CN113774510A - 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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- CN113774510A CN113774510A CN202110989607.7A CN202110989607A CN113774510A CN 113774510 A CN113774510 A CN 113774510A CN 202110989607 A CN202110989607 A CN 202110989607A CN 113774510 A CN113774510 A CN 113774510A
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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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- 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 terylene flame-retardant fabric, which 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 then carrying out esterification and polycondensation reaction to obtain expanded graphite flame-retardant polyester chips; 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, then carrying out melt spinning, and carrying out cross air cooling, bundling and oiling, drafting and texturing to obtain drawn textured yarns; (3) and (6) dyeing. 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, the phenomenon of melt dripping cannot occur, the spinning condition is good in the spinning process, and the phenomenon of filter blockage cannot occur.
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
In all the synthetic fiber varieties today, polyester (polyester) fiber accounts for over 60% of the world's synthetic fiber production and is the most widely used synthetic fiber variety. The fiber is mainly applied to special textile fabrics such as clothing fabrics, decorative materials, automobile roofs, medical antibacterial curtains, national defense and military industry and the like and other industrial fiber products. With the continuous and rapid increase of the economy of China and the continuous improvement of the consumption capacity of domestic residents, the demand of the polyester staple fibers in domestic areas is also continuously increased. However, polyester has no flame retardance, the oxygen index of the polyester is only about 20, the fiber product belongs to a flammable grade, and the requirement on the flame retardant product is increased along with the expansion of the application field of the polyester industrial yarn.
At present, three solutions in the field of polyester flame retardance are respectively that a flame retardant is added as a monomer for copolymerization flame retardance, a flame retardant coating is added for post-treatment for flame retardance on the surface of a fiber, inorganic flame-retardant master batches are added, or the flame retardant and polyester are blended for 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 method for preparing a phosphorus-based copolymerization flame-retardant recycled polyester chip comprises the steps of drying bubble materials obtained by melting polyester waste materials, melting by a screw to obtain a recycled polyester melt, adding a flame-retardant modulating agent into the recycled polyester melt, carrying out a homogenization polymerization reaction in a homogenization reaction kettle, filtering, discharging and dicing the melt to obtain the flame-retardant recycled polyester chip, melting the chip, extruding the chip by the screw to a spinneret for spinning, and carrying out drafting and heat setting to obtain the flame-retardant polyester. However, the viscosity of the conventional slice is difficult to control due to the regenerated slice, and the addition amount of the flame retardant has a large influence on polymerization, so that the polymerization is difficult when the addition amount is higher.
For example, the coating of flame-retardant PVC coated cloth of polyester filament yarn with application number CN201110318064.2 comprises 70-78 parts of polyvinyl chloride paste resin, 2-6 parts of acetyl tri-n-butyl citrate, 20-30 parts of light calcium carbonate, 21-32 parts of reinforcing agent, 80-120 parts of epoxidized soybean oil, 280 parts of dioctyl ester, 260 parts of paraffin wax, 180 parts of solution polymerized styrene-butadiene rubber and 80-140 parts of flame retardant, so as to increase the flame retardance of the flame retardant. The defects are that the polyester surface reaction groups are less, the coating is flame-retardant and only forms a flame-retardant film, the fastness is poor, the influence of external conditions is large, and the service life is long.
Compared with the problems in the two flame-retardant methods, the blending flame-retardant is a flame-retardant polyester yarn prepared by physically mixing the polyester chips with the inorganic flame-retardant master batch or the flame retardant, drying, melting, extruding by a screw rod to a spinneret plate for spinning, drafting for heat setting and blending for 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 polyester flame-retardant fabric disclosed in patent No. CN201810040880.3, which has a graphene content of 1.5-3.5%, is prepared by preparing a silica-graphene composite porous material, preparing a graphene dispersion suspension, preparing a mixed functional master batch, melt spinning, cooling, molding, and drawing. The defects are that the cost of the graphene is high, the mass production is not easy, and secondly, the PET polyester has the problem of melting and dripping.
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 the nanoscale expanded graphite is added in the polyester synthesis process, so that the prepared terylene fabric has excellent flame-retardant property, the phenomenon of melt dripping cannot occur, the spinning condition is good in the spinning process, and the phenomenon of filter blockage cannot occur.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an expanded graphite polyester 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 then carrying out esterification and polycondensation reaction to obtain expanded graphite flame-retardant polyester chips; 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, then carrying out melt spinning, and carrying out cross air cooling, bundling and oiling, drafting and texturing to obtain drawn textured yarns;
(3) dyeing: and weaving the stretch yarn, then dyeing, reducing and cleaning, and finally carrying out heat setting to obtain the polyester flame-retardant fabric.
