CN113248542A - Flame retardant, flame-retardant Lyocell fiber and preparation method thereof - Google Patents
Flame retardant, flame-retardant Lyocell fiber and preparation method thereof Download PDFInfo
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- CN113248542A CN113248542A CN202110568205.XA CN202110568205A CN113248542A CN 113248542 A CN113248542 A CN 113248542A CN 202110568205 A CN202110568205 A CN 202110568205A CN 113248542 A CN113248542 A CN 113248542A
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- 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 139
- 239000003063 flame retardant Substances 0.000 title claims abstract description 139
- 229920000433 Lyocell Polymers 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000835 fiber Substances 0.000 claims abstract description 43
- 239000011259 mixed solution Substances 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 36
- 238000009987 spinning Methods 0.000 claims abstract description 33
- 239000002245 particle Substances 0.000 claims abstract description 29
- 229920002678 cellulose Polymers 0.000 claims abstract description 25
- 239000001913 cellulose Substances 0.000 claims abstract description 25
- 229920003043 Cellulose fiber Polymers 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 230000008961 swelling Effects 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 66
- 239000006185 dispersion Substances 0.000 claims description 38
- 238000005406 washing Methods 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 33
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 25
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 25
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 24
- 239000013067 intermediate product Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 14
- 239000003208 petroleum Substances 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002612 dispersion medium Substances 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 5
- 239000011324 bead Substances 0.000 claims description 5
- 239000000080 wetting agent Substances 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229920001410 Microfiber Polymers 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims description 2
- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000003658 microfiber Substances 0.000 claims description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 235000021395 porridge Nutrition 0.000 claims description 2
- 239000004576 sand Substances 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 238000002166 wet spinning Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 40
- 230000001112 coagulating effect Effects 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- IVNPXOUPZCTJAK-UHFFFAOYSA-N 4-methylmorpholin-4-ium;hydroxide Chemical compound O.CN1CCOCC1 IVNPXOUPZCTJAK-UHFFFAOYSA-N 0.000 description 10
- 239000004480 active ingredient Substances 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- BMDVPRGEZHHGLJ-UHFFFAOYSA-N [S](Cl)(Cl)Cl.[P] Chemical compound [S](Cl)(Cl)Cl.[P] BMDVPRGEZHHGLJ-UHFFFAOYSA-N 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229960001124 trientine Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a flame retardant, a flame-retardant Lyocell fiber and a preparation method thereof, and belongs to the technical field of fibers. The flame-retardant Lyocell fiber comprises a cellulose fiber matrix and the flame retardant, wherein the flame retardant is dispersed in the cellulose fiber matrix. The preparation method comprises the following steps: premixing the flame retardant with an NMMO solution to obtain a first mixed solution, wherein the range of the particle size of the flame retardant in the first mixed solution is 0-5 μm; premixing, stirring and swelling the first mixed solution and cellulose fiber pulp in sequence to obtain a second mixed solution which is completely swelled; dehydrating the second mixed solution to completely dissolve the cellulose fibers to obtain a spinning solution; and spinning the spinning solution to prepare the flame-retardant Lyocell fiber, wherein the flame retardant accounts for 5-50% of the oven-dried mass percentage of the cellulose fiber pulp. The flame-retardant Lyocell fiber has excellent flame-retardant property, excellent durability, uniform blending of the flame retardant and cellulose, tight combination and better mechanical property and hand feeling.
Description
Technical Field
The invention relates to the technical field of fibers, in particular to a flame retardant, a flame-retardant Lyocell fiber and a preparation method thereof.
Background
Lyocell fiber, known as soluble fiber and known as green fiber in the 21 st century, uses N-methylmorpholine-N-oxide (NMMO) as a solvent and is used for regenerated cellulose fiber spun by a wet process. The waste can be naturally degraded, 99.5 percent of the amine oxide solvent in the production process can be recycled, and the method has the characteristics of extremely low toxicity and no environmental pollution. In the prior art, the flame retardant property of the Lyocell fiber is poor.
Disclosure of Invention
In view of the above, the invention provides a flame retardant, a flame-retardant Lyocell fiber and a preparation method thereof, wherein the flame-retardant Lyocell fiber has and maintains permanent flame retardance, so that the flame-retardant Lyocell fiber is more practical.
In order to achieve the first object, the technical scheme of the flame retardant provided by the invention is as follows:
the flame retardant provided by the invention comprises a compound component with the following chemical formula:
wherein X represents O or S; r represents an alkyl structure or a benzene ring structure of active amine; n represents any one or a mixture of 2, 3 and 4.
The flame retardant provided by the invention can be further realized by adopting the following technical scheme:
preferably, the alkyl structure of the active amine is selected from one or a mixture of ethylene diamine, diethylene triamine and triethylene tetramine.
Preferably, the benzene ring structure of the active amine is selected from any one of p-phenylenediamine and m-phenylenediamine or a mixture thereof.
