CN118547391B - Heat-accumulating flame-retardant polyester fiber based on modified cesium tungsten bronze and preparation method thereof - Google Patents
Heat-accumulating flame-retardant polyester fiber based on modified cesium tungsten bronze and preparation method thereof Download PDFInfo
- Publication number
- CN118547391B CN118547391B CN202410768794.XA CN202410768794A CN118547391B CN 118547391 B CN118547391 B CN 118547391B CN 202410768794 A CN202410768794 A CN 202410768794A CN 118547391 B CN118547391 B CN 118547391B
- Authority
- CN
- China
- Prior art keywords
- tungsten bronze
- cesium tungsten
- flame retardant
- modified
- polyester fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 110
- OHUPZDRTZNMIJI-UHFFFAOYSA-N [Cs].[W] Chemical class [Cs].[W] OHUPZDRTZNMIJI-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 85
- 239000010974 bronze Substances 0.000 title claims abstract description 85
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003063 flame retardant Substances 0.000 title claims abstract description 77
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000000835 fiber Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 36
- 239000010452 phosphate Substances 0.000 claims abstract description 36
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 35
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims abstract description 32
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000460 chlorine Substances 0.000 claims abstract description 28
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 28
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 26
- 238000005338 heat storage Methods 0.000 claims abstract description 24
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 23
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000009987 spinning Methods 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000007822 coupling agent Substances 0.000 claims abstract description 11
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- 238000002074 melt spinning Methods 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000004804 winding Methods 0.000 claims description 5
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 4
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- 229910052792 caesium Inorganic materials 0.000 claims 1
- 238000005453 pelletization Methods 0.000 claims 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- 239000010937 tungsten Substances 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 21
- 238000001035 drying Methods 0.000 description 17
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 11
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- 150000004671 saturated fatty acids Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000012792 core layer Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
本发明涉及一种基于改性铯钨青铜的蓄热阻燃聚酯纤维及其制备方法，属于功能纤维技术领域。本发明的制备方法包括以下步骤：S1、向纳米铯钨青铜溶液中滴加氨基硅烷偶联剂溶液进行搅拌反应，得到改性铯钨青铜；三氯化磷、季戊四醇和β‑苯乙醇于第一溶剂中进行反应，得到含氯环状磷酸酯阻燃剂；S2、将含氯环状磷酸酯阻燃剂分散在第二溶剂中，加入改性铯钨青铜进行反应，得到多功能铯钨青铜；S3、对多功能铯钨青铜和聚酯粉末进行造粒，得到多功能聚酯母粒；S4、对多功能聚酯母粒和聚酯切片进行纺丝，得到基于改性铯钨青铜的蓄热阻燃聚酯纤维，具有良好的蓄热性能和阻燃性能，且力学性能损伤较小。
The present invention relates to a heat storage flame retardant polyester fiber based on modified cesium tungsten bronze and a preparation method thereof, belonging to the technical field of functional fibers. The preparation method of the present invention comprises the following steps: S1, dropping an aminosilane coupling agent solution into a nano cesium tungsten bronze solution for stirring reaction to obtain modified cesium tungsten bronze; phosphorus trichloride, pentaerythritol and β-phenylethanol react in a first solvent to obtain a chlorine-containing cyclic phosphate flame retardant; S2, dispersing the chlorine-containing cyclic phosphate flame retardant in a second solvent, adding modified cesium tungsten bronze to react, and obtaining multifunctional cesium tungsten bronze; S3, granulating the multifunctional cesium tungsten bronze and polyester powder to obtain a multifunctional polyester masterbatch; S4, spinning the multifunctional polyester masterbatch and polyester chips to obtain a heat storage flame retardant polyester fiber based on modified cesium tungsten bronze, which has good heat storage performance and flame retardant performance, and less mechanical performance damage.
Description
Technical Field
The invention belongs to the technical field of functional fibers, and particularly relates to a heat-accumulating flame-retardant polyester fiber based on modified cesium tungsten bronze and a preparation method thereof.