According to the invention, the nano-scale expanded graphite is added in the polyester synthesis process, and 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 begin to expand, and a very thick porous carbonization layer is formed, and the carbonization layer has enough thermal stability to separate the fabric from a heat source, so that the decomposition of the polymer is delayed and terminated, and a good flame retardant effect is achieved; and the expanded graphite is nontoxic, does not generate toxic and corrosive gas when being heated, can greatly reduce the smoke quantity, and does not have the phenomenon of melting and dripping. Meanwhile, the dispersibility of the expanded graphite nano powder added by the method of the invention in the polyester can be well controlled, the spinning condition is good in the spinning process, and the filter cannot be blocked.
Preferably, the ratio of the total mass of the ethylene glycol to the mass of the terephthalic acid added in the step (1) is 1.15-1.35: 1; the addition amount of the catalyst is 0.02-0.06% of the mass of the terephthalic acid.
Preferably, the reaction conditions of 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 within 50-60 min until the vacuum degree is 1800-2200 Pa, and reacting for 1.5-3 h;
final polycondensation: heating to 273-282 ℃ after pre-polycondensation, vacuumizing to 60-80 Pa, and performing polycondensation reaction for 2-3 h.
Preferably, the drying conditions of the expanded graphite flame-retardant polyester chip 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.
Preferably, the size of the filter screen in the spinning assembly used in the melt spinning in the step (2) is 200-250 meshes. The invention ensures the even 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 oil agent used in the cluster oiling in the step (2) 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 17-20: 15-20: 5-10 parts by mass of polyol ester, fatty acid ester and refined vegetable oil; the degradable environment-friendly emulsifier comprises 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 HLB values 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 treatment cost of the oil is high, the treatment period is large, and the treatment technical requirement is high; 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, strong biodegradability, excellent lubricity and stability, high flash point, high temperature resistance, low volatility and good abrasion resistance.
The cardanol polyoxyethylene ether matched with a specific HLB value is used as a degradable environment-friendly emulsifier, compared with the traditional fatty alcohol polyoxyethylene ether emulsifier, the cardanol polyoxyethylene ether has the advantages of equivalent emulsifying power and hard water resistance, higher cloud point, lower foam performance, better detergency, lower toxicity and easier biodegradation; meanwhile, the research of the invention finds 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 only by proportioning the cardanol polyoxyethylene ethers with different HLB values according to a specific proportion, the oiling agent with good stability can be obtained, so that the oiling agent meets the spinning requirement.
The oil agent used in the invention adopts cardanol polyoxyethylene ether phosphate as a degradable antistatic agent, compared with the traditional alkyl phosphate and fatty alcohol polyoxyethylene ether phosphate antistatic agent, the biodegradability of the oil agent is improved, the oil agent is more environment-friendly, meanwhile, the antistatic agent can increase the moisture absorption of the fibers, can well adjust the dynamic friction coefficient between the fibers, can be adsorbed on the surfaces of the fibers in the high-speed spinning process, improves the conductivity, and reduces the accumulation of static electricity.
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 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 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 under a stirring state, and reacting for 2-4 h at 60-70 ℃; adding water and 20-30% by mass of hydrogen peroxide, reacting for 1-3 h at 70-80 ℃, and cooling to room temperature to obtain the cardanol polyoxyethylene ether phosphate; wherein the mass ratio of the added intermediate, phosphorus pentoxide and 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 preparation method of polyoxyethylene ether phosphate ester generally comprises the step of directly carrying out phosphorylation reaction on polyoxyethylene ether and phosphorus pentoxide, but because the reaction can emit a large amount of heat, the product is easy to coke and has a darker color, the color of the prepared polyester fiber can be influenced when the product is used in a spinning oil, and especially, black expanded graphite nano powder is added into a polyester slice, and if the color of the oil is too dark, the subsequent dyeing and use of fabrics are not facilitated. Therefore, the preparation method of the cardanol polyoxyethylene ether phosphate ester comprises the step of carrying out two-step reaction, firstly reacting a part of cardanol polyoxyethylene ether with phosphorus pentoxide to obtain an intermediate, and then reacting the intermediate with the cardanol polyoxyethylene ether and the phosphorus pentoxide to finally obtain the cardanol polyoxyethylene ether phosphate ester. The content of the cardanol polyoxyethylene ether phosphate monoester prepared by the method can reach 77%, the conversion rate can reach 97%, the product can be effectively prevented from being coked, and the color of the product can be controlled, so that the influence of the color of an oil solution on the color of fibers is avoided, and the subsequent dyeing of fabrics is facilitated.