In order to achieve the second object, the technical scheme of the preparation method of the flame retardant provided by the invention is as follows:
the preparation method of the flame retardant provided by the invention comprises the following steps:
the first component is formed by phosphorus trichloride or phosphorus oxychloride and neopentyl glycol in a molar ratio of 1 (1-1.5);
benzene or pyridine with the mole number accounting for 20-30% of the mole number of the neopentyl glycol forms a second component;
the first component and the second component react under the condition of dissolution to obtain a first intermediate product, wherein the value range of the reaction duration is 1h-3h, and the value range of the reaction temperature is 40-80 ℃;
washing the first intermediate product with water, and distilling to remove benzene or pyridine to obtain a second intermediate product;
the second intermediate product is sequentially recrystallized by using petroleum ether with the mole number of 20-40% of that of the second component, and is dried for 36-48 h by airflow at 50-60 ℃ to obtain a third intermediate product;
mixing the third intermediate product and the active amine in a mass ratio range (2.5-6.1): 1 to form a third component;
dichloroethane accounting for 40-70% of the third intermediate product by mass is taken as a fourth component;
reacting the third component and the fourth component under the condition of dissolution to obtain a fourth intermediate product, wherein the reaction temperature is in the range of 10-30 ℃, and the reaction duration is in the range of 3-6 h;
washing the fourth intermediate product with water to obtain a fifth intermediate product;
and recrystallizing the fifth intermediate product under the condition of ethanol to obtain the flame retardant, wherein the mass of the ethanol is equal to that of the dichloroethane, the recrystallization reaction temperature is in a range of 50-60 ℃, and the airflow drying duration time is in a range of 36-48 h.
In order to achieve the third purpose, the technical scheme of the flame-retardant Lyocell fiber provided by the invention is as follows:
the flame-retardant Lyocell fiber provided by the invention comprises a cellulose fiber matrix and the flame retardant provided by the invention, wherein the flame retardant is dispersed in the cellulose fiber matrix.
In order to achieve the fourth object, the technical scheme of the preparation method of the flame-retardant Lyocell fiber provided by the invention is as follows:
the preparation method of the flame-retardant Lyocell fiber provided by the invention comprises the following steps:
premixing the flame retardant and an NMMO solution to obtain a first mixed solution, wherein the range of the particle size of the flame retardant in the first mixed solution is 0-5 mu m;
premixing, stirring and swelling the first mixed solution and cellulose fiber pulp in sequence to obtain a second mixed solution with complete swelling;
dehydrating the second mixed solution to completely dissolve the cellulose fibers to obtain a spinning solution;
the flame-retardant Lyocell fiber is prepared by spinning the spinning solution,
wherein, the flame retardant accounts for 5 to 50 percent of the absolute dry mass percentage content of the cellulose fiber pulp.
The preparation method of the flame-retardant Lyocell fiber provided by the invention can be further realized by adopting the following technical scheme:
preferably, in the step of premixing the first mixed solution with cellulose-based fiber pulp in this order, stirring and swelling the mixture to obtain a second mixed solution which is completely swollen,
the stirring temperature is 70-80 ℃,
the value range of the swelling duration is 20min-60min,
the pulp in the second mixed solution is in a uniform and fine pulp porridge state with microfiber and no white core.
Preferably, in the step of obtaining a spinning solution by completely dissolving the cellulose-based fibers after the second mixed solution is dehydrated, the spinning solution is in a light brown transparent state.
Preferably, in the step of preparing the flame-retardant Lyocell fiber by spinning the spinning solution, the spinning specifically comprises the following steps:
and the spinning solution is subjected to dry-jet wet spinning, spinneret plate extrusion, solidification, drafting, water washing, cutting and drying in sequence to prepare the flame-retardant Lyocell fiber.
Preferably, the flame retardant provided by the invention is premixed with the NMMO solution to obtain a first mixed solution, wherein in the step process of the first mixed solution, the grain diameter of the flame retardant ranges from 0 μm to 5 μm,
directly adding the flame retardant into a Lyocell cellulose solution before spinning and forming; alternatively, the first and second electrodes may be,
according to the preparation process of Lyocell fibers, the flame retardant is prepared as a dispersion and added to an aqueous solution of Lyocell cellulose in NMMO.
Preferably, the flame retardant provided by the invention is premixed with the NMMO solution to obtain a first mixed solution, wherein in the step process of the first mixed solution, the particle size range of the flame retardant is 0 μm to 5 μm, the method specifically comprises the following steps:
preparing a flame-retardant mixture from a dispersion medium, a dispersing agent and a flame retardant in a grinding mode;
premixing the flame-retardant mixture with an NMMO solution to obtain a first mixed solution;
wherein, the grinding equipment is selected from one or more of a ball mill and a sand mill, the beads for grinding are selected from one or more of steel balls and zirconia beads, and the average particle size of insoluble substances in the flame-retardant mixture is 0.3-5 um.
Preferably, the flame-retardant mixture comprises the following components in parts by mass:
flame retardant: 10-50 parts;
dispersing agent: 2-20 parts;
defoaming agent: 1-5 parts;
wetting agent: 1-10 parts;
the balance of dispersion medium, wherein the dispersion medium is selected from water or an aqueous solution of NMMO.
Preferably, the dispersant is one or a mixture of several of sodium dodecyl benzene sulfonate, sodium maleate, sodium polyacrylate and tween-80.
