degreasing agent DS-1130 is 0.8g/L, and the pH of the dye liquor is 4.1; the dyeing condition is that the dyeing is started from 25 ℃, the temperature is raised to 85 ℃ at the heating rate of 1.5 ℃/min, the temperature is kept for 30min, the temperature is raised to 125 ℃ at the heating rate of 0.5 ℃/min, the temperature is kept for 45min, and the dyeing pressure is 0.5MPa;
the reduction cleaning process comprises the following steps: the bath ratio is 1:8, naOH with the concentration of 1.5g/L and sodium hydrosulfite with the concentration of 1.5g/L are added, the temperature is 75 ℃, and the time is 40min;
and (3) heat setting process: the temperature is 165 ℃, and the heat setting time is 1.5min.
Example 3:
a preparation method of an expanded graphite terylene flame retardant fabric comprises the following steps:
(1) Preparing polyester chips: adding expanded graphite nano powder (Qingdao Tianyuan graphite Co., ltd.) into ethylene glycol, and stirring uniformly to obtain a dispersion; adding terephthalic acid, ethylene glycol and an Sb catalyst into the dispersion liquid, pulping, and performing esterification and polycondensation reaction to obtain the expanded graphite flame-retardant polyester chip; wherein the mass of the expanded graphite nano powder is 6% of the mass of the expanded graphite flame-retardant polyester chip, and the ratio of the total amount of added ethylene glycol to the amount of terephthalic acid is 1.35:1; the addition amount of the Sb catalyst is 0.06% of the mass of terephthalic acid;
the reaction conditions are specifically as follows: esterification reaction: heating to 270 ℃ at a heating rate of 2.5/min ℃ for esterification reaction for 3h; pre-polycondensation: heating to 255 ℃ after the esterification reaction, vacuumizing to 2200Pa in 60min, and reacting for 1.5h; and (3) final polycondensation: heating to 282 ℃ after pre-polycondensation, vacuumizing to 80Pa, and carrying out polycondensation reaction for 2h.
(2) Spinning: drying the expanded graphite flame-retardant polyester chips, and then carrying out melt spinning, and obtaining the stretched elasticized yarn after cross-air cooling, bundling oiling, drafting and elasticizing;
wherein the slice drying conditions are as follows: drying at 145 ℃ for 10min, and then drying at 155 ℃ for 8h;
the spinning process comprises the following steps: screw temperature (screw one zone temperature: 290 ℃, two zone temperature: 293 ℃, three zone temperature: 296 ℃, four zone temperature: 299 ℃, five zone temperature: 302 ℃, six zone temperature: 305 ℃), filter (filtration size: 200 mesh), box (spinning box temperature: 285 ℃), side blow (wind speed: 0.4m/s, nozzle tip: cluster oiling), pre-wire netting device (0.08 MPa), -first hot roller (90 ℃) -second hot roller (125 ℃) -main wire netting device (0.35 MPa), winding forming (4800 m/min); the oiling agent used in the cluster oiling process comprises the following raw materials in parts by weight:
50 parts of high-temperature resistant smoothing agent, wherein 20 parts of environment-friendly polyol ester (Shandong Rui, neopentyl glycol dioleate), 20 parts of fatty acid ester (sea-safe petrochemical, isooctyl stearate) and 10 parts of refined vegetable oil (Shanghai Chen-expensive canola oil);
44.9 parts of degradable environment-friendly emulsifier, wherein 7 parts of cardanol polyoxyethylene ether with an HLB value of 4.5 and 14 parts of cardanol polyoxyethylene ether with an HLB value of 7; 4.5 parts of cardanol polyoxyethylene ether with an HLB value of 7.5; 4 parts of cardanol polyoxyethylene ether with an HLB value of 9, 7 parts of cardanol polyoxyethylene ether with an HLB value of 9.5 and 8.4 parts of cardanol polyoxyethylene ether with an HLB value of 13; the preparation method of cardanol polyoxyethylene ether was the same as in example 1;
5 parts of degradable antistatic agent, wherein the degradable antistatic agent adopts cardanol polyoxyethylene ether phosphate, and the preparation method comprises the following steps: a) 62kg of cardanol polyoxyethylene ether is heated to 50 ℃, then 12kg of phosphorus pentoxide is added under stirring, and the mixture reacts for 2 hours at 70 ℃; then adding 4L of water and 3.8L of 20wt% hydrogen peroxide, carrying out hydrolysis reaction for 1h at 80 ℃, and cooling to room temperature to obtain an intermediate; b) 36kg of intermediate is heated to 50 ℃, 22kg of phosphorus pentoxide and 98kg of cardanol polyoxyethylene ether are then added dropwise under stirring, and the mixture is reacted for 2 hours at 70 ℃; adding 3L of water and 20wt% of hydrogen peroxide solution 3L, reacting for 1h at 80 ℃, and cooling to room temperature to obtain the cardanol polyoxyethylene ether phosphate;
0.5 part of oil stabilizer (Dow chemical, triethanolamine).