Background
Cesium tungsten bronze is a material with excellent near infrared light absorption performance, effectively absorbs solar energy and converts the solar energy into heat energy, and is widely used in the fields of glass transparent heat insulation coating, solar film, glass heat insulation laminated film, infrared stealth and the like. The polyester fiber is the synthetic fiber with highest yield and the widest application at present, and has wide application in the fields of fillers, clothing, indoor home furnishings and the like. The preparation of heat-accumulating thermal-insulation polyester fiber material by cesium tungsten bronze becomes a research hot spot. However, cesium tungsten bronze powder is directly added and blended without modification, is easy to agglomerate in polyester, has poor dispersibility, and has high pressure on spinning equipment, so that the processing is difficult. In addition, the polyester fiber is extremely easy to burn, and the molten drop phenomenon is serious in the burning process, so that the application of the polyester fiber in the fields of fillers, indoor houses and the like is severely limited. The development of the heat-accumulating flame-retardant multifunctional polyester fiber has great significance.
Chinese patent (CN 110067038A) discloses a preparation method of nano intelligent fiber for heat storage, which takes polyvinyl butyral doped with cesium tungsten bronze as a shell layer, n-octadecane as a core layer, and prepares core-shell structure nano intelligent fiber with cesium tungsten bronze loaded on the shell layer by a coaxial electrostatic spinning method, however, the method can not solve the problem that cesium tungsten bronze powder is difficult to disperse in polyester fiber, and has poor flame retardant property.
Chinese patent (CN 115819934A) discloses a light-colored heating heat-accumulating fiber master batch and a preparation method thereof, mesoporous oxide and linear saturated fatty acid are respectively adopted to coat cesium tungsten bronze powder, so that the heat-accumulating fiber master batch is prepared, however, the linear saturated fatty acid is combined with mesoporous oxide modified cesium tungsten bronze only through weak interaction, the modification efficiency is poor, the dispersibility in the fiber still needs to be further improved, and a bracket effect is generated after the long carbon chain of the linear saturated fatty acid is combined with the polyester fiber, so that the combustion behavior of the polyester fiber is more complex, and the fire hazard is higher.
Based on the background, the development of the multifunctional cesium tungsten bronze powder with heat storage and flame retardance functions is significant in the multifunctional modification of polyester fibers.
Disclosure of Invention
In order to solve the technical problems, the invention provides a heat-accumulating flame-retardant polyester fiber based on modified cesium tungsten bronze and a preparation method thereof, firstly, an aminosilane coupling agent is adopted to modify nano cesium tungsten bronze, then synthesizing a cyclic phosphate flame retardant containing active chlorine groups by adopting phosphorus trichloride, pentaerythritol and beta-phenethyl alcohol, and treating the modified nano cesium tungsten bronze by using the cyclic phosphate flame retardant to obtain the multifunctional cesium tungsten bronze powder. And finally, granulating by adopting a melt blending mode and spinning by adopting a melt spinning mode through adopting a multifunctional cesium tungsten bronze and polyester material to prepare the heat-accumulating flame-retardant polyester fiber based on the modified cesium tungsten bronze.
The first object of the invention is to provide a preparation method of a heat-accumulating flame-retardant polyester fiber based on modified cesium tungsten bronze, which comprises the following steps:
s1, dropwise adding an aminosilane coupling agent solution into a nano cesium tungsten bronze solution to perform stirring reaction to obtain modified cesium tungsten bronze;
Reacting phosphorus trichloride, pentaerythritol and beta-phenethyl alcohol in a first solvent to obtain a chlorine-containing cyclic phosphate flame retardant;
S2, dispersing the chlorine-containing cyclic phosphate flame retardant in the second solvent, and adding the modified cesium tungsten bronze in the S1 for reaction to obtain the multifunctional cesium tungsten bronze;
s3, granulating the multifunctional cesium tungsten bronze and polyester powder in the step S2 to obtain multifunctional polyester master batches;
and S4, spinning the multifunctional polyester master batch and the polyester chips in the step S3 to obtain the heat-accumulating flame-retardant polyester fiber based on the modified cesium tungsten bronze.
