CN105821523A - Sodium alga acid flame retardant fibers loaded with metal ions and manufacture method thereof - Google Patents

Sodium alga acid flame retardant fibers loaded with metal ions and manufacture method thereof Download PDF

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Publication number
CN105821523A
CN105821523A CN201610277990.2A CN201610277990A CN105821523A CN 105821523 A CN105821523 A CN 105821523A CN 201610277990 A CN201610277990 A CN 201610277990A CN 105821523 A CN105821523 A CN 105821523A
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sodium alginate
metal ion
hybrid material
aqueous solution
fire resistance
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CN105821523B (en
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孙宾
纪晓寰
朱美芳
王斌
肖露露
周伊
李浩洋
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Donghua University
National Dong Hwa University
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Donghua University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/04—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of alginates
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • 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

Abstract

The invention provides sodium alga acid flame retardant fibers loaded with metal ions and a preparation method thereof. The sodium alga acid flame retardant fibers are prepared by the following steps: dissolving a water soluble sodium alga acid hybrid material loaded with metal ions in water to prepare a spinning solution, and performing a wet spinning process, wherein the water soluble sodium alga acid hybrid material loaded with metal ions is composed of sodium alga acid, stabilizer molecules and the metal ions with flame retardant effect. The fibers produced by the method disclosed by the invention have the characteristics of high flame retardant property and high breaking strength. The limit oxygen index of the fibers can be 34% and above, the tensile strength of the fibers is higher than 3.5cN/tex, and the linear density is 2.2-3.5dtex.

Description

A kind of sodium alginate fire resistance fibre of loaded metal ion and preparation method thereof
Technical field
Sodium alginate fire resistance fibre that the present invention relates to a kind of loaded metal ion and preparation method thereof, uses the sodium alginate hybrid material of loaded metal ion as spinning material, the sodium alginate Prospect for Flame Retardant Fiber Materials prepared by wet spinning process particularly to a kind of.
Background technology
At aspects such as work clothes, firefighter's garment, cloth system, system interior trim, system and commercial carpets, transport, military clothing and bedding, Fire-proof Finishing Agents for Textile performance requirement is the highest.Research to the fire resistance of Textile material is also constantly subjected to the concern of people.But environmental regulation limits the selection of some halogen series flame retardant material, the recycling to discarded fire proofing goods is the most very urgent simultaneously.The fire proofing used from now on, it is necessary to simultaneously meet the requirement of these two aspects.Environmental requirement to fire proofing has been imperative at present.Meanwhile, stricter flame retardant regulation also requires to use some heat stability height, low, the raw smoke of heat release rate little and the high efficiency flame retardant material of low toxicity.Have now been found that the biomass resource native cellulose based on plant and the biomass resource alginic acid based on marine organisms, there is the advantages such as rich reserves, renewable and non-secondary pollution, be the preferable living resources of human future.And the biomass resource alginic acid based on marine organisms is with the fire resistance of its excellence, of increased attention.
And the most traditional stock solution spin processes is to be placed in spinning liquid by nano metal when spinning, making flame-retardant textile, the great advantage of this method is that nano metal may be homogenously dispersed in fibrous inside, good endurance, and uses safety because stripping quantity is few.But nano metal surface can be the biggest, it is easy to assemble, spinning process easily blocks spinneret orifice, continuous comparision of production difficulty.It addition, be directly added into metal material often there is the problem in fibrous inside instability, affect the use of fire resistance fibre.Therefore solve metal nanoparticle dispersibility in sodium alginate fibrous matrix and stability is problem demanding prompt solution.
Summary of the invention
It is an object of the invention to as solving in existing sodium alginate fire resistance fibre, metal nanoparticle bad dispersibility and the problem of poor stability, it is provided that sodium alginate fire resistance fibre of a kind of loaded metal ion and preparation method thereof.The present invention uses the sodium alginate hybrid material of water soluble negative carrying metal ion as the raw material preparing fire resistance fibre, this hybrid material has good water solublity, this hybrid material stable being dispersed in water of energy i.e., its aqueous solution is not have obvious particulate matter to suspend or the transparent system of precipitation.In the preparation process of this hybrid material, by the pH value of regulation system, form metal ion to be bonded with the ionic bond between sodium alginate and stabilizer molecule and coordinate bond, metal ion can be supported on carrier sodium alginate class material with ionic state form always, and disperse in aqueous, and be easily reduced without the metal ion in aqueous solution during stabilizer molecular species stabilizer.Finally use wet spinning technology that this hybrid material raw material is prepared as sodium alginate fire resistance fibre so that the sodium alginate fire resistance fibre of loaded metal ion prepared by the present invention has the advantages such as inherent flame retardant, fracture strength height and biodegradable.
For achieving the above object, the present invention is achieved by the following technical programs:
A kind of sodium alginate fire resistance fibre of the loaded metal ion of the present invention, its by the sodium alginate hybrid material of water soluble negative carrying metal ion be dissolved in water prepare spinning solution through wet spinning technology prepare；The sodium alginate hybrid material of described water soluble negative carrying metal ion is by sodium alginate, stabilizer molecule and has the metal ion of flame retardant effect and forms；In the sodium alginate hybrid material of described water soluble negative carrying metal ion, by ionic bond and coordinate bond keyed jointing between the carboxyl of sodium alginate, the amino of stabilizer molecule and the metal ion with flame retardant effect；
In described sodium alginate and described stabilizer molecule, carboxyl-content, amino content and hydroxy radical content sum are more than or equal to described sodium alginate and the 160% of the mole sum of described stabilizer molecule；Carboxyl, amino and hydroxyl hydrophilic group in sodium alginate, stabilizer molecular complex is to ensure that the water miscible principal element of Compound complex, 160% this numerical value are to ensure that Compound complex can have water miscible minimum numerical value；
Described by ionic bond and the carboxyl of coordinate bond keyed jointing and described by the amino content sum of ionic bond and coordinate bond keyed jointing more than or equal to carboxyl and the 30% of amino mole sum in described sodium alginate and described stabilizer molecule；
Relative molecular weight >=10000 of described sodium alginate；
Relative molecular weight≤5000 of described stabilizer molecule, for chain length less than the one in the alkyl streptamine of 6 carbon, polyetheramine D230, polyetheramine D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, aliphatic amine polyoxyethylene ether AC-1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, aliphatic amine polyoxyethylene ether AC-1205, aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；Described chain length is n-propylamine, n-butylamine, n-amylamine or n-hexylamine less than the alkyl streptamine of 6 carbon；
The general structure of the sodium alginate hybrid material of described water soluble negative carrying metal ion is:
Wherein, strand repetitive number n > 0；
Wherein, the one during R is following functional group: cation group, anionic group or polar nonionic group；Described cation group is tertiary amine base or quaternary ammonium group；Described anionic group is carboxylic acid group；Described polar nonionic group is hydroxyl, ether, amino, amide groups, sulfydryl or halogen；
Mx+For having the metal ion of flame retardant effect, the value of valence state x is 1～3, for: Ag+、Fe2+、Fe3+、Zn2+Or Cu2+。
The mechanism that triangle bonding scheme stable in general structure schematic diagram is formed is as follows :-the COO in sodium alginate and stabilizer molecule-With-NH3 +Because the attraction of positive and negative charge, produce electrostatic attraction, i.e. form ionic bond；-COO-In hydroxyl oxygen on have lone pair electrons, therefore lone pair electrons enter metal ion unoccupied orbital be combined with metal ion generation covalent coordinate, formation coordinate bond；-NH3 +In atom N there is also lone pair electrons, lone pair electrons and metal ion can be provided equally to form coordinate bond and to be combined.Therefore the stable triangle bonding scheme in general structure schematic diagram is defined.