Preferably, the defoaming agent is one or a mixture of more of dyhi 4000, dyhi 902w and dyhi 810 w.
Preferably, the wetting agent is one or a combination of BYK-190, digao-245, digao 270 and GS-2082.
The flame retardant dispersion liquid with excellent stability can be prepared according to the method, the particle size is kept stable in the standing process, the compatibility with the NMMO solution is excellent, zero emission is realized in the production process, and the method is green and environment-friendly. The produced flame-retardant Lyocell fiber has excellent flame retardant property, excellent durability, uniform blending of the flame retardant and cellulose, tight combination and better mechanical property and hand feeling.
Detailed Description
In view of the above, the invention provides a flame retardant, a flame-retardant Lyocell fiber and a preparation method thereof, wherein the flame-retardant Lyocell fiber has and maintains permanent flame retardance, so that the flame-retardant Lyocell fiber is more practical.
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to a flame retardant, a flame retardant Lyocell fiber and a method for preparing the same according to the present invention, and the detailed embodiments, structures, characteristics and effects thereof. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The term "and/or" herein is merely an association describing an associated object, meaning that three relationships may exist, e.g., a and/or B, with the specific understanding that: both a and B may be included, a may be present alone, or B may be present alone, and any of the three cases can be provided.
Method for preparing flame retardant
Example 1
Step one, reacting phosphorus oxychloride and neopentyl glycol in a molar ratio of 1:1 for 1h at 40 ℃ under the condition that benzene with the mole number of 20% of that of the neopentyl glycol is dissolved, washing with water to obtain a product, and distilling to remove the benzene; then utilizing petroleum ether with the mole number of 20 percent of that of benzene for recrystallization, and carrying out airflow drying for 36h at the temperature of 50 ℃;
and step two, mixing the dried product with ethylenediamine according to the mass ratio of 6.1:1, reacting for 3 hours under the condition that dichloroethane with the mass accounting for 40% of the dried product is dissolved at 10 ℃, then washing to obtain a product, recrystallizing with ethanol with the mass of dichloroethane and the like, and drying for 36 hours at 50 ℃ by airflow to obtain the flame retardant.
Example 2
Firstly, reacting phosphorus oxychloride and neopentyl glycol in a molar ratio of 1:1.15 for 3 hours under the conditions of 80 ℃ and dissolution of benzene with the mole number of 30% of that of the neopentyl glycol, then washing with water to obtain a product, and distilling to remove the benzene; then utilizing petroleum ether with the mole number of 40 percent of that of benzene for recrystallization, and carrying out air flow drying for 48 hours at the temperature of 60 ℃;
and step two, mixing the dried product with p-phenylenediamine in a mass ratio of 3.4:1, reacting for 6 hours under the condition that dichloroethane accounting for 70% of the dried product is dissolved at 30 ℃, then washing to obtain a product, recrystallizing with ethanol with the mass of dichloroethane and the like, and drying for 48 hours at 60 ℃ by using airflow to obtain the flame retardant.
Example 3
Step one, reacting phosphorus oxychloride and neopentyl glycol in a molar ratio of 1:1.25 for 1.5 hours at 50 ℃ under the condition that benzene with the molar number of 25% of that of the neopentyl glycol is dissolved, washing with water to obtain a product, and distilling to remove the benzene; then utilizing petroleum ether with the mole number of 30 percent of that of benzene for recrystallization, and drying for 40 hours by air flow at 55 ℃;
and step two, mixing the dried product with triethylene tetramine according to the mass ratio of 2.5:1, reacting for 4 hours under the condition that dichloroethane with the mass accounting for 50% of the dried product is dissolved at 30 ℃, then washing to obtain a product, recrystallizing with ethanol with the mass of dichloroethane and the like, and drying for 40 hours at 55 ℃ by airflow to obtain the flame retardant.
Example 4
Step one, reacting phosphorus oxychloride and neopentyl glycol in a molar ratio of 1:1.35 for 2 hours under the conditions of 60 ℃ and dissolution of pyridine with the mole number of 25% of that of the neopentyl glycol, washing with water to obtain a product, and distilling to remove the pyridine; then utilizing petroleum ether with the mole number of 30 percent of that of pyridine to recrystallize, and drying for 42 hours by air flow at 55 ℃;
and step two, mixing the dried product with m-phenylenediamine in a mass ratio of 3.5:1, reacting for 5 hours under the condition that dichloroethane accounting for 60% of the dried product is dissolved at 30 ℃, then washing to obtain a product, recrystallizing with ethanol with the mass of dichloroethane and the like, and drying for 42 hours at 55 ℃ by using airflow to obtain the flame retardant.
Example 5
Step one, reacting phosphorus oxychloride and neopentyl glycol in a molar ratio of 1:1.5 for 2.7 hours at 70 ℃ under the condition that the neopentyl glycol is dissolved in pyridine with the molar number of 25% of that of the neopentyl glycol, washing with water to obtain a product, and distilling to remove the pyridine; then recrystallizing by using petroleum ether with the mole number of 35 percent of that of pyridine, and drying for 45 hours by using airflow at 55 ℃;
step two, using the dried product and active amine with the mass ratio of 3.55:1 as follows: mixing diethylenetriamine, reacting for 5h under the condition that dichloroethane with the mass accounting for 60% of the dried product is dissolved at 25 ℃, then washing to obtain a product, recrystallizing by using ethanol with the mass of dichloroethane and the like, and drying for 45h by using airflow at 55 ℃ to obtain the flame retardant.
Example 6
Step one, reacting trichloro-sulfur phosphorus and neopentyl glycol for 1h under the conditions of 40 ℃ and benzene dissolution with the mole number of 20% of that of the neopentyl glycol, washing with water to obtain a product, and distilling to remove benzene; then utilizing petroleum ether with the mole number of 20 percent of that of benzene for recrystallization, and carrying out airflow drying for 36h at the temperature of 50 ℃;
and step two, mixing the dried product with ethylenediamine according to the mass ratio of 6.64:1, reacting for 3 hours under the condition that dichloroethane with the mass accounting for 40% of the dried product is dissolved at 10 ℃, then washing to obtain a product, recrystallizing with ethanol with the mass of dichloroethane and the like, and drying for 36 hours at 50 ℃ by airflow to obtain the flame retardant.
Example 7
Step one, reacting trichloro-sulfur phosphorus and neopentyl glycol for 3 hours at 80 ℃ under the condition that benzene with the mole ratio of 1:1.5 accounts for 30% of the mole of the neopentyl glycol is dissolved, washing with water to obtain a product, and distilling to remove the benzene; then utilizing petroleum ether with the mole number of 40 percent of that of benzene for recrystallization, and carrying out air flow drying for 48 hours at the temperature of 60 ℃;
and step two, mixing the dried product with the p-phenylenediamine in the mass ratio of 3.69:1, reacting for 6 hours under the condition that dichloroethane accounting for 70% of the dried product is dissolved at 30 ℃, then washing to obtain a product, recrystallizing with ethanol with the mass of dichloroethane and the like, and drying for 48 hours at 60 ℃ by using airflow to obtain the flame retardant.
Example 8
Step one, reacting trichloro-sulfur phosphorus and neopentyl glycol for 1.5 hours at 50 ℃ under the condition that benzene with the mole ratio of 1:1.25 accounts for 25% of the mole of the neopentyl glycol is dissolved, washing with water to obtain a product, and distilling to remove the benzene; then utilizing petroleum ether with the mole number of 30 percent of that of benzene for recrystallization, and drying for 40 hours by air flow at 55 ℃;
and step two, mixing the dried product with m-phenylenediamine in a mass ratio of 3.7:1, reacting for 4 hours at the temperature of 30 ℃ under the condition that dichloroethane accounting for 50% of the dried product is dissolved, washing to obtain a product, recrystallizing with ethanol with the mass of dichloroethane and the like, and drying for 40 hours at the temperature of 55 ℃ by using airflow to obtain the flame retardant.
Example 9
Step one, reacting trichloro-sulfur phosphorus and neopentyl glycol in a molar ratio of 1:1.35 for 2 hours at 60 ℃ under the condition that pyridine with the molar number accounting for 25% of the molar number of the neopentyl glycol is dissolved, washing with water to obtain a product, and distilling to remove the pyridine; then utilizing petroleum ether with the mole number of 30 percent of that of pyridine to recrystallize, and drying for 42 hours by air flow at 55 ℃;
and step two, mixing the dried product with the mass ratio of 3.9:1 with diethylenetriamine, reacting for 5 hours under the condition that dichloroethane with the mass of 60 percent of the dried product is dissolved at 10 ℃, then washing to obtain a product, recrystallizing with ethanol with the mass of dichloroethane and the like, and drying for 42 hours at 55 ℃ by airflow to obtain the flame retardant.
Example 10
Step one, reacting trichloro-sulfur phosphorus and neopentyl glycol for 2.7 hours at 70 ℃ under the condition that pyridine with the mole ratio of 1:1.4 accounts for 25% of the mole of the neopentyl glycol is dissolved, washing with water to obtain a product, and distilling to remove the pyridine; then recrystallizing by using petroleum ether with the mole number of 35 percent of that of pyridine, and drying for 45 hours by using airflow at 55 ℃;
step two, using the dried product and active amine with the mass ratio of 2.73:1 as follows: mixing triethylene tetramine, reacting for 5 hours under the condition that dichloroethane with the mass accounting for 60% of the dried product is dissolved at 25 ℃, then washing to obtain a product, recrystallizing with ethanol with the mass of dichloroethane and the like, and drying for 45 hours at 55 ℃ by using airflow to obtain the flame retardant.
Preparation example of Dispersion
The aqueous dispersion of the compound of formula (1) is prepared as follows:
stirring and dissolving 3 parts of dispersing agent, 2 parts of defoaming agent, 5 parts of wetting agent and 75 parts of water in a dispersing cylinder, gradually adding 28.3 parts of flame retardant under the action of 4m/s shearing and stirring, uniformly stirring, transferring to a ball mill, grinding by using zirconia beads, and grinding at 1200r/min for 3 hours. Then, the dispersion liquid is filtered to obtain a flame retardant dispersion liquid with 25% of the effective component of the flame retardant.