In one embodiment of the present invention, in S1, the aminosilane coupling agent is selected from one or more of 3-aminopropyl methyldimethoxy silane, 3-aminopropyl methyldiethoxy silane and 3-aminopropyl trimethoxy silane.
In one embodiment of the present invention, in S1, the dropping speed is 3mL/min-5mL/min, for example, 3mL/min, 4mL/min, 5mL/min may be used.
In one embodiment of the present invention, in S1, the temperature of the stirring reaction is 60 ℃ to 70 ℃ for 3 hours to 4 hours.
In one embodiment of the present invention, in S1, the molar ratio of phosphorus trichloride to pentaerythritol is 2-2.2:1, for example, (2:1), (2.1:1), (2.2:1), and the molar ratio of phosphorus trichloride to β -phenethyl alcohol is 1:1-1.1, for example, (1:1), (1:1.1).
In one embodiment of the present invention, in S1, the preparation of the chlorine-containing cyclic phosphate flame retardant specifically includes the steps of:
s11, generating an intermediate product by nucleophilic substitution reaction of phosphorus trichloride and pentaerythritol in a first solvent;
s12, reacting the intermediate product of the S1 with beta-phenethyl alcohol to generate the chlorine-containing cyclic phosphate flame retardant.
In one embodiment of the invention, in S11, the temperature of the reaction is 30 ℃ to 35 ℃ for a period of 4 hours to 5 hours;
in one embodiment of the invention, in S12, the temperature of the reaction is 30 ℃ to 35 ℃ for a period of 2h to 3h.
In one embodiment of the invention, pentaerythritol contains four hydroxyl groups and can react with two moles of phosphorus trichloride to generate a cyclic phosphate structure, the phosphorus trichloride is slightly excessive to ensure that the pentaerythritol is completely reacted, and then beta-phenethyl alcohol is added for one-side end capping to obtain the chlorine-containing cyclic phosphate flame retardant with one-side end capped and one side reserved with active chlorine groups.
In one embodiment of the present invention, in S1, the nano cesium tungsten bronze solution includes nano cesium tungsten bronze powder and an ethanol solution.
In one embodiment of the present invention, in S1, the aminosilane coupling agent solution includes an aminosilane coupling agent and ethanol.
In one embodiment of the invention, in S2, the mass ratio of the chlorine-containing cyclic phosphate flame retardant to the modified cesium tungsten bronze is 1-1.3:1, for example, (1:1), (1.2:1) and (1.3:1), and the active chlorine of the chlorine-containing cyclic phosphate flame retardant reacts with the amino group of the modified cesium tungsten bronze to obtain the multifunctional cesium tungsten bronze.
In one embodiment of the invention, in S2, the temperature of the reaction is 30-35 ℃, such as 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃ and 35 ℃, and the time is 2h-3h, such as 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h and 3h.
In one embodiment of the invention, the first solvent and the second solvent are independently selected from chloroform and/or dichloromethane.
Further, the first solvent and the second solvent are chloroform.
In one embodiment of the present invention, prior to S3, further comprising the step of drying the multi-functional cesium tungsten bronze and polyester powder, the multi-functional cesium tungsten bronze has a drying temperature of 60 ℃ to 80 ℃, such as 60 ℃, 61 ℃, 62 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68 ℃, 69 ℃, 70 ℃, 71 ℃, 72 ℃, 73 ℃, 74 ℃, 75 ℃, 76 ℃, 77 ℃, 78 ℃, 79 ℃, 80 ℃; the drying time is 7h-9h, such as 7h, 8h and 9h, the drying temperature of the polyester powder is 120 ℃ to 130 ℃, such as 120 ℃, 121 ℃, 122 ℃, 123 ℃, 124 ℃, 125 ℃, 126 ℃, 127 ℃, 128 ℃, 129 ℃ and 130 ℃, and the drying time is 10h-12h, such as 10h, 11h and 12h.
In one embodiment of the invention, in S3, the granulation is performed by melt blending, extrusion molding and cooling granulation through a double screw extruder, the granulation temperature is 255-270 ℃, the processing temperature is too low, the multifunctional cesium tungsten bronze and the polyester powder cannot be uniformly mixed, the granulation is not facilitated, and the energy waste is caused by the too high temperature.