In the process, the pH value of reaction system is to-COO in system-、-NH3 +And Mx+The formation of bonding structure has a great impact.-NH in sodium alginate2< in the case of 7, formation-NH can be combined by the H proton of excess in solution at pH value3 +；Along with the rising of pH value, to neutrality or alkalescence, H proton free in solution reduces, it is impossible to form-NH again3 +Structure.For-the COOH in sodium alginate and stabilizer molecule, at strong acid condition pH value, < when 2, the dissociation of-COOH is suppressed ,-COO in system-Content less, therefore the complexing power of metal ion is weakened significantly；Along with pH value increases, it is gradually increased with the complexing power of metal ion, when solution ph reaches 5～7 ,-COO-Tend to maximum with metal ion combination degree；But when the pH value of system improves again ,-NH can be destroyed again3 +Structure, thus destroy the three-legged structure relation of stable system of making.Therefore, in order to form the stable stable triangle bonding scheme as shown in schematic diagram, so the pH value of necessary effective adjustment and control system, and ensure that pH value is in the range of 4～6.
As preferred technical scheme:
The sodium alginate fire resistance fibre of a kind of loaded metal ion as above, described stabilizer molecule also comprises hydroxyl or carboxyl.
The sodium alginate fire resistance fibre of a kind of loaded metal ion as above, described carboxyl is positioned at molecular backbone or side chain；Described amino is positioned at molecular backbone or side chain.
The sodium alginate fire resistance fibre of a kind of loaded metal ion as above, described stabilizer molecular backbone also includes element O, N or S common in Organic substance.
The sodium alginate fire resistance fibre of a kind of loaded metal ion as above, the load capacity of the metal ion in the sodium alginate hybrid material of described water soluble negative carrying metal ion with flame retardant effect is 10～825mg/g；The sodium alginate fire resistance fibre limited oxygen index of described loaded metal ion reaches more than 34%, and the hot strength of fiber is more than 3.5cN/tex, and line density is 2.2～3.5dtex.
Present invention also offers the preparation method of the sodium alginate fire resistance fibre of a kind of loaded metal ion, by sodium alginate aqueous solution and the aqueous solution containing stabilizer molecule, the pH value of regulation reaction system is to 4～6, then in mixed liquor, drip metal ion salt solution, stir after dropping, obtain the hybrid material aqueous solution of the sodium alginate of loaded metal ion, continuously stirred and add precipitant, precipitate is collected by filtration, after drying precipitate, i.e. obtains the sodium alginate hybrid material of water soluble negative carrying metal ion；The sodium alginate hybrid material of water soluble negative carrying metal ion is dissolved in deionized water, stirs, be made into wet spinning solution, use wet spinning technology, obtain the sodium alginate fire resistance fibre of loaded metal ion.
The preparation method of the sodium alginate fire resistance fibre of a kind of loaded metal ion as above, by the aqueous solution of sodium alginate and the aqueous solution containing stabilizer molecule, is under the conditions of 20～60 DEG C；Stirring is accompanied by during mixing；The pH value of regulation reaction system uses the H of HCl solution, 0.05～the 0.15mol/L of 0.1～0.3mol/L2SO4Solution or the HNO of 0.1～0.3mol/L3Solution regulates；Stirring after metal ion salt solution dropping, the persistent period is 1～2h；Drying precipitate uses vacuum drying oven to be dried.
The preparation method of the sodium alginate fire resistance fibre of a kind of loaded metal ion as above, described metal ion salt solution is AgNO3、FeCl2、FeCl3、ZnCl2Or CuSO4Aqueous solution；Described precipitant is ethanol or acetone.
When the preparation method of the sodium alginate fire resistance fibre of a kind of loaded metal ion as above, the aqueous solution of described sodium alginate and the aqueous solution containing stabilizer molecule, sodium alginate is 1:0.3～1 with the mol ratio of stabilizer molecule；
The mass percent concentration of described sodium alginate aqueous solution is 0.5%～3%；
The mass percent concentration of the described aqueous solution containing stabilizer molecule is 3%～10%；
The concentration of described metal ion salt solution is 0.005～2g/mL；
Described metal cation salt is 0.1～10:1 with the mol ratio of sodium alginate；
The mass percent concentration of the hybrid material aqueous solution of the sodium alginate of described loaded metal ion is 0.5%～10.5%；
Described precipitant is 2～4:1 with the volume ratio of the aqueous solution of the sodium alginate hybrid material of load factor metal ion；
The temperature of described drying precipitate is 25～30 DEG C, and vacuum is 0.09～-0.1MPa.
The preparation method of the sodium alginate fire resistance fibre of a kind of loaded metal ion as above, described wet spinning technology is: in spinning solution, the mass concentration percentage ratio of the sodium alginate hybrid material of loaded metal ion is 1～10%, spinning temperature is 10～60 DEG C, coagulating bath be mass percent concentration be calcium chloride solution or calcium chloride that mass percent concentration is 1%～15% and the zinc chloride mixed solution of 1%～15%, calcium chloride and calcium chloride in zinc chloride mixed solution and the mass ratio 1～3:1 of zinc chloride, coagulation bath temperature is 10～50 DEG C, draw ratio is 120%～300%.
Beneficial effect:
The sodium alginate fire resistance fibre of loaded metal ion prepared by the employing present invention has the advantages such as inherent flame retardant, fracture strength height and biodegradable, with natural sea sodium alginate fiber as carrier, with stabilizer molecule for auxiliary, stable for metal ion is dispersed on sodium alginate matrix.Less input for the instrument and equipment that preparation process uses, and operating process is the most easy to implement, and the raw material environmental friendliness and pollution-free used in course of reaction, impurity in products is few, it is easy to post processing, and whole course of reaction is conducive to industrial amplification production.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is expanded on further.Should be understood that these embodiments are merely to illustrate the present invention rather than limit the scope of the present invention.In addition, it is to be understood that after having read the content that the present invention lectures, the present invention can be made various changes or modifications by those skilled in the art, and these equivalent form of values fall within the application appended claims limited range equally.