(3) Dyeing: the stretched textured yarn was woven to a grammage of 150g/m 2 The weft jersey is dyed, reduced and cleaned, and finally heat-set to obtain the terylene flame retardant fabric;
the dyeing process comprises the following steps: the dosage of the SHF-BRS reactive blue dye is 7% of the weight of the fabric, the bath ratio is 1:10, the dosage of the degreasing agent DS-1130 is 1.2g/L, and the pH of the dye liquor is 5; the dyeing condition is that the dyeing is started from 35 ℃, the temperature is increased to 95 ℃ at the heating rate of 2.5 ℃/min, the temperature is kept for 20min, the temperature is increased to 135 ℃ at the heating rate of 1.5 ℃/min, the temperature is kept for 35min, and the dyeing pressure is 0.3MPa;
the reduction cleaning process comprises the following steps: the bath ratio is 1:10, naOH 2.5g/L and sodium hydrosulfite 2.5g/L are added, the temperature is 85 ℃, and the time is 20min;
and (3) heat setting process: the temperature is 175 ℃, and the heat setting time is 0.5min.
Comparative example 1:
the polyester chips of comparative example 1 were prepared without adding the expanded graphite nano powder, and the rest was the same as in example 1.
Comparative example 2 (expanded graphite nanopowder addition too much):
the mass of the expanded graphite nano powder added in the preparation of the polyester chips in comparative example 2 was 8% of the mass of the expanded graphite flame-retardant polyester chips, and the rest was the same as in example 1.
Comparative example 3 (cardanol polyoxyethylene ether with single HLB value was used in the oil):
in the oiling agent used in the cluster oiling in the spinning process of comparative example 3, the degradable environment-friendly emulsifier was cardanol polyoxyethylene ether with HLB value of 7.5, and the rest was the same as in example 1.
Comparative example 4 (change of HLB value match of cardanol polyoxyethylene ether in oil agent):
comparative example 4 in the oiling agent used in the bundle oiling process, the degradable environment-friendly emulsifier comprises the following components: 8.6 parts of cardanol polyoxyethylene ether with an HLB value of 9; 17 parts of cardanol polyoxyethylene ether with an HLB value of 13; 5 parts of cardanol polyoxyethylene ether with an HLB value of 4.5; 5 parts of cardanol polyoxyethylene ether with an HLB value of 7, 8.6 parts of cardanol polyoxyethylene ether with an HLB value of 7.5 and 10.7 parts of cardanol polyoxyethylene ether with an HLB value of 9.5; the remainder was the same as in example 1.
Comparative example 5 (cardanol polyoxyethylene ether phosphate prepared in one step in oil):
comparative example 5 preparation method of cardanol polyoxyethylene ether phosphate as degradable antistatic agent in oiling agent used in bundle oiling in spinning process comprises: 97.8kg of cardanol polyoxyethylene ether is heated to 45 ℃, then 21.3kg of phosphorus pentoxide is added under stirring, and the mixture reacts for 3 hours at 65 ℃; then adding 3L of water and 30wt% of hydrogen peroxide solution to perform hydrolysis reaction for 2 hours at 75 ℃, and cooling to room temperature to obtain the cardanol polyoxyethylene ether phosphate; the remainder was the same as in example 1.