Preferably, the dye is used in 3-7% of the weight of the fabric during dyeing in the step (3), the bath ratio is 1: 8-10, the oil removing agent is used in an amount of 0.8-1.2 g/L, and the pH value of the dye solution is 4-5; the dyeing condition is that 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 preserved 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 preserved for 35-45 min, and the dyeing pressure is 0.3-0.5 MPa.
Preferably, the reducing and cleaning conditions in the step (3) are as follows: the bath ratio is 1: 8-10, 1.5-2.5 g/L NaOH and 1.5-2.5 g/L sodium hydrosulfite 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, the phenomenon of melt dripping cannot occur, the spinning condition is good in the spinning process, and the phenomenon of filter blockage cannot occur;
(2) most raw materials in the oil used in the spinning process have the characteristic of easy biodegradation, so that the oil not only meets the requirements of on-machine production, but also can improve the degradation degree of the oil, reduce the treatment cost of the oil and greatly improve the environmental protection property of the oil;
(3) the preparation method of the antistatic agent in the oil agent is optimized, and the color of the product is controlled, so that the influence of the color of the oil 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 with reference to specific embodiments.
In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
a preparation method of an expanded graphite polyester 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 liquid; adding terephthalic acid, ethylene glycol and an Sb catalyst into the dispersion liquid, pulping, and then carrying out esterification and polycondensation reaction to obtain expanded graphite flame-retardant polyester chips; wherein the mass of the expanded graphite nano powder is 5% of that of the expanded graphite flame-retardant polyester chip, and the ratio of the total mass of the added glycol to the mass of the terephthalic acid is 1.25: 1; the addition amount of the Sb catalyst is 0.04 percent of the mass of the terephthalic acid;
the reaction conditions are specifically as follows: esterification reaction: heating to 250 ℃ at the heating rate of 2 ℃/min for esterification reaction for 4 h; pre-polycondensation: heating to 250 ℃ after esterification reaction, vacuumizing within 55min until the vacuum degree is 2000Pa, and reacting for 2 h; final polycondensation: heating to 280 ℃ after pre-polycondensation, vacuumizing to 70Pa, and carrying out polycondensation reaction for 2.5 h.
(2) Spinning: drying the expanded graphite flame-retardant polyester chips, then carrying out melt spinning, and carrying out cross air cooling, bundling and oiling, drafting and texturing to obtain drawn textured yarns;
wherein the drying conditions of the slices are as follows: drying at 140 deg.C for 15min, and drying at 150 deg.C for 9 h;
the spinning process comprises the following steps: the temperature of a screw (the temperature of a first zone of the screw is 290 ℃, the temperature of a second zone is 293 ℃, the temperature of a third zone is 296 ℃, the temperature of a fourth zone is 299 ℃, the temperature of a fifth zone is 302 ℃, the temperature of a sixth zone is 305 ℃), a filter (the filtration size is 200 meshes), a box body (the temperature of a spinning box body is 285 ℃), lateral blowing (the wind speed is 0.4m/s, an oil nozzle is used for oiling) a pre-networking device (0.08MPa), a first hot roller (90 ℃), a second hot roller (125 ℃), a main networking device (0.35MPa), and winding forming (4800 m/min); the oil agent used in cluster oiling 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 Ruijie, neopentyl glycol dioleate), 15 parts of fatty acid ester (Haian petrochemical, isooctyl stearate) and 5 parts of refined vegetable oil (Shanghai low erucic acid rapeseed oil);
54.9 parts of degradable environment-friendly emulsifier, wherein 8.6 parts of cardanol polyoxyethylene ether with the HLB value of 4.5 and 17 parts of cardanol polyoxyethylene ether with the HLB value of 7 are adopted; 5 parts of cardanol polyoxyethylene ether with the HLB value of 7.5; 5 parts of cardanol polyoxyethylene ether with the HLB value of 9, 8.6 parts of cardanol polyoxyethylene ether with the HLB value of 9.5 and 10.7 parts of cardanol polyoxyethylene ether with the 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 cashew nut shell oil to obtain cardanol; putting 157kg cardanol into a stainless steel reaction kettle, and adding 2.5kg sodium hydroxide solution prepared by dissolving 2.5kg sodium hydroxide in 30kg water; after the materials are added, heating by electric induction, decompressing, pumping out water vapor and air, and introducing nitrogen to replace the air in the kettle; filling nitrogen into the kettle, pressing ethylene oxide, uniformly heating to 135 ℃, reacting for 5 hours at 135 ℃, cooling to 80 ℃ after the reaction is finished, and neutralizing the product with acetic acid to obtain the cardanol polyoxyethylene ether. Adjusting the adding proportion of the ethylene oxide and the cardanol to obtain cardanol polyoxyethylene ethers with different HLB values;
7 parts of degradable antistatic agent, wherein the degradable antistatic agent is cardanol polyoxyethylene ether phosphate, and the preparation method comprises the following steps: A) heating 60kg of cardanol polyoxyethylene ether to 45 ℃, adding 11.7kg of phosphorus pentoxide under a stirring state, and reacting for 3h at 65 ℃; then adding 4L of water and 2.5L of 30 wt% hydrogen peroxide, carrying out hydrolysis reaction for 2h at 75 ℃, and cooling to room temperature to obtain an intermediate; B) heating 35kg of the intermediate to 45 ℃, dropwise adding 21.3kg of phosphorus pentoxide and 97.8kg of cardanol polyoxyethylene ether under the stirring state, and reacting for 3 hours at 65 ℃; adding 3L of water and 2L of 30 wt% hydrogen peroxide, reacting for 2h at 75 ℃, and cooling to room temperature to obtain the cardanol polyoxyethylene ether phosphate;
0.1 part of oil stabilizer (Tao chemical, triethanolamine).