A kind of sodium alginate fire resistance fibre of the loaded metal ion of the present invention by the sodium alginate hybrid material of water soluble negative carrying metal ion be dissolved in water prepare spinning solution through wet spinning technology prepare；The sodium alginate hybrid material of described water soluble negative carrying metal ion is by sodium alginate, stabilizer molecule and has the metal ion of flame retardant effect and forms；In the sodium alginate hybrid material of described water soluble negative carrying metal ion, by ionic bond and coordinate bond keyed jointing between the carboxyl of sodium alginate, the amino of stabilizer molecule and the metal ion with flame retardant effect；
In described sodium alginate and described stabilizer molecule, carboxyl-content, amino content and hydroxy radical content sum are more than or equal to described sodium alginate and the 160% of the mole sum of described stabilizer molecule；
Described by ionic bond and the carboxyl of coordinate bond keyed jointing and described by the amino content sum of ionic bond and coordinate bond keyed jointing more than or equal to carboxyl and the 30% of amino mole sum in described sodium alginate and described stabilizer molecule；
Relative molecular weight >=10000 of described sodium alginate；
Relative molecular weight≤5000 of described stabilizer molecule, for chain length less than the one in the alkyl streptamine of 6 carbon, polyetheramine D230, polyetheramine D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, aliphatic amine polyoxyethylene ether AC-1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, aliphatic amine polyoxyethylene ether AC-1205, aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；Described chain length is n-propylamine, n-butylamine, n-amylamine or n-hexylamine less than the alkyl streptamine of 6 carbon；
The general structure of the sodium alginate hybrid material of described water soluble negative carrying metal ion is:
Wherein, strand repetitive number n > 0；
Wherein, the one during R is following functional group: cation group, anionic group or polar nonionic group；Described cation group is tertiary amine base or quaternary ammonium group；Described anionic group is carboxylic acid group；Described polar nonionic group is hydroxyl, ether, amino, amide groups, sulfydryl or halogen；
Mx+For having the metal ion of flame retardant effect, the value of valence state x is 1～3, for: Ag+、Fe2+、Fe3+、Zn2+Or Cu2+。
The sodium alginate fire resistance fibre of a kind of loaded metal ion as above, described stabilizer molecule also comprises hydroxyl or carboxyl.
The sodium alginate fire resistance fibre of a kind of loaded metal ion as above, described carboxyl is positioned at molecular backbone or side chain；Described amino is positioned at molecular backbone or side chain.
The sodium alginate fire resistance fibre of a kind of loaded metal ion as above, described stabilizer molecular backbone also includes element O, N or S common in Organic substance.
The sodium alginate fire resistance fibre of a kind of loaded metal ion as above, the load capacity of the metal ion in the sodium alginate hybrid material of described water soluble negative carrying metal ion with flame retardant effect is 10～825mg/g；The sodium alginate fire resistance fibre limited oxygen index of described loaded metal ion reaches more than 34%, and the hot strength of fiber is more than 3.5cN/tex, and line density is 2.2～3.5dtex.
Embodiment 1
A kind of loaded Ag+The preparation method of sodium alginate fire resistance fibre, under the conditions of 20 DEG C, by the aqueous solution of n-amylamine that the aqueous solution of sodium alginate that mass percent concentration is 0.5% and mass percent concentration are 3%, sodium alginate is 1:0.3 with the mol ratio of n-amylamine, the relative molecular weight of sodium alginate and n-amylamine is respectively 25000 and 87.16, accompanying by stirring during mixing, with the HCl solution of 0.1mol/L, the pH value of system is adjusted to 4, then dripping concentration in mixed liquor is the AgNO of 0.005g/mL3Aqueous solution, AgNO3Being 0.1:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 1h, i.e. obtains loaded Ag+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 0.5%, continuously stirred and add precipitant ethanol, precipitant ethanol and loaded Ag+The volume ratio of hybrid material aqueous solution of sodium alginate be 2:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 2 times, precipitate is 25 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity loaded Ag under the conditions of 0.09MPa+Sodium alginate hybrid material, this hybrid material has the Ag of flame retardant effect+Load capacity be 42mg/g.
Water solublity loaded Ag by preparation+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 1%, use wet spinning technology, obtain loaded Ag+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 10 DEG C, coagulation bath composition be mass percent concentration be the calcium chloride solution of 1%, coagulation bath temperature is 10 DEG C, and draw ratio is 120%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.51cN/tex, and line density is 2.2dtex, and limited oxygen index is 34.1%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 2
A kind of load Fe2+The preparation method of sodium alginate fire resistance fibre, under the conditions of 60 DEG C, by the aqueous solution of n-butylamine that the aqueous solution of sodium alginate that mass percent concentration is 0.6% and mass percent concentration are 6%, sodium alginate is 1:0.7 with the mol ratio of n-butylamine, the relative molecular weight of sodium alginate and n-butylamine is respectively 250000 and 73.14, accompanying by stirring during mixing, with the HCl solution of 0.15mol/L, the pH value of system is adjusted to 6, then dripping concentration in mixed liquor is the FeCl of 0.2g/mL2Aqueous solution, FeCl2Being 2.5:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 2h, i.e. obtains loading Fe2+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 1.2%, continuously stirred and add precipitant acetone, precipitant acetone and load Fe2+The volume ratio of hybrid material aqueous solution of sodium alginate be 4:1, collected by suction precipitate, repeatedly rinse precipitate with acetone 3 times, precipitate is 30 DEG C in temperature, and vacuum the most i.e. obtains water solublity load Fe for vacuum drying oven under the conditions of-0.1MPa2+Sodium alginate hybrid material, this hybrid material has the Fe of flame retardant effect2+Load capacity be 263mg/g.
By the water solublity load Fe of preparation2+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 2%, use wet spinning technology, obtain loading Fe2+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 20 DEG C, coagulation bath composition be mass percent concentration be the calcium chloride solution of 3%, coagulation bath temperature is 15 DEG C, and draw ratio is 130%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.53cN/tex, and line density is 2.5dtex, and limited oxygen index is 35.3%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 3
A kind of load Fe3+The preparation method of sodium alginate fire resistance fibre, under the conditions of 25 DEG C, by the aqueous solution of polyetheramine D400 that the aqueous solution of sodium alginate that mass percent concentration is 1% and mass percent concentration are 4%, sodium alginate is 1:0.5 with the mol ratio of polyetheramine D400, the relative molecular weight of sodium alginate and polyetheramine D400 is respectively 10000 and 400, stirring is accompanied by during mixing, with the HCl solution of 0.2mol/L, the pH value of system being adjusted to 6, then dripping concentration in mixed liquor is the FeCl of 0.1g/mL3Aqueous solution, FeCl3Being 0.5:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 1.5h, i.e. obtains loading Fe3+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 1.5%, continuously stirred and add precipitant acetone, precipitant acetone and load Fe3+The volume ratio of hybrid material aqueous solution of sodium alginate be 3:1, collected by suction precipitate, repeatedly rinse precipitate with acetone 2 times, precipitate is 26 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity load Fe under the conditions of 0.09MPa3+Sodium alginate hybrid material, this hybrid material has the Fe of flame retardant effect3+Load capacity be 10mg/g.