Comparative and examples of Lyocell fiber preparation
Comparative example
The dope was extruded through a metering pump at a rate of 50ml/min from a spinneret with 0.075mm/100 holes, drawn in an air gap of 35mm length, and then coagulated in a 20% NMMO coagulation bath to separate out the fibers. The obtained fiber is subjected to a limit oxygen index test according to a method specified by FZT 50016-2011, and the LOI value is 15 percent; the fiber fineness is 1.3dtex, the dry breaking strength is 4.01CN/dtex, the dry elongation at break is 10 percent, the wet breaking strength is 3.6CN/dtex, and the wet elongation at break is 14.3 percent.
Example 1
A flame retardant dispersion liquid containing 25% by weight of an active ingredient was prepared according to the preparation example of the dispersion liquid, and 90% of the particle diameter was measured to be less than 5um by using a laser particle sizer. And adding a mixed solution of cellulose pulp, an NMMO aqueous solution and a flame retardant dispersion liquid into a reaction kettle in sequence, wherein the flame retardant accounts for 5% of the absolute dry weight of the pulp. The temperature is 70-80 ℃, the mixture is stirred and swelled for 20min, then the temperature is raised to 105-110 ℃, the vacuum pumping is carried out until the pressure is 0.095Mpa, and the vacuum dehydration lasts for 40-60min until the cellulose is completely dissolved. Extruding the spinning solution from a spinneret plate with 0.075mm/100 holes at the speed of 50ml/min by a metering pump, drawing in an air gap with the length of 35mm, and then coagulating and separating out fibers in a 20% NMMO/water coagulating bath; after washing the residual NMMO in the fibres for 30min with an ultrasonic cleaner, the fibres were dried at 105 ℃. The obtained fiber is subjected to a limit oxygen index test according to a method specified by FZT 50016-2011, and the LOI value is 18 percent; the fiber fineness is 1.55dtex, the dry breaking strength is 4.47CN/dtex, the dry breaking elongation is 11.02 percent, the wet breaking strength is 2.98CN/dtex, and the wet breaking elongation is 16.1 percent.
Example 2
A flame retardant dispersion liquid containing 25% by weight of an active ingredient was prepared according to the preparation example of the dispersion liquid, and 90% of the particle diameter was measured to be less than 5um by using a laser particle sizer. And adding a mixed solution of cellulose pulp, an NMMO aqueous solution and a flame retardant dispersion liquid into a reaction kettle in sequence, wherein the flame retardant accounts for 10% of the absolute dry weight of the pulp. The temperature is 70-80 ℃, the mixture is stirred and swelled for 25min, then the temperature is raised to 105-110 ℃, the vacuum pumping is carried out until the pressure is 0.095Mpa, and the vacuum dehydration lasts for 40-60min until the cellulose is completely dissolved. Extruding the spinning solution from a spinneret plate with 0.075mm/100 holes at the speed of 50ml/min by a metering pump, drawing in an air gap with the length of 35mm, and then coagulating and separating out fibers in a 20% NMMO/water coagulating bath; after washing the residual NMMO in the fibres for 30min with an ultrasonic cleaner, the fibres were dried at 105 ℃. The obtained fiber is subjected to a limit oxygen index test according to a method specified by FZT 50016-2011, and the LOI value is 24 percent; the fiber fineness is 1.55dtex, the dry breaking strength is 4.17CN/dtex, the dry elongation at break is 9.5 percent, the wet breaking strength is 3.38CN/dtex, and the wet elongation at break is 14.8 percent.
Example 3
A flame retardant dispersion liquid containing 25% by weight of an active ingredient was prepared according to the preparation example of the dispersion liquid, and 90% of the particle diameter was measured to be less than 5um by using a laser particle sizer. And adding a mixed solution of cellulose pulp, an NMMO aqueous solution and a flame retardant dispersion liquid into a reaction kettle in sequence, wherein the flame retardant accounts for 15% of the absolute dry weight of the pulp. Stirring and swelling at 70-80 deg.C for 30min, heating to 105-. Extruding the spinning solution from a spinneret plate with 0.075mm/100 holes at the speed of 50ml/min by a metering pump, drawing in an air gap with the length of 35mm, and then coagulating and separating out fibers in a 20% NMMO/water coagulating bath; after washing the residual NMMO in the fibres for 30min with an ultrasonic cleaner, the fibres were dried at 105 ℃. The obtained fiber is subjected to a limit oxygen index test according to a method specified by FZT 50016-2011, and the LOI value is 28 percent; the fiber fineness is 1.55dtex, the dry breaking strength is 3.56CN/dtex, the dry elongation at break is 8.9 percent, the wet breaking strength is 3.02CN/dtex, and the wet elongation at break is 12.1 percent.