In one embodiment of the present invention, in S3, the mass fraction of the multifunctional cesium tungsten bronze in the multifunctional polyester master batch is 20% -25%, for example, may be 20%, 21%, 22%, 23%, 24%, 25%.
In one embodiment of the present invention, before S4, the method further comprises a step of drying the multifunctional polyester master batch and the polyester chips, wherein the drying is performed by pre-crystallizing for 3 to 4 hours at 90 to 110 ℃ and then drying for 10 to 15 hours at 120 to 140 ℃ to ensure that the final moisture of the multifunctional polyester master batch and the polyester chips is lower than 100ppm.
In one embodiment of the invention, in the step S4, spinning is performed by a melt spinning machine, oiling, pre-drawing, winding and drawing after cooling, wherein the spinning process parameters are that the speed is 2500m/min-2800m/min, the temperature is 280-290 ℃, and the draw ratio is 1.5-2.
In one embodiment of the present invention, in S4, the mass fraction of the multifunctional polyester masterbatch in the heat-accumulating flame-retardant polyester fiber based on the modified cesium tungsten bronze is 15% -20%, for example, may be 15%, 16%, 17%, 18%, 19%, 20%.
The second object of the invention is to provide the heat-accumulating flame-retardant polyester fiber based on the modified cesium tungsten bronze, which is prepared by the method.
In one embodiment of the invention, the surface temperature of the heat accumulating flame retardant polyester fiber based on the modified cesium tungsten bronze is raised 19.8-22.4 ℃ higher than that of common fiber, the limiting oxygen index is 28.5-30.1%, and the breaking strength is 3.2cN/detx-3.4cN/detx.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) In the preparation method, an aminosilane coupling agent is adopted to modify nano cesium tungsten bronze, the silane coupling agent and hydroxyl on the surface of the nano cesium tungsten bronze undergo condensation reaction, the aminosilane coupling agent is grafted on the surface of the nano cesium tungsten bronze, and amino is introduced.
(2) According to the preparation method, active chlorine of the chlorine-containing cyclic phosphate flame retardant reacts with amino groups of the modified cesium tungsten bronze, so that the cyclic phosphate flame retardant coats silicon dioxide and the nanometer cesium tungsten bronze particles inside through covalent bonds, on one hand, the molecular structure of the cyclic phosphate flame retardant contains more six-membered rings, the tail end of the cyclic phosphate flame retardant contains benzene ring structures similar to the structure of polyester, so that the cyclic phosphate flame retardant and the modified cesium tungsten bronze can be combined through a similar compatibility principle, the compatibility is good, the dispersibility in polyester fibers is good, the heat storage and flame retarding efficiency is high, and the mechanical properties of the polyester fibers are less influenced, on the other hand, the cyclic phosphate flame retardant, the nanometer cesium tungsten bronze and the nanometer silicon dioxide have a synergistic flame retarding effect, and the organic-inorganic flame retardant system has higher flame retarding smoke suppression performance.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a schematic structural diagram of a multifunctional cesium tungsten bronze of example 1 of the present invention;
FIG. 2 is a graph showing the temperature difference between the modified polyester fiber and the unmodified polyester fiber in the test example 1 of the present invention in the near infrared light thermal storage test.
Detailed Description
The present invention will be further described in conjunction with the drawings and the detailed embodiments so that those skilled in the art may better understand and practice the invention and it is evident that the described embodiments are only some, but not all, of the embodiments of the invention. It should be understood that the detailed description is intended to illustrate the invention, but is not intended to limit the invention to the particular embodiments disclosed.
In the present invention, unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In the present invention, the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items, unless otherwise indicated.
In the present invention, unless otherwise indicated, all the experimental methods used in the examples of the present invention are conventional methods, and materials, reagents and the like used, unless otherwise indicated, are commercially available.
In the present invention, unless otherwise indicated, the nano cesium tungsten bronze used in the examples of the present invention was purchased from Jiangxi Wegener nanotechnology Co., ltd, and had a structure of Cs 0.33WO3 and a particle size of 30nm to 50nm.