By the water solublity load Fe of preparation3+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 3%, use wet spinning technology, obtain loading Fe3+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 25 DEG C, coagulation bath composition be mass percent concentration be the calcium chloride solution of 5%, coagulation bath temperature is 20 DEG C, and draw ratio is 140%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.58cN/tex, and line density is 2.5dtex, and limited oxygen index is 36.1%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 4
A kind of load Zn2+The preparation method of sodium alginate fire resistance fibre, under the conditions of 30 DEG C, by the aqueous solution of polyetheramine D2000 that the aqueous solution of sodium alginate that mass percent concentration is 1% and mass percent concentration are 5%, sodium alginate is 1:0.5 with the mol ratio of polyetheramine D2000, the relative molecular weight of sodium alginate and polyetheramine D2000 is respectively 30000 and 2000, stirring is accompanied by during mixing, with the HCl solution of 0.25mol/L, the pH value of system being adjusted to 5, then dripping concentration in mixed liquor is the ZnCl of 1g/mL2Aqueous solution, ZnCl2Being 0.5:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 1h, i.e. obtains loading Zn2+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 2.9%, continuously stirred and add precipitant ethanol, precipitant ethanol and load Zn2+The volume ratio of hybrid material aqueous solution of sodium alginate be 4:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 2 times, precipitate is 27 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity load Zn under the conditions of 0.09MPa2+Sodium alginate hybrid material, this hybrid material has the Zn of flame retardant effect2+Load capacity be 73mg/g.
By the water solublity load Zn of preparation2+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 2%, use wet spinning technology, obtain loading Zn2+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 30 DEG C, coagulation bath composition be mass percent concentration be the calcium chloride solution of 7%, coagulation bath temperature is 25 DEG C, and draw ratio is 150%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.63cN/tex, and line density is 2.6dtex, and limited oxygen index is 35.3%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 5
A kind of loaded Cu2+The preparation method of sodium alginate fire resistance fibre, under the conditions of 50 DEG C, by the aqueous solution of polyetheramine D4000 that the aqueous solution of sodium alginate that mass percent concentration is 1.5% and mass percent concentration are 8%, sodium alginate is respectively 66000 and 4000 with the relative molecular weight that mol ratio is 1:0.8 sodium alginate and polyetheramine D4000 of polyetheramine D4000, stirring is accompanied by during mixing, with the HCl solution of 0.3mol/L, the pH value of system being adjusted to 4, then dripping concentration in mixed liquor is the CuSO of 0.5g/mL4Aqueous solution, CuSO4Being 5:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 2h, i.e. obtains loaded Cu2+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 6.3%, continuously stirred and add precipitant acetone, precipitant acetone and loaded Cu2+The volume ratio of hybrid material aqueous solution of sodium alginate be 3:1, collected by suction precipitate, repeatedly rinse precipitate with acetone 3 times, precipitate is 28 DEG C in temperature, and vacuum the most i.e. obtains water solublity loaded Cu for vacuum drying oven under the conditions of-0.1MPa2+Sodium alginate hybrid material, this hybrid material has the Cu of flame retardant effect2+Load capacity be 70mg/g.
Water solublity loaded Cu by preparation2+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 4%, use wet spinning technology, obtain loaded Cu2+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 32 DEG C, coagulation bath composition be mass percent concentration be the calcium chloride solution of 8%, coagulation bath temperature is 25 DEG C, and draw ratio is 150%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.66cN/tex, and line density is 3.3dtex, and limited oxygen index is 35.5%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 6
A kind of loaded Ag+The preparation method of sodium alginate fire resistance fibre, under the conditions of 60 DEG C, by the aqueous solution of polyetheramine T403 that the aqueous solution of sodium alginate that mass percent concentration is 2% and mass percent concentration are 6%, sodium alginate is 1:0.8 with the mol ratio of polyetheramine T403, the relative molecular weight of sodium alginate and polyetheramine T403 is respectively 30000 and 400, stirring is accompanied by, with the H of 0.05mol/L during mixing2SO4The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is the AgNO of 0.03g/mL3Aqueous solution, AgNO3Being 8:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 2h, i.e. obtains loaded Ag+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 2.0%, continuously stirred and add precipitant acetone, precipitant acetone and loaded Ag+The volume ratio of hybrid material aqueous solution of sodium alginate be 2:1, collected by suction precipitate, repeatedly rinse precipitate with acetone 3 times, precipitate is 30 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity loaded Ag under the conditions of 0.09MPa+Sodium alginate hybrid material, this hybrid material has the Ag of flame retardant effect+Load capacity be 408mg/g.
Water solublity loaded Ag by preparation+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 5%, use wet spinning technology, obtain loaded Ag+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 35 DEG C, coagulation bath composition be mass percent concentration be the calcium chloride solution of 10%, coagulation bath temperature is 35 DEG C, and draw ratio is 170%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.59cN/tex, and line density is 3.4dtex, and limited oxygen index is 36.3%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 7
A kind of load Fe2+The preparation method of sodium alginate fire resistance fibre, under the conditions of 28 DEG C, by the aqueous solution of polyetheramine T3000 that the aqueous solution of sodium alginate that mass percent concentration is 1.7% and mass percent concentration are 9%, sodium alginate is 1:0.7 with the mol ratio of polyetheramine T3000, the relative molecular weight of sodium alginate and polyetheramine T3000 is respectively 36000 and 3000, stirring is accompanied by, with the H of 0.07mol/L during mixing2SO4The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is the FeCl of 1.6g/mL2Aqueous solution, FeCl2Being 0.5:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 1h, i.e. obtains loading Fe2+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 5.5%, continuously stirred and add precipitant ethanol, precipitant ethanol and load Fe2+The volume ratio of hybrid material aqueous solution of sodium alginate be 3:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 2 times, precipitate is 30 DEG C in temperature, and vacuum the most i.e. obtains water solublity load Fe for vacuum drying oven under the conditions of-0.1MPa2+Sodium alginate hybrid material, this hybrid material has the Fe of flame retardant effect2+Load capacity be 40mg/g.
By the water solublity load Fe of preparation2+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 6%, use wet spinning technology, obtain loading Fe2+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 40 DEG C, coagulation bath composition be mass percent concentration be the calcium chloride solution of 11%, coagulation bath temperature is 40 DEG C, and draw ratio is 180%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.56cN/tex, and line density is 3.5dtex, and limited oxygen index is 36.2%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 8
A kind of load Fe3+The preparation method of sodium alginate fire resistance fibre, under the conditions of 40 DEG C, by the aqueous solution of aliphatic amine polyoxyethylene ether AC-1210 that the aqueous solution of sodium alginate that mass percent concentration is 1.5% and mass percent concentration are 7%, sodium alginate is 1:0.6 with the mol ratio of aliphatic amine polyoxyethylene ether AC-1210, the relative molecular weight of sodium alginate and aliphatic amine polyoxyethylene ether AC-1210 is respectively 10000 and 1200, stirring is accompanied by, with the H of 0.1mol/L during mixing2SO4The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is the FeCl of 0.01g/mL3Aqueous solution, FeCl3Being 3:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 2h, i.e. obtains loading Fe3+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 3.1%, continuously stirred and add precipitant acetone, precipitant acetone and load Fe3+The volume ratio of hybrid material aqueous solution of sodium alginate be 2:1, collected by suction precipitate, repeatedly rinse precipitate with acetone 2 times, precipitate is 26 DEG C in temperature, and vacuum the most i.e. obtains water solublity load Fe for vacuum drying oven under the conditions of-0.1MPa3+Sodium alginate hybrid material, this hybrid material has the Fe of flame retardant effect3+Load capacity be 180mg/g.