Example 4
A flame retardant dispersion having an active ingredient of 20% by weight was prepared according to the preparation examples of the dispersion, and 90% of the particle diameter was measured to be less than 5um by using a laser particle sizer. And adding a mixed solution of cellulose pulp, an NMMO aqueous solution and a flame retardant dispersion liquid into a reaction kettle in sequence, wherein the flame retardant accounts for 20% of the absolute dry weight of the pulp. The temperature is 70-80 ℃, the mixture is stirred and swelled for 35min, then the temperature is raised to 105-110 ℃, the vacuum pumping is carried out until the pressure is 0.095Mpa, and the vacuum dehydration lasts for 40-60min until the cellulose is completely dissolved. Extruding the spinning solution from a spinneret plate with 0.075mm/100 holes at the speed of 50ml/min by a metering pump, drawing in an air gap with the length of 35mm, and then coagulating and separating out fibers in a 20% NMMO/water coagulating bath; after washing the residual NMMO in the fibres for 30min with an ultrasonic cleaner, the fibres were dried at 105 ℃. The obtained fiber is subjected to a limit oxygen index test according to a method specified by FZT 50016-2011, and the LOI value is 29.2 percent; the fiber fineness is 1.55dtex, the dry breaking strength is 3.18CN/dtex, the dry elongation at break is 7.4 percent, the wet breaking strength is 2.77CN/dtex, and the wet elongation at break is 11.4 percent.
Example 5
A flame retardant dispersion liquid containing 25% by weight of an active ingredient was prepared according to the preparation example of the dispersion liquid, and 90% of the particle diameter was measured to be less than 5um by using a laser particle sizer. And adding a mixed solution of cellulose pulp, an NMMO aqueous solution and a flame retardant dispersion liquid into a reaction kettle in sequence, wherein the flame retardant accounts for 25% of the absolute dry weight of the pulp. The temperature is 70-80 ℃, the mixture is stirred and swelled for 40min, then the temperature is raised to 105-110 ℃, the vacuum pumping is carried out until the pressure is 0.095Mpa, and the vacuum dehydration lasts for 40-60min until the cellulose is completely dissolved. Extruding the spinning solution from a spinneret plate with 0.075mm/100 holes at the speed of 50ml/min by a metering pump, drawing in an air gap with the length of 35mm, and then coagulating and separating out fibers in a 20% NMMO/water coagulating bath; after washing the residual NMMO in the fibres for 30min with an ultrasonic cleaner, the fibres were dried at 105 ℃. The obtained fiber is subjected to a limit oxygen index test according to a method specified by FZT 50016-2011, and the LOI value is 30 percent; the fiber fineness is 1.55dtex, the dry breaking strength is 3.21CN/dtex, the dry elongation at break is 8.6 percent, the wet breaking strength is 2.85CN/dtex, and the wet elongation at break is 12.5 percent.
Example 6
A flame retardant dispersion liquid containing 25% by weight of an active ingredient was prepared according to the preparation example of the dispersion liquid, and 90% of the particle diameter was measured to be less than 5um by using a laser particle sizer. And adding a mixed solution of cellulose pulp, an NMMO aqueous solution and a flame retardant dispersion liquid into a reaction kettle in sequence, wherein the flame retardant accounts for 30% of the absolute dry weight of the pulp. Stirring and swelling at 70-80 deg.C for 45min, heating to 105-. Extruding the spinning solution from a spinneret plate with 0.075mm/100 holes at the speed of 50ml/min by a metering pump, drawing in an air gap with the length of 35mm, and then coagulating and separating out fibers in a 20% NMMO/water coagulating bath; after washing the residual NMMO in the fibres for 30min with an ultrasonic cleaner, the fibres were dried at 105 ℃. The obtained fiber is subjected to a limit oxygen index test according to a method specified by FZT 50016-2011, and the LOI value is 33 percent; the fiber fineness is 1.55dtex, the dry breaking strength is 3.06CN/dtex, the dry elongation at break is 7.7 percent, the wet breaking strength is 2.72CN/dtex, and the wet elongation at break is 11.3 percent.
Example 7
A flame retardant dispersion liquid containing 25% by weight of an active ingredient was prepared according to the preparation example of the dispersion liquid, and 90% of the particle diameter was measured to be less than 5um by using a laser particle sizer. And adding a mixed solution of cellulose pulp, an NMMO aqueous solution and a flame retardant dispersion liquid into a reaction kettle in sequence, wherein the flame retardant accounts for 35% of the absolute dry weight of the pulp. The temperature is 70-80 ℃, the mixture is stirred and swelled for 50min, then the temperature is raised to 105-110 ℃, the vacuum pumping is carried out until the pressure is 0.095Mpa, and the vacuum dehydration lasts for 40-60min until the cellulose is completely dissolved. Extruding the spinning solution from a spinneret plate with 0.075mm/100 holes at the speed of 50ml/min by a metering pump, drawing in an air gap with the length of 35mm, and then coagulating and separating out fibers in a 20% NMMO/water coagulating bath; after washing the residual NMMO in the fibres for 30min with an ultrasonic cleaner, the fibres were dried at 105 ℃. The obtained fiber is subjected to a limit oxygen index test according to a method specified by FZT 50016-2011, and the LOI value is 35.8 percent; the fiber fineness is 1.55dtex, the dry breaking strength is 2.81CN/dtex, the dry elongation at break is 7.2 percent, the wet breaking strength is 2.16CN/dtex, and the wet elongation at break is 10.6 percent.
Example 8
A flame retardant dispersion liquid containing 25% by weight of an active ingredient was prepared according to the preparation example of the dispersion liquid, and 90% of the particle diameter was measured to be less than 5um by using a laser particle sizer. And adding a mixed solution of cellulose pulp, an NMMO aqueous solution and a flame retardant dispersion liquid into a reaction kettle in sequence, wherein the flame retardant accounts for 40% of the absolute dry weight of the pulp. The temperature is 70-80 ℃, the mixture is stirred and swelled for 55min, then the temperature is raised to 105-110 ℃, the vacuum pumping is carried out until the pressure is 0.095Mpa, and the vacuum dehydration lasts for 40-60min until the cellulose is completely dissolved. Extruding the spinning solution from a spinneret plate with 0.075mm/100 holes at the speed of 50ml/min by a metering pump, drawing in an air gap with the length of 35mm, and then coagulating and separating out fibers in a 20% NMMO/water coagulating bath; after washing the residual NMMO in the fibres for 30min with an ultrasonic cleaner, the fibres were dried at 105 ℃. The obtained fiber is subjected to a limit oxygen index test according to a method specified by FZT 50016-2011, and the LOI value is 35 percent; the fiber fineness is 1.55dtex, the dry breaking strength is 2.5CN/dtex, the dry elongation at break is 6.2 percent, the wet breaking strength is 2.1CN/dtex, and the wet elongation at break is 8.9 percent.
Example 9
A flame retardant dispersion liquid containing 25% by weight of an active ingredient was prepared according to the preparation example of the dispersion liquid, and 90% of the particle diameter was measured to be less than 5um by using a laser particle sizer. And adding a mixed solution of cellulose pulp, an NMMO aqueous solution and a flame retardant dispersion liquid into a reaction kettle in sequence, wherein the flame retardant accounts for 45% of the absolute dry weight of the pulp. Stirring and swelling at 70-80 deg.C for 60min, heating to 105-. Extruding the spinning solution from a spinneret plate with 0.075mm/100 holes at the speed of 50ml/min by a metering pump, drawing in an air gap with the length of 35mm, and then coagulating and separating out fibers in a 20% NMMO/water coagulating bath; after washing the residual NMMO in the fibres for 30min with an ultrasonic cleaner, the fibres were dried at 105 ℃. The obtained fiber is subjected to a limit oxygen index test according to a method specified by FZT 50016-2011, and the LOI value is 36.3 percent; the fiber fineness is 1.55dtex, the dry breaking strength is 2.21CN/dtex, the dry elongation at break is 5.4 percent, the wet breaking strength is 1.16CN/dtex, and the wet elongation at break is 8.4 percent.
Example 10
A flame retardant dispersion liquid containing 25% by weight of an active ingredient was prepared according to the preparation example of the dispersion liquid, and 90% of the particle diameter was measured to be less than 5um by using a laser particle sizer. And adding a mixed solution of cellulose pulp, an NMMO aqueous solution and a flame retardant dispersion liquid into a reaction kettle in sequence, wherein the flame retardant accounts for 50% of the absolute dry weight of the pulp. Stirring and swelling at 70-80 deg.C for 60min, heating to 105-. Extruding the spinning solution from a spinneret plate with 0.075mm/100 holes at the speed of 50ml/min by a metering pump, drawing in an air gap with the length of 35mm, and then coagulating and separating out fibers in a 20% NMMO/water coagulating bath; after washing the residual NMMO in the fibres for 30min with an ultrasonic cleaner, the fibres were dried at 105 ℃. The obtained fiber is subjected to a limit oxygen index test according to a method specified by FZT 50016-2011, and the LOI value is 39 percent; the fiber fineness is 1.55dtex, the dry breaking strength is 1.83CN/dtex, the dry elongation at break is 4.8 percent, the wet breaking strength is 1.26CN/dtex, and the wet elongation at break is 7.3 percent.
As can be seen from the examples and comparative examples, the limiting oxygen index of the fiber is obviously improved along with the increase of the addition amount of the flame retardant, the addition amount is higher than 25 percent, the flame retardant level is achieved, and the strength and the elongation are reduced.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (10)
1. A flame retardant comprising a compound component having the formula:
wherein X represents O or S; r represents an alkyl structure or a benzene ring structure of active amine; n represents any one or a mixture of 2, 3 and 4.
2. The flame retardant of claim 1, wherein the alkyl structure of the reactive amine is selected from one or more of ethylenediamine, diethylenetriamine, and triethylenetetramine.
3. The flame retardant of claim 1, wherein the benzene ring structure of the reactive amine is selected from any one of p-phenylenediamine and m-phenylenediamine or a mixture thereof.
4. A process for the preparation of the flame retardant of any of claims 1 to 3, characterized by comprising the steps of:
the first component is formed by phosphorus trichloride or phosphorus oxychloride and neopentyl glycol in a molar ratio of 1 (1-1.5);
benzene or pyridine with the mole number accounting for 20-30% of the mole number of the neopentyl glycol forms a second component;
the first component and the second component react under the condition of dissolution to obtain a first intermediate product, wherein the value range of the reaction duration is 1h-3h, and the value range of the reaction temperature is 40-80 ℃;
washing the first intermediate product with water, and distilling to remove benzene or pyridine to obtain a second intermediate product;
the second intermediate product is sequentially recrystallized by using petroleum ether with the mole number of 20-40% of that of the second component, and is dried for 36-48 h by airflow at 50-60 ℃ to obtain a third intermediate product;
mixing the third intermediate product and the active amine in a mass ratio range (2.5-6.1): 1 to form a third component;
dichloroethane accounting for 40-70% of the third intermediate product by mass is taken as a fourth component;
reacting the third component and the fourth component under the condition of dissolution to obtain a fourth intermediate product, wherein the reaction temperature is in the range of 10-30 ℃, and the reaction duration is in the range of 3-6 h;
washing the fourth intermediate product with water to obtain a fifth intermediate product;
and recrystallizing the fifth intermediate product under the condition of ethanol to obtain the flame retardant, wherein the mass of the ethanol is equal to that of the dichloroethane, the recrystallization reaction temperature is in a range of 50-60 ℃, and the airflow drying duration time is in a range of 36-48 h.
5. A flame retardant Lyocell fiber comprising a cellulosic fiber matrix and the flame retardant of any of claims 1 to 3, wherein said flame retardant is dispersed within said cellulosic fiber matrix.
6. The method for preparing the flame retardant Lyocell fiber according to claim 5, comprising the steps of:
the flame retardant of any one of claims 1-3 premixed with a solution of NMMO to produce a first mixed liquor, wherein the particle size of the flame retardant in the first mixed liquor ranges from 0 μm to 5 μm;
premixing, stirring and swelling the first mixed solution and cellulose fiber pulp in sequence to obtain a second mixed solution with complete swelling;
dehydrating the second mixed solution to completely dissolve the cellulose fibers to obtain a spinning solution;
the flame-retardant Lyocell fiber is prepared by spinning the spinning solution,
wherein, the flame retardant accounts for 5 to 50 percent of the absolute dry mass percentage content of the cellulose fiber pulp.
7. The method of claim 6, wherein during the steps of pre-mixing, agitating, and swelling the first mixed solution with the cellulose-based fiber pulp in sequence to obtain a second mixed solution with complete swelling,
the stirring temperature is 70-80 ℃,
the value range of the swelling duration is 20min-60min,
the pulp in the second mixed solution is in a uniform and fine pulp porridge state with microfiber and no white core.
8. The method according to claim 6, wherein the second mixture is dehydrated to completely dissolve the cellulose fiber, and the spinning solution is light brown and transparent during the step of obtaining the spinning solution.
9. The method for preparing the flame-retardant Lyocell fiber according to claim 6, wherein during the step of spinning the spinning solution to obtain the flame-retardant Lyocell fiber, the spinning specifically comprises the following steps:
and the spinning solution is subjected to dry-jet wet spinning, spinneret plate extrusion, solidification, drafting, water washing, cutting and drying in sequence to prepare the flame-retardant Lyocell fiber.
10. The method for preparing the flame-retardant Lyocell fiber according to claim 6, wherein the flame retardant according to any one of claims 1 to 3 is premixed with the NMMO solution to obtain a first mixed solution, wherein during the step of the first mixed solution, the particle size of the flame retardant ranges from 0 μm to 5 μm,
directly adding the flame retardant into a Lyocell cellulose solution before spinning and forming; alternatively, the first and second electrodes may be,
preparing a flame retardant into a dispersion liquid according to a preparation process of the Lyocell fiber, and adding the dispersion liquid into an aqueous solution of the Lyocell cellulose in NMMO;
preferably, the flame retardant according to any one of claims 1 to 3 is premixed with the NMMO solution to obtain a first mixed solution, wherein the step of the first mixed solution in which the particle size of the flame retardant ranges from 0 μm to 5 μm specifically includes the following steps:
preparing a flame-retardant mixture from a dispersion medium, a dispersing agent and a flame retardant in a grinding mode;
premixing the flame-retardant mixture with an NMMO solution to obtain a first mixed solution;
wherein, the grinding equipment is selected from one or more of a ball mill and a sand mill, the beads for grinding are selected from one or more of steel balls and zirconia beads, and the average particle size of insoluble substances in the flame-retardant mixture is 0.3-5 um;
preferably, the flame-retardant mixture comprises the following components in parts by mass:
flame retardant: 10-50 parts;
dispersing agent: 2-20 parts;
defoaming agent: 1-5 parts;
wetting agent: 1-10 parts;
the balance of a dispersion medium, wherein the dispersion medium is selected from water or an aqueous solution of NMMO;
preferably, the dispersant is one or a mixture of several of sodium dodecyl benzene sulfonate, sodium maleate, sodium polyacrylate and tween-80;
preferably, the defoaming agent is one or a mixture of more of dyhi 4000, dyhi 902w and dyhi 810 w;
preferably, the wetting agent is one or a combination of BYK-190, digao-245, digao 270 and GS-2082.
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| WO2024077915A1 (en) * | 2022-10-12 | 2024-04-18 | 中国纺织科学研究院有限公司 | Lyocell fiber modified by compound flame retardant and preparation method therefor |
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Application publication date: 20210813 |