Example 1
The heat-accumulating flame-retardant polyester fiber based on the modified cesium tungsten bronze and the preparation method thereof specifically comprise the following steps:
S1, uniformly mixing nano cesium tungsten bronze with an ethanol solution with the mass fraction of 30% according to the mass ratio of 1:25, then dropwise adding a 3-aminopropyl trimethoxysilane solution (the volume ratio of 3-aminopropyl trimethoxysilane to ethanol is 1:8) at the speed of 4mL/min, stirring and reacting for 3.5 hours at 65 ℃, centrifuging, washing for 3 times with water and ethanol in sequence, and then drying for 6 hours at 75 ℃ to obtain modified cesium tungsten bronze powder;
Uniformly mixing phosphorus trichloride and chloroform according to a mass ratio of 1:35, adding pentaerythritol according to a molar ratio of 2.1:1 of the phosphorus trichloride to the pentaerythritol, reacting for 4.5 hours at 32 ℃, then continuously adding beta-phenethyl alcohol according to a molar ratio of 1:1.1 of the phosphorus trichloride to the beta-phenethyl alcohol, reacting for 2.5 hours at 32 ℃, and purifying to obtain a chlorine-containing cyclic phosphate flame retardant;
S2, uniformly mixing the chlorine-containing cyclic phosphate flame retardant and chloroform according to the mass ratio of 1:35, gradually adding the modified cesium tungsten bronze powder according to the mass ratio of 1.2:1, reacting for 2.5 hours at 32 ℃, centrifuging, washing and drying to obtain the multifunctional cesium tungsten bronze powder (figure 1);
s3, vacuum drying the multifunctional cesium tungsten bronze powder for 8 hours at 70 ℃, vacuum drying the polyester powder for 11 hours at 125 ℃, mixing, and then carrying out melt blending, extrusion molding, cooling and granulating by a double-screw extruder, wherein the temperature of the double-screw extruder is 265 ℃, so as to obtain the multifunctional polyester master batch with the mass fraction of the multifunctional cesium tungsten bronze powder being 22%;
S4, pre-crystallizing the multifunctional polyester master batch and the polyester chips in a 100 ℃ blast oven for 3.5 hours, and then continuously drying at 130 ℃ for 13 hours to ensure that the final moisture of the multifunctional polyester master batch and the polyester chips is lower than 100ppm, spinning by a melt spinning machine, cooling, oiling, pre-drafting, winding and drafting, wherein the speed of the melt spinning machine is 2650m/min, the temperature is 285 ℃, the traction ratio is 1.8, and the heat-accumulating flame-retardant polyester fiber based on modified cesium tungsten bronze, of which the mass fraction of the multifunctional polyester master batch is 18%, is obtained.
Example 2
The heat-accumulating flame-retardant polyester fiber based on the modified cesium tungsten bronze and the preparation method thereof specifically comprise the following steps:
S1, uniformly mixing nano cesium tungsten bronze with an ethanol solution with the mass fraction of 20% according to the mass ratio of 1:20, then dropwise adding a 3-aminopropyl methyl diethoxy silane solution (the volume ratio of 3-aminopropyl methyl diethoxy silane to ethanol is 1:5) at the speed of 3mL/min, stirring and reacting for 4 hours at 60 ℃, centrifuging, sequentially washing 3 times with water and ethanol, and then drying for 7 hours at 70 ℃ to obtain modified cesium tungsten bronze powder;
uniformly mixing phosphorus trichloride and chloroform according to a mass ratio of 1:30, adding pentaerythritol according to a molar ratio of 2:1 of the phosphorus trichloride to the pentaerythritol, reacting for 5 hours at a temperature of 30 ℃, then continuously adding beta-phenethyl alcohol according to a molar ratio of 1:1 of the phosphorus trichloride to the beta-phenethyl alcohol, reacting for 3 hours at a temperature of 30 ℃, and purifying to obtain a chlorine-containing cyclic phosphate flame retardant;
s2, uniformly mixing the chlorine-containing cyclic phosphate flame retardant and chloroform according to the mass ratio of 1:30, gradually adding the modified cesium tungsten bronze powder according to the mass ratio of 1:1, reacting for 3 hours at 30 ℃, centrifuging, washing and drying to obtain the multifunctional cesium tungsten bronze powder;