By the water solublity load Fe of preparation3+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 7%, use wet spinning technology, obtain loading Fe3+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 45 DEG C, coagulation bath composition be mass percent concentration be the calcium chloride solution of 12%, coagulation bath temperature is 45 DEG C, and draw ratio is 190%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.68cN/tex, and line density is 3.5dtex, and limited oxygen index is 36.8%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 9
A kind of load Zn2+The preparation method of sodium alginate fire resistance fibre, under the conditions of 50 DEG C, by the aqueous solution of aliphatic amine polyoxyethylene ether AC-1810 that the aqueous solution of sodium alginate that mass percent concentration is 0.5% and mass percent concentration are 5%, sodium alginate is 1:0.8 with the mol ratio of aliphatic amine polyoxyethylene ether AC-1810, the relative molecular weight of sodium alginate and aliphatic amine polyoxyethylene ether AC-1810 is respectively 80000 and 1800, stirring is accompanied by, with the H of 0.12mol/L during mixing2SO4The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is the ZnCl of 0.05g/mL2Aqueous solution, ZnCl2Being 0.8:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 1h, i.e. obtains loading Zn2+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 2.2%, continuously stirred and add precipitant ethanol, precipitant ethanol and load Zn2+The volume ratio of hybrid material aqueous solution of sodium alginate be 2:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 3 times, precipitate is 29 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity load Zn under the conditions of 0.05MPa2+Sodium alginate hybrid material, this hybrid material has the Zn of flame retardant effect2+Load capacity be 27mg/g.
By the water solublity load Zn of preparation2+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 8%, use wet spinning technology, obtain loading Zn2+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 50 DEG C, coagulation bath composition be mass percent concentration be the calcium chloride solution of 14%, coagulation bath temperature is 50 DEG C, and draw ratio is 200%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.88cN/tex, and line density is 3.4dtex, and limited oxygen index is 36.1%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 10
A kind of loaded Cu2+The preparation method of sodium alginate fire resistance fibre, under the conditions of 20 DEG C, by the aqueous solution of aliphatic amine polyoxyethylene ether AC-1812 that the aqueous solution of sodium alginate that mass percent concentration is 2.5% and mass percent concentration are 5%, sodium alginate is 1:0.6 with the mol ratio of aliphatic amine polyoxyethylene ether AC-1812, the relative molecular weight of sodium alginate and aliphatic amine polyoxyethylene ether AC-1812 is respectively 10000 and 1900, stirring is accompanied by, with the H of 0.15mol/L during mixing2SO4The pH value of system is adjusted to 4 by solution, and then dripping concentration in mixed liquor is the CuSO of 0.16g/mL4Aqueous solution, CuSO4Being 0.6:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 1.5h, i.e. obtains loaded Cu2+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 4.2%, continuously stirred and add precipitant acetone, precipitant acetone and loaded Cu2+The volume ratio of hybrid material aqueous solution of sodium alginate be 2:1, collected by suction precipitate, repeatedly rinse precipitate with acetone 2 times, precipitate is 30 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity loaded Cu under the conditions of 0.02MPa2+Sodium alginate hybrid material, this hybrid material has the Cu of flame retardant effect2+Load capacity be 23mg/g.
Water solublity loaded Cu by preparation2+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 10%, use wet spinning technology, obtain loaded Cu2+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 55 DEG C, coagulation bath composition be mass percent concentration be the calcium chloride solution of 15%, coagulation bath temperature is 10 DEG C, and draw ratio is 210%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.77cN/tex, and line density is 3.5dtex, and limited oxygen index is 35.8%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 11
A kind of loaded Ag+The preparation method of sodium alginate fire resistance fibre, under the conditions of 40 DEG C, by the aqueous solution of aliphatic amine polyoxyethylene ether AC-1815 that the aqueous solution of sodium alginate that mass percent concentration is 2.8% and mass percent concentration are 6%, sodium alginate is 1:0.8 with the mol ratio of aliphatic amine polyoxyethylene ether AC-1815, the relative molecular weight of sodium alginate and aliphatic amine polyoxyethylene ether AC-1815 is respectively 32000 and 900, stirring is accompanied by, with the HNO of 0.1mol/L during mixing3The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is the AgNO of 0.18g/mL3Aqueous solution, AgNO3Being 3:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 2h, i.e. obtains loaded Ag+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 3%, continuously stirred and add precipitant ethanol, precipitant ethanol and loaded Ag+The volume ratio of hybrid material aqueous solution of sodium alginate be 4:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 2 times, precipitate is 26 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity loaded Ag under the conditions of 0.01MPa+Sodium alginate hybrid material, this hybrid material has the Ag of flame retardant effect+Load capacity be 148mg/g.
Water solublity loaded Ag by preparation+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 10%, use wet spinning technology, obtain loaded Ag+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 60 DEG C, coagulation bath composition be mass percent concentration be calcium chloride and the zinc chloride mixed solution of 1%, calcium chloride is 1:1 with the mass ratio of zinc chloride, coagulation bath temperature is 15 DEG C, and draw ratio is 220%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 4.12cN/tex, and line density is 3.5dtex, and limited oxygen index is 34.9%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 12
A kind of load Fe2+The preparation method of sodium alginate fire resistance fibre, under the conditions of 30 DEG C, by the aqueous solution of aliphatic amine polyoxyethylene ether AC-1205 that the aqueous solution of sodium alginate that mass percent concentration is 0.9% and mass percent concentration are 8%, sodium alginate is 1:1 with the mol ratio of aliphatic amine polyoxyethylene ether AC-1205, the relative molecular weight of sodium alginate and aliphatic amine polyoxyethylene ether AC-1205 is respectively 28000 and 1200, stirring is accompanied by, with the HNO of 0.15mol/L during mixing3The pH value of system is adjusted to 5 by solution, and then dripping concentration in mixed liquor is the FeCl of 0.006g/mL2Aqueous solution, FeCl2Being 0.6:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 1h, i.e. obtains loading Fe2+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 2.8%, continuously stirred and add precipitant ethanol, precipitant ethanol and load Fe2+The volume ratio of hybrid material aqueous solution of sodium alginate be 2:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 3 times, precipitate is 25 DEG C in temperature, and vacuum the most i.e. obtains water solublity load Fe for vacuum drying oven under the conditions of-0.09MPa2+Sodium alginate hybrid material, this hybrid material has the Fe of flame retardant effect2+Load capacity be 34mg/g.