(3) Dyeing: weaving stretch and draw yarn into a gramWeighing 150g/m2Dyeing and reduction cleaning the weft plain knitted fabric, and finally performing heat setting to obtain the polyester flame-retardant fabric;
the dyeing process comprises the following steps: the using amount of the SHF-BRS active blue dye is 5 percent of the weight of the fabric, the bath ratio is 1:9, the using amount of the oil removing agent DS-1130 is 1.0g/L, and the pH value of the dye solution is 4.5; dyeing at 30 deg.C, heating to 90 deg.C at a rate of 2 deg.C/min, maintaining for 25min, heating to 130 deg.C at a rate of 2 deg.C/min, and maintaining for 40min at a dyeing pressure of 0.4 MPa;
reduction cleaning process: adding 2g/L NaOH and 2g/L sodium hydrosulfite at a bath ratio of 1:9, and keeping the temperature at 80 ℃ for 30 min; a heat setting process: the temperature is 170 deg.C, and the heat setting time is 1 min.
Example 2:
a preparation method of an expanded graphite polyester 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 liquid; adding terephthalic acid, ethylene glycol and an Sb catalyst into the dispersion liquid, pulping, and then carrying out esterification and polycondensation reaction to obtain expanded graphite flame-retardant polyester chips; wherein the mass of the expanded graphite nano powder is 3.5 percent of that of the expanded graphite flame-retardant polyester chip, and the ratio of the total mass of the added glycol to the mass of the terephthalic acid is 1.15: 1; the addition amount of the Sb catalyst is 0.02 percent of the mass of the terephthalic acid;
the reaction conditions are specifically as follows: esterification reaction: heating to 230 ℃ at the heating rate of 1.5/min for esterification reaction for 5 h; pre-polycondensation: heating to 245 ℃ after esterification reaction, vacuumizing within 50min until the vacuum degree is 1800Pa, and reacting for 3 h; final polycondensation: heating to 273 ℃ after pre-polycondensation, vacuumizing to 60Pa, and carrying out polycondensation reaction for 3 hours.