S3, vacuum drying the multifunctional cesium tungsten bronze powder for 9 hours at 60 ℃, vacuum drying the polyester powder for 12 hours at 120 ℃, mixing, and then carrying out melt blending, extrusion molding, cooling and granulating by a double-screw extruder, wherein the temperature of the double-screw extruder is 255 ℃, so as to obtain the multifunctional polyester master batch with 20% of the weight fraction of the multifunctional cesium tungsten bronze powder;
S4, pre-crystallizing the multifunctional polyester master batch and the polyester chips in a 90 ℃ blast oven for 4 hours, and then continuously drying at 120 ℃ for 15 hours to ensure that the final moisture of the multifunctional polyester master batch and the polyester chips is lower than 100ppm, spinning, cooling, oiling, pre-drafting, winding and drafting by a melt spinning machine, wherein the speed of the melt spinning machine is 2500m/min, the temperature is 280 ℃, the traction ratio is 1.5, and the heat-accumulating flame-retardant polyester fiber based on the modified cesium tungsten bronze, the mass fraction of which is 15%, of the multifunctional polyester master batch, is obtained.
Example 3
The heat-accumulating flame-retardant polyester fiber based on the modified cesium tungsten bronze and the preparation method thereof specifically comprise the following steps:
S1, uniformly mixing nano cesium tungsten bronze with an ethanol solution with the mass fraction of 40% according to the mass ratio of 1:30, then dropwise adding a 3-aminopropyl methyl dimethoxy silane solution (the volume ratio of 3-aminopropyl methyl dimethoxy silane to ethanol is 1:10) at the speed of 5mL/min, stirring and reacting for 3 hours at 70 ℃, centrifuging, sequentially washing for 3 times with water and ethanol, and then drying for 5 hours at 80 ℃ to obtain modified cesium tungsten bronze powder;
Uniformly mixing phosphorus trichloride and chloroform according to a mass ratio of 1:40, adding pentaerythritol according to a molar ratio of 2.2:1 of the phosphorus trichloride to the pentaerythritol, reacting for 4 hours at 35 ℃, then continuously adding beta-phenethyl alcohol according to a molar ratio of 1:1 of the phosphorus trichloride to the beta-phenethyl alcohol, reacting for 2 hours at 35 ℃, and purifying to obtain a chlorine-containing cyclic phosphate flame retardant;
S2, uniformly mixing the chlorine-containing cyclic phosphate flame retardant and chloroform according to the mass ratio of 1:40, gradually adding the modified cesium tungsten bronze powder according to the mass ratio of 1.3:1, reacting for 2 hours at 35 ℃, centrifuging, washing and drying to obtain the multifunctional cesium tungsten bronze powder;
S3, vacuum drying the multifunctional cesium tungsten bronze powder for 7 hours at 80 ℃, vacuum drying the polyester powder for 10 hours at 130 ℃, mixing, carrying out melt blending, extrusion molding and cooling granulation by a double-screw extruder, wherein the temperature of the double-screw extruder is 270 ℃, and obtaining the multifunctional polyester master batch with the mass fraction of the multifunctional cesium tungsten bronze powder being 25%;
S4, pre-crystallizing the multifunctional polyester master batch and the polyester chips in a 110 ℃ blast oven for 3 hours, and then continuously drying the polyester master batch and the polyester chips at 140 ℃ for 10 hours to ensure that the final moisture of the multifunctional polyester master batch and the polyester chips is lower than 100ppm, spinning, cooling, oiling, pre-drafting, winding and drafting the mixture by a melt spinning machine, wherein the speed of the melt spinning machine is 2800m/min, the temperature is 290 ℃ and the traction ratio is 2, so that the heat-accumulating flame-retardant polyester fiber based on the modified cesium tungsten bronze, the mass fraction of which is 15%, of the multifunctional polyester master batch, is obtained.
Comparative example 1
Basically, the method is the same as in example 1, except that nano cesium tungsten bronze is directly adopted for granulation and spinning.