By the water solublity load Fe of preparation2+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 3%, use wet spinning technology, obtain loading Fe2+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 10 DEG C, coagulation bath composition be mass percent concentration be calcium chloride and the zinc chloride mixed solution of 8%, calcium chloride is 2.5:1 with the mass ratio of zinc chloride, coagulation bath temperature is 22 DEG C, and draw ratio is 210%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.95cN/tex, and line density is 3.47dtex, and limited oxygen index is 34.5%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 13
A kind of load Fe3+The preparation method of sodium alginate fire resistance fibre, under the conditions of 60 DEG C, by the aqueous solution of polyetheramine T5000 that the aqueous solution of sodium alginate that mass percent concentration is 3% and mass percent concentration are 10%, sodium alginate is 1:1 with the mol ratio of polyetheramine T5000, the relative molecular weight of sodium alginate and polyetheramine T5000 is respectively 36000 and 5000, stirring is accompanied by, with the HNO of 0.2mol/L during mixing3The pH value of system is adjusted to 4 by solution, and then dripping concentration in mixed liquor is the FeCl of 2g/mL3Aqueous solution, FeCl3Being 10:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 2h, i.e. obtains loading Fe3+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 8.3%, continuously stirred and add precipitant ethanol, precipitant ethanol and load Fe3+The volume ratio of hybrid material aqueous solution of sodium alginate be 2:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 3 times, precipitate is 30 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity load Fe under the conditions of 0.09MPa3+Sodium alginate hybrid material, this hybrid material has the Fe of flame retardant effect3+Load capacity be 49mg/g.
By the water solublity load Fe of preparation3+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 1%, use wet spinning technology, obtain loading Fe3+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 15 DEG C, coagulation bath composition be mass percent concentration be calcium chloride and the zinc chloride mixed solution of 3%, calcium chloride is 1.5:1 with the mass ratio of zinc chloride, coagulation bath temperature is 25 DEG C, and draw ratio is 240%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 4.56cN/tex, and line density is 3.17dtex, and limited oxygen index is 36.2%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 14
A kind of load Zn2+The preparation method of sodium alginate fire resistance fibre, under the conditions of 40 DEG C, by the aqueous solution of aliphatic amine polyoxyethylene ether AC-1215 that the aqueous solution of sodium alginate that mass percent concentration is 1.2% and mass percent concentration are 3%, sodium alginate is 1:0.5 with the mol ratio of aliphatic amine polyoxyethylene ether AC-1215, the relative molecular weight of sodium alginate and aliphatic amine polyoxyethylene ether AC-1215 is respectively 53000 and 800, stirring is accompanied by, with the HNO of 0.25mol/L during mixing3The pH value of system is adjusted to 5 by solution, and then dripping concentration in mixed liquor is the ZnCl of 0.12g/mL2Aqueous solution, ZnCl2Being 2:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 1h, i.e. obtains loading Zn2+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 2.9%, continuously stirred and add precipitant acetone, precipitant acetone and load Zn2+The volume ratio of hybrid material aqueous solution of sodium alginate be 2:1, collected by suction precipitate, repeatedly rinse precipitate with acetone 2 times, precipitate is 26 DEG C in temperature, and vacuum the most i.e. obtains water solublity load Zn for vacuum drying oven under the conditions of-0.1MPa2+Sodium alginate hybrid material, this hybrid material has the Zn of flame retardant effect2+Load capacity be 215mg/g.
By the water solublity load Zn of preparation2+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 2%, use wet spinning technology, obtain loading Zn2+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 20 DEG C, coagulation bath composition be mass percent concentration be calcium chloride and the zinc chloride mixed solution of 3%, calcium chloride is 1.8:1 with the mass ratio of zinc chloride, coagulation bath temperature is 28 DEG C, and draw ratio is 250%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.56cN/tex, and line density is 3.22dtex, and limited oxygen index is 35.9%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 15
A kind of loaded Cu2+The preparation method of sodium alginate fire resistance fibre, under the conditions of 30 DEG C, by the aqueous solution of n-butylamine that the aqueous solution of sodium alginate that mass percent concentration is 1.6% and mass percent concentration are 7%, sodium alginate is 1:0.9 with the mol ratio of n-butylamine, the relative molecular weight of sodium alginate and n-butylamine is respectively 80000 and 73.14, stirring is accompanied by, with the HNO of 0.3mol/L during mixing3The pH value of system is adjusted to 5 by solution, and then dripping concentration in mixed liquor is the CuSO of 0.8g/mL4Aqueous solution, CuSO4Being 6:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 1h, i.e. obtains loaded Cu2+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 10.5%, continuously stirred and add precipitant ethanol, precipitant ethanol and loaded Cu2+The volume ratio of hybrid material aqueous solution of sodium alginate be 3:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 3 times, precipitate is 28 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity loaded Cu under the conditions of 0.09MPa2+Sodium alginate hybrid material, this hybrid material has the Cu of flame retardant effect2+Load capacity be 825mg/g.
Water solublity loaded Cu by preparation2+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 5%, use wet spinning technology, obtain loaded Cu2+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 30 DEG C, coagulation bath composition be mass percent concentration be calcium chloride and the zinc chloride mixed solution of 5%, calcium chloride is 2:1 with the mass ratio of zinc chloride, coagulation bath temperature is 30 DEG C, and draw ratio is 260%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.99cN/tex, and line density is 3.22dtex, and limited oxygen index is 35.7%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 16
A kind of loaded Ag+The preparation method of sodium alginate fire resistance fibre, under the conditions of 20 DEG C, by the aqueous solution of n-amylamine that the aqueous solution of sodium alginate that mass percent concentration is 2.4% and mass percent concentration are 6%, sodium alginate is 1:0.4 with the mol ratio of n-amylamine, the relative molecular weight of sodium alginate and n-amylamine is respectively 80000 and 87.16, accompanying by stirring during mixing, with the HCl solution of 0.1mol/L, the pH value of system is adjusted to 6, then dripping concentration in mixed liquor is the AgNO of 0.06g/mL3Aqueous solution, AgNO3Being 0.8:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 2h, i.e. obtains loaded Ag+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 2.5%, continuously stirred and add precipitant acetone, precipitant acetone and loaded Ag+The volume ratio of hybrid material aqueous solution of sodium alginate be 3:1, collected by suction precipitate, repeatedly rinse precipitate with acetone 2 times, precipitate is 29 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity loaded Ag under the conditions of 0.09MPa+Sodium alginate hybrid material, this hybrid material has the Ag of flame retardant effect+Load capacity be 119mg/g.