(2) Spinning: drying the expanded graphite flame-retardant polyester chips, then carrying out melt spinning, and carrying out cross air cooling, bundling and oiling, drafting and texturing to obtain drawn textured yarns;
wherein the drying conditions of the slices are as follows: drying at 135 deg.C for 20min, and drying at 145 deg.C for 10 hr;
the spinning process comprises the following steps: the temperature of a screw (the temperature of a first zone of the screw is 290 ℃, the temperature of a second zone is 293 ℃, the temperature of a third zone is 296 ℃, the temperature of a fourth zone is 299 ℃, the temperature of a fifth zone is 302 ℃, the temperature of a sixth zone is 305 ℃), a filter (the filtration size is 200 meshes), a box body (the temperature of a spinning box body is 285 ℃), lateral blowing (the wind speed is 0.4m/s, an oil nozzle is used for oiling) a pre-networking device (0.08MPa), a first hot roller (90 ℃), a second hot roller (125 ℃), a main networking device (0.35MPa), and winding forming (4800 m/min); the oil agent used in cluster oiling 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 Ruijie, pentaerythritol), 20 parts of fatty acid ester (Haian petrochemical, trimethylolpropane oleate) and 7 parts of refined vegetable oil (Shanghai low erucic acid rapeseed oil);
49.9 parts of degradable environment-friendly emulsifier, wherein 7.8 parts of cardanol polyoxyethylene ether with the HLB value of 4.5 and 15.5 parts of cardanol polyoxyethylene ether with the HLB value of 7 are adopted; 4.7 parts of cardanol polyoxyethylene ether with the HLB value of 7.5; 4.7 parts of cardanol polyoxyethylene ether with the HLB value of 9, 7.7 parts of cardanol polyoxyethylene ether with the HLB value of 9.5 and 9.5 parts of cardanol polyoxyethylene ether with the HLB value of 13; the preparation method of cardanol polyoxyethylene ether is the same as that in example 1;
7 parts of degradable antistatic agent, wherein the degradable antistatic agent is cardanol polyoxyethylene ether phosphate, and the preparation method comprises the following steps: A) heating 58kg of cardanol polyoxyethylene ether to 40 ℃, adding 11kg of phosphorus pentoxide under a stirring state, and reacting for 4 hours at 60 ℃; then adding 4L of water and 3L of 25 wt% hydrogen peroxide, carrying out hydrolysis reaction for 3h at 70 ℃, and cooling to room temperature to obtain an intermediate; B) heating 34kg of the intermediate to 40 ℃, then dropwise adding 21kg of phosphorus pentoxide and 97kg of cardanol polyoxyethylene ether under the stirring state, and reacting for 4 hours at 60 ℃; adding 3L of water and 2.4L of 25 wt% of hydrogen peroxide, reacting for 3h at 70 ℃, and cooling to room temperature to obtain the cardanol polyoxyethylene ether phosphate;
0.3 part of oil stabilizer (Tao chemical, triethanolamine).
(3) Dyeing: weaving the drawn and textured yarn into a weight of 150g/m2The weft plain knitted fabric is dyed and reduced and cleaned, and finally heat-set to obtain the polyester flame-retardant fabricAn agent;
the dyeing process comprises the following steps: the using amount of the SHF-BRS active blue dye is 3 percent of the weight of the fabric, the bath ratio is 1:8, the using amount of the oil removing agent DS-1130 is 0.8g/L, and the pH value of the dye solution is 4.1; dyeing is carried out under the dyeing condition 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 0.5 MPa;
reduction cleaning process: adding 1.5g/L NaOH and 1.5g/L sodium hydrosulfite at 75 deg.C for 40min at bath ratio of 1: 8;
a heat setting process: the temperature is 165 ℃ and the heat setting time is 1.5 min.
Example 3:
a preparation method of an expanded graphite polyester 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 liquid; adding terephthalic acid, ethylene glycol and an Sb catalyst into the dispersion liquid, pulping, and then carrying out esterification and polycondensation reaction to obtain expanded graphite flame-retardant polyester chips; wherein the mass of the expanded graphite nano powder is 6% of that of the expanded graphite flame-retardant polyester chip, and the ratio of the total mass of the added glycol to the mass of the terephthalic acid is 1.35: 1; the addition amount of the Sb catalyst is 0.06 percent of the mass of the terephthalic acid;
the reaction conditions are specifically as follows: esterification reaction: heating to 270 ℃ at the heating rate of 2.5/min for esterification reaction for 3 h; pre-polycondensation: heating to 255 ℃ after the esterification reaction, vacuumizing within 60min until the vacuum degree is 2200Pa, and reacting for 1.5 h; final polycondensation: heating to 282 ℃ after pre-polycondensation, vacuumizing to 80Pa, and carrying out polycondensation reaction for 2 h.
(2) Spinning: drying the expanded graphite flame-retardant polyester chips, then carrying out melt spinning, and carrying out cross air cooling, bundling and oiling, drafting and texturing to obtain drawn textured yarns;
wherein the drying conditions of the slices are as follows: drying at 145 deg.C for 10min, and then at 155 deg.C for 8 h;
the spinning process comprises the following steps: the temperature of a screw (the temperature of a first zone of the screw is 290 ℃, the temperature of a second zone is 293 ℃, the temperature of a third zone is 296 ℃, the temperature of a fourth zone is 299 ℃, the temperature of a fifth zone is 302 ℃, the temperature of a sixth zone is 305 ℃), a filter (the filtration size is 200 meshes), a box body (the temperature of a spinning box body is 285 ℃), lateral blowing (the wind speed is 0.4m/s, an oil nozzle is used for oiling) a pre-networking device (0.08MPa), a first hot roller (90 ℃), a second hot roller (125 ℃), a main networking device (0.35MPa), and winding forming (4800 m/min); the oil agent used in cluster oiling 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 Ruijie, neopentyl glycol dioleate), 20 parts of fatty acid ester (Haian petrochemical, isooctyl stearate) and 10 parts of refined vegetable oil (Shanghai low erucic acid rapeseed oil);
44.9 parts of degradable environment-friendly emulsifier, wherein 7 parts of cardanol polyoxyethylene ether with the HLB value of 4.5 and 14 parts of cardanol polyoxyethylene ether with the HLB value of 7 are added; 4.5 parts of cardanol polyoxyethylene ether with the HLB value of 7.5; 4 parts of cardanol polyoxyethylene ether with the HLB value of 9, 7 parts of cardanol polyoxyethylene ether with the HLB value of 9.5 and 8.4 parts of cardanol polyoxyethylene ether with the HLB value of 13; the preparation method of cardanol polyoxyethylene ether is the same as that in example 1;
5 parts of degradable antistatic agent, wherein the degradable antistatic agent is cardanol polyoxyethylene ether phosphate, and the preparation method comprises the following steps: A) heating 62kg of cardanol polyoxyethylene ether to 50 ℃, adding 12kg of phosphorus pentoxide under a stirring state, and reacting for 2h at 70 ℃; then adding 4L of water and 3.8L of 20 wt% hydrogen peroxide, carrying out hydrolysis reaction for 1h at 80 ℃, and cooling to room temperature to obtain an intermediate; B) heating 36kg of the intermediate to 50 ℃, then dropwise adding 22kg of phosphorus pentoxide and 98kg of cardanol polyoxyethylene ether under a stirring state, and reacting for 2 hours at 70 ℃; adding 3L of water and 3L of 20 wt% hydrogen peroxide, reacting for 1h at 80 ℃, and cooling to room temperature to obtain the cardanol polyoxyethylene ether phosphate;
0.5 part of oil stabilizer (Tao chemical, triethanolamine).
(3) Dyeing: weaving the drawn and textured yarn into a weight of 150g/m2Dyeing and reduction cleaning the weft plain knitted fabric, and finally performing heat setting to obtain the polyester flame-retardant fabric;
the dyeing process comprises the following steps: the using amount of the SHF-BRS active blue dye is 7 percent of the weight of the fabric, the bath ratio is 1:10, the using amount of the oil removing agent DS-1130 is 1.2g/L, and the pH value of the dye solution is 5; dyeing at 35 deg.C, heating to 95 deg.C at a rate of 2.5 deg.C/min, maintaining for 20min, heating to 135 deg.C at a rate of 1.5 deg.C/min, and maintaining for 35min at a dyeing pressure of 0.3 MPa;
reduction cleaning process: adding 2.5g/L NaOH and 2.5g/L sodium hydrosulfite at a bath ratio of 1:10 at 85 deg.C for 20 min;
a heat setting process: the temperature is 175 ℃, and the heat setting time is 0.5 min.
Comparative example 1:
the polyester chips prepared in comparative example 1 were prepared without adding the expanded graphite nanopowder, and the rest was the same as in example 1.
Comparative example 2 (too much expanded graphite nanopowder addition):
the mass of the graphite nano powder which is added in the expansion mode when the polyester chip is prepared in the comparative example 2 is 8 percent of the mass of the expanded graphite flame-retardant polyester chip, and the rest is the same as that in the example 1.
Comparative example 3 (cardanol polyoxyethylene ether with a single HLB value was used in the oil):
comparative example 3 in the oil used in cluster oiling in the spinning process, cardanol polyoxyethylene ether with HLB value of 7.5 was used as degradable environment-friendly emulsifier, and the rest was the same as in example 1.
Comparative example 4 (changing the HLB value of cardanol polyoxyethylene ether in the oil formulation):
comparative example 4 in the oil used in cluster oiling in the spinning process, the degradable environment-friendly emulsifier comprises the following components: 8.6 parts of cardanol polyoxyethylene ether with the HLB value of 9; 17 parts of cardanol polyoxyethylene ether with the HLB value of 13; 5 parts of cardanol polyoxyethylene ether with the HLB value of 4.5; 5 parts of cardanol polyoxyethylene ether with the HLB value of 7, 8.6 parts of cardanol polyoxyethylene ether with the HLB value of 7.5 and 10.7 parts of cardanol polyoxyethylene ether with the HLB value of 9.5; the rest is the same as in example 1.