The performance indexes of the oils prepared in the above examples and comparative examples were tested and the results are shown in table 1.
Table 1: and (5) testing the performance index of the oiling agent.
As can be seen from Table 1, the oil solutions prepared by the formulation of the present invention in examples 1 to 3 have good performance indexes, meet the conditions of spinning test, and are suitable for microorganism growth and have good biodegradability. In comparative example 3, cardanol polyoxyethylene ether with a single HLB value is used as an emulsifier, and the HLB value of cardanol polyoxyethylene ether in the emulsifier is changed in comparative example 4, so that the stability of the oiling agent is reduced, and the oiling agent cannot be stably stored and spun on-machine for trial; in comparative example 5, cardanol polyoxyethylene ether phosphate is prepared by a one-step method as an antistatic agent, and the prepared oiling agent is darker in color and can influence the spinning color, so that the subsequent dyeing of the fabric is influenced.
The properties of the polyester fibers prepared in the above examples and comparative examples were tested, and the results are shown in table 2.
Table 2: and (5) polyester fiber performance test results.
As can be seen from Table 2, the polyester fibers and fabrics prepared by the method in examples 1-3 have an oxygen index of not less than 32%, excellent flame retardant performance and no melt dripping phenomenon during combustion; meanwhile, the fiber has good mechanical property and dyeing property. In comparative example 1, however, the flame retardance of the fabric is significantly reduced without adding the expanded graphite powder to the polyester chips; too much expanded graphite is added in comparative example 2, and beyond the scope of the present invention, the dispersibility of the expanded graphite powder in the fiber is reduced, resulting in reduced spinnability, filter clogging during spinning, and reduced mechanical properties of the fiber and uneven dyeing.
Claims (8)
1. The preparation method of the expanded graphite polyester flame-retardant fabric is characterized by comprising the following steps:
(1) Preparing polyester chips: adding the expanded graphite nano powder into ethylene glycol, and uniformly stirring to obtain a dispersion liquid; adding terephthalic acid, ethylene glycol and a catalyst into the dispersion liquid, pulping, and performing esterification and polycondensation reaction to obtain the expanded graphite flame-retardant polyester chip; the mass of the expanded graphite nano powder is 3.5-6% of that of the expanded graphite flame-retardant polyester chip;
(2) Spinning: drying the expanded graphite flame-retardant polyester chips, and then carrying out melt spinning, and obtaining the stretched elasticized yarn after cross-air cooling, bundling oiling, drafting and elasticizing;
(3) Dyeing: weaving the stretched textured yarn, dyeing, reducing and cleaning, and finally performing heat setting to obtain the terylene flame retardant fabric;
the oiling agent used in the step (2) during the cluster oiling comprises the following components in parts by weight: 40-50 parts of high-temperature resistant smoothing agent, 44.5-55 parts of degradable environment-friendly emulsifier, 5-7 parts of degradable antistatic agent and 0.1-0.5 part of oil stabilizer; the high-temperature-resistant smoothing agent comprises the components of polyol ester, fatty acid ester and refined vegetable oil in a mass ratio of 17-20:15-20:5-10; the components of the degradable environment-friendly emulsifier comprise cardanol polyoxyethylene ether with HLB values of 4.5, 7, 7.5, 9, 9.5 and 13 respectively; the mass ratio of cardanol polyoxyethylene ether with the HLB value of 4.5, 7, 7.5, 9, 9.5 and 13 is 7-9:14-17:4.5-5:4-5:7-9:8-11; the degradable antistatic agent comprises cardanol polyoxyethylene ether phosphate;
the preparation method of the cardanol polyoxyethylene ether phosphate comprises the following steps:
a) Heating cardanol polyoxyethylene ether to 40-50 ℃, adding phosphorus pentoxide in a stirring state, and reacting for 2-4 hours at 60-70 ℃; adding water and hydrogen peroxide with the mass fraction of 20-30%, reacting for 1-3 hours at 70-80 ℃, and cooling to room temperature to obtain an intermediate; the mass ratio of the added cardanol polyoxyethylene ether to the phosphorus pentoxide is 58-62:11-12; the mass volume ratio of the cardanol polyoxyethylene ether to the added water is 58-62 kg:4L; the volume ratio of the added water to the hydrogen peroxide is 4:2.5-3.8;
b) Heating the intermediate to 40-50 ℃, then dropwise adding phosphorus pentoxide and cardanol polyoxyethylene ether in a stirring state, and reacting for 2-4 hours at 60-70 ℃; adding water and hydrogen peroxide with the mass fraction of 20-30%, reacting for 1-3 hours at 70-80 ℃, and cooling to room temperature to obtain the cardanol polyoxyethylene ether phosphate; the mass ratio of the added intermediate to the phosphorus pentoxide to the cardanol polyoxyethylene ether is 34-36:21-22:97-98; the mass volume ratio of the intermediate to the added water is 34-36 kg/3L; the volume ratio of the added water to the hydrogen peroxide is 3:2-3.
2. The method for preparing the expanded graphite polyester flame-retardant fabric according to claim 1, wherein the ratio of the total amount of ethylene glycol added in the step (1) to the amount of terephthalic acid is 1.15-1.35:1; the addition amount of the catalyst is 0.02-0.06% of the mass of terephthalic acid.
3. The method for preparing the expanded graphite polyester flame retardant fabric according to claim 1 or 2, wherein the reaction conditions of the esterification and polycondensation reaction in the step (1) are as follows:
esterification reaction: heating to 230-270 ℃ at a heating rate of 1.5-2.5 ℃/min for esterification reaction for 3-5 h;
pre-polycondensation: heating to 245-255 ℃ after the esterification reaction, vacuumizing within 50-60 min until the vacuum degree is 1800-2200Pa, and reacting for 1.5-3 h;
and (3) final polycondensation: heating to 273-282 ℃ after pre-polycondensation, vacuumizing to 60-80 Pa, and carrying out polycondensation reaction for 2-3 hours.
4. The method for preparing the expanded graphite polyester flame-retardant fabric according to claim 1, wherein the drying conditions of the expanded graphite flame-retardant polyester chips in the step (2) are as follows: drying at 135-145 ℃ for 10-20 min, and then drying at 145-155 ℃ for 8-10 h.
5. The method for preparing the expanded graphite polyester flame-retardant fabric according to claim 1, wherein the size of a filter screen in a spinning assembly used in the melt spinning in the step (2) is 200-250 meshes.
6. The preparation method of the expanded graphite polyester flame-retardant fabric according to claim 1, wherein the dye consumption in the step (3) is 3-7% of the fabric weight, the bath ratio is 1:8-10, the degreasing agent consumption is 0.8-1.2 g/L, and the pH of a dye liquor is 4-5; the dyeing condition is that the dyeing is started from 25-35 ℃, the temperature is raised to 85-95 ℃ at the temperature raising rate of 1.5-2.5 ℃/min, the temperature is kept for 20-30 min, the temperature is raised to 125-135 ℃ at the temperature raising rate of 0.5-1.5 ℃/min, the temperature is kept for 35-45 min, and the dyeing pressure is 0.3-0.5 MPa.
7. The method for preparing the expanded graphite polyester flame retardant fabric according to claim 1 or 6, wherein the reduction cleaning condition in the step (3) is as follows: the bath ratio is 1:8-10, naOH with the concentration of 1.5-2.5 g/L and sodium hydrosulfite with the concentration of 1.5-2.5 g/L are added, the temperature is 75-85 ℃, and the time is 20-40 min.
8. The method for preparing the expanded graphite polyester flame-retardant fabric according to claim 1 or 6, wherein the heat setting temperature in the step (3) is 165-175 ℃, and the heat setting time is 0.5-1.5 min.
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