Water solublity loaded Ag by preparation+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 6%, use wet spinning technology, obtain loaded Ag+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 40 DEG C, coagulation bath composition be mass percent concentration be calcium chloride and the zinc chloride mixed solution of 9%, calcium chloride is 1:1 with the mass ratio of zinc chloride, coagulation bath temperature is 34 DEG C, and draw ratio is 270%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 4.26cN/tex, and line density is 3.5dtex, and limited oxygen index is 35.1%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 17
A kind of load Fe2+The preparation method of sodium alginate fire resistance fibre, under the conditions of 25 DEG C, by the aqueous solution of n-hexylamine that the aqueous solution of sodium alginate that mass percent concentration is 0.8% and mass percent concentration are 5%, sodium alginate is 1:0.7 with the mol ratio of n-hexylamine, the relative molecular weight of sodium alginate and n-hexylamine is respectively 21000 and 101.19, accompanying by stirring during mixing, with the HCl solution of 0.3mol/L, the pH value of system is adjusted to 4, then dripping concentration in mixed liquor is the FeCl of 0.08g/mL2Aqueous solution, FeCl2Being 3.5:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 2h, i.e. obtains loading Fe2+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 0.5%, continuously stirred and add precipitant acetone, precipitant acetone and load Fe2+The volume ratio of hybrid material aqueous solution of sodium alginate be 3:1, collected by suction precipitate, repeatedly rinse precipitate with acetone 3 times, precipitate is 29 DEG C in temperature, and vacuum the most i.e. obtains water solublity load Fe for vacuum drying oven under the conditions of-0.1MPa2+Sodium alginate hybrid material, this hybrid material has the Fe of flame retardant effect2+Load capacity be 795mg/g.
By the water solublity load Fe of preparation2+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 8%, use wet spinning technology, obtain loading Fe2+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 45 DEG C, coagulation bath composition be mass percent concentration be calcium chloride and the zinc chloride mixed solution of 10%, calcium chloride is 3:1 with the mass ratio of zinc chloride, coagulation bath temperature is 35 DEG C, and draw ratio is 280%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.86cN/tex, and line density is 2.77dtex, and limited oxygen index is 34.9%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 18
A kind of load Fe3+The preparation method of sodium alginate fire resistance fibre, under the conditions of 50 DEG C, by the aqueous solution of n-hexylamine that the aqueous solution of sodium alginate that mass percent concentration is 2.6% and mass percent concentration are 5%, sodium alginate is 1:0.5 with the mol ratio of n-hexylamine, the relative molecular weight of sodium alginate and n-hexylamine is respectively 40000 and 101.19, stirring is accompanied by, with the H of 0.05mol/L during mixing2SO4The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is the FeCl of 0.5g/mL3Aqueous solution, FeCl3Being 5:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 1h, i.e. obtains loading Fe3+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 7.3%, continuously stirred and add precipitant ethanol, precipitant ethanol and load Fe3+The volume ratio of hybrid material aqueous solution of sodium alginate be 2:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 2 times, precipitate is 27 DEG C in temperature, and vacuum the most i.e. obtains water solublity load Fe for vacuum drying oven under the conditions of-0.09MPa3+Sodium alginate hybrid material, this hybrid material has the Fe of flame retardant effect3+Load capacity be 669mg/g.
By the water solublity load Fe of preparation3+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 9%, use wet spinning technology, obtain loading Fe3+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 50 DEG C, coagulation bath composition be mass percent concentration be calcium chloride and the zinc chloride mixed solution of 11%, calcium chloride is 3:1 with the mass ratio of zinc chloride, coagulation bath temperature is 38 DEG C, and draw ratio is 285%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 4.11cN/tex, and line density is 3.12dtex, and limited oxygen index is 34.7%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 19
A kind of load Zn2+The preparation method of sodium alginate fire resistance fibre, under the conditions of 60 DEG C, by the aqueous solution of n-propylamine that the aqueous solution of sodium alginate that mass percent concentration is 1.4% and mass percent concentration are 3%, sodium alginate is 1:0.3 with the mol ratio of n-propylamine, the relative molecular weight of sodium alginate and n-propylamine is respectively 23800 and 59.11, stirring is accompanied by, with the H of 0.15mol/L during mixing2SO4The pH value of system is adjusted to 5 by solution, and then dripping concentration in mixed liquor is the ZnCl of 0.15g/mL2Aqueous solution, ZnCl2Aqueous solution is 0.6:1 with the mol ratio of sodium alginate, stirs after dropping, and the persistent period is 1h, i.e. obtains loading Zn2+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 2.1%, continuously stirred and add precipitant ethanol, precipitant ethanol and load Zn2+The volume ratio of hybrid material aqueous solution of sodium alginate be 2:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 3 times, precipitate is 26 DEG C in temperature, and vacuum is that vacuum drying oven the most i.e. obtains water solublity load Zn under the conditions of 0.09MPa2+Sodium alginate hybrid material, this hybrid material has the Zn of flame retardant effect2+Load capacity be 246mg/g.
By the water solublity load Zn of preparation2+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 10%, use wet spinning technology, obtain loading Zn2+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 60 DEG C, coagulation bath composition be mass percent concentration be calcium chloride and the zinc chloride mixed solution of 12%, calcium chloride is 1:1 with the mass ratio of zinc chloride, coagulation bath temperature is 40 DEG C, and draw ratio is 290%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.57cN/tex, and line density is 3.27dtex, and limited oxygen index is 35.1%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.
Embodiment 20
A kind of loaded Cu2+The preparation method of sodium alginate fire resistance fibre, under the conditions of 20 DEG C, by the aqueous solution of polyetheramine D230 that the aqueous solution of sodium alginate that mass percent concentration is 2.9% and mass percent concentration are 4%, sodium alginate is 1:0.6 with the mol ratio of polyetheramine D230, the relative molecular weight of sodium alginate and polyetheramine D230 is respectively 45000 and 230, stirring is accompanied by, with the HNO of 0.3mol/L during mixing3The pH value of system is adjusted to 6 by solution, and then dripping concentration in mixed liquor is the CuSO of 0.5g/mL4Aqueous solution, CuSO4Being 3:1 with the mol ratio of sodium alginate, stir after dropping, the persistent period is 2h, i.e. obtains loaded Cu2+The hybrid material aqueous solution of sodium alginate, its mass percent concentration is 10.5%, continuously stirred and add precipitant ethanol, precipitant ethanol and loaded Cu2+The volume ratio of hybrid material aqueous solution of sodium alginate be 4:1, collected by suction precipitate, repeatedly rinse precipitate with ethanol 3 times, precipitate is 25 DEG C in temperature, and vacuum the most i.e. obtains water solublity loaded Cu for vacuum drying oven under the conditions of-0.1MPa2+Sodium alginate hybrid material, this hybrid material has the Cu of flame retardant effect2+Load capacity be 544mg/g.
Water solublity loaded Cu by preparation2+Sodium alginate hybrid material be dissolved in deionized water, stir, be made into the wet spinning solution that mass percent concentration is 5%, use wet spinning technology, obtain loaded Cu2+Sodium alginate fire resistance fibre, spinning process condition is: spinning temperature is 10 DEG C, coagulation bath composition be mass percent concentration be calcium chloride and the zinc chloride mixed solution of 15%, calcium chloride is 3:1 with the mass ratio of zinc chloride, coagulation bath temperature is 50 DEG C, and draw ratio is 300%.The alginate fibre obtained carries out mechanical property and combustibility analysis, and test result is: hot strength is 3.83cN/tex, and line density is 3.22dtex, and limited oxygen index is 35.4%.Illustrate that the sodium alginate fiber being prepared by the method for the present invention has more excellent intensity and inherent flame retardancy.