Comparative example 5 (cardanol polyoxyethylene ether phosphate prepared by one-step method was used in the oil):
comparative example 5 preparation method of cardanol polyoxyethylene ether phosphate ester as degradable antistatic agent in oil used in cluster oiling in spinning process: heating 97.8kg of cardanol polyoxyethylene ether to 45 ℃, adding 21.3kg of phosphorus pentoxide under a stirring state, and reacting for 3h at 65 ℃; adding 3L of water and 2L of 30 wt% hydrogen peroxide, carrying out hydrolysis reaction for 2h at 75 ℃, and cooling to room temperature to obtain the cardanol polyoxyethylene ether phosphate; the rest is the same as in example 1.
The performance indexes of the oils prepared in the above examples and comparative examples were measured, and the results are shown in table 1.
Table 1: and (5) oil agent performance index test results.
As can be seen from table 1, the oil solutions prepared by the formulations of the present invention in examples 1 to 3 have good performance indexes, satisfy the conditions of trial spinning, are suitable for the growth of microorganisms, and have good biodegradability. In comparative example 3, cardanol polyoxyethylene ether with a single HLB value is used as an emulsifier, and in comparative example 4, the HLB value of the cardanol polyoxyethylene ether in the emulsifier is changed, so that the stability of the oil agent is reduced, and the cardanol polyoxyethylene ether cannot be stably stored and put into a spinning machine for trial spinning; in the comparative example 5, cardanol polyoxyethylene ether phosphate ester is prepared by a one-step method and used as an antistatic agent, and the prepared oil agent is dark in color and can affect the spinning color, so that the subsequent dyeing of the fabric is affected.
The performance of the polyester fibers prepared in the above examples and comparative examples was tested, and the results are shown in table 2.
Table 2: and (5) performance test results of the polyester fibers.
As can be seen from Table 2, the polyester fibers and fabrics prepared by the method in the invention in the examples 1-3 have oxygen index not less than 32%, excellent flame retardant property and no melt dripping phenomenon during combustion; meanwhile, the dye has good mechanical property and dyeing property. In contrast, in comparative example 1, the expanded graphite powder is not added to the polyester chip, so that the flame retardance of the fabric is remarkably reduced; the expanded graphite added in comparative example 2 is too much, and beyond the range of the present invention, the dispersibility of the expanded graphite powder in the fiber is reduced, resulting in a reduction in spinnability, a phenomenon of clogging the filter during spinning, a reduction in mechanical properties of the fiber, and a phenomenon of non-uniform dyeing.
Claims (10)
1. A preparation method of an 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 then carrying out esterification and polycondensation reaction to obtain expanded graphite flame-retardant polyester chips; 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, then carrying out melt spinning, and carrying out cross air cooling, bundling and oiling, drafting and texturing to obtain drawn textured yarns;
(3) dyeing: and weaving the stretch yarn, then dyeing, reducing and cleaning, and finally carrying out heat setting to obtain the polyester flame-retardant fabric.
2. The method for preparing the expanded graphite polyester fiber flame-retardant fabric as claimed in claim 1, wherein the ratio of the total mass of the ethylene glycol to the mass of the terephthalic acid added in the step (1) is 1.15-1.35: 1; the addition amount of the catalyst is 0.02-0.06% of the mass of the terephthalic acid.
3. The method for preparing an expanded graphite polyester fiber flame-retardant fabric as claimed in claim 1 or 2, wherein the esterification and polycondensation reaction conditions 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 1800-2200 Pa, and reacting for 1.5-3 h;
final polycondensation: heating to 273-282 ℃ after pre-polycondensation, vacuumizing to 60-80 Pa, and performing polycondensation reaction for 2-3 h.
4. The method for preparing the expanded graphite polyester fiber flame-retardant fabric as claimed in claim 1, wherein the drying conditions of the expanded graphite polyester fiber flame-retardant sheet 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 fiber 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 method for preparing expanded graphite polyester fiber flame-retardant fabric according to claim 1 or 5, wherein the oil agent used in cluster oiling in the step (2) 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 17-20: 15-20: 5-10 parts by mass of polyol ester, fatty acid ester and refined vegetable oil; the degradable environment-friendly emulsifier comprises 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 HLB values 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.
7. The preparation method of the expanded graphite polyester fiber flame-retardant fabric as claimed in claim 6, wherein 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 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 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 under a stirring state, and reacting for 2-4 h at 60-70 ℃; adding water and 20-30% by mass of hydrogen peroxide, reacting for 1-3 h at 70-80 ℃, and cooling to room temperature to obtain the cardanol polyoxyethylene ether phosphate; wherein the mass ratio of the added intermediate, phosphorus pentoxide and 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.