Comparative example 2
Essentially the same as in example 1, except that the modified cesium tungsten bronze was directly used for granulation and spinning.
Comparative example 3
Substantially the same as in example 1, except that phosphorus trichloride was not added in the preparation of the chlorine-containing cyclic phosphate flame retardant.
Comparative example 4
Substantially the same as in example 1, except that the chlorine-containing cyclic phosphate flame retardant was replaced with cyclic phosphate FRC-1.
Comparative example 5
Substantially the same as in example 1, except that no beta-phenethyl alcohol was added in the preparation of the chlorine-containing cyclic phosphate flame retardant.
Test example 1
The heat-accumulating flame-retardant polyester fibers (modified polyester fibers) based on modified cesium tungsten bronze prepared in examples 1 to 3 and comparative examples 1 to 5 were tested for flame retardant properties and the like:
Light and heat storage performance, namely, testing the light and heat storage performance of the heat storage flame-retardant polyester fiber based on the modified cesium tungsten bronze by referring to GB/T18319-2019 textile light and heat storage performance test method, wherein irradiance is 150W/m 2;
physical properties the breaking strength of the modified polyester fiber is tested by referring to GB/T14344-2022 method for testing tensile Property of chemical fiber filaments;
flame retardant Property the limiting oxygen index of the fiber is tested by referring to FZ/T50017-2011 oxygen index method of flame retardant Property test method of polyester fiber.
FIG. 2 is a graph of the near infrared thermal storage test of the unmodified polyester fibers and modified polyester fibers of example 1;
table 1 shows the final measured relevant properties of the unmodified and modified polyester fibers:
TABLE 1
As can be seen from table 1 and fig. 2, the modified polyester fiber has good heat-storage performance and flame-retardant performance, and has less damage to mechanical properties.
Compared with comparative example 1, the unmodified nano cesium tungsten bronze has poor compatibility with polyester fiber and no flame retardant property, so the modified polyester fiber has poor flame retardant property and serious mechanical property loss;
Compared with comparative example 2, the single aminosilane coupling agent modified nano cesium tungsten bronze modified polyester has better heat storage effect, but has poor flame retardant property, poor compatibility with polyester fiber and large mechanical property damage;
Compared with comparative example 3, the chlorine-containing cyclic phosphate flame retardant is not synthesized by phosphorus trichloride, pentaerythritol, beta-phenethyl alcohol and the like cannot react with the modified nano cesium tungsten bronze, so that the compatibility of the modified nano cesium tungsten bronze and the polyester fiber is still poor, the mechanical property is greatly damaged, and the flame retardant property is poor through simple blending of the components and the polyester fiber;
compared with comparative example 4, the conventional cyclic phosphate FRC-1 modified nano cesium tungsten bronze modified polyester fiber has good heat storage effect and good flame retardant effect, but has large damage to mechanical properties, and the cyclic phosphate flame retardant cannot be combined with the nano cesium tungsten bronze, so that the modification effect is poor and the dispersion is uneven in the polyester fiber;
Compared with comparative example 5, the preparation of the chlorine-containing cyclic phosphate flame retardant is carried out without adding beta-phenethyl alcohol for end capping, which results in poor compatibility of the modified nano cesium tungsten bronze and the polyester fiber, reduced dispersibility in the polyester fiber, reduced functionality and reduced mechanical property.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410768794.XA CN118547391B (en) | 2024-06-14 | 2024-06-14 | Heat-accumulating flame-retardant polyester fiber based on modified cesium tungsten bronze and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410768794.XA CN118547391B (en) | 2024-06-14 | 2024-06-14 | Heat-accumulating flame-retardant polyester fiber based on modified cesium tungsten bronze and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN118547391A CN118547391A (en) | 2024-08-27 |
| CN118547391B true CN118547391B (en) | 2025-03-07 |
Family