Claims (10)

1. a sodium alginate fire resistance fibre for loaded metal ion, is characterized in that: by the sodium alginate hybrid material of water soluble negative carrying metal ion be dissolved in water prepare spinning solution through wet spinning technology prepare；The sodium alginate hybrid material of described water soluble negative carrying metal ion is by sodium alginate, stabilizer molecule and has the metal ion of flame retardant effect and forms；In the sodium alginate hybrid material of described water soluble negative carrying metal ion, by ionic bond and coordinate bond keyed jointing between the carboxyl of sodium alginate, the amino of stabilizer molecule and the metal ion with flame retardant effect；
In described sodium alginate and described stabilizer molecule, carboxyl-content, amino content and hydroxy radical content sum are more than or equal to described sodium alginate and the 160% of the mole sum of described stabilizer molecule；
Described by ionic bond and the carboxyl of coordinate bond keyed jointing and described by the amino content sum of ionic bond and coordinate bond keyed jointing more than or equal to carboxyl and the 30% of amino mole sum in described sodium alginate and described stabilizer molecule；
Relative molecular weight >=10000 of described sodium alginate；
Relative molecular weight≤5000 of described stabilizer molecule, for chain length less than the one in the alkyl streptamine of 6 carbon, polyetheramine D230, polyetheramine D400, polyetheramine D2000, polyetheramine D4000, polyetheramine T403, polyetheramine T3000, polyetheramine T5000, aliphatic amine polyoxyethylene ether AC-1810, aliphatic amine polyoxyethylene ether AC-1812, aliphatic amine polyoxyethylene ether AC-1815, aliphatic amine polyoxyethylene ether AC-1205, aliphatic amine polyoxyethylene ether AC-1210 and aliphatic amine polyoxyethylene ether AC-1215；Described chain length is n-propylamine, n-butylamine, n-amylamine or n-hexylamine less than the alkyl streptamine of 6 carbon；
The general structure of the sodium alginate hybrid material of described water soluble negative carrying metal ion is:
Wherein, strand repetitive number n > 0；
Wherein, the one during R is following functional group: cation group, anionic group or polar nonionic group；Described cation group is tertiary amine base or quaternary ammonium group；Described anionic group is carboxylic acid group；Described polar nonionic group is hydroxyl, ether, amino, amide groups, sulfydryl or halogen；
Mx+For having the metal ion of flame retardant effect, the value of valence state x is 1～3, for: Ag+、Fe2+、Fe3+、Zn2+Or Cu2+。
The sodium alginate fire resistance fibre of a kind of loaded metal ion the most according to claim 1, it is characterised in that described stabilizer molecule also comprises hydroxyl or carboxyl.
The sodium alginate fire resistance fibre of a kind of loaded metal ion the most according to claim 1, it is characterised in that described carboxyl is positioned at molecular backbone or side chain；Described amino is positioned at molecular backbone or side chain.
The sodium alginate fire resistance fibre of a kind of loaded metal ion the most according to claim 1, it is characterised in that described stabilizer molecular backbone also includes element O, N or S.
The sodium alginate fire resistance fibre of a kind of loaded metal ion the most according to claim 1, it is characterised in that the load capacity of the metal ion in the sodium alginate hybrid material of described water soluble negative carrying metal ion with flame retardant effect is 10～825mg/g；The sodium alginate fire resistance fibre limited oxygen index of described loaded metal ion reaches more than 34%, and the hot strength of fiber is more than 3.5cN/tex, and line density is 2.2～3.5dtex.
6. the preparation method of the sodium alginate fire resistance fibre of a kind of loaded metal ion as according to any one of Claims 1 to 5, it is characterized in that: by sodium alginate aqueous solution and the aqueous solution containing stabilizer molecule, the pH value of regulation reaction system is to 4～6, then in mixed liquor, drip metal ion salt solution, stir after dropping, obtain the hybrid material aqueous solution of the sodium alginate of loaded metal ion, continuously stirred and add precipitant, precipitate is collected by filtration, after drying precipitate, i.e. obtains the sodium alginate hybrid material of water soluble negative carrying metal ion；The sodium alginate hybrid material of water soluble negative carrying metal ion is dissolved in deionized water, stirs, be made into wet spinning solution, use wet spinning technology, obtain the sodium alginate fire resistance fibre of loaded metal ion.
The preparation method of the sodium alginate fire resistance fibre of a kind of loaded metal ion the most according to claim 6, it is characterised in that by the aqueous solution of sodium alginate and the aqueous solution containing stabilizer molecule, be under the conditions of 20～60 DEG C；Stirring is accompanied by during mixing；The pH value of regulation reaction system uses the H of HCl solution, 0.05～the 0.15mol/L of 0.1～0.3mol/L2SO4Solution or the HNO of 0.1～0.3mol/L3Solution regulates；Stirring after metal ion salt solution dropping, the persistent period is 1～2h；Drying precipitate uses vacuum drying oven to be dried.
The preparation method of the sodium alginate fire resistance fibre of a kind of loaded metal ion the most according to claim 6, it is characterised in that described metal ion salt solution is AgNO3、FeCl2、FeCl3、ZnCl2Or CuSO4Aqueous solution；Described precipitant is ethanol or acetone.
The preparation method of the sodium alginate fire resistance fibre of a kind of loaded metal ion the most according to claim 6, it is characterized in that, when the aqueous solution of described sodium alginate and the aqueous solution containing stabilizer molecule, sodium alginate is 1:0.3～1 with the mol ratio of stabilizer molecule；
The mass percent concentration of described sodium alginate aqueous solution is 0.5%～3%；
The mass percent concentration of the described aqueous solution containing stabilizer molecule is 3%～10%；
The concentration of described metal ion salt solution is 0.005～2g/mL；
Described metal cation salt is 0.1～10:1 with the mol ratio of sodium alginate；
The mass percent concentration of the hybrid material aqueous solution of the sodium alginate of described loaded metal ion is 0.5%～10.5%；
Described precipitant is 2～4:1 with the volume ratio of the aqueous solution of the sodium alginate hybrid material of loaded metal ion；
The temperature of described drying precipitate is 25～30 DEG C, and vacuum is 0.09～-0.1MPa.
The preparation method of the sodium alginate fire resistance fibre of a kind of loaded metal ion the most according to claim 6, it is characterized in that, described wet spinning technology is: in spinning solution, the mass percent concentration of the sodium alginate hybrid material of loaded metal ion is 1～10%, spinning temperature is 10～60 DEG C, coagulating bath be mass percent concentration be calcium chloride solution or calcium chloride that mass percent concentration is 1%～15% and the zinc chloride mixed solution of 1%～15%, calcium chloride and calcium chloride in zinc chloride mixed solution and the mass ratio 1～3:1 of zinc chloride, coagulation bath temperature is 10～50 DEG C, draw ratio is 120%～300%.
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