8. The preparation method of the expanded graphite terylene flame-retardant fabric according to claim 1, wherein the dye is used in an amount of 3 to 7 percent of the weight of the fabric during dyeing in the step (3), the bath ratio is 1:8 to 10, the oil removing agent is used in an amount of 0.8 to 1.2g/L, and the pH of the dye solution is 4 to 5; the dyeing condition is that 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 preserved 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 preserved for 35-45 min, and the dyeing pressure is 0.3-0.5 MPa.
9. The method for preparing the expanded graphite terylene flame retardant fabric according to claim 1 or 8, wherein the reduction cleaning conditions in the step (3) are as follows: the bath ratio is 1: 8-10, 1.5-2.5 g/L NaOH and 1.5-2.5 g/L sodium hydrosulfite are added, the temperature is 75-85 ℃, and the time is 20-40 min.
10. The method for preparing the expanded graphite terylene flame retardant fabric according to claim 1 or 8, 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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114687212A (en) * | 2022-04-20 | 2022-07-01 | 浙江传化化学品有限公司 | High-temperature-resistant wear-resistant spinning oil and preparation method thereof |
| EP4364852A1 (en) * | 2022-11-04 | 2024-05-08 | Nouryon Chemicals International B.V. | Collector composition and flotation method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741250A (en) * | 2013-12-04 | 2014-04-23 | 太仓荣文合成纤维有限公司 | Inorganic/organic hybrid composite fire retardation agent and application of the same in PET fibers |
| CN105064019A (en) * | 2015-07-31 | 2015-11-18 | 浙江皇马科技股份有限公司 | Nylon 6 short fiber spinning oil agent, preparation method and application thereof |
| CN107460559A (en) * | 2017-09-05 | 2017-12-12 | 福州市晋安区技智企业管理咨询有限公司 | A kind of preparation method of graphene polyester fiber |
| CN107641845A (en) * | 2017-11-09 | 2018-01-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Polyester-base nano hydridization is fire-retardant/preparation method of antibiotic multifunction fiber and products thereof and application |
| CN109487562A (en) * | 2018-09-20 | 2019-03-19 | 桐乡市恒隆化工有限公司 | A kind of general composite emulsifier of spandex oil agent and preparation method thereof |
| US20190169397A1 (en) * | 2015-01-30 | 2019-06-06 | Resinate Materials Group, Inc. | Integrated process for treating recycled streams of pet and ptt |
| CN111592640A (en) * | 2020-05-12 | 2020-08-28 | 浙江恒澜科技有限公司 | Preparation method of graphene modified polyester composite material based on liquid phase stripping |
-
2021
- 2021-08-26 CN CN202110989607.7A patent/CN113774510B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103741250A (en) * | 2013-12-04 | 2014-04-23 | 太仓荣文合成纤维有限公司 | Inorganic/organic hybrid composite fire retardation agent and application of the same in PET fibers |
| US20190169397A1 (en) * | 2015-01-30 | 2019-06-06 | Resinate Materials Group, Inc. | Integrated process for treating recycled streams of pet and ptt |
| CN105064019A (en) * | 2015-07-31 | 2015-11-18 | 浙江皇马科技股份有限公司 | Nylon 6 short fiber spinning oil agent, preparation method and application thereof |
| CN107460559A (en) * | 2017-09-05 | 2017-12-12 | 福州市晋安区技智企业管理咨询有限公司 | A kind of preparation method of graphene polyester fiber |
| CN107641845A (en) * | 2017-11-09 | 2018-01-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Polyester-base nano hydridization is fire-retardant/preparation method of antibiotic multifunction fiber and products thereof and application |
| CN109487562A (en) * | 2018-09-20 | 2019-03-19 | 桐乡市恒隆化工有限公司 | A kind of general composite emulsifier of spandex oil agent and preparation method thereof |
| CN111592640A (en) * | 2020-05-12 | 2020-08-28 | 浙江恒澜科技有限公司 | Preparation method of graphene modified polyester composite material based on liquid phase stripping |
Non-Patent Citations (1)
| Title |
|---|
| 王俊等: "生物质腰果酚磺酸盐表面活性剂的合成及其乳化性能", 《化学研究》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114687212A (en) * | 2022-04-20 | 2022-07-01 | 浙江传化化学品有限公司 | High-temperature-resistant wear-resistant spinning oil and preparation method thereof |
| CN114687212B (en) * | 2022-04-20 | 2024-02-09 | 浙江传化化学品有限公司 | High-temperature-resistant wear-resistant spinning oil and preparation method thereof |
| EP4364852A1 (en) * | 2022-11-04 | 2024-05-08 | Nouryon Chemicals International B.V. | Collector composition and flotation method |
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