ID=92450028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410768794.XA Active CN118547391B (en) | 2024-06-14 | 2024-06-14 | Heat-accumulating flame-retardant polyester fiber based on modified cesium tungsten bronze and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118547391B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116024695A (en) * | 2022-12-09 | 2023-04-28 | 江苏集萃功能材料研究所有限公司 | Light-colored light energy heating thermal fiber and preparation method thereof |
| CN118126384A (en) * | 2024-05-10 | 2024-06-04 | 江苏恒力化纤股份有限公司 | Preparation method of flame-retardant smoke-suppressing polyester film |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233362B (en) * | 2017-05-25 | 2021-07-16 | 香港理工大学 | A kind of self-cleaning nanometer thermal insulation coating based on cesium tungsten bronze and preparation method thereof |
| CN116695446B (en) * | 2023-07-12 | 2024-02-02 | 吴江市兴业纺织有限公司 | Fabric with infrared shielding function and preparation method thereof |
-
2024
- 2024-06-14 CN CN202410768794.XA patent/CN118547391B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116024695A (en) * | 2022-12-09 | 2023-04-28 | 江苏集萃功能材料研究所有限公司 | Light-colored light energy heating thermal fiber and preparation method thereof |
| CN118126384A (en) * | 2024-05-10 | 2024-06-04 | 江苏恒力化纤股份有限公司 | Preparation method of flame-retardant smoke-suppressing polyester film |
Non-Patent Citations (1)
| Title |
|---|
| Cs_xWO_3/PMMA复合材料的制备及其透明隔热性能;杨静媛等;大连工业大学学报;20200715;39(04);296-301 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN118547391A (en) | 2024-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103173884B (en) | A kind of halogen-free flame-retardant polypropylene fiber and preparation method thereof | |
| CN118639341B (en) | A high-efficiency carbon-forming anti-drip flame retardant and its preparation method and application | |
| CN107868281A (en) | A kind of preparation of hypo-aluminum orthophosphate doping vario-property palygorskite and the application as fire retardant | |
| Liu et al. | Magnesium hydroxide nanoparticles grafted by DOPO and its flame retardancy in ethylene‐vinyl acetate copolymers | |
| CN115286871B (en) | A kind of halogen-free flame-retardant conductive polypropylene material | |
| CN115746467A (en) | Preparation method of brominated polystyrene-tubular kaolin composite material | |
| CN111334009B (en) | A kind of flame retardant masterbatch for low toxicity and low smoke polyester fiber and preparation method thereof | |
| CN111349981B (en) | Low-toxicity low-smoke flame-retardant polyester fiber and preparation method thereof | |
| CN118547391B (en) | Heat-accumulating flame-retardant polyester fiber based on modified cesium tungsten bronze and preparation method thereof | |
| CN114524959B (en) | Ceramic nanocellulose reinforced full-biodegradable material composite membrane and preparation method thereof | |
| CN119241937A (en) | A nano-modified polyethylene optical cable sheath material and preparation method thereof | |
| CN117534945B (en) | Multifunctional engineering plastic and production method thereof | |
| CN118685883A (en) | Flame retardant polyester fiber and preparation process thereof | |
| Zongren et al. | Preparation and characterization of rare earth fluorescent anti-counterfeiting fiber via sol-gel method | |
| CN118256033A (en) | Halogen-free flame-retardant modified master batch | |
| CN114539674B (en) | Polypropylene color master batch suitable for high-rate foaming process and preparation method thereof | |
| CN117210952A (en) | Preparation method of long-acting antistatic polypropylene fiber | |
| CN118600584B (en) | Multifunctional polyester fiber based on modified bamboo charcoal and preparation method thereof | |
| CN113913964A (en) | Halogen-free flame-retardant regenerated polyester fiber and preparation method thereof | |
| CN118206874B (en) | Flame-retardant anti-dripping chemical fiber master batch and preparation process thereof | |
| CN119463396A (en) | A transparent flame-retardant polymethyl methacrylate composite material and preparation method thereof | |
| CN117645764B (en) | High-temperature-resistant PVC pipe and manufacturing process thereof | |
| CN118497923A (en) | Thermal insulation flame-retardant polyester fiber and preparation method thereof | |
| CN119102002B (en) | Graphene modified multifunctional polyester fiber, preparation method and application thereof in down filling | |
| CN118667307B (en) | Blending type anti-dripping polymer material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |